Catalysts for hydrotreating of hydrocarbons and methods of preparing the same

Claim 1

A catalyst for hydrotreating hydrocarbons, which comprises a shaped body of a mixture composed of a carrier substance consisting essentially of an oxide of aluminium and/or an oxide hydrate of aluminium, at least one selected from water-soluble compounds of metals of Group VI and Group VIII of the Periodic Table and at least one organic compound selected from the group consisting of mercapto-carboxylic acids of a general formula: HS-(CH₂) n -COOR where n represents an integer of from 1 to 3; and R represents a hydrogen atom, or an alkali metla, an alkaline earth metal, an ammonium group, or an alkyl group having from 1 to 10 carbon atoms, thio-acids of a general formula: R′-COSH where R′ represents a monovalent hydrocarbon group having form 1 to 15 carbon atoms, amino-substituted mercaptans of a general formula: H₂N-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, dimercaptans of a general formula: HS-R˝-HS where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, and mercapto-alcohols of a general fromula: RaS-R‴-(OH) n where R‴ represents an alkyl group having form 1 to 15 carbon atoms, or a phenyl group; Ra represents a hydrogen atom or an alkyl group having from 1 to 2 carbon atoms; and n represents an integer of from 1 to 2.

Claim 11

A method for preparing a catalyst for hydrotreating hydrocarbons, which is characterized in that a carrier substance consisting essentially of an oxide of aluminium and/or an oxide hydrate of aluminium is blended and kneaded with a solution containing at least one selected from water-soluble compounds of metals of Group VI and Group VIII of the Periodic Table and at least one organic compound selected from the group consisting of mercapto-carboxylic acids of a general formula: HS-(CH₂) n -COOR where n represents an integer of from 1 to 3; and R represents a hydrogen atom, or an alkali metal, an alkaline earth metal, an ammonium group, or an alkyl group having from 1 to 10 carbon atoms, thio-acids of a general formula: R′-COSH where R′ represents a monovalent hydrocarbon group having from 1 to 15 carbon atoms, amino-substituted mercaptans of a general formula: H₂N-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, dimercaptans of a general formula: HS-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, and mercapto-alcohols of a general formula: RaS-R‴-(OH) n where R‴ represents an alkyl group having from 1 to 15 carbon atoms or a phenyl group; Ra represents a hydrogen atom or an alkyl group having from 1 to 2 carbon atoms; and n represents an integer of from 1 to 2, and the resulting blend is shaped and dried to prepare the said catalyst.

Claim 12

A method for preparing a catalyst for hydrotreating hydrocarbons, which is characterized in that a carrier substance consisting essentially of an oxide of aluminium and/or an oxide hydrate of aluminium is blended and kneaded with a solution containing at least one selected from water-soluble compounds of metals of Group VI and Group VIII of the Periodic Table and at least one organic compound selected from the group consisting of mercapto-carboxylic acids of a general formula: HS-(CH₂) n -COOR where n represents an integer of from 1 to 3; and R represents a hydrogen atom, or an alkali metal, an alkaline earth metal, an ammonium group, or an alkyl group having from 1 to 10 carbon atoms, thio-acids of a general formula: R′-COSH where R′ represents a monovalent hydrocarbon group having from 1 to 15 carbon atoms, amino-substituted mercaptans of a general formula: H₂N-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, dimercaptans of a general formula: HS-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, and mercapto-alcohols of a general formula: RaS-R‴-(OH) n where R‴ represents an alkyl group having from 1 to 15 carbon atoms or a phenyl group; Ra represents a hydrogen atom or an alkyl group having from 1 to 2 carbon atoms; and n represents an integer of from 1 to 2, and the resulting blend is shaped and dried to prepare the said catalyst.

Claim 13

A method for preparing a catalyst for hydrotreating hydrocarbons, which is characterized in that a carrier substance consisting essentially of an oxide of aluminium and/or an oxide hydrate of aluminium is blended and kneaded with an aqueous solution of at least one selected from water-soluble compounds of metals of Group VI and Group VIII of the Periodic Table, the resulting blend is shaped and then temporarily dried, and the thus dried shaped body is impregnated with a solution of at least one organic compound selected from the group consisting of mercapto-carboxylic acids of a general formula: HS-(CH₂) n -COOR where n represents an integer of from 1 to 3; and R represents a hydrogen atom, or an alkali metal, an alkaline earth metal, an ammonium group, or an alkyl group having from 1 to 10 carbon atoms, thio-acids of a general formula: R′-COSH where R′ represents a monovalent hydrocarbon group having from 1 to 15 carbon atoms, amino-substituted mercaptans of a general formula: H₂N-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, dimercaptans of a general formula: HS-R˝-SH where R˝ represents a divalent hydrocarbon group ahving from 1 to 15 carbon atoms, and mercapto-alcohols of a general formula: RaS-R‴-(OH) n where R‴ represents an alkyl group having from 1 to 15 carbon atoms or a phenyl group; Ra represents a hydorgen atom or an alkyl group having from 1 to 2 carbon atoms; and n represents an integer of from 1 to 2, and then again dried to prepare the said catalyst.

Claim 14

A method for preparing a catalyst for hydrotreating hydrocarbons, which is characterized in that a carrier substance consisting essentially of an oxide of aluminium and/or an oxide hydrate of aluminium is blended and kneaded with an aqueous solution of at least one selected from water-soluble compounds of metals of Group VI and Group VIII of the Periodic Table, the resulting blend is shaped and then temporarily dried, and the thus dried shaped body is impregnated with a solution of at least one organic compound selected from the group consisting of mercapto-carboxylic acids of a general formula: HS-(CH₂) n -COOR where n represents an integer of from 1 to 3; and R represents a hydrogen atom, or an alkali metal, an alkaline earth metal, an ammonium group, or an alkyl group having from 1 to 10 carbon atoms, thio-acids of a general formula: R′-COSH where R′ represents a monovalent hydrocarbon group having from 1 to 15 carbon atoms, amino-substituted mercaptans of a general formula: H₂N-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, dimercaptans of a general formula: HS-R˝-SH where R˝ represents a divalent hydrocarbon group ahving from 1 to 15 carbon atoms, and mercapto-alcohols of a general formula: RaS-R‴-(OH) n where R‴ represents an alkyl group having from 1 to 15 carbon atoms or a phenyl group; Ra represents a hydorgen atom or an alkyl group having from 1 to 2 carbon atoms; and n represents an integer of from 1 to 2, and then again dried to prepare the said catalyst.

Claim 15

A method for preparing a catalyst for hydrotreating hydrocarbon, which is characterized in that a carrier substance consisting essentially of an oxide of aluminium and/or an oxide hydrate of aluminium is blended and kneaded with an aqueous solution of at least one organic compound selected from the group consisting of mercapto-carboxylic acids of a general fromula: HS-(CH₂) n -COOR where n represents an integer of from 1 to 3; and R represents a hydrogen atom, an alkali metal, an alklaine earth metal, an ammonium group, or an alkyl group having from 1 to 10 carbon atoms, thio-acids of a general fromula: R′-COSH where R′ represents a monovalent hydrocarbon group having from 1 to 15 carbon atoms, amino-substituted mercaptans of a general formula: H₂N-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, dimercaptans of a general formula: HS-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, and mercapto-alcohols of a general formula: RaS-R‴-(OH) n where R‴ represents an alkyl group having from 1 to 15 carbon atoms or a phenyl group; Ra represents a hydrogen atom or an alkyl group having from 1 to 2 carbon atoms; and n represents an integer of from 1 to 2, the resulting belnd is shaped and then temporarily dried, and the thus dried shaped body is impregnated with an aqueous solution of at least one selected from water-soluble compounds of metals of Group VI and Group VIII of the Periodic Table, and then again dried to prepare the said catalyst.

Claim 16

A method for preparing a catalyst for hydrotreating hydrocarbon, which is characterized in that a carrier substance consisting essentially of an oxide of aluminium and/or an oxide hydrate of aluminium is blended and kneaded with an aqueous solution of at least one organic compound selected from the group consisting of mercapto-carboxylic acids of a general fromula: HS-(CH₂) n -COOR where n represents an integer of from 1 to 3; and R represents a hydrogen atom, an alkali metal, an alklaine earth metal, an ammonium group, or an alkyl group having from 1 to 10 carbon atoms, thio-acids of a general fromula: R′-COSH where R′ represents a monovalent hydrocarbon group having from 1 to 15 carbon atoms, amino-substituted mercaptans of a general formula: H₂N-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, dimercaptans of a general formula: HS-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, and mercapto-alcohols of a general formula: RaS-R‴-(OH) n where R‴ represents an alkyl group having from 1 to 15 carbon atoms or a phenyl group; Ra represents a hydrogen atom or an alkyl group having from 1 to 2 carbon atoms; and n represents an integer of from 1 to 2, the resulting belnd is shaped and then temporarily dried, and the thus dried shaped body is impregnated with an aqueous solution of at least one selected from water-soluble compounds of metals of Group VI and Group VIII of the Periodic Table, and then again dried to prepare the said catalyst.

Claim 17

The method for preparing a catalyst for hydrogenation of hydrocarbons as claimed in anyone of claims 10 to 12, in which the oxide of aluminium and/or oxide hydrate of aluminium for constituting the carrier substance is(are) at least one selected from γ-alumina, dehydrated boehmite and spray-dried boehmite.

Claim 18

The method for preparing a catalyst for hydrotreating hydrocarbons as claimed in anyone of claims 10 to 12, in which the water-soluble compounds of metals of Group VI of the Periodic Table are at least one selected from ammonium molybdate and ammonium tungstate, and ammonium molybdate and ammonium tungstate as prepared by treating molybdenum trioxide and tungsten tioxide, respectively, with ammonia gas; and the water-soluble compounds of metals of Group VIII of the Periodic Table are at least one selected from cobalt nitrate, cobalt carbonate, nickel nitrate and nickel carbonate; the said aqueous solution containing at least one selected from the said water-solbule compounds.

Claim 19

The method for preparing a catalyst for hydrotreating hydrocarbons as claimed in anyone of claims 10 to 12, in which the mercapto-carboxylic acids of a general formula: HS-(CH₂) n -COOR where n represents an integer of from 1 to 3; and R represents a hydrogen atom, or an alkali metal, an alkaline earth metal, an ammonium group, or an alkyl group having from 1 to 10 carbon atoms, are at least one selected from mercapto-­acetic acid and β-mercapto-propionic acid and alkali metal salts, alkaline earth metal salts and ammonium salts thereof and methyl mercapto-acetate, ethyl 2-mercapto-acetate, 2-ethylhexyl mercapto-acetate and methyl 3-mercapto-propionate.

Claim 20

The method for preparing a catalyst for hydrotreating hydrocarbons as claimed in anyone of claims 10 to 12, in which the thio-acids of a general formula: R′-COSH where R′ represents a monovalent hydrocarbon group having from 1 to 15 carbon atoms, are at least one selected from thio-­acetic acid and thio-benzoic acid.

Claim 21

The method for preparing a catalyst for hydrotreating hydrocarbons as claimed in anyone of claims 10 to 12, in which the amino-substituted mercaptans of a general formula: H₂N-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, are at least one selected from 2-­aminoethanethiol and 4-aminothiophenol.

Claim 22

The method for preparing a catalyst for hydrotreating hydrocarbons as claimed in anyone of claims 10 to 12, in which the dimercaptans of a general formula: HS-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, are at least one selected from ethanedithiol and 1,4-butanedithiol.

Claim 23

The method for preparing a catalyst for hydrotreating hydrocarbons as claimed in anyone of claims 10 to 12, in which the mercapto-alcohols of a general formula: RaS-R‴-(OH) n where R‴ represents an alkyl group having from 1 to 15 carbon atoms or a phenyl group; Ra represents a hydrogen atom or an alkyl group having from 1 to 2 carbon atoms; and n represents an integer of from 1 to 2, are at least one selected from 2-mercaptoethanol, 2-(methylthio)ethanol, 2-(ethylthio)ethanol, 3-mercapto-2-butanol, 4-mercaptophenol, 2-(methylthio)phenol, 4-(methylthio)phenol, 2-(ethylthio)phenol, 3-mercapto-1,2-­propanediol, 3-methylthio-1,2-propanediol and 3-ethylthio-1,2-­propanediol.

Claim 24

The method for preparing a catalyst for hydrotreating hydrocarbons as claimed in anyone of claims 10 to 12, in which the content of the metals of Groups VI and VIII of the Periodic Table in the catalyst is from 1 to 30 % by weight as the metal oxide, when the catalyst contains one metal of them, or the content of the metal of Group VI in the catalyst is from 5 to 30 % by weight as the metal oxide and that of the metal of Group VIII therein is from 1 to 8 % by weight as the metal oxide when the catalyst contains both the metals of Groups VI and VIII.

Claim 25

The method for preparing a catalyst for hydrotreating hydrocarbons as claimed in anyone of claims 10 to 12, in which the amount of the mercapto-carboxylic acids and other sulfurizing agents is from 1 to 3 equivalent times of the amount of the sulfur necessary for forming sulfides of the metals of Groups VI and VIII of the Periodic Table, the said sulfides being high active in hydrogenation reaction.

Claim 26

The method for preparing a catalyst for hydrotreating hydrocarbons as claimed in anyone of claims 10 to 12, in which the drying temperature falls within the scope of from 50 to 200°C and the drying time falls within the scope of from 2 to 20 hours.

Claim 37

A method for preparing a catalyst for hydrotreating hydrocarbons, which is characterized in that a carrier substance consisting essentially of an oxide of aluminium and/or an oxide hydrate of aluminium is blended and kneaded with a solution containing at least one selected from water-soluble compounds of metals of Group VI and Group VIII of the Periodic Table, phosphoric acid and at least one organic compound selected from the group consisting of mercapto-­carboxylic acids of a general formula: HS-(CH₂) n -COOR where n represents an integer of from 1 to 3; and R represents a hydrogen atom, or an alkali metal, an alkaline earth metal, an ammonium group, or an alkyl group having from 1 to 10 carbon atoms, thio-acids of a general formula: R′-COSH where R′ represents a monovalent hydrocarbon group having from 1 to 15 carbon atoms, amino-substituted mercaptans of a general formula: H₂N-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, dimercaptans of a general formula: HS-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, and mercapto-alcohols of a general formula: RaS-R‴-(OH) n where r‴ represents an alkyl group having from 1 to 15 carbon atoms or a phenyl group; Ra represents a hydrogen atom or an alkyl group having from 1 to 2 carbon atoms; and n represents an integer of from 1 to 2, and the resulting blend is shaped and dried to prepare the said catalyst.

Claim 38

A method for preparing a catalyst for hydrotreating hydrocarbons, which is characterized in that a carrier substance consisting essentially of an oxide of aluminium and/or an oxide hydrate of aluminium is blended and kneaded with a solution containing at least one selected from water-soluble compounds of metals of Group VI and Group VIII of the Periodic Table, phosphoric acid and at least one organic compound selected from the group consisting of mercapto-­carboxylic acids of a general formula: HS-(CH₂) n -COOR where n represents an integer of from 1 to 3; and R represents a hydrogen atom, or an alkali metal, an alkaline earth metal, an ammonium group, or an alkyl group having from 1 to 10 carbon atoms, thio-acids of a general formula: R′-COSH where R′ represents a monovalent hydrocarbon group having from 1 to 15 carbon atoms, amino-substituted mercaptans of a general formula: H₂N-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, dimercaptans of a general formula: HS-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, and mercapto-alcohols of a general formula: RaS-R‴-(OH) n where r‴ represents an alkyl group having from 1 to 15 carbon atoms or a phenyl group; Ra represents a hydrogen atom or an alkyl group having from 1 to 2 carbon atoms; and n represents an integer of from 1 to 2, and the resulting blend is shaped and dried to prepare the said catalyst.

Claim 39

A method for preparing a catalyst for hydrotreating hydrocarbons, which is characterized in that a carrier substance consisting essentially of an oxide of aluminium and/or an oxide hydrate of aluminium is blended and kneaded with an aqueous solution comprising at least one selected from water-soluble compounds of metals of Group VI and Gropu VIII of the Periodic Table and phosphoric acid, the resulting blend is shaped and then temporarily dried, and the thus dried shaped body is impregnated witn a solution of at least one organic compound selected from the group consisting of mercapto-­carboxylic acids of a general formula: HS-(CH₂) n -COOR where n represents an integer of from 1 to 3; and R represents a hydrogen atom, or an alkali metal, an alkaline earth metal, an ammonium group, or an alkyl group having from 1 to 10 carbon atoms, thio-acids of a general formula: R′-COSH where R′ represents a monovalent hydrocarbon group having from 1 to 15 carbon atoms, amino-substituted mercaptans of a general fromula: H₂N-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, dimercaptans of a general formula: HS-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, and mercapto-alcohols of a general formula: RaS-R‴-(OH) n where R‴ represents an alkyl group having from 1 to 15 carbpn atoms or a phenyl group; Ra represents a hydrogen atom or an alkyl group having from 1 to 2 carbon atoms; and n represents an integer of from 1 to 2, and then again dried to prepare the said catalyst.

Claim 40

A method for preparing a catalyst for hydrotreating hydrocarbons, which is characterized in that a carrier substance consisting essentially of an oxide of aluminium and/or an oxide hydrate of aluminium is blended and kneaded with an aqueous solution comprising at least one selected from water-soluble compounds of metals of Group VI and Gropu VIII of the Periodic Table and phosphoric acid, the resulting blend is shaped and then temporarily dried, and the thus dried shaped body is impregnated witn a solution of at least one organic compound selected from the group consisting of mercapto-­carboxylic acids of a general formula: HS-(CH₂) n -COOR where n represents an integer of from 1 to 3; and R represents a hydrogen atom, or an alkali metal, an alkaline earth metal, an ammonium group, or an alkyl group having from 1 to 10 carbon atoms, thio-acids of a general formula: R′-COSH where R′ represents a monovalent hydrocarbon group having from 1 to 15 carbon atoms, amino-substituted mercaptans of a general fromula: H₂N-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, dimercaptans of a general formula: HS-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, and mercapto-alcohols of a general formula: RaS-R‴-(OH) n where R‴ represents an alkyl group having from 1 to 15 carbpn atoms or a phenyl group; Ra represents a hydrogen atom or an alkyl group having from 1 to 2 carbon atoms; and n represents an integer of from 1 to 2, and then again dried to prepare the said catalyst.

Claim 41

A method for preparing a catalyst for hydrotreating hydrocarbons, which is characterized in that a carrier substance consisting essentailly of an oxide of aluminium and/or an oxide hydrate of aluminium is blended and kneaded with a solution comprising at least one selected from water-­soluble compounds of metals of Group VI and Group VIII of the Periodic Table and at least one organic compound selected from the group consisting of mercapto-carboxylic acids of a general formula: HS-(CH₂) n -COOR where n represents an integer of from 1 to 3; and R represents a hydrogen atom, or an alkali metal, an alkaline earth metal, an ammonium group, or an alkyl group having from 1 to 10 carbon atoms, thio-acids of a general formula: R′-COSH where R′ represents a monovalent hydrocarbon group having from 1 to 15 carbon atoms, amino-substituted mercaptans of a general formula: H₂N-R˝-SH where R˝ represents a divalent hydrocarobn group having from 1 to 15 carbon atoms, dimercaptans of a generla formula: HS-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, and mercapto-alcohols of a general formula: RaS-R‴-(OH) n where R‴ represents an alkyl group having from 1 to 15 carbon atoms or a phenyl group; Ra represents a hydrogen atom or an alkyl group having from 1 to 2 carbon atoms; and n represents an integer of from 1 to 2, the resulting blend is shaped and temporarily dried, and the thus dried shaped body is impregnated with an aqueous solution of phosphoric acid, and then again dried to prepare the said catalyst.

Claim 42

A method for preparing a catalyst for hydrotreating hydrocarbons, which is characterized in that a carrier substance consisting essentailly of an oxide of aluminium and/or an oxide hydrate of aluminium is blended and kneaded with a solution comprising at least one selected from water-­soluble compounds of metals of Group VI and Group VIII of the Periodic Table and at least one organic compound selected from the group consisting of mercapto-carboxylic acids of a general formula: HS-(CH₂) n -COOR where n represents an integer of from 1 to 3; and R represents a hydrogen atom, or an alkali metal, an alkaline earth metal, an ammonium group, or an alkyl group having from 1 to 10 carbon atoms, thio-acids of a general formula: R′-COSH where R′ represents a monovalent hydrocarbon group having from 1 to 15 carbon atoms, amino-substituted mercaptans of a general formula: H₂N-R˝-SH where R˝ represents a divalent hydrocarobn group having from 1 to 15 carbon atoms, dimercaptans of a generla formula: HS-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, and mercapto-alcohols of a general formula: RaS-R‴-(OH) n where R‴ represents an alkyl group having from 1 to 15 carbon atoms or a phenyl group; Ra represents a hydrogen atom or an alkyl group having from 1 to 2 carbon atoms; and n represents an integer of from 1 to 2, the resulting blend is shaped and temporarily dried, and the thus dried shaped body is impregnated with an aqueous solution of phosphoric acid, and then again dried to prepare the said catalyst.

Claim 43

A method for preparing a catalyst for hydrotreating hydrocarbons, which is characterized in that a carrier substance consisting essentially of an oxide of aluminium an/or an oxide hydrate of aluminium is blended and kneaded with a solution comprising phosphoric acid and at least one organic compound selected from the group consisitng of mercapto-­carboxylic acids of a general formula: HS-(CH₂) n -COOR where n represents an integer of from 1 to 3; and R represents a hydrogen atom, or an alkali metal, an alkaline earth metal, an ammonium group, or an alkyl group having from 1 to 10 carbon atoms, thio-acids of a general formula: R′-COSH where R′ represetns a monovalent hydrocarbon group having from 1 to 15 carbon atoms, amino-substituted mercaptans of a general formula: H₂N-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, dimercaptans of a general formula: HS-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, and mercapto-alcohols of a general formula: RaS-R‴-(OH) n where R‴ represents an alkyl group having from 1 to 15 carbon atoms or a phenyl group; Ra represents a hydrogen atom or an alkyl group having from 1 to 2 carbon atoms; and n represents an integer of from 1 to 2, the resulting blend is shaped and temporarily dried, and the thus dried shaped body is impregnated with an aqueous solution containing at least one selected from water-soluble compounds of metals of Group VI and Group VIII of the Periodic Table, and then again dried to prepare the said catalyst.

Claim 44

A method for preparing a catalyst for hydrotreating hydrocarbons, which is characterized in that a carrier substance consisting essentially of an oxide of aluminium an/or an oxide hydrate of aluminium is blended and kneaded with a solution comprising phosphoric acid and at least one organic compound selected from the group consisitng of mercapto-­carboxylic acids of a general formula: HS-(CH₂) n -COOR where n represents an integer of from 1 to 3; and R represents a hydrogen atom, or an alkali metal, an alkaline earth metal, an ammonium group, or an alkyl group having from 1 to 10 carbon atoms, thio-acids of a general formula: R′-COSH where R′ represetns a monovalent hydrocarbon group having from 1 to 15 carbon atoms, amino-substituted mercaptans of a general formula: H₂N-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, dimercaptans of a general formula: HS-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, and mercapto-alcohols of a general formula: RaS-R‴-(OH) n where R‴ represents an alkyl group having from 1 to 15 carbon atoms or a phenyl group; Ra represents a hydrogen atom or an alkyl group having from 1 to 2 carbon atoms; and n represents an integer of from 1 to 2, the resulting blend is shaped and temporarily dried, and the thus dried shaped body is impregnated with an aqueous solution containing at least one selected from water-soluble compounds of metals of Group VI and Group VIII of the Periodic Table, and then again dried to prepare the said catalyst.

Claim 45

A method for preparing a catalyst for hydrotreating hydrocarbons, which is characterized in that a carrier substance consisitng essentially of an oxide of aluminium and/or an oxide hydrate of aluminium is blended and kneaded with an aqueous solution of at least one selected from water-­soluble compounds of metals of Group VI and Group VIII of the Periodic Table, the resulting blend is shaped and temporarily dried, and the thus dried shaped body is impregnated with a solution comprising phosphoric acid and at least one organic compound selected from the group consisting of mercapto-carboxylic acids of a general formula: HS-(CH₂) n -COOR where n represetns an integer of from 1 to 3; and R represents a hydrogen atom, or an alkali metal, an alkaline earth metal, an ammonium group, or an alkyl group having from 1 to 10 carbon atoms, thio-acids of a general formula: R′-COSH where R′ represents a monovalent hydrocarbon group having from 1 to 15 carbon atoms, amino-substituted mercaptans of a general formula: H₂N-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, dimercaptans of a general fromula: HS-R˝-SH where R˝ represents a divalent hydorcarbon group having from 1 to 15 carbon atoms, and mercapto-alcohols of a general formula: RaS-R‴-(OH) n where R‴ represents an alkyl group having forml to 15 carbon atoms or a phenyl group; Ra represents a hydrogen atom or an alkyl group having from 1 to 2 carbon atoms; and n represents an integer of from 1 to 2, and then again dried to prepare the said catalyst.

Claim 46

A method for preparing a catalyst for hydrotreating hydrocarbons, which is characterized in that a carrier substance consisitng essentially of an oxide of aluminium and/or an oxide hydrate of aluminium is blended and kneaded with an aqueous solution of at least one selected from water-­soluble compounds of metals of Group VI and Group VIII of the Periodic Table, the resulting blend is shaped and temporarily dried, and the thus dried shaped body is impregnated with a solution comprising phosphoric acid and at least one organic compound selected from the group consisting of mercapto-carboxylic acids of a general formula: HS-(CH₂) n -COOR where n represetns an integer of from 1 to 3; and R represents a hydrogen atom, or an alkali metal, an alkaline earth metal, an ammonium group, or an alkyl group having from 1 to 10 carbon atoms, thio-acids of a general formula: R′-COSH where R′ represents a monovalent hydrocarbon group having from 1 to 15 carbon atoms, amino-substituted mercaptans of a general formula: H₂N-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, dimercaptans of a general fromula: HS-R˝-SH where R˝ represents a divalent hydorcarbon group having from 1 to 15 carbon atoms, and mercapto-alcohols of a general formula: RaS-R‴-(OH) n where R‴ represents an alkyl group having forml to 15 carbon atoms or a phenyl group; Ra represents a hydrogen atom or an alkyl group having from 1 to 2 carbon atoms; and n represents an integer of from 1 to 2, and then again dried to prepare the said catalyst.

Claim 47

A method for preparing a catalyst for hydrotreating hydrocarbons, which is characterized in that a carrier substance consisting essentially of an oxide of aluminium amd/or an oxide hydrate of aluminium is blended and kneaded with a solution of at least one organic compound selected from the group consisting of mercapto-carboxylic acids of a general formula: HS-(CH₂) n -COOR where n represents an integer of from 1 to 3; and R represents a hydrogen atom, or an alkali metal, an alkaline earth metal, an ammonium group, or an alkyl group having from 1 to 10 carbon atoms, thio-acids of a general formula: R′-COSH where R′ represetns a monovalent hydrocarbon group having from 1 to 15 carbon atoms, amino-substituted mercaptans of a general formula: H₂N-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon aotms, dimercaptans of a general formula: HS-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, and mercapto-alcohols of a general formula: RaS-R‴-(OH) n where R‴ represents an alkyl group having from 1 to 15 carbon atoms or a phenyl group; Ra represetns a hydrogen atom or an alkyl group having from 1 to 2 carbon atoms; and n represents an integer of from 1 to 2, the resulting blend is shaped and temporarily dried, and the thus dried shaped body is impregnated with an aqueous solution comprising at least one selected from water-­soluble compounds of metals of Group VI and Group VIII of the Periodic Table, and phosphoric acid, and then again dried to prepare the said catalyst.

Claim 48

A method for preparing a catalyst for hydrotreating hydrocarbons, which is characterized in that a carrier substance consisting essentially of an oxide of aluminium amd/or an oxide hydrate of aluminium is blended and kneaded with a solution of at least one organic compound selected from the group consisting of mercapto-carboxylic acids of a general formula: HS-(CH₂) n -COOR where n represents an integer of from 1 to 3; and R represents a hydrogen atom, or an alkali metal, an alkaline earth metal, an ammonium group, or an alkyl group having from 1 to 10 carbon atoms, thio-acids of a general formula: R′-COSH where R′ represetns a monovalent hydrocarbon group having from 1 to 15 carbon atoms, amino-substituted mercaptans of a general formula: H₂N-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon aotms, dimercaptans of a general formula: HS-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, and mercapto-alcohols of a general formula: RaS-R‴-(OH) n where R‴ represents an alkyl group having from 1 to 15 carbon atoms or a phenyl group; Ra represetns a hydrogen atom or an alkyl group having from 1 to 2 carbon atoms; and n represents an integer of from 1 to 2, the resulting blend is shaped and temporarily dried, and the thus dried shaped body is impregnated with an aqueous solution comprising at least one selected from water-­soluble compounds of metals of Group VI and Group VIII of the Periodic Table, and phosphoric acid, and then again dried to prepare the said catalyst.

Claim 49

A method for preparing a catalyst for hydrotreating hydrocarbons, which is characterized in that a carrier substance consisting essentially of an oxide of aluminium and/or an oxide hydrate of aluminium is blended and kneaded with an aqueous solution of phosphoric acid, the resulting blend is shaped and temporarily dried, and the thus dried shaped body is impregnated witn a solution comprising at least one selected from water-soluble compounds of metals of Group VI and Group VIII of the Periodic Table and at least one organic compound selected from the group consisting of mercapto-carboxylic acids of a general fromula: HS-(CH₂) n -COOR where n represents an integer of from 1 to 3; and R represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, or an alkyl group having from 1 to 10 carbon atoms, thio-acids of a general formula: R′-COSH where R′ represents a monovalent hydrocarbon group having from 1 to 15 carbon atoms, amino-substituted mercaptans of a general formula: H₂N-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carobn atoms, dimercaptans of a general formula: HS-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, and mercapto-alcohols of a general formula: RaS-R‴-(OH) n where R‴ represents an alkyl group having from 1 to 15 carbon atoms or a phenyl group; Ra represents a hydrogen atom or an alkyl group having from 1 to 2 carbon atoms; and n represents an integer of from 1 to 2, and then again dried to prepare the said catalyst.

Claim 50

A method for preparing a catalyst for hydrotreating hydrocarbons, which is characterized in that a carrier substance consisting essentially of an oxide of aluminium and/or an oxide hydrate of aluminium is blended and kneaded with an aqueous solution of phosphoric acid, the resulting blend is shaped and temporarily dried, and the thus dried shaped body is impregnated witn a solution comprising at least one selected from water-soluble compounds of metals of Group VI and Group VIII of the Periodic Table and at least one organic compound selected from the group consisting of mercapto-carboxylic acids of a general fromula: HS-(CH₂) n -COOR where n represents an integer of from 1 to 3; and R represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, or an alkyl group having from 1 to 10 carbon atoms, thio-acids of a general formula: R′-COSH where R′ represents a monovalent hydrocarbon group having from 1 to 15 carbon atoms, amino-substituted mercaptans of a general formula: H₂N-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carobn atoms, dimercaptans of a general formula: HS-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, and mercapto-alcohols of a general formula: RaS-R‴-(OH) n where R‴ represents an alkyl group having from 1 to 15 carbon atoms or a phenyl group; Ra represents a hydrogen atom or an alkyl group having from 1 to 2 carbon atoms; and n represents an integer of from 1 to 2, and then again dried to prepare the said catalyst.

Claim 51

The method for preparing a catalyst for hydrotreating hydrocarbons as claimed in anyone of claims 32 to 38, in which the oxide of aluminium and/or oxide hydrate of aluminium for constituting the carrier substance is(are) at least one selected from γ-alumina, dehydrated boehmite and spray-dried boehmite.

Claim 52

The method for preparing a catalyst for hydrotreating hydrocarbons as claimed in anyone of claims 32 to 38, in which the water-soluble compounds of metals of Group VI of the Periodic Table are at least one selected from ammonium molybdate and ammonium tungstate, and ammonium molybdate and ammonium tungstate as prepared by treating molybdenum trioxide and tungsten trioxide, resepctively, with ammonia gas; and the water-solbule compounds of metals of Group VIII of the Periodic Table are at least one selected from cobalt nitrate, cobalt carbonate, nickel nitrate and nickel carbonate; the said aqueous solution containing at least one selected from the said water-soluble compounds.

Claim 53

The method for preparing a catalyst for hydrotreating hydrocarbons as claimed in anyone of claims 32 to 38, in which the mercapto-carboxylic acids of a general formula: HS-(CH₂) n -COOR where n represents an integer of from 1 to 3; and R represents a hydrogen atom, or an alkali metal, an alkaline earth metal, an ammonium group, or an alkyl group having from 1 to 10 carbon atoms, are at least one selected from mercapto-­ acetic acid and β-mercapto-propionic acid and alkali metal salts, alkaline earth metal salts and ammonium salts thereof and methyl mercapto-acetate, ethyl 2-mercapto-acetate, 2-ethylhexyl mercapto-acetate and methyl 3-mercapto-propionate.

Claim 54

The method for preparing a catalyst for hydrotreating hydrocarbons as claimed in anyone of claims 32 to 38, in which the thio-acids of a general formula: R′-COSH where R′ represents a monovalent hydrocarbon group having from 1 to 15 carbon atoms, are at least one selected from thio-­acetic acid and thio-benzoic acid.

Claim 55

The method for preparing a catalyst for hydrotreating hydrocarbons as claimed in anyone of claims 32 to 38, in which the amino-substituted mercaptans of a general formula: H₂N-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, are at least one selected from 2-­aminoethanethiol and 4-aminothiophenol

Claim 56

The method for preparing a catalyst for hydrotreating hydrocarbons as claimed in anyone of claims 32 to 38, in which the dimercaptans of a general formula: HS-R˝-SH where R˝ represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, are at least one selected from ethanedithiol and 1,4-butandedithiol.

Claim 57

The method for preparing a catalyst for hydrotreating hydrocarbons as claimed in anyone of claims 32 to 38, in which the mercapto-alcohols of a general formula: RaS-R‴-(OH) n where R‴ represents an alkyl group having from 1 to 15 carbon atoms or a phenyl group; Ra represents a hydrogen atom or an alkyl group having from 1 to 2 carbon atoms; and n represents an integer of from 1 to 2, are at least one selected from 2-mercaptoethanol, 2-(methylthio)ethaol, 2-(ethylthio)ethanol, 3-mercapto-2-butanol, 4-mercaptophenol, 2-(methylthio)phenol, 4-(methylthio)phenol, 3-mercapto-1,2-propanediol, 3-methylthio-­1,2-propanediol and 3-ethylthio-1,2-propanediol.

Claim 58

The method for preparing a catalyst for hydrotreating hydrocarbons as claimed in anyone of claims 32 to 38, in which the content of the metals of Groups VI and VIII of the Periodic Table in the catalsyt is from 1 to 30 % by weight as the metal oxide, when the catalyst contains one metal of them, or the content of the metal of Group VI in the catalyst is from 5 to 30 % by weight as the metal oxide and that of the metal of Group VIII therein is from 1 to 8 by weight as the metal oxide when the catalyst contains both the metals of Groups VI and VIII.

Claim 59

The method for preparing a catalyst for hydrotreating hydrocarbons as claimed in anyone of claims 32 to 38, in which the amount of the mercapto-carboxylic acids and other sulfurizing agents is from 1 to 3 equivalent times of the amount of the sulfur necessary for forming sulfides of the metals of Groups VI and VIII of the Periodic Table, the said sulfides being high active in hydrogenation reaction.

Claim 60

The method for preparing a catalyst for hydrotreating hydrocarbons as claimed in anyone of claims 32 to 38, in which the amount of the phosphoric acid is about 3 % by weight or so as P₂O₅

Claim 61

The method for preparing a catalyst for hydrotreating hydrocarbons as claimed in anyone of claims 32 to 38, in which the drying temperature falls within the range of from 50 to 200°C and the drying time falls within the range of from 2 to 20 hours.