Sulfur methanol synthesis

Natural gas contains both organic and inorganic sulfur compounds that must be removed to protect both the reforming and downstream methanol synthesis catalysts. Hydrodesulfurization across a cobalt or nickel molybdenum—zinc oxide fixed-bed sequence is the basis for an effective purification system. For high levels of sulfur, bulk removal in a Hquid absorption—stripping system followed by fixed-bed residual clean-up is more practical (see Sulfur REMOVAL AND RECOVERY). Chlorides and mercury may also be found in natural gas, particularly from offshore reservoirs. These poisons can be removed by activated alumina or carbon beds. 

This direct, oxidative condensation of methane to acetic acid in one-pot could be competitive with the current three-step, capital intensive process for the production of acetic acid based on methane reforming to CO, methanol synthesis from CO, and generation of acetic acid by carbonylation of methanol. Key improvements required with the PdS04/H2S04 system, however, will be to develop more stable, faster, and more selective catalysts. Although it is possible sulfuric acid could be utilized industrially as a solvent and oxidant for this reaction, it would be desirable to replace sulfuric acid with a less corrosive material. This chemistry has recently been revisited, verified, and extended by Bell et al., who used Cu(II)/02 as the oxidizing system [22],... 

The modern methanol synthesis catalyst consists of copper, zinc oxide, and alumina. Copper metal is seen as the catalytically active phase, and ZnO as the promoter. It is well known that the interaction between the two components is essential for achieving a high activity, but the nature of the promoting effect is still a matter of debate. Loss of activity is caused by sintering of the Cu crystallites, and, if the feed gas contains impurities such as chlorine and sulfur, by poisoning. 

In order to prevent any sulfur or other poisons, such as hydrogen cyanide, from reaching the methanol synthesis catalyst, the make-up synthesis gas is passed over an absorbent catalyst and finally cooled for the suction of the synthesis gas circulator in the methanol synthesis loop. 

Sulfur poisoning is a key problem in hydrocarbon synthesis from coal-derived synthesis gas. The most important hydrocarbon synthesis reactions include methanation, Fischer-Tropsch synthesis, and methanol synthesis, which occur typically on nickel, iron, or cobalt, and ZnO-Cu catalysts, respectively. Madon and Shaw (2) reviewed much of the early work dealing with effects of sulfur in Fischer-Tropsch synthesis. Only the most important conclusions of their review will be summarized here. 

Methanol. Methanol is a water-soluble, low molecular weight alcohol that may be of increasing importance as a low-sulfur fuel, a chemical feedstock, and perhaps as a gasoline additive or an intermediate in gasoline production. The synthesis of methanol is accomplished by the catalytic conversion of synthesis gas containing two moles of hydrogen for each mole of carbon monoxide. Methanol synthesis is widely practiced in industry on a commercial scale. See Chapter 10 for a discussion of methanol manufacture. 

Temperature profiles, reactors ammonia synthesis, 582, 584 cement kiln, 590 cracking of petroleum, 595 endo- and exothermic processes, 584 jacketed tubular reactor, 584 methanol synthesis, 580 phosgene synthesis, 594 reactor with internal heat exchange, 584 sulfur dioxide oxidation, 580... 

SULFUR POISONING AND TOLERANCE OF METHANOL SYNTHESIS CATALYSTS CHAI GUOYONO. AIDAGANG, and LI CHENGYlJE ... 

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

This paper addresses sulfur poisoning and sulfur tolerance of methanol synthesis catalysts under laboratoiy and commercial conditions, effects of catalyst formulation on sulfur tolerance and the forms of sulfur compounds in poisoned catalysts. 

Effect of sulfur poisoning on methanol synthesis activity... 

The methanol synthesis activities of Samples 1-6 were determined before, during and after pulsing H2S end are tabulated in Table I. All the samples except 3 were in a single-pass tubular reactor. Sample 3 was tested in an internal recycle reactor, the amount of which (5 cm ) was about five times of those tested in the tubular reactor. For the same amount of fresh feed and pulsed H2S, the methanol yield of Sample 3 and its sulfur content were much lower than those of other samples. The typical effect of pulsing H2S to the feed gas stream is... 

L. R. Radovic and M. A. Vannice, Sulfur Tolerance of Methanol Synthesis Catalysts, Appl. Catal. 29(1987)1-20. 

Primary steam reforming Secondary steam reforming Carbon monoxide conversion Carbon monoxide methanation Ammonia synthesis Sulfuric acid synthesis Methanol synthesis Oxo synthesis Ethylene oxide Ethylene dichloride Vinylacetate Butadiene Maleic anhydride Phthalic anhydride Cyclohexane Styrene Hydrodealkylation Catalytic reforming Isomerization Polymerization (Hydro)desulfurization Hydrocracking... 

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