JP2000514353A - Method for producing metal-supported catalyst - Google Patents

Abstract

  (57) [Summary] The present invention relates to a method for preparing a metal-supported catalyst and a metal-supported catalyst prepared by the method. The method of preparing a metal-supported catalyst according to the present invention comprises adding a soluble metal salt to a support, and then heating the metal salt in the presence of a gaseous or liquid hydrocarbon that polymerizes upon heating to a metal. It comprises the step of reducing. According to the method of the present invention, a metal-supported catalyst having excellent catalytic activity in which a metal is scattered on a support can be prepared.

Description

DETAILED DESCRIPTION OF THE INVENTION   Method for producing metal-supported catalyst Technical field   The present invention relates to a method for preparing a metal-supported catalyst and to a metal-support prepared thereby. It relates to a catalyst. This preparation method involves adding a metal salt to a carrier and then heating to polymerize. Reducing the metal salt by heating in the presence of a hydrocarbon. Background of the Invention   Contains metals such as platinum supported on large surface area substrates Catalysts are used in a wide range of chemical reaction processes. As a result, their preparation and characteristics There is a great deal of knowledge about The most active catalysts are highly dispersed small It has generally been found that catalysts have excellent metal particles. These catalysts The method used to prepare depends on the size of the resulting metal particles and their Is very important to the activity of the catalyst as it determines the distribution of   Both zeolites and alumina are commonly used as catalyst supports, Olites have the advantage of being crystalline substances. This is the required reactant / A special zeolite was chosen to give product selectivity and Concentration is the active site distribution of the catalyst And to control hydrophobicity. For ion exchange of metal salts Since each metal cation binds to the zeolite anion (AL) site, The final distribution of positions becomes more homogeneous.   Generally, in the preparation of a platinum-supported catalyst, a platinum salt is impregnated (the added solution evaporates). All metal salts remain on the sample) or ion exchange (after the time when the exchange takes place) The sample is washed and only the bound metal salts remain). It is. After washing and drying, the platinum cations are reduced to platinum metal. This process During this time, some of the platinum tends to migrate and clump together to form large particles . If the platinum salt in the carrier is reduced by heating in hydrogen, large platinum particles Are formed in the carrier. Before the reduction, if the first firing in air is performed, Platinum particles are smaller and a catalyst with increased activity is obtained, but Lei et al. (J. Catal. 140, 601). In order for this firing to take place, a very high flow of dry air (200 cm^Three/ Min / g) It must be performed at a heating rate of 0.5 ° C. per minute. Uses platinum tetraamine salt If this is done, this calcination removes the ammonia ligand and removes the bare Pt.²⁺Cations It is believed that it is bound to the zeolite anion site. These bare Pt²⁺Later Reduced by hydrogen. Extremely high air flow during calcination or direct reduction in hydrogen If not, partial reduction of the platinum by the separating ammonia ligand will occur. This As a result, moving platinums are formed and aggregated to form large particles, Detrimentally affects the distribution and size of platinum particles. After all, the activity of the resulting catalyst is Detrimentally affected. Liquid phase reduction using sodium borohydride is also known. But not used on a large scale. Industrially produced platinum catalysts in hydrogen Is easily reduced.   Special methods have also been used for reducing other metal-containing compounds to metals. Came. For example, reduction of Fe by CO gas and reduction of Ag by decomposition of neo acids (Reported in US Pat. No. 4,555,501). Wide Other commonly used techniques include, for example, electrolysis in Al production. You.   Halcon SD Group Inc. . U.S. Pat. No. 4,555,501 to U.S. Pat. A method for oxidizing ethylene to ethylene oxide with molecular oxygen has been disclosed. Ag charge The preparation of supported catalysts is disclosed in detail in US Pat. No. 4,555,501 at columns 5 and 6. Have been. The catalysts use a hydrocarbon solution containing no silver neoate water on the support. It is described as being prepared by impregnation. Impregnation is carried out by silver salt / carbonization This is achieved by immersion in a hydrogen solution. Next, the catalyst The solvent is removed by heating the impregnated support, the neoate is decomposed, and the element Activated by returning to silver. Examples of the hydrocarbon solvent used include, for example, Charcoal such as ruene, cyclohexane, xylene, ethylene, benzene or cumene And hydrides. Hydrocarbon solvent used is heated before decomposition of Ag neoate Must be able to be removed by   Japanese Patent No. 59,04 granted to Cataler Industries, Ltd. No. 9,844 discloses a method of depositing platinum and rhodium on an activated alumina carrier, followed by water. A catalyst production method comprising impregnating a solution of a soluble carbohydrate and then calcining is described. Have been. Moisture must be removed before firing. Therefore, the water removal process is necessary. The carbohydrates used are high oxygen content compounds, such as Loin.   Accordingly, an object of the present invention is to provide a method for producing catalysts in which a metal is scattered on a support. Is to provide. Disclosure of the invention   The present invention includes a method for preparing a metal-supported catalyst, the method comprising preparing a soluble metal salt. Is added to the carrier, and then the metal salt is converted to a gaseous or liquid hydrocarbon that polymerizes on heating. In the presence of is reduced to a metal by heating.   Preferably, the metal is a transition metal.   Preferably, the metal is Pd, Rh, Re, Au, Ag, Cu, Co, Sn, Sb or Pb.   Preferably, the metal is Pt.   Preferably, the metal is Pt, Pd, Rh, or Au.   Preferably, the hydrocarbon polymerizes when heated in air, and the metal salt is reduced to a metal. Occurs when heating in air.   Preferably, the carrier plus the added metal salt is heated in the presence of a gaseous or liquid hydrocarbon. Before the metal salt is decomposed.   Preferably, the metal salt is a tetramine, chloride, nitrate, acetate or carbonate. You.   Preferably, the gaseous or liquid hydrocarbon contains no oxygen in the organization of the element Or contains oxygen only in the carboxyl group.   Preferably, the gaseous or liquid hydrocarbon contains no oxygen in the organization of the element Absent.   Preferably, the liquid hydrocarbon polymerizes before volatilizing.   Preferably, the liquid hydrocarbon is an oil in which the carrier + metal salt is soaked before heating.   Preferably, the oil is an unsaturated vegetable or mineral oil.   Preferably, the oil is linseed oil, olive oil, or cedar oil.   Preferably, the gaseous hydrocarbon is an unsaturated hydrocarbon.   Preferably, the gaseous hydrocarbon is ethylene, propene or butene.   Preferably, the gaseous or liquid hydrocarbon flows through the carrier + platinum salt at the same time Heated.   Preferably, the support is alumina, silica, zeolite, zeo type or meso structure is there.   Preferably, the carrier + metal salt + organic material is at about 300 ° C. to about 1000 ° C. Heat to a temperature or temperature range, more preferably about 450 ° C.   Preferably, the carrier + metal salt + gas or liquid hydrocarbon is from about 1 hour to about 10 hours. The temperature is maintained for a time ranging up to 0 hours.   Preferably, the soluble metal salt is added to the carrier, and then the combination Dried without decomposing the metal salt, then the metal salt polymerizes when heated in air A gas containing no elemental oxygen or containing only oxygen in the carboxyl group or It is reduced to metal by heating in air in the presence of liquid carbon hydrogen.   Preferably, the combination has a range of from about 80 ° C to about 120 ° C. Drying by heating to a temperature, more preferably to a temperature of about 100 ° C.   Preferably, the metal salt is a platinum salt.   Preferably, the platinum salt is combined with its chloride or nitrate. Platinum tetramine.   Preferably, the platinum salt is chloroplatinic acid.   A further limited aspect of the invention is: (A) adding a soluble metal salt to the carrier; (B) a temperature sufficient to dry the combined carrier + soluble metal salt; Heating to a temperature low enough to avoid decomposition of the soluble metal salt; (C) adding a gaseous or liquid hydrocarbon to the combination; (D) heating the carrier + soluble metal salt + hydrocarbon to a temperature at which the hydrocarbon is thermally decomposed Reducing soluble metal salts to their metals by Consists of   Preferably, the soluble metal salt is chloride or nitrate.   Preferably, the support is a zeolite or alumina.   Preferably, the hydrocarbon is a liquid hydrocarbon that pyrolyzes before volatilizing.   Preferably, the metal is Pt, Rh, Re, Au, Ag, Cu, Co, Sn, Sb. , Or Pb.   Preferably, the metal is Pt.   Preferably, the non-volatile hydrocarbon is ethylene, propene or butene.   Preferably, the non-volatile hydrocarbon is a vegetable oil or a mineral oil. And include, for example, pump oil, linseed oil, olive oil or cedar oil. You.   Preferably, the temperature for drying the combined carrier + soluble metal salt is about 80 ° C. Any temperature or temperature range from 0C to 120C.   Preferably, the temperature at which the non-volatile hydrocarbon is pyrolyzed is from about 300 ° C to about 100 ° C. Any temperature or temperature range between 0 ° C. Detailed description of the invention   The present invention relates to a method for preparing metal supported catalysts. The metal is Supported by a carrier as is known in the art, the catalyst converts a soluble metal salt to In addition to the carrier, the combination is then converted to a gaseous or liquid It is prepared by heating in the presence of a hydrocarbon.   This metal is preferably Pt, Pd, Cu, Rh, Co, Sn, Au, Ag. , Re, Sb, or Pb, or generally transition metals. Platinum and And palladium are most preferred. Mixtures of these metals can also be used.   The metal salt is supported on the catalyst using known methods such as ion exchange or impregnation. Added to the body. Preferably, the metal salt is a metal chloride or nitrate. If white If gold is used, preferred platinum salts are any anions, such as chloride or Platinum tet binding to nitrate Ramin. Other salts used include metal acetates and metal carbonates Is mentioned. These are, for example, more substructures of the carrier than when using its chlorides. Should be able to suppress the hydrolysis of Other suitable metals known in the art Salts or carriers can also be used. The carrier is alumina (powder or pellet) or zeolite Olite (as powder or pellets with alumina) or silica (as powder) Or pellets) or zeo type (powder or pellets) or mesoporous It may be a molecular sieve (powder or pellet).   If the liquid hydrocarbon is an oil, the carrier + metal salt is immersed in the oil before heating. Mind When body hydrocarbons are used, the gas is heated as it flows into the carrier . The use of oil requires special equipment to heat the carrier in the presence of gas. Is preferred. Oil also reduces the need for harmful gases and complex atmospheric controls. Brings simple steps to avoid. The carrier does not need to be saturated with oil. Implementation described later 26%, 50% and 125% oil by weight, as evident in Examples 50-52 Samples prepared by adding PEG to the carrier show little difference in “light-off” temperature. Not. As the temperature increases, the oil flows into the pore structure of the carrier, Seems to approach all metal parts.   Prior to polymerization, liquid hydrocarbons that do not evaporate on heating are preferred, but Hydrogen then volatilizes from the carrier This is because they are kept without emitting. Therefore, substantially non-volatile hydrocarbons are preferred. No. Volatile compounds can be used, but similar for gaseous hydrocarbons. A problem has occurred and requires the use of certain equipment that requires adjustment as discussed below. might exist. Ultimately, it is most preferred to avoid such liquid hydrocarbons.   When using gaseous hydrocarbons, certain high temperature and gas handling equipment are available in the art. Required as is known. One example is heating or gas preheating capability. In addition, there is a gas drying pressure vessel that consumes gas. These devices are generally high Made of quality stainless steel, but given high temperature reduction conditions May need to be made from special steel or glass lined containers However, this is expensive for technicians to use at temperatures above 250 ° C. It is difficult.   The gas is preferably ethylene and the oil is preferably mineral or linseed, Dough oil or olive oil. Other oils or gases, such as Santova trade name Pump oil from Santovac 5 or propene and butene are also used Are known in the art.   It is preferred to use hydrocarbons which contain little or no oxygen. The technique As is well known in the art, vegetable oils are a mixture of fatty acids, such as Contains COOH groups. These oils contain oxygen Since the amount is minimal, it can be used in the method of the invention.   Vegetable oils include, for example, cedar oil, coconut oil, corn oil, cottonseed oil, Flower raw oil, olive oil, coconut oil, coconut seed oil, rapeseed oil, soybean oil, sunflower oil, sesame oil Linseed oil, or castor oil (or mixtures thereof).   The carrier has a large surface area so that gaseous or liquid hydrocarbons Must be able to spread.   Regarding the use of platinum metal, platinum tetramine, after the salt is added to the catalyst support The combination is low enough to prevent decomposition of the platinum tetramine complex Drying at a temperature is preferred. As obvious to those skilled in the art. The temperature varies with the particular salt and carrier of the particular substance used, but is Individual temperatures or temperature ranges from up to about 120 ° C. are generally considered suitable. However, about 100 ° C. is preferred. After this, gaseous or liquid non-volatile hydrocarbons Added. The hydrocarbon is then removed from the sample in air, preferably in a covered vessel. Heat to the temperature at which pyrolysis occurs. This temperature is preferably between 300 ° C and 1000 ° C. And more preferably any temperature or temperature range from 300 ° C to 800 ° C. , Most preferably about 450 ° C. If necessary, remove the lid of the container The sample was further heated in air to remove the deposited black charcoal. Remove all.   The pyrolysis of the hydrocarbon creates a reducing atmosphere around the metal cations, Causes their reduction. If there is less oxygen around the metal cation, the resulting catalyst Is presumed to have an increased activity. The hydrocarbons used are gold when heated Polymerizes around the genus cation, creating a barrier between the cation and oxygen in the air However, the polymerization of the hydrocarbon is preferably performed. Therefore, the hydrocarbons used Hydrocarbons that should contain a minimum amount of oxygen in the tissue of the component, but contain oxygen Elementary is also not sufficiently effective, but can be helpful. Used in the embodiment of the present invention. The hydrocarbons used do not generally contain oxygen as part of their elemental structure, The vegetable oil used contains oxygen at its terminal COOH groups. In this way, the altitude An active catalyst is formed, which is formed by the polymerization of hydrocarbons and the pores and cavities of the support. This is because charcoal is finally formed in the inside. In addition to forming a reducing atmosphere, this Restricts the movement of metal cations during the original process, and suppresses agglomeration into large particles Control. For this reason, after reduction, the individual metal particles are uniformly deposited on the catalyst support. Be stacked. No further processing of the catalyst is required. Example Testing the catalyst   Standard tests utilizing the oxidation of ethylene have been developed , Rank the catalytic activity of each sample. Approximately 11 mg of sample is placed in a glass reactor tube A gas stream containing 1% ethylene in the air at 1 ml / min. Shed at a rate. The ethylene concentration at the reactor outlet was measured by a total hydrocarbon detector. Was. Reactor temperature is used to measure the temperature when ethylene is completely oxidized. This temperature (the “light-off” temperature) is used to rank the catalyst. Was used. Example 1   This example was exchanged for platinum tetramine chloride and reduced with the addition of linseed oil. For preparing zeolite Y (LZY52 from UOP) formed into pellets Is shown.   The pelleted zeolite NaY (9.5 g) is washed with water to remove excess alkali. The powdery material was removed and dried. 0.058% by weight of platinum tetramine chloride (P t (NH_Three)_FourCl_Two) (0.0098 g Pt) and 7% ammonia Solution (30 ml) was added, mixed well, and then added at room temperature for 45 hours. Was replaced. The sample was filtered, rinsed three times with distilled water and dried at 100 ° C. overnight (Sample 1). The ion exchange and washing solution is retained and evaporated to 30 ml, AA Was analyzed by The obtained result was 1.7 × 10^-8g of Pt remains in solution Showed that. Thus, the sample contained 0.1% by weight of Pt.   To reduce the platinum salt, 1.8 g of linseed oil was replaced by 3.5 g of platinum-exchanged zeolite. And mix well, then slowly heat to 450 ° C in a covered crucible Then, this temperature was maintained for 65 hours. If you try to break the catalyst pellets, An area (no charcoal left) and a light gray outer area appeared (in the outer shell of the pellet) Indicates that there is a high concentration of platinum). Example 2   In this example, 0.5 g of Sample 1 was heated in ethylene / air Reduction and further reduction in hydrogen. This sample was placed in air containing 1% ethylene (1 (00 ml / min) and heated to 300 ° C. at a rate of 0.5 ° C./min and held for 1 hour. This gas changes to hydrogen and the temperature is held at 300 ° C. for another hour before cooling. Was.   The activity of the catalysts prepared in these examples for ethylene oxidation is shown in Table 1. You. Reduction by heating in oil yields the most active catalyst (light H). This light-off temperature is heated in ethylene / air and then in hydrogen The treated catalyst rises further by 10 ° C, slowly oxidizes and then reduces 10 ° C. higher than the catalyst prepared (160 ° C.). Dissolution of sodium borohydride A catalyst having a light-off temperature of 160 ° C. was obtained by immersion in the liquid. Most active Lower catalysts were obtained when reduced only in hydrogen (1 Light off at 90 ° C). Example 3   In this example, 0.5 g of Sample 1 was prepared by Ahm et al. (J Catal). . 133, 191, 1992). By reduction in hydrogen. This sample is high from room temperature to 300 ° C Slowly heated in flow of oxygen (100 ml / min) (rate of 0.5 ° C./min) Held for 2 hours. The gas stream was changed to deoxygenated nitrogen (100 ml / min) and Purified at 00 ° C. for 2 hours, then cooled. This gas stream is hydrogen (100 ml / min) ) And heat the sample to 300 ° C. at a rate of 0.5 ° per minute and hold for 2 hours And cooled in hydrogen. Example 4   In this example, 0.5 g of sample 1 is immersed in a solution of sodium borohydride. Reduced. This sample is_FourIt was immersed in an alkaline solution of Na (1%) overnight. As reduction took place, it was observed to foam with the shoe shoe. This sample Rinse and dry at 100 ° C. Example 5   In this example, 0.5 g of Sample 1 was reduced by heating in hydrogen. This sample Heat slowly from room temperature to 300 ° C (at a rate of 0.5 ° C per minute) and hold for 2 hours And then cooled to room temperature. Hydrogen flow rate is 100 per minute ml. Results Examples 1-5   Table 1 shows the results of Examples 1 to 5. Table 1Range of platinum concentration (Examples 6 to 38)   In this series of examples, the concentration of platinum in the catalyst is required for observable catalytic activity. It varies from 2% by weight to 0% by weight to determine the platinum concentration. Zeolite Y (LZY52-UOP)   All examples were prepared in the same manner as Example 1, except that the only difference was that of platinum. It is the amount of addition. Pt concentration is 2%, 1%, 0.1%, 0.05%, 0.025%, 0.01%, 0.005%, 0.001% and 0% (Examples respectively) 6-14). Zeolite ZSM-5   A commercial sample HZSM-5 formed into a pellet was treated in the same manner as in Example 1. However, different zeolites were used, and the amount of added platinum was changed in each example. The resulting Pt concentrations were 2%, 1%, 0.5%, 0.1%, 0.05%, 0.025 %, 0.01%, 0.005%, 0.001% and 0% (real Examples 15 to 24). Zeolite H-beta   In the series of Examples 25-31, the powdery commercial sample zeolite H-beta was used. Was treated in the same manner as in Example 1, except that a different zeolite was used and a different Olive oil was used, and the amount of platinum added was varied for each example. Got Pt concentration is 1%, 0.5%, 0.1%, 0.05%, 0.01%, 0.005% And 0% (Examples 25 to 31 respectively). Zeolite Na-beta   In the series of Examples 32-34, the powdered commercial sample zeolite H-beta was 1 1.0 mol L -1 NaC / gram zeolite at 00 ° C for 2 hours 1 to form the Na-exchanged analog. The obtained Na-beta was the same as in Example 1. Olives processed in the same way but using different zeolites and different oils Oil was used and the amount of platinum added was varied for each example. The resulting Pt concentration was 1%, 0 . 5%, 0.1% (Examples 32 to 34, respectively). γ-alumina   In these examples, platinum was added to the γ-alumina catalyst (Harshaw A 1-111-61-R, Al-3991R lot number PP01), platinum concentration 2 %, 1%, 0.5%, and 0% (Examples 35-37, respectively). Obtained Γ-alumina was treated in the same manner as in Example 1, but using a different support. Olive oil, which is a different oil, was used, and the amount of Pt added was changed for each example ( As shown in Examples 35-38, respectively). Results Examples 6-38   Table 2 shows the obtained catalyst activities of Examples 6 to 38. Highest catalytic activity (lowest Lower "light-off" temperatures are obtained when the platinum concentration is highest.   For zeolite Y, the platinum concentration was reduced by a factor of 20 from 2% to 0.1%. The light-off temperature drops to only 40 ° C. Trace amount of platinum 0.001 % Of the sample is much lower than the 0% platinum catalyst (420 ° C.). Indicates the off temperature (300 ° C.). This is because a small amount of platinum is highly active and the platinum concentration (E.g., from 0.1% to 2%), most of the platinum Is precipitated with reduced activity.   For ZSM-5, the platinum concentration and catalytic activity A similar trend is observed, except that at about 0.1% Pt, zeolite Y More activity. The catalyst with platinum on alumina is slightly less than the zeolite sample. Shows low catalytic activity. However, a sample that does not contain platinum at all contains a platinum-free sample. It has higher activity for ethylene oxidation than olilite. Table 2 Various platinum addition methods Example 39   In this example, a 0.1% Pt zeolite Y catalyst was replaced with platinum instead of ion exchange. Prepared by impregnation with tetramine. 0.058% by weight platinum tetra Min chloride (Pt (NH_Three)_FourCl_Two) And a solution containing 7% ammonia. 36 g were added to 1 g of dried NaY (LZY52) with shaking. Of moisture Most were absorbed by the zeolite pellets and appeared to be slightly wet. The sample was allowed to air dry and then returned to flaxseed oil as in Example 1. Dried at 100 ° C. overnight before original. Various platinum salts Example 40   In this example, chloroplatinic acid was added to the NaY zeolite. Dissolved in 3g of water H_TwoPtCl₆・ 6H_TwoO (0.006 g) in 1 g of NaY (UOP L ZY52). The pH of the resulting solution was 4.6. After 24 hours, The material was washed with distilled water, filtered and air dried. 0.001 g of Pt in the cleaning solution A catalyst containing the remaining 0.13% by weight of Pt was obtained. One night at 100 ° C After drying, the sample was reduced using linseed oil as in Example 1. Example 41   In this example, chloroplatinic acid was replaced with HZSM-5 Zeola. Added to the site. H dissolved in 3 g of water_TwoPtCl₆・ 6H_TwoO (0.006g) The solution was added to 1 g of HZSM-5. The pH of the resulting solution was 3.8. 2 After 4 hours, the sample was washed with distilled water, filtered and air dried. Significant to the cleaning solution A catalyst containing no Pt and containing 0.23% by weight of Pt was obtained. 1 more night After drying at 00 ° C., the sample was reduced using linseed oil as in Example 1. Example 42   In this example, the NaY zeolite was exchanged for platinum tetramine hydroxide. 30 ml of Pt (NH_Three)_FourOH_Two(0.01 g Pt) and 7% NH_ThreeContaining solution It was added to 10 g of NaY (UOP LZY52) with stirring. 24 hours at room temperature After a while, the sample was filtered, rinsed three times and air dried. The remaining solution was analyzed At this time, 4 × 10^-Fiveg of Pt remains, and the sample contains 0.1% Pt. It was revealed that t was included. After drying overnight at 100 ° C, As in Example 1, the sample was reduced using linseed oil. Example 43   In this example, the zeolite HZSM-5 was exchanged for platinum tetramine hydroxide. Was. 30 ml of Pt (NH_Three)_FourOH_Two(0.01 g Pt) and 7% NH_ThreeContained The solution was added with stirring to 10 g of HZSM-5. After 24 hours at room temperature, Filter the material and rinse three times Air dried. Analysis of the remaining solution showed that 4 × 10^-FiveP less than g t remained and the sample was found to contain 0.1% Pt. Was. After drying at 100 ° C. overnight, the sample was treated with linseed oil in the same manner as in Example 1. Was reduced. Results Examples 39-43   Table 3 shows the catalytic activities of Examples 39 to 43 for ethylene oxidation.   Of zeolite Y containing 0.1% Pt prepared by impregnation (Example 39) The light-off temperature of the sample was 20 times that of the sample prepared by ion exchange (Example 8). The temperature was also high.   In Examples 40 to 43, various Pt salts can be used, and platinum tetramine chloride is used. Shows that an activity similar to that prepared by Largest phase A difference was observed when chloroplatinic acid was added to zeolite Y (Example 40). The light-off temperature of this catalyst was 20 ° C. higher than that of Example 8. Table 3Various oils as reducing agents   In this series of examples, a range of oils was tested for platinum tetramine exchanged ZSM-5. Used to reduce fees.   Sample 2 was prepared from 12 g of commercially available sample HZSM-5 / alumina pellets. 2 0 ml of Pt (NH_Three)_FourCl_Two/ 7% NH_ThreeStir the solution (0.056 g Pt) And left at room temperature for 100 hours. Drain the supernatant of this solution and repeat 3 times Rinse, then 10 ml of fresh Pt (NH_Three)_FourCl_Two/ 7% NH_ThreeSolution (0.02 8 g of Pt) were added, stirred and left for 24 hours. After rinsing and drying three times, The resulting zeolite contained 0.4% platinum. Example 44   In this example, Sample 2 was heated in air without adding oil. Sample 2 (0.2 g) was heated to 450 ° C. in air and held at that temperature for 16 hours. Example 45   In this example, cedar oil was added to sample 2 before heating. 0.5g seeder -Oil was added to 2 g of Sample 2. This was heated to 450 ° C. and held for 20 hours . Example 46   In this example, a diffusion pump oil having a trade name of Santovac 5 was used as a sample. 2 before heating. 0.1g Santovac 5 diffusion pump Oil was added to 0.2 g of Sample 2. Heat this to 450 ° C and hold for 20 hours did. Example 47   In this example, linseed oil was added to Sample 2 before heating. 0.15 g of linseed oil Was added to 0.52 g of sample 2. This was heated to 450 ° C. and held for 20 hours . Example 48   In this example, olive oil was added to Sample 2 before heating. 0.2g of olives The oil was added to 0.5 g of Sample 2. This was heated to 450 ° C. and held for 20 hours . Example 49   In this example, mineral oil (Johnson baby oil) was added to sample 2 before heating. Was. 0.25 g of mineral oil was added to 0.5 g of Sample 2. Heat this to 450 ° C For 20 hours. Example 50   In this example, 26% linseed oil was added to Sample 2 before heating. 0.15g Flaxseed oil was added to 0.52 g of Sample 2. Heat this to 450 ° C for 20 hours Held. Example 51   In this example, 50% linseed oil was added to Sample 2 before heating. 0.1 g of flax Nin oil was added to 0.2 g of Sample 2. Heat this to 450 ° C and hold for 20 hours Was. Example 52   In this example, 125% linseed oil was added to Sample 2 before heating. 0.45g Linseed oil was added to 0.2 g of Sample 2. This is heated to 450 ° C and kept for 20 hours. I carried it. Various amounts of linseed oil   Zeolite pellets rapidly absorb the added oil. Contains minimum amount of linseed oil Sample (26% by weight of zeolite-Example 50) has a dry appearance. The 50% additive oil sample (Example 51) has a slightly wet appearance Presented. For the 125% linseed oil addition (Example 52), the sample was in a pool of oil. I was immersed in. Various calcination conditions for samples added with linseed oil   Examples of this series are platinum amine exchanged HZS containing 50% linseed oil. The effect of various calcination conditions on the resulting catalyst activity of M-5 was investigated. Example 53   In this example, 0.2 g of sample 2 was added to 50% linseed oil and then cooled to 570 ° C. And kept for 10 hours. Example 54   In this example, after adding 50% linseed oil to 0.2 g of sample 2, the temperature was raised to 450 ° C. And kept for 10 hours. Example 55   In this example, 0.2 g of sample 2 was mixed with 50% linseed oil and then heated to 400 ° C. And held for 20 hours. Example 56   In this example, 0.2 g of sample 2 was mixed with 50% linseed oil and then sealed. The vessel was heated to 450 ° C. and kept for 20 hours. Remove the lid and sample At 450 ° C until no black char remains in the zeolite pellet core. Heated. Example 57   In this example, 50% linseed oil was added to 0.2 g of Sample 2. This on the flame Baked by rapid heating in a crucible with a covered lid. As a result, The flame burned on the catalyst. Various metals other than platinum   In the series of Examples 58-62, the constants exchanged for various metals other than platinum A range of samples were prepared. The metals were Pd, Cu, Rh, Co, Sn. . A solution containing 1% by weight of the desired metal chloride in metal is converted to a sodium-exchanged powder. Of zeolite type Y (CKD-100). Each sample at 100 ° C Changed for 2 hours and then overnight at room temperature. Each sample was filtered, washed three times with distilled water, Dried at 0 ° C. Next, each sample was reduced according to Example 48. Platinum and one other metal for bimetallic catalysts   In the series of Examples 63-69, platinum and one other metal were replaced. A range of bimetallic samples are prepared using zeolites Na-Y and H-Beta Was done. Other metals were Pd, Rh and Sn. 0.5% by weight of Pt (NH_Three)_Four Cl_TwoAnd 0.5% by weight of a solution containing 0.5% by weight of the desired metal chloride Of zeolite. Exchange each sample at 100 ° C for 2 hours, then at room temperature overnight did. Each sample was filtered, washed three times with distilled water and dried at 100 ° C. Next, The charge was processed according to Example 48. Various carriers   In Example 69, the support is [Al] -MCM-41 mesoporous molecular sieve A sample was prepared in the same manner as in Example 25 except for the above. MCM-41 sample₁₆(Me )_ThreeN⁺Br^-Standard S from template⁺X^-I * assembly route and tetraethyl Orthosilicate SiO_TwoPrepared using source. Results Examples 44-69   Table 4 shows the catalytic activity for ethylene oxidation of Sample 2 treated with various oils . When heated in air without oil (Example 44), the resulting catalyst has the least activity. won. Addition of oil to all tested substances before heating resulted in the resulting catalyst. Activity increased. The best catalysts were obtained using olive and mineral oils (actually Examples 48 and 49).   When the amount of linseed oil was changed (Examples 54 to 56), there was no significant difference in activity. However, the light-off temperature of the sample prepared using 125% linseed oil was 26% The light-off temperature of the sample prepared using linseed oil was 10 ° C. lower.   The calcination temperature appeared to significantly affect the catalytic activity. Heat to 450 ° C At lower temperatures of 400 ° C. and higher temperatures of 570 ° C. The activity of the resulting catalyst was lower when heated. The sample was placed in a closed container at 450 Heating to <RTIgt; C </ RTI> provided the most active catalyst. This makes the reduction conditions longer It should have kept time.   Rapid heating of the catalyst in a crucible placed on a flame causes a maximum The reactivity of the sample, which was initially inert to ethylene, was 10 It increased to 0% and remained constant for the remainder of the experiment (36 hours). Table 4   The above has been a description of the present invention, including the preferred embodiments. Changes and modifications are Obvious to those skilled in the art and defined by the appended claims Such inventions are within the scope of the invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B01J 29/44 B01J 29/44 Z 29/74 29/74 Z (81) Designated country EP (AT, BE, CH, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, NE, SN, TD, TG), AP (GH, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ) , TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE, H, HU, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ , PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZW (72) Inventor Bagshaw Stefan Alan New Zealand Kaikoue 0400 Tuyi Street 20

Claims (1)

[Claims] 1. Gaseous or liquid hydrocarbons that add soluble metal salts to the carrier and then polymerize on heating Reducing the metal salt to a metal by heating in the presence of A method for preparing a metal-supported catalyst as a feature. 2. The metal is Pd, Rh, Re, Au, Ag, Cu, Co, Su, Sb, Is selected from Pb or a mixture thereof. The method described in. 3. The method of claim 1, wherein said metal is Pt. 4. The method of claim 1, wherein said metal is a transition metal. . 5. The metal salt is tetramine, chloride, nitrate, carbonate, or acetate. The method according to any one of claims 1 to 4, characterized in that: 6. Wherein the hydrocarbon is a liquid hydrocarbon that thermally decomposes before volatilizing. A method according to any one of the preceding claims, wherein the method comprises: 7. Claims: The hydrocarbon is an unsaturated vegetable or mineral oil. 7. The method according to paragraph 6. 8. 2. The method according to claim 1, wherein the hydrocarbon is an unsaturated gaseous hydrocarbon. Item 6. The method according to any one of Items 1 to 5. 9. Heating the metal salt to a temperature in the range of about 300 ° C to about 1000 ° C; Wherein the metal is reduced to a metal by the method described in any one of the above claims. The described method. 10. (A) adding a soluble metal salt to the carrier;   (B) at a temperature sufficient to dry the combined carrier + soluble metal salt Heating to a temperature low enough to avoid decomposition of the soluble metal salt;   (C) Dry or gaseous or liquid hydrocarbons in the combination of carrier + metal salt Adding an element; and   (D) heating the carrier + metal salt + hydrocarbon to a temperature at which the hydrocarbon thermally decomposes. Reducing the metal salt to a metal with   A method for preparing a metal-supported catalyst, comprising: 11. The metal is Pd, Rh, Re, Au, Ag, Cu, Co, Su, Sb, P b. or a mixture thereof. Method. 12. 11. The method according to claim 10, wherein said metal is Pt. . 13. The metal is tetramine, chloride, nitrate, carbonate or acetate The method according to claim 10, characterized in that: 14． The hydrocarbon is an unsaturated vegetable or mineral oil; 11. The method according to claim 10, wherein the method comprises: 15. Claims: The hydrocarbon is an unsaturated gaseous hydrocarbon. Item 11. The method according to Item 10. 16. The metal salt heats to a temperature in a range from about 300 ° C. to about 1000 ° C. 11. The method according to claim 10, wherein the metal is reduced to a metal. Law. 17． The carrier + soluble metal salt is heated to a temperature ranging from about 80 ° C to about 120 ° C 11. The method according to claim 10, wherein the drying is performed by drying. 18. Add a soluble platinum salt to the carrier and then heat to form a gaseous or liquid carbon Reduction of platinum salts to platinum metal by heating in the presence of hydrogen. A method for preparing a platinum metal-supported catalyst, characterized in that: 19. (A) adding a soluble platinum salt to a carrier;   (B) at a temperature sufficient to dry the combined carrier + soluble platinum salt Heating to a temperature low enough to avoid decomposition of the soluble platinum salt;   (C) Dry, carrier or platinum salt combined with gaseous or liquid hydrocarbons Adding; and   (D) heating the carrier + platinum salt + hydrocarbon to a temperature at which the hydrocarbon is thermally decomposed And the platinum salt Reducing to platinum metal;   A method for preparing a platinum metal-supported catalyst, comprising: 20. The platinum salt is platinum tetramine combined with its chloride or nitrate A method according to claim 18 or claim 19, characterized in that: 21. 19. The method according to claim 18, wherein the platinum salt is chloroplatinic acid. Item 19. The method according to Item 19. 22. The hydrocarbon is a liquid hydrocarbon that is thermally decomposed before volatilizing. 20. The method of claim 19, wherein the method is characterized in that: 23. Wherein the hydrocarbon is an unsaturated vegetable or mineral oil. 20. The method of claim 18 or 19. 24. Claims: The hydrocarbon is an unsaturated gaseous hydrocarbon. Item 20. The method according to item 18 or 19. 25. Prepare a metal supported catalyst substantially as described in any of the Examples Way. 26. A metal support when prepared by the method of any one of the preceding claims. catalyst.