Methanol, production liquid phase process

Another way of avoiding less economical and toxic phosgene involves the use of dimethyl carbonate for the production of isocyanates and polycarbonates. In Japan, Ube have operated the first pilot plant for the highly selective gas-phase carbonylation of methanol. Further liquid-phase processes for the production of dimethyl carbonate are in operation at Daicel and Mitsui Sekka. 

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... 

The process of direct synthesis of DME includes reactions of methanol synthesis and methanol dehydration, which are catalyzed by two different catalysts. Although the technology for the production of methanol is generally considered mature, most of thran are gas phase process, and the performances of these catalysts are restricted remarkably in liquid phase process. Development of high performance bifunctional catalyst system is very... 

The methanol hydrocarbonylaiion is usually carried out in the liquid phase using discontinuous batch reactors and continuous liquid phase processes have also been examined. It was claimed that in these processes, side-product formation can be suppressed and ethanol yields can be improved [23, 50]. Continuous... 

Air Products, Liquid-Phase Methanol Process Development Unit Instaliation, Operation and Support Studies Topical Report Task 10 Liquid Entrained Operations in the La Porte PDU,... 

Commercial-Scale Demonstration of the Liquid Phase Methanol Process -Project Performance Summary, Air Products Liquid Phase Conversion Company, June 2004. 

Significant development has occurred within the industry over the last several years with respect to liquid-phase processes. One example of this process that is reasonably close to commercialization is that developed by Air Products. A pilot unit has been operated for several years at their La Porte, Texas location. The process is characterized briefly as using an inert hydrocarbon reaction medium in the liquid phase to absorb the synthesis heat of reaction conventional copper-zinc catalyst is fed to the reactor system as a slurry. This type of process appears to be particularly well suited to substoichiometric feeds (hi earbon eontent), such as those produced by partial oxidation or coal gasification. The Air Products process has been extensively deseribed in patent literature [14]. Kinetie data and liquid-phase reaetion systems have also been extensively diseussed by Lee in Methanol Synthesis Technology [15]. 

Coal gasification may likely find future application in methanol production for utilization in combined cycle power generation facilities. In this case, the methanol (stored on-site as a liquid) will be utilized as a peak shaving fuel and will be produced from excess ifier capacity as power demand is reduced. Several different schemes have been proposed for combining methanol production with coal ification in a power plant scenario. This particular arrangement may be most favorable for a liquid-phase process (see reference to the Air Product process in Sec. 3.2.7) that can utilize a substoichiometric feed with a reasonable once-throu conversion while passing on unconverted gas to the combined cycle gas turbine as a fuel... 

Liquid-phase oxidation of lower hydrocarbons has for many years been an important route to acetic acid [64-19-7]. In the United States, butane has been the preferred feedstock, whereas ia Europe naphtha has been used. Formic acid is a coproduct of such processes. Between 0.05 and 0.25 tons of formic acid are produced for every ton of acetic acid. The reaction product is a highly complex mixture, and a number of distillation steps are required to isolate the products and to recycle the iatermediates. The purification of the formic acid requires the use of a2eotropiag agents (24). Siace the early 1980s hydrocarbon oxidation routes to acetic acid have decliaed somewhat ia importance owiag to the development of the rhodium-cataly2ed route from CO and methanol (see Acetic acid). 

Herm/es/Djnamit JS obe/Process. On a worldwide basis, the Hercules Inc./Dynamit Nobel AG process is the dorninant technology for the production of dimethyl terephthalate the chemistry was patented in the 1950s (67—69). Modifications in commercial practice have occurred over the years, with several variations being practiced commercially (70—72). The reaction to dimethyl terephthalate involves four steps, which alternate between liquid-phase oxidation and liquid-phase esterification. Two reactors are used. Eirst, -xylene is oxidized with air to -toluic acid in the oxidation reactor, and the contents are then sent to the second reactor for esterification with methanol to methyl -toluate. The toluate is isolated by distillation and returned to the first reactor where it is further oxidized to monomethyl terephthalate, which is then esterified in the second reactor to dimethyl terephthalate. 

One of the most important characteristics of IL is its wide temperature range for the liquid phase with no vapor pressure, so next we tested the lipase-catalyzed reaction under reduced pressure. It is known that usual methyl esters are not suitable for lipase-catalyzed transesterification as acyl donors because reverse reaction with produced methanol takes place. However, we can avoid such difficulty when the reaction is carried out under reduced pressure even if methyl esters are used as the acyl donor, because the produced methanol is removed immediately from the reaction mixture and thus the reaction equilibrium goes through to produce the desired product. To realize this idea, proper choice of the acyl donor ester was very important. The desired reaction was accomplished using methyl phenylth-ioacetate as acyl donor. Various methyl esters can also be used as acyl donor for these reactions methyl nonanoate was also recommended and efficient optical resolution was accomplished. Using our system, we demonstrated the completely recyclable use of lipase. The transesterification took place smoothly under reduced pressure at 10 Torr at 40°C when 0.5 equivalent of methyl phenylthioacetate was used as acyl donor, and we were able to obtain this compound in optically pure form. Five repetitions of this process showed no drop in the reaction rate (Fig. 4). Recently Kato reported nice additional examples of lipase-catalyzed reaction based on the same idea that CAL-B-catalyzed esterification or amidation of carboxylic acid was accomplished under reduced pressure conditions. ... 

MTBE is a well known enhancer of the number of octanes in gasoline and as excellent oxygentated fuel additives that decrease carbon monoxide emissions. Therefore, MTBE has been one of the fastest growing chemicals of the past decade. MTBE is produced by reacting methanol with isobutylene from mixed-C4 stream liquid phase over a strong acid ion-exchange resin as catalyst. An excess of methanol is used in order to improve the reaction conversion. This excess has to be separated from the final product. The pervaporation technique, more energy efficient and with lower cost process, has been proposed as alternative to distillation [74],... 

The TPA process. The technology involves the oxidation of p-xylene, as shown already in Figure 18—2. The reaction takes place in the liquid phase in an acetic acid solvent at 400°F and 200 psi, with a cobalt acetate/ manganese acetate catalyst and sodium bromide promoter. Excess air is present to ensure the p-xylene is fully oxidized and to minimize by-products. The reaction time is about one hour. Yields are 90—95% based on the amount of p-xylene that ends up as TPA. Solid TPA has only limited solubility in acetic acid, so happily the TPA crystals drop out of solution as they form. They are continuously removed by filtration of a slipstream from the bottom of the reactor. The crude TPA is purified by aqueous methanol extraction that gives 99 % pure flakes. 

Carbonylation of methanol to form acetic acid has been performed industrially using carbonyl complexes of cobalt ( ) or rhodium (2 ) and iodide promoter in the liquid phase. Recently, it has been claimed that nickel carbonyl or other nickel compounds are effective catalysts for the reaction at pressure as low as 30 atm (2/4), For the rhodium catalyst, the conditions are fairly mild (175 C and 28 atm) and the product selectivity is excellent (99% based on methanol). However, the process has the disadvantages that the proven reserves of rhodium are quite limited in both location and quantity and that the reaction medium is highly corrosive. It is highly desirable, therefore, to develop a vapor phase process, which is free from the corrosion problem, utilizing a base metal catalyst. The authors have already reported that nickel on activated carbon exhibits excellent catalytic activity for the carbonylation of... 

As indicated in Table 3, reducing the excess methanol to only a 3 fold molar excess (rendering a nearly solvent free process) far exceeded expectations and allowed significant reductions in the catalyst levels. Under these conditions, catalyst turnover numbers exceeding 10,000 mol MPA/mol Pd were achieved with a turnover frequency of >3400 mol MPA/mol Pd/h. The reaction mixtures obtained from this process formed two liquid phases and the product spontaneously separated from the amine and amine hydrochloride. As a consequence of eliminating large methanol excesses, the methyl pivaloylacetate concentration in the product was raised to 26 wt. % without additional reaction time being required. This represents an additional ca. 2.5 fold improvement in reactor productivity. No attempt was made to reduce the methanol further. 

Acetic Acid. Carbonylation of methanol is the most important reaction in the production of acetic acid.189-192 BASF developed a process applying C0I2 in the liquid phase under extreme reaction conditions (250°C, 650 atm).122 193 The Monsanto low-pressure process, in contrast, uses a more active catalyst combining a rhodium compound, a phosphine, and an iodine compound (in the form of HI, Mel, or T2).122 194—196 Methanol diluted with water to suppress the formation of methyl acetate is reacted under mild conditions (150-200°C, 33-65 atm) to produce acetic acid with 99% selectivity at 100% conversion. 

The major conventional processes for the production of acetic acid include the carbonylation of methanol (originally developed by Monsanto, and now carried out by several companies, such as Celanese-ACID OPTIMIZATION, BP-CATIVA, etc.), the liquid-phase oxidation of acetaldehyde, still carried out by a few companies, and the liquid-phase oxidation of n-butane and naphtha. More recent developments include the gas-phase oxidation of ethylene, developed by Showa Denko K.K., and the liquid-phase oxidation of butenes, developed by Wacker [2a],... 

In homogeneous catalysis, the catalyst is in the same phase as the reactants and products. Here we will concentrate on homogeneous catalysis in the liquid phase. In the classic case, the reactant (also called the substrate) molecules and the catalyst are reacted in a solvent. For example, the transesterification of fatty acid triglycerides with methanol (Figure 1.10) is catalyzed by hydroxide (OH-) ions. This is an important process for making fatty acid methyl esters which are then used as biodiesel. 

Originally, acetic acid was produced by fermentation this is still the major process for the production of vinegar. Modern production is by acetaldehyde oxidation, liquid phase hydrocarbon oxidation and preferentially by methanol carbonylation. The latter process is to be preferred because of the low raw material and energy costs. As early as 1913 BASF described the carbonylation of methanol at high temperature and pressure ... 

Despite the obvious improvements achieved in the hydrocarbonylation of methanol, several problems remain to be solved before a technical realization of this process is achieved. One serious drawback is the formation of side products. Tlie liquid phase contains not only alcohols, aldehydes and acetals but also ethers, acetates, and minor amounts of acetic add accompanied by the... 

Recently, some researchers have suggested that ether or ester linkages are hydrolyzed in supercritical water even without any catalyst. Sakaki ct al. have investigated non-catalytic decomposition of cellulose in subcritical water, and cellulose was found to be decomposed to water solubles, which were decomposed further after their yield reached nearly 80%, On entering the second decomposition process, the water solubles were converted into gaseous products and methanol-soluble products, and solid products like char were formed from the liquid phase. The hydrolysate of cellulose obtained in this process was subjected to a fermentation test, and the formed glucose was successfully converted into ethanol. 

Several types of reactors have been proposed such as the liquid entrained reactor(l) and the Trickle bed reactor(2). The authors have been studying a liquid-phase methanol synthesis process in order to develop a new technology as an alternative for a gas-phase process, and reported that a new process employing liquid-liquid separation of the products from the solvent has several advantages in practical methanol synthesis(3). 

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