Acetic acid, production methanol

Figure 3 shows the production of acetaldehyde in the years 1969 through 1987 as well as an estimate of 1989—1995 production. The year 1969 was a peak year for acetaldehyde with a reported production of 748,000 t. Acetaldehyde production is linked with the demand for acetic acid, acetic anhydride, cellulose acetate, vinyl acetate resins, acetate esters, pentaerythritol, synthetic pyridine derivatives, terephthaHc acid, and peracetic acid. In 1976 acetic acid production represented 60% of the acetaldehyde demand. That demand has diminished as a result of the rising cost of ethylene as feedstock and methanol carbonylation as the preferred route to acetic acid (qv). 

About half of the wodd production comes from methanol carbonylation and about one-third from acetaldehyde oxidation. Another tenth of the wodd capacity can be attributed to butane—naphtha Hquid-phase oxidation. Appreciable quantities of acetic acid are recovered from reactions involving peracetic acid. Precise statistics on acetic acid production are compHcated by recycling of acid from cellulose acetate and poly(vinyl alcohol) production. Acetic acid that is by-product from peracetic acid [79-21-0] is normally designated as virgin acid, yet acid from hydrolysis of cellulose acetate or poly(vinyl acetate) is designated recycle acid. Indeterrninate quantities of acetic acid are coproduced with acetic anhydride from coal-based carbon monoxide and unknown amounts are bartered or exchanged between corporations as a device to lessen transport costs. 

Butane. Butane LPO has been a significant source for the commercial production of acetic acid and acetic anhydride for many years. At various times, plants have operated in the former USSR, Germany, Holland, the United States, and Canada. Only the Hoechst-Celanese Chemical Group, Inc. plants in Pampa, Texas, and Edmonton, Alberta, Canada, continue to operate. The Pampa plant, with a reported aimual production of 250,000 t/yr, represents about 15% of the 1994 installed U.S. capacity (212). Methanol carbonylation is now the dominant process for acetic acid production, but butane LPO in estabhshed plants remains competitive. 

Catalysts. Iodine and its compounds ate very active catalysts for many reactions (133). The principal use is in the production of synthetic mbber via Ziegler-Natta catalysts systems. Also, iodine and certain iodides, eg, titanium tetraiodide [7720-83-4], are employed for producing stereospecific polymers, such as polybutadiene mbber (134) about 75% of the iodine consumed in catalysts is assumed to be used for polybutadiene and polyisoprene polymeri2a tion (66) (see RUBBER CHEMICALS). Hydrogen iodide is used as a catalyst in the manufacture of acetic acid from methanol (66). A 99% yield as acetic acid has been reported. In the heat stabiH2ation of nylon suitable for tire cordage, iodine is used in a system involving copper acetate or borate, and potassium iodide (66) (see Tire cords). 

The whole is slowly heated to 85°C and stirred at this temperature for 45 minutes. The reaction mixture is cooled and the precipitated product is filtered off. It is washed successively with water and ethanol, dried and crystallized from a mixture of acetic acid and methanol, yielding methyl N-[5(6)-benzoyl-2-benzimidazolyl] carbamate MP 288.5°C. 

The carbonylation of methanol is currently one of the major routes for acetic acid production. The basic liquid-phase process developed by BASF uses a cobalt catalyst at 250°C and a high pressure of about 70... 

When equilibrium is reached in reaction (25), appreciable concentrations of all of the reactants may be present. If methyl acetate (the product on the right) alone is dissolved in water, it will react with water slowly to give acetic acid and methanol until equilibrium is attained ... 

The investigated cw-stilbene derivatives, 4-methoxy, 4,4 -dimethyl, unsubstituted, and 4,4 -bis(trifluoromethyl)stilbenes, had k2 values spanning 6-7 powers of ten both in methanol and in acetic acid. Products 2, 4, 5 and 6 were formed. Table 8 reports the results of the cis-trans isomerization test in acetic acid (ref. 29). No acid catalyzed or free radical process was found to be responsible for these isomerizations. 

This reversal has been demonstrated by both product and kinetic studies. In the absence of solvent nucleophilic assistance and of substituents favouring P-bromo-carbonium ion intermediates, the ionization of CTCs to bromonium (poly)bromide has been shown to occur not only for congested olefins, but more generally for "normal olefins both in aprotic chlorinated hydrocarbons and in protic solvents like acetic acid and methanol. 

The formation of C-C bonds is of key importance in organic synthesis. An important catalytic methodology for generating C-C bonds is provided by carbonylation. In the bulk chemicals arena this is used for the production of acetic acid by methanol carbonylation (Eqn. (9)) in the presence of rhodium- or, more recently, iridium-based catalysts (Maitlis et al, 1998). 

However, reaction of 1,2,3-benzothiadiazole 3 with 30% hydrogen peroxide in a mixture of acetic acid and methanol for 45 days afforded product 37 (Equation 7) in 60% yield <1990CJC1950>. Oxidation of 1,2,3-benzothiadiazole 3 with a variety of other oxidizing agents (w-chloroperoxybenzoic acid, 30% hydrogen peroxide, hydrogen peroxide in methylene chloride-acetic acid mixtures, etc.) was unsuccessful. 

A typical configuration for a methanol carbonylation plant is shown in Fig. 1. The feedstocks (MeOH and CO) are fed to the reactor vessel on a continuous basis. In the initial product separation step, the reaction mixture is passed from the reactor into a flash-tank where the pressure is reduced to induce vapourisation of most of the volatiles. The catalyst remains dissolved in the liquid phase and is recycled back to the reactor vessel. The vapour from the flash-tank is directed into a distillation train which removes methyl iodide, water and heavier by-products (e.g. propionic acid) from the acetic acid product. 

Sulphonated azo dyes were separated and quantitated in various food products by ion-pair liquid chromatography with DAD and electrospray MS detection. The chemical structure of sulphonated azo dyes included in the investigation are shown in Fig. 3.36. Dyes were separated in an ODS column (125 X 2.0 mm i.d. particle size 5 pm) using gradient elution. An aqueous solution of 3 mM triethylamine (pH adjusted to 6.2 with acetic acid) and methanol... 

In homogeneous catalytic systems we witnessed a new process for the production of acetic acid from methanol and carbon monoxide using a transition metal complex, thus displacing the earlier process employing ethylene as the starting material. The use of immobilized enzymes makes possible the commercial conversion of glucose into fructose. 

Conversion rates as high as 99% are not encountered very often in the petrochemical industry. That coupled with relatively mild operating conditions, made this route, the economic favorite since it was introduced. About 75% of the world s acetic acid production comes from the methanol route. 

In a kinetic study of the esterification of acetic acid with methanol in the presence of hydrogen iodide, iodimethane was identified as a by-product. The authors propose that this derives from iodide ion attack on protonated methanol. However, attack by iodide ion on protonated methyl acetate (10) is more likely, since acetic acid is a better leaving group than ethanol. 

As we shall also see, there are also many uses of CO. Examples are acetic acid production, which is made by reacting methanol with CO... 

Acetic Acid Production via Low-Pressure, Nickel-Catalyzed Methanol Carbonylation... 

Butane is used in the petrochemical industry to produce a variety of other compounds. Oxygenated products of n-butane include acetic acid (CH3COOH), methanol (CH3OH),... 

Whatever the source of synthesis gas, it is the starting point for many industrial chemicals. Some examples to be discussed are the hydroformylation process for converting alkenes to aldehydes and alcohols, the Monsanto process for the production of acetic acid from methanol, the synthesis of methanol from methane, and the preparation of gasoline by the Mobil and Fischer-Tropsch methods. 

Catalysts used to convert ethylene to vinyl acetate are closely related to those used to produce acetaldehyde from ethylene. Acetaldehyde was first produced industrially by the hydration of acetylene, but novel catalytic systems developed cooperatively by Farbwerke Hoechst and Wacker-Chemie have been used successfully to oxidize ethylene to acetaldehyde, and this process is now well established (7). However, since the largest use for acetaldehyde is as an intermediate in the production of acetic acid, the recent announcement of new processes for producing acetic acid from methanol and carbon monoxide leads one to speculate as to whether ethylene will continue to be the preferred raw material for acetaldehyde (and acetic acid). 

Backus, J., Fabiilli, M., Sanchez, D., and Wong, E. 2003. Acetic acid production via carbonylation of methanol Technical and economical feasibility study, Vol. I, Fugacitech, Inc., Ann Arbor, Michigan, April, 4 (online publication, http //www-personal.engin.umich.edu/ mfabiill/Report% 20rev06.doc). 

Methanol, also called methyl alcohol and once commonly know as wood alcohol, is a clear, volatile liquid mp, -98°C bp, 65°C). Until the early 1900s, the major commercial source of methanol was the destructive distillation (pyrolysis) of wood, a process that yields a product contaminated with allyl alcohol, acetone, and acetic acid. Now methanol is synthesized by the following reaction of hydrogen gas and carbon monoxide, both readily obtained from natural gas or coal gasification ... 

Charcoal was a valued commodity in antiquity. The ancient Egyptians used the volatile product of hardwood distillation, pyroligneous acid, for embalming. Before synthetic organic chemistry became well established, destructive hardwood distillation provided several important industrial chemicals, among these were acetone, acetic acid, and methanol (still often referred to as wood alcohol). Charcoal is a fine, smokeless fuel, prized for its smokeless nature and used extensively for outdoor cooking. Acetone was originally made by the dry distillation of calcium acetate made from wood-derived acetic acid, but better, cheaper sources are also available. 

In principle, the zeolite catalyst system would offer advantages over the existing homogeneous catalyst, particularly with respect to corrosion due to the absence of HC1 and chlorine-containing by-products. However, acetaldehyde and acetic-acid production via ethylene has recently become less economically attractive compared to methanol carboxylation chemistry. 

The novel synthesis required fewer process steps, and this resulted in lower costs and investment. In 1969, another advance was announced—the synthesis of acetic acid from methanol and carbon monoxide with essentially no by-products or co-products.15 16... 

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