Anaerobic treatment in the pulp & paper

industry

by

Leo Habets

Date: Thursday 2 April 2015

10-4-2017
 Contents:

1. Reasons for anaerobic treatment

2. Where can it be applied in P&P?
3. Which systems are available?
4. Some examples
5. Closed cycle applications
6. Gas treatment
7. Potential problems and how to solve them

10-4-2017
 Reasons for anaerobic (pre)treatment

• Reduction of aeration basins (80%)

• Reduction of sludge production (50 - 80%)
• Low energy consumption
• Small footprint
• Overall stable operation
• Energy production

3
 Aerobic process

COD + O2  H2O + CO2 + BIOMASS

CO2 + H2O

48

100 2
EFFLUENT

50

4 AEROBIC SLUDGE
 Anaerobic process

COD  CH4 + CO2 + BIOMASS

CH4 + CO2

78

100

20 EFFLUENT

2
5 ANAEROBIC SLUDGE
 Overall stable operation such as:
Improvement of aerobic sludge
sedimentation

6
 Bulking activated sludge

7
 Looking for the sludge bed profiel

8
 Some terms often used

VLR: Volumetric Loading Rate - kg COD/m3.d

SLR: Sludge Loading Rate - kg COD/kg VSS.d

Sludge activity:
COD conversion in kg COD/ kg VSS.d

Specific gas production:

m3 biogas/kg COD degraded

9 9
Application options in Chemical pulping

fresh water
wood
chemicals pulp mill bleaching paper mill paper

black wash water

chemicals liquor
recovery
boilers

condensate bleaching effluent white water

10
 Application for CTMP / APMP effluent

softwood
chemicals paper/
pulp mill bleaching paper mill
board

pulp mill bleaching white

effluent effluent water

TMP effluent
11
 Very popular process for recycled fiber mills

fresh water

fiber supply paper/board

paper mill

solids
removal

effluent
treatment
12
discharge to river
 MILL PROCESS FEASIBILITY OF ANAEROBIC
TREATMENT

Mechanical Pulping (APMP, CTMP, TMP etc.)

Hardwood ++
Softwood +

Semi Chemical Pulping

NSSC +
Soda pulping +
Chemical Pulping
Sulfite pulp condensate ++
Kraft pulp condensate ++
Pulp bleaching:E,O,P (TCF) +
Pulp bleaching:C,H,D -
Secondary Fibres
Wastepaper, also DIP ++
Non-wood (soda) Pulping
Straw +
Bagasse ++
Cotton linters +
E: Extraction, O: Oxygen, P: Peroxide, C: Chlorine,
13 H: Hypochlorite, D: Chlorine Dioxide
Sludge bed reactors most often applied
in P&P industry

Internal
UASB circulation EGSB
14
 Cumulative overview of applied
sludge bed reactors in P&P

15
 Typical design parameters of anaerobic
reactors in the pulp & paper industry

Volumetric loading Typical Reactor

rate Volume
(kg COD/m3.d) (m3 / ton COD.d)

CSTR contact 1-5 333

process

UASB 5-15 100

EGSB 10-20 60

IC 20-30 40

16
17 UASB reactor
 First UASB started in 1983 at
Smurfit Kappa Roermond Papier

18
 Granular sludge enables high velocities

19
 UASB at Industriewater Eerbeek (NL)
since 1985

20
 IC reactor

21
 IC detail: Gas release pot

22
23
 IC detail:
Influent distribution
24
 Possible treatment set up

25 25
 Alternative with round tanks

26 26
 Or both: rectangular and round

27
 Efficiency (%)

28
0,0
10,0
20,0
30,0
40,0
50,0
60,0
70,0
80,0
90,0
100,0
1-1-2004

15-1-2004

29-1-2004

12-2-2004

26-2-2004

11-3-2004

25-3-2004

8-4-2004

22-4-2004

6-5-2004

20-5-2004

3-6-2004

17-6-2004

1-7-2004

15-7-2004

29-7-2004

12-8-2004
IC Reactor COD removal efficiency (%)

26-8-2004

9-9-2004

23-9-2004

7-10-2004

21-10-2004

4-11-2004

18-11-2004

2-12-2004
Typical COD removal rate for CCM mills

16-12-2004

30-12-2004
 COD (mg/l)

29
100
120
140
160
180
200

0
20
40
60
80
1-1-2004

15-1-2004

29-1-2004

12-2-2004

26-2-2004

11-3-2004

25-3-2004

8-4-2004

22-4-2004

6-5-2004

20-5-2004

3-6-2004

17-6-2004

1-7-2004
Final Effluent COD

15-7-2004

29-7-2004

12-8-2004
Final effluent COD

26-8-2004

9-9-2004

23-9-2004

7-10-2004
(raw water had 5000 mg COD/l)

21-10-2004

4-11-2004

18-11-2004

2-12-2004

16-12-2004

30-12-2004
 Performance at fluctuating COD load
Efficiency versus Volumetric Loading Rate

100

90

80

70
COD efficiency

60

50

40

30

20

10

0
0,0 5,0 10,0 15,0 20,0 25,0 30,0 35,0 40,0 45,0
VLR kg/m3/d

30
 IC performance diagram

100% 50,0

90% 45,0

80% 40,0

VLR in kg COD/m3.d
70% 35,0
% COD removed

60% 30,0

50% 25,0

40% 20,0

30% 15,0

20% 10,0

10% 5,0

0% 0,0
JAN FEB MAR APR MAY JUN JUL AUG SEP

COD removal efficiency VLR

31
 Corresponding biogas production
at variable VLR

18.500 30

18.000 29
Biogas production in m3/h

28

VLR in kg COD / m3.d

17.500
27
17.000
26
16.500
25
16.000
24

15.500 23

15.000 22
JAN FEB MAR APR MAY JUN JUL AUG

Biogas production Nm3/h VLR in kg COD / m3.d

32
Some
examples

Wepa
Giershagen
Germany

Deinking
effluent from
tissue
production

33
 Shandong Chenming Paper
Shouguang, China
34 APMP effluent from aspen pulping
 Nine Dragon Paper mill, Donguan, China:
effluent from CCM production

35
 Shandong Linqing, China:
Effluent from straw pulping

36
 Tembec Temiscaming QC,
Canada:
Sulphite condensate combined with
BCTMP effluent and bleach extraction effluent
(total 180 tons of COD/d)

37
 Raw material and COD removal

Raw material COD efficiency %

OCC 75 – 85
MWP 65 - 75
MOW 60 - 70
ONP 50 - 55
Mech. pulp / spruce 50 - 55
Mech. pulp / aspen 65 - 75
Condensates 75 - 95

38
 Closed circuit operations

39
 Simplified treatment scheme

waste paper new paper

Paper mill

biogas
cleaning S°
O2 CO2

anaerobic aerobic
process process
clean water

Biomass +
CaCO 3 +
40
particles
 Averaged process water conditions
with and without in-line treatment

SK Zülpich Papier 1995 before after

(flow treated: 3 m3/ton)

COD mg/l 35,000 7,500

Ca mg/l 3,700 535
Sulphate mg/l 1,500 500
Chloride mg/l 550 450
Acetic acid mg/l 5,000 1,000
Propionic acid mg/l 700 250
Butyric acid mg/l 400 20
Lactate mg/l 5,800 800
pH - 6.25 7.25
Conductivity mS/cm 9.0 4.5

41
 Influence of process water on paper
quality at SK Zülpich Papier

Analyses of cold water extract from paper

parameter Unit before after

Chloride mg/kg 365 367

Sulfate mg/kg 1200 530
Formic acid g/kg 1.2 0.6
Acetic acid g/kg 5.9 0.6
Propionic acid g/kg 0.4 < 0.2
Buteric acid g/kg 0.6 < 0.2
Lactic acid g/kg 6.6 0.7

42
 Internal ánd external treatment

biogas

Aeration IC Conditioning

Cooling

(Quality B) Conditioning
Paper production

UASB
(Quality A)

Aeration

Sedimentation

Sand discharge
43 filtration
 The BIOPAQ®ICX schematic

Degassing and first

solids separation

Second solids
separation and
recycling

Influent
distribution

44
 General features of the ICX

1. Optimal biomass retention

2. 80% effective volume

3. Choice of circulation ratio

4. Modular internals

5. Various tanks shapes can be

chosen

45
 Gas treatment:
H2S removal by THIOPAQ® gas
scrubber

Gas out to gas motor, boiler, etc.

46
 Sulfur cycle

assimilatory desulfuration
sulfate Organic sulfur
reduction

Sulfate reduction
Sulfate Sulfide

Sulfide oxidation

sulfur sulphide
Sulfur oxidation
oxidation

47
 THIOPAQ® Applications

Digester biogas
Refinery
gas

Natural
gas
Anaerobic
WWTP
biogas

Associated gas Landfill gas

48
 Potential problems

1. Lack of granulation

2. Biomass losses

3. Contamination of inert material

4. Toxicity and inhibition

5. Overloading

49
 Fibers and wood particles accumulation

50
 Deposit of heavy material on
reactor bottom

51 51
 Deposit on gas hoods

52 52
 Blocked pipe line

53 53
 Scaling in aeration tank

54
 Biological reactions as a result of
reducing water consumption:

Reaction in the mill process water due to long HRT

Acidification of starch via glucose to acetic acid
C12H22O11 + 9 H2O  4H2CO3 + 4 CH3COO- + 4 H+ + 8 H2

Acidity is neutralized by CaCO3

2H+ + CaCO3  Ca2+ + H2O +CO2

Reaction in the treatment plant (and after)

Precipitation of Calcium Carbonate
Ca2+ + 2 HCO3-  CaCO3 + H2O+CO2

55
 Biomass quantity and activity
determines treatment capacity

1. Biomass retention (kg VSS)

2. Biomass activity: kg COD/kg VSS.d

(0,3 – 0,8)

Capacity (kg COD/d) = Biomass x Activity

56
 Biomass activity at various recycle mills
COD conversion in (kg COD/kg VSS.d)
Biomass Activity

0,9

0,8

0,7

0,6

0,5 kg COD/kg VSS.d

0,4

0,3

0,2

0,1

0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22

57
 Chemicals that can have an impact
on biomass behavior

•Organic solvents (chloroform, tetra)

•Oxidizing chemicals (Cl2, ClO2, NaOCl, NaClO2)
•Specific chemicals such as for wet strength and
volume building
•Retention aids
•Some anionic material (NO3 and high SO4)
•Hypobromite (NaBr or NH4Br with NaOCl)
•Nanoparticles
•Biocides, Slimicides
•Resin acids
58 •Oils
 Lab test facilities for activity and
toxicity

59
 Blanc test with acetic acid and
biomass

Blank act.test
Anaerobic Roerm ond granular sludge (3 feeds)
(Methane pressure vs tim e)
400

350

300
FEED 1
Pressure (hPa)

250

200 FEED 2

150 FEED 3

100

50

0
0 0.5 1 1.5 2 2.5 3 3.5 4
-50
Time (days)

60
 Thanks for your
attention

61