TH96547A - Methods of making alkenil alkanoate - Google Patents

Abstract

DC60 (09/02/48) This invention addresses at least four different aspects of the catalyst structure, the method of conducting the catalyst. And the method of using these catalysts for making alkylenyl alkanoates. Separately or together, in combination, the different aspects of this invention aimed This is especially true for improving the production of alkenyl alkanoates and VA, including reduction of By-products and improved production capability The first aspect of this invention is about the unique palladium / gold catalyst. Or advance catalyst (Sometimes sintered) containing rhodium or other metals. Second, the palladium / gold catalyst. Or catalyst The advance is by using a layered support material when one layer of the support can be considered free of Catalytic elements Third facet about the palladium / gold catalyst. Or catalyst Advance on a substrate containing a fourth zirconia on a palladium / gold catalyst or a pre-reaction catalyst produced from a chloride-free catalyst. The invention discusses at least four different aspects of the catalyst structure, the method of catalyst treatment, and the method of using them for alkenyl L treatment. Canoate Separately or together in combination, the aspects of this invention aim This is especially true for improving the production of alkenyl alkanoates and VA, including reduction of By-products and improved production capability The first aspect of this invention concerns the unique palladium / gold catalyst. Or accelerator Advance modality Second, the palladium / gold catalyst, or pre-reactor, is based on a layered substrate when one layer of the material. It can be considered as free from the accelerating element. Third terms with respect to the palladium / gold catalyst. Or catalyst Pre-on substrate containing fourth zirconia on palladium / gold catalyst or pre-catalyst produced from a holding catalytic element. Low chloride free

Claims (70)

1. Methods for producing suitable catalysts or pre-catalysts to aid in the production of alkenyl alkanoates include: contact of palladium and rhodium starting materials with the support; and reduction of palladium and rhodium starting materials by contacting the reducing environment with the support. 2. The method of claim 1, which is further comprised of contact between the gold starting material and the support material and the reduction of the gold starting material. 3. Method of Claim 1 or 2: Incineration of the exposed support material in a non-reducing atmosphere. 4. One of the methods of Claims 1-3 in which the contact procedure involves plating a gold starting material onto the substrate after plating with palladium and rhodium starting materials. 5. One of the methods of Claims 1-4 in which the contact procedure includes co-plating with palladium and rhodium starting materials followed by plating with gold starting materials. 6. One of the methods of Claims 1-5 in which the contact procedure includes co-plating of palladium, rhodium and gold starting materials. 7. One of the methods under Claims 1-6 in which the sintering procedure occurs after the plating of the gold starting material. 8. Any method under Claims 1-7 in which the sintering procedure occurs prior to the plating of the gold starting material. 9. Any method of claims 1-8, which is further comprised of at least one fixation step of at least one initial fixation substance with a fixation aid. 10. Any of the methods of Claims 1–9 in which the sequence of methods is composed includes: plating the support with an aqueous solution of ... solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of solution of 11. Any of the methods of Claims 1-10, in which the sequence of methods is composed: plating the support with an aqueous solution of ... 12. Any of the methods of Claims 1-11, in which the sequence of methods is composed: co-plating of the support with an aqueous solution of water-soluble palladium and rhodium starting materials; immobilization of the palladium and rhodium starting materials with an immobilizing agent; calcination of the immobilized palladium and rhodium starting materials; plating of the support with an aqueous solution of water-soluble gold starting materials; and reduction of the palladium, gold, and rhodium starting materials. 13. Any of the methods of Claims 1-12, in which the sequence of methods is composed: co-plating of the support with an aqueous solution of water-soluble palladium and rhodium starting materials; immobilization of the palladium and rhodium starting materials with an immobilizing agent; calcination of the immobilized palladium and rhodium starting materials; reduction of the palladium and rhodium starting materials; and plating of the support with an aqueous solution of water-soluble gold starting materials. 14. Any of the methods of Claims 1–13, in which the sequence of methods is composed: co-plating of the support with an aqueous solution of water-soluble palladium and rhodium starting materials; immobilization of the palladium and rhodium starting materials with a fixing agent; plating of the support with an aqueous solution of water-soluble gold starting materials; and calcination of the immobilized palladium, rhodium, and gold starting materials; and reduction of the palladium, gold, and rhodium starting materials. 15. Any of the methods of Claims 1-14, in which the sequence of methods is composed: co-plating of the substrate with an aqueous solution of water-soluble palladium, rhodium, and gold starting materials; calcination of the palladium, rhodium, and gold starting materials; and reduction of the palladium, rhodium, and gold starting materials. 16. One of the methods of claims 1-29, which is further combined with the contact of potassium acetate with the support material in an amount between approximately 10 and 70 g/L of catalyst. 17. One of the methods of Claim 1-34 in which the contact procedure involves contact between approximately 1 to approximately 10 g of palladium and approximately 0.5 to approximately 10 g of gold per liter of catalyst, with the amount of gold ranging from approximately 10 to approximately 125% by weight, using the weight of palladium as a base. 18. The method for the production of alkenyl alkanoates consists of: contact of a feedstock consisting of alkenes, alkanoic acids, and an oxidizing agent with a catalyst or pre-catalyst consisting of calcined palladium, calcined rhodium, and gold on a support material. 19. The method of claim 55, in which alkenes are ethylene, alkanoic acids are acetic acids, and the oxidizing agent is an oxygen-containing gas. 20. One of the methods of Claims 55-57 involves the catalyst or pre-catalyst containing between approximately 1 and approximately 10 grams of palladium and approximately 0.5 to approximately 10 grams of gold per liter of catalyst, with the amount of gold ranging from approximately 10 to approximately 125% by weight of the palladium. 21. The method for producing a suitable catalyst or pre-catalyst for the production of alkenyl alkanoates includes: layering a primary support material onto a secondary support material to produce a layered support material containing a catalytic element of palladium, gold, or a combination of these in the primary support of the layered support. 22. The method of claim 1, which is further incorporated by contacting the catalytic element with the initial support material prior to the layering step. 23. The method of claim 1 or 2, which is further incorporated by contacting the catalytic element with the primary support material after the layering step. 24. Any of the methods of claims 1-3 in which the catalyst is composed of palladium, gold, or a combination thereof. 25. Any of the methods of Claims 1-4, which are further combined with contact of palladium with the primary substrate before the layering step and contact of gold with the primary substrate after the layering step. 26. Any of the methods of Claims 1-5, which are further combined with contact of gold with the primary substrate before the layering step and contact of palladium with the primary substrate after the layering step. 27. Any of the methods of claims 1-6 in which the second supporting material is an inner layer and is deemed to be free of catalytic elements. 28. Any of the methods of claims 1-16, which are further combined with the contact of potassium acetate with the substrate prior to the layering step. 29. Any of the methods of claims 1-17, which are further combined with the contact of potassium acetate with the support material after the layering step. 30. Any of the methods of Claims 1-18, which are further combined with palladium plating of the primary support, sintering of the primary support, or gold plating of the primary support. 31. Any of the methods of Claims 1-19, which are further combined with the platinum plating of the first support, the layering of the first support on the second support, the sintering of the layered support, and the plating of the first support with gold. 32. Any of the methods of Claims 1-20, which are further combined with the combustion of the substrate layer before contact of the catalytic element with the substrate layer. 33. Any method of claims 1-23 in which the second supporting material is non-porous. 34. One of the methods of Claim 1-26 selects the primary support material from a group consisting of alumina, silica/alumina, zeolites, non-zeolite molecular sieves, titania, zirconia, niobium, silica, bentonite, clay, and a combination thereof. 35. Any method of Representation 1-28 selects a second support material from a group consisting of alumina, silicon carbide, zirconia, titania, steitite, niobium, silica, bentonite, clay, metal, glass, quartz, silicon nitride, alumina-silica, pumice, non-zeolite molecular sieves, and combinations thereof. 36. Any of the methods of claims 1-39, in which the layering process involves contact of an adhesive with the first or second substrate material to promote adhesion between those materials. 37. Any method under Claim 1-40 that selects an adhesive from organic and inorganic adhesives. 38. Any of the methods of Claim 1-41 in which the adhesive is a zirconia adhesive. 39. The method for the production of alkenyl alkanoates involves: contact of a feedstock consisting of alkenes, alkanoic acids, and an oxidizing agent with a catalyst or pre-catalyst consisting of palladium in combination with gold or rhodium on a layered substrate. 40. In accordance with claim 56, where the alkene is ethylene, the alkanoic acid is acetic acid, and the oxidizing agent is an oxygen-containing gas. 41. One of the methods of Claims 56-58 shall involve the catalyst or pre-catalyst containing between approximately 1 and approximately 10 g of palladium and approximately 0.5 to approximately 10 g of gold per liter of catalyst, with the amount of gold ranging from approximately 10 to approximately 125% by weight, using the weight of palladium as a base. 42. Methods for producing suitable catalysts or pre-catalysts to aid in the production of alkenyl alkanoates include: exposure of palladium and gold starting materials to zirconia-containing supports; and reduction of at least the palladium starting material by exposure of the reducing environment to the zirconia-containing support. 43. Any of the methods of Claims 1-3, which are further combined with the combustion of the exposed zirconia support material in a non-reducing atmosphere prior to the reducing step. 44. Any of the methods of Claims 1-4, in which the contact procedure involves plating a zirconia-containing substrate with a palladium and gold starting material. 45. Which of the following methods of claims 1-5 involves a plating procedure that includes sequential plating of palladium and gold starting materials onto a zirconia-containing substrate? 46. Any of the methods under Claims 1-6 in which the sintering procedure occurs prior to the plating of the gold starting material. 47. Any of the methods under Claims 1-8 in which the reducing step occurs prior to plating of the gold starting material. 48. Any of the methods of Claims 1-9 in which the plating procedure includes co-plating with a palladium and gold starting material. 49. Any of the methods of Claims 1-11, in which the plating procedure involves plating the zirconia-containing substrate with a presumed chloride-free, water-soluble starting solution. 50. Any of the methods of Claims 1-14 in which the plating procedure includes plating of the zirconia-containing substrate with a chloride-containing starter solution and followed by an immobilization procedure which includes immobilization with an immobilizing agent. 51. Any of the methods of Claims 1-8, in which the firing procedure involves heating the contact substrate containing zirconia to a temperature between approximately 200°C and approximately 700°C. 52. One of the methods of claims 1-22, further combined with the exposure of potassium acetate to a support containing zirconia in an amount between approximately 10 and 70 g per liter of catalyst. 53. One of the methods of Claim 1-25 in which the contact procedure involves contact between approximately 1 to approximately 10 g of palladium and approximately 0.5 to approximately 10 g of gold per liter of catalyst, with the amount of gold ranging from approximately 10 to approximately 125% by weight, using the weight of palladium as a base. 54. The method for the production of alkenyl alkanoates involves: contact of a feedstock consisting of alkenes, alkanoic acids, and an oxidizing agent with a catalyst or pre-catalyst consisting of palladium and gold on a zirconia-containing support. 55. In accordance with claim 47, the alkenes are ethylene, the alkanoic acids are acetic acid, and the oxidizing agents are oxygen-containing gases. 56. One of the methods of Claims 47-51 shall involve the catalyst or pre-catalyst containing between approximately 1 and approximately 10 g of palladium and approximately 0.5 to approximately 10 g of gold per liter of catalyst, with the amount of gold ranging from approximately 10 to approximately 125% by weight, using the weight of palladium as a base. 57. Methods for the production of catalysts or pre-catalysts suitable for assisting in the production of alkenyl alkanoates, comprising: exposure of at least one catalytic starter solution containing palladium and gold to a support, of which at least one catalytic starter solution is an aquatic solution considered to be chloride-free; and reduction of palladium or gold by exposure of the reducing environment to the support. 58. A method of claim 1 in which a palladium catalyst solution is made up of Pd(NH3)2(NO2)2, Pd(NH3)4(OH)2, Pd(NH3)4(NO3)2, Pd(NO3)2, Pd(NH3)4(OAc)2, Pd(NH3)2 (OAc)2, Pd(OAc)2 in KOH or NMe4OH or NaOH, Pd(NH3)4(HCO3)2, palladium oxalate, or a combination thereof. 59. The method of claim 1 or 2, in which a solution of the gold catalyst starter is combined with KAuO2, NaAuO2, NMe4AuO2, Au(OAc)3 in KOH or NMe4OH,HAu(NO3)4 in nitric acid, or a mixture of those. 60. Any method under Claim 1-3 in which the underlying material is composed of silica, alumina, silica-alumina, titanium, zirconia, niobium, silicate, aluminosilicate, titanate, spinel, silicon carbide, silicon nitride, carbon, steitite, bentonite, clay, metal, glass, quartz, pumice, zeolite, non-zeolite molecular sieves, or a combination thereof. 61. Any method of claims 1-7 in which the supporting material consists of a layered supporting material. 62. Any of the methods of claims 1-8 in which the layered substrate consists of an inner and an outer layer, the inner layer of which is deemed to be free of palladium and gold. 63. One of the methods of Claims 1-10, in which the contact procedure involves contact between approximately 1 to approximately 10 g of palladium and approximately 0.5 to approximately 10 g of gold per liter of catalyst with the support material, with the amount of gold ranging from approximately 10 to approximately 125% by weight, using the weight of palladium as a base. 64. Any method of claims 1-14 in which the contact procedure involves the separate plating of palladium and gold onto a substrate. 65. Any of the methods of Claims 1-15, which are further combined with the sintering procedure in a non-reducing atmosphere after palladium plating and before gold plating. 66. Any of the methods of Claims 1-16 in which the contact procedure involves co-plating of palladium and gold onto a substrate. 67. Any of the methods of Claims 1-17, which are further combined with a non-reducing atmosphere combustion step prior to the reducing step. 68. Any of the methods of claims 1-18, which are further combined with the contact of potassium acetate with the support material in an amount between approximately 10 and 70 grams per liter of catalyst. 69. The method for the production of alkenyl alkanoates involves: contact of a feedstock consisting of alkenes, alkanoic acid, and an oxidizing agent with a catalyst or pre-catalyst consisting of palladium and gold on a chloride-free support material, without washing. 70. In accordance with the claim of Article 45, whereby the alkenes are ethylene, the alkanoic acids are acetic acid, and the oxidizing agent is an oxygen-containing gas.