Ethylene oxide manufacturing methods

Ethylene oxide is prepared commercially by two basic methods direct oxidation processes and the process via ethylene chlorohydrin. The most commonly used process today involves the direct catalytic oxidation of ethylene with air or oxygen over a silver-based catalyst to yield ethylene oxide. The major by-products of this process are carbon dioxide and water. The reaction product is purified by distillation. In 1979, this method accounted for over 96 percent of the nameplate capacity of ethylene oxide manufacture in the United States and Puerto Rico [7]. 

Ethylene glycol was originally commercially produced in the United States from ethylene chlorohydrin [107-07-3J, which was manufactured from ethylene and hypochlorous acid (eq. 8) (see Chlorohydrins). Chlorohydrin can be converted direcdy to ethylene glycol by hydrolysis with a base, generally caustic or caustic/bicarbonate mix (eq. 9). An alternative production method is converting chlorohydrin to ethylene oxide (eq. 10) with subsequent hydrolysis (eq. 11). 

Three generations of latices as characterized by the type of surfactant used in manufacture have been defined (53). The first generation includes latices made with conventional (/) anionic surfactants like fatty acid soaps, alkyl carboxylates, alkyl sulfates, and alkyl sulfonates (54) (2) nonionic surfactants like poly(ethylene oxide) or poly(vinyl alcohol) used to improve freeze—thaw and shear stabiUty and (J) cationic surfactants like amines, nitriles, and other nitrogen bases, rarely used because of incompatibiUty problems. Portiand cement latex modifiers are one example where cationic surfactants are used. Anionic surfactants yield smaller particles than nonionic surfactants (55). Often a combination of anionic surfactants or anionic and nonionic surfactants are used to provide improved stabiUty. The stabilizing abiUty of anionic fatty acid soaps diminishes at lower pH as the soaps revert to their acids. First-generation latices also suffer from the presence of soap on the polymer particles at the end of the polymerization. Steam and vacuum stripping methods are often used to remove the soap and unreacted monomer from the final product (56). 

It is necessary to determine the bioburden and make cycle verification studies when ethylene oxide sterilization is used, as it is for other sterilization methods. The manufacturer of hospital sterilization equipment provides cycle recommendations based on the expected bioburden and the consideration of an appropriate safety factor. In ethylene oxide sterilization, it is necessary to determine if residues of the stefilant are absorbed by the sterilized article, and to examine the possible formation of other potentially toxic materials as a result of reaction with ethylene oxide. 

Ethylene oxide (qv) was once produced by the chlorohydrin process, but this process was slowly abandoned starting in 1937 when Union Carbide Corp. developed and commercialized the silver-catalyzed air oxidation of ethylene process patented in 1931 (67). Union Carbide Corp. is stiU. the world s largest ethylene oxide producer, but most other manufacturers Hcense either the Shell or Scientific Design process. Shell has the dominant patent position in ethylene oxide catalysts, which is the result of the development of highly effective methods of silver deposition on alumina (29), and the discovery of the importance of estabUshing precise parts per million levels of the higher alkaU metal elements on the catalyst surface (68). The most recent patents describe the addition of trace amounts of rhenium and various Group (VI) elements (69). 

Merck and Maeder have patented the manufacture of arecaidine by loss of water from l-methyl-4-hydroxypiperidine-3-carboxylic acid. A method of producing the latter has been describd by Mannich and Veit and has been developed by Ugriumov for the production of arecaidine and arecoline. With the same objective, Dankova, Sidorova and Preobrachenski use what is substantially McElvain s process,but start by converting ethylene oxide, via the chlorohydrin and the cyanohydrin, into -chloropropionic acid. The ethyl ester of this with methylamine in benzene at 140° furnishes methylbis(2-carbethoxyethyl) amine (I) which on refluxing with sodium or sodium Moamyloxide in xylene yields l-methyl-3-carbethoxy-4-piperidone (II). The latter is reduced by sodium amalgam in dilute hydrochloric acid at 0° to l-methyl-3-carbethoxy-4-hydroxypiperidine (III) which on dehydration, and hydrolysis, yields arecaidine (IV R = H), convertible by methylation into arecoline (IV R = CH3). 

A second manufacturing method for acetic acid utilizes butane from the C4 petroleum stream rather than ethylene. It is a very complex oxidation with a variety of products formed, but conditions can be controlled to allow a large percentage of acetic acid to be formed. Cobalt (best), manganese, or chromium acetates are catalysts with temperatures of 50-250 °C and a pressure of 800 psi. 

The primary manufacturing method of making ethylene glycol is from acid- or thermal-catalyzed hydration and ring opening of the oxide. Nearly all the glycol is made by this process. Either a 0.5-1.0% H2SO4 catalyst is used at 50-70°C for 30 min or, in the absence of the acid, a temperature of 195 C and 185 psi for 1 hr will form the diol. A 90% yield is realized when... 

There are two important methods for the manufacture of propylene oxide, each accounting for one half the total amount produced. The older method involves chlorohydrin formation from the reaction of propylene with chlorine water. Before 1969 this was the exclusive method. Unlike the analogous procedure for making ethylene oxide from ethylene, which now is obsolete, this method for propylene oxide is still economically competitive. Many old ethylene oxide plants have been converted to propylene oxide synthesis. 

Since approximately 2.2 lb of /-butyl alcohol would be produced per 1 lb of propylene oxide, an alternative reactant in this method is ethylbenzene hydroperoxide. This eventually forms phenylmethylcarbinol along with the propylene oxide. The alcohol is dehydrated to styrene. This chemistry was covered in Chapter 9, Section 6 as one of the syntheses of styrene. Thus the side product can be varied depending on the demand for substances such as /-butyl alcohol or styrene. Research is being done on a direct oxidation of propylene with oxygen, analogous to that used in the manufacture of ethylene oxide from ethylene and oxygen (Chapter 9, Section 7). But the proper catalyst and conditions have not yet been found. The methyl group is very sensitive to oxidation conditions. 

The primary manufacturing method of making ethylene glycol (ethane-1,2-diol, boiling point 197.6°C, density 1.1155, flash point 127°C) is from acid or thermal-catalyzed hydration and ring opening of the oxide. 

The methods of preparation of glassware are indicated in Chapter 8, and if sterilisation is monitored as described the glassware should not be a source of contamination. Likewise plasticware is obtained from the manufacturer in a sterile condition. Usually sterilisation of plastic is achieved using ethylene oxide or irradiation procedures and vessels are supplied wrapped in cellophane. 

Several addition reactions have been or are currently used on a large scale in industrial chemical plants. For example, an older method for the preparation of ethylene oxide employed the addition of chlorine to ethylene in water to form ethylene chlorohydrin or 2-chloroethanol. (In industry, ethene is almost always called ethylene.) Treatment of the chlorohydrin with calcium hydroxide results in the formation of ethylene oxide, which is an important intermediate in the manufacture of ethylene glycol and other products (see the Focus On box on page 375). However, this method is wasteful of... 

This route might be an environmentally benign alternative to the conventional method for the production of the very important fragrance 2-phenylethanol. This compound is still manufactured out of ethylene oxide and benzene in the presence of a high excess of A1C13 (2,5 molar), yielding unwanted toxic by-products such as dioxanes and several inorganic salts accompanied by corrosion problems. 

This method is now rarely used to synthesize ethylene oxide, but is still employed to manufacture propylene oxide. The main reactions involved in the process are the following ... 

Extrusion is a cost effective manufacturing process. Extrusion is popularly used in large scale production of food, plastics and composite materials. Most widely used thermoplastics are processed by extrusion method. Many biopolymers and their composite materials with petroleum-based polymers can also be extruded. These include pectin/starch/poly(vinyl alcohol) (Fishman et al. 2004), poly(lactic acid)/sugar beet pulp (Liu et al. 2005c), and starch/poly(hydroxyl ester ether) (Otey et al. 1980), etc. In this study, composite films of pectin, soybean flour protein and an edible synthetic hydrocolloid, poly(ethylene oxide), were extruded using a twin-screw extruder, palletized and then processed into films by compression molding process or blown film extrusion. The films were analyzed for mechanical and structural properties, as well as antimicrobial activity. 

Olefin epoxidation is not only important in the manufacture of bulk chemicals, e. g. ethylene and propylene oxides, but is also a widely used transformation in the fine-chemicals industry [1], Ethylene oxide is manufactured by vapor-phase oxidation of ethylene, with air or oxygen, over a supported silver catalyst [2], This method is not generally applicable as olefins containing allylic or other reactive C-H bonds give complex mixtures of products with low epoxide selectivity. The method has recently been extended to some other olefins that do not contain reactive allylic C-H bonds, e. g. butadiene, styrene, norbornene, and tert-butyl ethylene [3]. Some of these products, e. g. butadiene monoepoxide and styrene oxide, have potential applications as fine chemicals/intermediates. 

Ethylene oxide was originally manufactured by the two step chlorohydrin epoxidation process. This technology is no longer used, but is of historical interest, as it was the method by which ethylene oxide was first produced commercially. In this process, ethylene is reacted with chlorine to form a chlorohydrin intermediate which is then transformed to ethylene oxide by heating with calcium hydroxide. The chemistry is illustrated in equations (1) and (2) ... 

The Pd-Pb intermetallic catalyst and Au-NiO, nanoparticle catalyst developed and industrialized by Asahi Kasei are both unprecedented and unique aerobic oxidative esterification catalysts. We believe that three production processes - our oxidative esterification method (TEA to C4 isobutene hydrocarbon feedstock) in addition to the alpha process (C2 ethylene hydrocarbon feedstock) and the improved ACH process (C3 propene hydrocarbon to acetone feedstock see Chapter 7 in this book on the cumene-based phenol process) - will be competing for the top position in the global market as the MMA manufacturing method. 

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