Ethanol Fermentation and Potential

DWIGHT L. MILLER Northern Regional Research Laboratory, Agricultural Research Service, U.S. Department of Agriculture, Peoria, Illinois 61604

Ethyl alcohol (ethanol) has been used by men since the dawn of civilization. Originally, it was produced by the spontaneous fermentation of sugars and was consumed by ancient races for its intoxicating effects. The Arabs and Romans learned to isolate the alcohol and to employ it industrially in the preparation of perfumes, cosmetics, and medicines. Over the intervening centuries the production and purification of alcohol have advanced to their present high level. Today, ethyl alcohol preparation is based on two major procedures, namely, fermentation and chemical synthesis. The most important or potentially important raw materials for each procedure are as follows: Fermentation. Cereal grains (corn, wheat, barley, sorghum, or rye); sugarcane (molasses); sugar beets; fruit product wastes; other starch crops (potatoes or rice); sulfite liquors (paper pulping); and such high cellulose-containing materials as wood, crop residues, and cultivated fiber crops. Chemical synthesis. Petroleum and natural gas; coal; oil shales; and tar sands. More than 90% of beverage and industrial ethyl alcohol produced in the United States is now prepared from cereal grains or from petroleum-based raw materials. Synthetic alcohol from petroleum (oil and natural gas) has captured most of the approximately 300 million gallon annual industrial alcohol market. Sulfite liquors (a by-product of the paper industry) are the only wood or cellulosic-containing materials now used commercially for significant industrial alcohol production. Synthetic alcohol is not purer or better quality than fermentation
345 BiotechnoL & Bioeng. SYmp. No.5, 345-352 (197 5) 1975 by John Wiley & Sons, Inc.

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alcohol for industrial use. Chemically, both alcohols are essentially the same and may be used interchangeably. Fermentation ethyl alcohol is produced by the action of yeast on the starch and sugars present in the natural raw materials. Until about 1929, practically all U.S. ethyl alcohol was prepared from grains, molasses, and other materials high in starch or sugar. All beverage alcohol is still produced in the United States by the fermentation of such products. About 40 million bushels of grain (mostly corn, rye, barley) are used annually for distilled beverage alcohol. Fermentation alcohol is essentially not used for industrial markets because it cannot economically compete with synthetic alcohol. However, the developing petroleum shortages with much higher prices have resulted in renewed interests in the fermentation of natural products for industrial ethyl alcohol. Fermentative production of ethanol from cellulose is teclmically feasible. Its economic feasibility has not been resolved. Fermentable sugars can be obtained from wood and other high cellulosic materials. The preparation has been extensively reviewed earlier in this symposium. Therefore, fermentable sugar availability is assumed in my discussion. Fermentation practices, with cellulosic-derived sugars, are similar to the fermentation of sugars derived from starch.

ALCOHOL PRODUCTION PROCESSES

Chemical Synthesis
Practically all synthetic alcohol is now produced from ethylene, which is obtained from petroleum and natural gas. The original commercial synthetic process involved the reaction of ethylene with sulfuric acid and hydrolysis of the ethyl sulfate to ethyl alcohol. The direct catalytic hydration of ethylene with water is a later development and is increasingly used. Conversion yields of ethylene to alcohol up to 97% have been reported (Fig. 1). Commercial experience has shown that a pound of ethylene will yield 0 about 0.25 gal of 190 proof alcohol. Most new synthetic plants have a
CH =CH + H 0 Catalyst, C H OH 2 s 2 2 2 Ethylene Ethyl Alcohol
Fig. 1. Conversion of ethylene into ethyl alcohol.

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mInimum yearly alcohol capacity in the order of 50 million gal. At present, such a plant would cost approximately S32 million. Under these conditions, the alcohol conversion costs would be in the order of 21.5jgal as shown in Table I. Ethylene costs vary depending on location and included expenses. The effect of ethylene price on alcohol cost is shown in Table II. Ethylene prices were fairly stable at 3.0 to 3.5jlb until about 1972. They have now more than doubled. Some forecasts indicate the price of ethylene may increase to 15.0jlb by 1975. A price of 10.0 cents relatively soon is possible.

Grain (Starch) Fermentation

Conversion of starch and sugars to ethyl alcohol through fermentation is shown in Figure 2, Alcohol production is directly related to the starch or sugars in the raw materials. Thus, 180 Ib of dextrose theoretically should yield 92 Ib

TABLE I 0 Conversion Cost of 1900 and 200 Proof Ethyl Alcohol from Ethylene (Exclusive of cost of ethylene) [May 1974] Cost jgal

Alcohol 1900 Proof Base conversion cost Depreciation ($3.2 millionjyr, 10 yr, 50 million gal) Net 200 Proof Alcohol (1.048 gal at 21.5 jgal) Cost of dehydration Total cost (exclusive of ethylene, profit, packaging, and sales expenses)
0

15.1 6.4

21.5

22,S 2.6 25.1

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MILLER TABLE II Effect of Ethylene Cost on Ethyl Alcohol Cost [May 1974] Ethylene (/lb) 5.0 6.0 7.0 8.0

Alcohol 190 0 Proof Ethylene Conversion Total manufacturing cost/gal (exclusive of profit, packaging, and sales expenses) 200 0 Proof Ethylene Conversion Total manufacturing cost/gal (exclusive of profit, packaging, and sales expenses) 21.0 25.1 20.0 21.5

Cost/Gal (cents)

24.0 21.5

28.0 21.5

32.0 21.5

41.5

45.5

49.5

53.5

25.2 25.1

29.3 25.1

33.5 25.1

46.1

50.3

54.4

58.6

of ethanol. For starch, the theoretical yield of alcohol is 0.568 lb/lb of starch. In commercial operations, yields generally are 90 to 95% of theoretical. The average composition of typical cereal grains is given in Table III. The cost of ethanol depends on many conditions, such as location, regional labor rates, and raw materials used. A representative estimate for conversion costs in a practical-size grain fermentation plant

Fig. 2. Conversion of starch, cellulose, and sugars into ethyl alcohoL

ETHANOL FERMENTATION AND POTENTIAL TABLE III Average Composition of Cereal Grainsa

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Grain

Starch
(%)

Protein
(%)

Oil
(%)

Fiber
(%)

Other constituentsb
(%)

Hard wheat Soft wheat Dent corn Sorghum

64 69 72 71

14
10

10 13

2 2 5 3

2 2 2 2

18 17 11 11

aMoisture-free basis. bMinerals, sugars, pentosans, and vitamins.

processing 20,000 bushels of corn per day is shown in Table IV. A by-product feed credit has been taken in the 10.6/gal of alcohol conversion costs. This optimum size plant could produce 17.7 million
TABLE IV Fermentative Conversion Cost of 1900 and 200 0 Proof Ethyl Alcohol from Corn (Exclusive of cost of corn) [May 1974] Alcohol 190 0 Proof (2.82 gal/bu) Base conversion cost Depreciation ($1.54 million/yr, 10 yr, 17.7 million gal) By-product feed credit (6.8 lb/gal alcohol at $100/ton) Net 200 Proof (2.7 gal/bu) Alcohol (1.048 gal at 10.6 /gal) Cost of dehydration Total cost (exclusive of corn, profit, packaging, and sales expenses) 11.1 2.6
0

Cents/Gal

35.9 8.7

44.6 34.0 10.6

13.7

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gal of 190 proof alcohol annually. The plant investment would be approximately $15.4 million. The effects of corn cost on ethanol cost is shown in Table V. Recovered by-product feed (distiller's grains) is a valuable protein animal feed. Its recovery has significant effects on alcohol cost. The other major product is carbon dioxide which could be recovered. However, only in selected metropolitan regions would it be economical to do so. In these calculations, no credit for carbon dioxide recovery is included.

Wood (Cellulosic) Fermentation

The conversion of cellulose to sugars and fermentation of the sugars to ethanol is similar to the conversion of cereal starch to sugars followed by fermentation to ethanol. Most woods consist of about 50 to 60% cellulose, some 25 to 30% lignins and the remainder is not a very well-defined group of carbohydrates called hemicellulose. The potential total sugars and fermentable sugars are significantly different between various woods (and cellulosic residues and by-products). In general, the average of potential fermentable sugars from woods are in the order of 50% of the original wood dry weight.

TABLE V Effect of Corn Cost on Ethyl Alcohol Cost (Basis: 2.7 gal 200 0 proof alcohol/bu) [May 1974] Corn price/bushel 1.00 1.25 1.50 1.75 2.00 2.25 2.50 Alcohol cost/gal (cents) Corn 37.0 46.3 55.5 64.8 74.0 83.3 92.6 Conversion b
13.7 13.7

Total base cost b 50.7 60.0 69.2 78.5 87.7 97.0 106.3

13.7
13. 7 13.7

13.7
13.7

aThese costs do not include profits, packaging, and sales expenses. bBy-product grains credited at $1 OO/ton in conversion cost.

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A ton of dry wood converted to 50% fermentable sugars (as wood hydrolyzate) would theoretically yield 510 lb of alcohol or 82 gal of 95% ethanol. This compares to about 820 lb or 130 gal of 95% ethanol from a ton of dry corn. The sugar concentration in the wood hydrolyzate fermentation would probably be lower (approximately 5%) than cereal grain mash which is normally about 12%. Capital investment per gallon of alcohol from wood thus is higher than from grain. Processing costs would also be higher. Overall, these increases should total about 10%. In addition, distiller's by-product grains from grain fermentation are valuable animal feeds. Return on these grains defray a portion of the processing cost. Therefore, use of fermentable sugar from cellulose must be relatively low for the production of alcohol to be competitive with production from grains or from ethylene. Based on No.2 corn at S2.00 per bushel (56 lb, 14% moisture) or ethylene at l4.0jlb, sugars from cellulose would have a raw material value of about 2.2jlb. If sugar was free, competitive corn value would be about S1.l0 per bushel and ethylene price would be about 6.0jlb. In all wood-hydrolysis processes, lignin, amounting to at least 30% of the weight of the wood, remains as a residue. More than 11 lb are obtained for each gallon of alcohol. It now has little value except as fuel. Also, the nonfermentable materials in the organic material in wood hydrolyzate passes through the fermentation and constitutes a waste disposal problem. Upgrading the value of these by-products would directly increase the value of the cellulosic-derived sugars. SUMMARY Ethyl alcohol is one of the United States and world's major chemicals. Beverage alcohol in the United States must be prepared from cereal grains or other natural products. The U.S. industrial alcohol market has remained relatively stable for several years at approximately 300 million gallons annually. Most of this has been produced synthetically from petroleum raw material (gas and oil). These raw materials are experiencing major price increases and are in short supply. The production of ethyl alcohol from cereal grains and cellulosic raw materials by fermentation is technically feasible and has been proven. Alcohol produced from all such materials is equal to synthetic alcohol in

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quality and performance. Competitive economics have controlled the basic raw materials used. The major potential new ethyl alcohol market is as a component of automobile fuels. A lO% alcohol-gasoline blend in the United States would annually require over 10 billion gallons of anhydrous alcohol. Use of alcohol for this purpose is technically feasible. However, alcohol has not been economically competitive to date.