Interim results Generic Approach Interim results.
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Transcript of Interim results Generic Approach Interim results.
Generic Approach
Interim resultsInterim results
Goal
• Copyright
• Longer timeframe
- Current state of technology as benchmark
- BUT MAIN GOAL: Develop NEW process flow diagrammes (PFDs), two main reasons
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
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)
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
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)
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
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 ?
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?-
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?
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?
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.
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.
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.
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?
Ethanol
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.
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
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
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)
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].
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
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
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
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
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?
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)
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
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
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
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
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)
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
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
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
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
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
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?
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)
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
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)
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
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
(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
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
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
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
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
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
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)
Collection of energy data
…jump to Shortcut to GenericEnergy_1.xls
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
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
O:\WPs\WP2(TechnoEcon)\Generic_approach\Separation\ChainCompar\&[File]
Generic Approach - Comparative energy analysis (2/3)
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
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
Additional slides
Interim resultsInterim results
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
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)
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)
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