Production of methanol

LeBlanc, Robert V. Schneider, III, and Richard B. Strait The M. W. Kellogg Company, Houston, T exas 

It is reported [1] that methanol was first isolated in 1661 by Sir Robert Boyle by rectifying crude vine r over milk of lime. Independently, both Justus Von Liebig (18031873) and J. B. A. Dumas (18001884) determined the composition of methanol As a result of their work, the term methyl was introduced into chemistry in 1835. 

Commercially, the first process for the production of methanol was by the destructive distillation of wood, thus the souree of the eommon name wood alcohol. Wood was the source of methanol from about 1830 until the mid-1920s [2]. It was at that time that a proeess for the synthetic manufacture of methanol was put into commercial operation by Badische Anilin-und-Soda-Fabrik (BASF) in Germany. Before the BASF process, methanol was considered a specialty chemical With the introduction of synthetic methanol, the supply of methanol greatly increased. In the early 1920s in the United States, the demand for methanol was some 15,00030,0001 per year. By the early 1940s, the demand in the United States increased to over 180,0001. This sharp inerease reflected the use of methanol as a ehemical intermediate, a feedstock for downstream processes. 

BASF introduced the first large-scale commercial methanol plant in 1923. Perhaps this was not too surprising because BASF first commercialized the 

In the United States, a subsidiary of the DuPont Company, Lazote, Inc., made synthetic methanol at Belle, West Virginia. The Belle operation was part of the ammonia plant at the site. The methanol production was actually a step in the ammonia process for removing carbon monoxide, which was an impurity in the ammonia synthesis gas. Commercial Solvents was the first to employ the high-pressure synthesis process, developed by BASF, in the United States. The plant, located in Peoria, lUinois, began operation a few months after the Lazote plant at Belle. The Commercial Solvents plant used an off-gas from a fermentation operation. The off-gas contained carbon dioxide and hydrogen from the production of butanol from corn. This first of a kind plant in the United States was rated at about 4000 t per year. 

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Catalytic gas-phase reactions play an important role in many bulk chemical processes, such as in the production of methanol, ammonia, sulfuric acid, and nitric acid. In most processes, the effective area of the catalyst is critically important. Since these reactions take place at surfaces through processes of adsorption and desorption, any alteration of surface area naturally causes a change in the rate of reaction. Industrial catalysts are usually supported on porous materials, since this results in a much larger active area per unit of reactor volume. 

As an example of the application of a fixed-bed tubular reactor, consider the production of methanol. Synthesis gas (a mixture of hydrogen, carbon monoxide, and carbon dioxide) is reacted over a copper-based cat dyst. The main reactions are... 

Emissions from methanol vehicles are expected to produce lower HC and CO emissions than equivalent gasoline engines. However, methanol combustion produces significant amounts of formaldehyde (qv), a partial oxidation product of methanol. Eormaldehyde is classified as an air toxic and its emissions should be minimized. Eormaldehyde is also very reactive in the atmosphere and contributes to the formation of ozone. Emissions of NO may also pose a problem, especiaHy if the engine mns lean, a regime in which the standard three-way catalyst is not effective for NO reduction. 

Cyclopentadiene itself has been used as a feedstock for carbon fiber manufacture (76). Cyclopentadiene is also a component of supported metallocene—alumoxane polymerization catalysts in the preparation of syndiotactic polyolefins (77), as a nickel or iron complex in the production of methanol and ethanol from synthesis gas (78), and as Group VIII metal complexes for the production of acetaldehyde from methanol and synthesis gas (79). 

For the production of methanol, this mixture could he used directly with no further treatment except adjusting the H2/(CO + CO2) ratio to approximately 2 1. 

In order to indicate the hierarchical position of a section, the top of every page of text shows the headings of up to three connected sections that are superior in hierarchy. These running heads provide the context within which the title of the section under discussion becomes meaningful. As an example, the page of Volume 1 on which section 1.4.9.1.3 in the Production of Methanol starts, carries the running heads ... 

The synthesis gas is mainly used for the production of methanol (70%). Another part (20%) is used for electricity production. Waste gas products are incinerated the fate of any chlorine is not clear from the various descriptions available. Inorganic materials are converted into a slag, with low leaching characteristics (landfill class 1 according to the German TA Siedlungsabfall). 

When the selectivity of a reaction is controlled by differences in the way molecules are activated on different sites, the probability of the presence of different sites becomes important. An example again can be taken from the activation of CO. For methanation, activation of the CO bond is essential. This will proceed with low barriers at step-edge-type sites. If one is interested in the production of methanol, catalytic surfaces are preferred, which do not allow for easy CO dissociation. This will typically be the case for terrace sites. The selectivity of the reaction to produce methanol will then be given by an expression as in Eq. (1.29a) ... 

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... 

Photoreduction of CO2 to formate in metal sulfide colloids has been reported to provide a novel photosynthetic route for production of methanol as the end-product... 

Donnelly Ml, S Dagley (1980) Production of methanol from aromatic acids by Pseudomonas putida. J Bacterial 142 916-924. 

Photocatalytic Production of Methanol and Hydrogen from Methane and Water... 

Figure 2 shows the result of an experiment without photocatalyst where the reactor tenperature was maintained at 97°C during the run. Note that conversions of methane remain relatively constant at - 4% and production of hydrogen, methanol, oxygen, and carbon monoxide remain constant during the ejqjeriment. The large oscillations in the conversion of methane and the production of methanol were not observed during this ejqjeriment. 

Entina VS, Petrii OA, Rysikova VT. 1967. On the nature of products of methanol chemisorption on Pt + Ru electrode surface. Elektrokhimiya 3 758-761. 

Petukhova RP, Stenin VF, Podlovchenko BI. 1977. About the composition of the products of methanol electrooxidation on smooth platinum. Elektrokhimiya 14 755-756. 

Using on-line mass spectroscopy [65] carbon dioxide and formic acid were demonstrated as soluble products of methanol oxidation. The former gives the most intense MS signal according to the fact that it is the main product. There are two main problems to detect formic acid as such. In the presence of carbon dioxide most of the m/e signals of HCOOH overlap with signals of the major product. Besides this, in the presence of methanol, formic acid reacts to form the methyl ester ... 

The SNIFTIRS results presented here confirm the presence of formic acid and methyl formate as by-products of methanol oxidation. Other by-products such as formaldehyde could not be detected under our experimental conditions. In fact, formaldehyde hydrolyses (99.99%) in aqueous solutions to a gemdiol H2C(OH)2, and the typical aldehyde bands are, therefore, not expected. 

Hamelinck, C. Faaij, A. P. C., Future prospects for production of methanol and hydrogen from biomass. Journal of Power Sources 2002,111(1), 1-22. 

Larson, E. D. Katofsky, R. E., Production of Methanol and Hydrogen from Biomass. Center for Energy and Environmental Studies, School of Engineering and Applied Science, Princeton University, Princeton, NJ, 1992. 

The production of methanol from synthesis gas is a well-established process (23, 102), and there have been predictions that methanol itself could become the fuel of the future (103). Whether or not this prediction will prove correct is debatable4 meanwhile, Mobil suggests that coupling known methanol production technology with their new process provides an economically attractive alternative to both Fischer-Tropsch fuels and direct utilization of methanol (104). 

Two configurations of stirred-tank reactors are to be considered for carrying out the reversible hydrolysis of methyl acetate (A) to produce methanol (B) and acetic acid (C) at a particular temperature. Determine which of the following configurations results in the greater steady-state rate of production of methanol ... 

The molar rate of production of methanol from stage 1 is... 

Sulfur is a potential problem even at low levels for synthesis gas systems using certain types of catalysts. The production of methanol from synthesis gas, for example, uses catalysts that are poisoned by sulfur. Some tar cracking catalysts are also sulfur sensitive. In those systems, thorough removal of sulfur will be required. Fuel cell systems are also sulfur sensitive. 

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