Patent GB-1102345-A (GB)
Title: Improvements in or relating to catalysts
Inventor: ABSON JAMES WILLIAM
IPC: B01J27/04
Filed: 1963-09-25
Abstract: Material is activated to provide catalytic activity by contacting the material with an aqueous culture comprising bacteria and removing the culture from the material.  The bacteria may be sulphate-reducing bacteria, e.g.  Desulphovibrio desulphuricans, sulphide-oxidizing bacteria, e.g.  Thiobacillus thio-oxidans, iron-oxidizing bacteria, e.g.  Ferrobacillus ferro-oxidans. Bauxite may be activated by treatment with sulphate-reducing, sulphide-oxidizing (iron sulphate separation), or iron-oxidizing (ferric hydroxide separation) bacteria.  Metal sulphates may be treated with sulphate-reducing bacteria to produce sulphides which may <PICT:1102345/C1/1> hydrolyse to the hydroxide or oxide.  The oxide may be obtained by oxidation of the sulphide, and the elemental metal by reduction using hydrogen. The catalysts prepared using sulphate-reducing bacteria may be NiS, CoS, MnS, Fe2S3, V2S3, Mo2S3, NiO, CoO, Mo2O3, Fe2O3, Fe3O4, or mixtures thereof.  A nickel subsulphide catalyst may be prepared by heating a mixture of nickel nitrate and nickel sulphate to 300 DEG C. to give nickel oxide and nickel sulphate, contacting with sulphate reducing bacteria, removing the culture and treating with a reducing gas, e.g. coal gas.  The activity of "Nimox" (Registered Trade Mark) catalyst may be enhanced with sulphate reducing bacteria. Alumina catalyst may be prepared by contacting aluminium sulphate with the culture to give aluminium sulphide which hydrolyses to hydroxide, removing the culture, and heating the hydroxide.  The material to be activated may be a poisoned catalyst containing metal sulphate as a result of exposure to sulphur, say as sulphur dioxide or hydrogen sulphide, under oxidizing conditions, e.g. bauxite in the Claus sulphur recovery process which may then be further heated to produce aluminium oxide and remove bound water, Fe2O3, Fe3O4, CaO, NiO MnO, MgO, "Nimox" (Trade Mark), "Comox" (Trade Mark), a "Segas" catalyst. The reactivation may be carried out in the catalytic reactor.  The material may be impregnated on to a carrier before activation, e.g. by immersion of the carrier in a solution of the material, then evaporating to dryness under pressure or drying by vacuum distillation, by spraying the carrier and drying.  The impregnation and bacteria treatment may occur simultaneously.  The carrier may be bauxite, activated alumina, magnesia, silica, clay, silicon carbide, sepiolite, bentonite, zeolites, artificial molecular sieves, refractory materials such as fire-brick, mixtures and compounds thereof.  The bacterial culture may be passed continuously through a fixed bed of the material, or the bed may be alternately completely immersed in the culture and then drained.  After removal of the culture the material may be heated to fix its structure, say to 500 DEG  C.  Where sulphate-reducing bacteria is used, the culture may comprise a nutrient solution of low sulphate concentration, the bacteria being grown in this solution at between 23 DEG  and 32 DEG C., and the culture then contacted with the material at between 20 DEG  and 30 DEG  C., the bacteria being in the logarithmic growth phase throughout contacting and the ph of the culture being maintained between 5 and 8 throughout growth and contacting.  In Fig. 2 a fixed bed of metal sulphate in reactor 100 is activated by passing aqueous culture from tank 104 downwardly through the bed to a settling tank 102.  Clear culture from tank 102 is pumped by pump 103 back to the reactor 100. Inert gas, e.g. CO2 is passed into the reactor through line 116 and into tank 104 through line 118. Hydrogen sulphide from the bacterial reaction and inert gas from reactor 100 and tank 104 pass to vent 122.  Alkali for pH adjustment or nutrient may be added to tank 102 through line 128. The catalysts may be ground sieved, and pelleted.  A plant is also described (Fig. 1, not shown) for treating a waste gas containing H2S, e.g. 0 to 5% H2S, 95 to 100% CO2, wherein a bauxite catalyst is reactivated, the bauxite being used as a catalyst in the oxidation of the hydrogen sulphide to sulphur dioxide and subsequent recovering of elemental sulphur by reaction of the sulphur dioxide and further hydrogen sulphide in the waste gas.  The catalysts may be used as the main catalysts in the Claus sulphur recovery process, in dehydration reactions, the "shift" reaction, cracking, isomerization, dehydrogenation, defluorination, desulphurization, gasification of petroleum, hydrogenation, hydrogenolysis, polymerization, reforming, demethanation and oxidation of hydrocarbons; or as guard catalysts in reducing the concentration in gases of organic sulphur compounds, unsaturated hydrocarbons such as acetylene, to minimize the rate of poisoning of the main catalyst, e.g. in the detoxification of fuel gas by the "shift" reaction, the gasification of petroleum, reforming, and the hydrogenation of unsaturated compounds.ALSO:Material is activated to provide catalytic activity by contacting the material with an aqueous culture comprising bacteria and removing the culture from the material.  The bacteria may be sulphate-reducing bacteria, e.g. Desulphovibrio desulphuricans, sulphide-oxidizing bacteria, e.g. Thiobacillus thiooxidans, iron-oxidising bacteria, e.g. Ferrobacillus ferro-oxidans.  Bauxite may be activated by treatment with sulphate-reducing, sulphide-oxidizing (iron sulphate separation), or iron-oxidizing (ferric hydroxide separation) bacteria.  Metal sulphates may be treated with sulphate-reducing bacteria to produce sulphides which may hydrolyse to the hydroxide or oxide. The oxide may be obtained by oxidation of the sulphide, and the elemental metal by reduction using hydrogen.  The catalysts prepared using sulphate-reducing bacteria may be NS, CoS, MnS, Fe2S3, V2S3, Mo2S3, NlO, CoO, Mo2O3, Fe2O3, Fe3O4, or mixtures thereof.  A nickel sub-sulphide catalyst may be prepared by heating a mixture of nickel nitrate and nickel sulphate to 300 DEG C to give nickel oxide and nickel sulphate, contacting with sulphate reducing bacteria, removing the culture and treating with a reducing gas, e.g. coal gas.  The activity of "Nimox" (Registered Trade Mark) catalyst may be enhanced with sulphate reducing bacteria.  Alumina catalyst may be prepared by contacting aluminium sulphate with the culture to give aluminium sulphide which hydrolyses to hydroxide, removing the culture, and heating the hydroxide.  The material to be activated may be a poisoned catalyst containing metal sulphate as a result of exposure to sulphur say as sulphur dioxide or hydrogen sulphide, under oxidizing conditions, e.g. bauxite in the Claus sulphur recovery process which may then be further heated to produce aluminium oxide and remove bound water, Fe2O3, Fe3O4, CaO, NiO, MnO, MgO, "Nimox" (Trade Mark), "Comox" (Trade Mark), a "Segas" catalyst.  The reactivation may be carried out in the catalytic reactor.  The material may be impregnated on to a carrier before activation, e.g. by immersion of the carrier in a solution of the material, then evaporating to dryness under pressure or drying by vacuum distillation, by spraying the carrier and drying.  The impregnation and bacteria treatment may occur simultaneously.  The carrier may be bauxite, activated alumina, magnesia, silica, clay, silicon carbide, sepiolite, bentonite, zeolites, artificial molecular sieves, refractory materials such as fire-brick, mixtures and compounds thereof.  The bacterial culture may be passed continuously through a fixed bed of the material, or the bed may be alternately completely immersed in the culture and then drained.  After removal of the culture the material may be heated to fix its structure, say to 500 DEG C.  Where sulphate-reducing bacteria is used, the culture may comprise a nutrient solution of low sulphate concentration, the bacteria being grown in this solution at between 23 DEG  and 32 DEG C, and the culture then contacted with the material at between 20 DEG and 30 DEG C, the bacteria being in the logarithmic growth phase throughout contacting and the pH of the culture being maintained between 5 and 8 throughout growth and contacting.  In Figure 2 a fixed bed of metal sulphate in reactor 100 is activated by passing aqueous culture from tank 104 downwardly through the bed to a settling tank 102.  Clear culture from tank 102 is pumped by pump 103 back to the reactor 100. Inert gas, e.g. CO2 is passed into the reactor through line 116 and into tank 104 through line 118. Hydrogen sulphide from the bacterial reaction and inert gas from reactor 100 and tank 104 pass to vent 122.  Alkali for pH adjustment or nutrient may be added to tank 102 through line 128.  The catalysts may be ground sieved, and pelleted.  A plant is also described (Fig. 1 not shown) for treating a waste gas containing H2S, e.g. 0 to 5% H2S, 95 to 100% CO2 wherein a bauxite catalyst is reactivated, the bauxite being used as a catalyst in the oxidation of the hydrogen sulphide to sulphur dioxide and subsequent recovering of elemental sulphur by reaction of the sulphur dioxide and further hydrogen sulphide in the waste gas. The catalysts may be used as the main catalysts in the Claus sulphur recovery process, in dehydration reactions, the "shift" reaction, cracking, isomerisation, dehydrogenation, defluorination, desulphurisation, gasification of petroleum, hydrogenation, hydrogenolysis, polymerisation, reforming demethanation and oxidation of hydrocarbons; or as guard catalysts in reducing the concentration in gases of organic sulphur compounds, unsaturated hydrocarbons such as acetylene, to minimise the rate of poisoning of the main catalyst, e.g. in the detoxification of fuel gas by the "shift" reaction, the gasification of petroleum, reforming, and the hydrogenation of unsaturated compounds.