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Page 1: Interim results Generic Approach Interim results

Generic Approach

Interim resultsInterim results

  

Page 2: Interim results Generic Approach Interim results

Goal

• Copyright

• Longer timeframe

- Current state of technology as benchmark

- BUT MAIN GOAL: Develop NEW process flow diagrammes (PFDs), two main reasons

Page 3: Interim results Generic Approach Interim results

Current processes (bioprocesses and conventional): State-of-the-art

Future bioprocesses Horizon value for productivity Concentration glucose Scale

PFDs - Principle considerations (1/2)

Chemical Category (relevant examples)

10-20 KT

20-50 KT

50-100 KT

100-200 KT

200-400 KT

400-700 KT

700-1200 KT

Specialty solvents (Carbon Sulfide)

Specialty Polymers (Polycarbonate)

Textile Polymers (Polyamide)

Food Chemicals (Citric Acid)

Bulk Solvents (Acetone)

Bulk Polymers (PET, PVC)

Bulk Intermediates (Acetic Acid)

Bulk Chemicals (Methanol, Olefins)

TYPICAL PLANT SIZES

Page 4: Interim results Generic Approach Interim results

Future separation processes

Only continuous fermentation processes Plant size: Assume TODAY FUTURE Wherever possible, avoidance of energy intensive processes (e.g., distillation and evaporation); on the other hand

relatively high fuel requirements may be acceptable in view of the use of renewable energy from biowaste streams. Membrane processes are generally preferred due to their (expected) low energy use and the avoidance of high salt

loads. The avoidance of salt loads also makes electrodialysis an attractive option for the future. The high power requirements

are considered acceptable in view of on-site electricity production from biowaste streams. Extraction should be avoided, wherever possible. Alternatively, benign solvents should be used. Properties of

compounds and process design determine energy use. Adsorption may be somewhat less attractive due to common use of solvents for regeneration.

PFDs - Principle considerations (2/2)

Page 5: Interim results Generic Approach Interim results

Overview of schemes

O:\BREW\WPs\WP2(TechnoEcon)\Generic_approach\Separation\MassBalances\ TO_DO__MASS-BAL.xls

Product Inclusion? PFD?No.1 No.2 No.3 No.4 No.5 Excluded-1 Excluded-2 Excluded-3

Comment

1 ABE (Butanol) Yes X TODAY_1_(Distill)

TODAY_2_(GasStripping)

FUTURE_1_(DistMembDist)

FUTURE_2_(MembDistDist)

FUTURE_3_(Pervaporation)

FUTURE_4_(RO) FUTURE_5_(ADS)

2 Ethanol Yes X TODAY_1_(Evap&Distill)

Next steps? UCM?

3 PDO (1,3 --> 1,2) Yes X (SRI) TODAY_1_(Evap)

FUTURE_1_(Pervap)

FUTURE_2_(HyphobMmbr)

4 Acetic acid Yes X (all new) TODAY_1_(Extraction)

TODAY_2_(Evap&Dist)

FUTURE_1_(Extraction)

FUTUR_2_(Evap&Dist)

FUTURE_3_(ED)

5 LA (--> 2 Hydroxyprop.acid)

Yes X (partly SRI )

??LA_FUTURE

_1_(ED)FUTURE_2_(Extra

ction)LA_FUTURE_3_(S

RIlowpH)LA_FUTURE_4_(A

dsorption)

6 Adipic acid Yes X TODAY_1_(Cryst)

FUTURE_1_(Cryst)

FUTURE_2_(EDs)TODAY_1_(Solven

t)TODAY_1_(Ester+

Distill)

7 Succinic acid Yes X (partly SRI) TODAY_1_(Cryst)

TODAY_2_(1stageED)

FUTURE_1_(Cryst)

FUTURE_2_(2stageED)

8 Citric acid Yes X TODAY_1_(Extr&Cryst)

UCM?

9 Acrylic acid Yes

10 Caprolactam Yes X FUTURE_1_GEN

11 Lysine Yes X (SRI) TODAY (IonExch)

FUTURE_1_(ADS)

LOOKUP from glutamic acid

12 PHA Yes TODAY_1_(Extraction)

FUTURE_1_(Extraction)

Low molecular PHA +

membranes

13Biolubricants based on Vegetable oils (e.g., Oleyl oleate) - esters

? UCM?

14Monoglycerides and diglycerides of fatty acids (Biosurfactants) - esters

? UCM?

15[[Isopropyl miristate (Cosmetics) - esters]]

? UCM?

16 Polyglycerol monoester ? UCM?

17[[ Octyl octanoate (Cosmetics) - ESTER ]] ?

? UCM?

TO BE INCLUDED IN WP 1: - Phenol Excluded: Methanol - Butanetriol-1,2,4 Syngas-based processes

FOR EXCEL VERSION WITH LIST OF SCHEMES TO BE REVIEWED BY EACH PARTNER SEE:

Workpackages -> W

P2 -> Overview of g

eneric m

ass balance schemes

Page 6: Interim results Generic Approach Interim results

Product Broth concentration (g/l) Plant size

Average Range Ref. Average Range Ref. Average Range Ref.

1 ABE (Butanol) TODAY anaer. 33 (for total ABE) GA 0.36 0.42FUTURE anaer. 45 GA 35 0.85 200 kt

2 Ethanol TODAY anaer. 105 70 - 140 i) [1] 2 - 20-25 ii) [4, 5] 0.3-0.45FUTURE anaer. 100 0.47 200 kt

3 PDO TODAY anaer. 100 [1,2] 6 max. 31 [in 2] 0.48 iii) [2] 27 ktFUTURE anaer. 100 GA 50 0.57 GA 200 kt

4 Acetic acid TODAY anaer. 18 GA 0.15 GA 0.50 5 ktFUTURE anaer. 20 GA 15 0.90 250 kt

5 Lactic acid TODAY anaer. 100 80-135 [1] 2.5 2.5-10 0.85 0.91 [10] 140 ktFUTURE anaer. 120 GA 15.6 12-15.6-40 [3] 0.95 iv) [3] 200 kt

6 Adipic acid TODAY Aer. 20 17.4-36.8 [6] 0.42 0.17 20 ktFUTURE Aer. 40 [6] 10 0.61 v) [11] 200 kt

7 Succinic acid TODAY anaer. 80 70-95 [7,3] 1.5 1.32-2.5 [7,3] 1.00 0.9-1.0 [7,3]FUTURE anaer. 100 [2] 15 GA 1.00 (>)75 kt

8 Citric acid TODAY Aer. 150 100-170 [1] 3? 0.75-5-10 1.00 (?) 0.4-1.1 600 ktFUTURE Aer. 150 10 1.00 600 kt

9 Caprolactam FUTURE ??? 20 0.4 0.20 200 kt

10 Lysine TODAY Aer. 100 [8] 120 [1] [1,2,8] 1.7 [8] 0.40 [2, 8] 45 ktFUTURE Aer. 100 5.0 0.63 vi) GA 200 kt

11 PHA TODAY Aer. 150 [12] 3.0 0.35 20 ktFUTURE Aer. 150 [12] 5.0 0.37 150 kt

HORIZON VALUES FUTURE anaer. 50-100 0.90FUTURE Aer. 10-20 0.90

Note: Not covered in this table: Phenol, Butanetriol-1,2,4, acrylamide and esters

i) Only around 50 g/l acc. to BCI (Jennings Florida) and NREL (2002) (for the latter this may have to do with the use of lignocellulosics as feedstock).ii) 1.38 g/l/h acc. to NREL (2002) for production from lignocellulosics = TO BE DISCUSSEDiii) Maximal value for aerobic: 0.60iv) Higher than theoretical yield acc. to [10] (p.33: 1 g /g glucose) = stoichiometry to be recheckedv) Higher than theoretical yield acc. to [10] (p.47: 0.54 g /g glucose); patent yield acc. to [10], p.40: 0.216vi) CHECK: 70% yield for C6H12O6+2NH4OH? 1 (L-lysine) + 2H2O => 70% x 146 / 180 = 0.57 = search for more original sources

Productivity (g/(l*h)) Yield (g product/g substr)

Overview of key data

O:\WPs\WP2(TechnoEcon)\Generic_approach\Separation\MassBalances\CPY_1.xls

THIS VERSION NOW UPDATED. SEE:

Workpackages -> W

P2 -> Overview of K

ey data (CORRECTED VERSION, 2

4. Sept 2

004)

Page 7: Interim results Generic Approach Interim results

ABE

Overview of PFDs and authors

1.) ABE_TODAY_1_(Distillation) Tim Nisbet, Shell Chemicals2.) ABE_TODAY_2_(GasStripping) UU/Literature3.) ABE_FUTURE_1_(DistMembDist) Tim Nisbet, Shell Chemicals4.) ABE_FUTURE_2_(MembDistDist) Tim Nisbet, Shell Chemicals5.) ABE_FUTURE_3_(Pervaporation) UU/Literature

The following PFDs are also included in this file but are considered less promising:

6.) ABE_FUTURE_4_(RO=Reverse Osmosis)7.) ABE_FUTURE_5_(ADS = Adsorption)

For the following options, no PFDs were developed since they were neither considered promising:

8.) Extraction with supercritical CO2

Page 8: Interim results Generic Approach Interim results

ABE (1/7): ABE_TODAY_1_(Distillation)N u t r i e n t s

P r o c e s s w a t e rA u x i l i a r i e s G l u c o s e

( 1 ) ( 2 )

C o n t i n u o u s s t e r i l i z e r C o n t i n u o u s s t e r i l i z e r

1 3 0 ° C , 3 0 m i n . 1 3 0 ° C , 3 0 m i n .s u b s e q u e n t c o o l i n g s u b s e q u e n t c o o l i n g

( 3 )I n o c u l u m ( 4 ) P r e - s e e d

A i r 3 5 ° C( 5 )

( 1 0 ) ( 6 )( 7 )

A i r S e e d3 5 ° C ( 8 ) ( 9 )

( 1 0 )( 1 1 ) S e e d

( 1 2 ) P 2 m e d i u m n u t r i e n t sA u x i l i a r i e s S t e a mP r o c e s s w a t e r ( 1 3 ) r e q ' d .

W a s t e s o l i d s ( 1 4 ) E v a p o r a t i o n1 0 0 ° C , 1 b a r C o n c . r a f f i n a t e

( 1 5 ) A B E ( o v e r h e a d )

G a s f o r s t r i p p i n gC O 2 a n d H 2

( 1 6 )

O r g a n i c e x t r a c t a n t

P u r g e

D e w a t e r e d A B E

E t h a n o l ( o v e r h e a d )

N o t e s o n d o w n s t r e a m p r o c e s s i n g

( 2 0 )

E t h a n o lB u t a n o l A c e t o n e

E x t r a c t i v e d i s t i l l a t i o n ( p o l a r e n t r a i n e r t o b r e a k

b u t a n o l - w a t e r a z e o t r o p e )

1 2 0 ° C , 1 b a r

A c i d s , s u b s t r a t e e t c . i n r e m a i n i n g b r o t h

S i m p l e d i s t i l l a t i o n 2

1 2 0 ° C , 1 b a r

S i m p l e d i s t i l l a t i o n 3

1 2 0 ° C , 1 b a r

A c e t o n e ( o v e r h e a d )

U l t r a f i l t r a t i o n2 5 ° C , 1 b a r

S i m p l e d i s t i l l a t i o n 1

1 2 0 ° C , 1 b a r

F e r m e n t a t i o nB a t c h , 1 2 0 h6 0 ° C , 1 b a r

- T h i s w o r k u p s c h e m e ( s e t 3 d i s t i l l a t i o n c o l u m n s i n a r o w ) i s a s u g g e s t i o n b y T i m N i s b e t , S h e l l C h e m i c a l s :

1 . ) F e r m e n t a t i o n 2 . ) U F 3 . ) S i m p l e d i s t i l l a t i o n 1 A B E a r e l i g h t e r t h a n w a t e r o v e r h e a d 4 . ) E x t r a c t i v e d i s t i l l a t i o n - N e c e s s a r y d u e t o a z e o t r o p e

- D e w a t e r w i t h a p o l a r e n t r a i n e r - P r o d u c t s a t b o t t o m

5 . ) S i m p l e d i s t i l l a t i o n 2 A c e t o n e o v e r h e a d 6 . ) S i m p l e d i s t i l l a t i o n 3 E t h a n o l o v e r h e a d , b u t a n o l a t b o t t o m

. . . o r e v e n s e p a r a t e l y f o r 1 - b u t a n o l , 2 -m e t h y l - 1 - p r o p a n o l , 2 - b u t a n o l a n d 2 -m e t h y l - 2 - p r o p a n o l ?

Page 9: Interim results Generic Approach Interim results

ABE (2/7): ABE_TODAY_2_(GasStripping)Nutrients

Process waterAuxiliaries Glucose

(1) (2)

Continuous sterilizer Continuous sterilizer

130 °C, 30 min. 130 °C, 30 min.subsequent cooling subsequent cooling

(3)(4) Pre-seed

35 °C(5)

(10) (6)(7)

Seed35 °C (8) (9)

(10)(11) Seed

Steam exportSteam gen.

(12) P2 medium nutrientsAuxiliaries SteamProcess water (13) req'd. Flue gas

AshIntegrated ABE fermentation Waste solids (14) Evaporation Combustionwith in-situ removal 100 °C, 1 bar Conc. raffinate

(15)

Gas for stripping Acids, substrate etc. CO2 and H2 in remaining broth

(16) (17)

Vapour phase with stripped ABE

Purge gas (18)(energy credit)

(19)

(20)

Butanol

Ultrafiltration25 °C, 1 bar

Fermentation

Acetone Ethanol

Fractionated condensation of ABE vapors

120°C --> 50°C, 1 bar

Gas stripping

120 °C, 1 bar

Batch, 120h60 °C, 1 bar

Water vapour (to scrubber)

...or even separately for 1-butanol, 2-methyl-1-propanol, 2-butanol and 2-methyl-2-propanol?

- This workup scheme has been derived from the literature listed above.- The gas stripping unit consists of a counter-current stripping column and a cold trap or molecular sieve. See scheme in [6], p.138- The scheme in [6], p.138 does not show any filtration step between fermentation and gas stripping. Can this be skipped? If so, where and how do the waste solids leave the system?-

Page 10: Interim results Generic Approach Interim results

ABE (3/7): ABE_FUTURE_1_(DistMembDist)Nutrients

Process waterAuxiliaries Glucose

(1) (2)

Continuous sterilizer Continuous sterilizer

130 °C, 30 min. 130 °C, 30 min.subsequent cooling subsequent cooling

(3)(4) Pre-seed

35 °C(5)

(10) (6)(7)

Seed35 °C (8) (9)

(10)(11) Seed

Steam exportSteam gen.

(12) P2 medium nutrientsAuxiliaries SteamProcess water (13) req'd. Flue gas

Ash Waste solids (14) Evaporation Combustion

100 °C, 1 bar Conc. raffinate(15)

ABE (overhead)Gas for stripping

CO2 and H2

(16)

(18)

Dewatered ABE

Ethanol (overhead)

(20)

Ethanol

120 °C, 1 bar

Butanol Acetone

Acetone (overhead)

Simple distillation 2

120 °C, 1 bar

Simple distillation 3

120 °C, 1 bar in remaining broth

Hydrophobic membrane

30 °C, 1 bar

Ultrafiltration25 °C, 1 bar

Simple distillation 1 Acids, substrate etc.

Water vapour (to scrubber)

FermentationBatch, 120h60 °C, 1 bar

...or even separately for 1-butanol, 2-methyl-1-propanol, 2-butanol and 2-methyl-2-propanol?

OR WOULD A HYDROPHILIC MEMBRANE BE BETTER?

Page 11: Interim results Generic Approach Interim results

ABE (4/7): ABE_FUTURE_2_(MembDistDist)Nutrients

Process waterAuxiliaries Glucose

(1) (2)

Continuous sterilizer Continuous sterilizer

130 °C, 30 min. 130 °C, 30 min.subsequent cooling subsequent cooling

(3)(4) Pre-seed

35 °C(5)

(10) (6)(7)

Seed35 °C (8) (9)

(10)(11) Seed

Steam exportSteam gen.

(12) P2 medium nutrientsAuxiliaries SteamProcess water (13) req'd. Flue gas

Ash Waste solids (14) Evaporation Combustion

100 °C, 1 bar Conc. raffinate

(18)

Dewatered ABE

Ethanol (overhead)

(20)

Ethanol

120 °C, 1 bar

Butanol Acetone

Acetone (overhead)

Simple distillation A

120 °C, 1 bar

Simple distillation B

Hydrophobic membrane

30 °C, 1 bar

Ultrafiltration25 °C, 1 bar

Water vapour (to scrubber)

FermentationBatch, 120h60 °C, 1 bar

...or even separately for 1-butanol, 2-methyl-1-propanol, 2-butanol and 2-methyl-2-propanol?

Page 12: Interim results Generic Approach Interim results

ABE (5/7): ABE_FUTURE_3_(Pervaporation)Nutrients

Process waterAuxiliaries Glucose

(1) (2)

Continuous sterilizer Continuous sterilizer

130 °C, 30 min. 130 °C, 30 min.subsequent cooling subsequent cooling

(3)(4) Pre-seed

35 °C(5)

(10) (6)

Seed35 °C (8) (9)

(10)(11) Seed

P2 medium nutrientsAuxiliaries (12) Steam gen.

Process water Biomass Steam

(14) (13) req'd. Flue gasAsh

(15) Purge Waste solids (15) Evaporation Combustion100 °C, 1 bar Conc. raffinate

Integrated ABE fermentation (16)with in-situ removal Acids, substrate etc.

in remaining broth(17)

Vapour phase with ABE

(18)

(19)Broth recycle

(20) Butanol

FermentationBatch, 120h

Acetone Ethanol

25 °C, 1 bar

Pervaporation

30 °C, 1 bar

Fractionated condensation of ABE vapors

60 °C, 1 bar

Ultrafiltration

120°C --> 50°C, 1 bar

...or even separately for 1-butanol, 2-methyl-1-propanol, 2-butanol and 2-methyl-2-propanol?

Only this section differs from other ABE configurations for the future.

Page 13: Interim results Generic Approach Interim results

ABE (6/7): ABE_FUTURE_4_(RO)

NutrientsProcess water

Auxiliaries Glucose(1) (2)

Continuous sterilizer Continuous sterilizer130 °C, 30 min. 130 °C, 30 min.

subsequent cooling subsequent cooling

(3)(4) Pre-seed

35 °C(5)

(10) (6)(7)

Seed35 °C (8) (9)

(10)(11) Seed

Steam export P2 medium nutrients Steam gen. Auxiliaries (12) Process water Steam

(13) req'd. Flue gasAsh

Purge Biomass Waste solids (14) Evaporation Combustion100 °C, 1 bar Conc. raffinate

Integrated ABE fermentation (15)with in-situ removal

Acids, substrate etc. in remaining broth

(9)

(10)

(11)

ButanolAcetone Ethanol

Reverse Osmosis

30 °C, 1 bar

Fractionated distillation of organics (ABE)

120°C --> 50°C, 1 bar

Batch, 120h60 °C, 1 bar

Ultrafiltration25 °C, 1 bar

Water vapour (to scrubber)

Fermentation

...or even separately for 1-butanol, 2-methyl-1-propanol, 2-butanol and 2-methyl-2-propanol?

Only this section differs from other ABE configurations for the future.

Page 14: Interim results Generic Approach Interim results

ABE (7/7): ABE_FUTURE_5_(ADS)Nutrients

Process waterAuxiliaries Glucose

(1) (2)

Continuous sterilizer Continuous sterilizer

130 °C, 30 min. 130 °C, 30 min.subsequent cooling subsequent cooling

(3)(4) Pre-seed

35 °C(5)

(10) (6)(7)

Seed35 °C (8) (9)

(10)(11) Seed

Steam export P2 medium nutrients Steam gen. Auxiliaries (5) Process water Steam

(6) req'd. Flue gasAsh

Purge Biomass Waste solids (7) Evaporation Combustion100 °C, 1 bar Conc. raffinate

Integrated ABE fermentation (8)with in-situ removal

Acids, substrate etc. in remaining broth

(9)

Extractantcycle

(10)

(11)

ButanolAcetone Ethanol

Molecular sieves, adsorbent resins

30 °C, 1 bar

Fractionated distillation of organics (ABE)

120°C --> 50°C, 1 bar

Batch, 120h60 °C, 1 bar

Ultrafiltration25 °C, 1 bar

Water vapour (to scrubber)

Fermentation

...or even separately for 1-butanol, 2-methyl-1-propanol, 2-butanol and 2-methyl-2-propanol?

Only this section differs from other ABE configurations for the future.

Page 15: Interim results Generic Approach Interim results

Acetic acidOverview of PFDs

1.) AceticAc_TODAY_1_(Extraction)2.) AceticAc_TODAY_2_(Evap&Dist)3.) AceticAc_FUTURE_1_(Extraction)4.) AceticAc_FUTUR_2_(Evap&Dist)5.) AceticAc_FUTURE_3_(ED)

Questions to industry experts:

1.) Assumed conversion efficiency for FUTURE (see hand-written note): 100 g Glucose --> 90 g Acetic acid + 10 g Biomass + 0 g CO2 + 0 g H2O For TODAY, the yield is only 50g Ac. acid per 100 g Glucose. a) Do we agree with this? b) Do we agree that all non-converted glucose leaves the system and solid biomass? Or do we assume CO2 release (e.g. for cell maintenance)?

2.) Are the assumed workup schemes OK? Is anything missing, is anything superfluous?

3.) Limit to anaerobic since most infos available; no aerobic process [TN].

Detailed questions:- Is the relationship between waste solids in stream 7 and the input of nutrients in stream 6 reasonable?- The assumed key parameters for the extraction step arte given in sheet "AceticAc_TODAY_1_(Extraction)", cell X110 etc, AD 110 etc. and S139 etc. Could you please have a look whether these are OK?- We have assumed the solvent makeup to be identical with the solvent loss via the raffinate phase. Is this OK?- Ratio Water/product bleed has been set to 3% (see cell S139). Is this OK?

Page 16: Interim results Generic Approach Interim results

Ethanol

Page 17: Interim results Generic Approach Interim results

PDOOverview of PFDs and authors

1.) PDO_TODAY_1_(Evap) SRI

The following PFDs are also included in this file but may not be viable

2.) PDO_FUTURE_1_(Pervap) UU/Lit.3.) PDO_FUTURE_2_(HyphobMembr) UU/Lit.

Questions to industry experts:

Situation

- PDO is difficult to separate due to its high polarity (much more difficult than propanol and butanol).- Pervaporation is easier to put into practice than hydrophobic membranes (pervaporation makes use of size effects).- On the other hand, the advantage of pervaporation compared to distillation is rather limited (estimate TN: 25% energy saved).

--> what to keep, what to skip?

Notes:- The processes studied use only glucose as feedstock. An alternative is the use of glycerol. This is also covered by the SRI report but is not included as alternative generic design.

Page 18: Interim results Generic Approach Interim results

PDO (1/3): PDO_TODAY_1_(Evap)Nutrients

Process waterAuxiliaries Glucose

(1) (2)

Continuous sterilizer Continuous sterilizer130 °C, 30 min. 130 °C, 30 min.

subsequent cooling subsequent cooling

(3)(4) Pre-seed

35 °C(5)

(10) (6)(7)

Seed35 °C (8) (9) (10)

(11) SeedSteam gen.

(5) Nutrients

Auxiliaries SteamProcess water (6) req'd. Flue gas

Waste solids (7) Evaporation Combustion

100 °C, 1 bar(8) Conc. raffinate Ash

(6)

(9)

(11)

(12)

Batch, 50h35 °C, 1 bar

Fermentation

Ultrafiltration25 °C, 1 bar

Evaporation of PDO

170°C (top), 210°C (bottom)

Evaporation of water

70°C (top), 170°C (bottom)

0.4 bar

0.4 bar

PDO

Washing

DistillationNote: PDO has a high boiling point:bp (101.3 kPa) = 214 °Cbp (0.7 kPa) = 94 °C

Page 19: Interim results Generic Approach Interim results

PDO (2/3): PDO_FUTURE_1_(Pervap)Nutrients

Process waterAuxiliaries Glucose

(1) (2)

Continuous sterilizer Continuous sterilizer130 °C, 30 min. 130 °C, 30 min.

subsequent cooling subsequent cooling

(3)Pre-seed

35 °C(5)

(10) (6)(7)

Seed35 °C (8) (9) (10)

(11) SeedSteam gen.

(5) Nutrients

Auxiliaries SteamProcess water (6) req'd. Flue gas

Waste solids (7) Evaporation Combustion

100 °C, 1 bar(8) Conc. raffinate Ash

(6)PDO and other organics

(9)

(11)

(12)

FermentationBatch, 50h

35 °C, 1 bar

Ultrafiltration25 °C, 1 bar

Pervaporation (Hydrophilic membrane)

x bar, y°C

Evaporation of PDO0.4 bar

170°C (top), 210°C (bottom)

Washing

Distillation

PDO

Page 20: Interim results Generic Approach Interim results

PDO (3/3): PDO_FUTURE_2_(HyphobMembr)Nutrients

Process waterAuxiliaries Glucose

(1) (2)

Continuous sterilizer Continuous sterilizer130 °C, 30 min. 130 °C, 30 min.

subsequent cooling subsequent cooling

(3)(4) Pre-seed

35 °C(5)

(10) (6)(7)

Seed35 °C (8) (9) (10)

(11) SeedSteam gen.

(5) Nutrients

Auxiliaries SteamProcess water (6) req'd. Flue gas

Waste solids (7) Evaporation Combustion

100 °C, 1 bar(8) Conc. raffinate Ash

(6)Dewatered PDO

(9)

(11)

(12)

Washing

25 °C, 1 bar

x bar, y°C

FermentationBatch, 50h

35 °C, 1 bar

Ultrafiltration

Hydrophobic membrane

Distillation

PDO

Evaporation of PDO0.4 bar

170°C (top), 210°C (bottom)

Page 21: Interim results Generic Approach Interim results

Acetic acid

Overview of PFDs

1.) AceticAc_TODAY_1_(Extraction)2.) AceticAc_TODAY_2_(Evap&Dist)3.) AceticAc_FUTURE_1_(Extraction)4.) AceticAc_FUTUR_2_(Evap&Dist)5.) AceticAc_FUTURE_3_(ED)

Questions to industry experts:

1.) Assumed conversion efficiency for FUTURE (see hand-written note): 100 g Glucose --> 90 g Acetic acid + 10 g Biomass + 0 g CO2 + 0 g H2O For TODAY, the yield is only 50g Ac. acid per 100 g Glucose. a) Do we agree with this? b) Do we agree that all non-converted glucose leaves the system and solid biomass? Or do we assume CO2 release (e.g. for cell maintenance)?

2.) Are the assumed workup schemes OK? Is anything missing, is anything superfluous?

3.) Limit to anaerobic since most infos available; no aerobic process [TN].

Page 22: Interim results Generic Approach Interim results

Ac.acid (1/5): AceticAc_TODAY_1_(Extraction)

Water recycleSeed (25)

(3) (4)(24)

CO2 Bleed (water/acid)(5) Nutrients Condensation

AuxiliariesProcess water (7) 100% of acid Steam export

(21) Steam gen.Flue gas

(8) AshWaste solids Evaporation CombustionWater/acid 100 °C, 1 bar Conc. raffinate

(9) 99% of acid 1% of acid 2% of acid

Solvent: TOPO (10) Solvent make-up 1.5% of acid

(12)(11)

Extract (solvent/acetic acid/trace water) (20)(13) 98.5% of acid Water/trace acid

(14)

Solvent/acid/trace waterAcid/trace water

(15)(17)

Solvent recycle

(16) Water/trace acid(19)

(18)98% of acid

Glucose

FermentationBatch, 120h60 °C, 1 bar

Steam

Ultrafiltration25 °C, 1 bar

Raffinate (water/trace solvent)Counter current liq-liq

extraction25 °C, 1 bar

Distillation

100 °C, 1 bar

Acetic acid 99.5%

Solvent stripping (1)

110 °C, 1 bar

Solvent stripping (2)

130 °C, 1 bar

Page 23: Interim results Generic Approach Interim results

Ac.acid (2/5): AceticAc_TODAY_2_(Evap&Dist)

Seed (31)(3) (4)

Steam to plantCO2

(5) Nutrients SteamAuxiliaries Steam gen. exportProcess water 100% of acid

100 °C, 1 bar(28) Flue gas

water OPTION 2: Combustion (30)(7) Ash

(8) (29)Waste solids EvaporationWater/acid 100 °C, 1 bar

(9) 99% of acid 1% of acid OPTION 1:Filtered broth (10)

Water vapour(13) CO2

Water(14) recycle

Concentrated broth (12) to fermentor(11) Solvent/water 0.950

99% of acid 4% of acid 100 °C, 1 bar (19)(16) (15) solvent

Solvent top-up(21) (20)

Solvent recycle2% of acid water/solvent Bleed(water/trace solvent)25 °C, 1 bar (17) (18) 2% of acid

95% acetic acid98.5% of acid solvent bp? 0.050(22)

(23)Acetic acid

100 °C, 1 bar(26) (24)

Acetic acid recycle(27)

(25)Tars to furnace Acetic acid 99.5% ('glacial' acetic acid)

98% of acid

Condensation

X °C, 1 bar

Solvent stripping (2)

energy recovery

valuable by-product

02-protein enriched biomass

Condensation

Evaporation

Azeotropic Distillation

95 °C, 1 bar

Condensation

Decanter

100 °C, 1 bar

Purification still (Distillation)

130 °C, 1 bar

25 °C, 1 bar

Ultrafiltration25 °C, 1 bar

FermentationBatch, 120h

Storage, mixing

60 °C, 1 bar

Page 24: Interim results Generic Approach Interim results

Ac.acid (3/5): AceticAc_FUTURE_1_(Extraction)Water recycle

Seed (25)(3) (4)

(24)CO2 Bleed (water/acid)

(5) Nutrients CondensationAuxiliariesProcess water (7) 100% of acid Steam export

(21) Steam gen.Flue gas

(8) AshWaste solids Evaporation CombustionWater/acid 100 °C, 1 bar Conc. raffinate

(9) 99% of acid 1% of acid 2% of acid

Solvent: TOPO (10) Solvent make-up 1.5% of acid

(12)(11)

Extract (solvent/acetic acid/trace water) (20)(13) 98.5% of acid Water/trace acid

(14)

Solvent/acid/trace waterAcid/trace water

(15)(17)

Solvent recycle

(16) Water/trace acid(19)

(18)98% of acid

continuous60 °C, 1 bar

Glucose

Fermentation

Acetic acid 99.5%

25 °C, 1 bar

Solvent stripping (1)

110 °C, 1 bar

Solvent stripping (2)

Steam

130 °C, 1 bar

Distillation

100 °C, 1 bar

Ultrafiltration25 °C, 1 bar

Raffinate (water/trace solvent)Counter current liq-liq

extraction

Page 25: Interim results Generic Approach Interim results

Ac.acid (4/5): AceticAc_FUTUR_2_(Evap&Dist)

Seed (31)(3) (4)

Steam to plantCO2

(5) Nutrients SteamAuxiliaries Steam gen. exportProcess water 100% of acid

100 °C, 1 bar(28) Flue gas

water OPTION 2: Combustion (30)(7) Ash

(8) (29)Waste solids EvaporationWater/acid 100 °C, 1 bar

(9) 99% of acid 1% of acid OPTION 1:Filtered broth (10)

Water vapour(13) CO2

Water(14) recycle

Concentrated broth (12) to fermentor(11) Solvent/water 0.950

99% of acid 4% of acid 100 °C, 1 bar (19)(16) (15) solvent

Solvent top-up(21) (20)

Solvent recycle2% of acid water/solvent Bleed(water/trace solvent)25 °C, 1 bar (17) (18) 2% of acid

95% acetic acid98.5% of acid solvent bp? 0.050(22)

(23)Acetic acid

100 °C, 1 bar(26) (24)

Acetic acid recycle(27)

(25)Tars to furnace Acetic acid 99.5% ('glacial' acetic acid)

98% of acid

60 °C, 1 barCondensation

Fermentationcontinuous

energy recovery

Ultrafiltration 02-protein enriched biomass

25 °C, 1 bar

Solvent stripping (2)

95 °C, 1 bar X °C, 1 bar

valuable by-product

Evaporation

100 °C, 1 bar

Condensation

Condensation

Purification still (Distillation)

130 °C, 1 bar

Azeotropic Distillation Decanter

Page 26: Interim results Generic Approach Interim results

Ac.acid (5/5): AceticAc_FUTURE_3_(ED)

Water recycleSeed Glucose (25)

(3) (4)(24)

CO2 Bleed (water/acid)Nutrients CondensationAuxiliariesProcess water (7) Steam export

Steam gen.Flue gas

(8) AshWaste solids (21) Evaporation CombustionWater/acid 100 °C, 1 bar Conc. raffinate

(9)

(11)(20)

(13) Water/trace acid(14)

Solvent/acid/trace water

(15)

Steam

25 °C, 1 bar

Evaporation

Fermentationcontinuous

Water splitting ED

60 °C, 1 bar

25 °C, 1 bar

Acetic acid

115 °C, 1 bar

Ultrafiltration

There are three main possible approaches for organic acid recovery by electrodialysis (Kim and Moon, 2001; see also Lactic Acid):1. Two stage ED: a) desalting (i.e., or removal of acetic acid from nonionic species) b) water splitting for conversion to the acid c) with ion-exchange in between (because water splitting membranes get fouled by divalent cations)2. Nanofiltration + WSED3. One stage ED, which can be two or (better) three compartment

IS THIS ANOTHER HOW LONG IS THE STRING ISSUE?

- Ion exchange for polishing after evaporation?

Page 27: Interim results Generic Approach Interim results

Lactic acid

Overview of PFDs and authors

1.) LA_FUTURE_1_(Electrodialysis) UU/Literature, Tim Nisbet

The following PFDs are also included in this file but are not considered promising for the future

2.) LA_FUTURE_2_(Extraction)3.) LA_FUTURE_3_(SRIlowpH)4.) LA_FUTURE_4_(Adsorption)

Page 28: Interim results Generic Approach Interim results

LA (1/4): LA_FUTURE_1_(Electrodialysis)NutrientsProcess waterAuxiliaries

(2) (1)

Continuous sterilizer Continuous sterilizer130 °C, 20 min. 130 °C, 20 min.subsequent cooling subsequent cooling

Inoculum Pre-seed47 °C

Seed47 °C

Seed

(14) Base Exhaust gas to filterBase makeup (4)

(13)(3)

(6)Biomass

Purge(7) (5)

(9)(8) Base

Depleted broth recycle(10)

Water(12)

(11)

Lactic acid

Evaporation

Glucose

Fermentation 47 °C, pH 6.5

Microfiltration

Water splitting ED

Page 29: Interim results Generic Approach Interim results

LA (2/4): LA_FUTURE_2_(Extraction)

Seed

Acid Exhaust gas to filter

Organic extractantPurge Cells Extraction Purge

Back extraction Aqueous stripping phase

Heat stable grade lactic acid

Fermentation 47 °C, pH 3.9

Polishing: Carbon absorption

Evaporator

Polishing: Ion exchange

Polishing: Acidification

Page 30: Interim results Generic Approach Interim results

LA (3/4): LA_FUTURE_3_(SRIlowpH)

Seed

CaCO3 Exhaust gas to filter

Purge Biomass OctanolOctanol extraction

Extractant Aqueous phase Purge

Bottoms: solvent recycle

Octanol recycle

Water (recycled)

88 wt% Lactic acid

Vacuum evaporation

Decolorisation:

Ultrafiltration

Continuous fermentation, 47 °C, pH 3.9

Multiple stage continuous extraction

Vacuum distillation

Decantation

Page 31: Interim results Generic Approach Interim results

LA (4/4): LA_FUTURE_4_(Adsorption)

Seed

Acid Exhaust gas to filter

Purge Biomass

Eluant Spent broth

Lactic acid

Evaporation

Fermentation 47 °C, pH 3.9

Ultrafiltration

Adsorption

Page 32: Interim results Generic Approach Interim results

Adipic acid

Overview of PFDs and authors

1.) AdipAc_TODAY_1_(Cryst) UU/Literature, Tim Nisbet2.) AdipAc_FUTURE_1_(Cryst) UU/Literature, Tim Nisbet3.) AdipAc_FUTURE_2_(Electrodialys) Tim Nisbet

The following PFDs are also included in this file but are not considered viable

4.) AdipAc_TODAY_1_(Solvent)5.) AdipAc_TODAY_1_(Ester+Distill)

Page 33: Interim results Generic Approach Interim results

Ad.ac (1/5): AdipAc_TODAY_1_(Cryst)

(10)(11) Seed

Steam gen.(5) P2 medium nutrients

Auxiliaries SteamProcess water (6) cis,cis-Muconic Acid (ccMA) in broth req'd. Flue gas

Ash Waste solids (7) Evaporation Combustion

100 °C, 1 bar Conc. raffinate(8)

cis,cis-Muconic Acid (ccMA) in filtered broth

(9) Hydrogen (6)Catalyst cis,cis-Muconic Acid (ccMA), treated

(9) Adipic acid

(11)

Process water

(12)

Water recycle

(13)

(and some other acids)

Crystallizationca. 50 °C

Crystallization (Polishing)ca. 50 °C

Redissolutionca. 50 °C

Adipic acid 99.5%

Hydrogenationp=3400 kPa, 25 °C, 2.5 h

Activated carbon25 °C, 1 bar

Batch, 48h36 °C, 1 bar, pH=7

Ultrafiltration25 °C, 1 bar

Page 34: Interim results Generic Approach Interim results

Ad.ac (2/5): AdipAc_FUTURE_1_(Cryst)

(8) (9)(10)

Seed

(5) Steam gen.

Steam(6) cis,cis-Muconic Acid (ccMA) in broth req'd. Flue gas

Ash Purge Biomass Waste solids (7) Evaporation Combustion

100 °C, 1 bar Conc. raffinate(8)

cis,cis-Muconic Acid (ccMA) in filtered broth

Hydrogen (6)Catalyst cis,cis-Muconic Acid (ccMA), treated

(9) Adipic acid

(11)

Process water

(12)

Water recycle

(13)

(and some other acids)

Redissolutionca. 155 °C

Crystallization (Polishing)ca. 50 °C

Crystallizationca. 50 °C

Adipic acid 99.5%

Ultrafiltration25 °C, 1 bar

Hydrogenationp=3400 kPa, 25 °C, 2.5 h

Activated carbon25 °C, 1 bar

FermentationContinuous, 750 h36 °C, 1 bar, pH=7

Page 35: Interim results Generic Approach Interim results

Ad.ac (3/5): AdipAc_FUTURE_2_(Electrodialys)

(8) (9)(10)

Seed

(5) Steam gen.

Steam(6) cis,cis-Muconic Acid (ccMA) in broth req'd. Flue gas

Ash Purge Biomass Waste solids (7) Evaporation Combustion

100 °C, 1 bar Conc. raffinate(8)

cis,cis-Muconic Acid (ccMA) in filtered broth

Hydrogen (6)Catalyst cis,cis-Muconic Acid (ccMA), treated

(9) Adipic acid

(11)

(13)

(and some other acids)

FermentationContinuous, 750 h36 °C, 1 bar, pH=7

Ultrafiltration25 °C, 1 bar

Activated carbon25 °C, 1 bar

Hydrogenationp=3400 kPa, 25 °C, 2.5 h

Electrodialysisca. 50 °C ??

Adipic acid 99.5%

Crystallization (Polishing)ca. 50 °C

Page 36: Interim results Generic Approach Interim results

Ad.ac (4/5): AdipAc_TODAY_1_(Solvent)(8) (9)

(10)Seed

Steam exportSteam gen.

P2 medium nutrientsAuxiliaries SteamProcess water (6) cis,cis-Muconic Acid (ccMA) in broth req'd. Flue gas

Ash Waste solids (7) Evaporation Combustion

100 °C, 1 bar Conc. raffinate(6)

cis,cis-Muconic Acid (ccMA) in filtered broth

Hydrogen (6)Catalyst cis,cis-Muconic Acid (ccMA), treated

Adipic acid(9) Water/acid

(10)

Solvent make-up(12)

(11)Extractant

(13) Water/acid(14)

Possible solvents - ketone - methanol - ethanol Acid/water

(15)(17)

Solvent recycle

(16) Water/acid(19)

(18)

Raffinate (water phase)Counter current liq-liq

extraction

Activated carbon25 °C, 1 bar

Distillation

100 °C, 1 bar

Adipic acid 99.5%

Solvent stripping (1)

Conc. extractant

Solvent stripping (2)

Hydrogenation

p=3400 kPa, 25 °C, 2.5 h

130 °C, 1 bar

110 °C, 1 bar

Water vapour (to scrubber)

Ultrafiltration25 °C, 1 bar

FermentationBatch, 48h

36 °C, 1 bar, pH=7

25 °C, 1 bar

Page 37: Interim results Generic Approach Interim results

Ad.ac (5/5): AdipAc_TODAY_1_(Ester+Distill)

(8) (9)(10)

SeedSteam export

Steam gen.P2 medium nutrientsAuxiliaries SteamProcess water (6) cis,cis-Muconic Acid (ccMA) in broth req'd. Flue gas

Ash Waste solids (7) Evaporation Combustion

100 °C, 1 bar Conc. raffinate(8)

cis,cis-Muconic Acid (ccMA) in filtered broth

Hydrogen (6)Catalyst cis,cis-Muconic Acid (ccMA), treated

(9) Adipic acid

Methanol(11)

Methyl esters

(10)(12)

(13)

(and some other acids)Adipic acid 99.5%

Activated carbon25 °C, 1 bar

Esterification

Distillation

TO BE LOOKED UP

36 °C, 1 bar, pH=7

Ultrafiltration25 °C, 1 bar

TO BE LOOKED UP

Hydrogenationp=3400 kPa, 25 °C, 2.5 h

TO BE LOOKED UP

Hydrogenation

Water vapour (to scrubber)

FermentationBatch, 48h

Page 38: Interim results Generic Approach Interim results

Succinic acid

Overview of PFDs and authors

1) SA_TODAY_1_(Cryst) UU/Lit.

2) SA_TODAY_2_(1stageED) TNOs concept of a succinic acid plant in report R 2002/669, Meesters (2002)

3) SA_FUTURE_1_(Cryst) UU/Lit.

4) SA_FUTURE_2_(2stageED) SRIs design for a succinic acid plant in PEP report 236

Questions to industry experts:

- Which of the two ED options should we assume for the future?- Is it reasonable to assume also crystallization for the future?-

Detailed question- Should there be water recycle from solid biomass also in the case of fed-batch processes?

Page 39: Interim results Generic Approach Interim results

Succ.ac (1/4): SA_TODAY_1_(Cryst)

Seed(11)

P2 medium nutrients (5) Bleed (water/acid)Auxiliaries Condensation

Process water(6) Steam export

Steam gen.Steam Flue gas

Ash Purge Biomass Waste solids Evaporation Combustion

(7) 100°C, 1 bar Conc. raffinate(8)

(6)

(11)

Process water

(12)

Water recycle

(13)

(and some other acids)

Crystallization 10°C (?)

Succinic acid 99.5%

Crystallization10°C (?)

Redissolution150°C (?)

25°C, 1 bar

60 h36°C, 1 bar, pH=7

Ultrafiltration25°C, 1 bar

Fed-batch

Activated carbon

Taken over from AdipAc_FUTURE_1_(Cryst)

Page 40: Interim results Generic Approach Interim results

Succ.ac (2/4): SA_TODAY_2_(1stageED)Seed

Exhaust gas to filter Bleed (water/acid)Condensation

Storage Steam exportSteam gen.

Steam Flue gasAsh

Water Microfilter Biomass Evaporation Combustion100°C, 1 bar Conc. raffinate

Nanofilter Water

Electrodialysis NaOH

Bleed Filtrate Filtration

Drying Water

Succinic acid

Fed Batch Fermentation, 39°C,

pH 7

Crystallization by cooling, 25C

Page 41: Interim results Generic Approach Interim results

Succ.ac (3/4): SA_FUTURE_1_(Cryst)Seed(11)

P2 medium nutrients (5) Bleed (water/acid)Auxiliaries Condensation

Process water(6) Steam export

Steam gen.Steam Flue gas

Ash Purge Biomass Waste solids Evaporation Combustion

(7) 100°C, 1 bar Conc. raffinate(8)

(6)

(11)

Process water

(12)

Water recycle

(13)

(and some other acids)

Continuous750 h

36°C, 1 bar, pH=7

Ultrafiltration25°C, 1 bar

Activated carbon25°C, 1 bar

Crystallization10°C (?)

Redissolutionca. 155°C

Crystallization 10°C (?)

Adipic acid 99.5%

Taken over from AdipAc_FUTURE_1_(Cryst)

Page 42: Interim results Generic Approach Interim results

Succ.ac (4/4): SA_FUTURE_2_(2stageED)Fermenters (9), 39°C Exhaust gas to filter Bleed (water/acid)

<200 kg/hr167223 kg/hr

Steam exportSteam gen.

Steam Flue gasAsh

Water Ultrafilter Waste solids Evaporation36054 kg/hr (7) 100°C, 1 bar Conc. raffinate

187654 kg/hr 15624 kg/hr

20627 kg/hr Electrodialysis, 45°C

167027 kg/hr

Ion exchange (2)

87886 kg/hr

79141 kg/hr

Purge56197 kg/hr

13404 kg/hr Centrifuges (3)

Dryer

Packaging

Succinic acid9541 kg/hr

Crystallization 2 stages, 30 C, vacuum

Condensation

Combustion

Bipolar electrodialysis, 45°C

Page 43: Interim results Generic Approach Interim results

Citric acid

REFINED SUCROSE (a) Fungi: Aspergillus nigerFermentation medium (b)

Nutrients Sucrose* 140 g/lNH4NO3 2.5 g/l

Inoculo KH2PO3 2.5 g/lMgSO4.7H2O 0.25 g/l

Air Cu2+ 0.00006 g/lZn2+ 0.00025 g/lFe2+ 0.0013 g/l

(1) Mn2+ 0.001 g/l* optimal concentration sucrose 10-14% (2)

Wash water (2) (3) Wet biomass

(4) (5) Water

Raffinate (8)

(6) Recycled- extractant

(19) (9) (7)

(11)

(10)Water

(12)

(13)Water

(14) Mother liquid

(15)

(16)

(17)Water

(18)

(19)

(20) Citric acid monohydrate

(21)

(22)

FERMENTATION(b)

30ºC, 1atmcycle: 6-7days

FILTRATIONRotary Filter25ºC

STORAGE

EVAPORATION(c)

Multiple effect evaporation 100ºC, 0.9 atm

EXTRACTION(d1)

4 stages65ºC, 1atm

WASHING(d2)

65ºC, 1atm

BACK-EXTRACTION(d3)

4 stages50ºC, 1atm

EVAPORATION(e)

Multiple effect evaporation100ºC, 0.9 atm

ACTIVATED CARBON2 fixed-bed columns25ºC

CRISTALIZATION(f)

25ºC, 1atm

FILTRATION/DRYING/PACKING

Page 44: Interim results Generic Approach Interim results

(11) Seed

Steam gen.(6) P2 medium nutrients

Auxiliaries SteamProcess water (7) req'd. Flue gas

Ash Waste solids (8) Evaporation Combustion

100 °C, 1 bar Conc. raffinate(9)

(10)

WHAT? Residual salts Salt(11) (12) disposal

Caprolactam(13)

(12)

Solvent (which?) recycle

(13)

FermentationBatch, 120h60 °C, 1 bar

Ultrafiltration25 °C, 1 bar

Chemical transformationAssume: Similar to adipic

Caprolactam

ca. 50 °C

Crystallization (Polishing)

ca. 50 °C

acid hydrogenation

Conversion to caprolactam

Redissolution

*) According to DSM [1-3] fermentation yields a precursor which is converted to caprolactam (under release of salts). The name/type of the precursor is kept confidential by DSM. We assume here that this could bea) an alcohol (e.g. 6-Aminohexanol; bp=ca. 135C; mp = ca. 57C) or a derived ester (e.g. 6-Aminohexanoate; compare [4]) orb) an acid such as aminocaproic acid (mp=210C; acc. to [5] caprolactam is quantitatively converted to e-aminocaproic acid by hydrolysis with aqueous acids or alkalis)

Another option might be the production of alpha-Amino-epsilon-caprolactam (ACL) via the lysine production route. See Ritz et al. in Ullmann's [5]

**) Compare Ritz et al. in Ullmann's [5]

Caprolactam (1/1): CL_FUTURE_1_GEN

Page 45: Interim results Generic Approach Interim results

Lysine (1/2): Lysine_TODAY (IonExch)Seed Water recycle

(25) (24)Exhaust gas to scrubber Bleed (water/acid)

Condensation

Steam exportSteam gen.

Steam Flue gasAsh

Sulfuric acid Biomass (21) EvaporationWater to waste treatment 100 °C, 1 bar Conc. raffinate

Deionized waterEluant (dilute NH4OH) Effluent Wastewater Disposal

treatment

Vent to scrubberWater

HCl

Water

Filtrate

Water

L-lysine HCl 98.5%

Combustion

Continuous vacuum crystallization

Filtration

Continuous fluidized bed drying

Packaging

Fed Batch Ferment., air-lift 1 vvm, 35 °C,

pH 7-7.5

Ultrafilter

Double effect vacuum evaporation

Polishing: Activated carbon, acidification

Continuous ion-exchange

Page 46: Interim results Generic Approach Interim results

Lysine (2/2): Lysine_FUTURE_1_(ADS)

For Lysine_FUTURE_1_(ADS): Is it realistic to assume that Ultrafiltration can be skipped before adsorption (Degussa patent)?

Seed

Air Exhaust gas to scrubber

Purge Effluent broth

Eluantdilute H2SO4

Water

Water

Filtrate

Air Water

L-lysine sulfate 98.5%

Continuous vacuum crystallization

Filtration

Continuous fluidized bed drying

Packaging

Continuous Fermentation, air-lift 1 vvm, 40°C, pH7-7.5

Adsorption, zeolite bed

Double effect vacuum evaporation

Polishing: Activated carbon decolorization

Page 47: Interim results Generic Approach Interim results

PHA (1/2): PHA_TODAY_1_(Extraction)Water recycle

Seed (25)(3) (4)

(24)CO2 Bleed (water/acid)

(5) Nutrients CondensationAuxiliariesProcess water (7) Steam export

(21) Steam gen.Flue gas

(8) AshWaste solids Evaporation CombustionWater/acid 100 °C, 1 bar Conc. raffinate

(9)

(10) Solvent make-up

(12)(11)

Extract (solvent/PHA/trace water) (20)(13) Water/trace PHA

(14)

Solvent/PHA/trace water

Solvent recycle (15)

(16)

(18)

25 °C, 1 bar

Polishing? (how?)

100 °C, 1 bar

PHA

Solvent stripping

110 °C, 1 bar

Cristallization

10°C?, 1 bar

Steam

Ultrafiltration25 °C, 1 bar

Raffinate (water/trace solvent)Counter current liq-liq

extraction

Glucose

FermentationBatch, 120h60 °C, 1 bar

Page 48: Interim results Generic Approach Interim results

PHA (2/2): PHA_FUTURE_1_(Extraction)Water recycle

Seed (25)(3) (4)

(24)CO2 Bleed (water/acid)

(5) Nutrients CondensationAuxiliariesProcess water (7) Steam export

(21) Steam gen.Flue gas

(8) AshWaste solids Evaporation CombustionWater/acid 100 °C, 1 bar Conc. raffinate

(9)

(10) Solvent make-up

(12)(11)

Extract (solvent/PHA/trace water) (20)(13) Water/trace PHA

(14)

Solvent/PHA/trace water

Solvent recycle (15)

(16)

(18)

Glucose

FermentationBatch, 120h60 °C, 1 bar

Steam

Ultrafiltration25 °C, 1 bar

Raffinate (water/trace solvent)Counter current liq-liq

extraction25 °C, 1 bar

Solvent stripping

110 °C, 1 bar

Cristallization

10°C?, 1 bar

Polishing? (how?)

100 °C, 1 bar

PHA

Page 49: Interim results Generic Approach Interim results

Technology frontiers (“How long is the string?“)

Membrane: f(polarity) see e.g. PDO and LA Electrodialysis: i) 2-stage ii) NF + WS-ED iii) 1-stage Extracellular PHA [(Bio-based) Syngas as feedstock ] (Bio-based) Methanol as feedstock Biotechnological methanol

Page 50: Interim results Generic Approach Interim results

Products selection

O:\BREW\WPs\WP2(TechnoEcon)\CostData\Prices\PriceBREWproducts_1.xls

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

Ethan

ol

Aceto

ne (M

MA g

rade

)

Ethyle

ne

Aceto

ne (n

on-M

MA)

n-But

anol

Gluc

onic

acid

Acetic

acid

Ethyle

ne g

lycol

buty

l eth

erM

EK

Acrlyl

onitr

ile

Pheno

l

Citric

acid

(bulk

pric

e)

Adipic

acid

Glyc

erol

Lact

ic ac

id

Capro

lacta

m

Fumar

ic ac

id

Acryla

mide

Sebac

ic ac

id

Lysin

e

Source: Chemical Market Reporter, April 26, 2004.

Price (EUR/kg)

Page 51: Interim results Generic Approach Interim results

Collection of energy data

…jump to Shortcut to GenericEnergy_1.xls

Page 52: Interim results Generic Approach Interim results

O:\WPs\WP2(TechnoEcon)\Generic_approach\Separation\ChainCompar\&[File]

Generic Approach - Comparative energy analysis (1/3)

Case 1PDO by fermentation Comparision to PEP's utilities summary (see PEP 227)

Calc. PEP result Calc. PEP result Calc. PEP result Calc. PEP result %

Calculation kW 1,570 1,387 184 0 14,877 191%calibratedtoSRI kW 665 482 184 0 6,301 23%Calculation M LB/hr 40 0 40 0 45,360 -14%calibratedtoSRI M LB/hr 40 0 40 0 45,360 -14%Calculation M LB/hr 60 0 0 60 66,754 39%calibratedtoSRI M LB/hr 48 0 0 48 54,150 12%

Main processes involved - pre-seeding, seeding - Evaporation - Dewatering (single-effect, single-stage evap.)-fermentation (two stage) - Purification (multi-stage, multi-effect distillation)-ultrafiltration

Case 2Lactic acid by fermentation (PH=6)Comparision to PEP's utilities summary (see PEP 96-7)

Calc. PEP result Calc. PEP result Calc. PEP result Calc. PEP result %

Calculation kW 1,514 1,320 194 0 14,340 27%calibratedtoSRI kW 1,096 922 174 0 10,385 -8%Calculation M LB/hr 93 55 34 4 104,453 73%calibratedtoSRI M LB/hr 24 16 4 4 27,411 -55%

Main processes involved: - sterilization -agitation -base regeneration reaction-fermentation -product evaporation (multi-effect)-ultrafiltration-broth evaporation (multi-effect)

Case 3Lactic acid by fermentation at low PHComparision to PEP's utilities summary (see PEP 236)

Calc. PEP result Calc. PEP result Calc. PEP result %

Calculation kW 2,219 2,117 101 21,021 170%calibratedtoSRI kW 837 634 203 7,929 2%Calculation M LB/hr 8 8 0 9,255 38%calibratedtoSRI M LB/hr 8 8 0 9,255 38%Calculation M LB/hr 175 0 175 196,437 -26%calibratedtoSRI M LB/hr 214 0 214 239,817 -10%

Main processes involved: -sterilization -distillation-preseeding, seeding -vacuum evaporation-fermentation-ultrafiltration

Section 300

6,724

MJp / hr

7,797

265,592

Total Primary

MJp / hr

540 469 63 8 5,116

Total Section 100 Section 200

52,670

43 0 0 43 48,188

47 1 46 0

Electricity

Steam, 150 PSIG

Steam, 600 PSIG

Total Section 100 Section 200 Section 300 Total Primary

MJp / hr

Electricity 1,194 864 237 93 11,312

Steam, 150 PSIG 54 42 8

Total Section 100

4 60,515

Section 200 Total

Electricity 823 585 238

Steam, 150 PSIG 6 6 0

Steam, 600 PSIG 237 0 237

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Case 4Succinic acid by fermentationComparision to PEP's utilities summary (see PEP 236 p8-10)

Own Calc. PEP result Own Calc. PEP result Own Calc. PEP result %

Electricity Calculation kW 19,800 1,491 18,309 187,584 3%calibratedtoSRI kW 17,980 1,491 16,489 170,337 -7%

Steam, 150 PSIG Calculation M LB/hr 104 4 100 116,847 15%calibratedtoSRI M LB/hr 79 4 74 88,066 -14%

Main processes involved: -sterilization -Two-stage electrodialysis-fermentation -Crystallization-ultrafiltration -Centrifugation

Case 5Lysine-sulfate by fermentation with recovery by spray dryingComparision to PEP's utilities summary (see PEP Review 97-8)

Own Calc. PEP result Own Calc. PEP result Own Calc. PEP result %

Electricity Calculation kW 23,216 22,048 1,168 219,942 100%calibratedtoSRI kW 11,153 10,401 752 105,662 -4%

Steam, 150 PSIG Calculation M LB/hr 68 0 68 75,963 36%calibratedtoSRI M LB/hr 48 0 48 54,331 -3%

Main processes involved: - fermentation -double effect evaporation - ultrafiltration - spray drying - acidification

Case 6Lysine-HCl by fermentation with recovery by ion-exchangeComparision to PEP's utilities summary (see PEP Review 97-9)

Own Calc. PEP result Own Calc. PEP result Own Calc. PEP result %

Electricity Calculation kW 21,661 21,458 203 205,209 111%calibratedtoSRI kW 10,014 9,811 203 94,869 -3%

Steam, 150 PSIG Calculation M LB/hr 32 5 28 36,375 -17%calibratedtoSRI M LB/hr 32 5 28 36,375 -17%

Main processes involved: - sterilization - evaporation (multi-effect) - pre-seeding - acidification - seeding - crystallization - fermentation - drying - ultrafiltration

39 4 35 43,705

MJP / hr

10,285 9,806 479 97,437

Total Section 100 Section 300 Total Primary Energy

Section 100 Section 200

19,302

Total

91

1,889

6

17,413

85

182,861

101,978

Total Primary

MJ p / hr

Total Section 100 Section 200 Total Primary Energy

MJP / hr

11,614 10,868 746 110,027

50 0 50 56,032

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Generic Approach - Comparative energy analysis (2/3)

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O:\WPs\WP2(TechnoEcon)\Generic_approach\Separation\ChainCompar\&[File]

Generic Approach - Comparative energy analysis (3/3)

Case 7 Enzyme productionComparision to PEP Review 99-6. Comparision is only in section 100.

Own Calc. PEP result Own Calc. PEP result Own Calc. PEP result %

Electricity Calculation kW 1,802 1,797 5 17,024 450%calibratedtoSRI kW 329 324 5 3,069 -1%

Porcesses involved: - aerobic fermentation - ultrafiltrationNeglected processes:Cyclon, bag filtration, rotary drum filtration, conveying,mixing and storage, packaging and agitation in feed tanks.

Total Section 100 Section 200Total Primary Energy

In SECTION 100

MJP / hr

567 327 240 3,098

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O:\WPs\WP2(TechnoEcon)\Generic_approach\Separation\ChainCompar\&[File]

Calibrated energy data for the Generic Approach

Unit 2nd 1st Range SuperPro Calibrated to SRIEnergy consumption of fermentation operations chosen chosen

Sterilization kg steam/kg ferm. medium 0.1 0.1 0.1 - 0.8 - 0.1

Agitation kW/m3 of fermentation 0.5 1 0.1 - 12 0.10.25-0.5

1

kW/m3 3.5 5 4 - 6 - -vvm 1 0.2 - 2 0.5 -

Agitation and Aeration kW/m3 3 6 1 - 5 32.7

1.08CoolingEnergy consumption of seperation operations

1.5 1.5 0.7 - 2.5 - 1.57 7 6.2 - 25 -

Membrane Filtration - Microfiltration 2 2 1.2 - 2.6 2.5

- Ultrafiltration 5 5 3.5 - 16 2.5 2.5, 5

- Diafiltration 5 5 5 2.5 - Nanofiltration 7 7 1 - 7 - - Reverse osmosis 9 9 4.6 - 10 2.5

kg steam/kg productsee

below*)2 0.9 - 4.4 -

0.522.5

3.75MJe/kg product - - 0.07-0.14 -

Electrodialysis kWh/eq. 0.1 0.1 0.07 - 0.34 - 0.09kg steam/kg evap. 1.2 1.2 0.005 - 1.4 1.0764 1.20kWh/kg evap. 0.04 0.04 0.04 - 0.04

kg steam/kg evap.0.1-0.5

(depends on stages)

0.5 0.01 - 1.25 1.0764 0.06, 0.12, 0.3, 0.5

kWh/kg evap. 0.005 0.005 0.002 -0.0344 - 0.005, 0.01

kW/m2 exchanger surface 2.61 2.61

kg steam/kg evap.~0.8

(depends on stages)

0.8073 1.0764 0.6-0.8073

kg steam/kg evap. 1.5 1.5 0.24 - 3 2 1.25 - 1.5kWh/kg evap. 0.1 0.1 0.1 - 1 - 0.06-0.1

4.25 4.25

2.5 - 2.51 1

*) Estimation of energy use for distillation by multiplying the heat of evaporation by a reflux factor of 1.3. The heat requirements of the distillation column may be reduced substantially by vacuum. Electricity demand to generate vacuum can be negligible gy use for distillati

Aeration

Centrifugation

Drying

Evaporation

Distillation

Crystalisation

kWh/m3 permeate

kWh/m3 feed

Refrigeration kWh refrigeration /kWh power

Seperation processes that have not been verified/calibrated: - Microfitration - Diafiltration - Nanofiltration - Reverse osmosis

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Additional slides

Interim resultsInterim results

  

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Sugarcane price summary

Price Price$/t $/t

dry cane sugarBrazil 1990 10.08 72 1) C&T Brasil (2001)

Brazil 1999-00 9.55 68 ASSOCANA (2001)

Thailand 1997-98 13.98 100 2) Thailand - Office of Agricultural Economics (2001)

1999-00 11.42 82 2) Thailand - Office of Agricultural Economics (2001)

South Africa 1998-99 21.58 154 South African Sugar Association

1999-00 18.58 133 South African Sugar Association

2000-01 19.58 166 South African Sugar Association

2001-02 24.03 203 South African Sugar Association

2002-03 25.68 210 South African Sugar Association

United States 1997 25.42 182 3) US Department of Commerce (1999)

United States 1992 34.16 244 3) US Department of Commerce (1999)

United States (Hawaii)

1995-97 21.25 4) 152 5) Kinoshita and Zhou (1999)

Country Year Reference

Prices of sugar from sugarcane (reproduction with kind permission from Tim Nisbet, Shell)

CHECK WITH TIM NISBET

• WHETHER USE IS OK

• DISCUSS: TAKE ONE SINGLE PRICE FOR SUGARS TODAY OR DISTINGUISH BETWEEN ORIGINS (SUGARCANE ETC?

Assumed prices of fermentable sugar in Europe (NREL, 2002)

CurrentPotential near term

Year 2005 Year 2010Year 2010 -

Large capacity

Minimum sugar selling price (US $/t)

187 147 115 105 71

L:\BioBasedMat_Lit\feedstocks\sugars\Sugar_price\ Updated Sugar Price.xls

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L:\BioBasedMat_Lit\feedstocks\sugars\Sugar_cane\Sugarcane_feedstock_A_2.xls\Sheet Definition NREU and REU

Energy use and GHG emissions of sugar cane use

AVERAGE (medium sucrose content)

NREU REU TEU GHG6)

Current yield

Long term yield

Sugarcane production1)

1.9 48.0 49.9 185 0.153 0.082

Sugar processing3)

0.1 (10.0) (10.1) 6 -- --

Bagasse combustion (27.0) (27.0) -- --

Gross energy use4)

2.0 48.0 50.0 191 -- --

Exported power (surplus),

in primary energy terms 5) 16.9 -745 --- --

Net values -14.9 48.0 33.0 -364 0.153 0.082

1) Agricultural operations, transporation, fertilizers etc.2) Calorific value of sugar cane3) Milling, chemicals and evaporation

6) Sequestration of carbon from the atmosphere into products is not included in these values.

Land use

kg CO2 eq/t sucrose

GJprim/t sucrose

GJprim/t sucrose

GJprim/t sucrose

ha/t sucrose

5) Identical with bagasse input for export of power because multiplication with power generation efficiency leads to power output and division by the same efficiency gives power output in primary energy equivalents.

4) Calculated as total but excluding the the values in brackes since these are already included in the calorific value of sugarcane (48.0 GJ/t sucrose)

2)

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L:\BioBasedMat_Lit\feedstocks\sugars\Sugar_cane\Sugarcane_feedstock_B_2.xls\Sheet Definition NREU and REU

Energy use and GHG emissions of sugar cane use

ADVANCED (high sucrose content)

NREU REU TEU GHG6)

Current yield

Long term yield

Sugarcane production1)

1.4 33.9 35.3 131 0.108 0.058

Sugar processing3)

0.1 (7.1) (7.1) 4 -- --

Bagasse combustion (19.1) (19.1) -- --

Gross energy use4)

1.4 33.9 35.3 135 -- --

Exported power (surplus),

in primary energy terms 5) 12.0 -527 --- --

Net energy use and emissions -10.5 33.9 23.4 -257 0.108 0.058

1) Agricultural operations, transporation, fertilizers etc.2) Calorific value of sugar cane3) Milling, chemicals and evaporation

6) Sequestration of carbon from the atmosphere into products is not included in these values.

Land use

ha/t sucrose

4) Calculated as total but excluding the the values in brackes since these are already included in the calorific value of sugarcane (48.0 GJ/t sucrose)5) Identical with bagasse input for export of power because multiplication with power generation efficiency leads to power output and division by the same efficiency gives power output in primary energy equivalents.

GJprim/t sucrose

GJprim/t sucrose

GJprim/t sucrose

kg CO2 eq/t sucrose

2)

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Approach chosen in BREWtool

Energy use Energy useREU

(gross) REU

Co-production ofelectricity (in primaryenergy terms)

NREU(gross)

NREU

Energy credit Energy credit

Alternative approach (not applied in BREWtool)

Energy use Energy useREU

(gross)

Co-production ofelectricity (in primaryenergy terms) REU

NREU NREU(gross) (gross)

Energy credit Energy credit L:\BioBasedMat_Lit\feedstocks\sugars\Sugar_cane\Sugarcane_feedstock_A_2.xls\Sheet Definition NREU and REU

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