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Investigations on Catalyzed

Steam Gasification of Biomass

1. K. Mudge
S. L. Weber
D. H. Mitchell
L. J. Sealock, Jr.
R. J. Robertus

January1981

Prepared for the U.S. Department of Energy


under Contract DE-AC06-76RLO 1830

Pacific Northwest Laboratory


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by Battelle Memorial Institute % ,
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INVESTIGATIONS ON CATALYZED
STEAM GAS I F I CATION OF BIOMASS

L. K. Mudge
S. L. Weber
D. H. Mitchell
L. J. Sealock, J r .
R. J. Robertus

January 1981

Prepared f o r
t h e U.S. Department o f Energy
under Contract DE-AC06-76RLO-1830

P a c i f i c Northwest Laboratory
Richland, Washington 99352
SUMMARY

The P a c i f i c Northwest Laboratory (PNL) i s conducting an ongoing study,


sponsored by the Biomass Energy Systems D i v i s i o n o f the U.S. Department o f
Energy, on t h e g a s i f i c a t i o n o f biomass i n t h e presence o f c a t a l y s t s . The pur-
pose o f the study i s t o evaluate the t e c h n i c a l and economic f e a s i b i l i t y o f pro-
ducing s p e c i f i c gas products v i a t h e c a t a l y t i c g a s i f i c a t o n o f biomass. This
r e p o r t presents the r e s u l t s o f research conducted from December 1977 t o October
1980.

The study was comprised o f l a b o r a t o r y studies, process development, and


economic analyses. The l a b o r a t o r y s t u d i e s were conducted t o develop o p e r a t i n g
c o n d i t i o n s and c a t a l y s t systzms f o r generating methane- rich gas, synthesis
gases, hydrogen, and carbon monoxide; these s t u d i e s a l s o developed techniques
f o r c a t a l y s t recovery, regeneration, and r e c y c l i n g . A process development u n i t
(PDU) was designed and constructed t o evaluate 1aboratory systems a t c o n d i t i o n s
approximating commercial operations. The economic analyses, performed by Davy
McKee, Inc. f o r PNL, evaluated t h e f e a s i b i l i t y o f adapting the wood-to-methane
and wood-to-methanol processes t o f u l l - s c a l e commercial operations. Plants
were designed i n t h e economic analyses t o produce fuel- grade methanol from
wood and s u b s t i t u t e n a t u r a l gas (SNG) from wood v i a c a t a l y t i c g a s i f i c a t i o n w i t h
steam.

Conditions developed i n the l a b o r a t o r y f o r generation o f a methane- rich


gas and a synthesis gas f o r methanol production were confirmed i n t h e f l u i d -
bed, PDU operations. No p a r t i c u l a r problems w i t h scale- up were experienced.

C a t a l y t i c steam g a s i f i c a t i o n o f biomass has several advantages over con-


ventional gasification.

No oxygen i s r e q u i r e d f o r generation o f a methane-rich gas or a


methanol synthesis gas, therefore, no oxygen p l a n t i s needed.

L i t t l e or no t a r i s produced r e q u i r i n g o n l y simple gas cleaning and


waste-water treatment equipment.

No s h i f t r e a c t o r i s r e q u i r e d f o r methanol synthesis.
Methanation requirements are low r e s u l t i n g i n h i g h conversion
efficiency.

a Y i e l d s and e f f i c i e n c i e s are g r e a t e r .

The comnercial g a s i f i c a t i o n p l a n t s were designed t o process 2000 tons


(1800 t ) o f d r y wood per day and 10% of t h a t capacity. For t h e l a r g e - s c a l e
methanol p l a n t , p r o d u c t i o n i s 997 tons (900 t ) of methanol per day w i t h a
h i g h e r h e a t i n g value (HHV) o f 9784 B t u per pound. For t h e l a r g e - s c a l e SNG
3
p l a n t , p r o d u c t i o n i s 21.6 m i l l i o n s c f d (610,000 nm /day) o f SNG w i t h a HHV
3
o f 956 B t u per s c f (35,600 kJ/nm ) . A l l y i e l d s from the small- scale p l a n t s
are 10% o f t h e l a r g e - s c a l e p l a n t s . The p l a n t design i n c l u d e d a l l process and
support f a c i l i t i e s necessary t o convert wood. The p l a n t l o c a t i o n i s t h e
P a c i f i c Northwest.

The c a p i t a l c o s t s f o r t h e l a r g e - s c a l e wood-to-methanol and wood-to-methane


p l ants are, on a September 1980 basis, $120,830,000 and $95,115,000, respec-
tively. Production c o s t s t h a t a l l o w f o r r e t u r n on c a p i t a l were c a l c u l a t e d a t
various wood c o s t s f o r b o t h u t i l i t y and p r i v a t e i n v e s t o r f i n a n c i n g . A t a wood
c o s t t o the l a r g e - s c a l e p l a n t o f $20 per d r y t o n ( $ 2 2 / t d r y ) , t h e methanol c o s t
was $0.55/gal ($0.15/L) and $0.69/gal ($0.18/L) f o r u t i 1i t y and p r i v a t e inves-
t o r f i n a n c i n g , r e s p e c t i v e l y ; s i m i l a r l y , methane costs were $ 6 . 5 0 / m i l l i o n B t u
and $ 8 . 1 0 / m i l l i o n Btu, r e s p e c t i v e l y . S i m i l a r c o s t s f o r t h e small- scale p l a n t s
were 2-112 t o 3 times g r e a t e r than f o r t h e l a r g e - s c a l e p l a n t s . The c o s t c a l c u -
l a t e d by t h e u t i l i t y f i n a n c i n g method i n c l u d e s a r e t u r n on e q u i t y o f 15% and an
i n t e r e s t r a t e o f 10% on debt. The p r i v a t e i n v e s t o r f i n a n c i n g method, which i s
100% e q u i t y f i n a n c i n g , i n c o r p o r a t e d a discounted cash f l o w r e t u r n on e q u i t y o f
12%. Economics are presented as a f u n c t i o n o f wood cost and p l a n t size.

The thermal e f f i c i e n c y o f t h e wood-to-methanol p l a n t i s 53%. The thermal


e f f i c i e n c y o f t h e wood-to-methane p l a n t , w i t h o u t t a k i n g c r e d i t f o r byproduct
char, i s 58%.

Continued research i n c a t a l y t i c g a s i f i c a t i o n o f biomass w i 11 i n c l u d e labo-


r a t o r y s t u d i e s t o examine more c a t a l y s t s , PDU s t u d i e s t o t e s t r e s u l t s o f t h e
c a t a l y s t development, and economic analyses t o develop a computer code t h a t
w i l l determine t h e e f f e c t s o f changes i n process y i e l d s and requirements on
overa 11 p l ant economi cs .
CONTENTS

SUMMARY . iii

INTRODUCTION .
CONCLUSIONS .
RECOMMENDATIONS

LABORATORY STUD1ES .
EXPERIMENTAL EQUIPMENT .
FEED MATERIALS .
EFFECTS OF A L K A L I CARBONATES .
EFFECTS OF SECONDARY CATALYSTS

RECOVERY OF ALKALI CARBONATE CATALYSTS .


SYSTEMS FOR METHANE GENERATION

SYSTEMS FOR GENERATION OF METHANOL SYNTHESIS GAS

SYSTEMS FOR GENERATION OF AMMONIA SYNTHESIS GAS

SYSTEMS FOR GENERATION OF HYDROGEN .


SYSTEMS FOR GENERATION OF CARBON MONOXIDE .
EVALUATION OF ALTERNATIVE BIOMASS MATERIALS .
FUTURE LABORATORY STUDIES

PROCESS DEVELOPMENT U N I T STUDIES .


PDU DESCRIPTION

Gasifier .
Wood F e e d S y s t e m .
Gas S u p p l y S y s t e m s .
Gas C l e a n u p S y s t e m .
I n s t r u m e n t a t i o n and D a t a A n a l y s i s .
PDU OPERATION .
Test Procedures and S a f e t y Considerations

Feedstock f o r t h e PDU .
PDU Results w i t h t h e Agitated- Bed G a s i f i e r

PDU Results With the Fluid- Bed G a s i f i e r .


C a l c u l a t i o n o f E q u i l i b r i u m Gas Compositions

FEASIBILITY STUDIES .
ECONOMICS OF CATALYTIC GASIFICATION

Wood-to-Methane P l a n t .
Wood-to-Methanol P l a n t .
COMPUTER MODELLING STUDIES .
FUTURE MODELLING EFFORTS .
ACKNOWLEDGMENTS

REFERENCES
FIGURES

Sumnary o f Study A c t i v i t i e s .
Batch-Feed Reactor .
Continuous Wood-Feed Reactor .
Volume o f Gas Production f o r Catalyzed and Noncatalyzed Steam
G a s i f i c a t i o n o f Wood a t 5500C

Re1a t i v e C a t a l y s t E f f e c t i v e n e s s a t 6500C

E f f e c t o f Temperature on Gas Production With and Without


Potassium Carbonate C a t a l y s t .
E f f e c t o f Sodium Carbonate Concentration on Gas Y i e l d a t 6500C

Catalyzed Test Results on Remaining Carbon Versus Time .


Uncatalyzed Test Results on Remaining Carbon Versus Time

Reaction Constant V a r i a t i o n With 1/T f o r Catalyzed Steam


G a s i f i c a t i o n o f Wood .
Postulated E f f e c t i v e n e s s F a c t o r

Hydrogen Chemisorption Apparatus .


Pore D i s t r i b u t i o n i n Fresh and Coked C a t a l y s t .
Coked Ni-3266 C a t a l y s t , 3340X .
Unused Ni-3266 C a t a l y s t s , 10,021X .
R e l a t i v e Concentrations o f Elements on Fresh and Exposed
C a t a l y s t Surfaces Employed f o r Methanantion .
Pore D i s t r i b u t i o n i n C a t a l y s t Used f o r Synthesis Gas Generation

Regenerated Ni-3266 C a t a l y s t Employed For Hydrocarbon Synthesis


Gas Production, 10,021X .
SEM Micrograph o f Fresh Ni-3266, 3960X .
SEM Micrograph o f Ni-3266 A f t e r 28.6 h o f Operation, 13,200X .
SEM Micrograph o f Ni-3266 A f t e r 61 h o f Operation, 13,200X .
SEM Micrograph o f Carbon Layers on Ni-3266 A f t e r 72 h
o f Operation, 132X .
SEM Micrograph o f Coked N i -3266 A f t e r 88 h o f Operation, 132X

SEM Micrograph o f Coked Ni-3266 A f t e r 117 h o f Operation, 132X

R e l a t i v e Concentrations o f Exposed Elements on Ni-3266


C a t a l y s t Surfaces .
Schematic o f O r i g i n a l PCU .
Photograph o f O r i g i n a l PDU

Schematic o f t h e S t i rred-Bed G a s i f i e r

Bottom Head o f Stirred- Bed G a s i f i e r .


View o f G a s i f i e r Cross Section .
Schematic o f Fluidized- Bed G a s i f i e r .
View o f Lock Hopper .
Gas Heater and C o n t r o l s .
Gas Recycle System .
Electrostatic Precipitator

PDU Schematic As o f October 1980 .


Methane Y i e l d s from t h e Agitated- Bed G a s i f i e r as a Function
o f Temperature and C a t a l y s t .
Carbon Conversions f o r Methane Production i n t h e
Agitated- Bed G a s i f i e r

Synthesis Gas Y i e l d s as a Function o f Temperature


i n the Agitated- Bed G a s i f i e r .
Carbon Conversions f o r Synthesis Gas Production i n t h e
Agitated- Bed G a s i f i e r

E f f e c t o f Steam-to-Wood R a t i o on Gas Composition f r o m t h e


Fluid- Bed G a s i f i e r .
Temperature P r o f i l e s i n Fluid- Bed G a s i f i e r .

v i ii
Comparisons o f Catalyzed Versus Uncatalyzed Results
f o r Methane Production .
Comparisons o f Catalyzed versus Uncatalyzed Results
f o r Synthesis Gas Production .
Effects of Temperature on t h e Dry Gas E q u i l i b r i u m Composition
a t Atmospheric Pressure f o r Steam-to-Wood R a t i o o f 0.33 .
E f f e c t s o f Temperature on the Dry Gas E q u i l i b r i u m Composition
a t Atmospheric Pressure f o r Steam-to-Wood R a t i o o f 1 .
Potent ia1 Methane and Methanol Y i e l d s a t Atmospheric Pressure

E f f e c t o f Temperature on E q u i l i b r i u m Standard Heats o f Reaction

E f f e c t o f Pressure on E q u i l i b r i u m Standard Heats o f Reaction .


E f f e c t o f Pressure on Production o f a Methane-Rich Gas .
E f f e c t o f Pressure on Production o f a Methanol Synthesis Gas .
Wood-To-Methane Process Areas .
E f f e c t o f Wood P r i c e s on Gas Cost f o r 2000 t o n l d a y Dry Wood .
Wood-To-Methanol Process Area .
E f f e c t o f Wood P r i c e s on Methanol Cost f o r 2000 t o n l d a y Dry Wood
TABLES

1 Comparative Analysis of Wood and Bark . 13


2 Gas Yields at 6500C 19
3 Elemental Yields at 6500C 19
4 Gas Yield from Different Wood and Bark Materials at 6500C . 20
5 Reaction Rate Constants for Wood Char-Steam Reaction in the
Presence of Catalysts 24
6 Activation Energies for the Wood-Char/Steam Reaction . 25
7 Yields from Batch Experiments of Wood-Steam Gasification
in the Presence of Catalysts . 28
8 Carbon Conversions and Energy Efficiencies in Batch Experiments . 28
9 Catalysts Tested for Methane Production . 31
10 Results of a Catalyst Lifetime Test for Methane Production . 32
11 Catalyst Performance Following Catalyst Regeneration . 33
12 Catalyst Characterization Tests Performed on a Ni -3266
Catalyst Used For Methane Production 34
13 Lifetime and Regenerability of Catalysts Tested for
Methane Generation . 39
14 Catalysts Screened for Methanol Synthesi s Gas Production 40
15 Results of a Catalyst Lifetime Test for Hydrocarbon Synthesis
Gas Production . 41
16 Characteristics of a Ni-3266 Catalyst Employed for Synthesis
Gas Production . 41
17 Use of a Ni-Cu-Mo/A1203 Catalyst for Synthesis Gas
Generation . 49
18 Lifetime and Regenerability of Catalysts Tested for
Hydrocarbon Synthesis Gas Production at 7500C 50
19 Catalyst Systems Tested for Ammonia Synthesis Gas Production . 51
Experimental Results o f Lodgepole Wood Impregnated w i t h
17% K2CO3 i n the Presence o f A i r , Steam, G i r d l e r 6-3
and Si-A1 C a t a l y s t s . 52

Experimental Results o f Lodgepole Wood Impregnated w i t h


17% K2CO3 i n the Presence o f A i r , Steam, and Commercial
.
G i r d l e r 6-93 CO S h i f t C a t a l y s t 53

C a t a l y s t s Tested f o r Hydrogen Production Studies . 54

T y p i c a l Results f o r Lodgepole Wood Impregnated w i t h


17 w t % K2C03 i n the Presence o f Steam and Catalysts 55

Experimental Results f o r CO Production from Lodgepole Wood . 56

Steam G a s i f i c a t i o n o f Biomass f o r the Production o f


Hydrocarbon Synthesis Gas . 57

Compositions o f Feedstocks Used i n PDU Operations . 79

Ammonia Synthesis Gas Results from t h e Agitated-Bed G a s i f i e r . 86

Results o f PDU Tests Witn N i c k e l Extrudate C a t a l y s t 89

Results o f PDU Tests w i t h Nonporous Alumina Spheres 90

Results o f Fluid- Bed PDU Tests w i t h N i c k e l C a t a l y s t 93

Wood-to-Methane P l a n t Design Basis--2000 ton/day Dry Wood . 107

U l t i m a t e Analysis o f Feedstock . 109

Wood-To-Methane C a p i t a l Cost Summary--2000 ton/day Dry Wood . 112

D i r e c t Cost Sumnary f o r Wood-to-Methane Plant- - 2000 ton/day


Dry Wood . 113

T o t a l C a p i t a l Cost Requirement For Wood-to-Methane P l a n t - -


2000 ton/day Dry Wood 114

Annual D i r e c t Operating Costs For Wood-to-Methane Plants- -


2000 ton/day Dry Wood 115

Methane C o s t - U t i l i t y Financing Method--2000 ton/day Dry Wood . 118

Methane Cost - E q u i t y Financing Method--2000 ton/day Dry Wood 119

T o t a l C a p i t a l Requiremerit f o r 200-ton/day Wood-to-Methane P l a n t . 120

xii
40 Annual Direct Operating Costs for 200-tonlday Wood-to-Methane
Plant . 121

&
41 Gas Cost - Utility Financing Method--200 tonlday Dry Wood . 122
42 Gas Cost - Equity Financing Method--200 tonlday Dry Wood 123

* 43 Wood-to-Methanol Plant Design B1lsis--2000tonlday Dry Wood . 124


44 Wood-to-Methanol Capital Cost S~immary--2000tonlday Dry Wood . 128
45 Direct Cost Summary For Wood-to-Methanol Plant--2000 ton/day
Dry Wood . 129
46 Total Capital Required For Wood-to-Methanol Plant--2000 ton/day
Dry Wood . 130
47 Annual Direct Operating Costs For Wood-to-Methanol Plant--
2000 ton dry woodlday 131
48 Methanol Cost-Utility Financing Method--2000 tonlday Dry Wood . 133
49 Methanol Cost-Equ i ty Financing Method--2000 tonlday Dry Wood . 134
50 Total Capital Requirement for 210-ton Dry WoodIDay Methanol Plant . 135
51 Annual Direct Operating Costs f ~ 200-ton
r Dry WoodlDay
Methanol Plant . 136
52 Methanol Cost - Utility Financing Method--200 ton Dry WoodIDay . 138
53 Methanol Cost - Equity Financing Method--200 ton Dry WoodIDay . 139
GLOSSARY OF TERMS

acfm = cubic f e e t o f volume per minute a t actual c o n d i t i o n s


atm, ATM = atmosphere or atmospheric pressure
BC = booster compressor
BD = blow down
BFW = b o i l e r feed water
Btu = B r i t i s h thermal u n i t equal t o 1055 Joules
CS = carbon s t e e l
DC = d i r e c t c o s t
D/H = d i r e c t h i r e
DCF = discounted cash f l o w
DEA = diethanolamine
E,M, L = equipment, m a t e r i a l s , and labor
F = degrees Fahrenheit
ft = feet
2
f t = area i n square f e e t
3
f t = volume i n cubic f e e t
gpm = g a l l o n s per minute
HO = home o f f i c e
HHV = higher h e a t i n g value
hp = horsepower
HP = h i g h pressure
HT = h i g h temperature
I C I = I m p e r i a l Chemicals, Incorporated
I D = i n s i d e diameter
i n . = inches
K-0, KO = knock o u t
kW = k i l o w a t t
1b = pounds mass
LG = l e n g t h
LP = low pressure
M = thousand
MHR, MH = manhour
MHRS = manhours
MM = million
No., # = number
OC = overhead charges
OAH = overall height
, = diameter
PS = p r o f e s s i o n a l s e r v i c e s
P, AP = pressure, p r e s s u r e drop
P/O = purchase o r d e r
psi = pounds f o r c e p e r square i n c h
psig = p s i gauge, o r pressure i n p s i minus 14.7 p s i
S/C = subcontract
S/T = subtotal
scf = c u b i c f e e t o f volume a t standard c o n d i t i o n s o f 60°F and
1 atmosphere pressure
scfh = c u b i c f e e t o f volume per hour a t standard c o n d i t i o n s of
60°F and 1 atmosphere p r e s s u r e
scfm = c u b i c f e e t o f volume per minute a t standard c o n d i t i o n o f
60°F and 1 atmosphere pressure
SNG = s u b s t i t u t e n a t u r a l gas
SS = stainless steel
T-T, T/T = t a n g e n t - t o - t a n g e n t measurement
TIC = t o t a l installed cost
TPD = tons p e r day
TPH, t / h = tons p e r hour
WH = waste heat

xvi
INTRODUCTION

The P a c i f i c Northwest Laboratory (PNL) i s conducting s t u d i e s on steam


g a s i f i c a t i o n o f biomass i n the presence o f c a t a l y s t s . These ,studies are spon-
sored by t h e Biomass Energy Systems D i v i s i o n o f t h e U.S. Department o f Energy
(DOE).

G a s i f i c a t i o n processes are commonly used t o convert carbonaceous matter,


i n c l u d i n g biomass, i n t o gases and some condensible 1i q u i d s ( t a r s ) . A1 though
t h e r e are exceptions w i t h some r e f r a c t o r y carbonaceous m a t e r i a l s , t h e residues
from such processes comprise p r i n c i p a l l y t h e i n e r t m i n e r a l c o n s t i t u e n t s o f t h e
.
feed m a t e r i a1 These residues are essenti a1l y devoid o f s i g n i f i c a n t q u a n t i t i e s
o f carbon o r char. I n c o n t r a s t , t h e residues from many so- called p y r o l y s i s
processes are c l a s s i f i e d as chars because they c o n t a i n a s u b s t a n t i a l f r a c t i o n
o f t h e carbon from t h e o r i g i n a l carbonaceous feed m a t e r i a l .

Both g a s i f i c a t i o n and p y r o l y s i s o f carbonaceous m a t e r i a l s produce a mix-


t u r e o f gaseous products as a r e s u l t o f t h e complex p a r a l l e l , competitive, and
sequential chemical r e a c t i o n s . The p r e f e r r e d r e a c t i o n s , those t h a t produce the
most d e s i r a b l e products, are l i m i t e d and slow a t conventional processing tem-
peratures. However, t h e r a t e s can be enhanced by i n c l u s i o n o f c e r t a i n cata-
lysts. Furthermore, a v a r i e t y o f c a t a l y s t s are used i n d u s t r i a l l y t o promote
c e r t a i n r e a c t i o n s t o emphasize formation o f desired products from other gas
mixtures. For example, methanation c a t a l y s t s promote t h e f o r m a t i o n o f methane
from hydrogen and carbon mor~oxide, s h i f t c a t a l y s t s promote the formation o f
hydrogen from water, and carbon monoxide and g a s i f i c a t i o n c a t a l y s t s promote t h e
breakdown o f carbonaceous matter t o gases.

The s t a t e - o f - t h e - a r t procedure f o r conversion o f a carbonaceous m a t e r i a l


t o a synthesis gas i n v o l v e s several steps:

1) g a s i f i c a t i o n by p a r t i a l combustion w i t h pure oxygen and steam t o form


a m i x t u r e o f gases (CO, Hz, C02, CH4, H2S),

2) s h i f t conversion t o y i e l d a 2 : l H2:C0 r a t i o i n the gas mixture,

3) a c i d gas removal,
4) r e f o r m i ng o f hydrocarbons,

5) moisture removal, and

6) f u r t h e r gas cleanup t o remove t r a c e s o f s u l f u r compounds t h a t would


otherwise poison c a t a l y s t s .

P a r t i a1 combustion o f the carbonaceous m a t e r i a1 w i t h pure oxygen t o p r o v i d e


heat f o r t h e endothermic g a s i f i c a t i o n r e a c t i o n s i s c u r r e n t l y p r a c t i c e d f o r
g a s i f i c a t i o n t o produce synthesis gas mixtures. An expensive, energy-consuming
oxygen p l a n t i s r e q u i r e d f o r these g a s i f i c a t i o n processes t o avoid d i l u t i o n o f
t h e product gases w i t h nitrogen. Conversion o f wood t o hydrocarbon synthesis
gas i s s i m p l i f i e d somewhat because o f t h e n e g l i g i b l e s u l f u r content o f wood,
b u t the conversion s t i l l i n v o l v e s the steps of g a s i f i c a t i o n , s h i f t conversion,
reforming, C02 removal, and moisture removal.

The o v e r a l l o b j e c t i v e o f t h e PNL s t u d i e s i s t o evaluate t h e t e c h n i c a l and


economic f e a s i b i l i t y o f producing s p e c i f i c gas products v i a the c a t a l y t i c g a s i -
f i c a t i o n o f biomass. S p e c i f i c products t h a t are being s t u d i e d i n c l u d e
( a ) methane, ( b ) synthesis gases f o r production of ammonia, methanol, and
hydrocarbons, ( c ) hydrogen, and (d) carbon monoxide. I n t h e studies, y i e l d s o f
high- value, gaseous products from a s i n g l e - r e a c t i o n stage are enhanced by t h e
proper choice o f reactants, operating c o n d i t i o n s , and c a t a l y s t combinations.
Gaseous products, s u c c e s s f u l l y produced by t h e various steam g a s i f i c a t i o n sys-
tems employed t o date, i n c l u d e synthesis gases f o r hydrocarbon, methanol, and
ammonia generation and a methane- rich gas.

This r e p o r t d e t a i l s progress o f t h e l a b o r a t o r y studies, process develop-


ment u n i t (PDU) studies, and economic analyses conducted a t PNL from December
1977 t o October 1980. A c t i v i t i e s o f t h e p r o j e c t are sumnarized i n F i g u r e 1.
Appendices A through D present the economic a n a l y s i s o f wood-to-methane and
wood-to-methanol p l a n t s completed by Davy McKee, Inc., o f Cleveland, Ohio.
These conceptual p l a n t s use the c a t a l y t i c g a s i f i c a t i o n processes developed a t
PNL.
CONCLUSIONS

The following conclusions are based on current results from PNL studies
on catalyzed steam gasification of wood:
a Steam gasficiation of wood in the presence of catalysts to produce a
methane-rich gas and a methanol synthesis gas is technically
feasible.
a A nickel-on-silica-alumina catalyst was effective both for generation
of a methane-rich gas and for generation of a methanol synthesis gas
at respective temperatures of 550' and 750'~.
a Catalyst systems need not include an alkali carbonate primary
catalyst.
a Presence of an active nickel catalyst essentially eliminates produc-
tion of condensable liquids during the gasification processes.
a Potential yields of methane and methanol are significantly greater
from the catalytic processes than from conventional processes that
employ oxygen-steam gasification of wood in a fixed bed.
a Cost of methane from wood by catalytic gasification in a 2000-ton
(1800-t) dry wood per day plant is competitive with projected future
costs of substitute natural gas (SNG).
a Cost of methanol from wood by catalytic gasification in a 2000-ton
(1800-t) dry wood per day plant is competitive with the current price
of methanol.
a Major operating costs are for wood, labor, gasifier catalyst, and
taxes and insurance.
a Investment costs and high labor costs make production of methanol
and SNG in a 200-ton (180-t) dry wood per day plant economically
unattractive.
Further conclusions based on task studies are presented in the discussion.
RECOMMENDATIONS

Results from the studies on catalyzed steam gasification of wood show


considerable promise for commercial production of valuable chemical products.
Real ization of this promise depends on successful development of long-1 ife
catalyst systems and on avail abi 1 ity of commerci a1 quantities of feedstock.
We, therefore, recommend continuation of studies on the development of design
parameters for a commercial facility. Such studies may logically include
pilot-plant operations for production of one or more products at a site with a
wood residue source of 10 to 50 wet tons (9 to 45 t) per day.
Near-term studies are required before pilot-plant operations can be defi-
ni tively considered. Laboratory-scale studies on evaluation of special ly pre-
pared catalyst compositions should continue. These studies will evaluate
yields from the new catalysts as well as catalyst lifetime and regenerability.
Thermal requirements for the processes should also be determined. Systems for
generation of an ammonia synthesis gas should be evaluated further.
We recommend PDU studies to evaluate yields at pressures up to 7 atm from
the catalyst systems developed in the laboratory. Information on catalyst
durability in fluid-bed operations should be developed.
Feasibility studies have indicated that processes for generation of SNG
and methanol via catalytic gasification of wood are economic at large scale.
Yields and process inputs have been improved since completion of these studies.
We, therefore, recommend the continued development of the computer code system
to evaluate the effects of these process changes on the overall economics.
LABORATORY STUDIES

The l a b o r a t o r y s t u d i e s are designed t o develop a fundamental understanding


o f the c a t a l y t i c g a s i f i c a t i o n o f biomass, t o provide a sound b a s i s f o r design
and operation o f t h e PDU, and t o p r o v i d e support s e r v i c e s f o r PDU operation.
Results o f these studies, presented i n the f o l l o w i n g sections, are intended t o
d e f i n e f e a s i b l e r e a c t a n t - c a t a l y s t combinations and o p e r a t i n g c o n d i t i o n s .

EXPERIMENTAL EQUIPMENT

Two types o f experimental systems were employed i n t h e l a b o r a t o r y phase of


the project: 1 ) a batch- feed r e a c t o r shown i n F i g u r e 2, and 2) a continuous
wood-feed r e a c t o r , shown i n F i g u r e 3. The batch- feed r e a c t o r was used t o com-
p l e t e p r e l i m i n a r y c a t a l y s t screening studies, t o o b t a i n k i n e t i c data on t h e
steam r e a c t i o n w i t h wood char, and t o determine a l k a l i carbonate recovery
tests. The system was designed f o r atmospheric pressure operation and i s q u i t e
f l e x i b l e w i t h respect t o c o n t r o l o f experimental v a r i a b l e s i n c l u d i n g (1) sample
s i z e s up t o 15 g, ( 2 ) steam f l o w r a t e s , ( 3 ) temperatures up t o 850°c, ( 4 ) aux-
i l i a r y gas a d d i t i o n , and (5) recovery and q u a n t i f i c a t i o n o f gases, o i l / t a r s ,
and char produced d u r i n g g a s i f i c a t i o n .

The continuous wood-feed r e a c t o r was employed t o o b t a i n data regarding t h e


generation o f s p e c i f i c products from wood, t o screen c a t a l y s t systems, and t o
i n v e s t i g a t e c a t a l y s t l i f e t i m e and regeneration. The r e a c t o r system i s con-
s t r u c t e d p r i m a r i l y o f quartz, designed f o r atmospheric pressure operation, and
i s f l e x i b l e w i t h respect t o c o n t r o l o f experimental v a r i a b l e s i n c l u d i n g :
1 ) wood feed rates, 2) steam f l o w r a t e s , 3) temperatures up t o 850°c, and
4 ) a u x i l i a r y gas a d d i t i o n .

FEED MATERIALS

The wood samples used i n the l a b o r a t o r y g a s i f i c a t i o n s t u d i e s i n c l u d e sepa-


r a t e wood and bark samples o f western l a r c h (tamarack), lodgepole pine, douglas
fir, and cottonwood. The samples were hand picked from a small p r i v a t e c h i p -
p i n g o p e r a t i o n i n Usk, Washington. These samples were d r i e d and m i l l e d t o t h e
desired p a r t i c l e size. Chemical and p h y s i c a l c h a r a c t e r i z a t i o n o f these wood
WOOD AND I
SS LOCK HOPPER
I

GRADUATED
GAS
+COLD WATER OUT SAM PLE
BAG
LIQUID CONDENSER

FIGURE 2. Batch-Feed Reactor


T.C. 5 cm ABOVE
CATALYST BED

GRADUATED

5 . 7 cm I D QUARTZ REACTOR

WIRE FINGER STIRRER

CATALYSTBED

WATER PUMP

rtI /C-
--) WATER OUT

LIQUID CONDENSOR

n
3- WATER I N VENT

GAS
SAMPLE
COLLECTOR

WATER TEST
LIQUID COLD METER
COLLECTOR

FIGURE 3. Continuous Wood-Feed Reactor


samples are presented i n Table 1. Analysis of a f i e l d corn sample used as an
a l t e r n a t i v e feedstock i s a l s o given i n Table 1. Lodgepole p i n e and douglas fir
were the primary feedstocks used i n the l a b o r a t o r y studies.

The potassium carbonate, sodium carbonate, and borax g a s i f i c a t i o n cata-


l y s t s used i n the l a b o r a t o r y s t u d i e s were Baker analyzed reagents. Trona was
s u p p l i e d by S t a u f f e r Chemical Company o f Wyoming, Green River, Wyoming.

EFFECTS OF ALKALI CARBONATES

The c a t a l y t i c e f f e c t s o f d i f f e r e n t a l k a l i carbonates on t h e r e a c t i o n o f
steam w i t h wood and wood char were determined i n t h e laboratory. Results o f
these determinations are presented i n the f o l l o w i n g discussion.

I n view o f t h e heterogeneous nature o f t h e wood-catalyst-steam i n t e r a c -


t i o n s , we i n v e s t i g a t e d two methods o f c a t a l y s t mixing w i t h wood--dry m i x i n g and
s o l u t i o n impregnation. Sodium carbonate and lodgepole p i n e were s e l e c t e d as
the reference mater i a1 s.

The above catalyst/wood mixtures and wood were g a s i f i e d w i t h steam a t


5 5 0 ' ~ and 650'~. Results obtained a t 5 5 0 ' ~ w i t h a c a t a l y s t concentration of
3 x lom3 g-mole sodiumlg wood are shown i n F i g u r e 4. Also shown f o r comparison
i s t h e gas y i e l d f o r simple p y r o l y s i s o f wood under t h e same c o n d i t i o n s . These
data show t h a t impregnating the wood p a r t i c l e s w i t h sodium carbonate c a t a l y s t
i s a b e t t e r c o n t a c t i n g method than d r y m i x i n g t h e e q u i v a l e n t amount o f c a t a l y s t
w i t h the wood. Impregnation produces about 10% more gas than d r y m i x i n g w i t h
a s l i g h t increase i n r a t e o f gas production. Both c o n t a c t i n g methods s i g n i f i -
c a n t l y increase t o t a l gas production (75% t o 90% increase) and r a t e o f g a s i f i-
cation. However, u s i n g a b o i l i n g s o l u t i o n i n s t e a d o f an ambient s o l u t i o n o f
c a t a l y s t f o r impregnation had no a d d i t i o n a l e f f e c t .

The e f f e c t i v e n e s s o f f o u r d i f f e r e n t c a t a l y s t s (potassium carbonate, sodium


carbonate, t r o n a and borax) i n concentrations o f 3 x and 3 x g-mole
a l k a l i l g wood a t 550°C, 650°C, and 7 5 0 was
~ ~ also evaluated. These c a t a l y s t s
were chosen from t h e l a r g e number o f p o s s i b l e candidates because: 1) e x p e r i -
mental i n v e s t i g a t i o n s w i t h other m a t e r i a l s have shown these t o be t h e most
a c t i v e g a s i f i c a t i o n c a t a l y s t s , and 2) o f t h e l a r g e number o f p o s s i b l e
d h i n
O O C O
m r l C O
d C O 4
0
0
3
O U

0
0
2;:
0
?? 1 7
m-
.
mw o c s
m 0
k
CO rl
In-
.-
w-
e- .r
P E
5 wL
ul
n
w
.v ul
mcl
-..-
U L
n-
3

rC1
a
-0 E
n
u- n
0
h
w n
3
7-0
m w
--
> C,
0
w C
m C C m
a, w m w
w m r L m r L L
$ 0 0 3 0 a J w w
>c
.-CE
7
3
,

L
O L
,,m
I U

n
V

z
3z 25
)

L
L

m
O U -
4 2
m
V
g a s i f i c a t i o n c a t a l y s t s , these are r e l a t i v e l y inexpensive. Typical r e s u l t s
obtained a t 6 5 0 ' ~ f o r a c a t a l y s t concentration of 3 x gemole a l k a l i l g wood
and steam f l o w o f 1.2 glmin are shown i n F i g u r e 5. These data show a d i m i n i s h -
i n g order o f e f f e c t i v e n e s s f o r p o t a s s i um carbonate, sodium carbonate, t r o n a and
borax. The same r e l a t i v e order of effectiveness was observed a t o t h e r tempera-
t u r e s and c a t a l y s t concentrations. The e f f e c t o f temperature w i t h and w i t h o u t
potassium carbonate c a t a l y s t on gas y i e l d s i s shown i n F i g u r e 6; t h e e f f e c t o f
sodium carbonate concentration i s shown i n F i g u r e 7.

The steam g a s i f i c a t i o n r e a c t i o n s produce a char r e s i d u e and a gas m i x t u r e


c o n t a i n i n g some condensable v o l a t i les. The y i e l d s of these products (condens-
able v o l a t i l e s n o t included) are shown i n Tables 2 and 3. These products are
apparently formed from p y r o l y s i s o f wood t o y i e l d a m i x t u r e o f gas, condens-
able l i q u i d s , and char. F u r t h e r g a s i f i c a t i o n then takes p l a c e b y i n t e r a c t i o n
o f char and steam as shown i n Equation (1) and by i n t e r a c t i o n o f carbon monox-
i d e and steam i n t h e water-gas s h i f t r e a c t i o n shown i n Equation ( 2 ) :

A c l o s e examination o f the data i n Tables 2 and 3 shows t h a t the increased


y i e l d o f hydrogen and carbon d i o x i d e t h a t r e s u l t s from t h e use o f c a t a l y s t s
cannot e n t i r e l y be a t t r i b u t e d t o Equations (1) and ( 2 ) . Although t h e a l k a l i
carbonates are e f f e c t i v e c a t a l y s t s f o r these r e a c t i o n s , t h e increased y i e l d o f
carbon d i o x i d e and hydrogen i s a t t r i b u t e d t o the e f f e c t t h a t these a l k a l i car-
bonates have on t h e y i e l d s from p y r o l y s i s .

It has been shown t h a t a l k a l i n e c a t a l y s t s increase the y i e l d o f char from


p y r o l y s i s o f c e l l u l o s i c m a t e r i a l s a t t h e expense o f condensable v o l a t i l e s
(Mudge, Sealock and Weber 1979; Sealock, Weber and Mudge 1980; Mudge e t a l .
1980). The increased char y i e l d i l l u s t r a t e s t h e f a c t t h a t t h e c a t a l y s t s c o u l d
increase the amount o f hydrogen and carbon d i o x i d e w i t h o u t a p r o p o r t i o n a t e
r e d u c t i o n i n t h e f i n a l y i e l d o f carbon monoxide and char as expected from
- CATALYST CONCENTRATI 0 ~ = 3 x 1 0 -MOLE
~
ALKALI I g WOOD
-

-
TEMPERATURE=~~O~C

NO CATALYST

I
0 200 400 600 800 loo0 1200 1400 1600
TIME, s
FIGURE 5. Re1a t i ve C a t a l y s t E f f e c t i v e n e s s a t 6500C

Equations (1) and ( 2 ) . The increased gas y i e l d i s a t t r i b u t e d t o c r a c k i n g of


t a r s and o t h e r l i q u i d organics produced d u r i n g p y r o l y s i s .

Gas y i e l d s from wood and bark o f f o u r d i f f e r e n t species and from c e l l u l o s e


w i t h and w i t h o u t impregnated potassium carbonate c a t a l y s t are given i n Table 4
f o r steam g a s i f i c a t i o n a t 650'~. Concentration o f hydrogen i n t h e product gas
1 CATALYST CONCENTRATI O N = ~ X ~ OMOLE
- ~ Klg WOOD

TIME, s
FIGURE 6. E f f e c t o f Temperature on Gas Production With and
Without Potassium Carbonate C a t a l y s t

was about 60 v o l % f o r catalyzed and about 15 v o l % f o r uncatalyzed t e s t s . All


woods gave a s l i g h t l y h i g h e r hydrogen c o n c e n t r a t i o n and, i n most cases, a
s l i g h t l y lower carbon monoxide and methane c o n c e n t r a t i o n i n the product gas
than t h e i r r e s p e c t i v e barks. D i f f e r e n c e s w i t h wood v a r i e t y were considered
insignificant.
-

- 3 x lo4 MOLE OF Nalg WOOD


INa2C03)
-

- 3x MOLE OF Nalg WOOD


(Na2C03)

LODGEPOLE PINE

1 1
200 400 600 800 lo00 1200 1400 1600 1800 2000 2200 2400
TI ME, s
FIGURE 7. Effect of Sodium Carbonate Concentration on Gas Yield a t 6500C

Experiments were conducted t o examine the k i n e t i c s of catalyzed biomass


gasification. I n i t i a l l y , the r a t e correlations were expected t o be patterned
a f t e r those reported by Gardner, Sarnuels and W i lks (1979) and Johnson (1974).
This could not be accomplished, as our data based on gasification products
were not comparable t o t h e thermogravimetric data based on t h e t o t a l weight
loss used in these references. However, the data could be used t o generate
r a t e correlations i n a manner similar t o t h a t reported by Lefrancois, Barclay
and Skaperdas (1967) f o r t h e i r bench-scale studies on coal and coal char
gasification.
TABLE 2. Gas Y i e l d s a t 6500C

Volume o f Gas, m l l g wood ( b


H CO CH CH CH CO Total
-2- -2 -2-4 -2-6 4 - -
Potassium Carbonate 895 578 3 7 57 145 1685
Sodium Carbonate 581 407 4 8 59 116 1175
Trona 424 350 5 10 73 111 973
None 94 94 6 4 47 235 480

( a ) C a t a l y s t c o n c e n t r a t i o n = 3 x 10-3 g-mole a l k a l i l g wood.


( b ) Steam f l o w = 1.2 glmin, 25 min f o r r e a c t i o n w i t h 10 g wood.

TABLE 3. Elemental Y i e l d s a t 6500C

W t i n Gas Products
( W t i n Wood
C a t a l y s t' ( a ) (W t WCt ii nn Residue
Wood
Potassium Carbonate 130 188 75 22
Sodium Carbonate 97 138 58
Trona 79 132 56
None 32 69 38 31

( a ) C a t a l y s t c o n c e n t r a t i o n = 3 x 10-3 g-mole a l k a l i l g wood.


( b ) Steam f l o w - 1.2 glmin, 25 min f o r r e a c t i o n w i t h 10 g wood.

When wood i s contacted w i t h steam a t elevated temperatures, a s e r i e s o f


complex p h y s i c a l changes and chemical r e a c t i o n s are i n i t i a t e d . These phenom-
ena i n c l u d e 1 ) r a p i d v o l a t i 1i z a t i on ( p y r o l y s i s ) t o y i e l d gases, condensable
l i q u i d s , and a char r e s i d u e and 2 ) steam r e a c t i o n w i t h t h e p y r o l y s i s products.
Steam r e a c t i o n w i t h t h e char r e s i d u e occurs a t a slow r a t e r e l a t i v e t o
pyrolysis.
I

The model used t o analyze l a b o r a t o r y data assumes t h a t , as discussed


above, t h e o v e r a l l changes occur i n two consecutive stages: 1 ) p y r o l y s i s o f
e t h e wood and 2) steam g a s i f i c a t i o n o f t h e char residue. For t h i s a n a l y s i s t h e
r e a c t i o n s i n these stages are assumed t o occur c o n s e c u t i v e l y and t o be
independent.
TABLE 4. Gas Yield from Different Wood and Bark Materials a t 6500C

Volume g a s , ( a ) L/g biomass


Mater i a1 3 X gemole K2g3/g biomass No catalyst
Douglas f i r bark 2.2 0.7
Lodgepol e bark 2.1 0.7
Tamarack bark 2.0 0.6
Cottonwood bark 2.0 1.0
Lodgepole wood 2.0 0.6
Tamarack wood 2.0 0.5
Douglas f i r wood 1.9 0.5
Cottonwood wood 1.7 0.7
Cel lulose 1.5 0.6

( a ) Steam flow = 1.2 g/min, experiment 25 min in duration.

Kinetic data were obtained a t f i v e concentrations of impregnated potassi um


carbonate: 0, 4, 8, 12, and 17 wtX. Temperatures studies included 550°c,
650°c, 750°c, and 850'~. The t o t a l carbon gasified a t each sampling was
assumed t o be t h e carbon appearing in t h e product gas and was determined from
gas volume and gas composition data. The percent carbon was determined by d i f -
ference and plotted versus time on semi-log paper. Examples are shown in Fig-
ures 8 and 9 f o r catalyzed and uncatalyzed t e s t s , respectively. The r e s u l t s
i n Figures 8 and 9 can be interpreted by t h e two reaction stages previously
.
def i ned
During the f i r s t 160 s , the losses correspond t o pyrolysis of the wood.
The base carbon remaining i n t h e residue then reacts with the steam in the
gasification stage.
I t appears from the r e s u l t s in Figure 8 t h a t more base carbon remains in
the residue a f t e r the pyrolysis stage a t 650'~ than a f t e r the pyrolysis stage
a t 550°c, and i t appears from the r e s u l t s in Figure 9 t h a t more base carbon
I
40 I
I I 1 I

100 200 300 400 500 600


TIME, s

FIGURE 9. Uncatalyzed Test Results on Remaining Carbon Versus Time

remains a f t e r the p y r o l y s i s stage a t 7 5 0 ' ~ than a t 650'~. Since condensable


v o l a t i l e s were n o t i n c l u d e d i n t h e d e t e r m i n a t i o n o f remaining base carbon, t h i s
may or may not be the a c t u a l case.

The data p l o t t e d i n Figures 8 and 9 d e p i c t reasonably l i n e a r r e l a t i o n s h i p s


f o r t h e g a s i f i c a t i o n stage. Assuming p s e u d o - f i r s t - o r d e r k i n e t i c s , t h e f o l l o w -
i n g expression f o r t h e g a s i f i c a t i o n stage r e a c t i o n r a t e constant i s obtained:

where C1 i s t h e carbon remaining a t t h e time tl and C2 i s t h e amount o f carbon


remaining a t t h e t i m e tp.
The a c t i v a t i o n energy Ea i s obtained from a p l o t o f i n k vs 1000/T (see
F i g u r e 10) as i n d i c a t e d by t h e Arrhenius equation:

Gas p r o d u c t i o n rates, r a t e constants, and a c t i v a t i o n energies were determined


from these s t u d i e s u s i n g the techniques discussed. Carbon-steam r e a c t i o n r a t e
constants f o r t h e v a r i o u s a l k a l i carbonate c a t a l y s t concentrations are given i n
Table 5. Steam f l o w r a t e s o f 0.4 g/min and 1.2 g/min were employed i n these
experiments. An increase i n steam f l o w r a t e s i g n i f i c a n t l y increased t h e value
o f the carbon-steam r e a c t i o n r a t e constant. This i s an i n d i c a t i o n t h a t t h e

-2 5
0 WOOD IMPREGNATED WITH 3x10-~
MOLE Klg WOOD
-3.0 -

Y -35 -
-2?
-4.0 -

-45 - I I I
1 1.1 12

FIGURE 10. Reaction Constant V a r i a t i o n With 1/T f o r Catalyzed


Steam Gasi f ic a tion o f Wood
TABLE 5. Reaction Rate Constants f o r Wood Char-Steam
Reaction i n t h e Presence o f C a t a l y s t s

Reaction
Temperature, Steam Rate, Rate Constant,
oc g/mi n s-1
0.4 2.6 x
0.4 2.5 x
0.4 2.5 x 10'~
0.4 2.2 low5
0.4 2.6 x
1.2 1.4 x 10'~
1.2 1.1
1.2 1.0
0.4 1.3 x 10'~
0.4 1.2
0.4 8.6 x 10'~
0.4 8.0 x 10'~
0.4 4.0 x
1.2 3.4
1.2 9.3
1.2 9.9
0.4 3.1 x 10'~
0.4 3.1 x
0.4 3.1 x 10'~
0.4 2.5 x 10'~
0.4 8.2 x 10'~
1.2 9.9
1.2 2.0
0.4
0.4
0.4
0.4
0.4
reaction r a t e i s influenced by the mass transfer or diffusional properties in
the char. The activation energies calculated a t the lower steam r a t e are
presented in Table 6. A discussion of the postulated mechanism follows.
Experiments completed early in the program with a continuous wood-feed
reactor allowed visual observation of the reaction process. The presence of
the potassium carbonate catalyst was observed t o induce swelling of the wood
particle when exposed to reaction temperatures. Diffusion i s the controlling
mechanism f o r alkali carbonate catalyzed steam gasification of wood char as
indicated by 1) the f a c t that the reaction kinetics are dependent upon the
steam flow rate and 2 ) the f a c t that particle swelling i s induced by the alkali
carbonate.
I t i s postulated that the swelling of the wood particle increases the pore
diameters thus making the char surface more accessible. In contrasting a small
pore without the alkali carbonate to a large pore with the alkali carbonate,
the reaction r a t e in the smaller pore will be more diffusion limited a t the
higher temperatures. F i r s t order reaction r a t e equations that include diffu-
sional 1imitations conclude that the calculated reaction r a t e constant, k , i s
proportional to the square root of the true reaction r a t e constant k t , or
.
kakt1/2 Therefore, the true activation energy,EaTRUEi s equal to two times
the observed or calculated activation energy, EaOBS, or EaTRuE -- 2EaOBS The
effectiveness factors associated with diffusion limitations i s represented
graphically in Figure 11 and discussed below.

TABLE 6. Activation Energies for the Wood-Char/Steam Reaction(a1

( a ) Steam flow r a t e i s 0.4 g/min.


mL = L \ l k l ~

FIGURE 11. Postulated E f f e c t i v e n e s s Factor

Since t h e r e a c t i o n r a t e i s d i r e c t l y p r o p o r t i o n a l t o t h e r e a c t a n t concen-
t r a t i o n i n a f i r s t order r e a c t i o n , t h e average concentration near the p a r t i c l e
surface, A, compared t o t h e b u l k stream concentration, A, i s a measure o f how
much the r e a c t i o n r a t e i s a f f e c t e d by d i f f u s i o n . The r a t i o A/A i s defined as
t h e e f f e c t i v e n e s s f a c t o r E shown i n F i g u r e 11. .Therefore, t h e observed reac-
t i o n r a t e constant k i s equal t o t h e t r u e r e a c t i o n r a t e constant, kt, m u l t i -
p l i e d by t h e e f f e c t i v e n e s s f a c t o r , E. F i g u r e 11 i l l u s t r a t e s how E v a r i e s
w i t h i n the pore w i t h a p l o t o f E vs mL, o r E vs L m where:

m= W D
k = observed r e a c t i o n r a t e constant
D = diffusivity coefficient
L = l e n g t h o f pore

I d e a l l y E would equal mL, which equals 1. This would i n d i c a t e t h a t t h e l i m i t a -


t i o n by pore d i f f u s i o n i s e s s e n t i a l l y absent.
Major conclusions obtained from t h e k i n e t i c s t u d i e s are as f o l l o w s :

a The e f f e c t o f a l k a l i carbonate on t h e char-steam r e a c t i o n r a t e i s


negl i g i b l e a t temperatures be1ow 550'~.

a Char-steam r e a c t i o n r a t e constants increase w i t h increased a l k a l i


carbonate concentration a t temperatures from 6 5 0 ' ~ t o 850'~.

a The c a t a l y s t appears t o enhance t h e char-steam r e a c t i o n r a t e by


i n c r e a s i n g carbon surface area a v a i l able f o r r e a c t i o n .

a The carbon-steam r e a c t i o n r a t e appears t o become more d i f f u s i o n a l


l i m i t e d as a l k a l i carbonate concentration i s decreased.

EFFECTS OF SECONDARY CATALYSTS

Data obtained i n s t u d i e s w i t h a l k a l i carbonates show t h a t a t 5 5 0 ' ~ potas-


sium carbonate had l i t t l e e f f e c t on t h e carbon-steam r e a c t i o n b u t had an e f f e c t
on the i n i t i a l wood p y r o l y s i s r e a c t i o n and y i e l d s of p y r o l y s i s products.
Experiments were designed t h a t considered t h e f a c t t h a t l e s s carbon, a g r e a t e r
q u a n t i t y o f l i q u i d s , and a smaller q u a n t i t y of gases are produced d u r i n g gasi-
f i c a t i o n i n the absence o f the a l k a l i carbonate a t 550'~. T h e o r e t i c a l l y an
increase i n gas y i e l d c o u l d be accomplished i f l i q u i d s produced could be hydro-
cracked t o t h e desired gases i n the presence o f steam and c a t a l y s t s . Data
obtained from s t u d i e s completed i n t h e batch r e a c t o r demonstrated t h a t a t tem-
peratures ranging from 5 5 0 ' ~ t o 7 5 0 ' ~ a 1:l s i l i c a - a l u m i n a ( S i - A l ) t o NiO o r N i
c a t a l y s t combination s i g n i f i c a n t l y increased t h e gas volume, energy e f f i c i e n c y ,
and carbon conversion t o the gaseous phase over the y i e l d s w i t h t h e a l k a l i car-
bonate. Table 7 presents y i e l d s comparing batch experiments w i t h potassium
carbonate and those w i t h the Ni/Si-A1 c a t a l y s t mixture. Carbon conversions and
energy e f f i c i e n c i e s are shown i n Table 8.

The Ni and NiO c a t a l y s t s u t i l i z e d i n these s t u d i e s are proven and w e l l


known throughout i n d u s t r y f o r t h e i r hydrogenation c a p a b i l i t i e s . The s t r e n g t h
o f the s i l i c a - a l u m i n a c a t a l y s t l i e s i n i t s a c i d i c c r a c k i n g f u n c t i o n . This
c a t a l y s t i n c l u d e s a h i g h c o n c e n t r a t i o n o f Bronsted and Lewis a c i d centers.
Lewis a c i d s i t e s promote c r a c k i n g by removal o f h y d r i d e i o n s from t h e molecules
o f t h e reactants, thus g i v i n g a carbonium i o n intermediate. Bronsted a c i d
TABLE 7. Y i e l d s from Batch Experiment f Wood-Steam G a s i f i c a t i o n
i n the Presence o f C a t a l y s t s f a ?

Yields, w t %
Experiments Gases Liquids Char Water

- - -

( a ) A l l t e s t s u t i 1i z e d a 10-g charge o f lodgepole wood


w i t h a stream r a t e o f 0.4 glmin.

TABLE 8. Carbon Conversions and Energy E f f i c i e n c i e s i n Batch ~ x ~ e r i m e n(a)


ts

% Carbon
Exper iments Converted t o a Gas Btu Gas/Btu Wood x 100
At 550'~
17% K2C03 25 16
N i 1404:Si-A1 (1:l) 48 46

( a ) A l l t e s t s u t i l i z e d a 10-g charge o f lodgepole wood w i t h a stream


r a t e o f 0.4 glmin.
s i t e s y i e l d a proton t o the reactant molecules, i.e., o l e f i n s and aromatics,
r e s u l t i n g i n an in t e m e d i ate carbonium i o n formation (Andrew, M a r t i n and Noher
1971). With the l a r g e q u a n t i t y o f l i q u i d s produced from the wood during
p y r o l y s i s and t h e knowledge t h a t an aromatic r i n g must f i r s t be hydrogenated
before i t can be cracked, a hydrocracking r e a c t i o n should be i d e a l f o r t h i s
process. Combining these two c a t a l y s t s i n t o a s i n g l e system gives both
required c a t a l y t i c functions, hydrogenation and cracking, o r hydrocracki ng.
The presence o f steam gives a d d i t i o n a l reforming o f t h e organics. The data
and r e s u l t s presented here are reproducible and support the f a c t t h a t a t the
550'~-to-750'~ temperature range, a N i o r Ni0:Si-A1 c a t a l y s t system i s a more
e f f e c t i v e c a t a l y s t system f o r g a s i f i c a t i o n o f wood than 17 w t % impregnated
potassi um carbonate.

RECOVERY OF ALKALI CARBONATE CATALYSTS

Recovery and r e c y c ling o f a1k a l i carbonate i s required f o r those processes


t h a t use a primary g a s i f i c a t i o n c a t a l y s t . As presented i n l a t e r sections, t h e
alkali- carbonate primary c a t a l y s t i s needed f o r generation o f an ammonia syn-
t h e s i s gas and a hydrogen-rich gas. The o b j e c t i v e o f t h e a l k a l i carbonate
recovery t e s t s was t o determine primary c a t a l y s t loss per u n i t o f biomass pro-
cessed. Residues from g a s i f i c a t i o n experiments were used t o conduct t h e t e s t s .
The residues were selected from batch experiments conducted w i t h a potassium
carbonate c a t a l y s t a t 7 5 0 ' ~ w i t h a steam r a t e o f 0.4 glmin which gave an aver-
age o f 92% carbon conversion t o gas.

The recovery experiment consisted o f washing the residue w i t h water or a


water- solvent mixture. The wash was f i l t e r e d and t h e f i l t r a t e and residue
were r e t a i n e d f o r potassium analysis. The potassium i n the residue and f i l -
t r a t e was analyzed w i t h an i n d u c t i o n couple plasma ICP spectrometer instrument.
The parameters o f the studies included:
Leaching Solutions:
(a) water,
(b) waterlmethanol ( 1 : I ) ,
(c) a c i d i c (pH 3),
(d) water/acetone ( 1 : l )
a Solution/Residue Weight Ratio: 10 and 100
Leaching S o l u t i o n Temperature: 9 5 ' ~ (water o n l y ) and 2 5 ' ~
a Leaching Time: 2 h (water o n l y ) and 1 h.

Results o f these t e s t s can be summarized as f o l l o w s :

a 98% potassium recovery i s achieved w i t h a s o l u t i o n / r e s i d u e weight


r a t i o o f 100 f o r 1 ) a water wash, 2) an a c i d wash, o r 3) a water/
methanol wash a t 25'~.

a 95% potassium recovery i s obtained w i t h a 10/1 water wash a t 25'~.

a A leaching time o f 1 h y i e l d s t h e same r e s u l t s as a 2-h leaching


time.

a 2 5 ' ~ i s a b e t t e r leaching temperature than 95'~.

X-ray d i f f r a c t i o n s t u d i e s were performed t o i d e n t i f y t h e type o f a l k a l i


compound remaining i n the char residue. Results i n d i c a t e t h a t K2C03*H20 and
K2C03 are the o n l y a l k a l i compounds i n the residue.

With 95% recovery, t h e cost o f potassium carbonate and sodium carbonate


c a t a l y s t s a t September 1980 p r i c e s would be $2.60/dry t o n o f wood and $0.40/dry
t o n o f wood, r e s p e c t i v e l y . No l o s s i n e f f e c t i v e n e s s o f t h e recovered c a t a l y s t
was observed.

SYSTEMS FOR METHANE GENERATION

The o b j e c t i v e of these studies was t o f i n d c a t a l y s t combinations and oper-


a t i n g c o n d i t i o n s f o r generation o f a methane- rich gas. Favored systems devel-
oped i n the l a b o r a t o r y d i d n o t i n c l u d e the use o f a primary a l k a l i carbonate
catalyst.

Numerous secondary c a t a l y s t systems f o r generation o f a methane- rich gas


a t 5 5 0 ' ~ were t e s t e d w i t h the equipment shown i n F i g u r e 3. Favorable a c t i v i t y
f o r methane p r o d u c t i o n was observed w i t h some c a t a l y s t s t e s t e d i n these s t u d i e s
(see Table 9). C a t a l y s t s t h a t are e f f e c t i v e f o r generation o f a methane- rich
gas were determined t o have t h e f o l l o w i n g p r o p e r t i e s : a n i c k e l concentration
of 25 w t % o r greater, an a c i d i c support, a BET surface area o f g r e a t e r than
2 2
100 m /g, and a n i c k e l surface area of 30 m /g o r greater.
TABLE 9. Catalysts Tested f o r Methane Production

Harshaw Ni-0101
Harshaw ~ i - 1 4 0 4 ( ~ )
Harshaw ~ i - 3 2 6 6 ( ~ )
Harshaw N i - 3 2 1 0 ( ~ )
Harshaw ~i
-5142(~)
Harshaw Ni-Cu-Mo
Harshaw N i -Mo
Harshaw Ni-W
Hars haw Co-Mo
Grace Si-A1
Union Carbide Xeolte
Girdler ~ i - ~ - 5 6 ( ~ )
Girdler ~ i - ~ - 8 7 ( ~ )
N i -Ni/A1203 c a t a l y s t prepared a t Brigham Young U n i v e r s i t y ( a )
Strem Pd
Strem Ru
Strem R ~ I ( ~ )

(a) A c t i v e f o r methane generation.

A f t e r s e l e c t i o n o f s u i t a b l e c a t a l y s t systems, a t t e n t i o n was focused on


c a t a l y s t l i f e t i m e and regeneration. These studies c o i n c i d e w i t h t h e develop-
ment o f a s u i t a b l e c a t a l y s t f o r operation i n t h e PDU.

L i f e t i m e o f a Harshaw Ni-3266 c a t a l y s t was determined f o r generation o f a


methane-rich gas. Table 10 presents t e s t r e s u l t s and c o n d i t i o n s p r i o r t o cata-
l y s t deactivation. A wood-feed t o c a t a l y s t weight r a t i o o f 10 was obtained
before n o t i c e a b l e l o s s o f c a t a l y s t a c t i v i t y . Loss o f a c t i v i t y appears t o be
caused by carbon d e p o s i t i o n on t h e c a t a l y s t . The deactivated c a t a l y s t was
regenerated w i t h steam a t 6 5 0 ' ~ t o remove carbon from the c a t a l y s t surface;
TABLE 10. Results of a Catalyst Lifetime Test f o r Methane Production
Catalyst
Reactor Temperature
Catalyst Bed Temperature
Wood Feed Rate
Steam Rate
Carbon Conversion t o a Gas
Wood-Feed/Catalyst Weight Ratio
(BTU Gas/BTU Wood) x 100
scf CH4/ton Dry Wood (nm 3 /tj a )
Gas Composition
29.5 vol%
34.3 ~ 0 1 %
Trace vol%
25.4 vol%
10.8 vol%

( a ) Includes methanation of Hz and CO.

t h i s was followed by reduction with hydrogen a t a space velocity of 95 h - I


and a temperature of 450'~. The regenerated c a t a l y s t was then subjected t o
the t e s t conditions employed before deactivation. The regenerated c a t a l y s t
showed more renewed a c t i v i t y and longer l i f e than the fresh c a t a l y s t . A wood-
feed t o c a t a l y s t r a t i o of 52 was obtained before a second deactivation
occurred. Results following regeneration are presented in Table 11. The major
difference between gasification r e s u l t s shown in Tables 10 and 11 i s a decrease
in carbon conversion with the regenerated c a t a l y s t , a possible r e s u l t of some
l o s s in c a t a l y s t a c t i v i t y . No f u r t h e r regeneration of t h e c a t a l y s t was
attempted.
Catalyst characterization studies were completed on c a t a l y s t s exposed t o
gasification conditions f o r extended periods and on regenerated c a t a l y s t s .
Catalyst characterization equipment items included a hydrogen chemi sorption
TABLE 11. Catalyst Performance Fol lowing Catalyst Regeneration
Catalyst
Reactor Temperature
Catalyst Bed Temperature
Wood Feed Rate
Steam Rate
Carbon Conversion to Gas
Wood-FeedICatalyst Weight Ratio
(BTU GasIBTU Wood) x 100
scf CH4/ton Dry Wood (nm 3 It)(a) ,

Gas Composition
33.6 vol%
33.6 vol%
22.5 volX
10.31 vol%
Trace

(a) Includes methanation of Hz and CO.

apparatus, a BET surface area analyzer, a porosimeter, and a scanning electron


microscope (SEM) working in conjunction with an electron microprobe (EM). A
schematic of the hydrogen chemisorption apparatus is shown in Figure 12. Rela-
tive activities of the nickel catalysts are determined by measuring chemisorp-
tion of hydrogen on nickel which occurs as follows: Hz + 2Ni(s) + 2NiH.
Table 12 presents results of surface area studies on a Harshaw Ni-3266 catalyst
employed for methane production. A significant decrease in the BET and nickel
surface areas occurs upon deactivation (coking).

. The pore distribution in a fresh and coked (deactivated) Harshaw Ni-3266


. catalyst is shown in Figure 13. The catalyst was coked in operations to gener-
ate a methane-rich gas. Coking of the catalyst reduces the concentration of
smaller diameter micropores, which explains the drastic loss of BET and nickel
- surface areas as noted in Table 12.
PURGE
BUBE""

ROTAMETER

4
THREE WAY I
VALVE 1'1

.GAS STORAGE
BULB

MANOMETER

SAMPLE CEL

ru: RESERVOIR

FIGURE 12. Hydrogen Chemisorption Apparatus

TABLE 12. C a t a l y s t C h a r a c t e r i z a t i o n Tests Performed on a Ni-3266 C a t a l y s t


Used For Methane Production

Unused Ni-3266 Coked Ni-3266


2
BET Surface Area, m /g 145 47 -45
2
N i c k e l Surface Area, m /g 56 7

The SEM was used i n conjunction w i t h t h e EM t o study coke d e p o s i t i o n on a


NI-3266 c a t a l y s t . Figure 14 presents a micrograph o f a coked Ni-3266 c a t a l y s t
employed f o r generation o f a methane-rich gas.
D = PORE DIAMETER, MICRONS
100 10 1 .o 0.10 0.010
0.201 1111111 I I 11111 I I ' 1'""' ' ' I"'
0.18- /
0.16 - .-- COKED CATALYST /
/

FRESH CATALYST /
0.14- /
I
g 0.12-

0.10-
K
5 0.08-
2
0.06-

0.04 -

0.02 -
I 1 I l l l l l l I 1
0.00
1 10 100 1,000 10,000
P = ABSOLUTE PRESSURE, PSI

FIGURE 13. Pore Distribution in Fresh and Coked Catalyst

The micrograph shows that the majority of the catalyst surface is covered
with carbon. This can be contrasted to a micrograph of a fresh Ni-3266 cata-
lyst shown in Figure 15. The contrast in surface morphology explains why the
coked catalyst was inactive. The EM supplies information regarding the rela-
tive concentration of surface nickel sites available for reaction. Figure 16
illustrates a comparison of surface nickel concentrations of coked and fresh
catalyst. This figure indicates that the catalyst surface is being covered
with carbon prohibiting contact of reactants with the active sites on the cata-
lyst. A carbon-hydrogen-nitrogen (CHN) analysis indicated that the carbon con-
tent of the coked catalyst was 15 wt%.
Studies on catalyst lifetime and regeneration are in progress to determine
catalyst requirements. Catalyst systems that show favorable activity for gen-
eration of a methane-rich gas are also being studied. The weight'ratio of wood
FIGURE 14. Coked Ni- 3266 Catalyst, 3340X
FIGURE 15. Unused N i -3266 C a t a l y s t s , 10,021X
-

- UNUSED Ni -3266 N i (Ka)


--- COKED Ni -3266 I

Ni (KP)

Fe (Ka)

FIGURE 16. R e l a t i v e Concentrations o f Elements on Fresh and Exposed C a t a l y s t


Surfaces Employed f o r Methanantion
processed t o c a t a l y s t charge before d e a c t i v a t i o n i s given i n Table 13 f o r t h e
f r e s h and regenerated c a t a l y s t s t e s t e d t o date. A c a t a l y s t w i t h an i n h i b i t o r
f o r coke d e p o s i t i o n should g i v e extended l i f e . Such c a t a l y s t systems are being
developed.

SYSTEMS FOR GENERATION OF METHANOL SYNTHESIS GAS

The o b j e c t i v e o f these s t u d i e s was t o develop c a t a l y s t systems and oper-


a t i n g c o n d i t i o n s f o r the d i r e c t generation o f a hydrogen and carbon monoxide
gas m i x t u r e t h a t could be used f o r methanol o r hydrocarbon synthesis. Treat-
ment o f the gas m i x t u r e f o r carbon d i o x i d e removal was intended t o be t h e o n l y
necessary o p e r a t i o n t o make t h e m i x t u r e s u i t a b l e f o r methanol synthesis.

A 1i s t o f c a t a l y s t s t e s t e d f o r production o f a methanol, o r hydrocarbon,


synthesis gas i s presented i n Table 14. Favorable a c t i v i t y f o r synthesis gas
generation was observed i n some c a t a l y s t s as noted. Tests o f combinations o f
these c a t a l y s t s w i t h a primary ( a l k a l i carbonate) g a s i f i c a t i o n c a t a l y s t showed
t h a t gas y i e l d s were s i m i l a r w i t h o r w i t h o u t the primary c a t a l y s t . Therefore,
t h e primary g a s i f i c a t i o n c a t a l y s t was e l i m i n a t e d from f u r t h e r study.

P r e l i m i n a r y t e s t s performed w i t h the Ni-3266 f o r synthesis gas production


looked promising. T y p i c a l r e s u l t s are presented i n Table 15. A t 7 5 0 ' ~ a wood-
feed t o c a t a l y s t charge r a t i o o f 74 was obtained p r i o r t o c a t a l y s t deactiva-
tion. P o t e n t i a l methanol y i e l d i s shown as a weight f r a c t i o n o f d r y wood.

TABLE 13. L i f e t i m e and R e g e n e r a b i l i t y o f C a t a l y s t s Tested f o r


Methane Generation

Wood-Feed t o Wood-Feed To
Fresh C a t a l y s t C a t a l y s t Charge R a t i o
Catalyst Charge R a t i o F o l l o w i n g Regeneration
Harshaw Ni-3266 10 52
Laboratory- Prepared Ni/Si-A1 13 6
Laboratory-Prepared Ni /A1 203 5 Not Determined
Harshaw Ni-3266 28 Not Determined
Ni-3266:Si-A1 ( 3 : l ) 15 30
TABLE 14. C a t a l y s t s Screened f o r Methanol Synthesis Gas Production

Harshaw ~ i - 1 4 0 4 ' ~ )
Harshaw Ni-1404:Grace Si-A1 (Various r a t i o s ) ( a )
Harshaw Ni-Cu-Mo ( a )
Harshaw ~i
-3~66(~)
Harshaw Ni -3266:Grace Si-A1 (Various r a t i o s ) ( a )
G i r d l e r Ni-G-56:Grace S i -A1 (Various r a t i o s ) ( a )
G i r d l e r Cu-Zn
G i r d l e r Fe203
G i r d l e r Ni ~ - 1 3 - 3 ( ~ )
Grace Si-A1
Strem Mordenite Molecular Sieve
Strem Type Y Molecular Sieve
Harshaw Co-Mo: Molecular Sieve
10% Ni impregnated on Si-A1
30% N i impregnated on h i g h surface area A1203( a )
15% N i impregnated on low surface area Si-A1
Ni- Ni A1203 c a t a l y s t prepared a t BYU
Prepared Ni-Cu-Mo ( a )
Grace Ni

( a ) Favorable a c t i v i t y shown

Attempts t o regenerate t h e c a t a l y s t w i t h steam g a s i f i c a t i o n o f t h e deposited


carbon and subsequent hydrogen r e d u c t i o n were unsuccessful. C a t a l y s t charac-
t e r i z a t i o n s t u d i e s were subsequently performed. Table 16 presents BET and
hydrogen chemisorption r e s u l t s f o r t h e Ni-3266 c a t a l y s t before and a f t e r
t e s t i n g f o r synthesis gas production.

The pore d i s t r i b u t i o n determined f o r f r e s h and regenerated Ni-3266 cata-


l y s t used f o r synthesis gas generation i s shown i n F i g u r e 17. The concentra-
t i o n o f small diameter micropores i s o b v i o u s l y d r a s t i c a l l y decreased i n t h e
regenerated c a t a l y s t . T h i s decrease r e s u l t s i n l o s s o f o v e r a l l and a c t i v e s u r -
face area as shown i n Table 16.
TABLE 15. Results o f a C a t a l y s t L i f e t i m e Test f o r Hydrocarbon
Synthesis Gas Production

Catalyst
Reactor Temperature
C a t a l y s t Bed Temperature
Wood Feed Rate
Steam Feed Rate
Carbon Conversion t o a gas
Wood-FeedICatalyst Weight R a t i o
H2/C0 Mole R a t i o
(BTU Gas/BTU Wood) x 100
P o t e n t i a l Weight F r a c t i o n Wood as Methanol

Gas Composition
53.0 v o l %
16.9 v o l %
Trace v o l %
Trace v o l %
3.1 v o l %
27.0 v o l %

TABLE 16. C h a r a c t e r i s t i c s o f a Ni-3266 C a t a l y s t Employed f o r


Synthesis Gas Production

Unused Regenerated
2
BET Surface Area, m /g 145 1.4
2
N i c k e l Surface Area, m /g 56 0.4

The i n a b i l i t y t o r e s t o r e c a t a l y s t a c t i v i t y was undoubtedly t h e r e s u l t o f


SEM s t u d i e s show s i m i l a r r e s u l t s .
t h i s permanent loss of a c t i v e surface s i t e s .
F i g u r e 18 shows a micrograph o f a regenerated Ni-3266 c a t a l y s t . Contrasting
t h i s w i t h the micrograph o f an unused c a t a l y s t presented e a r l i e r i n F i g u r e 15
r e v e a l s a decrease i n surface concentration o f a c t i v e s i t e s on regenerated
D = PORE DIAMETER, MICRONS

0.161
---- COKED Ni-3266 CATALYST I
0.14- FRESH Ni-3266 CATALYST
.
0.12-

0.10-
P a
N
k 0.08-
2
0.06 -
0
0

---- -----
0.04 - e*)
H~
/

0.02 -
e4

9 ~ ) ~
O . O
&
O ~ . : I " ' I I I I I 1111 I I I I r 1 1 1 1 1
I r I I I 1 1 1 1 1

1 10 100 1,000 10,000


P = ABSOLUTE PRESSURE, PSI
FIGURE 17. Pore Distribution in Catalyst Used for Synthesis Gas Generation
FIGURE 18. Regenerated N i -3266 C a t a l y s t Employed For Hydrocarbon
Synthesis Gas Production, 10,021X

43
catalyst. T h i s i n d i c a t e s t h a t t h e regenerated c a t a l y s t has been s i n t e r e d and
s u p p o r t s t h e d a t a p r e s e n t e d i n Table 16 and t h e p o r e d i s t r i b u t i o n
determinations.
rn

A SEM was used i n c o n j u n c t i o n w i t h an EM t o examine t h e s u r f a c e changes of


a Ni- 3266 c a t a l y s t w i t h exposure t o c o n d i t i o n s f o r s y n t h e s i s gas g e n e r a t i o n .
C a t a l y s t samples were removed f r o m t h e r e a c t o r a t v a r i o u s exposure times i n a
t e s t f o r g e n e r a t i o n o f s y n t h e s i s gas. The micrographs presented i n F i g u r e s 19
t h r o u g h 24 show t h e gradual b u i l d u p o f char (carbon) on t h e n i c k e l c a t a l y s t
w i t h i n c r e a s e d exposure t i m e . The p o r e spaces a r e f i l l e d i n i t i a l l y , see F i g -
u r e 21, which decreases t h e s u r f a c e area a v a i l a b l e f o r r e a c t i o n . Carbon con- .
t i n u e s t o d e p o s i t on t h e c a t a l y s t u n t i l l a y e r s c o a t t h e surface, see F i g u r e 22.
F i g u r e s 23 and 24 show t h a t t h e s u r f a c e i s c o m p l e t e l y coated w i t h l a y e r s of
carbon a f t e r exposure t i m e s o f 88 and 117 h, r e s p e c t i v e l y .

FIGURE 19. SEM Micrograph o f Fresh Ni-3266, 3960X


FIGURE 20. SEM Micrograph o f Ni-3266 A f t e r 28.6 h o f Operation, 13,200X

FIGURE 21. SEM Micrograph of Ni-3266 A f t e r 61 h o f Operation, 13,200X

45
FIGURE 22. SEM Micrograph o f Carbon Layers on Ni-3266
A f t e r 72 h o f Operation, 132X

FIGURE 23. SEM Micrograph o f Coked Ni-3266 A f t e r


88 h o f Operation, 132X
FIGURE 24. SEM Micrograph o f Coked Ni- 3266 A f t e r 117 h o f Operation, 132X

E l e c t r o n microprobe scans o f t h e exposed c a t a l y s t s u r f a c e s a r e shown i n


F i g u r e 25. The r e l a t i v e c o n c e n t r a t i o n s o f n i c k e l , s i l i c o n and aluminum
decrease w i t h c a t a l y s t exposure time. The gradual decrease i n t h e n i c k e l peak,
w i t h exposure time, f u r t h e r i n d i c a t e s t h a t t h e c a t a l y s t s u r f a c e i s b e i n g coated
w i t h carbon.

As a r e s u l t o f t h e i n a b i l i t y t o regenerate t h e Ni-3266 c a t a l y s t , a t t e n t i o n
was s h i f t e d t o e v a l u a t i o n of a Ni-Cu-Mo a l l o y c a t a l y s t on an alumina s u p p o r t
f o r s y n t h e s i s gas generation. Preliminary studies w i t h t h i s a l l o y c a t a l y s t for
s y n t h e s i s gas g e n e r a t i o n has i n d i c a t e d e x c e l l e n t r e s i s t a n c e t o carbon deposi -
tion. Work on methanation r e a c t i o n s w i t h a Ni-Cu a l l o y c a t a l y s t by A r a k i and
Ponec (1976) demonstrated t h a t t h e presence o f copper d i l u t e s t h e number o f
. n i c k e l s i t e s , t h u s i n h i b i t i n g carbon f o r m a t i o n . Therefore, an a l l o y c a t a l y s t
- f o r s y n t h e s i s gas p r o d u c t i o n may have t h e l i f e t i m e needed f o r economic
a feasibility.
Experiments t o evaluate a Harshaw Ni-Cu-Mo a l l o y c a t a l y s t on alumina
showed a s i g n i f i c a n t increase i n c a t a l y s t l i f e t i m e . Data i n Table 17 present
average r e s u l t s obtained w i t h the a l l o y c a t a l y s t . E a r l y i n the experiment,
c a t a l y s t a c t i v i t y decreased s l i g h t l y . No f u r t h e r change i n a c t i v i t y occurred
f o r the next 175 h. Although s t i l l a c t i v e , t h e c a t a l y s t was then subjected t o
regenerat i o n w i t h steam a t 8 0 0 ' ~ f o l l owed by hydrogen reduct i o n a t 450'~.
C a t a l y s t a c t i v i t y was r e s t o r e d t o t h a t o f t h e o r i g i n a l c a t a l y s t by t h i s proce-
dure. The experiment was continued f o r an a d d i t i o n a l 210 h w i t h o n l y the
i n i t i a l s l i g h t deactivation. Regeneration again r e s t o r e d t h e s l i g h t a c t i v i t y
l o s t a f t e r which the experiment was continued another 24 h before the c a t a l y s t
was removed f o r c h a r a c t e r i z a t i o n studies.

TABLE 17. Use o f a Ni-Cu-Mo/A1203 C a t a l y s t f o r


Synthesis Gas Generation

Reactor Temperature
C a t a l y s t Temperature
Wood Feed Rate
Steam Rate
Wood FeedICatalyst Weight R a t i o 188 .O
Carbon Conversion t o a Gas 85.0%
(BTU Gas/BTU Wood) x 100 94.6
H2/C0 R a t i o
Gas Composition

L i f e t i m e and r e g e n e r a b i l i t y of c a t a l y s t s t e s t e d t o date are presented i n


Table 18. Conclusions derived from the c a t a l y s t systems s t u d i e d f o r hydrocar-
bon synthesis gas p r o d u c t i o n are given below:
Properties of the most effective catalyst tested for the production
of a methane-rich gas include a nickel content of 30 wt% or greater,
an acidic support, a BET surface area of 100 m2 /g or greater, and
a nickel surface area of 30 m2 /g or greater.
The nickel catalyst lifetime employed for methane production is
short. However, the catalyst is regenerable with steam and subse-
quent hydrogen reduction. Further tests need to be completed to
determine the nickel catalyst activity after repeated regenerations.
A Ni-Cu-Mo alloy catalyst looks promising for hydrocarbon synthesis
gas production, exhibiting good catalyst lifetime as well as
regenerability.

TABLE 18. Lifetime and Regenerability of Catalysts Tested for


Hydrocarbon Synthesis Gas Production at 7500C
Wood-Feed Wood-Feed to Catalyst
to Catalyst Charge Ratio
Catalyst Charge Ratio Fol lowing Regeneration
Harshaw Ni-Cu-Mo 188 (a)
Harshaw Ni-3266 74 4.4
Grace Si -A1 loo(b1
Harshaw Ni-1404 52 5
Girdler C-13-3 17 Not Determined
Prepared Ni -Cu-Mo 30 1st:23 2nd:10
15% Ni On Low Surface
Area Support 17 18
30% Ni On High Surface
Area Support 50 1st:16
Grace Ni Spheres 70 Not Determined

(a)' No deactivation - was subjected to regeneration scheme twice.


(b) No deactivation at 850%.
SYSTEMS FOR GENERATION OF AMMONIA SYNTHESIS GAS
The objective of these studies was to generate a gas mixture with the
proper hydrogen-to-nitrogen ratio for ammonia synthesis. The gas mixture is
produced by reacting air, steam and wood in the presence of catalysts. A
summary of catalyst systems tested is given in Table 19.

TABLE 19. Catalyst Systems Tested for Ammonia


Synthesis Gas Production
Girdler 6-3 Fe-Cr: Strem Si-A1 (3:l)
Girdler 6-93 Co-Mo
Girdler 6-3 Fe-Cr
Girdler G-9 Cu-Mn
Harshaw HT-100 Ni-Mo
Girdler 6-101 V205: Strem Si-A1 (3:l)
Girdler 6-66 A Cu-Zn
Harshaw 0301 Fe203

Effective catalyst systems for ammonia synthesis gas production were


found to be combinations of primary and secondary catalysts. The primary cata-
lyst was potassium carbonte (17 wt%) impregnated in the wood, and the secondary
catalyst was a Girdler 6-93 cobalt molybdate: si 1 ica-alumina (Si-A1 ) system at
a weight ratio of 3:l respectively, or a Girdler 6-3 chromium promoted iron
oxide and silica-alumina at a weight ratio of 3:l. Typical results using the
Girdler 6-3 catalyst with the silica-alumina are given in Table 20.
Various operating parameters, temperature, steam space velocity, and
wood-feed rate, were studied for production of ammonia synthesis gas. Results
obtained using the 6-93 Co-Mo CO shift catalyst are presented in Table 21.
Examination of the CO concentrations presented in Table 21 shows that
increasing the steam rate decreases the CO concentration via the water gas
shift reaction (CO + H20 + C02 + Hz) and that a gas consisting almost entirely
of Hz, N2 and C02 is produced. Carbon monoxide yields as low as 2% were
TABLE 20. Experimental Results of Lodgepole Wood Impregnated with 17%
K2CO3 in the Presence of Air, Steam, Girdler 6-3 and
Si-A1 Catalysts
Secondary Catalyst
Reactor Temperature
Catalytic Bed Temperature
Air Rate
Wood Feed Rate
Carbon Conversion to a Gas
H2/N2 Ratio
Cold Gas Efficiency
Gas Composition

obtained by increasing steam rates. The increased steam rate magnifies the
water gas shift reaction thus producing more Hz and C02, and less CO. Typical
results obtained by increasing steam rates while at the same time maintaining
the H2:N2 ratio at 3:l are included in Table 21.
Major conclusions of the completed ammonia synthesis gas studies are sum-
marized below:
a Girdler 6-3 chromium-promoted iron oxide or a Girdler 6-93 cobalt-
molybdate CO shift catalyst produced an optimum H2:N2 ratio of 3:l.
Of the catalysts tested, these catalysts produced the highest overall
conversions (65%) to the gaseous phase while maintaining the desired
product yields.
TABLE 21. Experimental Results o f Lodgepole Wood Impregnated w i t h
17% K2CO3 i n the Presence o f A i r , Steam, and Commercial
G i r d l e r 6-93 CO S h i f t C a t a l y s t

Steam Rate
0.64 g/min 1.0 g/min 1.2 g/min 1.6 g/min
Run number
Secondary C a t a l y s t
Reactor Temperature, OC

C a t a l y s t Bed Temperature,
O c
A i r Rate L/min
Wood Feed Rate, g/min
H2/N2 R a t i o
Cold Gas E f f i c i e n c y , %
Gas Composition, v o l %

2
N2
co

A maximum steam r a t e o f 4 times t h e wood feed r a t e produced CO y i e l d s


as low as 2% by volume f o r both c a t a l y s t systems described above.

a An a i r i n l e t r a t e o f approximately 40% by weight o f t h e wood feed


r a t e produced the desired H2:N2 r a t i o f o r both c a t a l y s t systems.

Steam g a s i f i c a t i o n r a t e s a t 5 5 0 ' ~ are t o o low t o m a i n t a i n a desired


H2:N2 r a t i o o f 3 : l a t a s i g n i f i c a n t gas production r a t e . Constant
wood feed r a t e s are c r i t i c a l i n m a i n t a i n i n g a 3 : l H2:N2 product
ratio.

An increase i n temperature enhances the o v e r a l l conversion t o gaseous


products.
SYSTEMS FOR GENERATION OF HYDROGEN
The objective of these studies was to select catalysts and operating con-
ditions for the direct production of hydrogen. A total of 22 experimental runs
were completed. The catalysts tested are presented in Table 22. Various oper-
ating parameters and catalyst systems were investigated. Twelve specific cata-
lyst systems were evaluated, and three temperature ranges (550°c, 650°c, and
750'~) were studied .
Two catalyst systems were found to be effective for hydrogen production:
1) Girdler Fe-Cr CO shift catalyst and a Harshaw Ni-1404 catalyst in a weight
ratio of 3:1, respectively, and 2) Girdler 6-93 Co-Mo CO shift catalyst and
Ni-1404 with the same 3:l ratio. In all cases the wood feed was impregnated
with 17 wt% potassium carbonate. Table 23 presents typical results employing
preferred catalysts at each temperature range. Data presented in Table 23 show
that 64 vol% hydrogen is obtained with a carbon conversion to gas of 78%.

TABLE 22. Catalysts Tested for Hydrogen Production Studies


Girdler 6-3 Fe-Cr
Gi rdl er 6-93 Co-Mo
Girdler 6-64 Fe203
Girdler 6-64 Fe203:Girdler 6-72 D ZnO (1:l)
Strem Si-A1
Girdler 6-3 Fe-Cr:Grace Si-A1 (1:1), (2:1), (3:l)
Gi rdl er 6-66 Cu-Zn
Girdler 6-3 Fe-Cr:Harshaw Ni-1404 (3:l)
Girdler 6-93 Co-Mo:Grace Si-A1 (2:l)
Girdler 6-3 Fe-Cr:Grace Si-A1 :Harshaw Nil404 (4:2:1)
Girdler 6-93 Co-Mo:Harshaw Ni-1404 (1:l)
TABLE 23. T y p i c a l Results f o r Lodgepole Wood Impregnated w i t h
17 w t % K2CO3 i n t h e Presence o f Steam and C a t a l y s t s

Catalyst

Steam Rate, g/min


Wood Feed Rate, g/min
Cold Gas E f f i c i e n c y , %
Carbon Conversion
t o Gases, %
Gas Composition, v o l %

Conclusions from experimental r e s u l t s f o r the hydrogen production case


are :

a 7 5 0 ' ~ i s the p r e f e r r e d o p e r a t i n g temperature o f t h e t h r e e tempera-


tures investigated.

Hydrogen production i s poor a t 550'~.

a Approximately 80% o f t h e carbon i n t h e wood was converted t o gas i n


t e s t s a t 750'~.

a The two c a t a l y s t systems p r e v i o u s l y described are s u i t a b l e f o r hydro-


gen production.

a High steam-to-wood feed r a t e s (order o f 4 : l ) are r e q u i r e d t o o b t a i n


t h e desired CO s h i f t r e a c t i o n needed f o r hydrogen production.
SYSTEMS FOR GENERATION OF CARBON MONOXIDE
The objective of the CO studies is to optimize the selective production
of CO by employing steam, oxygen, and C02 as reactants to gasify wood in the
presence of catalysts. Maximum results for CO production obtained up to this
point are presented in Table 24. Results to date appear unfavorable. There-
fore, the direct production of CO from biomass is not recommended.

EVALUATION OF ALTERNATIVE BIOMASS MATERIALS


Laboratory studies to investigate the production of hydrocarbon synthesis
gas (syngas) from alternative biomass materials were initiated this year. A
corn feedstock was examined to determine the applicability of this type of
feedstock. A proximate and ultimate analysis of the corn is presented in
Table 1. Hydrocarbon synthesis gas studies at 750'~ indicate that product

TABLE 24. Experimental Results for CO production from Lodgepole Wood


Primary Catalyst 17% K2C03
Secondary Catalyst Grace Si:Al
Reactor Temperature 850'~
Catalyst Bed Temperature 725'~ to 770'~
Wood Feed Rate 0.6 g/min
Steam Rate 0.1 g/min
O2 Rate 0.08 g/min
C02 Rate 1.5 g/min
Cold Gas Efficiency 127%
Carbon Conversion to Gas 93%
Gas Composition
2 15.7 vol%
C02 43.8 vol%
'zH4 0.6 vol%
'zH6 0.1 vol%
CH4 3.1 vol%
CO 36.7 vol%
y i e l d s and conversion e f f i c i e n c i e s f o r corn and wood are s i m i l a r . A comparison
o f steam g a s i f i c a t i o n o f corn and wood i s d e p i c t e d i n Table 25. A catalyst
system c o n s i s t i n g o f Ni-1404lSi-A1 a t a 1:l weight r a t i o was found t o be s u i t -
able f o r steam g a s i f i c a t i o n o f corn. A NiOISi-A1 c a t a l y s t system o r a
1:3 weight r a t i o o f t h e Ni-1404/Si-A1 c a t a l y s t system proved t o be u n s a t i s f a c -
t o r y f o r corn feedstock. These c a t a l y s t systems had worked e q u a l l y w e l l w i t h
wood as the feedstock. The p o t e n t i a l methanol y i e l d i n d i c a t e s t h a t about 5 g a l
o f methanol can be d e r i v e d from one bushel o f corn. F u r t h e r s t u d i e s on a l t e r -
n a t i v e feedstocks are planned.

TABLE 25. Steam G a s i f i c a t i o n o f Biomass f o r t h e Production


o f Hydrocarbon Synthesis Gas

Feed Corn Lodgepol e Wood

C a t a l y s t System Ni-1404:Si-A1 Ni -1404: S i - A 1


(1: 1 ) (1:3)

Reactor and C a t a l y s t Bed


Temperature , OC 750

Feed Rate, glmin 0.4 0.4

Steam Rate, g/min 0.2 0.2

Carbon Conversion t o a Gas, % 0.83 0.82

Cold Gas E f f i c i e n c y , % 94 98

P o t e n t i a l Weight F r a c t i o n
Y i e l d o f Methanol 0.63

Gas Composition, v o l %

"2 55.7 57.8


CO 30.3 27.7

co2 12.7 12.7

CH4 1.4 1.8


FUTURE LABORATORY STUDIES
Catalyst development, lifetime, regenerability, and characterization
studies will continue for both methane and hydrocarbon synthesis gas produc-
tion. Nickel alloys on various substrates will be obtained in the near future
from The Davison Chemical Division of W.R. Grace & Co. These will be tested
for both methane and hydrocarbon synthesis gas production. As a result of
these tests, catalysts may be prepared in the laboratory for testing.
Investigations to produce an amonia synthesis gas will resume this year.
Operating conditions at 750'~ wi 1 1 be optimized. Catalyst 1ifetime and regen-
erability will be studied for the favored catalyst system.
Alternative feedstocks, such as corn, alfalfa, and wheat straw, will be
investigated regarding the feasi bi 1 i ty of producing specific gases.
Thermal studies to determine the heat requirements (or release) in biomass
(wood, 1ignin, cellulose) pyrolysis were initiated in FY-1980. These studies
will continue and will include alkali carbonate catalyzed biomass. Methods
that will be used to study pyrolysis and gasification of biomass include dif-
ferent i a1 scanning calorimetry (DSC) , thermal gravimetr ic analysis (TGA), and
thermal mechanical analysis (TMA). Support studies for the PDU will also
conti nue.
PROCESS DEVELOPMENT UNIT STUDIES

The main objective of the PDU studies was to evaluate catalysts and oper-
ating conditions developed in the laboratory on a scale approximating commer-
cial operations to identify heat and mass transfer problems associated with
scale-up. Operations were structured to allow determination of material and
energy distribution in the system.
Design and procurement of equipment began in January 1978. The initial
design included a stirred-bed gasifier. By March 1980 the PDU was modified by
converting the stirred bed to a fluidized bed. The PDU designs and operations
are presented in the following discussion.

PDU DESCRIPTION
Design of the PDU with the stirred-bed gasifier was initiated before
design criteria were fully established in the laboratory. Therefore, the PDU
was designed for general purpose operation to develop the following
information:
a process yields, conversion efficiency, thermal efficiency, throughput
a required or desirable process features (catalyst recycle, feed mate-
ri a1 preparation, product gas treatment)
a equipment requirements (materials hand1ing, instrumentation, con-
struction materials, unit operations)
utility requirements
a emission control requirements.
A flow schematic of the original PDU with the stirred-bed gasifier is shown in
Figure 26. A photograph of the completed PDU is shown in Figure 27.
Gasifier
The stirred-bed gasifier is illustrated in Figure 28. The gasifier is a
250-psig pressure vessel. The shell is 2 ft (60 cm) sch 80 carbon steel pipe
10 ft (3 m) long. The bottom head of the gasifier contains the gas inlet
FIGURE 26. Schematic o f Original PDU
FIGURE 27. Photograph of Original PDU
l I 4 i N . TUBE BUNDLE
FOR S A M P L l NG AND
TEMPERATURE PROBES

CASTABLE REFRACTORY

TUBE LINEZS - 3 IN. I


FEED PORT

D l STR l B UTOR PLATE

SOLIDS SAMPLER HOUSING

CERAMIC TUBE LINERS-


I D OPENING 4 I N .

FIGURE 28. Schematic o f the Stirred-Bed Gasifier


nozzle and gas distributor plate. A drain line in the bottom head allows an
operator to remove materials that fall through the distributor plate. Three
small lines permit sampling of solids from three different levels in the gasi-
fier. Figure 29 is a photograph of the bottom head section with the solid sam-
pling and removal lines.
Three nozzles above the distributor plate on the gasifier allow addition
of biomass at different levels in the four foot bed. We have, however, only
used the lowest feed port. An internal auger about 8 in. (20 cm) in diameter
was used to stir the 4-ft-deep bed of catalyst and char.
Energy was supplied to the gasifier by heaters surrounding an 11-in.
(28-cm) diameter, 310 stainless steel 1 i ner. Heater leads leave the gasifier
through glands in three flanged ports. In the early experiments two types of
heaters were tested. The original heaters were nichrome resistance heaters
embedded in ceramic. Several different configurations were tried, however,
these heaters could not withstand the reducing environment. They were rep1aced
with incoloy-sheathed heaters wrapped around the stainless steel liner. These
heaters lasted we1 1 in the gasifier, however, their heat transfer characteris-
tics did not allow operation at bed temperatures above 550'~.
The reactor has an internal refractory lining 14 in. (36 cm) I.D. by
16 in. (41 cm) O.D. The remainder of the shell insulation is provided by
~aowool8. Figure 30 shows the refractory and ~ a o w o o lin~ the reactor as well
as the three electrical ports at 120' spacing and three biomass feed ports.
The stirred-bed gasifier was equipped with three instrument bundles. A
bundle consisted of seven stainless steel tubes welded in a close-packed con-
figuration. Each tube extended to different levels in the gasifier. One bun-
dle was used to measure pressures at seven points in the bed. Bundle two had
seven thermocouples at different levels. The third bundle was used for sam-
m
pling the gas composition at different levels.
The exterior of the reactor was painted with temperature sensitive paint
which changes colors as the temperature exceeds certain values. This is useful
.
8 Registered Trademark of Babcock and Wi lcox.
FIGURE 29. Bottom Head o f Stirred-Bed G a s i f i e r

64
in identifying hot gas circulation between the shell and refractory. Seven
thermocouples were glued to the shel 1 exterior to monitor shel 1 temperatures.
From October 1979 to March 1980 the PDU was modified extensively. The
most significant change was the modification of the gasifier vessel to operate
in a fluid-bed mode.
During the agitated-bed testing it became apparent that the agitated sys-
tem was difficult to model, and very difficult to scale up. Also, and perhaps
most importantly, the agitator was presumed to be the cause of severe catalyst
attrition. Finally the system did not have good heat transfer characteristics
which prohibited operation at temperatures above 600'~ without the use of oxy-
gen. For these reasons it was decided to convert the PDU to allow fluidized-
bed operation.
The modifications involved removal of the agitator and the agitator
support-drive system, installation of a new gas inlet section, a new distribu-
tor plate, a new stainless steel liner and gasifier heaters.
With the auger removed from the bed, the effective cross-sectional area of
the reactor was 0.66 ft2 (610 cm2) instead of 0.35 ft2 (330 cm2) with the
auger. The larger area meant that the gas flows would need to double to main-
tain the same linear velocity. For this reason a new liner for the bed was
constructed for an inside effective area of 0.31 ft2 (290 cm2 ) . The new liner,
also made of 310 stainless steel, had an I.D. of 7.75 in. (20 cm).
A new gasifier bottom head and gas distributor were procured to accommo-
date the smaller diameter bed. This assembly was intentionally designed to
decrease the heat loss in the gas inlet section. Only one bed-draining device
is used in the new bottom head assembly. The distributor plate was reposi-
tioned from 14 in. (36 cm) to 2 in. (5 cm) below the wood-feed port. This
allows the feed to be reacted with the hottest gas in the system.
Ceramic fiber heaters, with nichrome elements were clad to the new bed
liner. These heaters failed after only several days use. They were replaced
by sheathed heaters which are still in service.
A problem remained in getting enough heat into the gasifier bed. This was
solved by installing six cartridge heaters directly into the bed of char and
catalyst. These heaters have a total capacity of 30 kW and have performed very
well to date.
The top head of the gasifier had to be replaced for the installation of
the cartridge heaters. The modified head does not utilize the instrument bun-
dles described earlier. Instead, individual tubes for thermocouples and pres-
sure sensors extend into different levels of the gasifier from the top head.
Figure 31 shows a schematic of the fluidized-bed gasifier as it now
exists.
Wood Feed System
Wood is introduced to the gasifier using a lockhopper and an auger feeder.
The lockhopper is a 4-ft3 (0.11-m 3 ) chamber with pneumatically operated ball
valves on the top and bottom. Figure 32 shows the lower portion of the lock-
hopper. A level indicator in the lockhopper signals when wood loading is
required. Operators raise weighed batches of wood to the hopper via a
hydraulic-electric crane. The hopper valves are closed and the hopper is
purged with Cop. After purging, the top hopper valve is opened, and the wood
is added to the hopper. The top valve is closed. Air is purged from the hop-
per, and the bottom hopper valve is then opened. The wood drops to the auger
feeder. Interlock mechanisms prevent operators from opening both hopper valves
at the same time. Upon loss of power or supply air, the bottom valve fails to
the closed position, and the top valve fails open to ensure safety.
The screw feeder consists of two metering screws approximately 2 in.
( 5 cm) in diameter. These operate with a variable-speed hydraulic drive at
about 20 to 40 rpm. They push the wood onto a third screw oriented 90' from
the metering screws. The third screw (injector screw) is also about 2 in.
( 5 cm) in diameter. It operates at about 150 to 200 rpm with a variable speed
hydraulic motor. At this speed, wood is rapidly moved into the gasifier. The
injector screw also is connected to a hydraulic ram that gives the screw 6 in.
(15 cm) of travel. This feature is helpful in breaking jams in the injection
PRODUCT GAS
OUTLET

KAOWOOL BLANKET
8 cm THICK

CASTABLE REFRACTORY
3 cm THICK

15-cnI PIPE WITH CERAMIC 6 EACH SUBMERGED


TUBE LINERS - 8-cm CARTRIDGE HEATERS
FEED PORT

EXTERNAL BED
HEATERS

FEED PORT

120-cm BED CATALYST


A N D CHAR

METAL LINER
2 0 cm I D x 1 3 7 cm DISTRIBUTOR PLATE
LONG

BED SAMPLING DEVICE


GAS INLET NOZZLE

FIGURE 31. Schematic of Fluidized-Bed Gasifier


<
FIGURE 32. View of Lock Hopper

69
section. Controls for the feeder include two tachometers, control valves, and
an electric interlock that prohibits operation of the metering screws without
the injector screw in operation.
Gas Supply Systems
Reactant gases include steam, oxygen, air, and carbon dioxide. Steam is
supplied with a 150-lb/h (68-kg/h) 100-psi (690-kPa) generator. The saturated
steam is heated to 110'~ with trace heaters prior to the steam control valve
and orifice meter. A pneumatic integral orifice meter and controller are used
for steam control. Oxygen can be fed to the gasifier if desired. Since oxygen
requirements are low, the oxygen is supplied with 380 1b (170 kg) liquid oxygen
storage cylinders. Oxygen flow is measured by a rotameter. Low pressure air
is available as a feed gas. Air is metered using a pitot tube sensor. Carbon
dioxide is available from a 6-ton (5-t) storage tank and is metered using a
pitot tube apparatus. Carbon dioxide is sometimes used for purge gas on the
plant. Nitrogen is available from standard gas cylinders. It is used as a
quench gas in case of automatic shutdown. It is also used for purge gas. All
feed gas temperatures are recorded on a datalogger. Pressures and flow rates
are recorded in data books by operators. All feed gas lines contain check
valves to eliminate backflow in the lines.
The feed gases mix in a header system and then travel through a 1-in.
(2.5-cm) ball valve. This valve is interlocked with the datalogger. If gasi-
fier temperatures exceed a preset point (usually 800°c), the valve will auto-
matically close, thereby preventing runaway temperatures in the reactor. When
the valve closes, another valve on the nitrogen quench system opens, and the
gases in the gasifier are flushed out of the system. The feed gases then pass
through the gas preheater. This unit uses electric heaters to bring the gases
to about 700'~. The controls for this heater and a portion of the heater are
shown in Figure 33.
Provisions were made for recycling a portion of the product gas through
the gas heater to the gasifier. This would be useful for boosting velocities
in the gasifier. The blower used for recycle gas was a rotory lobe-type with
a variable speed drive. A packed-bed contactor was placed upstream of the
r e c y c l e blower t o c o o l t h e r e c y c l e gas by d i r e c t c o n t a c t w i t h water i f neces-
sary. F i g u r e 34 shows t h e c o n t a c t o r and r e c y c l e blower. Recycle gas flow
r a t e s were measured by d i f f e r e n t i a l pressure produced w i t h a p i t o t tube. The
automatic shutdown system described p r e v i o u s l y a1so stops t h e r e c y c l e blower.

Hot feed gases e x i t the gas heater through a 3- in. (7.5-cm) s t a i n l e s s


s t e e l l i n e l e a d i n g t o t h e g a s i f i e r i n l e t nozzle. This l i n e (about 20 f t ( 6 m)
l o n g ) was w e l l i n s u l a t e d , however, heat loss was s t i l l high. Heaters were
added t o p o r t i o n s o f t h e feed l i n e t o counteract t h e heat loss. Feed gases
now reach t h e g a s i f i e r a t temperatures between 7 5 0 ' ~ and 800'~.

Gas Cleanup System

Gas c l e a n i n g i s r e q u i r e d t o separate and recover t h e products f o r analy-


sis. T h i s i n v o l v e s s e p a r a t i n g t h e s o l i d s and l i q u i d s from t h e gas and c o o l i n g
the gas.

The p r i m a r y means o f s o l i d s separation i s by a d r y cyclone o p e r a t i n g about


10 f t ( 3 m) downstream o f t h e g a s i f i e r . The cyclone u s u a l l y operates i n t h e
temperature range o f 3 0 0 ' ~ t o 5 0 0 ~
depending
~ on g a s i f i e r c o n d i t i o n s . Inside
diameter o f t h e cyclone i s 6 i n . (15 cm). The cyclone i s i n s u l a t e d t o prevent
condensation on i t s w a l l s . S o l i d s were drained from t h e cyclone i n t o a drum
which was weighed and sampled a f t e r a day's t e s t . I t was d e s i r a b l e t o sample
more f r e q u e n t l y t o o b t a i n c o l l e c t i o n r a t e s a t steady s t a t e . A l o c k hopper sys-
tem was b u i l t f o r t h e cyclone. It consisted of a 2- in. (5-cm) p i p e w i t h b a l l
valves a t each end. This cyclone hopper i s drained a t 1/2-h i n t e r v a l s .

Downstream o f t h e cyclone (see F i g u r e 26), a wet v e n t u r i scrubber was used


f o r gas c o o l i n g and f i n a l p a r t i c u l a t e removal. The scrubber contacted water
w i t h t h e h o t gas i n a v a r i a b l e t h r o a t v e n t u r i . Water c o u l d be c i r c u l a t e d i n
t h e system o r passed through the system on a once-through basis. Circulation
was d i f f i c u l t because f l o w meters and water l i n e s plugged w i t h char and t a r .
Most o f the time t h e water t o t h e scrubber was n o t r e c i r c u l a t e d . Yields o f
char and t a r were determined by c o l l e c t i n g timed l i q u i d samples and performing
s o l i d s a n a l y s i s and measuring t o t a l organic carbon i n the l i q u i d phase.

The clean gas was then measured w i t h a p i t o t tube and subsequently w i t h


an o r i f i c e meter. The p i t o t tube was u n r e l i a b l e w i t h i t s opening t e n d i n g t o
plug. The o r i f i c e meter has been a r e l i a b l e gas m e t e r i n g d e v i c e f o r t h i s
a p p l i c a t i o n . A f t e r sampling and metering, t h e gas i s burned i n a gas burner.

Poor performance o f t h e v e n t u r i scrubber r e s u l t e d i n i t s replacement w i t h .


an e l e c t r o s t a t i c p r e c i p i t a t o r (ESP) shown i n F i g u r e 35. The p r e c i p i t a t o r i s a
5 - i n . (13-cm) p i p e w i t h a 1 - i n . (2.5-cm) e l e c t r o d e down t h e c e n t e r o f t h e pipe. .
I o n i z i n g d i s k s a r e l o c a t e d on t h e lower p o r t i o n of t h e e l e c t r o d e . Gas e n t e r s
a t t h e bottom o f t h e p r e c i p i t a t o r and e x i s t s a t t h e top. The ESP i s designed
f o r 100 p s i g (690 kPa) o p e r a t i o n . The u n i t can operate w i t h e i t h e r a d r y w a l l
o r a wetted w a l l . C u r r e n t l y , water i s c i r c u l a t e d through t h e p r e c i p i t a t o r t o
c o o l t h e gas and remove t h e p a r t i c u l a t e s c o l l e c t e d on t h e w a l l . A schematic of
t h e PDU c o n f i g u r a t i o n as o f October 1980 i s shown i n F i g u r e 36.

I n s t r u m e n t a t i o n and Data A n a l y s i s

A n a l y t i c a l equipment f o r gas a n a l y s i s c o n s i s t s o f c o n t i n u o u s analyzers


f o r instantaneous compositions and gas chromatographs f o r p e r i o d i c d e t a i l e d
analysis.

Four continuous u n i t s are used. Two Beckman i n f r a r e d analyzers measure


carbon monoxide and carbon d i o x i d e l e v e l s . Oxygen i s measured w i t h a Beckman
p o l a r o g r a p h i c sensor. Hydrogen i s measured by thermal c o n d u c t i v i t y i n a Mine
S a f e t y Appliances analyzer. Continuous readings a r e recorded e v e r y 15 min b y
an o p e r a t o r .

D e t a i l e d gas analyses are processed every 20 min w i t h a C a r l e thermal con-


d u c t i v i t y gas chromograph. The chromatograph i s combined w i t h a Spectrophysics
SP 4000 microprocessor f o r automatic i n t e g r a t i o n . The gases measured are CO,
C02, Hp, N2, O2 and C1 t o C4 p a r a f f i n s and o l e f i n s . Occasionally a Hewlett
Packard flame p h o t o m e t r i c chromatograph i s used f o r hydrogen s u l f i d e measure-
ment i n the p a r t s per m i l l i o n range.

Samples from the PDU are drawn t o the a n a l y t i c a l equipment w i t h a vacuum


pump. The continuous samples are drawn from t h e r e a c t o r e x i t gas l i n e . The
chromatograph samples are n o r m a l l y taken a f t e r t h e gas i s cleaned and cooled,
however, these samples can be drawn f r o m 10 o t h e r l o c a t i o n s i n t h e p l a n t u s i n g
a 1 2 - p o s i t i o n v a l v e on t h e sample l i n e s .
Water content o f the gas from t h e g a s i f i e r i s an important f a c t o r i n the
mass balances. The water content was o r i g i n a l l y measured w i t h a dewpoint
hygrometer. However, t h i s u n i t was u n r e l i a b l e , and poor s e r v i c e from the f a c -
t o r y r e s u l t e d i n i t s discontinued use. Water content i s now determined several
times during a t e s t by drawing a gas sample, condensing the water, and mea-
s u r i n g t h e water c o l l e c t e d and t h e d r y gas volume.

Temperatures are scanned continuously and recorded a t 20-min i n t e r v a l s on


a 60-channel, p r i n t i n g datalogger. The datalogger can a l s o a u t o m a t i c a l l y
shutdown gas feed t o the PDU should a temperature excursion occur. The tem-
peratures monitored on t h e datalogger i n c l u d e each feed gas, t h e heated gas,
7 p o i n t s i n the g a s i f i e r , 7 r e a c t o r surface temperatures, o f f gas temperatures
and c o o l i n g water temperatures. Alarms on t h e datalogger a l l o w operators t o
see where problems may be developing and t o take appropriate actions. Tempera-
t u r e s from t h e datalogger tapes are keypunched, and temperature p l o t s are gen-
erated by a computer.

Pressures, d i f f e r e n t i a1 pressures, c o n t r o l l e r s e t t i n g s , and meter readings


are recorded a t 112-h i n t e r v a l s i n a data book by an operator. This data book
also contains records o f wood a d d i t i o n and cyclone c o l l e c t i o n rates. After a
t e s t , these data along w i t h gas compositions and recorded temperatures are
processed on a minicomputer t o gain a p r e l i m i n a r y estimate o f the t e s t r e s u l t s .
The r e s u l t s o f analyses subsequently performed on t h e l i q u i d s and s o l i d s are
l a t e r entered i n t o the computer f o r a f i n a l t e s t analysis. Data are stored on
magnetic disks. O r i g i n a l raw data are a l s o kept f o r f u t u r e reference.

PDU OPERATION

The purpose o f the PDU operations was t o t e s t c a t a l y s t systems developed


i n t h e l a b o r a t o r y and t o evaluate t h e i r p r a c t i c a l i t y f o r large- scale operation.
PDU operations were completed w i t h the s t i r r e d - b e d g a s i f i e r and the fluid- bed
g a s i f i e r ; r e s u l t s are presented i n t h e f o l l o w i n g discussion.

Successful operation o f the f l u i d - b e d g a s i f i e r i l l u s t r a t e d the t e c h n i c a l


f e a s i b i l i t y o f t h e c a t a l y t i c processes. Results w i t h t h e s t i r r e d - b e d g a s i f i e r
were o f l i t t l e value since operations w i t h o u t oxygen were l i m i t e d t o tempera-
t u r e s under 6 0 0 ' ~ and since scale-up o f the g a s i f i e r appears t o be i m p r a c t i c a l .

Test Procedures and S a f e t y Considerations

Documents were prepared t o assure s a f e t y o f the PDU o p e r a t i o n before


s t a r t u p was permitted. The f i r s t document, " Operational S a f e t y Analysis Review
f o r C a t a l y t i c Biomass G a s i f i c a t i o n PDU," contained an a n a l y s i s o f p o t e n t i a l
problems and hazards o f each piece o f equipment i n t h e PDU and described t h e
s a f e t y f e a t u r e s t o be incorporated i n t o the o r i g i n a l p l a n t design. The second
document, "Safe Operating Procedures," 1i sted t h e steps f o r p l a n t s t a r t u p ,
shutdown, normal operation, and emergency conditions.

Normal t e s t procedures begin w i t h h e a t i n g t h e p l a n t t o t h e d e s i r e d tem-


perature, which takes 3 t o 4 h. When a t the desired temperature, wood i s
introduced, and t h e p l a n t i s operated a t steady c o n d i t i o n s f o r 3 t o 5 h. Wood
feed i s then stopped, and the p l a n t i s e i t h e r p a r t i a l l y o r t o t a l l y shutdown
depending on whether o r n o t i t w i l l be operated t h e f o l l o w i n g day.

Feedstock f o r the PDU

Wood feedstock f o r the PDU was l i m i t e d i n s i z e by the screw feeder, which


could d e l i v e r chips w i t h a maximum dimension o f about 112 i n . (13 mm). Origi-
n a l l y , wood was purchased t h a t had been s p e c i a l l y processed i n a hammer m i l l .
L a t e r we found a supply o f headrig sawdust (maple and a l d e r ) t h a t was s u i t a b l e
f o r use i n the PDU.

Another m a t e r i a l t h a t was used f o r several t e s t s was f o r e s t residue. This


was c o l l e c t e d from t h e f o r e s t i n t h e same manner wood residues are c o l l e c t e d
commercially. The wood has a d i f f e r e n t composition, c o n t a i n i n g much more ash
from t h e s o i l s than t h e normal p l a n t feedstock. The compositions o f t h e two
feeds are given i n Table 26.

Wood moisture content markedly i n f l u e n c e s PDU performance. Wet wood tends


t o b r i d g e i n t h e l o c k hopper and g r e a t l y increases t h e heat load t h a t must be
supplied t o the g a s i f i e r . For these reasons, t h e wood feedstock was u s u a l l y
d r i e d t o 1 t o 5 w t % moisture b e f o r e use i n t h e PDU.
TABLE 26. Compositions of Feedstocks Used i n PDU Operations

Feedstock Headrig Sawdust Forest Residue


Weight %, d r y basis:
Carbon 46 46
Hydrogen 6 6
Oxygen 48 39
ash 0.1 9
Heat o f combust ion, d r y basis,
B t u / l b (kJ/kg) 8300 (19,300) 8700 (20,200)

PDU Results w i t h t h e Agitated- Bed G a s i f i e r

The i n i t i a l operation o f the PDU w i t h the agitated- bed g a s i f i e r began i n


t h e f a l l o f 1978 and continued u n t i l t h e f a l l o f 1979. Modifications t o
improve PDU o p e r a b i l i t y were i n i t i a t e d a t the end o f t h i s t e s t period. Opera-
t i o n o f t h e PDU w i t h t h e agitated- bed g a s i f i e r was successful i n o b t a i n i n g data
on generation o f several s p e c i f i c gas products- - a methane- rich gas, a methanol
synthesis gas, and an ammonia synthesis gas. Results are presented i n t h e f o l -
lowing discussion.

Problems were encountered i n operation o f the agitated- bed g a s i f i e r


i n c l u d i n g f a i l u r e o f t h e e l e c t r i c a l heaters, u n r e l i a b l e wood feeding, and
p l u g g i n g o f the v e n t u r i scrubber. The primary problem was i n s t a l l a t i o n and
o p e r a t i o n o f t h e i n t e r n a l e l e c t r i c a l heaters. Several designs were t r i e d , b u t
none proved t o be completely successful. The maximum temperature obtained was
600°c, which i s 1 5 0 ' ~ below the desired upper temperature f o r operation.

The wood feeding problems were e l i m i n a t e d by replacement o f t h e i n i t i a l


single- screw design. The o r i g i n a l feeder used a s i n g l e screw f o r metering and
s l o w l y i n j e c t i n g wood t o t h e g a s i f i e r . We speculated t h a t t a r s deposited i n
the screw channel, causing severe b i n d i n g o f the screw. The system c u r r e n t l y
i n use separates t h e metering and i n j e c t i o n f u n c t i o n s . Two screws meter wood
from the l o c k hopper onto a t h i r d screw which r a p i d l y i n j e c t s wood i n t o t h e
bed o f c a t a l y s t . The i n j e c t i o n screw i s connected t o a h y d r a u l i c ram capable
o f a 6 - i n . (15-cm) t r a v e r s e f o r removal of any p l u g t h a t m i g h t form.

The v e n t u r i scrubber gave problems w i t h t a r r y s o l i d s p l u g g i n g t h e water


circulation lines. T h i s problem was reduced by once- through scrubbing w i t h
water i n s t e a d o f water r e c y c l i n g .

F i g u r e s 37 and 38 summarize t h e e f f e c t s o f temperature and c a t a l y s t com-


b i n a t i o n s on p r o d u c t i o n o f a methane- rich gas i n t h e agitated- bed g a s i f i e r .
I n i t i a l l y we hoped t h e p r i m a r y g a s i f i c a t i o n c a t a l y s t , potassium carbonate,
would promote t h e steam-char r e a c t i o n t h e r e b y i n c r e a s i n g y i e l d s o f CO and Hz
and producing a h i g h methane gas i n t h e presence o f a secondary methanation
catalyst. T h i s d i d n o t happen, however. A t low temperatures, t h e g a s i f i c a t i o n
c a t a l y s t r e t a r d e d b o t h methane p r o d u c t i o n and carbon conversion r e l a t i v e t o
y i e l d s w i t h secondary c a t a l y s t s o n l y . For purposes o f comparing o t h e r
processes, F i g u r e 37 g i v e s t h e methane y i e l d s i n t o t a l s possible- - assuming a l l
CO and Hz was converted. I n t h e 525OC t o 5 7 5 ' ~ temperature range, r e s i d u a l Hz
and CO were b o t h 10% t o 15% i n t h e PDU p r o d u c t gas. Another methanation s t e p
would be needed t o c o n v e r t these r e s i d u a l s t o methane.

The shaded areas i n F i g u r e s 37 and 38 r e p r e s e n t maximum s c a t t e r o f t h e


data. The s o l i d l i n e s show t r e n d s f o r t h e o p e r a t i o n s where few problems
occurred. The t o t a l p o s s i b l e methane p r o d u c t i o n was d e f i n i t e l y lowered by
potassium carbonate a t low temperatures b u t p o i n t s were t o o s c a t t e r e d t o see a
r e a l d i f f e r e n c e between c o n c e n t r a t i o n s o f 5% and 10% by weight potassium
carbonate.

We speculate t h a t one e f f e c t o f t h e p r i m a r y c a t a l y s t was t o a t t a c k t h e


n i c k e l methanation c a t a l y s t and d e a c t i v a t e i t . A t t h e same time, t h e potassium
carbonate l o s t some o f i t s e f f e c t i v e n e s s . Several o b s e r v a t i o n s support t h i s
hypothesis b u t a r e n o t n e c e s s a r i l y c o n c l u s i v e . First, the catalyst pellets
were d i s c o l o r e d a f t e r these these t e s t s b u t n o t when t h e potassium carbonate
was absent. Hydrocarbon s y n t h e s i s gas t e s t s w i t h o u t t h e n i c k e l c a t a l y s t
(potassium carbonate + S i A l o n l y ) show a b e n e f i c i a l e f f e c t o f t h e potassium
carbonate was absent. Hydrocarbon s y n t h e s i s gas t e s t s w i t h o u t t h e n i c k e l
c a t a l y s t (potassium carbonate + S i A l o n l y ) showed a b e n e f i c i a l e f f e c t o f t h e
*ASSUMES ALL CO + Hz
ARE CONVERTED TO METHANE

- SiAl + N i ONLY

- PD U 172 K2C03 + SiAl + Ni


K2COJ + SiAl + N i

I I I

AVERAGE BED TEMPERATURE, OC

FIGURE 37. Methane Y i e l d s from the Agitated- Bed G a s i f i e r as a


Function o f Temperature and C a t a l y s t
A LAB STUDY SiAl + N i

AVE RA GE BED TEM PERATU RE, OC

FIGURE 38. Carbon Conversions for Methane Production


in the Agitated-Bed Gasifier

potassium carbonate i n terms of increasing gas yields. Our ammonia synthesis


gas tests clearly showed the effectiveness of the alkali in promoting the
water-gas-shift reaction (H20 + CO + Hz + Cop).
Laboratory studies showed that the alkali carbonate primary catalyst
increases the yield of char, increases gas yield, and reduces condensable
l i q u i d y i e l d a t temperatures below 6 5 0 ' ~ w i t h no secondary c a t a l y s t . The
secondary s i l i c a alumina and n i c k e l c a t a l y s t s a l s o e f f e c t i v e l y crack and r e f o r m
l i q u i d s from p y r o l y s i s o f wood thereby i n c r e a s i n g gas y i e l d s over those
obtained w i t h t h e primary c a t a l y s t . F i g u r e 38 shows t h e same e f f e c t s o f these
catalysts. The constant carbon conversion w i t h temperature i n t h e presence o f
secondary c a t a l y s t i n d i c a t e s t h a t o n l y p y r o l y s i s o f t h e wood i s a f f e c t e d and i s
as complete a t 4 5 0 ' ~ as a t 600'~. The water-gas r e a c t i o n (C + H20 + CO + Hz)
becomes s i gn i f icant a t about 650'~.

Tests on methanol, o r hydrocarbon, synthesis gas production i n the


agitated- bed g a s i f i e r concentrated on generation o f a 2 : l H2:C0 molar r a t i o
i n t h e gas stream. Figures 39 and 40 summarize f i n d i n g s f o r these t e s t s . We
found t h a t the g a s i f i c a t i o n c a t a l y s t was e f f e c t i v e both i n i n c r e a s i n g gas
y i e l d s and carbon conversions. The b e n e f i t s o f u s i n g t h e a l k a l i were most
apparent a t higher ( - ~ 7 0 0 ~temperatures.
~) The primary c a t a l y s t (a1k a l i car-
bonate) e f f e c t i v e l y promoted the water-gas r e a c t i o n (C + H20 + CO + Hz) a t
temperatures above 650'~.

The p r e f e r r e d temperature f o r generation o f a 2H2:1C0 mole r a t i o gas i s


850'~. The heaters were inadequate f o r maintaining temperatures above 6 0 0 ' ~
i n the PDU, and pure oxygen was needed t o o b t a i n even 700'~. Yields are
markedly improved a t t h e higher temperatures and w i t h o u t a d d i t i o n o f pure oxy-
gen. A r e a c t o r c o n f i g u r a t i o n f o r steam g a s i f i c a t i o n o f the wood a t 8 5 0 ' ~ was
needed. Conceptually, tube bundles i n a f l u i d i z e d bed o f c a t a l y s t could be
used t o provide the r e q u i r e d endothermic heat o f r e a c t i o n .

From an o p e r a t i o n a l standpoint, t h e g a s i f i c a t i o n c a t a l y s t caused problems.


When l o c a l h o t spots developed, the carbonate melted f u s i n g together the sec-
ondary c a t a l y s t and any char i n t h e bed. This problem occurred several times
and prompted a search f o r other c a t a l y s t (non m e l t i n g ) combinations t h a t would
a l s o enhance gas y i e l d s and carbon conversion. The n i c k e l and s i l i c a - a l u m i n a
combination looked very promising i n the laboratory. The low gas y i e l d s i n
t h e PDU were a l i t t l e puzzling. We n o t i c e d a f t e r these t e s t s t h a t l a r g e
amounts o f the secondary c a t a l y s t s were entrained from t h e g a s i f i e r . (It is
n o t easy t o d e t e c t t h i s d u r i n g a t e s t . ) We now speculate t h e r e was i n s u f f i -
c i e n t c a t a l y s t i n the bed t o promote g a s i f i c a t i o n o f the wood and char. Also,
- 0 4% K2C03
A S i A l ONLY
STEAM ONLY

- S i A l + Ni

- A

I
YA 1 I

500 600 700


AVERAGE BED TEMPERATURE, OC

FIGURE 39. Synthesis Gas Y i e l d s as a F u n c t i o n o f Temperature


i n t h e Agitated- Bed G a s i f i e r

we have s i n c e determined t h a t t h e presence o f oxygen d e s t r o y s t h e n i c k e l c a t a -


lyst. L a t e r t e s t s w i t h t h e f l u i d - b e d g a s i f i e r (presented i n a l a t e r s e c t i o n )
showed e x c e l l e n t r e s u l t s w i t h a nickel- on- alumina secondary c a t a l y s t .

Comparing t h e carbon conversion p l o t f o r s y n t h e s i s gas p r o d u c t i o n w i t h t h e


s i m i l a r p l o t f o r methane p r o d u c t i o n shows an apparent c o n t r a d i c t i o n . We see
h i g h carbon conversions a t low temperatures f o r a l k a l i - c a t a l y z e d t e s t s i n F i g -
u r e 40 and low conversions i n F i g u r e 38. However, no methane t e s t ever used
a i r o r oxygen t o m a i n t a i n bed temperatures, whereas s y n t h e s i s gas t e s t s used
some oxygen. A t times, t h e r e a c t o r heaters were n o t working so even f o r low
10%K2C03 + SiAl

- 0 4% K2C03
n S i A l ONLY, PDU
- A S i A l ONLY, LAB STUDY
S i A l + N i + K2CO3, LAB STUDY
S i A l + Ni, LAB STUDY

500 600 700 . 800


AVERAGE BED TEMPERATURE, OC
.-
FIGURE 40. Carbon Conversions f o r synthesis Gas Production
i n t h e Agitated-Bed G a s i f i e r

temperature cases oxygen was added. For a p a r t i c u l a r synthesis gas t e s t show-


i n g 80% carbon conversion ( w i t h O2 a d d i t i o n ) t h e f i g u r e drops t o 65% when t h e
carbon burned i s deducted.

A second order d i l u t i o n e f f e c t was also p o s s i b l e i n t h e methane p r o d u c t i o n


runs. Because product gases were recycled, o n l y 75% ( o r l e s s ) o f t h e feed gas
t o the g a s i f i e r was a reactant. By c o n t r a s t , 100% o f the feed gas t o t h e gasi -
f i e r d u r i n g synthesis gas production was a reactant.

The amnonia synthesis gas s t u d i e s were conducted t o determine the e f f e c t s


o f temperature and g a s i f i c a t i o n c a t a l y s t on product gas f l o w s and compositions,
as w e l l as wood conversions. A l l t e s t s used a s i l i c a - a l u m i n a cracking c a t a l y s t
p l u s an iron-chromium s h i f t c a t a l y s t . P r i o r l a b o r a t o r y s t u d i e s recommended a
4 t o 1 steam/wood weight r a t i o t o minimize CO i n the product gases. The PDU
s t u d i e s used r a t i o s c l o s e t o t h i s . We r e c o g n i z e t h a t t h e h i g h steam f l o w s
r e p r e s e n t a s i g n i f i c a n t energy p e n a l t y f o r any commercial o p e r a t i o n .

I n order t o m a i n t a i n d e s i r e d bed temperatures, pure oxygen was added t o .


t h e a i r stream t o burn a p o r t i o n o f t h e wood feed. From an o p e r a t i o n a l stand-
p o i n t our procedure was 1) e s t a b l i s h t h e d e s i r e d operat i n g temperature u s i n g .
p r e c a l c u l a t e d o x y g e n l a i r r a t i o s , 2 ) n o t e hydrogen c o n c e n t r a t i o n s and p r o d u c t
f l o w s a t steady s t a t e , and 3) r e a d j u s t oxygen and a i r f l o w s t o g i v e t h e d e s i r e d
3:l H2/N2 mole r a t i o .
A d e t a i l i s i m p o r t a n t here when examining t h e gas compositions shown i n
Table 27. N i t r o g e n compositions depend s o l e l y on t h e a i r f l o w r a t e s . With
a d d i t i o n o f pure O2 and a i r , t h e two sources o f oxygen can be t r a d e d t o g e t
whatever n i t r o g e n c o n c e n t r a t i o n i s desired. Only o p e r a t o r i n e x p e r i e n c e and

TABLE 27. Ammonia Synthesis Gas R e s u l t s from t h e Agitated- Bed G a s i f i e r

Bed Temperature, OC 62 7 654 732 0' 735


W t % K2C03 ( a 0 10 0 10
kg steamlkg d r y wood 5.2 4.0 4.7 3.8
kg a i r / k g d r y wood
kg 02/kg d r y wood

Dry Gas Composition, v o l %

Carbon Conversion t o a Gas, % 94 95 91 93


3
m d r y gas/kg d r y wood 1.37 1.81 1.37 1.75
Cold Gas E f f i c i e n c y , % 46 63 53 57

( a ) Dry mixed w i t h wood


imprecise f l o w c o n t r o l prevented our g e t t i n g e x a c t l y t h e 3 : l H2:N2 r a t i o i n t h e
p r o d u c t gas. The i m p o r t a n t numbers a r e r e s i d u a l CO and gas y i e l d s as tempera-
t u r e s change and/or g a s i f i c a t i o n c a t a l y s t i s added. Observations from these
t e s t s are:

The g a s i f i c a t i o n c a t a l y s t (10 w t % d r y mix K2C03) markedly s h i f t s t h e


CO t o Hz a t b o t h 6 5 0 ' ~ and 750'~.

A d d i t i o n o f t h e g a s i f i c a t i o n c a t a l y s t increased gas y i e l d s n o t i c e a b l y .

Although i t i s n o t shown i n Table 27, t h e water c o n t e n t o f t h e e x i t gases


i s o f interest. I n a l l cases i t exceeded 70 mole% o f t h e p r o d u c t stream. This
suggests a huge excess o f steam was p r e s e n t and supports our e a r l i e r conten-
t i o n t h a t more work i s needed a t lower steam f l o w r a t e s . The e f f e c t o f t h e
decreased steam f l o w on CO c o n c e n t r a t i o n w i l l be o f prime i n t e r e s t .

PDU Results With t h e Fluid- Bed G a s i f i e r

The PDU w i t h t h e f l u i d - b e d g a s i f i e r was operated f o r a s e r i e s o f t e s t s i n


t h e temperature range o f 5 0 0 ' ~ t o 7 5 0 ' ~ w i t h s e v e r a l secondary c a t a l y s t s and
w i t h o u t secondary c a t a l y s t f o r v a r i o u s steam r a t e s . Most t e s t s i n c l u d e d a t
l e a s t 4 h o f o p e r a t i o n a t steady s t a t e .

The i n i t i a l t e s t s e r i e s used a Harshaw Ni-3266 c a t a l y s t i n t h e form o f a


1116-in. (1.6-mn) e x t r u d a t e . These t e s t s were a l l a t a temperature o f about
5 0 0 ' ~ f o r generation o f a methane- rich gas. Because o f t h e c a t a l y s t size,
s u b s t a n t i a l amounts o f r e c y c l e gas had t o be used t o f l u i d i z e t h e c a t a l y s t bed.
The h i g h gas v e l o c i t y and t h e low temperature i n t h e bed were p r o b a b l y respon-
s i b l e f o r t h e low carbon conversion compared t o subsequent t e s t s a t lower
l i n e a r v e l o c i t i e s and h i g h e r temperatures. F i g u r e 41 shows t h e e f f e c t o f vary-
i n g t h e steam-to-wood r a t i o on t h e p r o d u c t gas composition f o r these t e s t s .
Table 28 summarizes t h e d a t a from these t e s t w i t h t h e Harshaw Ni-3266 c a t a l y s t .

Several o f t h e t e s t s used f o r e s t r e s i d u e o f t h e composition shown i n


Table 26. The f o r e s t r e s i d u e had a h i g h ash c o n t e n t compared t o t h e t y p i c a l
h e a d r i g sawdust t h a t was used f o r most t e s t s . No d i s c e r n a b l e d i f f e r e n c e i n t h e
performance o f the PDU w i t h t h e f o r e s t r e s i d u e feedstock was noted.
CATALYST Ni 3266 FLU I D BED =500~~

0 I I 1 I I I I I I I
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 .O
WE1 GHT R A T I O OF STEAM TO WOOD

FIGURE 41. E f f e c t o f Steam-to-Wood R a t i o on Gas Composition


f r o m t h e Fluid- Bed G a s i f i e r

A t t r i t i o n problems w i t h t h e e x t r u d a t e c a t a l y s t prompted t h e purchase o f


s p h e r i c a l m a t e r i a l f o r use i n t h e f l u i d bed. The m a t e r i a l was s i z e d t o a l l o w
f l u i d bed o p e r a t i o n a t a lower v e l o c i t y than r e q u i r e d f o r t h e e x t r u d a t e . Inert
spheres o f nonporous alumina (U.S. Screen -20 + 40 mesh) and c a t a l y s t spheres
(U.S. Screen -16 +30 mesh) o f n i c k e l on a ceramic s u b s t r a t e were o b t a i n e d f o r
t e s t i n g t o compare r e s u l t s w i t h and w i t h o u t a c a t a l y s t . Tests w i t h t h e i n e r t
spheres were completed a t 550°, 600°, and 750'~. R e s u l t s o f these t e s t s
are shown i n Table 29.

Operation w i t h s p h e r i c a l p a r t i c l e s and heaters submerged i n t h e bed


improved t h e g a s i f i e r performance i n s e v e r a l ways. Heat t r a n s f e r was g r e a t l y
improved a1l o w i n g o p e r a t i on a t 750'~. Temperature c o n t r o l was markedly
improved. The bed became i s o t h e r m a l w i t h f i v e thermocouples i n t h e bed d i f -
f e r i n g l e s s than 5'~. With t h e a g i t a t e d bed and w i t h t h e f l u i d bed o f l a r g e r
c a t a l y s t size, t h e temperatures i n t h e bed v a r i e d as much as 1 0 0 ~ ~ F. i g u r e 42
TABLE 28. Results o f PDU Tests With N i c k e l Extrudate C a t a l y s t

Test No. 1 2 3 4 5 6 7
Temperature, OC 550 470 495 495 450 505 510
Feedstock Headrig Headrig Headrig Headrig Forest Forest Headrig
Sawdust Sawdust Sawdust Sawdust Residue Residue Sawdust
Weight R a t i o
Steam-to-Wood .93 .29 .34 .54 .40 -0- -0-

Gas Composition, v o l %
41 26 28 34 31 18 15
2
CH4 15 22 22 22 23 27 30
CO 4 8 8 6 33 7 11
C02 40
43 41 38 42 48 43
0.0 0.2 0.2 0.0 0.0 0.0 0.2
2
0.0 0.3 0.2 0.2 0.2 0.0 0.1
C3

Cold Gas
Efficiency, % 62 36 42 66 43 48 43

Carbon Conversion, %
gas 67 44 47 64 49 52 48
1i q u i d -- 1 1 1 1 1 2
solid 4 44 51 33 23 30 17

P o t e n t i a1 CH4
s c f /ton 9500 5400 6400 9000 6700 5900 6000
( nm3/t (300) (170) (ZOO) (280) (210) (180) (190)

shows a comparison o f t h e bed temperature p r o f i l e s f o r a case w i t h 1) t h e


extruded c a t a l y s t w i t h o u t submerged heaters and 2) t h e s p h e r i c a l c a t a l y s t w i t h
submerged heaters.
TABLE 29. R e s u l t s o f PDU Tests w i t h Nonporous Alumina Spheres

T e s t No.
Temperature, OC

Gas Composition, v o l %

CH4
co
C02
C2,C3yC4

Weight R a t i o Steam:Wood
s c f p r o d u c t / l b wood
( nm3/kg )
Carbon Conversion, %
gas
1i q u i d
char

Cold Gas E f f i c i e n c y , %
P o t e n t i a1 CH4
scf /ton
( nm3/t

Using s p h e r i c a l media i n t h e bed allowed o p e r a t i o n w i t h o u t r e c y c l i n g p r o -


d u c t gas. Steam was t h e o n l y r e a c t a n t gas. As a r e s u l t o f t h e consequent low
v e l o c i t i e s i n t h e g a s i f i e r , t h e char residence t i m e increased. Gas y i e l d s
increased d r a m a t i c a l l y . The char decreased i n s i z e and a f i n e char d u s t was
blown f r o m t h e g a s i f i e r t o t h e gas cleanup system. The system was i n c a p a b l e
o f adequately c l e a n i n g t h i s gas a t low v e l o c i t i e s and t h e downstream p i p i n g
plugged f r e q u e n t l y .
PROFILE WITH EXTRU DATE CATALYST

AT SCREW FEEDER
1 ft ABOVE FEEDER
A 2 A ABOVE FEEDER
0 3 ft ABOVE FEEDER
v 4 ft ABOVE FEEDER

0
0 33 66 99 132 165 198 231 264 297 330
TlME ( m i n ) AFTER START OF WOOD FEED

0 AT SCREW FEEDER
0 1 ft ABOVE FEEDER
* 2 ft ABOVE FEEDER
o 3 A ABOVE FEEDER
v 4 A ABOVE FEEDER

0
0 22 44 66 88 110 132 154 176 198 220
TIME ( m i n ) AFTER START OF WOOD FEED

FIGURE 42. Temperature P r o f i l e s i n Fluid- Bed G a s i f i e r


A spherical catalyst was obtained from W. R. Grace & Co., The Davison
Chemical Division of Baltimore, Maryland. The catalyst composition is proprie-
tary but has the following general properties:
main constituents - alumina, nickel
U.S. Screen Size - -16 +30 mesh
particle density - 92 1b/ft3 (1480 kg/m3)
bulk density - 55 1b/ft3 (880 kg/m3)
Results of tests with the spherical catalyst before and after regeneration are
presented in Table 30.
The catalyst was regenerated with steam at 750'~ followed by hydrogen
reduction at 450'~ after ~ e s t4. Regeneration was effective as can be deter-
mined from the data in Table 30 (Test 5). However, the catalyst appears to
deactivate rapidly after regeneration (Tests 6 and 7).
Graphical comparisons of catalyzed versus uncatalyzed results are shown in
Figure 43 for methane production and Figure 44 for synthesis gas production.
The advantages of catalyzed gasification are obvious.
Calculation of Equilibrium Gas Compositions
A computer program that calculates chemical equilibrium between solid car-
bon and gases was developed in 1980. The program was needed to determine the
deviations from equilibrium in both the laboratory-scale gasifier and the PDU
gasifier. The program was useful for estimating gasifier performance at 10 atm
pressure for the economic evaluation of methane and methanol production.
Finally, the program was used to determine the effects of varying the steam-
to-wood ratio at 7 atm to help provide design data for future pressurized
operation.
The equilibrium program describes a batch system. Wood and steam are put
into the system and equilibrium compositions at a specified temperature and
pressure are calculated. It can be easily modified for other feedstocks and
other reacting gases.
TABLE 30. R e s u l t s o f F l u i d Bed PDU Tests w i t h N i c k e l C a t a l y s t

T e s t No.
Temperature, OC

Gas Composition, v o l %

H2
CH4
CO

C02
2
C3

Weight R a t i o Steam:Wood 1.0 0.60 0.63 0.76 0.75 0.6 0.7

Product Gas Y i e l d
s c f / 1b wood 21.7 19.4 21.9 18.6 27.2 18.5 16.1
( nm3/kg) (1.35) (1.21) (1.37) (1.16) (1.70) (1.15) (1.01)

Carbon Conversion, %
gas 78 74 70 73 82 66 72
liquid 1 1 1 3 1 1 2
solid 26 15 18 23 22 21 23

P o t e n t i a l Methane Y i e l d
scf/ton 11,000 10,900 9,800 9,200 11,500 8,500 8,900
( nm3/t (340) (340) (310) (290) (360) (260) (280)

P o t e n t i a1 Methanol Y i e l d
w i t h o u t reforming,
w t / w t d r y wood 0.34 0.29 0.44 0.35 0.58 0.37 0.28

Cold Gas E f f i c i e n c y 79 77 75 71 88 65 67
UNC ATALYZED AT 750'~

WE lGHT TO TO TO CHq CO Hz CO2 WE1 GHT RATIO,


RATIO GAS SOLIDS LIQUID METHANOL TO
STEAM MOLE FRACTIONS IN GAS WOOD
CARBON CONVER S l ON S
TO
WOOD

FIGURE 44. Comparisons o f Catalyzed versus Uncatalyzed Results f o r Synthesis Gas Production
The assumptions used i n the program are:
no l i q u i d phase present
the o n l y gas species considered are H2, H20, CH4, CO, and C02
any s o l i d i s 100% carbon and has an a c t i v i t y o f 1
a l l hydrogen and oxygen i n the wood are converted t o gas.

The method o f s o l u t i o n i s an i t e r a t i v e Newton-Raphson s o l u t i o n o f seven


equations and seven unknowns. The equations include an element balance f o r
carbon, hydrogen, and oxygen, ( t h r e e equations), t h r e e equi 1ibrium equations,
and one equation expressing D a l t o n ' s law o f p a r t i a l pressures. The e q u i l i b r i u m
equations are f o r t h e f o l l o w i n g heterogeneous reactions:

E q u i l i b r i u m constants f o r these r e a c t i o n s were obtained f o r a temperature


range o f 7 0 0 ' ~ t o 1 2 0 0 ~from
~ Gumz (1950) and f i t t e d t o equations o f t h e form
2
K = exp (A + B/T + C/T ), where K i s the e q u i l i b r i u m constant, T i s absolute
temperature, and A, B, and C are constants.

Figures 45 and 46 show the e f f e c t s o f temperatures on the d r y gas e q u i l i b -


r i u m composition a t atmospheric pressure f o r steam-to-wood r a t i o s o f
0.33 and 1, r e s p e c t i v e l y . These r a t i o s were suggested from e a r l y l a b o r a t o r y
experiments f o r methane production and synthesis gas production, r e s p e c t i v e l y .
Note the increase i n the carbon conversion t o gas w i t h i n c r e a s i n g temperature.
Results from one PDU t e s t and l a b o r a t o r y - s c a l e r e a c t o r t e s t s are p l o t t e d w i t h
t h e 1 atm e q u i l i b r i u m c a l c u l a t i o n s f o r comparison. P o t e n t i a l methane and metha-
n o l y i e l d s are p l o t t e d i n F i g u r e 47. The e f f e c t o f temperature on e q u i l i b r i u m
standard heats o f r e a c t i o n i s shown i n F i g u r e 48. Figure 49 shows t h e e f f e c t
o f pressure on t h e standard heats o f r e a c t i o n .

For the economic scale-up o f biomass g a s i f i c a t i o n f o r methane o r synthesis


gas production, i t may be d e s i r a b l e t o operate a t elevated pressures t o reduce
t h e downstream compression costs. The e q u i l i b r i u m program has been used t o
estimate t h e e f f e c t s o f o p e r a t i n g a t 10 atm f o r use i n t h e economic f e a s i b l i t y
studies.
1.0 -
P=latm
/
0.9 - STEAM : WOOD = 0.333 :1
DRY BAS l S
'
I
CARBON
0. 8
O
LABORATORY SCALE
REACTOR DATA / CONVERS I01

PDU DATA
o
CARBON
CONVERSION r
i
CONVERS I 0 V f -- - - H2
0

TEM PERATURE (OC 1

FIGURE 45. Effects of Temperature on the Dry Gas Equilibrium Composition


at Atmospheric Pressure for Steam-to-Wood Ratio of 0.33
TEMPERATURE (OC

FIGURE 46. E f f e c t s o f Temperature on the Dry Gas E q u i l i b r i u m Composition


a t Atmospheric Pressure f o r Steam-to-Wood R a t i o o f 1
400 500 600 700 800 900
TEMPERATURE, OC

FIGURE 47. P o t e n t i a1 Methane and Methanol Yields


a t Atmospheric Pressure

F i g u r e 50 shows the e q u i l i b r i u m d r y gas composition o f a simulated SNG


production case. Methane production i s g r e a t l y favored by increased pressure.
Carbon conversion t o gas i s s l i g h t l y a f f e c t e d .

F i g u r e 5 1 shows t h e pressure e f f e c t o f a simulated synthesis gas case. By


equi 1ibrium c a l c u l a t i o n s , carbon conversion i s 100% a t 750'~. Again, methane
production increases w i t h pressure. Methane i s n o t d e s i r a b l e above c e r t a i n
l e v e l s o f methanol synthesis. The f i n a l d e c i s i o n o f the desired g a s i f i c a t i o n
pressure w i l l have t o weigh t h e increased methane content o f t h e gas against
the reduced compression costs.

One other advantage o f pressure operation i s t h a t the o v e r a l l r e a c t i o n


becomes l e s s endothermic and i n some cases becomes exothermic. This f a c t can
g r e a t l y reduce the complexity o f the g a s i f i e r . Less heat t r a n s f e r area w i l l
be needed a t higher pressures.
I I 1 I I I I
450 500 550 600 650 700 750 800
TEMPERATURE OC

FIGURE 48. E f f e c t o f Temperature on E q u i l i b r i u m


Standard Heats o f Reaction
FIGURE 49. E f f e c t o f Pressure on E q u i l i b r i u m
Standard Heats o f Reaction
0.6 1 CARBON

- CH4
/-

C02

S
'
z
o
0.3
T = 55O0c
STEAM : WOOD= 0.3333 :1
DRY BAS1 S

0 10 20 30 40
PRESSURE (dm)

FIGURE 50. E f f e c t o f Pressure on Production o f a Methane-Rich Gas


T = 750'~
STEAM : WOOD = 1:l
ALL CARBON CONVERTED
DRY B A S I S

PRESSURE (atrn)

FIGURE 51. E f f e c t o f Pressure on P r o d u c t i o n o f a Methanol Synthesis Gas


FEASIBILITY STUDIES

Information on process economics is needed to determine which options


offer significant cost advantages and should, therefore, be further investi-
gated. For this study, Davy McKee of Cleveland, Ohio evaluated the economics
of using catalytic steam gasification of wood in two commercial operations.
Two process plants were designed for the study: 1) for the conversion of wood
to methane and 2) for the conversion of wood to methanol. Results of the study
are sumnarized in the following discussion and detailed in Appendices A through
D of this report.
Since the catalytic processes are still in the development stage, process
conditions and outputs are constantly changing. Already, yields from catalytic
gasification are improved over those transmitted to Davy McKee for use in their
evaluations. Because these changes can significantly affect process economics,
a computer code is being developed to evaluate the effect of process modifica-
tions on overall economic feasibility.

ECONOMICS OF CATALYTIC GASIFICATION


Two different plants and plant capacities were considered for application
of catalytic gasificaton of wood: a wood-to-methane plant and a wood-to-
methanol plant, each at 2000 and 200 tons (1800 and 180 t) per day dry wood.
Design bases and descriptions of these plants are presented in the following
discussion. Capital and operating costs estimated by Davy McKee are summarized
for the plants. Product selling prices are presented for utility and private
investor financing. Details are presented in Appendices A through D of this
report.
Wood-to-Methane Plant
The design basis for the wood-to-methane plant was developed in the lab-
oratory and PDU studies and adjusted to operation at 10 atm pressure. The main
adjustment was an increase in the methane concentration in the gases from the
gasifier. Overall gas yield from the gasifier used in the design is less than
more recent PDU yields as presented in earlier discussion.
The design basis f o r t h e p l a n t i s summarized i n Table 31. A block diagram
f o r t h e wood-to-methane p l a n t i s shown i n F i g u r e 52. Wood t o t h e p l a n t i s con-
sidered t o be 60% f o r e s t residue, 20% fir, and 20% a l d e r w i t h the composition
shown i n Table 32. The design b a s i s f o r t h e small p l a n t i s simply scaled t o
t h e c a p a c i t y o f 200 tonslday d r y wood (180 t l d a y ) .

Char and c a t a l y s t ( n i c k e l on s i l i c a - a l u m i n a ) are c o l l e c t e d from t h e gas


by the gas c l e a n i n g system and combined w i t h the overflow from the g a s i f i e r .
The r a t i o o f char t o c a t a l y s t by weight i s 50:l. Half the catalyst material
i s recovered i n the raw gas from the g a s i f i e r and h a l f comes w i t h t h e o v e r f l o w
from t h e g a s i f i e r . The e n t r a i n e d p a r t i c u l a t e has t h e f o l l o w i n g s i z e
distribution:

Size, p Weight %
+I49 10
-149 + l o 5 5
-105 +74 5
-74 +53 5
-53 +10 55
-10 20

Fines i n the c h a r - c a t a l y s t m i x t u r e are p r i m a r i l y char. Very l i t t l e cata-


l y s t i s i n t h e f i n e s t h a t are removed by screening. The char and c a t a l y s t i n
the coarse f r a c t i o n can then be separated by a magnetic r o l l separator. Cata-
l y s t recovery i s 95% f o r t h e wood-to-methane p l a n t .

The c a t a l y s t i s regenerated by passing steam a t 6 5 0 ' ~ over t h e c a t a l y s t


f o r 20 h. The t o t a l steam requirement i s 20 times t h e weight o f c a t a l y s t . The
c a t a l y s t i s reduced by product gas from t h e g a s i f i e r . The consumption o f
hydrogen t o reduce the c a t a l y s t i s 6.4 X 1 b - m o l e l l b (g-molelg) o f cata-
lyst. A l l o t h e r operations i n t h e schematics shown i n F i g u r e 5 1 are based on
commercially a v a i l a b l e technology. A b r i e f d e s c r i p t i o n o f the p l a n t s i s pre-
sented i n t h e f o l l o w i n g discussion.

The wood-to-methane p l a n t s were designed t o process 2000 t o n l d a y


(1800 t l d a y ) o f d r y wood and 10% o f t h i s capacity. Production f o r t h e l a r g e
TABLE 31. Wood-to-Methane P l a n t Design Basis--2000 ton/day Dry Wood

Wood-to-Methane
Capacity, Dry Tons Woodlday ( t / d a y ) 2000 (1800)
Location P a c i f i c Northwest
Product S p e c i f i c a t i o n s SNG:
HHV - 960 B t u / s c f
3
- (36 mJ/nm )
co
0.1 ~ 0 1 %

H2S - 0.25 g/100 s c f


3
- (0.57 g/lOO nm )
Water - 7 lb/106 s c f
- (110 kg/lO 6 nm3 )

G a s i f i e r Conditions
Temper a t ure, OC 550
Pressure, atm 10
Steam Rate, w t / w t Dry Wood 0.33
Char production, w t / w t M A F ( ~ Wood
) 0.24
Char Heating Value, B t u / l b (kJ/kg) 13,500 (31,400)
Gas Production, w t / w t MAF wood 1.09
Cold Gas E f f i c i e n c y , % 65

Gas Composition, v o l %
38.0
11.2

CH4 23.6

C02 19.5
CO 7.7

( a ) MAF i s m o i s t u r e ash f r e e .
FRESH
FLUE GAS CATALYST
A
RECYCLE
CATALYST

WOOD DELIVERED
TO PLANT
WOOD RECEIVING
ANDSTORAGE
WOOD
DRYING
-* GASIFICATION
CATALYTIC
0

? COMPRESSION 4
SHIFT
CONVERSION
- . PRIMARY
METHANATI ON

I AIR
t
EXCESS
CHAR CHAR CATALYST
RECOVERY AND
REGENERATION w

- AC l D GAS
REMOVAL
FLUE GAS, LIME

I
AIR b

- STEAM
BLOWDOWN
b 3
.
-.
WASTEWATER
TREATMENT c
FINAL
METHANATI ON

1 1 1 1
RAW WATER RAW WATER
TREATMENT
ASH
TO HEAT RECOVERY
SYSTEMS
. TREATED
WATER
SLUDGE
-
PRODUCT
GAS DRYING
AND FINAL
COMPRESSION
1
COOLING PRODUCT GAS
TOWER

I
LOSSES

FIGURE 52. Wood-To-Methane Process Areas


TABLE 32. U l t i m a t e Analysis o f Feedstock

Weighted
Fir Average
W t % Dry
Carbon
Hydrogen
Nitrogen
Oxygen
Ash
w t % Moisture (as received)
Btu/dry 1b

3
p l a n t i s 21.6 m i 11i o n s c f d (610,000 nm /day) o f SNG w i t h a HHV o f 956 Btu/scf
(35,600 k ~ / n r n ~ ) . A1 1 process and support f a c i 1it i e s necessary t o convert
wood t o SNG are included i n t h e c o s t estimates.

The thermal e f f i c i e n c y o f the plants, as defined by Equation (8), i s


58.3%. When t h e heating value o f t h e excess char i s included i n t h e output,
t h e thermal e f f i c i e n c y i s 62.6%.

SNG, HHV
% = loo
Wood, HHV + E l e c t r i c i t y + Diesel Fuel

Wood storage, handling, and d r y i n g are major c a p i t a l c o s t o u t l a y s f o r t h e


plants. A b r i e f d e s c r i p t i o n o f the systems f o r the l a r g e p l a n t f o l l o w s .

The bulk o f t h e feedstock i s received already chipped. The chips a r e


d e l i v e r e d by t r u c k - t r a i l e r r i g s t h a t are weighed on one o f the two t r u c k scales
when e n t e r i n g and l e a v i n g t h e unloading area. S i x unloading s t a t i o n s are
i n s t a l l e d t o permit a maximum unloading r a t e o f 1200 ton/h (1090 t / h ) , which
represents 48 t r u c k s l h . The c a p a c i t y t o handle t h i s number o f t r u c k s ensures
continuous unloading p a r t i c u l a r l y when t r u c k s are making d e l i v e r i e s from sev-
e r a l l o g g i n g s i t e s and may a r r i v e i n groups. Each truck- unloading s t a t i o n con-
s i s t s o f a h y d r a u l i c t r u c k dumper, a t r u c k dump hopper, and a chain feeder.
Each chain feeder t r a n s p o r t s the c h i p s onto a t r i p p e r / s t a c k e r b e l t con-
veyor or onto a r e c l a i m i n g b e l t conveyor. The t r i p p e r / s t a c k e r conveyor d e l i v -
ers the chips t o one o f the two primary storage p i l e s v i a a double wing
stacker. Each primary p i l e i s l i m i t e d t o approximately 40 f t (12 m) high, as
some bark and f i n e s are supplied along w i t h the chips. The stacker b u i l d s a
25-day c a p a c i t y storage; any enlargement of t h e storage i s done by two b u l l -
dozers spreading the p i l e s . Each o f the two primary storage p i l e s i s 2800 f t
(850 m) long and 80 f t (24 m) wide f o r t h e 25-day capacity, w i t h p o s s i b l e
enlargement t o 240 f t (73 m) w i d t h f o r a 125-day capacity.

The r e c l a i m i n g o f chips from t h e primary storage i s done w i t h 14 chain


reclaimers ( 8 f t (2.4 m) wide), seven f o r each p i l e . Each reclaimer has a
c a p a c i t y o f 700 ton/h (630 t / h ) which represents t h e t o t a l r e q u i r e d r e c l a i m i n g
r a t e based on 8 h/day, 5 days/week. The bulldozers are used t o push c h i p s
towards reclaimers when needed. Two r e c l a i m i n g b e l t conveyors, one f o r each
p i l e , c o l l e c t c h i p s from the r e s p e c t i v e chain reclaimers and d e l i v e r them t o
t h e primary screening s t a t i o n . The primary screening s t a t i o n c o n s i s t s o f
equipment f o r rock and tramp i r o n removal and f o r r e c h i p p i n g o f oversize chips.

Screened chips are transported by a t r i p p e r / s t a c k e r conveyor t o t h e


secondary storage p i l e . Stacking and r e c l a i m i n g o f the c h i p s are i d e n t i c a l t o
t h e method used f o r primary storage. Two p i l e s , each 1800 f t (550 m) long and
80 f t (24 m) wide form a 14-day storage. Also a p r o v i s i o n i s made t o bypass
secondary storage by using one o f t h e two r e c l a i m i n g b e l t conveyors.

The c h i p s from secondary storage are screened t o remove any i n c i d e n t a l


oversize t r a s h and conveyed by chain conveyors t o t h e surge b i n s f o r t h e
dryers. Two conveying strands and two secondary screens are used t o ensure
u n i n t e r r u p t e d c h i p supply.

S i x r o t a r y drum dryers complete w i t h a burner, ash removal cyclone,


exhaust dust cyclone, ducting, and a l l necessary appurtenances are i n s t a l l e d t o
reduce the moisture content o f green chips from 50 w t % o f t o t a l feed t o 10 wt%.
The by-product char from t h e g a s i f i e r i s used t o f u e l t h e burners f o r t h e
dryers. F i v e dryers normally operate w h i l e the s i x t h d r y e r i s on standby.
D r i e d c h i p s are conveyed from t h e d r y e r s t o a surge b i n o f one hour
capacity. The c h i p i n v e n t o r y o f t h i s b i n a l l o w s a s t a r t u p o f t h e standby
dryer. The c h i p s from t h i s b i n are conveyed t o t h r e e g a s i f i e r l o c k hopper sys-
tems e q u a l l y spaced a t 120'. The c h i p s are then screw f e d c o n t i n u o u s l y t o t h e
base o f t h e g a s i f i e r a t an a d j u s t a b l e r a t e f r o m each l o c k hopper.

Three g a s i f i e r s are provided f o r t h e l a r g e p l a n t . Each g a s i f i e r i n t h e


l a r g e p l a n t i s c y l i n d r i c a l w i t h dimensions o f 15 f t (4.3 m) I D by 45 f t
(13.7 m) t o t a l h e i g h t . Each i s p r o v i d e d w i t h 440 f t 2 ( 4 1 m2 ) o f 2- in. (5-cm)
t u b i n g (RA-533 o r I n c o l o y 800 H) f o r heat a d d i t i o n t o t h e f l u i d bed o f wood
char and c a t a l y s t . The o p e r a t i n g depth o f t h e f l u i d bed i s 10 f t ( 3 m). A
s i n g l e scaled-down v e r s i o n o f t h i s g a s i f i e r i s p r o v i d e d f o r t h e 200-ton/day
plant.

The wood c h i p s are g a s i f i e d i n t h e presence o f c a t a l y s t w i t h steam t o pro-


duce a gas c o n t a i n i n g methane, carbon d i o x i d e , hydrogen, carbon monoxide, and
water. G a s i f i c a t i o n i s n o t complete and t h e r e i s a char r e s i d u e by- product.
The g a s i f i e r operates a t c o n d i t i o n s o f 10 atm (150 p s i a ) and 5 5 0 ~( 1~0 0 0 ~ ~ ) .
The steam-carbon r e a c t i o n i s h i g h l y endothermic, w h i l e t h e methanation r e a c t i o n
i s exothermic. The n e t g a s i f i c a t i o n r e a c t i o n s are s l i g h t l y exothermic; how-
ever, a heat i n p u t i s needed t o a s s i s t heatup o f r e a c t a n t s . The heat i s sup-
p l i e d by h o t combustion gases (up t o 1 0 0 0 ~ ~f l )o w i n g through a bank o f tubes
imnersed i n t h e r e a c t i o n bed. Char r e s i d u e by- product i s t h e f u e l f o r t h e
g a s i f i e r heater. After leaving the gasifier, t h e combustion gases pass through
a s e r i e s o f heat exchangers t o recover heat. The gases a r e used t o superheat
steam t o t h e g a s i f i e r o p e r a t i n g temperature, t o generate 600 p s i g steam, and
t o preheat t h e combustion a i r t o t h e char burner.

The remainder o f t h e g a s i f i c a t i o n area i s devoted t o heat recovery, cata-


l y s t recovery, r e g e n e r a t i o n and r e c y c l e , and char recovery. The raw gas f r o m
t h e g a s i f i e r passes through a s e r i e s o f exchangers t h a t recover heat by gener-
a t i n g superheated steam. These exchangers a r e a s e r i e s o f c o i l s i n a r e f r a c -
t o r y - l i n e d s h e l l through which t h e raw gas flows. These exchangers are, i n
t h e order t h a t t h e raw gas sees them, t h e steam superheater, t h e b o i l e r , and
t h e b o i l e r feedwater preheater. The gas i s cooled t o 1 7 5 ' ~ ( 3 5 0 ' ~ ) i n these
exchangers. The gas c o n t a i n s p a r t i c u l a t e s i n t h e form o f e n t r a i n e d char and
catalyst. The gas i s then cleaned by a cyclone f o l l o w e d by a bag f i l t e r con-
t a i n i n g a h i g h temperature g l a s s f a b r i c . The gas then f l o w s t o t h e n e x t
processing area. The c a t a l y s t recovery area c o n s i s t s o f screens and a magnetic
separator and i s completely enclosed t o prevent a i r c o n t a c t w i t h t h e c a t a l y s t .

Commercially a v a i l a b l e systems comprise the remainder o f the p l a n t . Acid


gas removal i s by t h e B e n f i e l d process.

A l l l i q u i d wastewater streams f o r t h e p l a n t are t r e a t e d i n a n e u t r a l i z i n g


b a s i n and a subsequent three- stage b i o l o g i c a l treatment system b e f o r e being
allowed t o o v e r f l o w t o drainage.

The c a p i t a l c o s t estimate f o r the 2000-ton/day p l a n t as determined by Davy


McKee, Inc., i s sumnarized i n Table 33. The c a p i t a l c o s t estimates (September
1980 b a s i s ) f o r t h e 2000-ton (1800-t)/day d r y wood p l a n t i s $95,115,000. Esti-
+ 25%.
mate accuracy i s r e p o r t e d t o be -

Breakdown o f t h e t o t a l d i r e c t costs by p l a n t area i s given i n Table 34 f o r


t h e 2000-ton d r y wood/day p l a n t . The major c o s t areas are wood storage and

TABLE 33. Wood-To-Methane C a p i t a l Cost Sumnary--2000 ton/day Dry Wood

Cost ($1,000)
Equipment 33,320
D i r e c t Purchase M a t e r i a l 10,690
Subcontract: M a t e r i a l 590
Labor (385,000 MHR) 10,370
D i r e c t H i r e Labor (685,000 MHR)
SIT D i r e c t Costs
Field Indirects
Pro- Services
Other
9/12/80 T o t a l I n s t a l l e d Cost (T.I.C.)

Exclusions: Property
S t a r t - u p Costs
P l a n t ~oadways
Demolition o f Underground Obstructions
Premium Time
Operating and Maintenance Costs
Contingency
TABLE 34. D i r e c t Cost Sumnary f o r Wood-to-Methane P l a n t - -
2000 t o n l d a y Dry Wood

Cost ($1,000)
Wood Storage and Handling 17,704
Wood Drying 6,821
G a s i f i c a t i o n Area 11,986
Compression 1,926
S h i f t Conversion 2,998
Primary Methanation 2,192
Acid Gas Removal 2,143
' F i n a l Methanation and Product Gas D r y i n g 2,964
C a t a l y s t Regeneration 1,512
Waste Water Treatment 1,801
Raw Water and Cooling Water Treatment 2,483
B o i l e r s and BFW Systems 7,290
Miscellaneous U t i l i t y Systems 1,928
TOTAL $ 63,748

handling, g a s i f i c a t i o n and wood d r y i n g . The g a s i f i c a t i o n area i n c l u d e s t h e


g a s i f i e r s , heat recovery equipment, char and c a t a l y s t recovery equipment, and
wood and c a t a l y s t feed hoppers.

The production c o s t o f methane from wood i s c a l c u l a t e d based upon t h e


c a p i t a l c o s t s and o p e r a t i n g costs. The methods o f c a l c u l a t i n g these c o s t s a r e
those presented i n "Coal G a s i f i c a t i o n Commercial Concepts Gas Costs Guide-
lines," a paper prepared f o r t h e U.S. Energy Research and Development Adminis-
t r a t i o n and the American Gas Association by C. F. Braun & Co. (NTIS 8463).
There are two p o t e n t i a l methods o f f i n a n c i n g a p l a n t o f t h i s type, 1) u t i l i t y
f i n a n c i n g, and 2) p r i v a t e i n v e s t o r f i n a n c i n g . Production costs are c a l c u l a t e d
u s i n g both procedures.

The t o t a l p l a n t investment i s estimated t o be $95,115,000 (September 1980


basis). The t o t a l c a p i t a l requirement f o r t h e p l a n t i s obtained by a d d i t i o n o f
an allowance f o r funds d u r i n g c o n s t r u c t i o n , s t a r t - u p costs, and working
capital. These costs and the basis for their calculation are shown in
Table 35. The total capital requirement for this plant is $115,191,000.
The annual direct operating costs for wood conversion to methane are shown
in Table 36. These costs include raw materials, utilities, catalysts and
chemicals, labor, administration and general overhead, supplies, and taxes and
insurance, with a credit for by-product char. Total maintenance costs are cal-
culated as a percentage of plant investment as suggested by the guidelines. The
annual costs are $29,990,000. The most significant costs are wood, gasifier
catalysts, labor, and taxes and insurance. Labor costs are not very easy to
reduce significantly, while taxes depend upon local conditions and incentives.
The major variable costs are wood and catalyst usage in the gasifier. Studies
to improve catalyst life are in progress. At $20/dry ton for wood, which is
the value used for the base case shown in Table 36, wood costs are almost 45%
of the total direct costs and almost one-third of the total production costs
with utility financing. Thus, either lowering the wood cost or improving
yields from the wood have more impact on costs than any other single variable.
The production costs have also been calculated for wood costs of $5, $10, and
$40 per dry ton delivered to the plant, and the impact is i 1 lustrated in
Figure 53.

TABLE 35. Total Capital Cost Requirement For Wood-to-Methane Plant--


2000 ton/day Dry Wood
Cost ($1,000)
Total Plant Investment 95,115
Allowance for Funds During Construction
(Total Plant Investment x 1.25 yr x 0.09)
Start-up Costs (20% of Total Annual Gross
Operating Costs)
Working Capital [Sum of (1) raw material
inventory of 14 days at full rate,
(2) materials and supplies at 0.9% of total
plant investment, and (3) net receivables
at 1/24 annual gas and by-product revenue
at calculated sales price]
Total Capital Requirement
TABLE 36. Annual Direct Operating Costs For Wood-to-Methane
Plants--2000 tonlday Dry Wood
Operating Factor: 330 dayslyr
Cost
Cost Component Annual Use $/Unit $1000/yr
Raw Material
Wood 660,000 dry tons 201dry ton 13,200
Utilities
Water 332,640 M a1
Electricity 3.25 x 109 kwh
Diesel Fuel 108,900 gal
Catalysts and Chemicals
Chemicals
Shift Catalyst 1500lft3
Methanation Catalyst 1020/ft3
Gasifier Catalyst 380,160 1b
Labor
E s s Operating 51 men @ 2080 h
Maintenance @ 60% of total
maintenance
Supervision @ 20% of process
operating and
maintenance labor
Administration and General Overhead @ 60% of total labor
Supp 1i es
Operat i ng @ 30% of process
operati ng 1abor
Maintenance @ 40% of total
maintenance cost
Taxes and Insurance @ 2.7% of total plant
investment
Total Gross Operating Cost Per Year
By-Product Cred its
Char 28,050 tons
Total Net Operating Cost Per Year
-
-

-
-

-
-
-

-
-
- - UTILITY FINANCING

- A - PRIVATE INVESTOR FINANCING

I I I I I I I I I I I I I

WOOD, $1 DRY TON

FIGURE 53. E f f e c t o f Wood P r i c e s on Gas Cost f o r 2000 ton/day Dry Wood


Tables 37 and 38 g i v e t h e methods f o r c a l c u l a t i n g p r o d u c t i o n costs based
on u t i 1i t y f i n a n c i n g and p r i v a t e i n v e s t o r f i n a n c i n g , r e s p e c t i v e l y . The c a l cu-
l a t i o n s f o r t h e base case of a wood cost o f $20/dry t o n are shown. For u t i l i t y
f i n a n c i n g , t h e SNG p r o d u c t i o n c o s t s are $5.09, $5.56, $6.50, and $8.34 per m i l -
l i o n B t u f o r wood p r i c e s o f $5, $10, $20, and $40 per d r y ton. For p r i v a t e
i n v e s t o r f i n a n c i n g , t h e SNG p r o d u c t i o n c o s t s are $6.62, $7.11, $8.10 and $10.06
per m i 11i o n B t u f o r t h e corresponding wood costs.

The same design b a s i s was used t o determine o p e r a t i n g c o s t s f o r a 200-dry-


t o n wood/day (180 t l d a y ) p l a n t f o r p r o d u c t i o n o f SNG. A1 1 y i e l d s are 10% o f
the y i e l d s from t h e l a r g e r plant. The o n l y d i f f e r e n c e i n t h e system was
o n - s i t e c h i p p i n g o f t h e wood residue. D e t a i l s are presented i n Appendix C and
sumnarized below.

The t o t a l investment f o r t h e 200- dry- tonlday ( 1 8 0 - t i d a y ) p l a n t was e s t i -


mated t o be $26,680.000 (September 1980 b a s i s ) . To o b t a i n t h e t o t a l c a p i t a l
requirement f o r t h e p l a n t , a d d i t i o n a l c o s t s must be added t o t h e e s t i m a t e d
p l a n t investment. These c o s t s are an a1 1owance f o r funds d u r i n g c o n s t r u c t i o n ,
s t a r t - u p costs, and working c a p i t a l . These costs and t h e b a s i s f o r t h e i r c a l -
c u l a t i o n are shown i n T a b l e 39. The t o t a l c a p i t a l requirement f o r t h i s p l a n t
i s $31,805,000.

The annual d i r e c t o p e r a t i n g c o s t s f o r t h e small p l a n t were c a l c u l a t e d and


are shown i n Table 40. These c o s t s i n c l u d e raw m a t e r i a l s , u t i l i t i e s , c a t a l y s t s
and chemicals, labor, a d m i n i s t r a t i o n and general overhead, s u p p l i e s , and taxes
and insurance, w i t h a c r e d i t f o r by- product char. T o t a l maintenance c o s t s were
c a l c u l a t e d as percentage o f p l a n t investment as suggested b y t h e g u i d e l i n e s .
These annual c o s t s are $6,833,600. The most s i g n i f i c a n t c o s t s are wood, g a s i -
f i e r c a t a l y s t , labor, and taxes and insurance. Labor c o s t s would n o t be v e r y
easy t o reduce s i g n i f i c a n t l y , w h i l e taxes w i l l depend upon l o c a l c o n d i t i o n s
and i n c e n t i v e s . The major v a r i a b l e c o s t s are wood and c a t a l y s t usage i n t h e
gasifier. At $20/dry t o n f o r wood, which i s t h e value used f o r t h e base case
shown i n T a b l e 40, wood c o s t s are almost 20% o f t h e t o t a l d i r e c t costs and
almost 15% o f t h e t o t a l p r o d u c t i o n c o s t s u s i n g u t i l i t y f i n a n c i n g . Thus, e i t h e r
TABLE 3 7 . Methane Cost-Utility Financing Method--2000 ton/day Dry Wood
Bases:
20-yr project life
5% year straight line depreciation on total capita1 requirement
excluding work capital
48% federal income tax rate
75/25 debtlequity ratio
10% interest on debt
15% return on equity

Def i nit i on of Terms:


C = Total capital requirement, lo6$
W = Working capital, 106$
N = Total net operating cost, lo6 $/yr
G = Annual gas production, 1012 Btulyr
d = Fraction debt
i = Interest on debt, %/yr
r = Return on equity, %/yr
p = Return on rate base, %/yr

Equation for Return on 2ate Base:


p = (d) i + (1-d) r

General Gas Cost Equation:


Average gas cost, $/million Btu =

N + 0.05 (C-W) + 0.005 (p + 48/52 (1-d) r) (C + W)


G

Calculation:

Average gas cost, $/mi llion Btu =


TABLE 38. Methane Cost - E q u i t y Financing Method--2000 ton/day Dry Wood

Bases:

20-yr p r o j e c t l i f e
16- yr sum-of-the-years' - d i g i t s d e p r e c i a t i o n on t o t a l p l a n t
investment

100% e q u i t y c a p i t a l
12% DCF r e t u r n r a t e
48% federal income t a x r a t e

D e f i n i t i o n o f Terms:

I lo6 $
= T o t a l p l a n t investment,
S
W
= Start- up cost, 106 8
= Working c a p i t a l , 10 $
N = T o t a l n e t operating cost, 106 $ / y r
G = Annual gas production, 1012 B t u l y r

Gas Cost Equation a t 12% DCF Return

Gas Cost, $/lo6 Btu =

Calculation:

Gas cost, $ / l o 6 Btu =


TABLE 39. T o t a l C a p i t a l Requirement f o r 200-ton/day
Wood-to-Methane P l a n t
Cost ($1,000)
T o t a l P l a n t Investment 26,680
A1 1owance f o r funds During Construction
( T o t a l P l a n t Investment x 1.25 years x 0.09)

Start- up Costs (20% o f T o t a l Annual Gross


o p e r a t i n g Costs)

Working C a p i t a l (Sum o f ( 1 ) raw m a t e r i a l


i n v e n t o r y o f 14 days a t f u l l r a t e , ( 2 ) m a t e r i a l s
and s u p p l i e s a t 0.9% o f t o t a l p l a n t investment 56 (1)
and ( 3 ) n e t r e c e i v a b l e s a t 1/24 annual gas and 240 (2)
by- products revenue a t calcu 1ated sales p r i c e ) 452 (3)

T o t a l C a p i t a l Requirement $ 31,805

lowering the wood cost or improving y i e l d s from the wood would have more impact
on c o s t s than any o t h e r s i n g l e v a r i a b l e .
The p r o d u c t i o n c o s t s have a l s o been
c a l c u l a t e d f o r wood costs o f $5, $10, and $40 per d r y ton d e l i v e r e d t o the
plant.

I n Tables 41 and 42 t h e methods f o r c a l c u l a t i n g production costs are given


based upon u t i l i t y f i n a n c i n g and p r i v a t e i n v e s t o r f i n a n c i n g , r e s p e c t i v e l y . The
c a l c u l a t i o n s f o r t h e base case o f a wood cost o f $20/dry t o n are shown. For
u t i l i t y f i n a n c i n g , t h e SNG p r o d u c t i o n costs are $14.34, $14.83, $15.86, and
$17.84 per m i l l i o n Btu f o r wood p r i c e s o f $5, $10, $20, and $40 per d r y ton.
For p r i v a t e i n v e s t o r financing, t h e SNG p r o d u c t i o n costs are $18.76, $19.26,
$20.28, and $22.31 per m i l l i o n Btu f o r the corresponding wood costs.

Wood-to-Methanol P l a n t

The design basis f o r the wood-to-methanol p l a n t was developed i n t h e l a b -


o r a t o r y and PDU s t u d i e s and adjusted t o o p e r a t i o n a t 10 atm pressure. The main
adjustment was an increase i n t h e methane concentration i n the gases from t h e
gasifier. O v e r a l l gas y i e l d used i n t h e design b a s i s i s l e s s than r e c e n t oper-
a t i n g r e s u l t s from the PDU as presented above.

The design b a s i s f o r t h e 2000-ton (1800- t) d r y wood/day p l a n t i s shown i n


Table 43. A schematic f l o w diagram showing process areas i s given i n
TABLE 40. Annual Direct Operating Costs for 200-ton/day Wood-to-Methane Plant
Operating Factor: 330 days/yr
Cost
Cost Component Annual Use $/Uni t $1000/yr
Raw Mater i a1
Wood 66,000 dry tons 20/dry ton 1,320.0
Utilities
Water 33,264 Mgal O.SO/Mgal 16.6
Electricity 7.76 x 106 kwh 0.03/kWh 232.8
Diesel Fuel 10,890 gal l.OO/gal 10.9
Catalysts and Chemicals
Chemicals
Shift Catalyst
Methanation Catalyst
Gasifier Catalyst
Labor
Process Operating 44 men @ 2080 h 10.70/h 979.3
Mai ntenance @ 60% of total
maintenance 760.8
Supervision @ 20% of process
operati ng and
maintenance labor 348.0
Administration and General Overhead @ 60% of total labor 1252.9
Supp 1 i es
Operati ng @ 30% of process
operating labor
Maintenance @ 40% of total
maintenance
Taxes and Insurance @ 2.7% of total
investment
Total Gross Operating Cost per Year
By-Product Credits
Char 2805 tons 15.35/ton (43.1)
Total Net Operating Cost per Year
TABLE 41. Gas Cost - U t i l i t y Financing Method--200 t o n l d a y Dry Wood

Bases :

20- yr p r o j e c t l i f e
5% year s t r a i g h t l i n e d e p r e c i t a t i o n on t o t a l c a p i t a l requirement
e x c l u d i n g working c a p i t a l
48% f e d e r a l income t a x r a t e
75/25 d e b t l e q u i t y r a t i o
10% i n t e r e s t on debt
15% r e t u r n on e q u i t y

Defin i ti on o f Terms:

C lo6 $
= T o t a l C a p i t a l Requirement,
W = Working C a p i t a l , lo6 $
N = T o t a l Net Operating Cost, lo6 $/yr
G = Annual Gas Production, 1012 Btu/yr
d = F r a c t i o n debt
i = I n t e r e s t on debt, %/yr
r = Return on e q u i t y , %/yr
p = Return on r a t e basis, %/yr

Equation f o r Return on Rate Base:

p = ( d ) i + (1-d) r

General Gas Cost Equation:

Average Gas Cost, $/mil 1i o n Btu =

N + 0.05 (C-W) + 0.005 ( p + 48/52 (1-d) r ) (C + W)


G

Calculation:

Average gas cost, $ / m i l l i o n Btu =


TABLE 42. Gas Cost - E q u i t y Financing Method--200 ton/day Dry Yaod

Bases:

20- yr p r o j e c t f i l e
16- yr sum-of-the-years' -
d i g i t s d e p r e c i a t i o n on t o t a l p l a n t
investment
100% e q u i t y c a p i t a l
12% DCF r e t u r n r a t e
48% f e d e r a l income t a x r a t e

D e f i n i t i o n o f Terms:

I = T o t a l p l a n t investment, lo6 $
s = Start- up costs, 106 $
W = Working C a p i t a l , lo6 $
N = T o t a l n e t o p e r a t i n g cost, 106 $/yr
G = Annual gas production, 1012 B t u l y r

Gas Cost Equation a t 12% DCF Return:

Gas cost, $/lo6 Btu =

Calculation:

Gas cost, $/lo6 Btu =


TABLE 43. Wood-to-Methanol P l a n t Design Basis--2000 t o n l d a y Dry Wood

Wood-to-Methanol
Capacity, Dry Tons Woodlday ( t l d a y ) 2000 (1800)
Locat ion P a c i f i c Northwest
Product S p e c i f i c a t i o n s Methanol : 99.3% p u r i t y

G a s i f i e r Conditions
Temperature, OC 750
Pressure, atm 10
Steam Rate, w t l w t Dry Wood 0.75

Char Production, w t l w t MAF Wood 0.15

Char Heating Value, B t u l l b (kJ/kg) 14,000 (33,000)

Gas Production, w t / w t MAF wood 1.60


Cold Gas E f f i c i e n c y , % 88

Gas Composition, v o l %

CH4
C02
co

F i g u r e 54. The design b a s i s f o r the small p l a n t i s simply scaled t o a


c a p a c i t y o f 200 t o n l d a y d r y wood (180 t l d a y ) . Wood feedstock i s t h e same as
presented i n Table 32.

The wood-to-methanol p l a n t s are designed t o process 2000 tons (1800 t )


p e r day o f d r y wood and 10% o f t h i s capacity. Production f o r t h e l a r g e p l a n t
FLUE GAS

WOOD DELIVERED
TO PLANT
WOOD RECEIVING
AND STORAGE

CHAR TO DRYER
WOOD
DRYING
a
CATALYTIC
GASIFICATION
A A
7 CO SHIFT _
- ACIDGAS
REMOVAL
I
CON DENSATE
-
FRESH
AIRTODRYER CATALYST STEAM

- -
CHAR AND 4
I
I CHAR AND v
v

CATALYST COMPRESSION
RECOVERY CATALYST CATALYST

-
WOOD PURGE GAS
REFORMING
CHAR 9
BOILER
4 METHANOL METHANOL
SYNTHES lS PRODUCT

TO HEAT RECOVERY v
SYSTEMS

-
WASTE
WATER
TREATMENT
LIME
1
PRODUCT
RAW WATER RAW WATER
a STORAGE AND
TREATMENT b
TREATED WATER SHIPPING

COOLING
TOWER
.WASTE
WATER
SLUDGE 1
METHANOL
1 PRODUCT

LOSSES

FIGURE 54. Wood-To-Methanol Process Area


i s 997 tons (900 t ) per day o f methanol w i t h a HHV o f 9784 Btu per pound
(22,700 kJ/kg). A l l process and support f a c i l i t i e s necessary t o convert wood
t o methanol are included i n t h e estimate.

The thermal e f f i c i e n c y o f the p l a n t i s d e f i n e d as

* = loo
Methanol, HHV
Wood, HHV + E l e c t r i c i t y + Diesel Fuel

The thermal e f f i c i e n c y i s 53%.


Wood storage, handling, and d r y i n g are i d e n t i c a l t o t h e systems described
p r e v i o u s l y f o r t h e wood-to-methane p l a n t , The small p l a n t i n c l u d e s o n - s i t e
c h i p p i n g o f the residue.

Three g a s i f i e r s are provided f o r t h e 2000 t o n (1800 t ) / d a y p l a n t . Each


g a s i f i e r i s c y l i n d r i c a l w i t h dimensions o f 15 f t (4.3 m) I D by 50 f t (15 m)
2 2
t o t a l height. Each i s provided w i t h 3900 f t (360 m ) o f 2- in. (5-cm) t u b i n g
(RA-533 o r I n c o l o y 800 H) f o r heat a d d i t i o n t o t h e f l u i d bed o f wood char and
catalyst. The o p e r a t i n g depth o f the f l u i d bed i s 10 f t ( 3 m). A single,
scaled-down v e r s i o n o f t h e i r design i s provided f o r t h e 200 t o n l d a y p l a n t .

Fines i n the c h a r - c a t a l y s t m i x t u r e are p r i m a r i l y char. Very l i t t l e cata-


l y s t i s i n t h e f i n e s which are removed by screening. The char and c a t a l y s t i n
t h e coarse f r a c t i o n can then be separated by a magnetic r o l l separator. Cata-
l y s t recovery i s 90% f o r t h e wood-to-methanol p l a n t . No regeneration o f c a t a -
l y s t i s considered.

A l l other operations i n the schematics shown i n F i g u r e 54 are based on


commercially a v a i l a b l e technology. A b r i e f description o f the plants i s pre-
sented i n the f o l l o w i n g discussion.

Wood c h i p s from the g a s i f i e r feed b i n s are c o n t i n u o u s l y f e d by screw con-


veyors t o t h e f l u i d i z e d - b e d g a s i f i e r . High pressure steam i s f e d i n t o each bed
t o g a s i f y t h e wood as w e l l as f l u i d i z e t h e s o l i d s . Contained w i t h i n t h e bed i s
t h e c a t a l y s t r e q u i r e d f o r t h e r e a c t i o n , a 318-in. (9.5-mm) diameter s p h e r i c a l
b a l l o f n i c k e l c a t a l y s t on a s i l i c a - a l u m i n a s t r u c t u r e . The g a s i f i e r s i n t h e
wood-to-methanol p l a n t s operate a t a temperature o f 7 5 0 ' ~ (1380'~) and a pres-
sure o f 10 atm (150 p s i a). A t these c o n d i t i o n s most hydrocarbons are cracked
t o g i v e a crude synthesis gas c o n s i s t i n g p r i m a r i l y o f hydrogen and carbon
oxides w i t h o n l y a small amount o f methane.

About 285 tons per day ( d r y b a s i s ) (259 t / d a y ) ( o r 10% o f t h i s f o r t h e


small p l a n t ) o f t h e wood s u p p l i e d t o t h e g a s i f i c a t i o n area are burned t o supply
the necessary heat i n p u t t o the g a s i f i e r . This i s accomplished by f i r s t a l l o w -
i n g the h o t combusti on gases- - approximately 9 8 0 ' ~ ( 1 8 0 0 ~ F ) - - t o c i r c u l a t e
through tube bundles l o c a t e d i n each g a s i f i e r bed. These gases upon e x i t i n g
t h e tube bundles are then used t o preheat t h e g a s i f i e r f l u i d i z i n g steam and
combustion a i r f o r t h e wood burners.

The remainder o f the g a s i f i c a t i o n area i n t h e p l a n t i s devoted t o heat


recovery, c a t a l y s t recovery and recycle, and char recovery. The raw gas f r o m
t h e g a s i f i e r passes through a s e r i e s o f exchangers t h a t recover heat by gener-
a t i n g superheated steam. These exchangers are a s e r i e s o f c o i l s i n a r e f r a c -
t o r y l i n e d s h e l l through which t h e raw gas flows. These exchangers are, i n t h e
order t h a t t h e raw gas sees them, t h e steam superheater, t h e CO s h i f t p r e -
heater, t h e b o i l e r , and t h e b o i l e r feedwater preheater. The gas i s cooled t o
1 7 5 ' ~ (350'~) i n these exchangers. The gas contains p a r t i c u l a t e i n t h e form o f
e n t r a i n e d char and c a t a l y s t . The gas i s then cleaned by a cyclone f o l l o w e d by
a bag f i l t e r c o n t a i n i n g a high temperature glass f a b r i c . The gas then f l o w s t o
t h e next processing area. The c a t a l y s t recovery area c o n s i s t s o f screens and
a magnetic separator and i s completely enclosed t o prevent a i r c o n t a c t w i t h t h e
catalyst.

Commercially a v a i l a b l e systems comprise t h e remainder o f t h e p l a n t . Acid


gas removal i s by t h e B e n f i e l d process. The I C I low pressure methanol process
i s used f o r t h e methanol synthesis. A l l l i q u i d wastewater streams f o r t h e
p l a n t are t r e a t e d i n a n e u t r a l i z i n g b a s i n and a subsequent t h r e e stage b i o l o g i -
c a l treatment system b e f o r e being allowed t o o v e r f l o w t o drainage.

The c a p i t a l c o s t estimate as determined b y Davy McKee, Inc., i s summarized


i n Table 44 f o r the 2000-ton d r y wood/day p l a n t . The c a p i t a l c o s t estimate
(September 1980 b a s i s ) f o r t h e 2000-ton d r y wood (1800-t)/day p l a n t i s
$120,830.000. Estimate accuracy i s r e p o r t e d t o be + 25%.
TABLE 44. Wood-to-Methanol C a p i t a l Cost Sumnary--2000 ton/day Dry Wood

Cost ($1,000)
Equipment 35,390
D i r e c t Purchase M a t r i a l 10,840
Subcontract: M a t e r i a l 650
Labor (403,000 MHRS) 11,600
D i r e c t H i r e Labor (665,000 MHRS) 8,530
SIT D i r e c t Costs 67,010
Field Indirects 14,150
Pro- Services 15,920
Other 1,750
METHANOL PLANT (By Lake1and-T. I.C. )
9/12/80 T o t a l I n s t a l l e d Cost (T. I.C.)

Exclusions : Property
S t a r t - u p Costs
P l a n t ~oadways
Demolition o f Underground Obstructions
Premium Time
Operating and Maintenance Costs
Contingency

Breakdown o f t h e t o t a l d i r e c t costs by p l a n t area i s given i n Table 45 f o r


t h e 2000-ton (1800-t) d r y wood/day p l a n t . The major c o s t areas are wood s t o r -
age and hand1ing, g a s i f i c a t i o n and wood drying. The g a s i f i c a t i o n area includes
t h e g a s i f i e r s heat recovery equipment, char and c a t a l y s t recovery equipment,
and wood and c a t a l y s t feed hoppers.

The production c o s t o f fuel- grade methanol from wood i s c a l c u l a t e d based


upon t h e c a p i t a l c o s t s and o p e r a t i n g costs. The methods o f c a l c u l a t i n g these
costs are those presented i n "Coal G a s i f i c a t i o n Commercial Concepts Gas Cost
Guidelines" , a paper prepared f o r t h e United States Energy Research and Devel-
opment A d m i n i s t r a t i o n and the American Gas Association by C. F. Braun & Co.
(NTIS 8463). Production c o s t s are c a l c u l a t e d u s i n g two p o t e n t i a l methods o f
f i n a n c i n g a p l a n t o f t h i s type, ( 1 ) u t i l i t y f i n a n c i n g , and ( 2 ) p r i v a t e i n v e s t o r
financing.

The t o t a l investment f o r the 2000-ton (1800-t)/day d r y wood p l a n t i s e s t i -


mated t o be $120,830,000 (September 1980 b a s i s ) . The t o t a l c a p i t a l requirement
TABLE 45. Direct Cost Sumnary For Wood-to-Methanol Plant--
2000 tonlday Dry Wood
Cost ($1,000)
Wood Storage and Handling 17,704
Wood Drying 6,821
Gasification Area 17,889
Shift Conversion 850
Acid Gas Removal 4,539
Compressi on 5,412
Methanol Synthesis
(T. I.C. by Davy Powergas-Lakeland, FL)
Purge Gas Reforming
Waste Water Treatment
Raw Water and Cooling Water Treatment
Boilers and BFW Systems
Miscellaneous Utility Sytems
Storage and Loadi ng-Product and Ut i 1it i es
TOTAL

for the plant is obtained by addition of an allowance for funds during con-
struction, start-up costs, and working capital. These costs and the basis for
their calculation are shown in Table 46. The total capital requirement for
this plant is $145,571,000.
The annual direct operating costs for the 2000-ton/day dry wood plant have
been calculated and are shown in Table 47. These costs include raw materials,
utilities, catalyst and chemicals, labor, administration and general overhead,
supplies, and taxes and insurance. Maintenance costs are calculated as a per-
centage of capital investment, as suggested by the cited guidelines and are
$36,464,000. The most significant costs are wood, gasifier catalyst, labor,
and taxes and insurance. Labor costs are not very easy to reduce signifi-
cantly, while taxes will depend upon local conditions and incentives. The
major variable costs are wood and catalyst usage in the gasifier. Studies on
improvement of catalyst life are in progress. At $20/dry ton for wood, which
is the value used for the base case shown in Table 47, wood costs are about
one-third of the total direct costs and one-fourth of the total production
costs. Thus, either lowering the wood cost or improving yields from the wood
have more impact on costs than any other single variable. The production costs
TABLE 46. Total Capital Required For Wood-to-Methanol Plant--
2000 tonlday Dry Wood
Cost ($1,000)
Total Plant Investment 120,830
Allowance for Funds During Construction
(Total Plant Investment x 1.25 yr x 0.09)
Start-up Costs (20% of Total Annual Gross
Operating Costs)
Working Capital (Sum of (1) raw material
inventory of 14 days at full rate,
(2) materials and supplies at 0.9% of total
plant investment, and (3) net receivables
at 1/24 annual methanol revenue at
calculated sales price)
Total Capital Requirement

have also been calculated for wood costs of $5, $10, and $40 per dry ton, and
the impact is illustrated in Figure 55. These prices for wood include delivery
to the plant.
In Tables 48 and 49 methods are given for calculating production costs
based upon utility financing and private investor financing, respectively. The
calculations for the base case of a wood cost of $20/dry ton are shown. For
utility financing, the methanol production costs are $0.45, $0.48, $0.55, and
$0.69 per gallon for wood prices of $5, $10, $20, and $40 per dry ton. For
private investor financing, the methanol production costs are $0.59, $0.62,
$0.69, and $0.83 per gallon for the corresponding wood costs.
The same design basis was used to determine operating costs for a 200-ton
dry wood (180-t) per day plant for production of fuel grade methanol. All
yields are 10% of the yields from the larger plant. Details are presented in
Appendix D and sumnarized below.
The total plant investment was estimated to be $34,830,000 September 1980
basis. To obtain the total capital requirement for the plant, additional costs
must be added to the estimated plant investment. These costs are an a1lowance
TABLE 47. Annual Direct Operating Costs For Wood-to-Methanol Plant--
2000 ton dry wood/day
Operating factor: 330 dayslyr
Cost
Cost Component Annual Use $/Unit $1000/yr
Raw Mater i a1
Wood 660,000 dry tons 20/dry ton 13,200
Utilities
Water 526,522 M a1 0.50lMgal 263
Electricity 1.76 x 10I Kwh 0.03/kWh 5,280
Diesel Fuel 108,900 gal l.OO/gal 109
Catalysts and Chemicals
Gasifi er Catalyst 330,660 I b 8.5111 b 2,814
Shift catalystv 150 ft3 107/ft3 16
Chloride Guard Catalyst 3,300 ft3 151/fj3 498
Sulfur Guard Catalyst 2,500 ft3 75/ft 188
Methanol Catalyst Confidential -- 360
Reformer Catalyst 140 ft3 235/ft3 33
Labor
Process Operating 55 men @ 2080 h 10.70/h 1,224
Maintenance 8 60% of total 3,160
maintenance
Supervision @ 20% of process
operating and
maintenance labor 877
Administration and General Overhead @ 60% of total labor
Supp 1 i es
Operating @ 30% of process
operating 1abor
Maintenance @ 40% of total
maintenance cost
Taxes and Insurance @ 2.77% of total
plant investment
Total Operating Cost Per Year $ 36,912
-
-
-
-

- - UTILITY FINANCING
- A -PRIVATE INVESTOR FINANCING

I I I I I I I I I I I I I

WOOD $/DRY TON

FIGURE 55. E f f e c t o f Wood P r i c e s on Methanol Cost f o r 2000 tonlday Dry Wood


TABLE 48. Methanol C o s t - U t i l i t y Financing Method--2000 ton/day Dry Wood

Bases:

20-yr p r o j e c t l i f e
5%/yr s t r a i g h t l i n e d e p r e c i a t i o n on t o t a l c a p i t a l requirement
excluding working c a p i t a l
48% f e d e r a l income t a x r a t e
75/25 d e b t l e q u i t y r a t i o
10% i n t e r e s t on debt
15% r e t u r n on e q u i t y

D e f i n i t i o n o f Terms:

C = T o t a l c a p i t a l requirement, 106 $
W = Working c a p i t a l , 106 $
N = T o t a l net operating cost, lo6 $ / y r
G = Annual f u e l production, lo6 g a l l y r
d = F r a c t i o n debt
i = I n t e r e s t on debt, %/yr
r = Return on e q u i t y , % / y r
p = Return on r a t e base, %/yr

Equation f o r Return on Rate Base

p = ( d ) i + (1-d) r

Average methanol cost, $/gal =

N + 0.05 (C-W) + 0.005 (p + 48/52 (1-d) r ) (C+W)


G

Calculation:

Average methanol c o s t =
TABLE 49. Methanol Cost- Equity Financing Method--2000 ton/day Dry Wood

Bases :

20-yr p r o j e c t l i f e
16-yr sum-of-the years' - d i g i t s d e p r e c i a t i o n on t o t a l p l a n t
investment
100% e q u i t y capi t a l
12% DCF r e t u r n r a t e
48% f e d e r a l income t a x r a t e

D e f i n i t i o n o f Terms:

I = T o t a l p l a n t investment, lo6 $
S = Start- up costs, 106 $
W = Working c a p i t a l , lo6 $
N = T o t a l n e t operating cost, lo6 t / y r
G = Annual methanol production, 10 g a l / y r

Methanol Cost Equation a t 12% DCF Return

Methanol cost, $/gal =

Calculation:

Average methanol cost =


for funds during construction, start-up costs, and working capital. These
costs and the basis for their calculation are shown in Table 50. The total
capital requirement for this plant is $41,221,000.

TABLE 50. Total Capital Requirement for 200-ton Dry Wood/Day Methanol Plant
Cost ($1,000)
Total Plant Investment 34.830
Allowance for Funds During Construction 3;918
(Total Plant Investment x 1.25 yr x 0.09)
Start-up Costs (20% of Total Annual Gross 1,559
Operating Costs)
Working Capital (Sum of (1) Raw Material 56 (1)
Inventory of 14 days at full rate,
(2) Materials and Supplies at 0.9% of 313 (2)
Total Plant Investment, and (3) Net 545 (3)
Receivables at 1/24 annual methanol
revenue at calculated sales price)
Total Capital Requirement 41,221

The annual direct operating costs were calculated and are shown in
Table 51. These costs include raw materials, utilities, catalyst and chemi-
cals, labor, administration and general overhead, supplies, and taxes and
insurance. Maintenance costs are calculated as a percentage of capital invest-
ment, as suggested by the cited guidelines. These annual costs are $7,794,800.
The most significant costs are wood, gasifier catalyst. labor, and taxes and
insurance. Labor costs would not be very easy to reduce significantly, while
taxes will depend upon local conditions and incentives. The major variable
costs are wood and catalyst usage in the gasifier. At $20/dry ton for wood,
which is the value used for the base case shown in Table 51, wood costs are
about 17% of the total direct costs and are 10% of the total production costs.
Thus, either lowering the wood cost or improving yields from the wood have more
impact on costs than any other single variable. The production costs have also
been calculated for wood costs of $5, $10, and $40 per dry ton. These prices
for wood include delivery to the plant.
TABLE 51. Annual D i r e c t ~ p e r a t ' i n gCosts f o r 200-ton Dry Wood/Day Methanol P l a n t

Operating Factor: 330 d a y s l y r

Cost
Cost Component Annual Use $/Unit $1000/yr

Raw Materi a1
Wood 66,000 Dry Ton 20/Dry Ton 1,320.0

Utilities
Water 52,652 Mgal 0.50/Mga 1 26.3
Electricity 2.43 x 107 kwh 0.03/kwh 729.6
D i e s e l Fuel 10,890 g a l l.OO/gal 10.9

C a t a l y s t s and Chemicals
Gasifier Catalyst 33,066 1b 8.51/7b 281.4
S h i f t catalystv 15 f t 3 107/f t 3 1.6
C h l o r i d e Guard C a t a l y s t 330 f t 3 151/ft3 50.0
S u l f u r Guard C a t a l y s t 250 f t 3 75/f t 3 18.8
Methanol C a t a l y s t Confidenti a1 ------ 36.0
Reformer C a t a l y s t 15 f t 3 235/f t 3 3.5

Labor
Process Operating 48 Men @ 2080 h 10.70/h 1,068.3
Maintenance @ 60% o f T o t a l 873.6
Maintenance
Supervision @ 20% o f process 213.7
o p e r a t i n g and
maintenance l a b o r

A d m i n i s t r a t i v e and General Overhead 8 60% o f T o t a l Labor 1,293.4

Supplies
Operating @ 30% o f Process
Operating Labor
Maintenance 8 40% o f T o t a l
Maintenance Cost

Taxes and Insurance @ 2.77% o f T o t a l


P l a n t Investment

T o t a l Gross Operating Costs Per Year ( a > 7,794.8

( a ) No c r e d i t s were taken f o r any by- product so t h a t T o t a l Net Operating Costs


are t h e same as t h e T o t a l Gross.
Tables 52 and 53 g i v e the methods f o r c a l c u l a t i n g production c o s t s based
upon u t i l i t y f i n a n c i n g and p r i v a t e i n v e s t o r f i n a n c i n g , r e s p e c t i v e l y . The c a l -
c u l a t i ons f o r the base case o f a wood c o s t o f $20/dry t o n are shown. For
u t i 1i t y financing, t h e methanol p r o d u c t i o n c o s t s are $1.20, $1.23, $1.30 and
$1.44 per g a l l on f o r wood p r i c e s o f $5, $10, $20, and $40 per d r y ton. For
p r i v a t e i n v e s t o r f i n a n c i n g , t h e methanol p r o d u c t i o n c o s t s a r e $1.60, $1.63,
$1.70 and $1.84 per g a l l o n f o r the corresponding wood costs.

COMPUTER MODELLING STUDIES

Computer modelling work i s underway t o develop a program t h a t w i l l


describe commercial p l a n t s f o r producing methane and methanol by c a t a l y t i c
g a s i f i c a t i o n o f biomass. The model w i l l do heat and m a t e r i a l balance c a l c u l a -
t i o n s and then economic evaluations. The e f f e c t s on o v e r a l l economics o f
changing process parameters should be e a s i l y determined.

The h e a r t o f t h e modelling e f f o r t i s t h e ASPEN computer code being devel-


oped a t Massachusetts I n s t i t u t e o f Technology. ASPEN i s an acronym f o r
Advanced Simulation f o r Process Engineering analysis. One o f t h e p r i m a r y
o b j e c t i v e s o f the ASPEN p r o j e c t i s t o develop a p r o t o t y p e simulator and demon-
s t r a t e t h e a b i l i t y t o simulate s p e c i f i c f o s s i l f u e l conversion processes o f
i n t e r e s t t o DOE.

This simulator i s f l e x i b l e and w i l l model a v a r i e t y o f u n i t operations.


It performs heat and m a t e r i a l balance c a l c u l a t i o n s , does crude equipment s i z i n g
calcu 1a t i ons and computes several economic parameters. I t i s considered a
s t a t e - o f - t h e - a r t s i m u l a t i o n code and i s s t i l l being r e v i s e d and tested. It i s
the o n l y known p u b l i c l y a v a i l a b l e code t h a t w i l l handle streams w i t h s o l i d s or
model s o l i d s handling equipment.

Several chemical r e a c t o r models are avai 1able i n ASPEN, b u t a1 1 are i d e a l


d e s c r i p t i o n s such as an e q u i l i b r i u m model, a p l u g f l o w model and a backmix
model. None o f these adequately describes the batch r e a c t o r used i n our lab-
o r a t o r y s t u d i e s o r t h e f l u i d - b e d r e a c t o r i n t h e PDU. F o r t u n a t e l y t h e ASPEN
code i s designed t o a l l o w t h e user t o supply h i s own models when necessary.
TABLE 52. Methanol Cost - U t i l i t y Financing Method--200 t o n Dry WoodlDay

Bases :

20-yr p r o j e c t l i f e
5% year s t r a i g h t l i n e d e p r e c i a t i o n on T o t a l C a p i t a l Requirement
e x c l u d i n g Working C a p i t a l
48% f e d e r a l income t a x r a t e
75/25 debt/equi t y r a t i o
10% i n t e r e s t on debt
15% r e t u r n on e q u i t y

Def in i t ion o f Terms :

C = T o t a l C a p i t a l Requirement, 106 $
W = Working Capital, 106 $
N = T o t a l Net Operating Cost, l o 6 $ / y r
G = Annual Fuel Production, 106 g a l / y r
d = F r a c t i o n Debt
i= I n t e r e s t on Debt, %/yr
r = Return on equity, % / y r
p = Return on Rate Base, %/yr

Equation f o r Return on Rate Base:

Average Methanol Cost, $./gal =

N + .05 (C-W) + .005 ( p + 48/52 ( 1 - d ) r ) (C+W)


G

Calculation:

Average Methanol Cost =


TABLE 53. Methanol Cost - Equity Financing Method--200 ton Dry Wood/Day
Bases:
20-yr project life
16-yr sum-of-the-years' digits depreciation on Total Plant
Investment
100% equity capital
12% DCF return rate
48% federal income tax rate

Definition of Terms:
I = Total Plant Investment, lo6 $
S = Start-up Costs, 106 $
W = Working Capital, 106 $
N = Total Net Operating Cost, 106 i/yr
G = Annual Methanol Production, 10 gal/yr

Methanol Cost Equation at 12% DCF Return


Methanol Cost, $/gal =

Calculation:
Average methanol cost =
The r e a c t o r models e x i s t i n g i n t h e ASPEN program a r e n o t a c c u r a t e d e s c r i p -
t i o n s o f o u r experimental u n i t s p r i m a r i l y because mass and h e a t t r a n s f e r
e f f e c t s a r e ignored. Thus, much t i m e has been spent a n a l y z i n g our d a t a t o
q u a n t i f y any d i f f u s i o n a l l i m i t a t i o n s .

Some o f t h e l a b o r a t o r y work showed an i n c r e a s e i n r e a c t i o n r a t e as t h e


steam f l o w r a t e increased. T h i s suggests a t l e a s t t h e p o s s i b i l i t y o f d i f f u -
s i o n a l l i m i t a t i o n s i n t h e system. Furthermore, some of t h e h i g h temperature
( 8 5 0 ' ~ ) d a t a d i d n o t f i t w i t h t h e r e s t on a standard a c t i v a t i o n energy p l o t .
The apparent a c t i v a t i o n energy decreased a t t h e h i g h e r temperatures. Once
again t h i s suggests d i f f u s i o n a l l i m i t a t i o n s . These o b s e r v a t i o n s were j u s t i f i -
c a t i o n f o r t r y i n g t o q u a n t i f y r e l a t i v e k i n e t i c and d i f f u s i o n a l r a t e s .

The a n a l y s i s s t a r t e d simple by assuming steam was t h e p r i m a r y r e a c t i n g


species. Furthermore, i t was assumed t h a t a g l o b a l k i n e t i c e x p r e s s i o n c o u l d
describe the actual g a s i f i c a t i o n reaction. For a s i n g l e p a r t i c l e we t h e n g e t
t h e f o l l o w i n g b y e q u a t i n g t h e r a t e of steam t r a n s f e r t o t h e s u r f a c e t o t h e
r a t e o f steam consumption by chemical r e a c t i o n :

- r = kmA ( C - C ) = k C
P B S R S
where r = Rate o f steam r e a c t i o n
km = Mass t r a n s f e r c o e f f i c i e n t
A = Surface area o f p a r t i c l e
P
CB = Bulk steam c o n c e n t r a t i o n
C S = P a r t i c l e s u r f a c e steam c o n c e n t r a t i o n
kR = F i r s t o r d e r k i n e t i c r a t e c o n s t a n t

The mass t r a n s f e r c o e f f i c i e n t i s a f u n c t i o n o f t h e Schmidt and Reynolds


numbers. I t was e v a l u a t e d u s i n g t h e j f a c t o r .
dpu.
where: j = 0.357 For f i x e d bed w i t h Re = - between 3 and 2000
(RE10.359' u
p = Mass d e n s i t y
p* = Molar d e n s i t y
u = Gas v e l o c i t y
p = Gas v i s c o s i t y
D = Diffusion coefficient
d = P a r t i c l e diameter
P

A d i f f u s i o n c o e f f i e c i e n t f o r steam i n t h e o t h e r gases wa's evaluated u s i n g


techniques i n Reid, P r a u s n i t z , and Sherwood (1977).

By r e a r r a n g i n g t h e r a t e equations we get a form f o r t h e r a t e expression


t h a t i n c l u d e s mass t r a n s f e r e f f e c t s .

The l i m i t i n g cases a r e worth n o t i n g


I f k A >> kR then r = kR CB Kinetics l i m i t overall rate
m P
I f kR >> k A then r =k A CB Mass t r a n s f e r l i m i t s r a t e
mP m P
If kR = kmAp then r = 112 kR CB Both mass t r a n s f e r and
kinetics influence r a t e

A problem a r i s e s i n d e t e r m i n i n g kR from t h e batch r e a c t o r data. Experi-


mental d a t a were c o l l e c t e d f o r t h e expression.

where Wc = Weight o f carbon. I n terms of carbon conversion t o gases (Xc)


t h i s becomes
Where Wc = i n i t i a l weight o f carbon present.
0
NO simple r e l a t i o n s h i p e x i s t s between k c and kR because t h e s t o i c h i o m e t r y
f o r steam r e a c t i n g w i t h wood i s n o t w e l l defined f o r v a r y i n g steamlwood r a t i o s
and temperatures. Furthermore, t h e c o n c e n t r a t i o n o f steam i n t h e r e a c t o r a t
any t i m e was n o t measured. From m a t e r i a l balance c o n s i d e r a t i o n s a steam con-
c e n t r a t i o n was c a l c u l a t e d and a "pseudo s t o i c h i o m e t r y " proposed a t each tem-
p e r a t u r e . T h i s allowed c a l c u l a t i o n of kR values from t h e measured k c r a t e con-
stants. Then one can compute a r a t i o o f kR/kmAp.

Some p r e l i m i n a r y r e s u l t s a r e

Temperature, OC
550

Although t h e r e a r e many u n c e r t a i n t i e s i n t h e c a l c u l a t e d values f o r kR, t h e


t r e n d shown i s i n t e r e s t i n g . These r e s u l t s suggest s u r f a c e d i f f u s i o n cannot be
ignored and i t tends t o l i m i t r a t e s a t h i g h temperatures i n t h e b a t c h r e a c t o r .
The p r i m a r y reason f o r t h i s i s b e l i e v e d t o be t h e low gas v e l o c i t i e s ( t 2 c m l s ) .
A s i m i l a r a n a l y s i s of t h e PDU d a t a showed t h e mass t r a n s f e r r a t e was h i g h
enough a t 5 0 0 ' ~ so k i n e t i c s a r e p r o b a b l y l i m i t i n g there. Gas v e l o c i t i e s a t
5 0 0 ~were
~ ,100 cmls. No good PDU d a t a a t 8 5 0 ' ~ a r e a v a i l a b l e t o check t h e
model a t h i g h temperatures.

B u t t and Weekman (1974) have t a b u l a t e d a s e r i e s of t e s t c r i t e r i a t o d e t e r -


mine whether heat and/or mass t r a n s f e r e f f e c t s a r e i m p o r t a n t f o r c a t a l y t i c
reactions. The c r i t e r i a check f o r surface d i f f u s i o n as w e l l as p o r e d i f f u s i o n
resistances. The f o r m u l a t i o n s can a p p l y e q u a l l y w e l l t o wood p a r t i c l e s i f t h e
pore c h a r a c t e r i s t i c s a r e known. I n f o r m a t i o n on pore s t r u c t u r e i n wood was
taken from Boyd e t a l . (1979). R e s u l t s from a p p l y i n g t h e c r i t e r i a o f B u t t and
Weekman supported t h e f o l l o w i n g conclusions:

1) Mass t r a n s f e r does a f f e c t o v e r a l l r e a c t i o n r a t e s i n t h e b a t c h
reactor.

2) Heat t r a n s f e r r a t e s i n t h e b a t c h r e a c t o r r a t e a r e low enough t h a t


p a r t i c l e temperatures ( a t steady s t a t e ) a r e 20-40°c ( a t 5 5 0 ' ~ and
850°c, r e s p e c t i v e l y ) lower than t h e gas temperatures. (Radiation
e f f e c t s a r e ignored i n Weekman's a n a l y s i s ) .

3) N e i t h e r heat nor mass t r a n s f e r l i m i t a t i o n s occur i n t h e PDU ( a t l e a s t


not a t 5 0 0 ~ ~ ) .

4) Pore d i f f u s i o n l i m i t a t i o n s do n o t e x i s t i n e i t h e r t h e batch r e a c t o r
o r t h e PDU.

An i m p o r t a n t q u a l i f i e r here i s t h a t several of Weekman's c r i t e r i a r e q u i r e t h e


same kR value mentioned e a r l i e r . U n c e r t a i n i t i e s i n g e t t i n g t h a t number have
a l r e a d y been mentioned.

E f f o r t s t o d e r i v e a p u r e l y k i n e t i c model a r e based on d e s c r i b i n g t h e PDU


s i n c e mass and heat t r a n s f e r l i m i t a t i o n s do n o t appear t o be important. A fair
amount of i n f o r m a t i o n i n t h e l i t e r a t u r e e x i s t s f o r d e s c r i b i n g t h e p y r o l y s i s o f
c o a l s and c e l l u l o s e and then g a s i f i c a t i o n o f a wide v a r i e t y o f chars (Lowry
1963). U n f o r t u n a t e l y n e a r l y a l l t h e r a t e expressions a r e intended t o p r e d i c t
o n l y carbon conversions. Few go on t o g i v e methods f o r p r e d i c t i n g gas y i e l d s .
No one has s u c c e s s f u l l y model l e d g a s i f i c a t i o n of c o a l o r wood by p r e d i c t i n g
b o t h conversions and gas compositions. Our p l a n i s t o :

1) Assume p y r o l y s i s occurs r a p i d l y and i s n o t a f f e c t e d by steam. We


a l l o w t h e p y r o l y s i s r e a c t i o n t o g i v e e q u i l i b r i u m y i e l d s o f carbon
and produce known amounts o f gases. Pure carbon i s t h e assumed s o l i d
product. Tar f o r m a t i o n i s ignored.
2) Take t h e p y r o l y s i s products as t h e s t a r t i n g m i x t u r e f o r t h e f o l l o w i n g
set o f reactions

Not a1 1 o f these r e a c t i o n s are m u t u a l l y independent. Reaction a) - b) w i l l


g i v e e) on a p u r e l y s t o i c h i o m e t r i c basis. However, r e a c t i o n e) i s c a t a l y z e d b y
some o f t h e c a t a l y s t s used i n our t e s t s . Hence, i n c l u d i n g i t was t h e e a s i e s t
way t o account f o r t h i s c a t a l y t i c e f f e c t .

The e q u i l i b r i u m p r e d i c t i o n s appear reasonable. Rate data f o r t h e s o l i d


r e a c t i o n s (a,b,c) come from Lowry b u t are f o r coconut s h e l l charcoal and a r e
based on u n i t mass o f carbon i n t h e system. Coconut s h e l l charcoal was t h e
c l o s e s t t h i n g t o wood f o r which data were a v a i l a b l e . Reaction r a t e constants
f o r t h e gas phase r e a c t i o n s have a l s o been found based on u n i t c a t a l y s t weight.
When a1 1 r a t e s are adjusted t o a common molesltime basis, t h e gas phase reac-
t i o n r a t e s are about 3 orders o f magnitude h i g h e r than t h e slowest carbon reac-
t i o n r a t e ( a t 550'~). T h i s means no more carbon disappears a f t e r p y r o l y s i s
so gas phase compositions are changed o n l y by r e a c t i o n s d and e. The r e s u l t i n g
carbon conversions are lower than e x p e r i m e n t a l l y observed and gas compositions
do n o t agree e i t h e r . E f f o r t s now are d i r e c t e d toward f i n d i n g b e t t e r r a t e d a t a
and checking f o r any e r r o r s i n c o n v e r t i n g a l l information t o a c o n s i s t e n t s e t
of units.

FUTURE
- MODELLING EFFORTS

A f t e r a c o n s i s t e n t s e t o f k i n e t i c data i s determined t h a t w i l l agree w i t h


t h e PDU data, t h e g a s i f i e r model w i l l be coded t o f i t i n t o t h e ASPEN computer
program. The ASPEN program can then generate heat and m a t e r i a l balance i n f o r -
mation f o r s e l e c t e d changes i n o p e r a t i n g c o n d i t i o n s . A visual inspection o f
these r e s u l t s w i l l show which equipment needs t o be r e s i z e d (based on a com-
p a r i son w i t h Davy McKee base-1 i n e s t u d i e s ) . T h e o r e t i c a l l y t h e ASPEN code can
a u t o m a t i c a l l y go from heat and m a t e r i a l balance c a l c u l a t i o n s t o equipment
sizing to equipment costing and then to economic evaluations. The manual
inspection is desirable if only one or two pieces of equipment will change
size. The savings in computer run time will be significant.
i
Once equipment costs are defined ASPEN generates a report on the economics
of the process. The calculations and format of the report follow ESCOE
6 guidelines.
ACKNOWLEDGMENTS

The authors are e s p e c i a l l y g r a t e f u l t o T. J. Kendron, 0. A. Kuby,


M. McClintock, and J. H. Rooker o f Davy McKee, Inc., who completed t h e economic
evaluations. Special a p p r e c i a t i o n i s a l s o extended t o J. E. Leonard,
W. F. Riemath, G. L. Roberts, E. D. Smith, and W . A. Wilcox, o f PNL, whose
e f f o r t s have been v i t a l t o t h e success of t h e experimental program.
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