Pengantar Indusri

Kimia

Biohydrocarbon and
process integration
Biohydrocarbon
production
Biohydrocarbon (in this text) refers to any
hydrocarbon from biomass that can be use as
liquid fuel mixture or substitutes.
Biohydrocarbon can be classified as
1. Oxygenated hydrocarbon : having high
oxygen content, i.e ethanol and biodiesel
2. Deoxygenated hydrocarbon : having low (or
even no) oxygen content.
3. Cracked hydrocarbon.
 Deoxygenated
hydrocarbon
Oxygen in hydrocarbon molecules increase its
polarity cause limitation in fuel mixture
application. Commercial acceptance for
oxygenated biodiesel 20%v
Technology for removing oxygen atom from
hydrocarbon are hydrodeoxygenation and
decarboxylation.
The goal of these technologies : producing n-
paraffin ( in this text was focused on triglycerides
raw material)
 Involved
reactions

Main difference :
Hydrodeoxygenation need additional
hydrogen
Decarboxylation no need hydrogen
 Previously in Biology
solar
energy
H2O CO2

The Calvin Cycle

Light
reactions
ADP +
NADP +

NADPH
P

Calvin
cycle
Reactions
ATP

Metabolites of the Calvin Cycle

stroma RuBP ribulose-1,5-bisphosphate

O2 CH2O
3PG 3-phosphoglycerate
3CO2

intermediate BPG 1,3-bisphosphoglycerate

G3P glyceraldehyde-3-phosphate
3 C6

6 3PG
3 RuBP C3
C5 CO2 6
fixation ATP

These ATP and

CO2
Calvin cycle 6 ADP + 6 P NADPH molecules
3 ADP + 3 P reduction were produced by
the light reactions.
regeneration
of RuBP
6 BPG
C3
These ATP
molecules were 3
produced by the ATP 5 G3P 6 NADPH
light reactions. C3
6 G3P
C3
6 NADP+

net gain of one G3P

Other organic molecules Glucose

 Fate of G3P
The building block
G3P
Gliceraldehyde 3 Phosphate,
(3 carbon atoms,) which
release one carbon in
fatty acid amino acid
everytime attached to the
glucose
phosphate synthesis synthesis next molecules to form
straight chain hydrocarbon.
Thus straight hydrocarbon
+
will always be in even
fructose number of carbon
phosphate

Sucrose (in leaves, Starch (in roots Cellulose (in trunks,

fruits, and seeds) and seeds) roots, and branches)

Herman Eisenbeiss/Science Source

 Hydrodeoxygenation and decarboxylation
Other difference
Decarboxylation releasing oxygen in term of Carbondioxide, number of
carbon atom of the product will be less one carbon atom odd number of
carbon atom
Hydrodeoxygenation, three hydrogen molecules required for releasing two
oxygen atom in form of two water molecules. Number of carbon atom in the
product similar with the fatty acid even number of carbon atom.
Hydrodeoxygenation will give some side reaction

Reverse Water Gas Shift

Metal-soap Pyrolysis for decarboxylation

v= number of valens electron of the metal.

Application of this reaction for production process is still in reseach scale.
A very promising route due to its mild temperature and pressure.
Metal-soap Pyrolysis for decarboxylation
 Commercial scale process
Crude Oil
compatible fraction

Vegetable oil

Co-process main concept was

to conduct hydrotreating
process for Crude oil fraction
and vegetable oil in a same
reactor. Compatibility concern
are acidity, hydrogen
consumption and reaction
enthalpy
 Commercial scale process
Vegetable oil

Stand alone process

usually consist of two
series of reactor,
deoxygenation reactor
and isomerization
/cracking reactor.
The product then become a tailormade green diesel with high cetane number and
even suitable for jet fuel.
Existing green diesel
producer
(data
Company updated
Location in 2014)
Capacity (annual) Brand name
UOP LLC Honeywell Illinois US 1.000.000 ton Honeywell green Diesel
Eni SpA Italy 300.000 ton Ecofining Technology
Diamond Alternative Louisiana, USA 1200 ton Green Diesel
Energy
Neste Oil Co, Porvoo (FIN) 2 plants @ 190.000 NExBTL
1.000.000
Finlandia Roterdam (NED) Add to 2.400.000
Singapore
Petrobras Araucaria, Parana, 725.000 ton H-Bio Technology
(10% veg oil mixture)
Biocombustvel Brazil
BSBios, Passo Fundo 85.000 ton
Haldor Topsoe Copenhagen, @ 26000 Green Diesel
260.000 ( various raw material)
Denmark (HQ)
14 Refinaries
ConocoPhillip Inc. Whitegate Refinery 40.500 ton Green Diesel
di Cork, Irlandia
 Technical challange
1. Exothermic reaction and hydrogen consuming
For hydrodeoxygenation, raw material with high double bond
(Iodine Value) consuming more hydrogen. Elimination
reaction also release energy that need to be managed. Lack
of hydrogen in reactor or ractor overheat can cause catalyst
deactivation.
UOP-Honeywell approach selective catalyst
Neste Oil, Sytroleum and Haldor-Topsoe total hydrogenation
2. Gaseous side products ( Propane, Methane, CO2, CO)
Ineffective separation process can cause Hydrogen run off
with side products
CO that remain in reactor can deactivated catalyst
 Cracked Hydrocarbon
Mainly evolved from existing
technology Fluidizide Cracking
Catalysis (FCC).
The technology is proven and reliable
for Vacuum Gas Oil ( a fraction of
crude oil) and developed to be
applied for Vegetable Oil either as co-
processing or as stand alone process.
Uniqueness of this process relied on
its reactor design that accommodate
the catalyst lifetime which only 2-5
detik.
Reactor was consist of reactor and
regenerator.
 VG Oil and Veg Oil
comparison
Physical characteristic
VG Oil and Veg Oil is
realy comparable.
If ( somehow) oxygen
atom from Veg Oil can
be removed, thus it can
be considered drop in
biofuel.
Cracking scheme

LHCO (Light Heavy Cycle Oil )

Boiling point 325-360oC

LCO (Light Cycle Oil)

215-325oC
Commercial scale process
Non of developed process was proven to be economically feasible (in
condition crude oil price US$ 70 per barrel)
The competition for finding feasible production process still open.

TD = Tidak Dilaporkan
General pyrolysis
The oldest method for liquefying or
gasifying biomass.
Operate in 400 600 oC. The
pyrolysis reaction itself is an
exothermic reaction. Thus, energy
input was required to meet this
required temperature.
Current commercial application
was using fluidized bed reactor or
rotating cone reactor
Possible reaction
in pyrolysis
General pyrolysis
Based on retention time
in the reactor, (or in
other word, heating rate)
pyrolysis were
categorized as
fast pyrolysis (10 to 1000
oC per second, 5 second
in reaction temp (400
650 C)
Slow pyrolysis ( 0.1 1
oC per second, hours in
reaction temp)
Hydrothermal scheme
Gasification scheme
Possible reaction
in gasification
Gasifier type
Advantages
High carbon conversion
Low tar yield
Low ash in syn gas
Long resisting time
Easy start up
Disadvantage
Difficult for scaling up
process
Uniform size of raw
material required and
dried
High slag formation rate
 Gasifier type
Advantages
High thermal efficiency
Compatible for different size and type
of raw material
Able to process raw material with
moisture content up to 50 %
Easy to scale up
Disadvantage
High tar content in syngas
Low hydrogen production
Tar treatment were required at the
downstream
Long start up
Gasifier type
Advantages
Better gas solid contact
Better temperature
control
Product has high heat
capacity
Able to process wide
varian raw material
Easy start up and shut
down
Disadvantage
Large carbon loss ( as ash)
Uniform size of raw
material required and
dried
Limited scaling up
Gasifier type
Advantages
Better gas solid contact
Better temperature
control
Better control of carbon
loss
Product has high heat
capacity
Able to process wide
varian raw material
Easy start up, shut down
and scaling up
Disadvantage
Uniform size of raw
material required and
dried
 Gasifier type
Advantages
Free tar syngas
High syngas conversion (low
CH4)
Disadvantage
Large ashes were produced
(high carbon loss)
Under high pressure
condition ( high safety cost)
 Technical challange
1. Increasing hydrogen demand by diversification.
Currently 95% hydrogen in market was used as chemical
raw material, ammonia (50%) petroleum hydrotreating
(37%) dan produksi methanol (8%)
Diversification for methanol
Temperature 200 - 300C
Pressure 50-100 bar
Catalyst Cu/ZnO

H2 : CO = 2.1:1
Diversification for alkane
Temperature 200 oC

Direct use for Fuel cell. ( efficiency to electricity 60%,

compare to Internal combustion engine 20 38%)
Process integration to agroindustry
Banana trunks strategic advantages for process integration in NTF. NTF having papaya
plantation for producing papain enzyme and cassava plantation for tapioca . NTF
needs ethanol for papain purification, besides for energy.

Clean ethanol Used ethanol

Papaya sap coagulation drying

papain
endapan
Hydrolysis process using Hydrochloric acid might be applied to banana trunks without put any
harm to environment
Banana Ion exchange Fertilizer for
trunks KOH KCl banana plantation
regeneration
HCl
Thermo- ethanol
mechanical Acid Cl- Ion
pulping hydrolysis exchange
distillation

Pulp / Sugar fermentation

cellulose Energy from burning
solution cassava tree
 Process integration to community
Clean Development Mechanism for Renewable Energy Source
proposed project for NTT was an example for process
integration to community

East Nusa Tenggara is an archipelago which is consists of 566

islands. Only 246 islands had been named. There are 4 big
islands, Flores, Sumba, Timor and Alor Which is usually called
FLOBAMORA and become the center of culture and activities
It`s archipelago is just like miniature of Indonesia
T low HDI opportunity

HDI can be used as

the indicator for the
benefit of this
project.
Since NTT is the
second lowest HDI
among Indonesia`s
province, big
opportunity for
climbing up.
Increasing NTT GDP
by selling energy
Proposed project scheme
Bio-ethanol
Project supporting potency
Research Center for Biology and Research Center for Chemistry, Indonesian Institute of Science
initiated the 1st generation of development
introducing the bio-ethanol production technology as a part of a program for Lontar
(Borassus sundaicus L.) and Gewang (Corypha utan Lamk.)
socializing the new economical added value of these two plants to the local community
increase social awareness for replanting and conservation

The biggest population is in Rote Island in

about 20.000 ha. From those vegetation the
natural glucose (nira), that are produced in a
semester up to 275.040.kl.
 Project supporting potency
Potential solar energy source 4.825 kWh
per m2 per day
Study for geothermal potential energy source in
East Nusa Tenggara by Research Center for Geo-
technology of Indonesian Institute of
Science, Kastiman Sitorus and Dany Aswin.
not less than 1055 MWe of Geothermal energy
are available in East Nusa Tenggara needs
more accurate observation for geological
assurance of the exploration point unit should
be build.
Mataloko field : A research well called MT-2 was
built.
the temperature is 270 360 0C.
The reservoir zone is at 1 km depth
resistive layer which is directly covered by
500 600 m of clay cap.