low temperature conversion of biomass for...

Ernst A. StadlbauerErnst A. Stadlbauer11, Franz Petz, Franz Petz22, Sebastian Bojanowski, Sebastian Bojanowski11, , Astrid FiedlerAstrid Fiedler11, , SajjadSajjad HossainHossain11

1 1 University of Applied Sciences University of Applied Sciences GiessenGiessen, Germany, Germany22Abwasserzweckverband Abwasserzweckverband FüssenFüssen, , FüssenFüssen, Germany, Germany

LOW TEMPERATURE LOW TEMPERATURE CONVERSION OF BIOMASS FOR CONVERSION OF BIOMASS FOR PRODUCTION OF ENERGY AND PRODUCTION OF ENERGY AND

CHEMICALSCHEMICALS

[email protected]@mni.fh--giessen.degiessen.de

mailto:[email protected]

mailto:[email protected]

Agenda

Laboratory for Waste Treatment Processes let.mni.fh-giessen.de

♦♦♦♦♦♦

Devoted to the memory of lateProfessor Bayer, University of

Tübingen and spiritus rector of LTC

♦ Low Temperature Conversion of biomass: principle & layout

♦ Animal fat to hydrocarbon based bio-fuel in laboratory scale

♦ Design and performance of a pilot-scale Thermo-Catalytic Reactor

at a waste water treatment plant

♦ Environmental impact study

♦ Conclusions

♦ New markets for organic residues from WWT and rendering plants

Looking for new markets for MBM and animal fat in Europe due to BSE

Laboratory for Waste Treatment Processes let.mni.fh-giessen.de

1.7 Mio. tonnes/y

2.7 Mio. tonnes/y

Strategy: Explore a biomass to liquid fuel scheme

♦

Looking for new markets sewage sludge in Europe due new to soil protection legislation

Laboratory of Waste Treatment Processes let.mni.fh-giessen.de

Sewage sludge10 Mio. tonnes / year

3.5 x volume of cheops pyramid


Low Temperature Conversion (LTC): Basic Principle

CHNOS CHT > 380°CExternal or in-situ catalysts

LTC = Removal of functional groups in the presence of catalysts

1900: Dry destillation to produce „Dippels oil“, char and phosphate from bones

1982: Science of LTC by E. Bayer, University of Tübingen, Germany

1990: LTC at Environmental Canada (Licence of Bayer‘s Patent)

2000: LTC at Perth WWTP, Australia (Licence of Bayer‘s Patent)

2001-04: LTC Lab Niteroi, St. Maria, Brasil; pilot Rehau & Füssen, Germany

2005: Design of technical plant: Mintraching, Germany

Main elements of biomass Main elements of oil

100 200 300 400 500 600Temperature, °C

0

20

40

60

80

100TG /%

-15

-10

-5

0DTG /(%/min)

Animal Fat pureAnimal Fat with CatalystCatalyst pure

Thermogravimetry as micro LTC:Animal fat with and without an acidic zeolite as catalyst


First derivative

♦♦♦


Low Temperature Conversion (LTC): Layout♦♦

TIR TIR

el .TIC

substrate

TIRTIR TIRTIR

el .TICTIC

cooling water

Bio-fuel

solidresidue

catalyst

reaction water

NCG


Hydrocarbons from animal fat (H/C=1.9) in thepresence of an acidic zeolite catalyst

♦♦♦

C57H110O6C57H110O6 CH3-(CH2)n-CH3C6H5-R CH3-(CH2)n-CH3C6H5-

(T = 400 – 550°C)

Zeolite

(T = 400 –

H2C

H2C

O C C17H35

CO

OH C C17H35

O

OC

C17H35O

Animalfat

Diffusion H35C17

CO

C

O

CO

CH35C17

O

HC O C C17H35

O

CH3

CH3

CH3H2

H2

Reaction

Animal fat

Si OH

Al


Production of bio-fuel from animal fat in laboratory scale

1H-NMR of bio-fuel from animal fat at 400°C (Catalyst: Wessalith)

1.00

00

8.82

32

Inte

gral

8.61

96

7.44

717.

2519

7.08

566.

8991

5.51

835.

4900

3.17

522.

9668

2.60

222.

4139

2.35

862.

1038

1.71

28

1.38

07

1.00

100.

9778

(ppm)123456789

*** Current Data Parameters ***

NAME : ok13gsEXPNO : 10PROCNO : 1

*** Acquisition Parameters ***AQ_mod : dqdBF1 : 300.1300000 MHz

CPDPRG :DATE_d : Oct 13 2003

INSTRUM : spectNS : 16O1 : 1650.71 Hz

O2 : 0.00 HzPULPROG : zg30RG : 20.2000008

SFO1 : 300.1316507 MHzSFO2 : 300.1300000 MHz

SOLVENT : CDCl3SW : 20.5671 ppmTD : 32768

*** Processing Parameters ***GB : 0.0000000LB : 0.10 Hz

MI : 0.20 cmOFFSET : 15.745 ppm

PHC0 : 54.078 degreePHC1 : -0.996 degreeSI : 32768

SW_p : 6172.8395062

IV CDCl3

8.82

32

1.38

07

1.00

100.

9778

(ppm)1.01.21.4

8 27 4 36 5 1ppm

9


DEPT-135 NMR of bio-fuel from animal fat at 400°C (Catalyst: Wessalith)

150 140 30 20130 120 4080 70 60 50110 100 90 10ppm


♦♦♦

CH2LTC preserves mother nature`s syntheticachievement of long chain hydrocarbons

1H-NMR of bio-fuel from animal fat at 550°C (Catalyst: Pentasil)



Yields and physical characteristics of biofuels fromanimal fat using different zeolites and temperatures

♦♦♦

Animal fat and PZ-2/50H (550°C)

Animal fat and PZ-2/50H (400°C)

Animal fat and Wessalith (400°C)

Yield, % 31,48 56,74 72,9NCV, MJ/kg 40,06 39,95 41,88Density, g/ml - 0,85 0,8Viscosity, mm2/s - 1,01 2,29C, % 88,6 84,5 86,1H, % 10,7 12,5 13,8N, % <0,14 <0,14 <0,14S, % <0,34 <0,34 <0,34

Work in process: Pilot scale at oil refining plant withfluid catalytic cracking (FCC)

Comparison of GC-Fingerprint of bio fuel from animal fat (Catalyst: Wessalith, 400 °C) and Diesel


C20

C16

C12

C24

Diesel

C20 C24

C16C28

Bio fuel


Zeolite catalysis gives access to tailored hydro-carbons due to structure, acidity and temperature

Y-Zeolite

Mordenite Beta

Pentasil

Source: Atlas of Zeolites Framework Types, www.iza-structure.org/databases

♦♦♦

http://www.iza-structure.org/databases

0

20

40

60

80

activatedsludge

digestedsludge

UASBgranules

animalmeal

MBM

mas

s yi

eld,

%

residual solid bio-crudereaction water saltNCG

VS=87% VS=59% VS=77% VS=81% VS=62%

Mass yields of products from LTC of organic residueswith O,N,S heteroatoms and in-situ catalysts


♦♦♦

Msludge,90%DM = 560 t/y


The Füssen WWTP & LTC Reactor

Qd,av = 5,200 m3/d;

CCOD= 580 gO2/m3

Population equivalent: 76 000

a Reservoir

b Screw con-veyor (in)

d Screw con-veyor (out)

c Reactor

e Condenser

f Oil separator

aa

dd bb

cc

ee

ff

♦♦♦♦

1H-NMR of bio-fuel from digested sludge (LTC at T = 400°C)


♦♦♦

8 7 6 5 4 3 2 1chemical shift, ppm

DEPT-135 13C-NMR of bio-fuel from digested sludge(LTC at T = 400°C)


chemical shift, ppm140 120 100 80 60 40 20

CH2

♦♦♦

LTC with in situ catalysts conservesmother nature`s synthetic achievement of long chain hydrocarbons, too


Results from conversion of digested sludge in pilotscale reactor with pipe condenser at Füssen WWTP

Solid residue Oil WaterYield (%) 60 6±1 20VS (%) 30.0 - -NCV (MJ/kg) 7.5 37.5 -pH (-) 7.2 - 9.1C (%) 23.5 83.7 5.0H (%) 1.3 14.6 12.2N (%) 2.7 2.4 2.5S (%) 1.2 0.3 0.1Density (kg/m³) 876 901 -ν40°C (mm²/s) - 5.9 -COD (g/L) - - 104BOD (g/L) - - 50NH4-N (g/L) - - 26CH3COOH (g/L) - - 8.3

♦♦♦♦

FTIR spectrum of bio-crude from digested sludge in comparison to spectrum of bio-fuel from animal fat (LTC at T = 400°C)


3344

2923

2853

1707

air peak

wave number, cm-14000 3200 2400 1800 1400 1000 540

% tr

ansm

issi

on

80

84

88

92

96

100

4000,0 3000 2000 1500 1000 540,085,0

86

88

90

92

94

96

98

100,0

%T

3023,9

2922,8

2858,0

2360,1

1604,8

1494,7

1454,5

1376,7

1030,2

768,5

728,3

693,1

676,6

1

♦♦♦


Combustion performance test of LTC-oils from animalfat (Bio fuel) and sewage sludge (bio-crude)


Results of combustion performance test of LTC-oilsin comparison to commercial heating oil

Parameter Heating oil Heating oil /Biofuel 1:1

Bio fuel Bio crude

NCV [MJ/kg] 42.0 41.5 41.3 38.0 O2 in % 5.5 5.5 5.6 2.7 TGas in °C 134 134 133 157.2 λ 1.34 1.34 1.37 1.15 CO2 [%] 11.0 11.5 11.3 13.4 NOx [ppm] 68 78 98 936 SO2 [ppm] 30 9 0 - SPN in % 0.0 0.4 0.4 >3 NCV = Net Calorific Value SPN = Smoke Pot Number


Yields and physical characteristics of biocrude and biofuels from animal fat used in combustion tests

Bio crude (Sludge, 400°C)

Bio fuel (AF / Wassalith, 400°C)

Yield, % 6 72.9NCV, MJ/kg 38.0 41.3Density, g/ml 0.9 0.8Viscosity, mm2/s 5.9 2.29C % 83.7 86.1H % 14.6 13.8N % 2.4 <0.14S % 0.3 <0.34

External CatalystT = 400°C

CC66HH55--R;R; CHCH33--(CH(CH22))nn--CHCH33

Bio Bio FuelFuel

CH3-(CH2)n-CH3

CH3-(CH2)n-COOH

Bio Crude

C60H96O38N1S0,1

H/C = 1,6

LTC from sewage sludge to fuel

In situ Catalysts

T = 380-450°C


Use of products: char, oil, gas

Fate of persistent organic compounds such as disinfectants, antibiotics, endocrine disrupters and cytostatic drugs in sludge& profiles for heavy metals

Return load to WWTP from LTC reaction water

Energy balance

PCDD/PCDF equivalents for oil & char (< 100 ng/kg)

ΣPAH, PCB (< 0.2 mg/kg) for oil & char

PCDD/PCDF equivalents for gas (< 0.1 ng/m3)

ΣPAH, PCB, CO, SOx , NOx, particle for gas (17. BImSchV)

Parameters for Environmental Impact Study of LTC

Reduction of Octachlorodibenzodioxin (OCDD) by LTC of MBM in laboratory scale (T=420°C)

0,99

8,1

0123456789

OC

DD

in n

g/kg

TS

(FK

M)

FKM NTK-ÖlMBM LTC-OilOCDD-levels of solid residue and reaction water are below detection limit

Reduction of persistent organic compounds (PCDD/F) by LTC of sewage sludge in laboratory scale (T=420°C)

22,82

0,44

23,26

0

10

20

30

40

50

60

70

80

90

100

KS Füssen NTK-Kohle NTK-Öl Summe Prod.

Vert

eilu

ng P

CD

D/P

CD

F [%

]

Sludge LTC-Coal LTC-Oil Sum of Products

Dis

tribu

tion

PC

DD

/F [%

]

1870

0

50

100

150

200

250

300

350

400

450

500

4 5 6 7 8 4 5 6 7 8

Geh

alt P

CD

D/P

CD

F in

ng/

kg K

lärs

chla

mm

TS

bzw

. N

TK-G

leic

hgew

icht

smas

se m

(PC

DD

/PC

DF)

in n

g Klärschlamm FüssenNTK-KohleNTK-ÖlNTK-RW

Dioxine (PCDD) Furane (PCDF)

Sewage SludgeSolid ResidueLTC-OilReaction Water

Am

ount

PCD

D/F

[ng/

kg s

ewag

esl

udge

DS]

Am

ount

PCD

D/F

-Con

gene

rsin

LTC

-pro

duct

sin

eq

uilib

rium

with

1 kg

dry

sew

age

slud

ge[n

g]

Amounts of single congeners of PCDD/F in LTC products in equilibrium with 1 kg dry sludge (laboratory scale at T = 420°C)


SEM & X-ray analysis for bulk elements in solid residues


Element Weight-%

O 35.58Mg 0.79Al 0.80Si 1.10P 7.78K 0.90Ca 16.44Fe 1.61

(WWTP, Füssen)


Results of heavy metal distribution in LTC productsof digested sludge (LTC at T = 400°C, ICP-MS)

Cr Ni Cu Zn As Cd Hg PbLTC-Oil

Reaction WaterNCG

Solid Residue0

1020304050

60

70

80

90

100

Rec

over

yR

ate

[%]


0

100

200

300

400

activatedsludge

digestedsludge

UASBgranules

animalmeal

MBM

mg

PO4 /

g s

olid

resi

due phosphate

citric acid solutable phosphate

97.494.2

17.1

86.6

98.8

recovery, %

Leachability of phosphate from residual solids

phosphate (aqua regia)phosphate (citric acid)


10BACB2.D: EIC 212.5 ±All

2

10KADA2.D: EIC 212.5 ±All

2

NT10AC2.D: EIC 212.5 ±All

WA2.D: EIC 212.5 ±All

0

2

4

6

4x10Intens.

0

1

2

3

4

5

64x10

0

1

2

3

4

5

6

4x10

0

1

2

3

4

5

64x10

5 10 15 20 25 Time [min]

10µg/ml benzalkonium chloride

extraction of residual solid of digested sludge(0,1% trifluoracetic acid/70% acetonitrile)

extraction of digested sludge(0,1% trifluoroacetic acid/70% acetonitrile)

water

Decomposition of a persitent disinfectant during LTC analytically followed by LC/MS (fragment mass 212)

[RNR3+Cl-]


1 tD ig . sludge(90%TS),11.15 GJ

3 .00 tD ig . sludge(30%TS), 11.15 GJ

Input

Biocr ude

Coo ling wa ter

2.80 GJ

1 .2 8 GJ

LTC- Reactor and Condensation

5.20 GJ

R esidu a l so lid , wa ter,N CG

0.94 GJ

Output

So la r dr ying

Thermocatalysis (Wth):Output - Input = 8.94 GJ - 1.28 GJ = 7.66 GJ

Drying

Wel = 0 .18 GJ

Heat balance per 1t of digested sludge with 90% dry matter

♦♦♦♦♦


Look-out

- Application for EU LIFE project in progress:

-- Demonstration plant for WWTP (population equivalence:65.000, 1400 t sludge p.a. with 90% DS

-- Project Partners: AZV Pfattertal, MintrachingBrick Manufacturer Venus, Schwarzach


Conclusion

A thermo-catalytic process can convert sludge, fat, animal meal and meat & bone meal to fuel products or chemicals.

For a given H/C ratio the efficiency of conversion to hydrocarbonfuels increases with both higher volatile solids and lower heteroatomcontents.

Animal fat is most suitable for bio-fuel generation. Solid residuesfrom LTC of MBM are a source of phosphate in times of BSE.

Results of the environmental impact study as well as the availabilityof markets for bio-crude and char are critical for commericalapplication of LTC at WWTP.

This work is supported by DBU (German EnvironmentalFoundation), Osnabrück, Germany, Grant-No 18 153.

♦♦♦♦♦♦

4,2

13,1

7,8

5,5

11,2

0

2

4

6

8

10

12

14

0 20 40 60 80 100recycle ratio residual solid, %

kine

mat

ic v

isco

sity

ν40

°C, m

m2 /s

Influence of recycling ratio of residual solids on kinematic viscosities of bio-crude (LTC at T = 400°C)


♦♦♦

13C-NMR of bio-fuel from animal fat at 400°C (Catalyst: Wessalith)

129.

0374

128.

2305

127.

8821

126.

0482

125.

7822

77.4

218

77.0

000

76.5

782

32.0

140

29.8

041

29.7

583

29.5

657

29.4

557

29.1

256

28.0

436

22.7

619

22.6

610

22.2

117

19.6

717

19.2

224

14.4

084

14.1

149

11.4

007

(ppm)102030405060708090100110120130140

*** Current Data Parameters ***NAME : ok13gsEXPNO : 11PROCNO : 1*** Acquisition Parameters ***AQ_mod : qsimBF1 : 75.4677190 MHzCPDPRG : waltz16DATE_d : Oct 13 2003INSTRUM : spectNS : 4000O1 : 7497.00 HzO2 : 1650.71 HzPULPROG : zgpg30RG : 4597.6000977SFO1 : 75.4752160 MHzSFO2 : 300.1316507 MHzSOLVENT : CDCl3SW : 300.4395 ppmTD : 32768*** Processing Parameters ***GB : 0.0000000LB : 1.00 HzMI : 0.20 cmOFFSET : 249.104 ppmPHC0 : 141.257 degreePHC1 : 58.984 degreeSI : 32768SW_p : 22675.7369615

IV CDCl3

150 140 30 20130 120 4080 70 60 50110 100 90 10ppm


DEPT-135 NMR of bio-fuel from animal fat at 400°C (Catalyst: Wessalith)

128.

2215

32.0

141

29.7

950

29.7

584

29.5

658

29.4

558

22.7

620

22.6

611

19.2

225

14.4

085

11.4

008

(ppm)102030405060708090100110120130140

*** Current Data Parameters ***

NAME : ok13gsEXPNO : 12

PROCNO : 1

*** Acquisition Parameters ***AQ_mod : dqd

BF1 : 75.4677190 MHzCPDPRG : waltz16

DATE_d : Oct 13 2003

INSTRUM : spectNS : 1600

O1 : 7497.00 HzO2 : 1650.71 Hz

PULPROG : dept135

RG : 6502.0000000SFO1 : 75.4752160 MHz

SFO2 : 300.1316507 MHzSOLVENT : CDCl3

SW : 300.4395 ppm

TD : 32768*** Processing Parameters ***

GB : 0.0000000

LB : 1.00 HzMI : 0.20 cm

OFFSET : 249.104 ppmPHC0 : -71.549 degree

PHC1 : 15.156 degree

SI : 32768SW_p : 22675.7369615

IV CDCl3

150 140 30 20130 120 4080 70 60 50110 100 90 10ppm


CH2

1H-NMR of bio-fuel from animal fat at 400°C (Catalyst: Wessalith)

8 27 4 36 5 1ppm

9


13C-NMR of bio-fuel from animal fat at 500°C (Catalyst: Wessalith)

150 140 30 20130 120 4080 70 60 50110 100 90 10ppm


Thermogravimetry of digested sludge

100 200 300 400 500 600

60.0

65.0

70.0

75.0

80.0

85.0

90.0

95.0

100.0

TG, %

-2.5

-2.0

-1.5

-1.0

-0.5

0

DTG, %/min

Mass change -11.83 %

Mass change -21.90 %

Mass change -9.14 %

Residue 57.02 %


♦♦

Mass- and energy yield of activated sludge(NCV = 19.6 MJ/kg)


0,0

20,0

40,0

60,0

80,0

residualsolid

bio-crude reactionwater

salt NCG

yiel

d, %

mass yield

energy yieldNCV = 19.8 MJ/kg

NCV = 28.8 MJ/kg

NCV = 28.3 MJ/kg

♦♦

Mass- and energy yield of digested sludge(NCV = 11.1 MJ/kg)


0

20

40

60

80

residualsolid


salt NCG

yiel

d, %

mass yield

energy yield

NCV = 9.3 MJ/kg

NCV = 36.3 MJ/kg NCV =

27.4 MJ/kg

♦♦

Mass- and energy yield of animal meal(NCV = 18.4 MJ/kg)


0

20

40

60

80

residualsolid


salt NCG

yiel

d, %

mass yield

energy yieldNCV = 13.9 MJ/kg

NCV = 30.4 MJ/kg

NCV = 32.9 MJ/kgNCV =

0.71 MJ/kg

♦♦

C-NMR of bio-fuel from digested sludge at 400°C


♦♦

chemical shift, ppm160 140 120 100 80 60 40 20 0


♦ Fate of trace contaminants

Disinfectant: Benzalkonium chloride (QAV)

Antibiotic: Ciprofloxacin

Cytostatic drug: Mitoxantron

Heavy metals


♦ Organic residues containing O,N,S heteroatoms, H/C<1.9 and production of in-situ catalysts for LTC


Back load to WWTP from LTC reaction water

Return water from LTC Plant ≈ 33 kgCOD/d

V ≈ 0,33 m3/d; COD ≈ 100 kg/m3

Dry weather input ≈ 3000 kgCOD/d

V ≈ 5.200m3/d; COD ≈ 0.58 kg/m3

Back load ≈ 1%

Input at light load period: 8 p.m. to 8 a.m.

(total sludge conversion: 600 t / a (20% reaction water))

Parameter of different LTC substrates


♦♦

Organic residue/ LTC-Substrate

Volatile Solids(VS) [%]

Percent Composition [%] H/C Ratio

Activated Sludge 87 46.5%C; 6.8%H; 6.0%N; 1.2%S 1.75Digested Sludge 59 28.9%C; 4.9%H; 4.2%N; 1.3%S 2.03UASB Granules 77 40.3%C; 6.2%H; 9.0%N; 4.3%S 1.85Animal Meal 81 45.0%C; 6.5%H; 8.8%N; 0.5%S 1.73Meat and BoneMeal

62 31.6%C; 4.8%H; 7.8%N; 0.3%S 1.82


Results of heavy metal distribution in LTC productsof digested sludge (LTC at T = 400°C, Pilot)

Cr Ni Cu Zn As Cd Hg PbLTC-Oil

Centrifuged SolidCentrifuged Reaction Water

Solid Residue0

10

20

30

40

50

60

70

80

Rec

over

yR

ate

[%]

21,9

2,0

16,3

3,6

0

10

20

30

40

50

60

70

80

90

100

KS Füssen NTK-Kohle NTK-Öl NTK-Ölschlamm

Summe Prod.

Vert

eilu

ng P

CD

D/P

CD

F [%

]

Reduction of persistent organic compounds (PCDD/F) by LTC of sewage sludge in pilot scale (T<400°C)

Dis

tribu

tion

PC

DD

/F [%

]

Sludge LTC-Coal LTC-Oil LTC Oil sludge Sum of Products

2530

0

50

100

150

200

250

300

350

400

450

500

4 5 6 7 8 4 5 6 7 8

c (P

CD

D/P

CD

F) in

ng/

kg K

lärs

chla

mm

TS

bzw

. N

TK-G

leic

hgew

icht

smas

se m

(PC

DD

/PC

DF)

in n

g

Klärschlamm FüssenNTK-KohleNTK-ÖlNTK-Ölschlamm

Dioxine (PCDD) Furane (PCDF)

Sewage SludgeSolid ResidueLTC-OilReaction Water

Amounts of single congeners of PCDD/F in LTC products in equilibrium with 1 kg dry sludge (pilot scale at T = 400°C)

Am

ount

PCD

D/F

[ng/

kg s

ewag

esl

udge

DS]

Am

ount

PCD

D/F

-Con

gene

rsin

LTC

-pro

duct

sin

eq

uilib

rium

with

1 kg

dry

sew

age

slud

ge[n

g]

low temperature conversion of biomass for...

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