Alumina carrier, method of preparing the same, and silver catalyst

Patent metadata

Field	Value
Publication number	US-9592491-B2
Application number	US-201414525635-A
Country	US
Kind code	B2
Filing date	Oct 28, 2014
Priority date	Oct 29, 2013
Publication date	Mar 14, 2017
Grant date	Mar 14, 2017

Abstract

The present disclosure discloses an α-alumina carrier, comprising the elements of lanthanum and silicon both dispersed in the interior and on the surface of the carrier. The mass ratio of the element of lanthanum to the element of silicon is in the range from 0.1:1 to 20:1. The inventors of the present disclosure have made extensive researches into the field of the silver catalyst and alumina carrier thereof, and added the elements of lanthanum and silicon (i.e., bulk phase addition) in preparing the alumina carrier used in the silver catalyst. The carrier thus obtained contains the elements of silicon and lanthanum both in the interior and on the surface thereof, and has improved specific surface area and strength. The silver catalyst prepared with the carrier can react in a low reaction temperature (has a high reaction activity) and has a high selectivity in producing ethylene oxide through oxidation of ethylene.

First claim

The invention claimed is:

1. A method of preparing an α-alumina carrier, comprising the steps of:
I) preparing a mixture comprising components of: a) trihydrate alumina in a particle size ranging from 50 meshes to 500 meshes, b) pseudo bohemite in a particle size equal to or greater than 200 meshes, d) a fluoride mineralizer, and e) lanthanum and/or a lanthanum-containing compound and silicon and/or a silicon-containing compound, and adding an acid solution into the mixture and kneading the acid solution and the mixture; and
II) molding, drying, and calcining the resulting material in step I) to obtain the α-alumina carrier;
wherein the α-alumina carrier comprises elements of lanthanum and silicon both dispersed in an interior and on a surface of the carrier.

2. The method of claim 1 , wherein a mass ratio of the element of lanthanum to the element of silicon is in the range from 2:1 to 10:1.

3. The method of claim 1 , wherein the total content of the elements of silicon and lanthanum accounts for 0.01 wt % to 3.0 wt % of the carrier.

4. The method of claim 1 , wherein the α-alumina carrier has one or more of the following characteristics:
1) a specific surface area in the range from 0.7 m 2 /g to 2.0 m 2 /g,
2) a pore volume in the range from 0.35 ml/g to 0.85 ml/g,
3) water absorption equal to or higher than 30%,
4) side crushing strength in the range from 60 N/particle to 200 N/particle, and
5) a content of α-Al 2 O 3 higher than 70 wt % based on the total weight of the carrier.

5. The method of claim 1 , wherein the content of component e), calculated on the basis of the elements of silicon and lanthanum, is in the range from 0.01 wt % to 3.0 wt % of the total weight of the mixture.

6. The method of claim 1 , wherein the mass ratio of the lanthanum and/or lanthanum-containing compound to the silicon and/or silicon-containing compound based on the elements of lanthanum and silicon is in the range from 2:1 to 10:1.

7. The method of claim 1 , wherein the lanthanum-containing compound is at least one selected from the group consisting of lanthanum oxide, lanthanum carbonate, lanthanum nitrate, lanthanum chloride, and lanthanum sulfate, while the silicon-containing compound is at least one selected from the group consisting of sodium silicate, tetraethyl orthosilicate, nano-silicon, and silica gel.

8. The method of claim 1 , wherein the mixture further contains component c): an alkaline earth metal compound, the content of which is not higher than 1.5 wt % based on the total weight of the mixture, and wherein the alkaline earth metal compound is at least one selected from the group consisting of oxides, sulfates, acetates, carbonates, nitrates, and oxalates of strontium or barium.

9. The method of claim 1 , wherein based on the total weight of the mixture, the contents of the trihydrate alumina, the pseudo bohemite, the fluoride mineralizer, and the acid solution are in the range from 44 wt % to 90 wt %, 5 wt % to 50 wt %, 0.1 wt % to 3.0 wt %, and 2 wt % to 60 wt %, respectively.

10. The method of claim 1 , wherein the mixture comprises an alumina sol, and the total content of the pseudo bohemite and the alumina sol based on alumina accounts for 5 wt % to 50 wt % of the mixture.

11. A method of preparing an α-alumina carrier, comprising the steps of:
I) preparing a mixture comprising components of: trihydrate alumina in the range from 50 meshes to 500 meshes, an alumina sol, a fluoride mineralizer, and lanthanum and/or a lanthanum-containing compound and silicon and/or a silicon-containing compound, and kneading the mixture; and
II) molding, drying, and calcining the resulting material in step I) to obtain the α-alumina carrier;
wherein the α-alumina carrier comprises elements of lanthanum and silicon both dispersed in an interior and on a surface of the carrier.

12. The method of claim 11 , wherein calculated on a basis of the elements of silicon and lanthanum, the total content of the lanthanum and/or lanthanum-containing compound and silicon and/or silicon-containing compound based on the total weight of the mixture is in the range from 0.01 wt % to 3.0 wt %.

13. The method of claim 11 , wherein the mass ratio of the lanthanum and/or lanthanum-containing compound to the silicon and/or silicon-containing compound based on the elements of lanthanum and silicon is in the range from 2:1 to 10:1.

14. A silver catalyst used in producing ethylene oxide through oxidation of ethylene, comprising:
an α-alumina carrier, the α-alumina carrier prepared by a method comprising the steps of:
I) preparing a mixture comprising components of: a) trihydrate alumina in a particle size ranging from 50 meshes to 500 meshes, b) pseudo bohemite in a particle size equal to or greater than 200 meshes, d) a fluoride mineralizer, and e) lanthanum and/or a lanthanum-containing compound and silicon and/or a silicon-containing compound, and adding an acid solution into the mixture and kneading the acid solution and the mixture; and
II) molding, drying, and calcining the resulting material in step I) to obtain the α-alumina carrier, or the α-alumina carrier prepared by a method comprising the steps of:
III) preparing a mixture comprising components of: trihydrate alumina in the range from 50 meshes to 500 meshes, an alumina sol, a fluoride mineralizer, and lanthanum and/or a lanthanum-containing compound and silicon and/or a silicon-containing compound, and kneading the mixture; and
IV) molding, drying, and calcining the resulting material in step III) to obtain the α-alumina carrier,
1 wt % to 40 wt % of a silver compound based on silver,
0 ppm to 2,000 ppm of an alkali metal additive based on the alkali metal,
0 ppm to 10,000 ppm of an alkaline earth metal additive based on the alkaline earth metal, and
0 ppm to 2,000 ppm of a rhenium additive based on rhenium;
wherein the α-alumina carrier comprises elements of lanthanum and silicon both dispersed in an interior and on a surface of the carrier.

15. A method of producing ethylene oxide by oxidation of ethylene, wherein ethylene is oxidized into ethylene oxide in the presence of the silver catalyst of claim 14 .

16. The method of claim 1 , wherein the elements of lanthanum and silicon are homogeneously dispersed in the interior and on the surface of the carrier.

17. The method of claim 1 , wherein a mass ratio of the element of the lanthanum to the element of silicon is in the range from 2:1 to 20:1.

18. The method of claim 1 , wherein a mass ratio of the lanthanum and/or lanthanum-containing compound to the silicon and/or silicon-containing compound based on the elements of lanthanum and silicon is in the range from 2:1 to 20:1.

19. The method of claim 11 , wherein a mass ratio of the lanthanum and/or lanthanum-containing compound to the silicon and/or silicon-containing compound based on the elements of lanthanum and silicon is in the range from 2:1 to 20:1.

20. The method of claim 1 , wherein a mass ratio of the element of lanthanum to the element of silicon is in the range from 2:1 to 10:1, and wherein the total content of the elements of silicon and lanthanum accounts for 0.01 wt % to 3.0 wt % of the carrier.

21. The method of claim 11 , wherein a mass ratio of the element of lanthanum to the element of silicon is in the range from 2:1 to 10:1, and wherein the total content of the elements of silicon and lanthanum accounts for 0.01 wt % to 3.0 wt % of the carrier.

22. The silver catalyst of claim 14 , wherein a mass ratio of the el

Assignees

• China Petroleum & Chem Corp
• Beijing Res Inst Chemical Ind China Petroleum & Chemical Corp

Inventors

• Li Xianfeng
• Li Jinbing
• Sun Xinxin
• Chen Jianshe
• Cao Shuyuan
• Gao Lixin
• Wang Hui
• Liang Rujun
• Xue Qian
• Zhang Zhixiang

Classifications

• C04B2111/0081

  as catalysts or catalyst carriers · CPC title

• C04B35/10

  based on aluminium oxide · CPC title

• B01J35/40

  characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77) · CPC title

• B01J35/37

  Crush or impact strength · CPC title

• B01J2235/00

  Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties · CPC title