Commercially operating processes

KINPTR Simulations of Commercial Operation Process Variable Effects"... 

From process studies carried out in this pilot plant over several years, parameters were defined to permit process and engineering designs of full commercial operations. Process economics indicated the cost of this active carbon would be greater than currently available commercial carbons. However, hundreds of evaluations in a full spectrum of applications showed that this active carbon would be competitive in many of those applications on a cost-performance basis. It will be commercially available mid-85 in various forms, trademarked as SUPER-A, from Anderson Development Company in Adrian, Michigan,... 

Although this is the major process in operation, there also is at least one commercially operated process for converting isobutylene and/or tert-butanol to methacrylic acid followed by esterification with methanol. A new process based on acetone cyanohydrin also has been reported. It avoids corrosive sulfuric acid and byproduct salts while coproducing formamide, which can be converted to HCN for recycle to the process. 

There are three commercially operated processes for the manufacture of hydroxylamine ... 

An Rh(I) complex containing CO and PRj ligands can catalyze the formation of butan-l-al from propene (CH2=CHCH3 -I- H2 + CO CH3CH2CH2CHO), a commercially operated process. 

To judge the different processes of multiphase catalyzes is rather unfair because of the wide range in the status of the variants, which include commercially operating processes such as Ruhrchemie/Rhone-Poulenc and SHOP, some processes that are in the first stages of commercial demonstration of their reliabilty, and what are more or less process proposals in the other cases. This is specially relevant when economic figures have to be compared. But it is possible to recognize and distinguish basic trends. 

Formaldehyde. The only commercially operated process (until 1968) is that developed by DuPont and involves the carbonylation of formaldehyde over an acid catalyst to give glycolic acid. 

In 1997, UOP announced the PX-Plus process which also uses a selectivated catalyst to convert toluene to para-rich xylenes. Pina commercialized a TDP process known as the (T2PX) process in 1984 (70). It uses a proprietary catalyst to react toluene at 42—48% conversion with selectivities to benzene of 42 wt % and to xylenes of 46 wt %. The xylenes produced are at equiUbrium. Typical commercial operating conditions of 390—495°C, H2 partial pressure of 4.1 Mpa, H2/hydrocarbon molar ratio of 4 1, and LHSV of 1—2/h. Pina s first commercial implementation occurred in 1985 at their Port Arthur refinery. 

In contrast to trace impurity removal, the use of adsorption for bulk separation in the liquid phase on a commercial scale is a relatively recent development. The first commercial operation occurred in 1964 with the advent of the UOP Molex process for recovery of high purity / -paraffins (6—8). Since that time, bulk adsorptive separation of liquids has been used to solve a broad range of problems, including individual isomer separations and class separations. The commercial availability of synthetic molecular sieves and ion-exchange resins and the development of novel process concepts have been the two significant factors in the success of these processes. This article is devoted mainly to the theory and operation of these Hquid-phase bulk adsorptive separation processes. 

There have been many variations in the design of electric arc reactors but only three have been commercialized. The most important is the installation at Hbls. The other commercial arc processes were those of Du Pont (3) (a high speed rotating arc) and a Romanian process that produced both ethylene and acetylene. The Hbls process and the Romanian process (at Borzesti, Romania) are still operating, but the Du Pont process has been shut down since 1969. 

Most by-product acetylene from ethylene production is hydrogenated to ethylene in the course of separation and purification of ethylene. In this process, however, acetylene can be recovered economically by solvent absorption instead of hydrogenation. Commercial recovery processes based on acetone, dimetbylform amide, or /V-metby1pyrro1idinone have a long history of successfiil operation. The difficulty in using this relatively low cost acetylene is that each 450, 000 t/yr world-scale ethylene plant only produces from 7000 9000 t/yr of acetylene. This is a small volume for an economically scaled derivatives unit. 

This process is one of the three commercially practiced processes for the production of acetic anhydride. The other two are the oxidation of acetaldehyde [75-07-0] and the carbonylation of methyl acetate [79-20-9] in the presence of a rhodium catalyst (coal gasification technology, Halcon process) (77). The latter process was put into operation by Tennessee Eastman in 1983. In the United States the total acetic anhydride production has been reported to be in the order of 1000 metric tons. 

Almost all battery scrap and paste is converted to impure lead or lead alloys by pyrometaHurgical processes employing blast, reverberatory, rotary, Isasmelt, or electric furnaces. In many plants, a furnace combination is used. PIectrowinning technologies have also been developed but as of this writing none is yet in fliU commercial operation. 

Methanol Synthesis. AH commercial methanol processes employ a synthesis loop, and Figure 6 shows a typical example as part of the overall process flow sheet. This configuration overcomes equiUbtium conversion limitations at typical catalyst operating conditions as shown in Figure 1. A recycle system that gives high overall conversions is feasible because product methanol and water can be removed from the loop by condensation. 

Researchers at Phillips Petroleum Company developed a commercially viable process for the synthesis of PPS involving the polymerization of /)-dich1orohenzene and a sodium sulfide source in a polar organic compound at elevated temperature and pressure. This Phillips process was patented in 1967 (18). Between 1967 and 1973, Phillips built and operated a pilot plant, estabhshed market demand, and constmcted a hiU-scale commercial plant. In 1973, the world s first PPS plant came on-stream in Phillips faciUty in Borger, Texas. 

Additional operations essential to commercial bauxite processing are steam and power generation, heat recovery to minimise energy consumption, process liquor evaporation to maintain a water balance, impurity removal from process liquor streams, classification and washing of ttihydrate, lime caustication of sodium carbonate [497-19-8] to sodium hydroxide [1310-73-2] repair and maintenance of equipment, rehabiUtation of mine and residue disposal sites, and quaUty and process control. Each operation in the process can be carried out in a variety of ways depending upon bauxite properties and optimum economic tradeoffs. 

Most commercial processes produce polypropylene by a Hquid-phase slurry process. Hexane or heptane are the most commonly used diluents. However, there are a few examples in which Hquid propylene is used as the diluent. The leading companies involved in propylene processes are Amoco Chemicals (Standard OH, Indiana), El Paso (formerly Dart Industries), Exxon Chemical, Hercules, Hoechst, ICl, Mitsubishi Chemical Industries, Mitsubishi Petrochemical, Mitsui Petrochemical, Mitsui Toatsu, Montedison, Phillips Petroleum, SheU, Solvay, and Sumimoto Chemical. Eastman Kodak has developed and commercialized a Hquid-phase solution process. BASE has developed and commercialized a gas-phase process, and Amoco has developed a vapor-phase polymerization process that has been in commercial operation since early 1980. 

Hydroperoxide Process. The hydroperoxide process to propylene oxide involves the basic steps of oxidation of an organic to its hydroperoxide, epoxidation of propylene with the hydroperoxide, purification of the propylene oxide, and conversion of the coproduct alcohol to a useful product for sale. Incorporated into the process are various purification, concentration, and recycle methods to maximize product yields and minimize operating expenses. Commercially, two processes are used. The coproducts are / fZ-butanol, which is converted to methyl tert-huty ether [1634-04-4] (MTBE), and 1-phenyl ethanol, converted to styrene [100-42-5]. The coproducts are produced in a weight ratio of 3—4 1 / fZ-butanol/propylene oxide and 2.4 1 styrene/propylene oxide, respectively. These processes use isobutane (see Hydrocarbons) and ethylbenzene (qv), respectively, to produce the hydroperoxide. Other processes have been proposed based on cyclohexane where aniline is the final coproduct, or on cumene (qv) where a-methyl styrene is the final coproduct. 

The fatty acids obtained from the process can be used directly or further manipulated for improved or modified performance and stabiUty. Hardening is an operation in which some fraction of the unsaturated bonds present in the fatty acids are eliminated through hydrogenation or the addition of H2 across a carbon—carbon double bond. This process was initially intended to improve the odor and color stabiUty of fatty acids through elimination of the polyunsaturated species. However, with the growth in the use of specialty fatty acids, hydrogenation is a commercially important process to modify the physical properties of the fatty acids. 

Hori ntalEetort. In 1800, the first commercial zinc process made use of the horizontal retort. In 1980, only three such plants remain because they are not competitive in terms of labor and fuel costs. Furthermore, the dust produced presents a serious pollution problem. Nevertheless, in 1956, the tonnage of zinc produced from horizontal retorts was above that of any previous year. The only remaining operation is in Russia with a capacity of 10,000 annual MT. 

Pure zirconium tetrachloride is obtained by the fractional distillation of the anhydrous tetrachlorides in a high pressure system (58). Commercial operation of the fractional distillation process in a batch mode was proposed by Ishizuka Research Institute (59). The mixed tetrachlorides are heated above 437°C, the triple point of zirconium tetrachloride. AH of the hafnium tetrachloride and some of the zirconium tetrachloride are distiUed, leaving pure zirconium tetrachloride. The innovative aspect of this operation is the use of a double-sheU reactor. The autogenous pressure of 3—4.5 MPa (30—45 atm) inside the heated reactor is balanced by the nitrogen pressure contained in the cold outer reactor (60). However, previous evaluation in the former USSR of the binary distiUation process (61) has cast doubt on the feasibHity of also producing zirconium-free hafnium tetrachloride by this method because of the limited range of operating temperature imposed by the smaH difference in temperature between the triple point, 433°C, and critical temperature, 453°C, a hafnium tetrachloride. 

A completely new approach for BTX production has emerged in recent years. It converts to paraffins into aromatics using a modified ZSM-5 zeoHte catalyst which contains gallium (19). An example of this approach, the Cyclar process, has been in commercial operation by British Petroleum at Grangemouth, Scotiand since August 1990 (20). It uses C —feed and employs UOP s CCR technology to compensate for rapid catalyst coking. 

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