Bases BASF process

The Texaco, Polymer Cracking, VEBA and BASF processes all produce mainly liquid organics or gases that replace primary oil- or gas-based resources. However, it has to be acknowledged that both BASF and VEBA have been closed down or will be closed down shortly, and that the other two processes have not yet been realised on a large scale. 

Economics. Comparison of the material and energy balance for our process and the cobalt-based BASF higher olefin process (8), we foimd that our process reduced the capital investment required by over 50% due to the fact that we require far fewer unit operations, and because the operating pressure is much lower. In sutmnary, the thermomorphic solution developed by TDA allows easy catalyst recycle, which, when coupled with the lower pressure operation possible with Rh catalysts (compared to the cobalt-based process) lowers both capital and operating costs for current oxidation (oxo) plants of similar capacity. 

The high catalyst loading typical of sol gel entrapped catalysts ensures a desirably high substrate/catalyst (S/C) ratio as the major part of the heterogeneous catalyst weight originates from the silicate matrix. For example, in a preparative-scale reaction of the alcohol raol-(2-naphthyl)-ethanol only 250 mg of sol-gel CaLB immobilizate could be used per 10 g of substrate. For comparison, all this makes the process based on sol-gel immobilized lipase very competitive with the commercial BASF process using lipase immobilized on Amberlite to produce the amine at a scale of 1000 tons per year. 

Other methods for the preparation of acetic acid are partial oxidation of butane, oxidation of ethanal -obtained from Wacker oxidation of ethene-, biooxidation of ethanol for food applications, and we may add the same carbonylation reaction carried out with a cobalt catalyst or an iridium catalyst. The rhodium and iridium catalysts have several distinct advantages over the cobalt catalyst they are much fester and fer more selective. In process terms the higher rate is translated into much lower pressures (the cobalt catalyst is operated by BASF at pressures of 700 bar). For years now the Monsanto process (now owned by BP) has been the most attractive route for the preparation of acetic acid, but in recent years the iridium-based CATTVA process, developed by BP, has come on stream. 

Among the various reactions catalyzed by bases, we have selected (i) the polymerization of ethylene oxide catalyzed by MgO (260), (ii) the closely related reaction of ethylene oxide with alcohols on basic hydrotalcites to give polyoxyethylene polymer (the Henkel process), (iii) the phenol alkylation with methanol on MgO (General Electric and BASF processes) (261), and (iv) phenol animation to give aniline on MgO (the USS process) (262). 

Ans. In the BASF process more Fischer-Tropsch by-products are formed. In Rh -based catalysis rhodium is maintained in the lower oxidation state, ensuring that 4.1 concentration is higher than 4.12 and the acetic acidforming cycle dominates. 

Since its discovery some 55 years ago, the synthesis of caprolactam has been the subject of intense research and development. Interest in alternative routes continues today and current activities receiving a lot of attention are carbon monoxide-based routes under development by DSM, EniChem and DuPont [32]. Numerous routes using a variety of feedstocks have been patented and many have been piloted, however, only seven have actually been commercialized. The first was the process developed by I. G. Farben based on Schlack s chemistry known today as the Rashig or conventional route. Other commercial routes are the CAPROPOL process, the BASF process, the DSM-HPO process, the Allied process, the Toray PNC process, and the SNIA Viscosa process. 

Compared to amines, which have traditionally been used as HQ-scavengers in this type of readion, the BASF process based on 1-methylimidazole circumvents the problematic, time-consuming and expensive filtration of a solid ammonium hydrochloride cake by yielding an ionic liquid, the 1-methylimidazolinium... 

With the advent of petrochemistry, BASF gradually replaced phenol by cyclohexane as the starting material. Development of a new continuous caprolactam process based on cyclohexane was started by BASF in 1950, and a full-scale plant went on stream in 1960 [20]. Similar processes based on cyclohexane were developed by DSM, Bayer and Inventa. A number of alternative processes were developed by other companies (Fig. 3). To name only some of them the cumene/phenol based process of Allied (on stream in 1958), the photonitrosation process of Toyo Rayon (1962), the toluene based Snia process (1964), and DuPont s nitrocyclohexane process (in operation from 1961 to 1966). 

Before 1970, acetic acid was manufactured by the BASF process utilizing cobalt-based catalysts, and high temperatures and pressures. Replacement of this procedure by the Monsanto process brought advantages of milder conditions and greater selectivity (Table 25.3). The Monsanto process uses a rhodium-based catalyst, and involves two interrelated... 

In the BASF process, methanol and CO are converted in the liquid phase by a homogeneous Co-based catalyst. The reaction takes place in a high-pressure Hastelloy reactor. In recent decades the BASF process has been increasingly replaced by low-pressure alternatives mainly due to lower investment and operating costs. In the low-pressure Monsanto process methanol and CO react continuously in liquid phase in the presence of a Rhl2 catalyst. In 1996, BP developed a new attractive catalyst based on iridium (Cativa process) the oxidative addition of methyl iodide to iridium is 150-times faster than to rhodium. The search for acetic acid production processes with even lower raw material costs has led to attempts to produce acetic acid by ethane oxidation. In the near future ethane oxidation will most likely not compete with methanol carbonylation (even though ethane is a very cheap and attractive raw material) because of the low ethane conversions, product inhibition problems, and a large variety of by-products. 

Fig. 6. Generic flow chart for the IL-based separation process [BASF, 2011 Maase, 2008]...

The industrial manufacture of acetic acid by methanol carbonylation (Equation (1)) has utilized catalysts based upon all three of the group 9 metals, since the initial development by BASF of a cobalt/iodide-based system. " The BASF process required harsh conditions of temperature and pressure, and suffered from relatively low selectivity. It was soon superceded by highly selective, low-pressure rhodium/iodide-based catalysts developed by Monsanto. The Monsanto process (and related variants operated by other manufacturers) quickly became dominant and remains one of the most successful examples of the commercial application of homogeneous catalysis.Rhodium catalysts for methanol carbonylation are discussed in Chapter 7.03. 

E. Leung, U. Mueller, N. Tmkhan, H. Mattenheimer, G. Cox, and S. Blei (BASF), Process for preparing porous metal-organic frameworks based on aluminum fumarate, WO 2012042410, 2012. 

The high temperatures and pressures used in the BASF process are conditions under which the FT reactions with soluble cobalt catalyst can take place. Based on the known reactions of cobalt carbonyls, the catalytic cycle shown in Figure 4.13 has been suggested. 

Mitsui Toatsu Chemical, Inc. disclosed a similar process usiag Raney copper (74) shortiy after the discovery at Dow, and BASF came out with a variation of the copper catalyst ia 1974 (75). Siace 1971 several hundred patents have shown modifications and improvements to this technology, both homogeneous and heterogeneous, and reviews of these processes have been pubHshed (76). Nalco Chemical Company has patented a process based essentially on Raney copper catalyst (77) ia both slurry and fixed-bed reactors and produces acrylamide monomer mainly for internal uses. Other producers ia Europe, besides Dow and American Cyanamid, iaclude AUied CoUoids and Stockhausen, who are beheved to use processes similar to the Raney copper technology of Mitsui Toatsu, and all have captive uses. Acrylamide is also produced ia large quantities ia Japan. Mitsui Toatsu and Mitsubishi are the largest producers, and both are beheved to use Raney copper catalysts ia a fixed bed reactor and to sell iato the merchant market. 

Patents claiming specific catalysts and processes for thek use in each of the two reactions have been assigned to Japan Catalytic (45,47—49), Sohio (50), Toyo Soda (51), Rohm and Haas (52), Sumitomo (53), BASF (54), Mitsubishi Petrochemical (56,57), Celanese (55), and others. The catalysts used for these reactions remain based on bismuth molybdate for the first stage and molybdenum vanadium oxides for the second stage, but improvements in minor component composition and catalyst preparation have resulted in yields that can reach the 85—90% range and lifetimes of several years under optimum conditions. Since plants operate under more productive conditions than those optimum for yield and life, the economically most attractive yields and productive lifetimes maybe somewhat lower. 

World installed capacity for formic acid is around 330,000 t/yr. Around 60% of the production is based on methyl formate. Of the remainder, about 60% comes from Hquid-phase oxidation and 40% from formate salt-based processes. The largest single producer is BASF, which operates a 100,000 t/yr plant at Ludwigshafen in Germany. The only significant U.S. producer of formic acid is Hoechst-Celanese, which operates a butane oxidation process. 

Until 1982, almost all methyl methacrylate produced woddwide was derived from the acetone cyanohydrin (C-3) process. In 1982, Nippon Shokubai Kagaku Kogyo Company introduced an isobutylene-based (C-4) process, which was quickly followed by Mitsubishi Rayon Company in 1983 (66). Japan Methacryhc Monomer Company, a joint venture of Nippon Shokubai and Sumitomo Chemical Company, introduced a C-4-based plant in 1984 (67). Isobutylene processes are less economically attractive in the United States where isobutylene finds use in the synthesis of methyl /i / butyl ether, a pollution-reducing gasoline additive. BASF began operation of an ethylene-based (C-2) plant in Ludwigshafen, Germany, in 1990, but favorable economics appear to be limited to conditions unique to that site. 

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