Ethanol process, direct

Ethanol via Direct Hydration. The Shell Ih-ocess. The production of ethanol by the direct addition of water to ethylene is being carried out successfully on a commercial scale. In the Shell process a phosphoric acid-on Celite catalyst is used in the reaction ... 

The cellulose-to-ethanol process has five basic steps as shown in Figure I. They are feedstock handling and pretreatment, enzyme production, yeast production, simultaneous saccharification/fermentation (SSF) and ethanol recovery. Cellulose is the most abundant organic material on the earth. It is annually renewable, and not directly useful as a foodstuff. It is a polymer of glucose linked /8-1,4 as compared with the a-1,4 linked polymer starch which by contrast is easily digestible by man. There are three basic classes of potential cellulose feedstocks. These are agricultural by-products, industrial and municipal wastes, and special crops. The availability of these materials in the U.S. is shown in Table I. For economic reasons, we are concentrating our efforts on those materials that are collected for some other reason. 

The second step in the direct ethanol process is that of enzyme production. The Gulf process utilizes a mutant strain of Trichoderma reesei, grown continuously to produce a complete cellulase system. The residence time is 48 hours. Enzyme production begins on a spore plate with subsequent scale-up to the enzyme production vessel size to be used. Our pilot plant facility has 300-gal enzyme reactors. 

The third step in the direct ethanol process is to produce the yeast necessary for converting the glucose to ethanol. Varieties of organisms have been screened for compatibility with the Trichoderma reese/cellulase system. The optimum temperature for the cellulase system is 45 to 50 C. Most yeasts have a temperature optima less than that, e.g., 30 to 35 C. We have tested a variety of strains, including Saccharomyces cerevisiae. S. carlsbergensis, and Candida brassicae. A temperature of 40 C has been identified as optimum for the combined cellulase and yeast systems. 

The fourth step in the direct ethanol process is considered to be key to the economic viability of the bioconversion of cellulose to chemicals. The pretreated cellulose slurry is simultaneously converted to glucose and the glucose to ethyl alcohol in the same vessel in a continuous or semi-continuous mode. The enzyme sample is the whole culture from the enzyme production vessel. The feedstock is a slurry of 7.5% to 15% cellulose. The yeast is either added as a cake or recycled as a cream. 

FIGURE 26.9 Direct hydration process for ethanol manufacture. (Direct hydration of ethylene for the production of ethanol is carried out at high pressure (75 kg/cm ) and high temperature (300°C). The major by-product is diethyl ether, which is recycled back to the reactor to form ethanol.)... 

Figure 4.8 CCC of the ethanol dehydration process direct steam injection of 25 MW steam to the ethylene reactor is considered a process requirement and therefore not included...

Figure 4.9 Background/foreground analysis of the ethanol production and ethanol dehydration process direct delivery of ethanol between the processes is accounted for in the stream data...

Ethanol, being a t> pical primary alcohol containing the -CH OH group, gives on oxidation first acetaldehyde and then acetic acid. This process, when carried out by an aqueous oxidising agent, probably consists in the direct... 

Acetaldehyde, first used extensively during World War I as a starting material for making acetone [67-64-1] from acetic acid [64-19-7] is currendy an important intermediate in the production of acetic acid, acetic anhydride [108-24-7] ethyl acetate [141-78-6] peracetic acid [79-21 -0] pentaerythritol [115-77-5] chloral [302-17-0], glyoxal [107-22-2], aLkylamines, and pyridines. Commercial processes for acetaldehyde production include the oxidation or dehydrogenation of ethanol, the addition of water to acetylene, the partial oxidation of hydrocarbons, and the direct oxidation of ethylene [74-85-1]. In 1989, it was estimated that 28 companies having more than 98% of the wodd s 2.5 megaton per year plant capacity used the Wacker-Hoechst processes for the direct oxidation of ethylene. 

Butane-Naphtha Catalytic Liquid-Phase Oxidation. Direct Hquid-phase oxidation ofbutane and/or naphtha [8030-30-6] was once the most favored worldwide route to acetic acid because of the low cost of these hydrocarbons. Butane [106-97-8] in the presence of metallic ions, eg, cobalt, chromium, or manganese, undergoes simple air oxidation in acetic acid solvent (48). The peroxidic intermediates are decomposed by high temperature, by mechanical agitation, and by action of the metallic catalysts, to form acetic acid and a comparatively small suite of other compounds (49). Ethyl acetate and butanone are produced, and the process can be altered to provide larger quantities of these valuable materials. Ethanol is thought to be an important intermediate (50) acetone forms through a minor pathway from isobutane present in the hydrocarbon feed. Formic acid, propionic acid, and minor quantities of butyric acid are also formed. 

Most large-scale industrial methacrylate processes are designed to produce methyl methacrylate or methacryhc acid. In some instances, simple alkyl alcohols, eg, ethanol, butanol, and isobutyl alcohol, maybe substituted for methanol to yield the higher alkyl methacrylates. In practice, these higher alkyl methacrylates are usually prepared from methacryhc acid by direct esterification or transesterification of methyl methacrylate with the desired alcohol. 

Fig. 8. Combustion turbines with process heat recovery (a) represents direct use of exhaust gas for process heating where industrial process includes refinery, chemicals, food processing, and ethanol production and (b) exhaust-to-water heat exchanger where industrial process includes material drying,...

There are two main processes for the synthesis of ethyl alcohol from ethylene. The eadiest to be developed (in 1930 by Union Carbide Corp.) was the indirect hydration process, variously called the strong sulfuric acid—ethylene process, the ethyl sulfate process, the esterification—hydrolysis process, or the sulfation—hydrolysis process. This process is stiU in use in Russia. The other synthesis process, designed to eliminate the use of sulfuric acid and which, since the early 1970s, has completely supplanted the old sulfuric acid process in the United States, is the direct hydration process. This process, the catalytic vapor-phase hydration of ethylene, is now practiced by only three U.S. companies Union Carbide Corp. (UCC), Quantum Chemical Corp., and Eastman Chemical Co. (a Division of Eastman Kodak Co.). UCC imports cmde industrial ethanol, CIE, from SADAF (the joint venture of SABIC and Pecten [Shell]) in Saudi Arabia, and refines it to industrial grade. 

Direct Hydration of Ethylene. Hydration of ethylene to ethanol via a Hquid-phase process cataly2ed by dilute sulfuric acid was first demonstrated more than a hundred years ago (82). In 1923, the passage of an ethylene-steam mixture over alumina at 300°C was found to give a small yield of acetaldehyde, and it was inferred that this was produced via ethanol (83). Since the late 1920s, several industrial concerns have expressed interest in producing ethanol synthetically from ethylene over soHd catalysts. However, not until 1947 was the first commercial plant for the manufacture of ethanol by catalytic hydration started in the United States by Shell the same process was commerciali2ed in the United Kingdom in 1951. 

Other Methods of Preparation. In addition to the direct hydration process, the sulfuric acid process, and fermentation routes to manufacture ethanol, several other processes have been suggested. These include the hydration of ethylene by dilute acids, the hydrolysis of ethyl esters other than sulfates, the hydrogenation of acetaldehyde, and the use of synthesis gas. None of these methods has been successfilUy implemented on a commercial scale, but the route from synthesis gas has received a great deal of attention since the 1974 oil embargo. 

The other process (183) hydrogenates the acetic acid directly to ethanol. 

Ethanol s use as a chemical iatemiediate (Table 8) suffered considerably from its replacement ia the production of acetaldehyde, butyraldehyde, acetic acid, and ethyUiexanol. The switch from the ethanol route to those products has depressed demand for ethanol by more than 300 x 10 L (80 x 10 gal) siace 1970. This decrease reflects newer technologies for the manufacture of acetaldehyde and acetic acid, which is the largest use for acetaldehyde, by direct routes usiag ethylene, butane (173), and methanol. Oxo processes (qv) such as Union Carbide s Low Pressure Oxo process for the production of butanol and ethyUiexanol have totaUy replaced the processes based on acetaldehyde. For example, U.S. consumption of ethanol for acetaldehyde manufacture declined steadily from 50% ia 1962 to 37% ia 1964 and none ia 1990. Butadiene was made from ethanol on a large scale duriag World War II, but this route is no longer competitive with butadiene derived from petroleum operations. 

Ethyl Ether. Most ethyl ether is obtained as a by-product of ethanol synthesis via the direct hydration of ethylene. The procedure used for production of diethyl ether [60-29-7] from ethanol and sulfuric acid is essentially the same as that first described in 1809 (340). The chemical reactions involved in the production of ethyl ether by the indirect ethanol-from-ethylene process are like those for the production of ether from ethanol using sulfuric acid. 

Other Derivatives and Reactions. The vapor-phase condensation of ethanol to give acetone has been well documented in the Hterature (376—385) however, acetone is usually obtained as a by-product from the cumene (qv) process, by the direct oxidation of propylene, or from 2-propanol. 

Manufacture. Much of the diethyl ether manufactured is obtained as a by-product when ethanol (qv) is produced by the vapor-phase hydration of ethylene (qv) over a supported phosphoric acid catalyst. Such a process has the flexibiHty to adjust to some extent the relative amounts of ethanol and diethyl ether produced in order to meet existing market demands. Diethyl ether can be prepared directly to greater than 95% yield by the vapor-phase dehydration of ethanol in a fixed-bed reactor using an alumina catalyst (21). 

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