Direct oxidation process

Propylene oxide [75-56-9] (methyloxirane, 1,2-epoxypropane) is a significant organic chemical used primarily as a reaction intermediate for production of polyether polyols, propylene glycol, alkanolamines (qv), glycol ethers, and many other useful products (see Glycols). Propylene oxide was first prepared in 1861 by Oser and first polymerized by Levene and Walti in 1927 (1). Propylene oxide is manufactured by two basic processes the traditional chlorohydrin process (see Chlorohydrins) and the hydroperoxide process, where either / fZ-butanol (see Butyl alcohols) or styrene (qv) is a co-product. Research continues in an effort to develop a direct oxidation process to be used commercially. 

Ethylene oxide [75-21-8] was first prepared in 1859 by Wurt2 from 2-chloroethanol (ethylene chlorohydrin) and aqueous potassium hydroxide (1). He later attempted to produce ethylene oxide by direct oxidation but did not succeed (2). Many other researchers were also unsuccesshil (3—6). In 1931, Lefort achieved direct oxidation of ethylene to ethylene oxide using a silver catalyst (7,8). Although early manufacture of ethylene oxide was accompHshed by the chlorohydrin process, the direct oxidation process has been used almost exclusively since 1940. Today about 9.6 x 10 t of ethylene oxide are produced each year worldwide. The primary use for ethylene oxide is in the manufacture of derivatives such as ethylene glycol, surfactants, and ethanolamines. 

Ethylene oxide has been produced commercially by two basic routes the ethylene chlorohydrin and direct oxidation processes. The chlorohydrin process was first iatroduced dufing World War I ia Germany by Badische Anilin-und Soda-Eabfik (BASE) and others (95). The process iavolves the reaction of ethylene with hypochlorous acid followed by dehydrochlofination of the resulting chlorohydrin with lime to produce ethylene oxide and calcium chloride. Union Carbide Corp. was the first to commercialize this process ia the United States ia 1925. The chlorohydrin process is not economically competitive, and was quickly replaced by the direct oxidation process as the dominant technology. At the present time, all the ethylene oxide production ia the world is achieved by the direct oxidation process. 

Air-Based Direct Oxidation Process. A schematic flow diagram of the air-based ethylene oxide process is shown in Figure 2. Pubhshed information on the detailed evolution of commercial ethylene oxide processes is very scanty, and Figure 2 does not necessarily correspond to the actual equipment or process employed in any modem ethylene oxide plant. Precise information regarding process technology is proprietary. However, Figure 2 does illustrate all the saUent concepts involved in the manufacturing process. The process can be conveniently divided into three primary sections reaction system, oxide recovery, and oxide purification. 

Fig. 2. Air-based direct oxidation process for ethylene oxide (96,102,109,117—119)).

Table 10. Ranges of Reaction System Variables in the Direct Oxidation Process for Ethylene Oxide ...

Ethylene Oxide Catalysts. Of all the factors that influence the utihty of the direct oxidation process for ethylene oxide, the catalyst used is of the greatest importance. It is for this reason that catalyst preparation and research have been considerable since the reaction was discovered. There are four basic components in commercial ethylene oxide catalysts the active catalyst metal the bulk support catalyst promoters that increase selectivity and/or activity and improve catalyst life and inhibitors or anticatalysts that suppress the formation of carbon dioxide and water without appreciably reducing the rate of formation of ethylene oxide (105). 

Unsteady-State Direct Oxidation Process. Periodic iatermption of the feeds can be used to reduce the sharp temperature gradients associated with the conventional oxidation of ethylene over a silver catalyst (209). Steady and periodic operation of a packed-bed reactor has been iavestigated for the production of ethylene oxide (210). By periodically varyiag the inlet feed concentration of ethylene or oxygen, or both, considerable improvements ia the selectivity to ethylene oxide were claimed. 

Modop [Mobil Oil Direct Oxidation Process] A process for removing residual sulfur-containing gases from the tail gas from the Claus process. The catalyst is titanium dioxide pelletized with calcium sulfate. Developed in the 1980s by Rhone-Poulenc, Procatalyse, and Mobil Oil. Three plants were operating in Germany in 1995 and one in the United States. European Patents 60,742 78,690. 

See also Fluidized-bed entries Fluid-bed direct oxidation process, 10 656 Fluid-bed dryers, 9 122-123, 130-131 two-stage, 9 125 Fluid-bed roasters, 16 141 Fluid catalytic cracking (FCC), 11 678-699, 700-734 18 651, 653 20 777 24 257, 271. See also FCC entries Fluidized-bed catalytic cracking (FCC) clean fuels production and, 11 686-689 defined, 11 700... 

Ethylene oxide was formerly made in a two-stage process by first adding HOCl to ethylene and then removing HCl. However, in the 1960s Scientific Design, Union Carbide, and Shell Oil developed a one-step direct oxidation process that has largely replaced the old chlorohydrin process. 

The two primary approaches to removal of sulfurous compounds from process gas streams are 1) the direct-oxidation processes and 2) the acid-gas removal systems9,10. in the direct-oxidation processes, hydrogen sulfide is selectively removed from the process gas, and the sulfur is recovered in its elemental form. The acid-gas removal processes, as a group, remove acidic components (H2S, CO2, HCN, etc.) and regenerate these species into a separate side stream. 

In general, the direct-oxidation processes employ a redox couple that has sufficient oxidation potential to convert H2S into elemental sulfur but insufficient potential to oxidize sulfur to higher states. Examples of materials that have this redox potential are vanadium compounds, arsenic compounds, iron compounds, and certain organic species. Typically, the redox materials, dissolved in a hot potassium carbonate solution with the species in its oxidized form, contacts the I S-laden gas and the H2S dissolves as the hydrosulfide. This sulfur reacts with the redox couple, forming elemental sulfur and the reduced state of the couple. Airblowing of the solution reoxidizes the couple and removes the elemental sulfur from solution as a product froth. 

Direct-oxidation processes can conveniently remove H2S from the process gas to levels of 100 ppm. At significantly greater cost, levels of perhaps 10 ppm can be achieved. The systems are characterized by relatively low sulfur-carrying capacities and, therefore, high liquor recirculation rates. They are not generally applicable to gas streams with high partial pressures of carbon dioxide the carbon dioxide also dissolves in the solution, causing a pinch in the column and a reduction of sulfur purification capability. 

The direct-oxidation processes for recovery of sulfur from raw gases are also applicable on acid-gas streams. Usually, a direct oxidation process would be applied when a nonselective acid-gas removal system had been employed and the sulfur concentration in the acid gas is relatively low. At higher H2S concentrations, as achieved through selective acid-gas removal, the conventional Claus process appears to be more economic. 

Ethylene and Propylene Oxides. Ethylene oxide (26) and its derivatives are among the important aliphatic chemicals the 1950 production amounted to between 400,000,000 and 500,000,000 pounds. The chlorohydrin process was introduced in the early 1920 s and the direct oxidation process in the 1930 s, both based on ethylene. In the older process, the one most used today, the ethylene reacts in solution with hypo-chlorous acid at room temperature. 

Acetic Anhydride. Other products recovered from the oxidation of light hydrocarbons (6) are acetic acid and acetic anhydride as well as acetaldehyde, acetone, and isopropyl alcohol, all of which may be converted to acetic acid or the anhydride. The direct oxidation process supplements the production of acetic anhydride from acetone derived from propylene, which has been the principal commercial source of the anhydride. The increasing production of cellulose acetate within recent years has been attributed to the low cost of acetic anhydride from the latter process (44). 

The mechanisms are easily distinguished. The homogeneous mechanisms lead to rates that are proportional to the concentrations of the mediator ions in solution and continue after the current is switched off (until the high valency form ofthe ions is consumed). The direct oxidation process stops when the current is turned off. 

Fig. 10.8. Air-based direct oxidation process for ethylene oxide. (Encyclopedia of ChemicalTechnology, Kirk and Othmer, Web site ed., ethylene oxide, manufacture, 2002. Copyright by John Wiley Sons, Inc. and reproduced by permission of the copyright owner.)...

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