Methanol, methyl chloride from

Zinc chloride is also a catalyst for a liquid-phase process using concentrated hydrochloric acid at 100-150°C. Hydrochloric acid may be generated in situ by reacting sodium chloride with sulfuric acid. As mentioned earlier, methyl chloride may also be produced directly from methane with other chloromethanes. However, methyl chloride from methanol may be further chlorinated to produce dichloromethane, chloroform, and carbon tetrachloride. 

Figure 1.6 Simplified representation of inputs and outputs of a reaction to produce methyl chloride from methanol.

The reaction mechanism and rates of methyl acetate carbonylation are not fully understood. In the nickel-cataly2ed reaction, rate constants for formation of methyl acetate from methanol, formation of dimethyl ether, and carbonylation of dimethyl ether have been reported, as well as their sensitivity to partial pressure of the reactants (32). For the rhodium chloride [10049-07-7] cataly2ed reaction, methyl acetate carbonylation is considered to go through formation of ethyUdene diacetate (33) ... 

If attention at first is confined to the production of methyl silicone from the previously accepted raw materials, the chemical processes must include reduction of silica to silicon, preparation of the methyl chloride from methane or methanol, reaction of the methyl chloride with silicon, and hydrolysis of the methylchlorosilanes. If the same conventions are used as in the discussion of the,Grignard method, and the methanol process for methyl chloride is elected, the steps are ... 

Two oxidative carbonylation processes to DMC have been commercialized, one by EniChem uses a copper chloride catalyst the other, developed by Ube and Bayer uses methyl nitrite (from methanol, NO and oxygen). 

Ogura et al. [124] studied the photochemical and electrochemical oxidation of methane to methyl chloride and methanol. This room-temperature process evolved chlorine at a platinum anode followed by photochemical generation of CT (chloride radical) from CI2. The chloride radical subsequently oxidized methane gas (fed to the anode) to the methyl radical (CH3). The methyl radical reacted with chlorine gas to form methyl chloride which was immediately hydrolyzed to methanol. The formation of methyl chloride and methanol began at t.l V vs. SCE, which corresponds to the onset of chlorine evolution. 

Derivation (1) From kraft pulping black liquor by heating with inorganic sulfur compounds (2) by interaction of a solution of potassium sulfide and methyl chloride in methanol. 

OSi Specialties, a subsidiary of Witco, was nudged into action by the U. S. Environmental Protection Agency.53 The problem was loss of methyl and ethyl chloride in the wastewater from a process of making ethers from polyethylene oxide and polypropylene oxide. A complete study of all of the waste streams at the plant resulted in a solution that cost 600,000 dollars and saved 800,000 dollars. This was done by adding a unit that converted the excess methyl chloride from the process to methanol, which could be sold. An attorney for the company says, But if it hadn t made economic sense, we wouldn t have done it. If dimethyl carbonate could be used for the end-capping, there would be no waste salts produced and almost no wastewater. 

Analytical procedures used in the routine analysis of glycoproteins often involve methanolysis and subsequent N-acetylation of the liberated amino-sugars. However, it has been demonstrated that partial 0-acetylation of alditols (commonly employed as internal standards) accompanies the N-acetylation of amino-sugars. It was also shown that a hot neutral solution of methyl chloride in methanol releases L-fucose, sialic acid, and some D-galactose residues from aj-acid... 

Methyl Chloride. Most of the HCl consumed in the manufacture of methyl chloride [74-87-3] from methanol (qv) is a recycled product. The further reaction of methyl chloride with chlorine to produce higher chlorinated methanes generates significant amounts of HCl which are fed back into methyl chloride production. Another source of recycled HCl is siUcone production based on methyl chloride. 

The equihbrium shown in equation 3 normally ties far to the left. Usually the water formed is removed by azeotropic distillation with excess alcohol or a suitable azeotroping solvent such as benzene, toluene, or various petroleum distillate fractions. The procedure used depends on the specific ester desired. Preparation of methyl borate and ethyl borate is compHcated by the formation of low boiling azeotropes (Table 1) which are the lowest boiling constituents in these systems. Consequently, the ester—alcohol azeotrope must be prepared and then separated in another step. Some of the methods that have been used to separate methyl borate from the azeotrope are extraction with sulfuric acid and distillation of the enriched phase (18), treatment with calcium chloride or lithium chloride (19,20), washing with a hydrocarbon and distillation (21), fractional distillation at 709 kPa (7 atmospheres) (22), and addition of a third component that will form a low boiling methanol azeotrope (23). 

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. 

LiquidPha.se. The methyl chloride process with the widest use in the United States is the Hquid-phase methanol hydrochlorination process. SHicone producers use methyl chloride in its manufacture and produce an aqueous hydrochloric acid stream as a by-product. This by-product HCl is converted back to methyl chloride by hydrochlorination. In fact, it is possible to produce methyl chloride directiy from the chioromethylsilane hydrolysis step in the siHcone process (18,19) (see Silicon compounds, silicones). 

Methanol, heated at 250°C with chloroform or carbon tetrachloride in contact with active carbon, is converted in part to methyl chloride (52). Methyl chloride has been produced from methoxymagnesium chloride, CH OMgCl, a by-product from the manufacture of certain organo—sHicon compounds, by heating over 200°C (53). 

A representative technical grade of methyl chloride contains not more than the following indicated quantities in ppm of impurities water, 100 acid, such as HCl, 10 methyl ether, 20 methanol, 50 acetone, 50 residue, 100. No free chlorine should be detectable. Traces of higher chlorides are generally present in methyl chloride produced by chlorination of methane. The boiling point should be between —24 and —23° C, and 5—95% should distill within a range of about 0.2°C. It should be clear, colorless, and free from visible impurities. 

The procedure for preparing methyl coumalate is based on a method described by von Pechmann. Methyl coumalate has also been prepared by direct esterification of the reaction mixture from malic acid and fuming sulfuric acid and from comnalyl chloride and methanol. ... 

Acetylene is passed for 1 hr through a mixture consisting of 0.5 g (72 mg-atoms) of lithium in 100 ml of ethylene-diamine. A solution prepared from 1 g (3.5 mmoles) of rac-3-methoxy-18-methylestra-l,3,5(10)-trien-I7-one and 30 ml of tetrahydrofuran is then added at room temperature with stirring over a period of 30 min. After an additional 2 hr during which time acetylene is passed through the solution the mixture is neutralized with 5 g of ammonium chloride, diluted with 50 ml water, and extracted with ether. The ether extracts are washed successively with 10% sulfuric acid, saturated sodium hydrogen carbonate and water. The extract is dried over sodium sulfate and concentrated to yield a solid crystalline material, which on recrystallization from methanol affords 0.95 g (87%) of rac-3-methoxy-18-methyl-17a-ethynyl-estra-l,3,5(10)-trien-17jB-ol as colorless needles mp 161°. 

Chloro-1 -methyl-5-phenyl-s-trizolo[4,3-a]quinoline A stirred mixture of 6triethyl-orthoacetate (0.925 g,0.0057 mol) and xylene (100 ml) was refluxed, under nitrogen, for 2 hours 40 minutes. During this period the ethanol formed in the reaction was removed by distillation through a short,glass helix-packed column. The mixture was concentrated to dryness In vacuo and the residue was crystallized from methanol-ethyl acetate to give 1.28 g of 7-chloro-1-methyl-5-phenyl-s-triazolo[4,3-a]-quinoline (83.9% yield). The analytical sample was crystallized from methylene chloride methanol and had a melting point 252.5°-253.5°C. 

The reaction mixture is acidified with N hydrochloric acid (200 cc) and the oil formed is extracted with methylene chloride (200 cc). The methylene chloride solution is washed with water (210 cc), treated with decolorizing charcoal (5 grams), dried over anhydrous sodium sulfate and concentrated to dryness under reduced pressure (20 mm Hg) giving an oil (77 grams) which is crystallized from methanol (300 cc) to yield methyl ethyl (7-meth-oxy-10-methyl-3-phenthiazinyl)-malonate (62.4 grams) melting at 80°-82°C. 

To 5 grams of N,N -bis[1-methyi-3-(2,2,6-trimethylcyclohexyl)propyl]-N,N -dimethyl-1,6-hexanediamine dissolved in 100 ml of methanol, at 4°C, were added 100 ml methanol containing 10 grams of methyl chloride. The solution was heated in a closed vessel at 60°C for 15 hours. The colorless solution was concentrated and the resulting white solid crystallized from ethanol-acetonitrile-ether to obtain N,N -bis[1-methyl-3-(2,2,6-trimethylcyclo-hexyOpropyl] -N,N -dimethyl-1,6-hexanediamine bis(methochloride) hemihydrate. 

An alternative way to produce methyl chloride (monochloromethane) is the reaction of methanol with HCl (see later in this chapter, Chemicals from Methanol ). Methyl chloride could he further chlorinated to give a mixture of chloromethanes (dichloromethane, chloroform, and carhon tetrachloride). 

All of the above high-volume organic chemicals are obtained from petroleum or natural gas. This is why the modern organic chemical industry is frequently referred to as the petrochemical industry. The high-volume status of some of these compounds is due to their use to make others lower on the list. For example, ethylene is used to make ethylene dichloride, which, in turn, is used to make vinyl chloride. Ethyl benzene, made from benzene and ethylene, is used to make styrene. Methyl r-butyl ether is made from methanol and butylene, a captive intermediate for which production data is not available. 

Of the factors associated with the high reactivity of cyanuric chloride (high exother-micity, rapid hydrolysis in presence of water-containing solvents, acid catalysed reactions, liberation of up to 3 mol hydrogen chloride/mol of chloride, formation of methyl chloride gas with methanol, formation of carbon dioxide from bicarbonates), several were involved in many of the incidents recorded [1] (and given below). The acid catalysed self acceleration and high exothermicity are rated highest [2]. It is also a mildly endothermic compound (AH°f (s) +91.6 kJ/mol, 0.49 kJ/g). 

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