Supported Mo—O—K—MexOy catalyst for the synthesis of methanethiol from high H2S-containing syngas

Patent metadata

Field	Value
Publication number	US-9409153-B2
Application number	US-81068808-A
Country	US
Kind code	B2
Filing date	Nov 28, 2008
Priority date	Dec 28, 2007
Publication date	Aug 9, 2016
Grant date	Aug 9, 2016

Abstract

This invention is related to a preparation method of a supported catalyst Mo—O—K-Me x O y for the synthesis of methanethiol from H 2 S-containing syngas. The catalyst comprises of an active component of Mo—O—K-based species, an active promoter and a support denoted as metal (or metals)-carrier. The support is prepared by electroless plating method in such a way that the metal or metals chosen are plated onto the surface of the carrier. Transition metal, especially Fe, Co or Ni are selected to be the plating metal, while SiO 2 , Al 2 O 3 or TiO 2 are selected to be carrier. The catalyst thus prepared is found to be efficient for the synthesis of methanethiol from H 2 S-containing syngasor carbon oxides/hydrogen mixtures, especially regarding a minor formation of the by-product CO 2 .

First claim

The invention claimed is:

1. A catalyst comprising
a) a support consisting of a porous carrier and a metal A selected from Ni or Co, wherein the porous carrier is SiO 2 and the metal A is deposited on the carrier by electroless deposition to form an activated metal carrier;
b) a Mo—O—K based active component impregnated on the activated metal carrier, wherein the Mo—O—K based active component is K 2 MoO 4 or MoO 3 and K 2 O; and
c) optionally an active promoter Me x O y , which is impregnated on the activated metal carrier, where Me is Ni or Co, wherein x and y depend on the valence of the metal, and
wherein the weight ratios of the catalyst are:
K 2 MoO 4 /Me x O y /metalA-carrier=(5-20)/(0.0-25.0)/(0.5-8.0)-100; or
MoO 3 /K 2 O/Me x O y /metalA-carrier=(15-20)/(10-15)/(0.0-25.0)/(0.5-8.0)-100.

2. The catalyst according to claim 1 , wherein the support comprises reduced Pd and P components.

3. Method of producing the catalyst of claim 1 comprises the steps:
a) activating a SiO 2 carrier, wherein the activation comprises the steps of first treating the carrier with a solution of a Pd-component and a reducing agent;
b) impregnating said treated carrier with a solution comprising a solution of a metal salt whereby the metal is chosen from the group comprising Co and Ni, to achieve electroless deposition of said metal on the treated carrier to produce the catalyst support;
c) impregnating said support with an impregnation liquid of an aqueous solution of K 2 MoO 4 or (NH 4 )Mo 7 O 24 plus a potassium compound or MoO 3 plus a potassium compound; and optionally a precursor of said active promoter Me x O y , wherein Me is Ni or Co, followed by drying the received product to obtain the desired catalyst.

4. The process according to claim 3 , wherein said support is prepared by electroless plating method, the preparation processes include:
(i) the preparation of metal-plating solution;
a given quantity of soluble metal salt wherein the metal salt is chosen from Ni or Co salt, chosen and a given quantity of coordinating agent are dissolved in given quantity of distilled water successively to produce a metal-plating solution, in which the concentration of the metal ion varies from 1 g/l to 20 g/l, preferably 5-7 g/l; keeping stirring for 10 minutes, then a given quantity of a stabilizing agent are added one after another to the plating solution obtained above, stirring for another 20 minutes, followed by adding some NH 3 .H 2 0 to adjust the pH of the plating solution to 7.0-13.0, preferably 8.0-12.0; finally, suitable amount of distilled water is used to adjust the volume of the solution in such a way that the concentration of metal salt chosen in the plating solution varies from 1 g/l to 20 g/l, preferably 5-7 g/l;
(ii) pretreatment of the SiO 2 carrier chosen comprising the steps of
a) the carrier should be washed with distilled water, and then dried, followed by treatment of the clean carrier by immersing it into a solution of 4.5 mol/1H 2 SO 4 +0.88 mol/1H 2 0 2 (1:1) for 5 minutes under agitating, and then washed with distilled water three times;
b) the cleaned carrier is immersed in an aqueous solution of activation agent under agitation, said activation agent is PdCl 2 /HCl, the concentration of the activation agent varies from 0.05 g/l to 1.0 g/l, preferably from 0.1 g/l to 0.5 g/l; keeping ultrasonically agitating for 30-35 minutes, then washed with distilled water three times;
c) the activated carrier is immersed in an aqueous solution of reduction agent under agitation, the concentration of the reduction agent varies from 20 g/l to 30 g/l, keeping agitating for 10 seconds;
(iii) plating of metal onto carrier is conducted by putting the activated carrier produced in step (2) into the plating solution at 30-90° C. for 30-40 minutes, wherein the metal-platted carrier is washed with distilled water three times and then dried at 110° C. for 6 hours.

5. The process according to claim 3 , wherein said reduction agent is NaH 2 PO 3 .H 2 O or NaBH 4 .

6. The process according to claim 3 , wherein said stabilizing agent is ammonium sulfate or ammonium chloride.

7. The process according to claim 3 , wherein said coordinating agent is at least one chosen from Na 3 C 6 H 5 O 7 .2H 2 O, C 6 H 8 O 7 .H 2 O, C 2 H 8 N 2 or NaKC 4 H 4 O 6 .4H 2 O, the concentration of the chelating agent varies from 1 g/l to 60 g/l.

8. The process according to claim 3 , wherein the pH value of the electroless plating solution varies from 7.0 to 13.0, preferably from 8.0 to 12.0.

9. The process according to claim 4 , wherein at least one chelating reagent should present in the imprecation solution.

10. The process according to claim 4 , wherein the chelating reagent is chosen from the group of citric acid, ammonium citrate tribasic, L-glutamic acid, tartaric acid and ethylenediaminetetraacetic acid(EDTA); and the amount of chelating agent added correspondingly is 0.1-0.6 times as much as that of the support, more preferably is 0.3-0.6 times as much as that of the support.

11. The process according to claim 3 , wherein the pH value of the impregnation solution is adjusted to 8-12, preferably 8-10 by ammonia.

12. A method for preparing methyl mercaptan in a catalytic process comprising:
a) providing the supported catalyst of claim 1 ; and
b) utilizing said catalyst reacting carbon oxides, sulphur and/or hydrogen sulphide and hydrogen to form methyl mercaptan.

Assignees

• Yang Yiquan
• Hao Yingjuan
• Chen Aiping
• Wang Qi
• Yang Lingmei
• Li Qiaoling
• Dai Shenjun
• Fang Weiping
• Barth Jan-Olaf
• Weckbecker Christoph
• Huthmacher Klaus
• Evonik Degussa Gmbh

Inventors

• Yang Yiquan
• Hao Yingjuan
• Chen Aiping
• Wang Qi
• Yang Lingmei
• Li Qiaoling
• Dai Shenjun
• Fang Weiping
• Barth Jan-Olaf
• Weckbecker Christoph
• Huthmacher Klaus

Classifications

• B01J23/8872

  Alkali or alkaline earth metals · CPC title

• B01J2523/00

  Constitutive chemical elements of heterogeneous catalysts · CPC title

• B01J23/002

  Mixed oxides other than spinels, e.g. perovskite · CPC title

• B01J37/16

  Reducing · CPC title

• B01J21/063

  Titanium; Oxides or hydroxides thereof · CPC title