Methanol industrial production

Thermal chlorination of methane was first put on an industrial scale by Hoechst in Germany in 1923. At that time, high pressure methanol synthesis from hydrogen and carbon monoxide provided a new source of methanol for production of methyl chloride by reaction with hydrogen chloride. Prior to 1914 attempts were made to estabHsh an industrial process for methanol by hydrolysis of methyl chloride obtained by chlorinating methane. 

Methanol synthesis served as the model for the true mechanism. Stoichiometry, thermodynamics, physical properties, and industrial production rates were all taken from the methanol literature. Only the reaction mechanism and the kinetics of methanol synthesis were discarded. For the mechanism a four step scheme was assumed and from this the... 

In Russia in the 1960s, an industrial production of sebacic acid, HCOOC (CH2)4 COOH (an important intermediate for different plastics), was started which involves the anodic condensation of monomethyl adipate CH300C(CH2)4C00 . Dimethyl sebacate is obtained via the scheme of (15.58), and then hydrolyzed in autoclaves to the final product. Methanol is used as a solvent to lower the rates of side reactions. The reaction occurs with current yields attaining 75% and with chemical yields (degrees of utilization of the original adipate) of 82 to 84% (Vassihev et al., 1982). Upon introduction of this process it was no longer necessary to use castor oil, an expensive raw material that was needed to produce sebacic acid by the chemical process. 

The oxidative carbonylation of alcohols and phenols to carbonates can be catalyzed by palladium or copper species [154-213]. This reaction is of particular practical importance, since it can be developed into an industrial process for the phosgene-free synthesis of dimethyl carbonate (DMC) and diphenyl carbonate (DPC), which are important industrial intermediates for the production of polycarbonates. Moreover, DMC can be used as an eco-friendly methylation and carbonylation agent [214,215]. The industrial production of DMC by oxidative carbonylation of methanol has been achieved by Enichem [216] and Ube [217]. 

This method of transesterification is of high technical interest. Particularly the reaction of bisphenol A with diphenyl carbonate is a preferred phosgene-free process because biphenyl carbonate can be obtained directly from phenol and dimethyl carbonate.The latter is an industrial product made from CO and methanol. 

The above reaction is utilized in large-scale industrial production of methanol. Reaction with boron trichloride over a hot tungsten or tantalum filament yields boron and hydrogen chloride ... 

Methanol (methyl alcohol, wood alcohol) is widely used in the industrial production of synthetic organic compounds and as a constituent of many commercial solvents. In the home, methanol is most frequently found in the form of "canned heat" or in windshield-washing products. Poisonings occur from accidental ingestion of methanol-containing products or when it is misguidedly ingested as an ethanol substitute. 

The Methanol Institute is the trade association representing the methanol industry in the United States. One of its goals is to protect and expand markets for methanol. The single largest market for methanol is in the production of methyl tertiary butly ether (MTBE), the oxygenate additive used in cleaner-burning reformulated gasoline (RFG). 

MTBE is used on a large scale as an octane number boosting additive in unleaded gasoline. Sulfonic acid resins are applied as efficient catalysts for the industrial production of MTBE from methanol and isobutylene (222). Since 1987, investigations of the synthesis of MTBE with reactants in the gas phase have been performed with zeolites HY (223-225), H-Beta (226), HZSM-5 (224,225), and H-BZSM-5 (227) as catalysts. 

The synthesis of methyl /-butyl ether (MTBE) from isobutylene and methanol on TS-1 has been investigated. This reaction is catalyzed by acids and the industrial production is carried out with sulfonic acid resin catalysts. It has been reported that at 363-383 K the reaction proceeds in the presence of the acidic HZSM-5, but also on TS-1, which is much more weakly acidic. However, the characterization of the catalysts used is not completely satisfactory for instance, the IR spectra reported do not show the 960-cm 1 band that is always present in titanium-containing silicas. It is therefore possible that the materials with which the reaction has been studied are not pufe-phase TS-1. The catalytic activity for MTBE synthesis is, in any case, an interesting result, and further investigations with fully characterized catalysts are expected to provide a satisfactory interpretation of these results (Chang et al., 1992). 

In the industrial production of acetic acid the main production routes are based on the carbonylation of methanol, a process which was first developed in the 1940s. Although the process remains cheap, the availability and pricing of raw materials have forced the development of new processes based on the direct oxidation of ethylene to form acetic acid (Table 3, entry 24). Complex multimetal oxide... 

The industrial production of Crixivan (9 H2S04) took advantage of the chirality of (IS,2R)-aminoindanol to set the two central chiral centers of 9 by an efficient diastereoselective alkylation-epoxidation sequence.17 The lithium enolate of 12 reacted with allyl bromide to give 13 in 94% yield and 96 4 diastereoselective ratio. Treatment of a mixture of olefin 13 and V-chlorosuccinimide in isopropyl acetate-aqueous sodium carbonate with an aqueous solution of sodium iodide led to the desired iodohydrin in 92% yield and 97 3 diastereoselectivity. The resulting compound was converted to the epoxide 14 in quantitative yield. Epoxide opening with piperazine 15 in refluxing methanol followed by Boc-removal gave 16 in 94% yield. Finally, treatment of piperazine derivative 16 with 3-picolyl chloride in sulfuric acid afforded Indinavir sulfate in 75% yield from epoxide 14 and 56% yield for the overall process (Scheme 24.1).17-22... 

Methyl chloride is an important industrial product, having a global annual capacity of ca. 900 000 tons. Its primary use is for the manufacture of more highly chlorinated materials such as dichloromethane and chloroform and for the production of silicone fluids and elastomers. It is usually manufactured by the reaction of methanol with hydrogen chloride with a suitable acid catalyst, such as alumina. To develop a site-specific reaction mechanism and a kinetics model for the overall process, one first needs to identify all the reagents present at the catalyst surface and the nature of their interactions with the surface. The first step in the reaction is dissociative adsorption of methanol to give adsorbed methoxy species. Diffuse reflectance IR spectroscopy (29d) showed the expected methoxy C-H stretch and deformations, but an additional feature, with some substructure, at 2600 cm was... 

Manufacture. Chlorine gas is introduced into benzene voider sunlight or a fluorescent lamp. The reaction temperature is 25 0°C. Or chlorine gas is introduced into 1 2% sodium hydroxide solution in water, on which benzene is floated. Lindane is manufactured by the purification of industrial products by methanol. 

Normally, gasifier capacity is proportional to Vp.32 The pressure may be as high as 10 MPa in a GE gasification system. Also, the operating pressure is selected based on the purpose of the gas product in the ammonia industry, the operating pressure ranges from 8.5 to 10MPa, while in methanol industry, the pressure is 6-7 MPa. 

Indeed, the methanol industry all but abandoned support for the methanol fuel vehicle market it helped launch in 1988, as demand for MTBE consumed most of the world supply for methanol needed to produce it. At the end of the decade, the use of MTBE began to decline over concerns about water quality impacts, but ethanol use continues to grow at a steady pace. If making a market for agricultural products was a goal, we are increasingly successful. 

Even though new MTBE plants are not being built in North America, CD is used currently for the production of other oxygenates such as TAME or ETBE, which being less soluble in water (i.e., less tendency to be transported in groundwater) are being considered or used as alternative octane enhancers. Ethyl-tert-butyl ether is produced from the etherification of ethanol and isobutylene while TAME production requires isoamylene and methanol. A simulation of the industrial production of a green octane enhancer from... 

Presently industrial production of biodiesel from waste edible oil is performed by chemical alkaline catalysts, but it has been found that high content of free fatty acid (FFA) in waste edible oil (FFA>2%) would decrease the yield sharply due to soaps formed in the process (7). Several studies showed that enzymatic methanolysis with waste edible oil was a promising alternative owing to its mild reaction condition and free of chemical waste (2, 5). However, this conventional protocol was associated with many drawbacks such as deactivation of lipase caused by methanol and absorption of glycerol to lipase surface, thus resulting in serious negative effect on the reaction (4,5). 

Although the current industrial methanol synthesis is highly selective to methanol, side products are formed in quantities determined by the specific catalyst used and by the reaction conditions. These side reactions involve... 

Only a few studies of the poisoning of copper/zinc oxide catalysts have been reported (refs. 4-6). Whether copper or zinc is most susceptible to attack by sulfur is still a question. The literature findings on the sulfur tolerance of methanol synthesis catalyst are inconsistent with industrial experience. For example, observations from industrial production suggest that a... 

Methyl terf-butyl ether (MTBE) is an important industrial product used as oxygenate additive in reformulated gasoline. Environmental concern makes its future uncertain, however. Although mainly manufactured by reaction of isobutylene with methanol, it is also produced commercially from methanol and fcrr-butyl alcohol, a by-product of propylene oxide manufacture. Numerous observations from the use of heteropoly acids have been reported. These compounds were used either as neat acids [74], or supported on oxides [75], silica or K-10 montmorillonite [76]. They were also used in silica-included form [77] and as acidic cesium salts [74,77]. Other catalysts studied were sulfated ZrOj [76], Amberlyst 15 ion-exchange resin [76], HZSM-5 [76], HF-treated montmorillonite, and commercial mineral acid-activated clays [75]. Hydrogen fluoride-treatment of montmorillonite has been shown to furnish particularly active and stable acid sites thereby ensuring high MTBE selectivity (up to 94% at 413 K) [75]. 

Catalytic processes today dominate the production of sulfuric acid, ammonia, methanol, and many other industrial products. The cracking of mineral oils, the hydrogenation, transformation, and synthesis of hydrocarbons are almost all centered around catalytic conversions carried out with many different catalysts including some of highly specific action. Many more catalyzed reactions are being carried out in batch processes and in continuous operations, in heterogeneous and in homogeneous systems. 

In the large-scale industrial production of methylamines, methanol and NH3 are reacted at 350-500 °C and ca. 20 bar in the presence of AI2O3. A mixture of mono-, di-, and trimethylamine is obtained with an equilibrium content of ca. 62 % tri-methylamine. However, trimethylamine is of only minor economic importance. 

A remarkable application of reactions of this type would be if carbonylation with CO is replaced by reaction with CO2. An example of this is the use of sc CO2 in the catalytic production of dimethylformamide (DMF), a very important organic solvent. The present industrial production of DMF is based on the carbonylation of dimethylamine in the presence of methanol. Recent studies have shown that DMF can also be produced by reacting dimethylamine, sc CO2, and hydrogen in the presence of a homogeneous ruthenium catalyst (Jessop et al., 1994a). Reactions of this type can add a new dimension to the more conventional carbonylation by CO in the presence of a homogeneous catalyst (see Chapter 8). 

K. D., Flickinger, M.C., and Ellingsen, T.E. (2007) Bacillus methanolicus a candidate for industrial production of amino acids from methanol at 50 °C. Appl. Microbiol. Biotechnol., 74, 22-34. 

---