Manufacturing of Ethanol from Ethene

Ethanol is manufactured by the hydration of ethene using steam in the presence of a phosphoric acid catalyst.

The reaction has a theoretical atom economy of 100%, but some side reactions occur producing by-products such as methanol, ethanal, poly(ethene) and ethoxyethane. Conditions Low temperatures, high pressures and a moderately high steam concentration favour this exothermic reaction. In practice, a temperature of 300C, a pressure of 60-70 atmospheres, and a steam:ethene ratio of 0.6:1 is used. Using these conditions, around 5% conversion to ethanol occurs per pass through the plant. By continually recycling the unreacted ethene and steam, an overall yield of 95% is achieved in a continuous process. Ethanol is produced as part of an integrated system of petrochemical production.

Purification The reactions involved in the production of synthetic ethanol produce an ethanol and water mixture. Fractional distillation always results in a mixture of 96% ethanol and 4% water (instead of 100% pure or absolute ethanol). This is known as an azeotropic or constant boiling mixture. Conventionally, this last 4% water is removed from the azeotropic mixture either by refluxing with calcium oxide, a dehydrating agent, or by mixing with benzene, which breaks up the azeotrope and produces pure ethanol when further distilled. Both these processes increase the energy costs of production, and benzene is also highly toxic and carcinogenic. New Purification Methods New purification techniques involve the use of zeolites, which have structures with holes that can absorb and hence remove water from the final mixture. Several zeolites have a particularly strong attraction, and they act as dehydrating agents at normal temperatures and pressures and can then be dried by heating and re-used. This produces considerable savings in energy and removes the need to use toxic substances like benzene.

The zeolites used are referred to as 3 (angstrom) zeolites, as the holes are 3 in diameter. The angstrom is a unit of length, 10-10 m. 10 = 1nm. The holes are larger than a water molecule, but considerably smaller than ethanol. Feedstock Composition Feedstock may include purpose-grown crops (including maize and corn), crop waste, paper mill sludge, forest residues and household waste (including sewage). These are mostly lignocellulosic materials containing cellulose, hemicellulose and lignin. Cellulose and hemicellulose are long chain polymers that make up the bulk of plant material, and lignin is the chemical "glue" that holds them together.

Hydrolysis This process breaks the long cellulose and hemicellulose chains into simple sugars. Cellulose yields primarily glucose (a six-carbon sugar) whereas hemicellulose, in the region of 20% of the material, gives a mixture including several five-carbon sugars. Methods of hydrolysis include using enzymes and using dilute or concentrated acids. Whereas in the past hydrochloric or hydrofluoric acid may have been used, sulphuric acid is found in newer processes. Sugar Separation After hydrolysis, the sugar for fermentation must be separated from the acid. A new process developed by the company Arkenol in the United States, which is still at the pilot stage, makes use of ion exchange to improve the separation, allowing a greater proportion of the acid to be concentrated and re-used. Final traces of acid are precipitated as "gypsum" (calcium sulphate) by addition of lime.

Fermentation Fermentation is a complex series of reactions, which convert carbohydrates, mainly sugars and starches, into ethanol and carbon dioxide. Several enzymes, such as zymase in yeasts, catalyse these reactions. Yeast is a living organism, and these are the products of anaerobic respiration.

Conditions Fermentation with yeast works best at temperatures in the range 25 - 37C, in the absence of oxygen (anaerobic) and will produce aqueous solutions of up to 14% ethanol. Below 25C the reaction rate is too slow, but at higher temperatures the enzymes start to denature and lose efficiency. If oxygen is present, aerobic respiration will occur producing carboxylic acids, in this case ethanoic acid (vinegar). The toxicity of ethanol to the organisms used limits the ethanol concentration possible. Solving the 5-carbon problem Conventional yeasts cannot make use of five-carbon sugars that arise from the hydrolysis of hemicellulose. Conventional methods for ethanol fermentation do not utilise this resource, which may count as 20% of the feedstock. The process developed by Arkenol uses specially bred yeast (not genetically engineered) that feeds preferentially on C5 sugars, as well as on C6 sugars. In this way, a greater proportion of the feed is utilized.

Fermentation using bacteria Yeast is very good at converting glucose, and other six-carbon sugars into ethanol. Unfortunately, a significant proportion of waste biomass consists of complex natural polymers made from sugars that are not "digested" readily by yeast enzymes. These include hemicellulose, which on hydrolysis produces a range of sugars including mannose, xylose, arabinose and galactose, depending on the original source.

KO11 A genetically modified bacterium, developed by the microbiologist Lonnie Ingram, has enabled these sugars to be converted to ethanol. The bacterium, referred to as KO11, would normally produce acids, but the modification means ethanol is produced instead. The advantage over yeast is that a wider range of sugars can be processed, enabling the utilization of biomass waste such as wood waste, corn stalks, rice hulls, and other organic waste, which would otherwise require disposal by some other method, or which could only be partially utilized by conventional fermentation methods, making them uneconomic.

Commercial Development The BC International Corporation is attempting to develop this approach commercially in the United States, focusing on: areas where legislation prohibits burning of agricultural waste conventional ethanol plants suitable for conversion and refurbishment

Reference: http://www.uyseg.org/greener_industry/pages/ethanol/ethanol6PM1.htm