The British Petroleum Company, P.l.c.

William J Ball

David G Stewart

Keith W Palmer

Leonard Cotton

Sami A Barri

Dennis Young

The present invention relates to a process for producing crystalline aluminosilicates having in the hydrogen form an X-ray diffraction pattern substantially as set forth in Table 1 of this specification and the following composition in terms of the mole ratios of the oxides:

Method of preparing crystalline aluminosilicates

A process for the production of a catalyst based on a crystalline aluminosilicate having a silica to alumina molar ratio greater than 12:1 which is obtained by mixing a source of silica, a source of alumina, a source of alkali metal, water and a source of ammonium ions in defined proportions, crystallizing the mixture, recovering the crystalline aluminosilicate so-formed, cation-exchanging and/or impregnating the recovered crystalline aluminosilicate and finally calcining, wherein either the recovered crystalline aluminosilicate or the cation-exchanged aluminosilicate or the impregnated aluminosilicate is washed with a solution containing either an organic base, a carboxylic acid, an alcohol, a glycol, a phenol or an ester. The washing treatment results in a reduction in the rate of decline in catalytic activity in reactions such as the conversion of aliphatic to aromatic hydrocarbons.

Process for the production of catalysts based on crystalline

C.sub.1 to C.sub.4 oxygenated hydrocarbons are produced by contacting synthesis gas at a temperature in the range 150.degree. C. to 450.degree. C. and a pressure in the range of 1 to 700 bars with a catalyst comprising a supported mixture of a rhodium component and a silver component. The preferred support is silica. Other metal components which may be incorporated on the support are iron, manganese, molybdenum, tungsten, ruthenium, chromium, thorium and zirconium. Furthermore the support can be activated prior to incorporation of the metal components.

Process for the production of C.sub.1 to C.sub.4 oxygenated hydrocarbons

An oxygenated hydrocarbon product comprising methanol and ethanol is produced by hydrogenating carbon monoxide at a temperature in the range 150.degree. to 450.degree. C. and a pressure in the range 1 to 700 bars in the presence as catalyst of a supported mixture of the metals rhodium, silver, zirconium and molybdenum and optionally also one or more of the metals iron, manganese, rhenium, tungsten, ruthenium, chromium, thorium and potassium. The preferred support is silica.

Process for the production of oxygenated hydrocarbons by the catalytic

The invention relates to a method for preparing a crystalline aluminosilicate having a high silica to alumina molar ratio and an X-ray diffraction pattern substantially the same as that of ZSM-5 zeolite which method comprises mixing a source of silica, a source of alumina, a source of alkali metal, water and at least one alkanolamine according to Formula (I): ##STR1## wherein any two of R.sup.1, R.sup.2 and R.sup.3 are independently alkylol groups and the remaining one of R.sup.1, R.sup.2 and R.sup.3 is a hydrogen atom or all of R.sup.1, R.sup.2 and R.sup.3 are independently alkylol group, the alkylol groups being --CH.sub.2 --R--OH, wherein R is --CH.sub.2 --, --CH.sub.2 CH.sub.2 --, or --CH(CH.sub.3)--, the ratio of said source of silica to said source of alumina being at least 20:1 based on the equivalent moles of silica and alumina in said respective sources, maintaining said mixture at a temperature above about 120.degree. C. and recovering the crystalline aluminosilicate formed.

Crystalline aluminosilicates

Crystalline aluminosilicates having a silica to alumina molar ratio greater than 12 are produced by mixing a source of silica, a source of alumina, a source of alkali metal, water and a source of ammonium ions, e.g. ammonia or an ammonium salt, in the absence of an alcohol or alkylene oxide, in the molar proportions (expressed in the case of the silica and alumina sources in terms of the equivalent moles of the oxide, in the case of the alkali metal source in terms of the equivalent moles of the hydroxide (MOH) and in the case of the source of ammonium ions in terms of free ammonia):

Process for the production of crystalline aluminosilicates and their use

Method for producing crystalline aluminosilicates and their use as

Crystalline aluminosilicates having a high silica to alumina molar ratio are prepared by mixing a source of silica, a source of alumina, a source of alkali metal, water and one or more substituted neopentylamines having the formula: ##STR1## wherein R.sup.2 is H, OH or NH.sub.2 and R.sup.1 is a C.sub.1 to C.sub.6 alkyl group, and maintaining the mixture under conditions of elevated temperature and pressure, typically in the range from 80.degree. to 210.degree. C. and autogenous pressure for a time sufficient to effect formation of the aluminosilicate, typically not less than 4 hours. The molar ratio of silica to alumina in the initial mixture is suitably in the range from 10:1 to 150:1 and the amounts of alkali metal and neopentylamine are suitably in the range from 2:1 to 0.02:1 and 10:1 to 0.02:1 respectively moles per mole equivalent of total silica and alumina in the respective sources. Depending on the ratio of silica to alumina in the initial mixture crystalline aluminosilicates having a mordenite structure or a ZSM-5 type zeolite structure or mixtures thereof may be prepared. Mordenites having a silica to alumina ratio greater than 10:1 can be prepared.

Method for preparing crystalline aluminosilicates

A process for the production of aromatic hydrocarbons which process comprises contacting at elevated temperature and in the vapor phase a C.sub.2 to C.sub.12 aliphatic hydrocarbon feedstock with a catalyst comprising a crystalline aluminosilicate having a silica to alumina molar ratio greater than 12:1 which has been modified by incorporation therein of aluminium either by exchange or impregnation.

Process for the production of aromatic hydrocarbons

Crystalline aluminosilicates having a high (greater than 10:1) silica to alumina molar ratio and an X-ray diffraction pattern substantially the same as that of ZSM-5 zeolite are prepared by mixing a source of silica, a source of alumina, a source of alkali metal, water and at least one monoalkanolamine selected from monoethanolamine and monopropanolamine or their precursors, the ratio of the source of silica to the source of alumina being at least 20:1 based on the equivalent moles of silica and alumina in their respective sources, and maintaining the mixture at a temperature of about 120.degree. C. or 135.degree. C. or more for a time such that crystallization occurs. Typical crystallization conditions are a temperature in the range 120.degree. to 210.degree. C., a pressure in the range from autogenous to 400 psig and a time not less than 4 hours and up to and in excess of 7 days. The crystalline product so-produced is useful, particularly after modification such as reduction of the alkali metal content as a conversion catalyst and catalyst support.

Method for producing aluminosilicates, their use as catalysts and

Oxygenated hydrocarbon compounds containing from one to four carbon atoms, e.g. acids, alcohols and/or aldehydes are produced by reacting carbon monoxide with hydrogen in the presence of a supported mixture of a rhodium component and a chromium component, optionally incorporating also iron, manganese, molybdenum, tungsten or ruthenium at elevated temperature and generally at elevated pressure. A preferred support is silica which may be activated by the addition of metal and non-metal activators followed by calcination, prior to incorporation of the rhodium and chromium components.

Amorphous aluminosilicates useful as catalysts, particularly for the decomposition of methanol to synthesis gas, are produced by reacting a source of silica, a source of alumina, a source of alkali metal, water and one or more polyamines other than a diamine. A class of effective polyamines is that known as polyethylene polyamines of which triethylene is representative. The catalytic activity of the aluminosilicate may be enhanced in particular by incorporation of the metals copper, zinc, gallium, bismuth, chromium, thorium, iron, cobalt, ruthenium, rhodium, nickel, palladium, iridium or platinum.

Process for the production of amorphous aluminosilicates and their use

Amorphous aluminosilicates useful as catalysts, particularly for the decomposition of methanol to synthesis gas, are produced by reacting a source of silica, a source of alumina, a source of alkali metal, water and one or more polyamines other than a diamine. A class of effective polyamines is that known as polyethylene poly amines of which triethylene is representative. The catalytic activity of the aluminosilicate may be enhanced in particular by incorporation of the metals copper, zinc, gallium, bismuth, chromium, thorium, iron, cobalt, ruthenium, rhodium, nickel, palladium, iridium or platinum.

Aluminosilicates containing an organic nitrogen cation are prepared by mixing sources of silica, alumina and an alkali metal, water and either mono-ethanolamine or mono-propanolamine, or a derivative, or the precursors or a combination thereof and maintaining the mixture at a temperature in the range from 80.degree. to 210.degree. C. and a pressure in the range from 70 to 400 psig for over 4 hours. In a preferred embodiment the alkanolamines are prepared in situ` by reaction of the corresponding alkylene oxide with ammonia. Aluminosilicates so-prepared can be used without modification as catalysts and catalyst supports. Catalytic activity can be enhanced by, for example, reducing the sodium content or impregnating with a compound of one or more metals belonging to Groups 1B, 11B, 111A, 1VA, VA and V111 or reaction with a compound of one or more non-metals of Group 111A and VA of the Periodic Table.

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Capel, United Kingdom

William J Ball