US20170101363A1 - Method and catalyst composite for production of vinyl acetate monomer - Google Patents
Method and catalyst composite for production of vinyl acetate monomer Download PDFInfo
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- US20170101363A1 US20170101363A1 US15/386,573 US201615386573A US2017101363A1 US 20170101363 A1 US20170101363 A1 US 20170101363A1 US 201615386573 A US201615386573 A US 201615386573A US 2017101363 A1 US2017101363 A1 US 2017101363A1
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- 239000003054 catalyst Substances 0.000 title claims abstract description 134
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 32
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 39
- 229910052737 gold Inorganic materials 0.000 claims abstract description 37
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 71
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 58
- 239000000203 mixture Substances 0.000 claims description 35
- 235000011056 potassium acetate Nutrition 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 102000002322 Egg Proteins Human genes 0.000 abstract description 45
- 108010000912 Egg Proteins Proteins 0.000 abstract description 45
- 210000003278 egg shell Anatomy 0.000 abstract description 45
- 239000010931 gold Substances 0.000 description 47
- 238000001035 drying Methods 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 238000000151 deposition Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000004115 Sodium Silicate Substances 0.000 description 5
- 239000003637 basic solution Substances 0.000 description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 5
- 235000019795 sodium metasilicate Nutrition 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 150000003841 chloride salts Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000012018 catalyst precursor Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- DTNJZLDXJJGKCM-UHFFFAOYSA-K sodium;trichlorogold Chemical compound [Na].Cl[Au](Cl)Cl DTNJZLDXJJGKCM-UHFFFAOYSA-K 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
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- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
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- C07C67/055—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their compounds
Definitions
- aspects of the invention relate to catalyst compositions, methods for preparing catalysts and methods using the catalyst to produce vinyl acetate monomer.
- Vinyl acetate monomer is a compound having the formula CH 3 COOCH ⁇ CH 2 . According to some estimates, world production capacity for VAM was 4.7 million metric tons in 2010. VAM is an important ingredient in a wide variety of products, including polymers and as an intermediate in coatings, textiles, paints, etc. For example, VAM is the precursor to polyvinyl acetate, which is an important vinyl polymer. Polyvinyl acetate is used in many applications, including several relating to glues and adhesives.
- VAM is typically synthesized by reacting ethylene and acetic acid with oxygen in the gas phase and in the presence of a palladium and/or gold catalyst with potassium acetate promoter.
- the reaction is typically carried out using a fixed bed reactor filed with catalyst composites.
- catalyst composites which are more active than previously used composites.
- a catalyst composite comprising: a support comprising silica and about 1 to about 3 wt % alumina, wherein the support has a surface area of about 175 to about 300 m 2 /g; an eggshell layer on the support comprising Pd and Au.
- the catalyst composition comprises about 2 wt % alumina.
- the support has a surface area of about 200 to about 250 m 2 /g. In a further embodiment, the support has a surface area of about 225 m 2 /g.
- Various embodiments are listed below. It will be understood that the embodiments listed below may be combined not only as listed below, but in other suitable combinations in accordance with the scope of the invention.
- the eggshell catalyst layer may comprise gold present in an amount of about 0.9 to about 5 g per liter of catalyst composition and palladium in an amount of about 3 to about 10 g per liter of catalyst composition. In some embodiments, the eggshell layer further comprises potassium acetate in an amount of about 25 to about 60 g per liter of catalyst composition.
- a second aspect of the invention relates to a method of making a catalyst composite.
- the method comprises providing a support comprising silica and about 1 to about 3 wt % alumina, wherein the support has a surface area of about 175 to about 300 m 2 /g; depositing Pd and Au onto the support to provide a support with an eggshell catalyst layer; impregnating the support with eggshell catalyst layer with potassium acetate; and reducing the support with eggshell catalyst layer at a temperature of about 90° C. to about 150° C. in a forming gas comprising hydrogen gas and nitrogen gas to form a catalyst composite.
- the hydrogen gas and nitrogen gas are present in a ratio range from about 5 to about 1 to about 1 to about 5.
- the support with eggshell catalyst layer is reduced for about one to about four hours.
- the support has a surface area of about 200 to about 250 m 2 /g. In some embodiments, the support has a surface area of about 225 m 2 /g.
- the gold present in an amount of about 0.9 to about 5 g per liter of catalyst composition and palladium is present in an amount of about 3 to about 10 g per liter of catalyst composition.
- depositing Pd and Au onto the support to provide a support with eggshell catalyst layer comprises impregnating the support with a solution containing chloride salts of Pd and Au and subsequently contacting the support with a basic solution.
- the method further comprises washing and drying the support with eggshell catalyst layer.
- impregnating the support with eggshell catalyst layer with potassium acetate comprises impregnating the support with a solution containing potassium acetate and drying said support.
- a third aspect of the invention relates to a method of making a catalyst composite.
- the method comprises providing a support comprising silica and about 1 to about 3 wt % alumina, wherein the support has a surface area of about 175 to about 300 m 2 /g; depositing Pd and Au onto the support to form a support with eggshell catalyst layer; reducing the support with eggshell catalyst layer at a temperature of about 200 to about 500° C. in a reducing gas comprising about 20% to about 100% hydrogen gas for about 1 to about 4 hours; and impregnating the support with eggshell catalyst layer with potassium acetate.
- the eggshell catalyst layer is reduced for about 2 to about 3 hours.
- the reducing gas further comprises nitrogen gas or ethylene.
- the nitrogen and hydrogen gases may be present in a ratio from about 5 to 1 to almost pure hydrogen.
- depositing Pd and Au onto the support to form a catalyst layer on the support comprises impregnating the support with a solution containing chloride salts of Pd and Au and subsequently contacting the support with a basic solution.
- the support has a surface area of about 200 to about 250 m 2 /g. In a some embodiments, the support has a surface area of about 225 m 2 /g. In one or more embodiments, the gold present in an amount of about 0.9 to about 5 g per liter of catalyst composition and palladium is present in an amount of about 3 to about 10 g per liter of catalyst composition.
- the method further comprises washing and drying the support with eggshell catalyst layer.
- impregnating the support with eggshell catalyst layer with potassium acetate comprises impregnating the support with a solution containing potassium acetate and drying said support under vacuum.
- a fourth aspect of the invention relates to a method of producing vinyl acetate monomer.
- the method comprises contacting a gas comprising ethylene, acetic acid and oxygen with a catalyst composition comprising: a support comprising silica and about 1 to about 3 wt % alumina, wherein the support has a surface area of about 175 to about 300 m 2 /g; and an eggshell catalyst layer comprising gold or palladium.
- the catalyst composition comprises about 2 wt % alumina.
- the support has a surface area of about 200 to about 250 m 2 /g. In one or more embodiments, the support has a surface area of about 225 m 2 /g.
- the eggshell catalyst layer comprises gold and palladium. In one or more embodiments, the gold present in an amount of about 0.9 to about 5 g per liter of catalyst composition and palladium is present in an amount of about 3 to about 10 g per liter of catalyst composition
- FIG. 1 shows the space-time-yield of a catalyst composition according to one or more embodiments of the invention and a catalyst composition of the prior art.
- the catalyst composite comprises a support comprising silica and about 1 to about 3 wt % alumina, wherein the support has a surface area of about 175 to about 300 m 2 /g, and an eggshell layer on the support comprising palladium (Pd) and gold (Au).
- surface area refers to the internal surface area.
- the term “eggshell layer,” “catalyst layer” or “eggshell catalyst layer” refers to a thin layer of catalyst on the outer regions of the support. It is not necessarily a layer that rests exclusively over the support, but rather that the outer regions of the support contain catalyst. In one or more embodiments, the eggshell layer is continuous around the support. In one or more embodiments, the catalyst penetrates the support at a depth of less than about 500, 450, or 400 ⁇ m.
- the amount of alumina may range from about 1 to about 3 wt % alumina. In a further embodiment, the amount of alumina may range from about 1.5 to about 2.5 wt % alumina. In a yet further embodiment, the amount of alumina may be about 2 wt % alumina.
- surface area of the support may range from about 175 to about 300 m 2 /g. In a further embodiment, the surface area may range from about 200 to about 250 m 2 /g. In yet a further embodiment, the surface area of the support may be about 225 m 2 /g.
- the catalyst used comprises gold and/or palladium.
- Au and Pd are present in a ratio of Au to Pd of about 0.3 to about 0.5.
- the amount of Au and/or Pd may be described as amount per liter of total catalyst composition.
- Pd is present in an amount of about 3 to about 10 grams per liter of catalyst composition.
- Au is present in an amount of about 0.9 to about 5 grams per liter of catalyst composition.
- the catalyst composite comprises about 25 to about 60 g/L of potassium acetate. In further embodiments, the catalyst composite comprises about 35 to about 45 g/L.
- Another aspect of the invention relates to a process for making one or more of the catalyst composites described herein.
- the method comprises providing a support comprising silica and about 1 to about 3 wt % alumina, wherein the support has a surface area of about 175 to about 300 m 2 /g; depositing Pd and Au onto the support to provide a support with an eggshell catalyst layer; impregnating the support with an eggshell catalyst layer with potassium acetate; and reducing the resulting catalyst precursor on the support at about 90° C. to about 150° C. in a forming gas comprising hydrogen gas and nitrogen gas to form a catalyst composite.
- a spherical support is used.
- the size of the support may be any that is otherwise suitable for use in the production of vinyl acetate monomer.
- suitable supports have a particle diameter of from about 3 to about 7 mm, or more specifically a diameter of from about 4.5 to about 6 mm, or even more specifically from about 5.1 to about 5.6 mm.
- the support may have a surface area of about 200 to about 250 m 2 /g, or surface area of about 225 m 2 /g. In one or more embodiments, the support may comprise about 2 wt % alumina.
- Pd and Au may be deposited with an aqueous solution containing compounds of both elements.
- depositing Pd and Au onto the support to form a catalyst layer on the support comprises impregnating the support with a solution containing chloride salts of Pd and Au and subsequently contacting the support with a basic solution.
- separate solutions may be used, one containing a Pd compound and the other a Au compound.
- suitable water-soluble Pd compounds include, but are not limited to, palladium (II) chloride, sodium palladium (II) chloride and palladium (II) nitrate.
- suitable water-soluble Au compounds include, but are not limited to, gold (III) chloride and tetrachloroauric (III) acid.
- the resulting amounts of catalyst can be calculated to achieve the desired amount of Au and/or Pd.
- the Pd is present in an amount of about 3 to about 10 g per liter of catalyst composition and/or the Au is present in an amount of about 0.9 to about 5 g per liter of catalyst composition.
- the ratio of gold to palladium is about 0.3 to about 0.5.
- the process may further comprise washing the support with eggshell layer to remove residual alkali metals and halogens leftover from the precursors and then drying the support with eggshell catalyst layer.
- the support with an eggshell catalyst layer is impregnated with potassium acetate.
- impregnation with potassium acetate may be carried out either before or after reduction of the support with eggshell layer in forming gas. This may be carried out after depositing Pd and/or Au by covering the eggshell catalyst layer with a solution of the potassium acetate.
- impregnating the catalyst layer on the support with potassium acetate comprises impregnating the support with a solution containing potassium acetate and drying said support. In one embodiment, drying the support comprises drying under vacuum.
- the support with eggshell catalyst layer may then be reduced at about 90° C. to about 150° C. in a gas mixture comprising hydrogen gas and nitrogen gas.
- the temperature range is from about 100 to about 140, 130 or 120° C.
- the temperature is about 118° C.
- the gas mixture contains from about 4% hydrogen to about 100% hydrogen.
- the catalyst layer on the support is reduced for about one to about four hours. In one or more embodiments, the gas mixture contains more than 20% hydrogen.
- the invention in another aspect, relates to a second method of making the catalyst composites described herein.
- the method comprises providing a support comprising silica and about 1 to about 3 wt % alumina, wherein the support has a surface area of about 175 to about 300 m 2 /g; depositing Pd and Au onto the support to form an support with eggshell catalyst layer; reducing the support with eggshell catalyst layer at a temperature of about 200 to about 500° C. in a reducing gas comprising about 4% to about 100% hydrogen gas for about 1 to about 4 hours; and impregnating the support with eggshell catalyst layer with potassium acetate.
- a spherical support is used.
- the size of the support may be any that is otherwise suitable for use in the production of vinyl acetate monomer.
- suitable supports have a particle diameter of from about 3 to about 7 mm, and in more specific embodiments, from about 4.5 to about 6 mm, or even more specifically from about 5.1 to about 5.6 mm.
- any of the above-described variants in the catalyst support may be used.
- the support may have a surface area of about 200 to about 250 m 2 /g, or surface area of about 225 m 2 /g.
- the support may comprise about 2 wt % alumina.
- depositing Pd and Au onto the support to form a catalyst layer on the support comprises impregnating the support with a solution containing chloride salts of Pd and Au and subsequently contacting the support with a basic solution.
- a solution containing chloride salts of Pd and Au e.g., sodium palladium (II) chloride and palladium (II) nitrate.
- suitable water-soluble Au compounds include, but are not limited to, gold (III) chloride and tetrachloroauric (III) acid.
- the resulting amounts of catalyst can be calculated to achieve the desired amount of Au and/or Pd.
- the Pd is present in an amount of about 3 to about 10 grams per liter of catalyst composition and/or the Au is present in an amount of about 0.9 to about 5 grams per liter of catalyst composition.
- the ratio of Au to Pd is about 0.3 to about 0.5.
- the process may further comprise washing the support with eggshell layer to remove residual alkali metals and halogens leftover from the precursor and then drying the support with eggshell catalyst layer.
- the catalyst layer on the support is reduced at a temperature of about 200 to about 500° C. in a reducing gas comprising about 4% to about 100% hydrogen gas for about 1 to about 4 hours. In a further embodiment, the catalyst layer is reduced for about 2 to about 3 hours.
- the reducing gas may further comprise nitrogen gas or ethylene. In further embodiments, the nitrogen and hydrogen gases are present in a ratio from about 5 to 1. In one or more embodiments, the reducing gas contains pure hydrogen. In one embodiment, the term “reducing gas” in this context is in the flammable regime.
- the support with eggshell catalyst layer is impregnated with potassium acetate after reduction. This may be carried out after depositing Pd and/or Au by covering the eggshell catalyst layer with a solution of the potassium acetate.
- impregnating the catalyst layer on the support with potassium acetate comprises impregnating the support with a solution containing potassium acetate and drying said support. In one or more embodiments, drying the support comprises drying under vacuum.
- the catalyst composites described herein may be used for the production of vinyl acetate monomer. Accordingly, another aspect of the invention relates to a method of producing vinyl acetate monomer. The method comprises contacting a gas comprising ethylene, acetic acid and oxygen with a catalyst composition comprising a support comprising silica and about 1 to about 3 wt % alumina, wherein the support has a surface area of about 175 to about 300 m 2 /g; and a catalyst comprising Au or Pd.
- the catalyst composition may be contacted with the gas as part of a fixed bed type reactor.
- the catalyst composites which are commonly in the form of small spheres, are poured into a fixed bed reactor. Then, the reagent gas is allowed to flow through, thereby allowing contact between the gas and catalyst composites.
- catalyst composites described above may be used to produce the vinyl acetate monomer.
- improvements of 15-30% in space-time-yield have been achieved over currently available catalyst composites.
- the catalyst compositions described herein may be used in other reactions. Such reactions include, but are not limited to, those involving olefins, oxygen, and carboxylic acid.
- a comparative example was prepared using a commercial support.
- the support had an alumina content of 3 wt %, and a surface area of 150 m 2 /g.
- the 5.0-5.3 mm spheres were first spray impregnated with sodium palladium chloride and sodium gold chloride salt solutions and deionized (DI) water to incipient wetness.
- the Pd and Au were precipitated by soaking the wet impregnated spheres in a basic solution of sodium metasilicate and DI water.
- 8 moles of sodium metasilicate was added for every mole of metal to be precipitated. This led to a 500 micrometers eggshell.
- the spheres were washed to remove residual sodium and chloride to levels below 100 microsiemens per centimeter in the wash water. After which, the support with an eggshell layer was dried at 150° C. for 12 hrs.
- the catalytic metals were then reduced at 118° C. with 80% H 2 in N 2 .
- the catalyst is impregnated to incipient wetness with an aqueous solution of potassium acetate and vacuum dried at 100° C. until the resulting catalyst contained less than 2% water.
- a catalyst composite was prepared using a support having an alumina content of 1 wt % and a surface area of 225 m 2 /g.
- the support was spray impregnated with Pd and Au and then soaked in an aqueous solution of sodium metasilicate to form an eggshell layer, followed by washing and drying.
- the catalyst was then reduced at 100° C. for 2 hrs in 80% H 2 in N 2 , followed by an impregnation with potassium acetate and vacuum drying.
- a catalyst composite was prepared using a support having an alumina content of 2 wt % and a surface area of 225 m 2 /g.
- the support was spray impregnated with Pd and Au and then soaked in an aqueous solution of sodium metasilicate to form an eggshell layer, followed by washing and drying.
- the catalyst was then reduced at 100° C. for 2 hrs in 80% H 2 in N 2 , followed by an impregnation with potassium acetate and vacuum drying.
- a catalyst composite was prepared using a support having an alumina content of 3 wt % and a surface area of 225 m 2 /g.
- the support was spray impregnated with Pd and Au and then soaked in an aqueous solution of sodium metasilicate to form an eggshell layer, followed by washing and drying.
- the catalyst was then reduced at 100° C. for 2 hrs in 80% H 2 in N 2 , followed by an impregnation with potassium acetate and vacuum drying.
- Examples 1-3 and C1 were tested in an isothermal stacked pellet “differential” reactor. The reported results are after 20 hours of operation.
- the operating conditions for the reactor were as follows:
- TON turnover number
- ethylene selectivity ethylene selectivity
- Examples 1-3 provide much more active catalysts than the comparative example. Examples 1 and 3 provided around a 50 mol VAM/ mol Pd/hr higher space-time-yield, while Example 2 provided an increase of almost 107 mol VAM/ mol Pd/hr.
- a second comparative example was prepared using a commercial support.
- the support had an alumina content of 3 wt %, and a surface area of 150 m 2 /g.
- the support was used to produce a catalyst composite by using an optimized preparation technique.
- the eggshell layer was prepared, washed, and dried as with C1, but the catalyst was reduced at 230, 300, 350, 400, and 500° C. in 20% H 2 for 2 to 3 hours.
- the catalyst precursor was then impregnated with potassium acetate and vacuum dried to reduce the water content to below 2%.
- An example was prepared with a support having an alumina content of 2 wt %, and a surface area of 225 m 2 /g.
- the support was used to produce a catalyst composite by using an optimized preparation technique.
- Pd and Au were deposition precipitated as with Examples 1-3, but the catalyst was reduced at 200, 300, 400, and 500° C. in 20% H 2 for 2 to 3 hours.
- the catalyst precursor was then impregnated with potassium acetate and vacuum dried to reduce the water content to below 2%.
- Examples C2 and 4 were tested as described above for examples 1-3 and C1.
- the FIG. 1 shows the TON versus the reduction temperature, and the percentages of the FIG. 1 show the ethylene selectivity.
- the TON of Example 4 is consistently and significantly higher compared to the comparative example. Additionally, the data demonstrates that as the reduction temperature is increased, the TON also increases for both supports. Even with the increase in the space-time-yield, Example 4 maintains a higher yield than C2.
- Example 4 also demonstrates comparable selectivity.
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Abstract
Provided are catalyst composites useful for the production of vinyl acetate monomer, as well as methods of making using same. The catalyst composites may comprise a support comprising silica and about 1 to about 3 wt % alumina, wherein the support has a surface area of about 175 to about 300 m2/g; and an eggshell layer on the support comprising Pd and Au.
Description
- This application is a divisional application of U.S. application Ser. No. 13/932,233, filed on Jul. 1, 2013, which claims priority to U.S. Provisional Application No. 61/667,188, filed on Jul. 2, 2012, the entire contents of which are herein incorporated by reference.
- Aspects of the invention relate to catalyst compositions, methods for preparing catalysts and methods using the catalyst to produce vinyl acetate monomer.
- Vinyl acetate monomer (VAM) is a compound having the formula CH3COOCH═CH2. According to some estimates, world production capacity for VAM was 4.7 million metric tons in 2010. VAM is an important ingredient in a wide variety of products, including polymers and as an intermediate in coatings, textiles, paints, etc. For example, VAM is the precursor to polyvinyl acetate, which is an important vinyl polymer. Polyvinyl acetate is used in many applications, including several relating to glues and adhesives.
- VAM is typically synthesized by reacting ethylene and acetic acid with oxygen in the gas phase and in the presence of a palladium and/or gold catalyst with potassium acetate promoter. The reaction is typically carried out using a fixed bed reactor filed with catalyst composites. However, there is a continuing need for catalyst composites which are more active than previously used composites.
- One aspect of the invention relates to a catalyst composite. comprising: a support comprising silica and about 1 to about 3 wt % alumina, wherein the support has a surface area of about 175 to about 300 m2/g; an eggshell layer on the support comprising Pd and Au. In one or more embodiments, the catalyst composition comprises about 2 wt % alumina. In one or more embodiments, the support has a surface area of about 200 to about 250 m2/g. In a further embodiment, the support has a surface area of about 225 m2/g. Various embodiments are listed below. It will be understood that the embodiments listed below may be combined not only as listed below, but in other suitable combinations in accordance with the scope of the invention.
- In one or more embodiments, the eggshell catalyst layer may comprise gold present in an amount of about 0.9 to about 5 g per liter of catalyst composition and palladium in an amount of about 3 to about 10 g per liter of catalyst composition. In some embodiments, the eggshell layer further comprises potassium acetate in an amount of about 25 to about 60 g per liter of catalyst composition.
- A second aspect of the invention relates to a method of making a catalyst composite. The method comprises providing a support comprising silica and about 1 to about 3 wt % alumina, wherein the support has a surface area of about 175 to about 300 m2/g; depositing Pd and Au onto the support to provide a support with an eggshell catalyst layer; impregnating the support with eggshell catalyst layer with potassium acetate; and reducing the support with eggshell catalyst layer at a temperature of about 90° C. to about 150° C. in a forming gas comprising hydrogen gas and nitrogen gas to form a catalyst composite.
- In one or more embodiments, the hydrogen gas and nitrogen gas are present in a ratio range from about 5 to about 1 to about 1 to about 5. In some embodiments, the support with eggshell catalyst layer is reduced for about one to about four hours. In one or more embodiments, the support has a surface area of about 200 to about 250 m2/g. In some embodiments, the support has a surface area of about 225 m2/g. In one or more embodiments, the gold present in an amount of about 0.9 to about 5 g per liter of catalyst composition and palladium is present in an amount of about 3 to about 10 g per liter of catalyst composition. In some embodiments, depositing Pd and Au onto the support to provide a support with eggshell catalyst layer comprises impregnating the support with a solution containing chloride salts of Pd and Au and subsequently contacting the support with a basic solution. In one or more embodiments, the method further comprises washing and drying the support with eggshell catalyst layer. In some embodiments, impregnating the support with eggshell catalyst layer with potassium acetate comprises impregnating the support with a solution containing potassium acetate and drying said support.
- A third aspect of the invention relates to a method of making a catalyst composite. The method comprises providing a support comprising silica and about 1 to about 3 wt % alumina, wherein the support has a surface area of about 175 to about 300 m2/g; depositing Pd and Au onto the support to form a support with eggshell catalyst layer; reducing the support with eggshell catalyst layer at a temperature of about 200 to about 500° C. in a reducing gas comprising about 20% to about 100% hydrogen gas for about 1 to about 4 hours; and impregnating the support with eggshell catalyst layer with potassium acetate.
- There are many variants of the method. For example, in one or more embodiments, the eggshell catalyst layer is reduced for about 2 to about 3 hours. In some embodiments, the reducing gas further comprises nitrogen gas or ethylene. The nitrogen and hydrogen gases may be present in a ratio from about 5 to 1 to almost pure hydrogen. In a third embodiment, depositing Pd and Au onto the support to form a catalyst layer on the support comprises impregnating the support with a solution containing chloride salts of Pd and Au and subsequently contacting the support with a basic solution.
- Additionally, any of the variants in the composite discussed above can be used. For example, in a fourth embodiment, the support has a surface area of about 200 to about 250 m2/g. In a some embodiments, the support has a surface area of about 225 m2/g. In one or more embodiments, the gold present in an amount of about 0.9 to about 5 g per liter of catalyst composition and palladium is present in an amount of about 3 to about 10 g per liter of catalyst composition.
- In a one or more embodiments, the method further comprises washing and drying the support with eggshell catalyst layer. In some embodiments, impregnating the support with eggshell catalyst layer with potassium acetate comprises impregnating the support with a solution containing potassium acetate and drying said support under vacuum.
- A fourth aspect of the invention relates to a method of producing vinyl acetate monomer. The method comprises contacting a gas comprising ethylene, acetic acid and oxygen with a catalyst composition comprising: a support comprising silica and about 1 to about 3 wt % alumina, wherein the support has a surface area of about 175 to about 300 m2/g; and an eggshell catalyst layer comprising gold or palladium.
- Again, any variants of the composite discussed above can be used. For example, in one or more embodiments, the catalyst composition comprises about 2 wt % alumina. In some embodiments, the support has a surface area of about 200 to about 250 m2/g. In one or more embodiments, the support has a surface area of about 225 m2/g. In some embodiments, the eggshell catalyst layer comprises gold and palladium. In one or more embodiments, the gold present in an amount of about 0.9 to about 5 g per liter of catalyst composition and palladium is present in an amount of about 3 to about 10 g per liter of catalyst composition
- The
FIG. 1 shows the space-time-yield of a catalyst composition according to one or more embodiments of the invention and a catalyst composition of the prior art. - Before describing several exemplary embodiments of the invention, it is to be understood that the invention is not limited to the details of construction or process steps set forth in the following description. The invention is capable of other embodiments and of being practiced or being carried out in various ways.
- One aspect of the invention relates to a catalyst composite. The catalyst composite comprises a support comprising silica and about 1 to about 3 wt % alumina, wherein the support has a surface area of about 175 to about 300 m2/g, and an eggshell layer on the support comprising palladium (Pd) and gold (Au).
- As used herein, the term “surface area” refers to the internal surface area.
- As used herein, the term “eggshell layer,” “catalyst layer” or “eggshell catalyst layer” refers to a thin layer of catalyst on the outer regions of the support. It is not necessarily a layer that rests exclusively over the support, but rather that the outer regions of the support contain catalyst. In one or more embodiments, the eggshell layer is continuous around the support. In one or more embodiments, the catalyst penetrates the support at a depth of less than about 500, 450, or 400 μm.
- In one or more embodiments, the amount of alumina may range from about 1 to about 3 wt % alumina. In a further embodiment, the amount of alumina may range from about 1.5 to about 2.5 wt % alumina. In a yet further embodiment, the amount of alumina may be about 2 wt % alumina.
- In some embodiments, surface area of the support may range from about 175 to about 300 m2/g. In a further embodiment, the surface area may range from about 200 to about 250 m2/g. In yet a further embodiment, the surface area of the support may be about 225 m2/g.
- In one or more embodiments, the catalyst used comprises gold and/or palladium. In one or more embodiments, Au and Pd are present in a ratio of Au to Pd of about 0.3 to about 0.5. The amount of Au and/or Pd may be described as amount per liter of total catalyst composition. Thus, in one or more embodiments, Pd is present in an amount of about 3 to about 10 grams per liter of catalyst composition. In one or more embodiments, Au is present in an amount of about 0.9 to about 5 grams per liter of catalyst composition.
- In one or more embodiments, the catalyst composite comprises about 25 to about 60 g/L of potassium acetate. In further embodiments, the catalyst composite comprises about 35 to about 45 g/L.
- Another aspect of the invention relates to a process for making one or more of the catalyst composites described herein. The method comprises providing a support comprising silica and about 1 to about 3 wt % alumina, wherein the support has a surface area of about 175 to about 300 m2/g; depositing Pd and Au onto the support to provide a support with an eggshell catalyst layer; impregnating the support with an eggshell catalyst layer with potassium acetate; and reducing the resulting catalyst precursor on the support at about 90° C. to about 150° C. in a forming gas comprising hydrogen gas and nitrogen gas to form a catalyst composite.
- In one or more embodiments, a spherical support is used. The size of the support may be any that is otherwise suitable for use in the production of vinyl acetate monomer. Examples of suitable supports have a particle diameter of from about 3 to about 7 mm, or more specifically a diameter of from about 4.5 to about 6 mm, or even more specifically from about 5.1 to about 5.6 mm.
- Any of the above-described variants in the catalyst support may be used. Thus, for example, the support may have a surface area of about 200 to about 250 m2/g, or surface area of about 225 m2/g. In one or more embodiments, the support may comprise about 2 wt % alumina.
- In one or more embodiments, Pd and Au may be deposited with an aqueous solution containing compounds of both elements. Thus, in one embodiment, depositing Pd and Au onto the support to form a catalyst layer on the support comprises impregnating the support with a solution containing chloride salts of Pd and Au and subsequently contacting the support with a basic solution. Alternatively, separate solutions may be used, one containing a Pd compound and the other a Au compound. Examples of suitable water-soluble Pd compounds include, but are not limited to, palladium (II) chloride, sodium palladium (II) chloride and palladium (II) nitrate. Examples of suitable water-soluble Au compounds include, but are not limited to, gold (III) chloride and tetrachloroauric (III) acid.
- The resulting amounts of catalyst can be calculated to achieve the desired amount of Au and/or Pd. Thus, for example, in one or more embodiments, the Pd is present in an amount of about 3 to about 10 g per liter of catalyst composition and/or the Au is present in an amount of about 0.9 to about 5 g per liter of catalyst composition. In one or more embodiments, the ratio of gold to palladium is about 0.3 to about 0.5.
- The process may further comprise washing the support with eggshell layer to remove residual alkali metals and halogens leftover from the precursors and then drying the support with eggshell catalyst layer.
- In one or more embodiments, the support with an eggshell catalyst layer is impregnated with potassium acetate. It should be noted that impregnation with potassium acetate may be carried out either before or after reduction of the support with eggshell layer in forming gas. This may be carried out after depositing Pd and/or Au by covering the eggshell catalyst layer with a solution of the potassium acetate. In one embodiment, impregnating the catalyst layer on the support with potassium acetate comprises impregnating the support with a solution containing potassium acetate and drying said support. In one embodiment, drying the support comprises drying under vacuum.
- The support with eggshell catalyst layer may then be reduced at about 90° C. to about 150° C. in a gas mixture comprising hydrogen gas and nitrogen gas. In a further embodiment, the temperature range is from about 100 to about 140, 130 or 120° C. In a further embodiment, the temperature is about 118° C. In one or more embodiment, the gas mixture contains from about 4% hydrogen to about 100% hydrogen. In some embodiments, the catalyst layer on the support is reduced for about one to about four hours. In one or more embodiments, the gas mixture contains more than 20% hydrogen.
- In another aspect, the invention relates to a second method of making the catalyst composites described herein. The method comprises providing a support comprising silica and about 1 to about 3 wt % alumina, wherein the support has a surface area of about 175 to about 300 m2/g; depositing Pd and Au onto the support to form an support with eggshell catalyst layer; reducing the support with eggshell catalyst layer at a temperature of about 200 to about 500° C. in a reducing gas comprising about 4% to about 100% hydrogen gas for about 1 to about 4 hours; and impregnating the support with eggshell catalyst layer with potassium acetate.
- In one or more embodiments, a spherical support is used. The size of the support may be any that is otherwise suitable for use in the production of vinyl acetate monomer. Examples of suitable supports have a particle diameter of from about 3 to about 7 mm, and in more specific embodiments, from about 4.5 to about 6 mm, or even more specifically from about 5.1 to about 5.6 mm. As with the previous aspect, any of the above-described variants in the catalyst support may be used. Thus, for example, the support may have a surface area of about 200 to about 250 m2/g, or surface area of about 225 m2/g. In one or more embodiments, the support may comprise about 2 wt % alumina.
- Again, Pd and Au may be deposited with an aqueous solution containing compounds of both elements. Thus, in one embodiment, depositing Pd and Au onto the support to form a catalyst layer on the support comprises impregnating the support with a solution containing chloride salts of Pd and Au and subsequently contacting the support with a basic solution. Alternatively, separate solutions may be used, one containing a Pd compound and the other a gold compound. Examples of suitable water-soluble Pd compounds include, but are not limited to, palladium (II) chloride, sodium palladium (II) chloride and palladium (II) nitrate. Examples of suitable water-soluble Au compounds include, but are not limited to, gold (III) chloride and tetrachloroauric (III) acid.
- The resulting amounts of catalyst can be calculated to achieve the desired amount of Au and/or Pd. Thus, for example, in one or more embodiments, the Pd is present in an amount of about 3 to about 10 grams per liter of catalyst composition and/or the Au is present in an amount of about 0.9 to about 5 grams per liter of catalyst composition. In one or more embodiments, the ratio of Au to Pd is about 0.3 to about 0.5.
- The process may further comprise washing the support with eggshell layer to remove residual alkali metals and halogens leftover from the precursor and then drying the support with eggshell catalyst layer.
- In one or more embodiments, the catalyst layer on the support is reduced at a temperature of about 200 to about 500° C. in a reducing gas comprising about 4% to about 100% hydrogen gas for about 1 to about 4 hours. In a further embodiment, the catalyst layer is reduced for about 2 to about 3 hours. In some embodiments, the reducing gas may further comprise nitrogen gas or ethylene. In further embodiments, the nitrogen and hydrogen gases are present in a ratio from about 5 to 1. In one or more embodiments, the reducing gas contains pure hydrogen. In one embodiment, the term “reducing gas” in this context is in the flammable regime.
- In one or more embodiments, the support with eggshell catalyst layer is impregnated with potassium acetate after reduction. This may be carried out after depositing Pd and/or Au by covering the eggshell catalyst layer with a solution of the potassium acetate. In one embodiment, impregnating the catalyst layer on the support with potassium acetate comprises impregnating the support with a solution containing potassium acetate and drying said support. In one or more embodiments, drying the support comprises drying under vacuum.
- The catalyst composites described herein may be used for the production of vinyl acetate monomer. Accordingly, another aspect of the invention relates to a method of producing vinyl acetate monomer. The method comprises contacting a gas comprising ethylene, acetic acid and oxygen with a catalyst composition comprising a support comprising silica and about 1 to about 3 wt % alumina, wherein the support has a surface area of about 175 to about 300 m2/g; and a catalyst comprising Au or Pd.
- The catalyst composition may be contacted with the gas as part of a fixed bed type reactor. Typically, the catalyst composites, which are commonly in the form of small spheres, are poured into a fixed bed reactor. Then, the reagent gas is allowed to flow through, thereby allowing contact between the gas and catalyst composites.
- Any of the variations in catalyst composites described above may be used to produce the vinyl acetate monomer. In one or more embodiments, improvements of 15-30% in space-time-yield have been achieved over currently available catalyst composites.
- In one or more embodiments, the catalyst compositions described herein may be used in other reactions. Such reactions include, but are not limited to, those involving olefins, oxygen, and carboxylic acid.
- Without intending to limit the invention in any manner, embodiments of the present invention will be more fully described by the following examples.
- A comparative example was prepared using a commercial support. The support had an alumina content of 3 wt %, and a surface area of 150 m2/g. The 5.0-5.3 mm spheres were first spray impregnated with sodium palladium chloride and sodium gold chloride salt solutions and deionized (DI) water to incipient wetness. The Pd and Au were precipitated by soaking the wet impregnated spheres in a basic solution of sodium metasilicate and DI water. In order to ensure the proper eggshell thickness and complete precipitation 8 moles of sodium metasilicate was added for every mole of metal to be precipitated. This led to a 500 micrometers eggshell.
- After precipitation, the spheres were washed to remove residual sodium and chloride to levels below 100 microsiemens per centimeter in the wash water. After which, the support with an eggshell layer was dried at 150° C. for 12 hrs.
- The catalytic metals were then reduced at 118° C. with 80% H2 in N2.
- Finally, the catalyst is impregnated to incipient wetness with an aqueous solution of potassium acetate and vacuum dried at 100° C. until the resulting catalyst contained less than 2% water.
- Similar to the procedure outlined for Example C1, a catalyst composite was prepared using a support having an alumina content of 1 wt % and a surface area of 225 m2/g. The support was spray impregnated with Pd and Au and then soaked in an aqueous solution of sodium metasilicate to form an eggshell layer, followed by washing and drying. The catalyst was then reduced at 100° C. for 2 hrs in 80% H2 in N2, followed by an impregnation with potassium acetate and vacuum drying.
- Similar to the procedure outlined for Example C1, a catalyst composite was prepared using a support having an alumina content of 2 wt % and a surface area of 225 m2/g. The support was spray impregnated with Pd and Au and then soaked in an aqueous solution of sodium metasilicate to form an eggshell layer, followed by washing and drying. The catalyst was then reduced at 100° C. for 2 hrs in 80% H2 in N2, followed by an impregnation with potassium acetate and vacuum drying.
- Similar to the procedure outlined for Example C1, a catalyst composite was prepared using a support having an alumina content of 3 wt % and a surface area of 225 m2/g. The support was spray impregnated with Pd and Au and then soaked in an aqueous solution of sodium metasilicate to form an eggshell layer, followed by washing and drying. The catalyst was then reduced at 100° C. for 2 hrs in 80% H2 in N2, followed by an impregnation with potassium acetate and vacuum drying.
- Examples 1-3 and C1 were tested in an isothermal stacked pellet “differential” reactor. The reported results are after 20 hours of operation. The operating conditions for the reactor were as follows:
-
- Temperature=150° C.
- Pressure=120 PSIG
- GHSV=35,000 hr−1
- Catalyst Bed Size=7.76 mL (50-80 pellets)
- Feed Composition:
- 72% Ethylene
- 20% Acetic Acid
- 7% Oxygen
- 1% Water
- Results from the performance testing are tabulated as turnover number (TON) (also referred to as turnover frequency) [mol VAM/mol Pd/hr] and ethylene selectivity. The TON was calculated to correct for differences in metal loading. The Pd was assumed to be fully dispersed. It was not possible to measure the Pd dispersion because of the confounding effects from the Au and potassium acetate present on the catalyst. The results are shown below in Table 1:
-
Al2O3 TON (wt- (mol VAM/mol Selectivity Example %) Pd/hr) (%) C1 3 327 94.3 1 1 381 93.2 2 2 434 93.8 3 3 373 93.8 - As shown in Table 1, Examples 1-3 provide much more active catalysts than the comparative example. Examples 1 and 3 provided around a 50 mol VAM/ mol Pd/hr higher space-time-yield, while Example 2 provided an increase of almost 107 mol VAM/ mol Pd/hr.
- A second comparative example was prepared using a commercial support. The support had an alumina content of 3 wt %, and a surface area of 150 m2/g. The support was used to produce a catalyst composite by using an optimized preparation technique. The eggshell layer was prepared, washed, and dried as with C1, but the catalyst was reduced at 230, 300, 350, 400, and 500° C. in 20% H2 for 2 to 3 hours. The catalyst precursor was then impregnated with potassium acetate and vacuum dried to reduce the water content to below 2%.
- An example was prepared with a support having an alumina content of 2 wt %, and a surface area of 225 m2/g. The support was used to produce a catalyst composite by using an optimized preparation technique. Pd and Au were deposition precipitated as with Examples 1-3, but the catalyst was reduced at 200, 300, 400, and 500° C. in 20% H2 for 2 to 3 hours. The catalyst precursor was then impregnated with potassium acetate and vacuum dried to reduce the water content to below 2%.
- Examples C2 and 4 were tested as described above for examples 1-3 and C1. The
FIG. 1 shows the TON versus the reduction temperature, and the percentages of theFIG. 1 show the ethylene selectivity. As seen in theFIG. 1 , the TON of Example 4 is consistently and significantly higher compared to the comparative example. Additionally, the data demonstrates that as the reduction temperature is increased, the TON also increases for both supports. Even with the increase in the space-time-yield, Example 4 maintains a higher yield than C2. Example 4 also demonstrates comparable selectivity. - Reference throughout this specification to “one embodiment,” “certain embodiments,” “one or more embodiments” or “an embodiment” means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. Thus, the appearances of the phrases such as “in one or more embodiments,” “in certain embodiments,” “in one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily referring to the same embodiment of the invention. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments.
- Although the invention herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It will be apparent to those skilled in the art that various modifications and variations can be made to the method and apparatus of the present invention without departing from the spirit and scope of the invention. Thus, it is intended that the present invention include modifications and variations that are within the scope of the appended claims and their equivalents.
Claims (12)
1. A catalyst composite comprising an inner region and an outer region:
the outer region comprising Pd and Au;
the inner region comprises a spherical support comprising silica and about 1 to about 3 wt % alumina and the inner region being free of Pd and Au;
wherein:
the outer region has a depth from the surface of the catalyst composite to about 500μm;
the catalyst composite has a surface area of about 175 m2/g to about 300 m2/g; and
the catalyst composite has a diameter of about 3 mm to about 7 mm;
2. The catalyst composite of claim 1 , wherein the inner region comprises about 2 wt % alumina.
3. The catalyst composite of claim 1 , wherein the catalyst composite has a surface area of about 200 m2/g to about 250 m2/g.
4. The catalyst composite of claim 3 , wherein the catalyst composite has a surface area of about 225 m2/g.
5. The catalyst composite of claim 1 , wherein the Au is present in the outer region in an amount of about 0.9 g per liter to about 5 g per liter of catalyst composition and palladium in an amount of about 3 g per liter to about 10 g per liter of catalyst composition.
6. The catalyst composite of claim 5 , wherein the outer region further comprises potassium acetate in an amount of about 25 g per liter to about 60 g per liter of catalyst composition.
7. A method of producing vinyl acetate monomer, the method comprising
contacting a gas comprising ethylene, acetic acid and oxygen with particles of a catalyst composite;
wherein:
individual particles of the catalyst composite comprise an inner region and an outer region:
the outer region comprising Pd and Au;
the inner region comprises a spherical support comprising silica and about 1 to about 3 wt % alumina and the inner region being free of Pd and Au;
the outer region has a depth from the surface of the catalyst composite to about 500 μm;
the catalyst composite has a surface area of about 175 m2/g to about 300 m2/g; and
the particles having a diameter of about 3 mm to about 7 mm.
8. The method of claim 7 , wherein the inner region comprises about 2 wt % alumina.
9. The method of claim 7 , wherein the catalyst composite has a surface area of about 200 m2/g to about 250 m2/g.
10. The method of claim 9 , wherein the catalyst composite has a surface area of about 225 m2/g.
11. The method of claim 7 , wherein the Au is present in the outer region in an amount of about 0.9 g per liter to about 5 g per liter of catalyst composition and palladium in an amount of about 3 g per liter to about 10 g per liter of catalyst composition.
12. The method of claim 11 , wherein the outer region further comprises potassium acetate in an amount of about 25 g per liter to about 60 g per liter of catalyst composition.
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US15/386,573 US20170101363A1 (en) | 2012-07-02 | 2016-12-21 | Method and catalyst composite for production of vinyl acetate monomer |
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US201261667188P | 2012-07-02 | 2012-07-02 | |
US13/932,233 US9556100B2 (en) | 2012-07-02 | 2013-07-01 | Method and catalyst composite for production of vinyl acetate monomer |
US15/386,573 US20170101363A1 (en) | 2012-07-02 | 2016-12-21 | Method and catalyst composite for production of vinyl acetate monomer |
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US (2) | US9556100B2 (en) |
EP (1) | EP2866932B1 (en) |
JP (1) | JP6392218B2 (en) |
CN (1) | CN104582838A (en) |
BR (1) | BR112015000030A2 (en) |
RU (1) | RU2015103051A (en) |
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WO (1) | WO2014008187A1 (en) |
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US10029237B2 (en) * | 2015-03-05 | 2018-07-24 | IFP Energies Nouvelles | Catalyst comprising dispersed gold and palladium, and its use in selective hydrogenation |
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US10525448B2 (en) * | 2015-07-22 | 2020-01-07 | Basf Corporation | High geometric surface area catalysts for vinyl acetate monomer production |
BR102018068589A2 (en) * | 2018-09-13 | 2020-03-24 | Frank Bollmann | MODULAR SYSTEM OF CONSTRUCTION, CONDUCTION AND FIXATION OF ELEMENTS OF TUBULAR STRUCTURES AND CORRESPONDING TUBULAR STRUCTURE |
CN115286483B (en) * | 2022-08-11 | 2023-09-19 | 万华化学集团股份有限公司 | Method for preparing trifluoroethanol from vinylidene fluoride |
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US6821922B1 (en) * | 1998-09-24 | 2004-11-23 | Degussa - Huls Ag | Supported catalyst for the production of vinyl acetate monomer |
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US5225388A (en) * | 1989-12-05 | 1993-07-06 | Hoechst Aktiengesellschaft | Method for making a catalyst |
DE3940125A1 (en) * | 1989-12-05 | 1991-06-06 | Hoechst Ag | METHOD FOR PRODUCING VINYL ACETATE |
DE19501891C1 (en) | 1995-01-23 | 1996-09-26 | Degussa | Process for the preparation of a supported catalyst and its use for the production of vinyl acetate |
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DE19827844A1 (en) | 1998-06-23 | 1999-12-30 | Aventis Res & Tech Gmbh & Co | Production of shell catalysts useful in e.g. hydrogenation and oxidation, especially gas phase production of vinyl acetate |
US6794332B2 (en) | 2000-07-07 | 2004-09-21 | Saudi Basic Industries Corporation | Highly selective shell impregnated catalyst of improved space time yield for production of vinyl acetate |
DE10163180A1 (en) * | 2001-12-21 | 2003-07-10 | Degussa | supported catalyst |
TW200704436A (en) * | 2005-06-24 | 2007-02-01 | Bp Chem Int Ltd | Vinyl acetate catalyst and support |
DE102007025444A1 (en) * | 2007-05-31 | 2008-12-11 | Süd-Chemie AG | VAM shell catalyst, process for its preparation and its use |
US7855303B2 (en) * | 2008-11-14 | 2010-12-21 | Celanese International Corporation | Integrated process for the production of vinyl acetate from acetic acid via ethylene |
-
2013
- 2013-07-01 JP JP2015520623A patent/JP6392218B2/en active Active
- 2013-07-01 WO PCT/US2013/048923 patent/WO2014008187A1/en active Application Filing
- 2013-07-01 CN CN201380045181.3A patent/CN104582838A/en active Pending
- 2013-07-01 SG SG11201500029VA patent/SG11201500029VA/en unknown
- 2013-07-01 EP EP13813659.3A patent/EP2866932B1/en active Active
- 2013-07-01 BR BR112015000030A patent/BR112015000030A2/en not_active IP Right Cessation
- 2013-07-01 RU RU2015103051A patent/RU2015103051A/en not_active Application Discontinuation
- 2013-07-01 US US13/932,233 patent/US9556100B2/en active Active
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US6821922B1 (en) * | 1998-09-24 | 2004-11-23 | Degussa - Huls Ag | Supported catalyst for the production of vinyl acetate monomer |
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US10029237B2 (en) * | 2015-03-05 | 2018-07-24 | IFP Energies Nouvelles | Catalyst comprising dispersed gold and palladium, and its use in selective hydrogenation |
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EP2866932A4 (en) | 2016-03-16 |
WO2014008187A1 (en) | 2014-01-09 |
EP2866932B1 (en) | 2021-05-19 |
RU2015103051A (en) | 2016-08-20 |
CN104582838A (en) | 2015-04-29 |
SG11201500029VA (en) | 2015-02-27 |
BR112015000030A2 (en) | 2017-08-01 |
JP2015527927A (en) | 2015-09-24 |
EP2866932A1 (en) | 2015-05-06 |
JP6392218B2 (en) | 2018-09-19 |
US9556100B2 (en) | 2017-01-31 |
US20140039218A1 (en) | 2014-02-06 |
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