Ethylene oxide catalyst and process

• US 5,597,773 A
• Filed: 12/29/1994
• Issued: 01/28/1997
• Est. Priority Date: 12/30/1993
• Status: Expired due to Term

• Current Assignee: Shell Oil Company (Shell Plc)
• Original Assignee: Shell Oil Company (Shell Plc)
• Inventors: Mesters, Carolus M. A. M., Evans, Wayne E.
• Primary Examiner(s): Pal, Asok
• Assistant Examiner(s): Yildirim, Bekir L.
• Application Number:
  US08/366,069
• Time in Patent Office: 761 Days
• Field of Search: 502/348, 502/308, 502/319, 502/321, 502/344, 502/349, 502/347, 502/350
• US Class Current: 502/348
• CPC Class Codes: B01J 23/688 with manganese, technetium or rhenium
• CPC Class Codes: C07D 301/10 with catalysts containing silver or gold
• CPC Class Codes: Y02P 20/52 using catalysts, e.g. selective catalysts

Abstract

This invention relates to ethylene oxide catalyst for the vapor phase production of ethylene oxide from ethylene and oxygen prepared by impregnating a porous, refractory support having a surface area ranging from about 0.05 to about 10 m² /g with a solubilized catalytically effective amount of silver, a solubilized promoting amount of alkali metal, a solubilized promoting amount of rhenium, and a solubilized promoting amount of hafnium metal, wherein the Group IVB metal is provided in the form of Group IVB oxycation-containing salts. The catalyst provide substantial initial activity improvement as well as long term selectivity and activity stability improvement over prior art rhenium promoted catalyst, without any loss of initial selectivity advantage.

Claims

1. A catalyst comprising a porous refractory support having deposited thereon a catalytically effective amount of silver, a promoting amount of alkali metal, a promoting amount of rhenium, and a promoting amount of Group IVB metal applied to the support in the form of oxycation-containing compound(s), wherein said Group IVB metal is selected from the group consisting of titanium, zirconium, and hafnium.

3. The catalyst according to claim 1, wherein the support comprises at least about 85 percent by weight of alpha alumina, having a water pore volume from about 0.1 cc/g to about 0.75 cc/g, and having a surface area from about 0.03 m² /g to about 10 m² /g.

4. The catalyst according to claim 3, wherein the amount of silver is in the range of from about 1 to about 30 percent by weight expressed as the metal based on the total weight of the catalyst, the amount of Group IVB metal is in the range of from about 0.01 micromoles to about 10 micromoles per gram of the total catalyst, expressed as the metal, the amount of alkali metal is in the range of from about 10 to about 3000 parts per million, expressed as the metal, by weight of total catalyst, the amount of rhenium is in the range of from about 0.1 to about 10 micromoles, expressed as the metal, per gram of the total catalyst.

5. The catalyst of claim 3, wherein said support has a crush strength of at least about 5 pounds and a settled packing density of at least about 30 pounds/cubic foot and which support comprises first and second alpha alumina components with a first alpha alumina component in the form of particles having a median crystallite size of from about 0.4 to about 4 microns providing from about 95% to about 40% of the total weight of alpha alumina in the carrier and a second alpha alumina component generated in situ by a sol-gel process and providing the balance of the alpha alumina in the carrier.

6. The catalyst of claim 5 wherein said support further comprises from about 0.05% by weight to about 1% by weight of titania, based on the weight of alumina in the carrier.

7. The catalyst of claim 6, wherein said support has a pore volume of from about 0.3 to about 0.6 cc/gram.

8. The catalyst of claim 4, wherein said hafnium metal applied to the support is selected from the group consisting of hafnium oxyhalide, hafnium oxynitrate or hafnium oxycarbonate.

12. The catalyst of claim 4, which further comprises a rhenium co-promoter selected from sulfur, molybdenum, tungsten, chromium and mixtures thereof.

2. A catalyst comprising a porous refractory support having deposited thereon a catalytically effective amount of silver, a promoting amount of alkali metal, a promoting amount of rhenium, and a promoting amount of hafnium metal applied to the support in the form of oxycation-containing compound(s).

9. The catalyst of claim 2, wherein said alkali metal promoter is selected from the group consisting of lithium, potassium, rubidium, cesium, and mixtures thereof.

10. The catalyst of claim 2, wherein said alkali metal promoter comprises cesium.

11. The catalyst of claim 2, wherein said alkali metal promoter comprises cesium plus at least one additional alkali metal.

13. A catalyst prepared by impregnating a porous, refractory support with

(a) a solubilized catalytically effective amount of silver,

(b) a solubilized promoting amount of alkali metal,

(c) a solubilized promoting amount of rhenium metal, and

(d) a solubilized promoting amount of hafnium metal in the form of Group IVB metal oxycation-containing compound(s).

14. The catalyst of claim 13, wherein the support is impregnated with sufficient amount of silver, alkali metal, rhenium and hafnium oxycation-containing compounds to deposit on the support

(i) from about 1 to about 30 percent by weight of silver compound(s) expressed as the metal based on the total weight of the catalyst,

(ii) from about 0.01 micromoles to about 10 micromoles per gram of the total catalyst of hafnium metal, expressed as the metal, which is applied to the catalyst support in the form of an oxycation-containing compound,

(iii) from about 10 to about 3000 parts per million of alkali metal, expressed as the metal, by weight of total catalyst,

(iv) from about 0.1 to about 10 micromoles of rhenium, expressed as the metal, per gram of the total catalyst,

to provide the catalyst with a catalytically effective amount of silver, a promoting amount of alkali metal, a promoting amount of rhenium, and a promoting amount of hafnium metal;

wherein said support comprises at least about 85 percent by weight of alpha alumina having a surface area ranging from about 0.03 to about 10 m² /g.

15. The catalyst of claim 14, wherein after impregnation, the silver is reduced to metallic silver.

16. The catalyst of claim 14, wherein after impregnation, the impregnated support is heated to between about 50°

C. and about 600°

C. in the presence of a gas stream selected from the group consisting of (1) air, (2) oxygen containing gas, (3) hydrogen containing gas, (4) an inert gas, and (5) mixtures thereof for a period of time sufficient to reduce a major amount of the silver to silver metal.

17. The catalyst of claim 14, wherein after impregnation, intimately contacting, over a temperature range of about 170°

C. to about 600°

C., the impregnated support with a gas comprising at least 4 volume percent of hydrogen.

18. A catalyst comprising a porous refractory support comprising at least about 85 percent by weight of alpha alumina having water pore volume from about 0.3 cc/g to about 0.5 cc/g and a surface area from about 0.1 m² /g to about 3 m² /g having deposited thereon a catalytically effective amount of silver, a promoting amount of alkali metal, a promoting amount of rhenium, and a promoting amount of hafnium metal applied to the support in the form of oxycation-containing compound(s), which catalyst is prepared by impregnating said support with

(a) a solubilized catalytically effective amount of silver,

(b) a solublilized promoting amount of cesium metal,

(c) a solubilized promoting amount of at least one other alkali metal selected from the group consisting of lithium, sodium, potassium, and rubidium,

(d) a solubilized promoting amount of rhenium, and

(e) a solubilized promoting amount of hafnium oxycation-containing compound(s), sufficient to deposit on the support

(i) from about 5 to about 20 percent by weight of silver compound(s) expressed as the metal based on the total weight of the catalyst,

(ii) from about 0.1 micromoles to about 2 micromoles per gram of the total catalyst of hafnium,

(iii) from about 50 to about 1500 ppm of cesium, expressed as the metal,

(iv) from about 0.5 to about 100 micromoles of at least one other alkali metal selected from the group consisting of lithium, sodium, and potassium, expressed as the metal, per gram of total catalyst, and

(v) from about 0.2 to about 5 micromoles of rhenium, expressed as the metal, per gram of the total catalyst;

wherein subsequent to the impregnation step, the impregnated support is heated to reduce silver to silver metal.

19. The catalyst of claim 18, wherein the impregnated support is heated to between about 50°

C. and about 600°

C. in the presence of a gas stream selected from the group consisting of (1) air, (2) oxygen containing gas, (3) hydrogen containing gas, (4) an inert gas, and (5) mixtures thereof for a period of time sufficient to reduce a major amount of the silver to silver metal.

20. The catalyst of claim 18, wherein said support has a crush strength of at least about 5 pounds and a settled packing density of at least about 30 pounds/cubic foot and which support comprises first and second alpha alumina components with a first alpha alumina component in the form of particles having a median crystallite size of from about 0.4 to about 4 microns providing from about 95% to about 40% of the total weight of alpha alumina in the carrier and a second alpha alumina component generated in situ by a sol-gel process and providing the balance of the alpha alumina in the carrier;

and wherein said support further comprises from about 0.05% by weight to about 1% by weight of titania, based on the weight of alumina in the carrier; and

wherein said support has a pore volume of from about 0.3 to about 0.6 cc/gram.

21. A process for preparing a catalyst which comprises the steps of:

(1) impregnating a porous, refractory support with

(a) a solubilized catalytically effective amount of silver,

(b) a solubilized promoting amount of alkali metal,

(c) a solubilized promoting amount of rhenium, and

(d) a solubilized promoting amount of Group IVB metal in the form of Group IVB metal oxycation-containing compound(s);

(2) reducing the silver to metallic silver.

22. The process of claim 21, wherein the support is impregnated with sufficient amount of silver, alkali metal, rhenium and hafnium oxycation-containing compounds to deposit on the support

(i) from about 1 to about 30 percent by weight of silver compound(s) expressed as the metal based on the total weight of the catalyst,

(ii) from about 0.01 micromoles to about 10 micromoles per gram of the total catalyst of hafnium metal, expressed as the metal, which is applied to the catalyst support in the form of an oxycation-containing compound,

(iii) from about 10 to about 3000 parts per million of alkali metal, expressed as the metal, by weight of total catalyst,

(iv) from about 0.1 to about 10 micromoles of rhenium, expressed as the metal, per gram of the total catalyst,

to provide the catalyst with a catalytically effective amount of silver, a promoting amount of alkali metal, a promoting amount of rhenium, and a promoting amount of hafnium metal;

wherein said support comprises at least about 85 percent by weight of alpha alumina having a surface area ranging from about 0.03 to about 10 m² /g and has a crush strength of at least about 5 pounds and a settled packing density of at least about 30 pounds/cubic foot and has a pore volume of from about 0.3 to about 0.6 cc/gram;

wherein said support comprises first and second alpha alumina components with a first alpha alumina component in the form of particles having a median crystallite size of from about 0.4 to about 4 microns providing from about 95% to about 40% of the total weight of alpha alumina in the carrier and a second alpha alumina component generated in situ by a sol-gel process and providing the balance of the alpha alumina in the carrier;

wherein said support comprises from about 0.05% by weight to about 1% by weight of titania, based on the weight of alumina in the carrier.

23. The process of claim 21, in step (1), the impregnated support is heated to between about 50°

C. and about 600°

C. in the presence of a gas stream selected from the group consisting of (1) air, (2) oxygen containing gas, (3) hydrogen containing gas, (4) an inert gas, and (5) mixtures thereof for a period of time sufficient to reduce a major amount of the silver to silver metal.

24. A process for the production of ethylene oxide comprising the steps of contacting ethylene in the vapor phase with an oxygen-containing gas at ethylene oxide forming conditions at a temperature ranging between about 180°

C. and 330°

C. in the presence of a catalyst comprising a porous refractory support having deposited thereon a catalytically effective amount of silver, a promoting amount of alkali metal, a promoting amount of rhenium, and a promoting amount of Group IVB metal applied to the support in the form of oxycation-containing compound(s), wherein said Group IVB metal is selected from the group consisting of titanium, zirconium, and hafnium.

25. A process for the epoxidation of olefins having no allylic hydrogen comprising the steps of contacting the olefins in the vapor phase with an oxygen-containing gas maintain at a ratio of olefin to oxygen in the range of 0.01 up to 20, at epoxide forming conditions at a temperature in the range of from about 75°

C. to about 325°

C. in the presence of an organic halide, inorganic halides, acid halides, or elemental halogens, and a catalyst comprising a porous refractory support having deposited by impregnation thereon a catalytically effective amount of silver, a promoting amount of alkali metal, a promoting amount of rhenium, and a promoting amount of Group IVB metal applied to the support in the form of oxycation-containing compound(s);

wherein after the impregnation of the metals, the catalyst is put in intimate contact with a gas comprising a gas containing at least about 4 volume percent of hydrogen.