Methods for gas phase oxidative desulphurization of hydrocarbons using CuZnAl catalysts promoted with group VIB metals

Patent metadata

Field	Value
Publication number	US-11603341-B2
Application number	US-202117140667-A
Country	US
Kind code	B2
Filing date	Jan 4, 2021
Priority date	Jan 4, 2016
Publication date	Mar 14, 2023
Grant date	Mar 14, 2023

Abstract

A catalytic composition is disclosed, which exhibits an X-ray amorphous oxide with a spinel formula, and crystals of ZnO, CuO, and at least one Group VIB metal oxide, and preferably, at least one acidic oxide of B, P. or Si, as well. The composition is useful in oxidative processes for removing sulfur from gaseous hydrocarbons.

First claim

We claim:

1. A method of oxidizing sulfur in a sulfur containing hydrocarbon, comprising contacting a gaseous hydrocarbon to a catalytic composition in the presence of an oxygen containing gas at a temperature in the range of from 300-600° C. and a pressure in the range of from 1-30 bars to oxidize sulfur, the catalytic composition comprising copper oxide in an amount ranging from 10 weight percent (wt. %) to 50 wt. %, zinc oxide in an amount ranging from 5 wt. % to less than 20 wt. %, aluminum oxide in an amount ranging from 20 wt. % to 70 wt. %, and at least one promoter selected from the group consisting of a Group VIB metal oxide, wherein said catalytic composition has an X-ray amorphous oxide phase with a formula Cu x Zn 1-x Al 2 O 4 wherein x ranges from 0 to 1, crystalline ZnO and CuO.

2. The method of claim 1 , wherein said promoter is Mo or W.

3. The method of claim 1 , wherein said promoter further comprises an acidic oxide of Si, B, or P.

4. The method of claim 1 , wherein said promoter is present in an amount up to 20 wt. % of said catalyst.

5. The method of claim 1 , wherein said hydrocarbon is a gaseous hydrocarbon.

6. The method of claim 1 , wherein said oxygen containing gas is pure oxygen.

7. The method of claim 1 , comprising oxidizing said hydrocarbon in the absence of hydrogen gas.

8. The method of claim 3 , wherein said acidic oxide is B 2 O 3 .

9. A process for making a catalytic composition comprising copper oxide in an amount ranging from 10 weight percent (wt. %) to 50 wt. %, zinc oxide in an amount ranging from 5 wt. % to less than 20 wt. %, aluminum oxide in an amount ranging from 20 wt. % to 70 wt. %, and at least one promoter selected from the group consisting of a Group VIB metal oxide, wherein said catalytic composition has an X-ray amorphous oxide phase with a formula Cu x Zn 1-x Al 2 O 4 wherein x ranges from 0 to 1, crystalline ZnO and CuO, the process, comprising:
(i) combining an aqueous solution containing each of copper nitrate, zinc nitrate, and aluminum nitrate with an alkaline solution containing NaOH and/or at least one of (NH 4 ) 2 CO 3 , Na 2 CO 3 and NH 4 HCO 3 , at a temperature of from about 50° C. to about 65° C., and a pH of from about 6.5 to about 14, to form a precipitate containing at least one of (a) a carbonate containing Cu, Zn, and Al, (b) a hydroxide containing Cu, Zn, and Al, and (c) a hydroxycarbonate containing Cu, Zn, and Al;
(ii) aging said precipitate;
(iii) filtering and washing said precipitate;
(iv) drying said precipitate for at least 10 hours, at a temperature of at least 100° C.;
(v) calcining the said dried precipitate for at least 4 hours at a temperature of at least 400° C.;
(vi) adding a solution containing at least one Group VIB compound to said precipitate;
(vii) impregnating said Group VIB compound in said precipitate via incipient wetness, and
(viii) calcinating said precipitate for from about 2 to about 4 hours, at a temperature of at least about 450-500° C.

10. The process of claim 9 , wherein said aqueous solution further comprises cerium nitrate, and said carbonate, hydroxide, and hydrocarbonate contain Ce.

11. The process of claim 10 , further comprising combining the precipitate of (i) with a binder selected from the group consisting of poly-ethylene oxide, polyvinyl alcohol, a sol of aluminum pseudoboehmite, silica gel and mixtures thereof, said binder being added in amount ranging from 1 to 10 weight % of said precipitate, to form an extrudable mixture, extruding said mixture through a die to form an extrudate, drying said extrudate for 24 hours at room temperature to 500° C., at a rate of from 2-5° C./minute, to calcine said extrudate for from 2-4 hours.

12. The process of claim 9 , wherein said precipitate comprises hydroxides, said process further comprising combining said precipitate with a binder selected from the group consisting of polyethylene oxide, polyvinyl alcohol, a sol of aluminum pseudoboehmite, silica gel, and mixtures thereof, said binder being added in an amount ranging from 3 to 20 weight percent of said precipitate, to form an extrudable mixture, extruding said mixture through a die to form an extrudate, drying said extrudate for 24 hours at room temperature, followed by drying at 100° C. for from 2-4 hours, and raising temperature to 500° C., at a rate of from 2-5° C./minute, to calcine said extrudate for from 2-4 hours.

13. The process of claim 9 , comprising adding a solution containing a water soluble Mo(VI) or W(VI) compound to provide an MoO 3 or WO 3 phase upon calcination.

14. The process of claim 9 , comprising further adding a solution containing a water soluble compound of B(III) to provide B 2 O 3 upon calcination.

Assignees

• Saudi Arabian Oil Co
• Boreskova Inst Kataliza Sibir

Inventors

• Koseoglu Omer Refa
• Jin Yaming Luisa
• Ismagilov Zinfer
• Yashnik Svetlana Letizia
• SALNIKOV Anton
• Kerzhentsev Mikhail
• Parmon Valentin

Classifications

• C10G2300/202

  Heteroatoms content, i.e. S, N, O, P · CPC title

• B01D2257/306

  Organic sulfur compounds, e.g. mercaptans · CPC title

• B01D2256/24

  Hydrocarbons · CPC title

• B01D2255/9207

  Specific surface · CPC title

• B01D2255/9205

  Porosity · CPC title