Sulfur catalysts synthesis

Molybdenum and tungsten are unique in that they are resistant to sulfur, and, in fact, are commonly sulfided before use. The Bureau of Mines tested a variety of molybdenum catalysts (32). They are moderately active but relatively high temperatures are required in order to achieve good conversion, even at low space velocities. Selectivity to methane was 79-94%. Activity is considerably less than that of nickel. Although they are active with sulfur-bearing synthesis gas, the molybdenum and tungsten catalysts are not sufficiently advanced to be considered candidates for commercial use. 

During the first operating period (750-950 hrs), the plant was run with the ZnO emergency catchpot on line. Sulfur content could be decreased to 0.04 mg total sulfur/m3 synthesis gas and 0.02 mg H2S/m3. Conversion in the first 6.3% of the catalyst bed decreased from 50 to 46% while no change in conversion was detectable in the first 23.8% of the bed. 

One stage in the manufacture of sulfuric acid is the formation of sulfur trioxide by the reaction of S02 with 02 in the presence of a vanadium(V) oxide catalyst. Predict how the equilibrium composition for the sulfur trioxide synthesis will tend to change when the temperature is raised. 

Additionally, the following factors are believed to have an increase in the amount of carbon deposited on cobalt catalysts higher reaction temperature,39-63 lower H2/CO ratio,63 higher CO partial pressures,59 and cleaner (sulfur-free) synthesis gas.33-64... 

Topsoe, H.F.A. andNielsen, A. (1948). The Action of Vanadium Catalysts in the Sulfur Trioxide Synthesis. Trans. Dan. Acad. Techn. Sci. 1, 3-24... 

D. Farcasiu and J. Q. Li, Preparation of sulfated zirconia catalysts with improved control of sulfur content, 111 effect of conditions of catalyst synthesis on physical properties and catalytic activity,... 

In industrial practice, catalytic surfaces are often very complex, not only structurally but also chemically. An example is shown in Fig. 1 from Chianelli et al. [6] for hydrodesulfurization catalysts. The data indicate that maximum dibenzothiophene hydrodesulfurization activity is achieved at intermediate heats of formation of metal sulfides, i.e., at intermediate metal-sulfur bond strengths. Again, while such surface energetic considerations do not have ab initio predictive ability, they are valuable tools for catalyst synthesis and prescreening. 

Although metals or even promoted metals have very low sulfur tolerances in synthesis reactions, other materials, such as metal oxides, nitrides, borides, and sulfides, may have greater tolerance to sulfur poisoning because of their potential ability to resist sulfidation (18). The extremely low steady-state activities of Co, Ni, and Ru metals in a sulfur-contaminated stream actually correspond to the activities of the sulfided metal surfaces. However, if more active sulfides could be found, their activity/selectivity properties would be presumably quite stable in a reducing, H2S-containing environment. This is, in fact, the basis for the recent development of sulfur active synthesis catalysts (211-215), which are reported to maintain stable activity/ selectivity properties in methanation and Fischer-Tropsch synthesis at H2S levels of 1% or greater. Happel and Hnatow (214), for example, reported in a recent patent that rare-earth and actinide-metal-promoted molybdenum oxide catalysts are reasonably active for methanation in the presence of 1-3% H2S. None of these patents, however, have reported intrinsic activities... 

Along with nitrogen, inclusion of other heteroatoms in the catalyst synthesis, including sulfur, may play a role in enhancing ORR activity of non-PGM catalysts. Extremely high ORR activity has been achieved with a catalyst consisting of CogSg nanoparticles surrounded... 

A highly active sulfur-tolerant shift-conversion catalyst has been developed for use with high sulfur concentration synthesis gas. This catalyst utilizes mixed metal sulfides and requires the presence of sulfur compounds in the gas to remain active (Nielsen and Hansen. 1981). The sulfur tolerant catalyst can operate over a wide range of temperatures (390°-890"F), and offers the advantage of allowing sulfur and carbon dioxide removal to be accomplished in one step (Haldor Topsde, Inc., 199IB). 

For many years, the overwhelming feedstock of choice for methanol producers has been natural As of 1990, some 75% of the world s methanol production capacity was based on a natural feedstock. Steam reforming with its low sulfur feed (typically, feeds to a reformer contain less than 0.1 ppmv total sulfur) makes synthesis that is particularly well suited to feed a loop containing Cu-Zn catalyst. With the advent of the low-pressure process (pressures of 10 MPa, 100 atm, or less), it became advantageous to feed gases to a loop that were not necessarily stoichiometric because of the overall reduction in compression requirements. 

The synthesis of 2,4-dihydroxyacetophenone [89-84-9] (21) by acylation reactions of resorcinol has been extensively studied. The reaction is performed using acetic anhydride (104), acetyl chloride (105), or acetic acid (106). The esterification of resorcinol by acetic anhydride followed by the isomerization of the diacetate intermediate has also been described in the presence of zinc chloride (107). Alkylation of resorcinol can be carried out using ethers (108), olefins (109), or alcohols (110). The catalysts which are generally used include sulfuric acid, phosphoric and polyphosphoric acids, acidic resins, or aluminum and iron derivatives. 2-Chlororesorcinol [6201-65-1] (22) is obtained by a sulfonation—chloration—desulfonation technique (111). 1,2,4-Trihydroxybenzene [533-73-3] (23) is obtained by hydroxylation of resorcinol using hydrogen peroxide (112) or peracids (113). 

In 1974 a 1000 t/d ammonia plant went into operation near Johaimesburg, South Africa. The lignitic (subbituminous) coal used there contains about 14% ash, 36% volatile matter, and 1% sulfur. The plant has six Koppers-Totzek low pressure, high temperature gasifiers. Refrigerated methanol (—38° C, 3.0 MPa (30 atm)) is used to remove H2S. A 58% CO mixture reacts with steam over an iron catalyst to produce H2. The carbon dioxide is removed with methanol (at —58° C and 5.2 MPa (51 atm)). Ammonia synthesis is carried out at ca 22 MPa (220 atm) (53) (see Ammonia). 

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. 

Other Specialty Chemicals. In fuel-ceU technology, nickel oxide cathodes have been demonstrated for the conversion of synthesis gas and the generation of electricity (199) (see Fuel cells). Nickel salts have been proposed as additions to water-flood tertiary cmde-oil recovery systems (see Petroleum, ENHANCED oil recovery). The salt forms nickel sulfide, which is an oxidation catalyst for H2S, and provides corrosion protection for downweU equipment. Sulfur-containing nickel complexes have been used to limit the oxidative deterioration of solvent-refined mineral oils (200). 

The saturated, cleaned raw synthesis gas from a Texaco partial oxidation system is first shifted by use of a sulfur resistant catalyst. Steam required for shifting is already present ia the gas by way of the quench operation ia the generator. The shifted gas is then processed for hydrogen sulfide and carbon dioxide removal followed by Hquid nitrogen scmbbiag. 

HTS catalyst consists mainly of magnetite crystals stabilized using chromium oxide. Phosphoms, arsenic, and sulfur are poisons to the catalyst. Low reformer steam to carbon ratios give rise to conditions favoring the formation of iron carbides which catalyze the synthesis of hydrocarbons by the Fisher-Tropsch reaction. Modified iron and iron-free HTS catalysts have been developed to avoid these problems (49,50) and allow operation at steam to carbon ratios as low as 2.7. Kinetic and equiUbrium data for the water gas shift reaction are available in reference 51. 

Acid-Gatalyzed Synthesis. The acid-catalysed reaction of alkenes with hydrogen sulfide to prepare thiols can be accompHshed using a strong acid (sulfuric or phosphoric acid) catalyst. Thiols can also be prepared continuously over a variety of soHd acid catalysts, such as seoHtes, sulfonic acid-containing resin catalysts, or aluminas (22). The continuous process is utilised commercially to manufacture the more important thiols (23,24). The acid-catalysed reaction is commonly classed as a Markownikoff addition. Examples of two important industrial processes are 2-methyl-2-propanethiol and 2-propanethiol, given in equations 1 and 2, respectively. 

Most current industrial vitamin C production is based on the efficient second synthesis developed by Reichstein and Grbssner in 1934 (15). Various attempts to develop a superior, more economical L-ascorbic acid process have been reported since 1934. These approaches, which have met with htde success, ate summarized in Crawford s comprehensive review (46). Currently, all chemical syntheses of vitamin C involve modifications of the Reichstein and Grbssner approach (Fig. 5). In the first step, D-glucose (4) is catalytically (Ni-catalyst) hydrogenated to D-sorbitol (20). Oxidation to L-sotbose (21) occurs microhiologicaRy with The isolated L-sotbose is reacted with acetone and sulfuric acid to yield 2,3 4,6 diacetone-L-sorbose,... 

Work on the process for the production of these acids has continued in recent years. One patent discloses the use of 2eohte catalysts (34) for the synthesis of neopentanoic acid from isobutylene. The use of a copper catalyst in a strong acid, such as sulfuric acid, operating at lower pressures, has also been claimed (35). 

Although copper catalysts were known to be highly active for this reaction for many years, it was not until the late 1960s that gas purification processes for synthesis gas were introduced that would allow the commercial use of these catalysts, which require very low sulfur, chlorine, and phosphoms feed impurity levels to maintain catalyst activity. 

The performance of many metal-ion catalysts can be enhanced by doping with cesium compounds. This is a result both of the low ionization potential of cesium and its abiUty to stabilize high oxidation states of transition-metal oxo anions (50). Catalyst doping is one of the principal commercial uses of cesium. Cesium is a more powerflil oxidant than potassium, which it can replace. The amount of replacement is often a matter of economic benefit. Cesium-doped catalysts are used for the production of styrene monomer from ethyl benzene at metal oxide contacts or from toluene and methanol as Cs-exchanged zeofltes ethylene oxide ammonoxidation, acrolein (methacrolein) acryflc acid (methacrylic acid) methyl methacrylate monomer methanol phthahc anhydride anthraquinone various olefins chlorinations in low pressure ammonia synthesis and in the conversion of SO2 to SO in sulfuric acid production. 

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