Modified carrier for silver based ethylene oxide catalyst
Silver based ethylene oxide catalysts having enhanced stability are disclosed. The enhanced stability silver based ethylene oxide catalysts include an alumina carrier which has been modified to include cavities on the surface of the carrier. The presence of the cavities on the surface of the modified carrier stops or at least impedes the motion of silver particles on the surface of the carrier during an epoxidation process. In particular, the cavities on the surface of the alumina carrier effectively trap and/or anchor silver particles and prevent them from further motion.
1. A method of forming an alumina carrier, said method comprising:
providing an admixture of reactive particles dispersed on a surface of alumina particles, wherein said reactive particles comprise a different material than said alumina particles;
forming said admixture into a predetermined shape;
sintering the admixture to form an alumina carrier having said predetermined shape and comprising sacrificial particles located on the surface and embedded within a portion of each alumina particle, wherein each sacrificial particle comprises a material containing an element of the reactive particle-Al—O, has a different phase than the alumina particles, and has a higher solubility in a solvent than the alumina particles; and
removing at least a portion of said sacrificial particles from each of the alumina particles using the solvent to form cavities in the surface of each of the alumina particles.
2. The method of claim 1 , wherein said providing the admixture comprises adding a dispersion of said reactive particles to said alumina particles.
3. The method of claim 1 , wherein said reactive particles comprise metal oxide particles.
4. The method of claim 3 , wherein said metal oxide particles are selected from the group consisting of zinc (Zn) oxide, calcium (Ca) oxide, magnesium (Mg) oxide, boron (B) oxide and mixtures thereof.
5. The method of claim 1 , wherein said reactive particles comprise non-oxides selected from the group consisting of native metals, sulfides, sulfates, carbonates, carbides, nitrides and any combination thereof.
6. The method of claim 1 , wherein from 1 to 10 weight percent of said reactive particles are dispersed on said surface of said alumina particles.
7. The method of claim 1 , wherein said sintering is performed in air and at a temperature from 1000° C. to 1600° C.
8. The method of claim 1 , wherein said solvent is an aqueous alkaline solvent or an aqueous acidic solvent.
9. The method of claim 1 , wherein said reactive particles comprise zinc oxide and said sacrificial particles comprise a Zn—Al—O phase.
10. The method of claim 1 , wherein each cavity has a diameter from 2 nm to 5 microns.
11. A method of forming a silver based ethylene oxide catalyst, said method comprising:
forming an alumina carrier, wherein said forming said alumina carrier comprises:
(i) providing an admixture of reactive particles dispersed on a surface of alumina particles, wherein said reactive particles comprise a different material than said alumina particles;
(ii) forming the admixture into a predetermined shape;
(iii) sintering the admixture to form an alumina carrier having said predetermined shape and comprising sacrificial particles located on the surface and embedded within a portion of each alumina particle, wherein each sacrificial particle comprises a material containing an element of the reactive particle-Al—O, has a different phase than the alumina particles, and has a higher solubility in a solvent than the alumina particles; and
(iv) removing at least a portion of said sacrificial particles from each of the alumina particles using the solvent to form cavities in the surface of each of the alumina particles; and
depositing silver on said alumina carrier, wherein said depositing comprises utilizing an impregnation solution containing from about 0.5% to 45% silver.
12. The method of claim 11 , further comprising depositing a promoting amount of one or more promoters deposited on said alumina carrier, wherein said depositing said promoting amount of one or more promoters is performed prior to, coincident with, or after said depositing said silver on said alumina carrier.
13. The method of claim 11 , wherein said reactive particles comprise metal oxide particles.
14. The method of claim 13 , wherein said metal oxide particles are selected from the group consisting of zinc (Zn) oxide, calcium (Ca) oxide, magnesium (Mg) oxide, boron (B) oxide and mixtures thereof.
15. The method of claim 11 , wherein said reactive particles comprise non-oxides selected from the group of native metals, sulfides, sulfates, carbonates, carbides, nitrides and any combination thereof.
16. The method of claim 11 , wherein from 1 to 10 weight percent of said reactive particles are dispersed on said surface of said alumina particles.
17. The method of claim 11 , wherein said sintering is performed in air and at a temperature from 1000° C. to 1600° C.
18. The method of claim 11 , wherein said solvent is an aqueous alkaline solvent or an aqueous acidic solvent.
19. The method of claim 11 , wherein said reactive particles comprise zinc oxide and said sacrificial particles comprise a Zn—Al—O phase.
20. A carrier comprising a plurality of bound alumina particles, wherein each alumina particle contains a plurality of cavities located within a surface of the alumina particle, and wherein each cavity has a diameter from 2 nm to 5 microns.
21. The carrier of claim 20 further comprising pores located between at least some of the alumina particles.
22. The carrier of claim 21 , wherein said alumina particles comprise alpha-alumina particles.
23. The carrier of claim 21 , wherein at least some of the cavities include a material having a different phase and solubility than said alumina particles embedded therein.
24. The carrier of claim 23 , wherein said material comprises M-Al—O, wherein M is at least one of zinc (Zn), calcium (Ca), magnesium (Mg), and boron (B).
25. The carrier of claim 24 , wherein M is Zn, and said material has a Zn—Al—O phase.
26. An ethylene epoxidation catalyst comprising:
a carrier comprising a plurality of bound alumina particles, wherein each alumina particle contains a plurality of cavities located within a surface of the alumina particle, and wherein each cavity has a diameter from 2 nm to 5 microns; and
silver and a promoting amount of one or more promoters deposited on and/or in said carrier.
27. The catalyst of claim 26 , wherein the one or more promoters is cesium.
28. The catalyst of claim 26 , wherein the one or more promoters is potassium.
29. The catalyst of claim 26 , wherein the one or more promoters is rhenium.
30. The catalyst of claim 29 , further comprising a promoting amount of an alkali or alkaline earth metal.
31. The catalyst of claim 29 , further comprising a promoting amount of at least one of cesium, lithium, tungsten, and sulfur.
32. The catalyst of claim 26 wherein said carrier further comprises pores located between at least some of the alumina particles.
33. The catalyst carrier of claim 26 , wherein said alumina particles of said carrier comprise alpha-alumina particles.
34. The catalyst carrier of claim 26 , wherein said carrier comprises non alpha-alumina particles.
35. The catalyst of claim 26 , wherein at least some of the cavities of said carrier include a material having a different phase and solubility than said alumina particles embedded therein.
36. The catalyst of claim 35 , wherein said material comprises M-Al—O, wherein M is at least one of zinc (Zn), calcium (Ca), magnesium (Mg), and boron (B).
37. The catalyst of claim 36 , wherein M is Zn, and said material has a Zn—Al—O phase.