WO2007094903A2 - Preparation of palladium-gold catalysts - Google Patents
Preparation of palladium-gold catalysts Download PDFInfo
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- WO2007094903A2 WO2007094903A2 PCT/US2007/000600 US2007000600W WO2007094903A2 WO 2007094903 A2 WO2007094903 A2 WO 2007094903A2 US 2007000600 W US2007000600 W US 2007000600W WO 2007094903 A2 WO2007094903 A2 WO 2007094903A2
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- palladium
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- catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
- C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
Definitions
- the invention relates to supported palladium-gold catalysts. More particularly, the invention relates to supported palladium-gold catalysts that have increased catalytic activity and activity stability in acetoxylation.
- Palladium-gold catalysts are known. They are used in acetoxylation. For instance, the oxidation of ethylene in the presence of a palladium-gold catalyst and acetic acid produces vinyl acetate, which is a useful monomer for the polymer industry.
- Acetoxylation is commonly performed by the vapor phase reaction using supported palladium-gold catalyst.
- Methods for supporting palladium-gold catalysts are known. In general, the method involves depositing a mixture of palladium and gold salts onto a support and then reducing the palladium and gold to metals.
- the supported palladium-gold catalysts are often deactivated in acetoxylation.
- the catalyst would have increased activity or productivity but would not incur increased cost.
- the invention is a method for preparing a supported palladium-gold catalyst.
- the method comprises sulfating a titanium dioxide support.
- the sulfated support is calcined.
- the calcined support is then treated with a solution containing a palladium salt, a gold salt, and an alkali metal or ammonium compound.
- the alkali metal or ammonium compound reacts with the palladium and gold salts during impregnation of the support.
- the impregnated support is calcined to cause partial decomposition of the palladium and gold salts.
- the calcined product undergoes reduction to reduce palladium and gold to metals.
- the invention includes the palladium-gold catalyst prepared according to the
- the invention also includes the use of the catalyst in acetoxylation for preparing vinyl acetate and allyl acetate. Compared to the palladium-gold catalysts known in the art, the catalysts prepared according to the method of the invention show improved catalytic activity stability in acetoxylation.
- the method of the invention comprises sulfating a titanium dioxide support.
- sulfating I mean introducing sulfate into titanium dioxide support. Sulfating can be done either in the titanium dioxide production process or by post treatment after the titanium dioxide is made. In the sulfate titanium dioxide process, one may control the amount of sulfate residue. Alternatively, the sulfating step can be done by treating a titanium dioxide with a sulfating agent. The sulfate-containing titanium dioxide from a sulfate titanium dioxide process or any other sources may, or may not, be further sulfated.
- Suitable sulfating agents include sulfuric acid, persulfuric acid, and their salts, the like, and mixtures thereof.
- the sulfating agent is a salt of sulfuric acid or persulfuric acid. The salts are more convenient to handle than the acid because they are less hazardous.
- the above sulfated titanium dioxide contains greater than or equal to 0.01 wt % of sulfur (S). More preferably, the sulfated titanium dioxide contains from 0.01 wt % to about 5 wt % of S. Most preferably, the sulfated titanium dioxide contains from 0.1 wt% to about 1.0 wt % of S.
- the titanium dioxide for use in the post treatment is produced by hydrolysis of titanium oxychloride or titanyl sulfate, is nano-structured and is crystalline anatase.
- the sulfated titanium dioxide is then calcined.
- the calcination is performed by heating the titanium dioxide at a temperature preferably within the range of 500 0 C to 900 0 C 1 more preferably 600 0 C to 800 0 C, and most preferably 65O 0 C to 750 0 C.
- the calcined titanium dioxide has pore volumes within the range of
- the pore volumes are within the range of 0.10cm 3 /g to 0.65 cm 3 /g; the surface areas are within the range of 1 m 2 /g to 200 m 2 /g. Most preferably, the surface area is from 2 m 2 /g to 50 m 2 /g.
- calcining the sulfated support significantly increases the acetoxylation activity of the palladium-gold catalyst prepared therefrom.
- One possible effect of calcining the sulfated titanium dioxide support is sintering and modifying the support surface and thus makes it a better fit for the palladium and gold metals that are supported thereupon.
- the calcined support is impregnated. Any suitable impregnation methods can be used. For instance, U.S. Pat. No. 6,022,823 teaches how to impregnate the support.
- the support can be simultaneously or successively treated with a palladium salt, a gold salt, and an alkali metal or ammonium compound.
- the impregnation is performed in aqueous solutions.
- concentration of the solutions and the amount of each solution used is governed by the concentration of palladium and gold desired in the final catalyst product.
- Suitable palladium salts include palladium chloride, sodium chloropalladite, palladium nitrate, palladium sulfate, the like, and mixtures thereof.
- Suitable gold salts include auric chloride, tetrachloroauric acid, sodium tetrachloroaurate, the like, and mixtures thereof.
- Sodium tetrachloroaurate and palladium chloride or sodium chloropalladite are most commonly used.
- Suitable alkali metal or ammonium compounds include alkali metal or ammonium hydroxides, alkali metal or ammonium carbonates, alkali metal or ammonium bicarbonates, alkali metal or ammonium metasilicates, the like, and mixtures thereof.
- One method to impregnate the support involves first treating the support with an aqueous solution of an alkali metal or ammonium compound.
- the support which has been treated with the aqueous solution containing the alkali metal or ammonium compound is then contacted with an aqueous solution containing palladium and gold salts.
- the impregnation with the palladium and gold solutions is carried out before treatment with the aqueous solution of the alkali metal or ammonium compound.
- the absorptive capacity of the support is essentially completely filled with the aqueous solution of palladium and gold salts. Typically, this is accomplished by dropping the solution onto the support until incipient wetness is achieved.
- the support impregnated with the palladium and gold salts is then contacted with the alkali metal or ammonium compound.
- a third method involves mixing the alkali or ammonium compound and precious metal compounds prior to contacting with the support.
- the contact with the support can be done by dropping or spraying the mixture onto the support until incipient wetness or by making a slurry of a powdered support in the solution.
- the impregnated catalyst is preferably washed with water to remove alkali metal salts such as chlorides formed during the impregnation and dried prior to calcination.
- the impregnated support is calcined, i.e., heated at an elevated temperature in a non-reducing atmosphere.
- the calcination is performed under such a condition that a portion of the palladium and gold salts are decomposed. More preferably, at least 10% of the palladium and gold salts are decomposed during the calcination.
- the calcination of the impregnated support is carried out at a temperature within the range of about 100 0 C to about 600 0 C. More preferably, the temperature is within the range of 100 0 C to 300 0 C. Most preferably, the temperature is within the range of 15O 0 C to 25O 0 C.
- Suitable non-reducing gases used for the calcination include inert or oxidizing gases such as helium, nitrogen, argon, neon, nitrogen oxides, oxygen, air, carbon dioxide, the like, and mixtures thereof.
- the calcination is carried out in an atmosphere of nitrogen, oxygen or air or mixtures thereof.
- the degree of decomposition of the palladium and gold salts depends on the temperature used, the deposited salt, and the length of time the deposited sulfate- containing titanium dioxide is calcined and can be followed by monitoring volatile decomposition products. For example, when the support is impregnated with palladium and gold carbonates, the amount of carbon dioxide (CO2) evolved can be measured.
- CO2 carbon dioxide
- the resulting product is reduced to convert the palladium and gold salts to the corresponding metals.
- the reduction is performed by heating in the presence of a reducing agent.
- Suitable reducing agents include ammonia, carbon monoxide, hydrogen, hydrocarbons, olefins, aldehydes, alcohols, hydrazine, primary amines, carboxylic acids, carboxylic acid salts, carboxylic acid esters, the like, and mixtures thereof.
- Hydrogen, ethylene, propylene, alkaline hydrazine and alkaline formaldehyde are preferred reducing agents and ethylene and hydrogen are particularly preferred.
- Temperatures employed for the reduction can range from ambient up to about 600 0 C.
- the reduction temperature is within the range of 300 0 C to 60O 0 C.
- the reduction temperature is within the range of 450 0 C to 55O 0 C.
- the reduction results in a supported palladium-gold catalyst.
- the invention includes the supported palladium-gold catalyst made according to the method of the invention.
- the supported palladium-gold catalyst comprises 0.1 wt % to 3 wt % of palladium and 0.1 wt % to 3 wt % of gold, and the weight ratio of palladium to gold is within the range of 5/1 to 1/3. More preferably, the supported palladium-gold catalyst comprises 0.5 wt % to 1.5 wt % of palladium and 0.25 wt % to 0.75 wt % of gold; the weight ratio of palladium to gold is within the range of 2.5/1 to 1/1.5.
- the supported palladium-gold catalysts made according to the invention have many uses. It can be used, for example, in the partial oxidation, hydrogenation, carbonylation, ammonia synthesis, selective hydrogenation, acetyloxylation, catalytic combustion or complete oxidation, three way catalysis, NOx removal, methanol synthesis, hydrogen peroxide synthesis, hydroformylation, alkylation and alkyl transfer, oxidative carbonylation, coupling of olefins with aromatics, and the preparation of methyl isobutyl ketone from acetone.
- the supported palladium-gold catalysts made according to the invention are particularly useful for the productions of vinyl acetate and allyl acetate.
- Various processes for the productions of vinyl acetate and allyl acetate are known.
- U.S. Pat. Nos. 3,743,607 and 3,775,342 teach how to prepare vinyl acetate using palladium-gold catalysts.
- the supported palladium-gold catalyst is preferably treated with a potassium compound such as potassium acetate.
- the potassium treatment can be done by mixing the catalyst with a potassium acetate solution, filtering, and drying the treated catalyst.
- vinyl acetate can be made by the oxidation of ethylene in the presence of acetic acid and the supported palladium-gold catalyst. Allyl acetate can be made by a similar manner but using propylene rather than ethylene.
- the catalysts made according to the invention give not only high catalytic activity but also high activity stability.
- One problem in the existing palladium-gold catalysts is that the catalysts lose activity with time. This invention provides a solution to the problem.
- a titanium dioxide (20 grams, GP350 from Millennium Chemicals, prepared from hydrolysis of an aqueous solution of titanium oxychloride) is mixed with 50 ml of a 0.05 mole/l aqueous solution of ammonium persulfate at room temperature with stirring for at least two hours. The slurry is filtered, and the solid is dried for at least
- the sulfated titanium dioxide is calcined at 700 0 C for six hours. It has a final surface area of 32.5 m 2 /g, a pore volume of 0.20 ml/g r and a sulfur content of 0.23 wt %.
- the sulfur content is measured according to the following method.
- a titanium dioxide sample (0.5 gram) is mixed with hydrofluoric acid (5 ml) in a sealable microwavable vessel. The mixture is heated under pressure in the microwave until in solution. After cooling, it is diluted to 50 ml with deionized water. Measurements are done using an IRIS Intrepid Il inductively coupled plasma emission spectrometer and reported as percent sulfur.
- NaAuCI 4 (0.194 gram), Na 2 PdCI 4 (0.496 gram), and NaHCO 3 (0.510 grams) are dissolved in water (20 ml).
- the solution is mixed with the above calcined titanium dioxide (10 grams) to form a slurry.
- the slurry is kept overnight to allow the metal compounds to deposit onto the surface of titanium dioxide.
- the mixture is filtered.
- the solid is washed by mixing with water (20 ml) and filtering again. It is then dried in an oven at 105 0 C for at least 16 hours.
- the above impregnated titanium dioxide is calcined in a reactor at 200 0 C in flowing air for three hours to affect a partial decomposition in excess of 10% of the deposited precious metal salts.
- the reactor is purged with nitrogen, and then a mixture of 5% hydrogen in nitrogen is introduced into the vessel.
- the temperature is ramped to 50O 0 C at a rate of 10 0 C /min. The temperature is held at this reading for three hours.
- the reactor is purged with nitrogen and the resultant catalyst is then cooled to room temperature in flowing nitrogen. Upon cooling, the sample is washed to remove any remaining chloride as determined by testing with a silver nitrate solution, and then dried at 105 0 C in an oven.
- the above resultant catalyst (5 grams) is contacted with an excess (>10 ml) of 5 w% aqueous solution of potassium acetate at room temperature for 10 minutes.
- the mixture is filtered; the potassium treated catalyst is dried at 105 0 C in an oven for at least 4 hours.
- the potassium treated catalyst is mixed with, in a ratio of 1 to 9, an inert alumina support to minimize effects of thermal gradients.
- the mixture (0.5 gram) is placed in a quartz glass reactor.
- the temperature is raised to 11O 0 C and then the material is exposed to a gas feed composition of 77% ethylene, 11% helium, 9% oxygen and 3% acetic acid at atmospheric pressure and a gas-hourly space velocity of 13,200.
- the reactor effluent is analyzed using a mass spectrometer.
- the temperature is then ramped from 11O 0 C to 160 0 C and cooled again to 110 0 C repeatedly at a rate of 2°C/min.
- the performance of the catalyst is compared by calculating the rate as interpolated at 135°C at specified times on stream and is calculated from the data taken between 11O 0 C and 16O 0 C. Calibrations are made by injecting known amounts of vinyl acetate. The results are listed in Table 1, which show that the catalyst exhibits high activity. Table 1 also lists the catalyst activities measured at the 1 st hour and the 6 th hour on stream. The results show that the catalyst activity increases with increased exposure to reaction conditions. Table 1 Catalyst Activity and Activity Stability in Vinyl Acetate Production
- Example 1 The general procedure of Example 1 is repeated with the exception that the GP350 titanium oxide is not treated with ammonium persulfate. As shown in Table 1, the catalyst activity is significantly lower than that of Example 1, and the activity declines from the 1 I St hour to the 6 th hour.
- Example 1 The general procedure of Example 1 is repeated with the exceptions that the titanium dioxide (DT51, from Millennium Chemicals) is made using sulfate precursors and that the titanium dioxide is not treated with ammonium persulfate.
- the titanium dioxide contains 0.47 wt % of sulfur. After the titanium dioxide is calcined at 700 0 C, its sulfur content reduces to 0.14 wt %.
- Table 1 the catalyst shows improved activity stability compared to the catalyst of Comparative Example 2.
- Example 3 The general procedure of Example 3 is repeated with the exception that the titanium dioxide is treated with 0.05 molar ammonium persulfate. As shown in Table 1, the catalyst shows improved activity compared to the catalyst of Example 3 and improved activity stability compared with the catalyst of Comparative Example 2. Table 2 Effect of Calcination Temperatures on Catalyst Activity
- Example 3 The general procedure of Example 3 is repeated with exceptions that the titanium dioxide DT51 is calcined at various temperatures (no calcination, 700, 800, or 900 0 C) and that the impregnated support is also calcined at various temperatures (190 0 C or 220 0 C).
- the results are shown in Table 2, which indicate that the calcinations of the titanium dioxide prior to and after impregnation are both important to achieve high catalyst activity and stability.
- Example 3 The catalyst prepared in Example 3 is used to prepare allyl acetate, which follows the same manner as the vinyl acetate preparation in Example 1 with the exception that the gas composition is 29% propylene, 60% helium, 7.7% oxygen and 3.3% acetic acid and the gas-hourly space velocity is 12,400(ml/ml)/hr.
- the catalyst has an average rate of 4.48x10 "3 micromoles/s measured at the 6 th hour on stream.
- Example 4 The general procedure of Example 4 is repeated with the exception that the ammonium persulfate concentration is varied from 0 to 0.1 molar in 0.025 molar increments. The results are shown in Table 3, which indicate that an optimum performance may exist at the ammonium persulfate concentrations between 0.05 and 0.075 molar.
Abstract
Description
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07748869.0A EP1984113B1 (en) | 2006-02-02 | 2007-01-10 | Catalyst for co oxidation comprising dispersed gold atoms |
CA2636558A CA2636558C (en) | 2006-02-02 | 2007-01-10 | Preparation of palladium-gold catalysts |
KR1020087018913A KR101357188B1 (en) | 2006-02-02 | 2007-01-10 | Preparation of palladium-gold catalyst |
JP2008553243A JP5198288B2 (en) | 2006-02-02 | 2007-01-10 | Production of palladium-gold catalyst |
BRPI0706798A BRPI0706798B1 (en) | 2006-02-02 | 2007-01-10 | method for preparing a palladium and gold based catalyst, palladium and gold supported catalyst, methods for preparing vinyl acetate and allyl acetate |
Applications Claiming Priority (2)
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US11/346,500 US8168562B2 (en) | 2006-02-02 | 2006-02-02 | Preparation of palladium-gold catalysts |
US11/346,500 | 2006-02-02 |
Publications (3)
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WO2007094903A2 true WO2007094903A2 (en) | 2007-08-23 |
WO2007094903A3 WO2007094903A3 (en) | 2007-10-18 |
WO2007094903A8 WO2007094903A8 (en) | 2008-09-04 |
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PCT/US2007/000600 WO2007094903A2 (en) | 2006-02-02 | 2007-01-10 | Preparation of palladium-gold catalysts |
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US (1) | US8168562B2 (en) |
EP (1) | EP1984113B1 (en) |
JP (1) | JP5198288B2 (en) |
KR (1) | KR101357188B1 (en) |
CN (2) | CN103801291A (en) |
BR (1) | BRPI0706798B1 (en) |
CA (1) | CA2636558C (en) |
WO (1) | WO2007094903A2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US8168562B2 (en) | 2006-02-02 | 2012-05-01 | Lyondell Chemical Technology, L.P. | Preparation of palladium-gold catalysts |
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US20100121100A1 (en) * | 2008-11-12 | 2010-05-13 | Daniel Travis Shay | Supported palladium-gold catalysts and preparation of vinyl acetate therewith |
US8263801B2 (en) * | 2009-09-30 | 2012-09-11 | Lyondell Chemical Technology, L.P. | Process for producing allyl acetate |
EP2512654A1 (en) * | 2009-12-16 | 2012-10-24 | Lyondell Chemical Technology, L.P. | Preparation of palladium-gold catalyst |
US8507720B2 (en) * | 2010-01-29 | 2013-08-13 | Lyondell Chemical Technology, L.P. | Titania-alumina supported palladium catalyst |
US8273682B2 (en) * | 2009-12-16 | 2012-09-25 | Lyondell Chemical Technology, L.P. | Preparation of palladium-gold catalyst |
US8329611B2 (en) * | 2009-12-16 | 2012-12-11 | Lyondell Chemical Technology, L,P. | Titania-containing extrudate |
GB201111819D0 (en) | 2011-07-11 | 2011-08-24 | Johnson Matthey Plc | Catalyst and method for its preparation |
KR101964275B1 (en) | 2015-09-01 | 2019-04-01 | 주식회사 엘지화학 | Manufacturing method of catalyst for production of acrylic acid and the catalyst therefrom |
CN107754777B (en) * | 2016-08-19 | 2021-01-01 | 中国科学院大连化学物理研究所 | Catalyst for oxidation reaction and preparation and application thereof |
KR20180065494A (en) * | 2016-12-08 | 2018-06-18 | 고려대학교 산학협력단 | Method of preparing Pd catalyst for synthesis of hydrogen peroxide using sonication, and Method of preaparing heydrogen oxide using the Pd catalyst |
KR101990025B1 (en) * | 2017-09-07 | 2019-06-17 | 고려대학교 산학협력단 | Method of preparing Pd catalyst for synthesis of hydrogen peroxide using alkali metal, and Method of preaparing heydrogen oxide using the Pd catalyst |
CN109833865A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of load type sulfur-tolerant combustion catalyst and preparation method |
CN111569874B (en) * | 2020-05-28 | 2023-02-17 | 台州学院 | Active carbon-palladium-gold-gallium liquid alloy composite catalyst and preparation method and application thereof |
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US8168562B2 (en) | 2006-02-02 | 2012-05-01 | Lyondell Chemical Technology, L.P. | Preparation of palladium-gold catalysts |
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WO2007094903A8 (en) | 2008-09-04 |
CN103801291A (en) | 2014-05-21 |
KR101357188B1 (en) | 2014-02-03 |
CN101378834A (en) | 2009-03-04 |
BRPI0706798B1 (en) | 2016-10-04 |
EP1984113A2 (en) | 2008-10-29 |
JP5198288B2 (en) | 2013-05-15 |
CA2636558A1 (en) | 2007-08-23 |
KR20080091791A (en) | 2008-10-14 |
US20070179310A1 (en) | 2007-08-02 |
EP1984113B1 (en) | 2019-02-27 |
BRPI0706798A2 (en) | 2011-04-05 |
JP2009525174A (en) | 2009-07-09 |
CA2636558C (en) | 2015-03-24 |
US8168562B2 (en) | 2012-05-01 |
WO2007094903A3 (en) | 2007-10-18 |
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