ABE Fermentation

Production of butanol by the anaerobic fermentation is one of the oldest industrial method for obtaining this organic solvent. Butanol can be obtained using several chemical technologies. It is also possible to produce butanol in the process of fermentation by means of bacteria of the genus Clostridium. This process occurs under anaerobic conditions, and butanol as one of the products - called Biobutanol. The most popular bacteria species used for fermentation is Clostridium acetobutylicum. Such fermentation is so called ABE (acetone-butanol-ethanol), due to the names of the main products of this process, the typical ratio of these compounds being 3:6:1. The final concentration of butanol is about 3% In the course of industrial production of Biobutanol, using a fermentation process one must take into account three factors, evaluation of the process profitability: the cost of raw material and its pretreatment, a relatively small amount of product obtained its significant toxicity, cost of product recovery from fermentation broth. Clostridium acetobutylicum belongs to the amylolytic bacteria; therefore a good substrate for production of butanol for these bacteria is starch. Nevertheless, the use for the fermentation crop products is not very economical, primarily because of too high price due to demand for these products from food industries. Therefore, for the production of butanol there are commonly used agricultural wastes for example: straw, leaves, grass, spoiled grain and fruits etc which are much more profitable from an economic point of view. One looks for other sources of plant biomass, which production does not require a lot of work and costs (e.g. algae culture) Modern research on the production process of Biobutanol focuses on finding the best kind of substrate for fermentation process and for efficient strain of bacteria. Potentially, one can use all the waste containing monosaccharide, and polysaccharides and waste glycerol. Analogously, the biomass of algae is one example of such a substrate. Algae culture does not require intensive labor and high costs. Some of the micro-algae contain relatively high percentage of sugars in dry matter, such as Chlorella contains about 30-40% of sugars, which greatly increases their usefulness in the production of Biobutanol. There is also carried out research on the genetic modification the bacteria Clostridium acetobutylicum and Clostridium beijerinckii in order to increase the resistance of bacteria to the concentration of butanol in the fermentation broth.

Process Description:
The process is divided into two major sections: the fermentation section, where the pretreated glucose is converted to acetone, butanol, and ethanol by a novel strain of Clostridium and the separation section, where acetone, butanol, and ethanol are separated to streams of the purity needed for sale. Fermenter has a heat exchanger that removes the heat generated in the reaction at transfers it to cooling water. The cells are used in fermentation batch and then they are dried to 9% moisture and sold as fertilizer, keeping the time each cell is used under the 500 hours successfully used by Ezeji, Qureshi, and Blaschek (2005). To avoid contamination, all of the incoming feed is sterilized in a pasteurizer consisting of two heat exchangers. First, the fresh feed is contacted with the recently sterilized feed, to cool the outgoing feed and pre-heat the incoming feed. The fresh feed is then heated to 212F with low-pressure steam and held for five minutes before being considered sterile, when it is then contacted with fresh, cool incoming feed. In addition to sterilizing the feed, the process also has regular built-in cleaning time for the fermentation section, when the fermentation vessels are cleaned with caustic. Estimation for the amount of caustic required for this process is obtained by scaling up an estimate for the ethanol process by McAloon et al. (2000). With these procedures in place, according to the problem statement, the plant still suffers from, on average, one contaminated batch in fermenter every 11 days. For this reason, a scale-up produces 36 enough cells to seed the growth phase tanks every 11 days. The liquid fermentation products are pumped from the fermenters into a holding tank so that the fermentation section can be run in batch mode but the separation can be run continuously. The products are first fed into a gas stripper, in which N2 is fed into the bottom and strips the organics from the water. The bottoms water stream is then divided into two streams, one that is recycled back to the fermenters and the other that is sold back to the mill to keep the process zero-discharge. Since any water sold back to the mill must have less than 10 ppm organics, the water is first sent through a steam heat exchanger and a phase separator to concentrate the water stream. This phase separator produces an ethanol impurity stream that is fed into a decanter with the stripper condensate, consisting mostly of acetone, butanol, water, and ethanol. The decanter produces two liquid streams, one butanol-rich stream containing most of the acetone and ethanol and a water-rich stream containing small concentrations of organics. This water-rich stream is recycled back to the fermentation section to avoid the loss of product. The organic stream containing most of the products are sent to molecular sieves, which dehydrate the stream, eliminating the butanol-water and ethanol-water azeotrope and greatly simplifying the distillation sequence. The water stream is also recycled back to the fermenters and the organic stream is fed into two distillation columns, one that takes butanol off in the bottoms, at 99.9% purity, and one that separates acetone at 99.5% purity and ethanol at 99.5% purity. These are the necessary purity specifications for sale. The ethanol is denatured with 5% gasoline to prevent human consumption.

Material balance
95CHO -----------> 60CHOH +30CHCOCH +10CHOH +220CO +120H +30HO A:B:E = 3:6:1 Capacity: 500 TPA Working Days per Year: 300 Time required for one batch: 264 (11days) Total batches run per year: 27.2727

Material balance across pretreatment of wheat straw:

32 gm. Of glucose = 100 gm. Of WS 1kg. of glucose = (.1/.032) kg. Of WS 78453.439 kg. of glucose = 201162.66 kg. Wheat straw (for one batch) Total wheat straw required = 5,486,254.364 kg.

Material balance across the reactor:

95CHO -----------> 60CHOH +30CHCOCH +10CHOH +220CO +120H + 30HO 95*180=17100kg. 60*74=4440kg. 30*18=540kg. S. No. 1 2 3 4 5 6 7 8 Component Glucose Water Microbes Acetone Butanol Ethanol CO H 30*58=1740kg. 10*46=460kg. 220*44=9680kg. 120*2=240kg. Outlet (kg.) 7845.344 237590.05 7845.34 7184.68 18333.33 1899.399 39969.96 990.99 Output = 321659.093 kg. 4

Inlet (kg.) 78453.439 235360.32 7845.34 0 0 0 0 0 Input = 321659.099 kg.

Material Balance across Gas Stripper:

Stream No. Flow rate (kg. /hr) Comp. Composition Acetone Butanol Ethanol Water Nitrogen CO H Glucose 0.008 0.016 0.003 0.970 0.000 0.00003 0.000 0.003 0.000 0.000 0.000 0.000 1.000 0.000 0.000 0.000 0.02 0.001 0.002 0.003 0.96 0.006 2*10^-6 0.000 0.04 0.04 0.008 0.02 0.88 0.005 2*10^-6 0.000 8*10^-7 8*10^-7 6*10^-5 0.99 0.000 0.000 0.000 0.003 1 1188.61 3 4773.52 7 500.46 4 4879 11 1067.54

Material Balance across splitter :

Stream No. Flow rate (kg. /hr.) Comp. Composition Acetone Butanol Ethanol Water N CO H Glucose 0 0 6*10^-5 0.99 0 0 0 0.003 0 0 6*10^-5 0.99 0 0 0 0.003 8*10^-7 8*10^-7 6*10^-5 0.99 0.000 0.000 0.000 0.003 12 533.77 13 533.77 11 1067.54

Material balance across Phase separator:

Stream No. 14 15 16 5

Flow rate (kg. /hr.) Comp. Composition Acetone Butanol Ethanol Water N CO H Glucose

533.77

10.30

523.46

0 0 6*10^-5 0.99 0 0 0 0.003

0 0 1*10^-5 0.99 0 0 0 3.4*10^-3

0 0 1*10^-5 0.99 0 0 0 3.4*10^-3

Material balance across 2nd phase separator:

Stream No. Flow rate (kg. /hr.) Comp. Composition Acetone Butanol Ethanol Water N CO H Glucose 0.025 0.001 0.002 0.003 0.963 0.006 2*10^-6 0.000 0.024 0.001 0.002 0.003 0.96 0.006 0 0.000 0.236 0.475 0.077 0.206 0.006 4*10^-4 0 0 0.04 0.04 0.008 0.02 0.88 0.005 2*10^-6 0.000 6 4007.49 8 3507.03 9 402 5 4879

Material Balance across Decanter:

Stream No. Flow rate (kg. /hr.) Comp. Composition 6 20 77.54 21 334.76 17 402 19 10.30

Acetone Butanol Ethanol Water N CO H Glucose

8*10^-5 8*10^-5 1.6*10^-3 0.99 0 0 0 0

0.284 0.571 0.093 0.046 6.7*10^-3 4.6*10^-4 0 0

0.236 0.475 0.077 0.206 0.006 4*10^-4 0 0

0 0 1*10^-5 0.99 0 0 0 3.4*10^-3

Material Balance across Molecular sieve:

Stream No. Flow rate (kg. /hr.) Comp. Composition Acetone Butanol Ethanol Water N CO H Glucose 0.047 0.095 0.015 0.753 0.083 0.007 0 0 0.299 0.602 0.098 1.23*10^-4 1.78*10^-3 0 0 0 0.281 0.571 0.093 0.046 6.7*10^-3 4.6*10^-4 0 0 27 140.44 25 136.59 23 167.38

Material Balance across Distillation Column1:

Stream No. Flow rate (kg./hr.) Comp. Composition Acetone Butanol 0.299 0.602 0.753 5.4*10^-4 0.31 0 1.5*10^-4 0.999 7 28 273.18 29 108.40 30 0.0804 31 164.56

Ethanol Water N CO H Glucose

0.098 1.2*10^-4 1.7*10^-3 0 0 0

0.246 2.3*10^-4 3.8*10^-4 0 0 0

0.036 0 0.646 0 0 0

6.1*10^-4 0 0 0 0 0

Material Balance across Distillation Column2:

Stream No. Flow rate (kg. /hr.) Comp. Composition Acetone Butanol Ethanol Water N CO H Glucose 0.995 0 4.2*10^-3 3.09*10^-4 5.15*10^-4 0 0 0 0.454 0 0 0 0.636 0 0 0 2.55*10^-3 2.23*10^-3 0.995 0 0 0 0 0 0.753 5.4*10^-4 0.246 2.3*10^-4 3.8*10^-4 0 0 0 32 130.55 33 0.0005 34 26.24 29 108.40

ENERGY BALANCE
Std. enthalpy of formation = -1271 KJ/mole = H H (Acetone) = -248.2 (l) KJ/mole H (Ethanol) = -277.63 (l) KJ/mole H (Butanol) = -328 (l) KJ/mole H (CO) = -248.2 (g) KJ/mole H (H) = 0 (g) KJ/mole 8

H (HO) = -285.8 (l) KJ/mole

Heat of the reaction:

95CHO -----------> 60CHOH +30CHCOCH +10CHOH +220CO +120H +30HO H = -248.2*30 - 328*60 - 277.63*10 393.5*220 + 1271*95 H = -4301.3 KJ/mole

Energy Balance across the fermenter:

435*H = m*4.2*(70-30) m = 4.02 kg/hr

Temperature dependency of specific heat of component:

Cp (N) (g) = 0.2911*10 + 0.0861*10*T + 1.7016*10*T +0.001*10*T + 909.79*T Cp (CO) (g) = 0.2937*10 + 0.345*10*T + 1.428*10*T + 0.264*10*T + 588*T Cp (H) (g) = 0.2762*10 + 0.0956*10*T + 2.466*10*T + 0.0376*10*T + 567.6*T Cp (acetone) (g) = 0.5704*10 + 1.632*10*T + 1.607*10*T + 0.968*10*T + 731.5*T Cp (butanol) (g) = 0.7454*10 + 2.590*10*T + 1.6073*10*T + 1.732*10*T + 712.4*T Cp (water) (g) = 0.3336*10 + 0.2679*10*T + 2.6105*10*T + 0.089*10*T + 1169*T Cp (ethanol) (g) = 0.492*10 + 1.4577*10*T + 1.6628*10*T + 0.939*10*T + 744.7*T Cp (acetone) (L) = 1.3560*10 - 1.77*10*T + 0.2837*T + 6.89*10*T Cp (butanol) (L) = 1.912*10 - 7.304*10*T + 2.2998 Cp (water) (L) = 2.7637*10 - 2.0901*10*T + 8.125*T - 1.4116*10*T + 9.3701*10*T Cp (ethanol) (L) = 1.0264*10 - 1.3963*10*T 3.0341*10*T + 2.0386*10*T

Control strategy for distillation column

Degrees of Freedom Analysis: Degrees of Freedom Analysis in Process Control to determine the number of control degrees of freedom in a distillation column. C.D.F. = Total No. of Streams - No. of Phases Present + 1 C.D.F :- Control degree of freedom

C.D.F :- Control degree of freedom

Total Streams = 8 Extra Phases = -3 Degrees of Freedom = 5 So the number of degrees of freedom is 5. However, a typical control strategy for such a process would use only 4 of these feed rate, column pressure, top and bottom composition. This is because the column and condenser are normally maintained at the same pressure. However, a valve could be placed in the line between. This would actually be undesirable as reducing the condenser pressure will decrease the temperature driving force available from the cooling medium.

Pressure, Overhead Rate and Bottoms Composition 10

This scheme should work satisfactorily as all adjustments are made at the same end of the column as the related measurements. The pressure control scheme is the so-called hot gas bypass. Note that the layout of condenser and reflux drum shown is critical to the operation of this method, which is actually a variation on the flooded condenser approach. The bypass is a very small pipe which bleeds vapour into the reflux drum where it does not immediately condense. The pressure in the system rises as the bypass valve is opened.

Figure - Overhead Rate and Bottoms Composition

References
1.

http://www.google.co.in/url?sa=t&rct=j&q=production%20of%20bio-butanol%20from %20abe%20fermentation&source=web&cd=1&cad=rja&ved=0CCQQFjAA&url=http %3A%2F%2Fwww.chemsystems.com%2Freports%2Fsearch%2Fdocs%2Fprospectus %2Fmc08_biobutanol_prospectus.pdf&ei=T1KRUK3_B4XqrAenjIGIBA&usg=AFQjC NFXq0UZIvoz33HIkgXrQZTw_mANUQ http://www.google.co.in/url? sa=t&rct=j&q=&esrc=s&source=web&cd=1&ved=0CCcQFjAA&url=http%3A%2F

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2.

%2Frepository.upenn.edu%2Fcgi%2Fviewcontent.cgi%3Farticle%3D1003%26context %3Dcbe_sdr&ei=m3iUUOKAAojyrQfpxICwAw&usg=AFQjCNEThp_Dpjg1LXU7vpuB68BDFYS_w&sig2=7s544axYn6QnVkmorQLxLA
3. 4.

http://repository.upenn.edu/cgi/viewcontent.cgi?article=1016&context=cbe_sdr Perry's ChE Handbook

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