CN113694941A - Supported metal catalyst and preparation method and application thereof - Google Patents

Supported metal catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN113694941A
CN113694941A CN202010428855.XA CN202010428855A CN113694941A CN 113694941 A CN113694941 A CN 113694941A CN 202010428855 A CN202010428855 A CN 202010428855A CN 113694941 A CN113694941 A CN 113694941A
Authority
CN
China
Prior art keywords
fluorine
chlorine
alumina
aqueous solution
carrier
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010428855.XA
Other languages
Chinese (zh)
Other versions
CN113694941B (en
Inventor
乐毅
毛祖旺
铁锴
杨晨熹
彭晖
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to CN202010428855.XA priority Critical patent/CN113694941B/en
Publication of CN113694941A publication Critical patent/CN113694941A/en
Application granted granted Critical
Publication of CN113694941B publication Critical patent/CN113694941B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
    • B01J27/13—Platinum group metals
    • 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
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • C07C5/05—Partial hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
    • C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a supported metal catalyst and a preparation method and application thereof, wherein the supported metal catalyst comprises an alumina carrier, a catalytic component Pd and a cocatalyst component, and the catalytic component Pd and the cocatalyst component are loaded on the surface of the alumina carrier; a halogen element is added into the alumina carrier, the weight ratio of the halogen element to the alumina carrier is (0.01-3): 100, and the promoter component is selected from at least one of Sn, Pb, Co, Ni, IVB group and VB group; at least one of La, Ce, Pr, Li, K and Ba elements is optionally contained in the alumina carrier. Wherein, halogen-containing organic matters are added when the alumina carrier is prepared. The supported metal catalyst obtained by the method can be used for the carbon four liquid phase selective hydrogenation reaction, and the selectivity of the catalyst can be obviously improved.

Description

Supported metal catalyst and preparation method and application thereof
Technical Field
The invention belongs to the field of metal catalysts, and particularly relates to a supported metal catalyst and a preparation method thereof, which can be used for removing alkyne through selective hydrogenation of mixed C-C and increasing the yield of butadiene through selective hydrogenation of butadiene high-alkyne tail gas.
Background
The petroleum hydrocarbon cracking ethylene preparing device produces a large amount of mixed carbon four as a byproduct, wherein the cracking mixed carbon four contains 40-60 wt% of 1, 3-butadiene, 0.5-2.0 wt% of Vinyl Acetylene (VA) and about 0.2 wt% of Ethyl Acetylene (EA), and the balance of butane, butylene and a small amount of 1, 2-butadiene, carbon three and carbon five. Usually, the 1, 3-butadiene is separated from the mixed C.sub.C.by extractive distillation or the like.
The cracking mixed C4 is industrially refined by a two-stage solvent extraction rectification process to obtain a butadiene product, wherein the butadiene yield is usually 97-98.5%. The alkyne separated contains 20-40 wt% of VA and EA and 3-40 wt% of 1, 3-butadiene, and the material is called high alkyne tail gas or butadiene tail gas, and in industrial production, in view of safety, the alkyne is usually diluted by a carbon four fraction and then subjected to torch treatment, so that resource waste and environmental pollution are caused.
The alkyne in the carbon four fraction can be removed by adopting a selective hydrogenation method, and can be generally divided into pre-hydrogenation and post-hydrogenation according to different processes: before the mixed C4 raw material enters a butadiene extraction rectification device (a butadiene extraction device), a selective hydrogenation reactor is arranged to be called front hydrogenation, and selective hydrogenation is carried out on butadiene tail gas to be called rear hydrogenation; there is also a process in which butadiene tail gas is mixed with mixed carbon four and then hydrogenated. The alkyne in the carbon four fraction removed by the pre-hydrogenation can not only make full use of the carbon four alkyne, but also simplify the carbon four separation process. The subsequent hydrogenation can hydrogenate VA in the butadiene tail gas to generate 1, 3-butadiene, and can improve the yield of the butadiene of the device. The purpose of mixing the butadiene tail gas with the mixed C4 and then hydrogenating is to hydrogenate C-C alkyne to generate butadiene and butene, thereby reducing or eliminating tail gas emission and improving the economy of the device. No matter any one of the three processes is adopted, a high-selectivity carbon four hydrogenation catalyst is needed, alkyne is effectively removed, meanwhile, the loss of 1, 3-butadiene is reduced to the greatest extent for the pre-hydrogenation, and butadiene is generated to the greatest extent for the post-hydrogenation; in addition, high stability is also important for long-term, low-cost operation.
The catalyst taking Pd as the catalytic component has high activity for selective hydrogenation alkyne removal reaction, and the selectivity of the catalyst is greatly different due to different carriers, cocatalyst components and preparation methods.
U.S. Pat. No. 4,4547600 found that Pd was lost in large quantities after 720 hours of use of the Pd-only catalyst, and the quantity of acetylene remaining in the late stage of the reaction was therefore increased considerably, indicating a deterioration in the selectivity of the catalyst. The patent found that the addition of Ag to the above-mentioned single Pd catalyst was effective in preventing the loss of Pd, but the selectivity of the modified catalyst was not changed, and the amount of acetylene remaining was substantially the same as that of the single Pd catalyst.
U.S. Pat. No. 5,7288686 to Pd/Al2O3The catalyst is added with the cocatalyst components of Ag, Zn, Bi and the like. The acetylene residue of the modified catalyst is greatly reduced to 1ppm at least, and the loss of 1, 3-butadiene is reduced compared with that before the modified catalyst is modified, thereby showing the improvement effect of the auxiliary agents on the selectivity of the Pd catalyst. It should be noted that, although there is some improvement in selectivity, 1, 3-butadiene is still lost by about 7.5% (based on the total butadiene) which is still a significant distance from the amount of butadiene lost that is acceptable for practical use.
The Chinese patent CN1321544A modifies the Pd catalyst by taking Cu, Ag, Bi, Zr and the like as auxiliary agents, and the result shows that when the total alkyne content is less than 15ppm, the loss of 1, 3-butadiene can be less than 3 percent (based on the total butadiene), and the better alkyne removal selectivity is shown.
However, the selectivity of the metal catalyst disclosed in the prior art in catalytic hydrogenation, especially in selective hydrogenation of alkynes in the carbon four-cut fraction, still needs to be further improved, and thus a metal catalyst with high selectivity is needed.
Disclosure of Invention
In order to overcome the problems in the prior art, a supported metal catalyst is provided, which can be used for selectively hydrogenating alkyne in carbon four-cut fraction to generate butadiene and butene.
One purpose of the invention is to provide a supported metal catalyst, which comprises an alumina carrier, a catalytic component Pd and a cocatalyst component, wherein the catalytic component Pd and the cocatalyst component are loaded on the surface of the alumina carrier; wherein, a halogen element is added into the alumina carrier, the weight ratio of the halogen element to the alumina carrier is (0.01-3): 100, and the cocatalyst component is selected from at least one of Sn, Pb, Co, Ni, IVB group and VB group; at least one of La, Ce, Pr, Li, K and Ba elements is optionally contained in the alumina carrier.
In a preferred embodiment, the weight ratio of the catalytic component Pd to the alumina carrier is (0.005-2), preferably (0.05-1): 100, more preferably (0.05-0.5): 100.
In a preferred embodiment, the promoter component is selected from at least one of Sn, Pb, Co, Ni, Ti, Zr, and V.
In a further preferred embodiment, the weight ratio of the co-catalyst component to the alumina carrier is (0.01-10): 100, preferably (0.01-6): 100.
In a preferred embodiment, the alumina carrier has a specific surface area of 5 to 150m2(iv) per gram, bulk density of 0.3 to 0.9g/mL, pore volume of 0.25 to 1.00 mL/g.
In a more preferred embodiment, the alumina support has a specific surface area of 10 to 100m2The specific surface area per gram (g), the bulk density is 0.55-0.85 g/mL, the pore volume is 0.35-1.00 mL/g, and the water absorption rate is more than 40%.
The shape of the alumina carrier includes but is not limited to powder, granule, sphere, sheet, tooth sphere, strip or clover and other irregular strip shapes.
In a preferred embodiment, the halogen element is fluorine and/or chlorine.
In a further preferred embodiment, the weight ratio of fluorine to the carrier is (0.01-1): 100, and the weight ratio of chlorine to the carrier is (0.01-2): 100.
In a further preferred embodiment, the weight ratio of fluorine to the carrier is (0.05-0.8): 100, and the weight ratio of chlorine to the carrier is (0.05-1): 100.
In a preferred embodiment, the alumina support optionally contains Si element.
In a more preferred embodiment, the weight ratio of the Si element to the carrier is (0-1.5): 100, preferably (0-1): 100, and more preferably (0-0.5): 100.
In a preferred embodiment, the weight ratio of at least one of La, Ce, Pr, Li, K and Ba elements to the carrier in the alumina carrier is (0-1.5): 100, preferably (0-1): 100.
Wherein, the elements such as La, Ce, Pr, Li, K, Ba and the like can further adjust parameters such as strength, specific surface area, pore volume and the like of the carrier.
The second purpose of the present invention is to provide a method for preparing the supported metal catalyst, which comprises the following steps:
step 1, mixing powdery raw materials;
step 2, adding an acidic aqueous solution into the powdery raw materials, and then kneading and molding;
step 3, adding halogen-containing organic matters, preferably fluorine-containing and/or chlorine-containing organic matters into the powdery raw materials in the step 1 and/or into the acidic aqueous solution in the step 2 and/or during kneading and molding;
step 4, drying and roasting to obtain an alumina carrier;
and 5, loading the catalytic component Pd and the cocatalyst component on the alumina carrier obtained in the step 3, and drying and roasting to obtain the supported metal catalyst.
In a preferred embodiment, the amount of the fluorine-containing organic substance is 0.01 to 1 wt%, preferably 0.05 to 0.8 wt%, and more preferably 0.01 to 0.7 wt% of the total amount of the powdery raw materials, wherein the amount of the fluorine-containing organic substance is based on the weight of the fluorine element therein.
In a further preferred embodiment, the amount of the chlorine-containing organic compound is 0.01 to 2 wt%, preferably 0.05 to 1 wt% of the total amount of the powdery raw materials, wherein the amount of the chlorine-containing organic compound is based on the weight of chlorine element therein.
In a preferred embodiment, the fluorine-containing and/or chlorine-containing organic substance is selected from at least one of a fluorine-containing and/or chlorine-containing polymer, a suspension of a fluorine-containing and/or chlorine-containing polymer, and a fluorine-containing and/or chlorine-containing organic compound.
In a further preferred embodiment, when the fluorine-containing and/or chlorine-containing organic substance is a fluorine-containing and/or chlorine-containing polymer powder, it is added to the powdery raw material; when the fluorine-containing and/or chlorine-containing organic matter is a fluorine-containing and/or chlorine-containing polymer suspension, adding the fluorine-containing and/or chlorine-containing organic matter into the acidic aqueous solution; when the fluorine-containing and/or chlorine-containing organic compound is a fluorine-containing and/or chlorine-containing organic compound, adding the fluorine-containing and/or chlorine-containing organic compound into the acidic aqueous solution, or adding the fluorine-containing and/or chlorine-containing organic compound during kneading molding.
In the invention, the pore structure of the alumina carrier can be effectively adjusted by adding the organic matter containing halogen. (1) Under the high-temperature condition, part of fluorine and chlorine can form gas-phase compounds to diffuse and separate from the carrier, part of the gas-phase compounds can be tightly combined with alumina and can be retained on the carrier, and carbon and hydrogen in organic matters are gasified and decomposed during roasting, so that a large number of micropores can be formed, and the pore structure of the alumina carrier can be increased; (2) the halogen enters the alumina framework, and alumina microcrystal is more easily converted into a flaky shape during high-temperature roasting, so that the pore structure of the alumina is influenced, the pore volume is generally promoted to be increased, the specific surface area is increased, and the bulk density is reduced; (3) in addition, the halogen has strong electronegativity and can also influence the surface acidity of the prepared alumina carrier, and the halogen (particularly fluorine atoms and chlorine atoms) on the alumina carrier can pull electrons on aluminum atoms and attract electrons of hydroxyl groups around the aluminum atoms, so that hydrogen protons on the hydroxyl groups are more easily ionized to form Bronsted acid sites.
Compared with the method that organic matters are respectively added to increase the pore volume and the specific surface area of the alumina carrier, inorganic matters added with fluorine and chlorine change the pore structure of the alumina, and the organic matters added with fluorine and/or chlorine can simultaneously act with fluorine and/or chlorine elements in the high-temperature roasting process of the alumina, so that the alumina carrier with better comprehensive performance is prepared, the addition times of the auxiliary agents are reduced, and the forming method is simplified.
In a preferred embodiment, the fluorine-containing and/or chlorine-containing polymer is selected from one or more of, but not limited to, polytetrafluoroethylene, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/ethylene copolymer, polyvinylidene fluoride, polyvinyl fluoride, polychlorotrifluoroethylene, chlorotrifluoroethylene/ethylene copolymer, polyvinyl chloride, polyvinylidene chloride, chlorinated polypropylene, chlorinated polyethylene, vinyl chloride/vinylidene chloride copolymer.
In a further preferred embodiment, the fluorine-and/or chlorine-containing polymer is selected from one or more of polytetrafluoroethylene powder, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/ethylene copolymer, polyvinylidene fluoride, polyvinyl chloride, chlorinated polypropylene, chlorinated polyethylene.
In a further preferred embodiment, the fluorine-and/or chlorine-containing polymer has a particle diameter of less than 100. mu.m, preferably less than 50 μm, which facilitates uniform mixing with the alumina powder.
In a preferred embodiment, the fluorine-and/or chlorine-containing polymer suspension is selected from, but not limited to, polytetrafluoroethylene suspensions.
In a further preferred embodiment, the weight concentration of the fluorine-and/or chlorine-containing polymer suspension is from 20% by weight to 90% by weight, preferably from 40% by weight to 70% by weight.
In a preferred embodiment, the fluorine-and/or chlorine-containing organic compound is a water-soluble organic compound containing fluorine and/or chlorine elements.
In a further preferred embodiment, the fluorine-and/or chlorine-containing organic compound is selected from, but not limited to, at least one of tetrafluoropropanol, trifluoroethanol, trifluoroacetaldehyde, chloroacetic acid, dichloroacetic acid, trichloroacetic acid and trichloroethanol.
In a preferred embodiment, in step 1, the powdered raw material comprises alumina powder, optionally a Si-containing compound, and optionally a shaped pore former, wherein the alumina powder is selected from pseudo-boehmite powder and optionally other alumina powder.
In a further preferred embodiment, the mass content of Na and Fe in the pseudo-boehmite powder is less than 0.1%, the mass reduction after high-temperature roasting is not more than 40 wt%, and the powder particle size is less than 200 μm.
In a still further preferred embodiment, the other alumina powder is selected from at least one of alumina powder trihydrate, fast deoxidized alumina powder, and composite phase alumina powder.
In a preferred embodiment, the alumina trihydrate is selected from at least one of gibbsite, bayerite, and nordstrandite.
In a further preferred embodiment, the alumina trihydrate is used in an amount of 0 to 30 wt%, preferably 0 to 20 wt%, based on the total amount of alumina powder.
In a preferred embodiment, the fast deoxidized aluminum powder is obtained by fast dehydration of aluminum hydroxide, wherein the weight content of Na and Fe is less than 0.1 wt%.
In a further preferred embodiment, the amount of the fast deoxidized aluminum powder is 0 to 30 wt%, preferably 0 to 20 wt%, of the total amount of the aluminum oxide powder.
In a preferred embodiment, the composite phase alumina is obtained by high temperature calcination of an aluminum hydroxide selected from the group consisting of alumina trihydrate or alumina monohydrate (e.g., gibbsite, bayerite, boehmite, etc.).
In a further preferred embodiment, the amount of the composite phase alumina is 0 to 30 wt%, preferably 0 to 20 wt%, based on the total amount of the alumina powder.
In a preferred embodiment, the Si-containing compound is a water-insoluble Si-containing compound, preferably selected from at least one of, but not limited to, dry silica gel, nano-silica, silicon carbide.
In a further preferred embodiment, the nano silica and dry silica gel have an average particle size of less than 120 nm.
In a further preferred embodiment, the amount of the Si-containing compound is 0 to 1.5 wt%, preferably 0 to 1 wt%, and more preferably 0 to 0.5 wt% of the total amount of the alumina powder, wherein the amount of the Si-containing compound is based on the weight of Si element therein.
In a preferred embodiment, the pore-forming agent is at least one selected from sesbania powder, starch, cellulose, high molecular polymer and decomposable alkaline substance.
In a further preferred embodiment, the cellulose is selected from at least one of methylcellulose, hydroxypropylmethylcellulose, sodium hydroxymethylcellulose; the high molecular polymer is selected from at least one of polyethylene microspheres, polystyrene, polyethylene oxide, polyethylene glycol, polyvinyl alcohol, sodium polyacrylate, polyethylene glycol and polyacrylate acrylic acid; the decomposable alkaline substance is at least one selected from urea, methylamine, ethylenediamine, ammonium carbonate and ammonium bicarbonate.
In a further preferred embodiment, the amount of the formed pore-forming agent is 0 to 20 wt%, preferably 0 to 10 wt%, of the total amount of the alumina powder.
In step 1, the powder mixing may be performed in a dedicated mixer, or the powder may be added to a kneader and then dry-mixed without adding a solution for a certain time. The time required for mixing can be determined empirically by one skilled in the art. Powder mixing is an important step for preparing a carrier, and the uniform mixing of the powder can be ensured by optimizing the structure of a mixer, prolonging the mixing time and the like.
In a preferred embodiment, in step 2, the acidic aqueous solution is at least one selected from the group consisting of an aqueous hydrochloric acid solution, an aqueous nitric acid solution, an aqueous sulfuric acid solution, an aqueous acetic acid solution, an aqueous oxalic acid solution, an aqueous citric acid solution, an aqueous phosphoric acid solution and an aqueous ammonium dihydrogen phosphate solution, and is preferably at least one selected from the group consisting of an aqueous nitric acid solution, an aqueous acetic acid solution, an aqueous oxalic acid solution and an aqueous citric acid solution.
In a further preferred embodiment, the concentration of the acidic aqueous solution is 0.1 to 10 wt%, preferably 0.1 to 5 wt%.
In a further preferred embodiment, in step 2, the weight ratio of the acidic aqueous solution to the powdery raw material is (0.5 to 5):1, preferably (0.6 to 2): 1.
The amount of the acid in the acidic aqueous solution can be adjusted by those skilled in the art according to the plasticity of the kneaded blank and the specific surface area, strength, bulk density and other data of the carrier after high-temperature roasting.
In a preferred embodiment, in step 2, a soluble auxiliary selected from at least one inorganic substance of La, Ce, Pr, Li, K and Ba is added to the acidic aqueous solution.
In a further preferred embodiment, the soluble auxiliary agent is selected from at least one nitrate compound and/or oxide of La, Ce, Pr, Li, K and Ba.
In a further preferred embodiment, the amount of the soluble assistant is 0 to 1.5 wt%, preferably 0 to 1 wt%, based on the total amount of the alumina powder, wherein the amount of the soluble assistant is calculated by the weight of La, Ce, Pr, Li, K or Ba.
In the step 2, the kneading molding is to add the acidic aqueous solution into the uniformly mixed powder, mix and knead continuously, react part of the alumina powder with acid to form a plastic blank, and extrude and mold the blank into a required shape and size. The time for kneading and molding, the pressure for extrusion molding, and the like are related to the size of the equipment used, the composition of the alumina powder, the composition of the acid solution, and the like, and can be determined empirically by those skilled in the art.
In a preferred embodiment, in the step 4, the drying temperature is 60 to 150 ℃, and the drying time is 3 to 48 hours.
In a further preferred embodiment, in the step 4, the drying temperature is 80 to 150 ℃, and the drying time is 5 to 25 hours.
In a preferred embodiment, in the step 4, the roasting temperature is 800-1200 ℃, and the roasting time is 3-48 hours.
In a further preferred embodiment, in the step 4, the roasting temperature is 1000 to 1200 ℃, and the roasting time is 4 to 10 hours.
In a more preferred embodiment, the temperature rise rate is 30 to 150 ℃/hr (preferably 50 to 120 ℃/hr) when the firing is performed at 600 ℃ or lower, and the temperature rise rate is 280 ℃/hr (preferably 150 to 250 ℃/hr) when the firing is performed at 600 ℃ or higher.
Wherein, the drying and roasting step is to dry, knead and shape the moisture in the green body, the solid phase reaction occurs in the high temperature roasting process, and the alumina particles are bonded together to form the alumina carrier with certain strength.
In a preferred embodiment, in step 5, the catalytic component Pd is 0.005-2 wt%, preferably 0.05-1 wt%, and more preferably 0.05-0.5 wt% of the total weight of the alumina carrier.
In a preferred embodiment, in step 5, the Co-catalytic component is selected from at least one of Sn, Pb, Co, Ni, group IVB and VB, preferably at least one of Sn, Pb, Co, Ni, Ti, Zr and V.
In a further preferred embodiment, the promoter component is present in an amount of 0.01 to 10 wt% based on the total weight of the alumina support.
In step 5, the supporting manner is not particularly limited as long as the supporting can be successfully carried out, and the alumina carrier can be supported by using an impregnation method commonly used in the preparation of catalysts, such as spraying, equal-volume impregnation, supersaturated impregnation, and the like. When the supersaturated impregnation method is used, if the active component precursor in the impregnation liquid can not be completely adsorbed by the carrier, the volume of the impregnation liquid and the concentration of the active component should be determined according to the adsorption ratio so as to ensure that the content of the active component loaded on the carrier meets the preset requirement.
When two or more catalytic components are contained in the catalyst, a one-step impregnation method or a stepwise impregnation method may be employed. The carrier can be impregnated by dissolving several active ingredient precursors in the same solution using a one-step impregnation method. For the active component precursors which cannot be prepared into the same solution, a stepwise impregnation method can be adopted, and several active component precursors are respectively prepared into solutions to impregnate the carrier, and the carrier may need to be dried after each impregnation.
In a preferred embodiment, in step 5, the drying is performed at 50 to 200 ℃ for 5 to 48 hours.
In a further preferred embodiment, in the step 5, the drying is performed at 50 to 120 ℃ for 5 to 24 hours.
In a preferred embodiment, in step 5, the roasting is performed at 300-600 ℃ for 2-10 h.
In a further preferred embodiment, in the step 5, the calcination is performed at 400 to 500 ℃ for 4 to 8 hours.
The carrier after loading the catalytic component is calcined at a high temperature to decompose the metal active component precursor into an oxide.
The third object of the present invention is to provide a supported metal catalyst obtained by the preparation method according to the second object of the present invention.
The fourth purpose of the invention is to provide the supported catalyst which is one of the purposes of the invention or the third purpose of the invention for the selective hydrogenation and alkyne removal reaction of carbon four liquid phases.
Compared with the prior art, the invention has the following beneficial effects:
(1) the alumina carrier adopted by the invention is added with halogen-containing organic matters during preparation, so that various performances of the alumina carrier are effectively improved, including high specific surface area, high pore volume, low bulk density and the like;
(2) the supported metal catalyst is used for hydrogenation reaction, especially for hydrocarbon four liquid phase selective hydrogenation alkyne removal reaction, and the selectivity of the catalyst can be obviously improved.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.
[ example 1 ]
1.00g of concentrated nitric acid and 3.00g of oxalic acid are weighed and added into 210g of deionized water to prepare a mixed solution. 200g of pseudo-boehmite powder, 6g of sesbania powder, 5g of starch and 3g of crosslinked polyethylene microspheres with the particle size of about 40 mu m are weighed, uniformly mixed in a mixer and transferred into a kneader. Slowly adding the mixed solution, kneading for 20 minutes, then dropwise adding 1.25g of trifluoroethanol, continuously kneading for 10 minutes, and then extruding, molding and granulating to obtain particles with the particle size of 4-6 mm. Oven drying at 120 deg.C for 12hr, and calcining at 1080 deg.C for 6hr to obtain alumina carrier with F loading of about 0.5%.
PdCl with a concentration of 25mgPd/mL is measured212mL of solution, diluted to 50mL with deionized water, Na2CO3The pH was adjusted to 3.0 and the solution was diluted to 65 mL. Weighing the Al2O3100g of the support, onto which the PdCl thus prepared was sprayed2And (3) solution. The sample was dried at 120 ℃ for 6h and then decomposed in a tube furnace with air at 450 ℃ for 6h to give an intermediate sample with a Pd content of 0.3 wt%.
Taking Pb (NO)3)20.16g, dissolved in 65mL of deionized water, was sprayed onto the 100g of intermediate sample. The sample was dried at 120 ℃ for 6 hours and decomposed at 450 ℃ for 6 hours by introducing air into a tube furnace to obtain a catalyst A1 having a Pd content of 0.3 wt% and a Pb content of 0.1 wt%.
[ example 2 ]
2.00g of concentrated nitric acid and 0.195g of potassium nitrate were weighed and added to 190g of deionized water to prepare a mixed solution. 200g of pseudo-boehmite powder, 8g of sesbania powder, 10g of starch and 0.48g of polyvinylidene fluoride powder are weighed, mixed uniformly in a mixer and transferred into a kneader. Slowly adding the mixed solution, fully kneading, extruding, molding and granulating to obtain particles with the particle size of 4-6 mm. Oven drying at 120 deg.C for more than 12hr, and calcining at 1150 deg.C for 4hr to obtain alumina carrier with F content of about 0.2% and K content of about 0.05%.
Pd (NO) was measured at a concentration of 25mgPd/mL3)212mL of the solution was added 20mgAg/mL of Co (NO)3)25mL of the solution was diluted to 65mL with deionized water. Weighing the Al2O3100g of the carrier, onto which the prepared solution was sprayed. The sample was dried at 120 ℃ for 6h and then decomposed at 450 ℃ for 6h in a tube furnace by passing air through it to give catalyst A2 having a Pd content of 0.3 wt% and a Co content of 0.1 wt%.
[ example 3 ]
1.00g of concentrated nitric acid, 2.00g of citric acid and 0.15g of 60% polytetrafluoroethylene concentrated dispersion are weighed and added into 190g of deionized water to prepare a mixed solution. 200g of pseudo-boehmite powder, 6g of sesbania powder and 6g of starch are weighed, mixed uniformly in a mixer and transferred into a kneader. Slowly adding the mixed solution, fully kneading, extruding, molding and granulating to obtain particles with the particle size of 4-6 mm. Oven drying at 120 deg.C for more than 12hr, and calcining at 1120 deg.C for 6hr to obtain alumina carrier with fluorine loading of about 0.05%.
PdCl with a concentration of 25mgPd/ml is measured2The solution was diluted to 12mL with deionized water to 50mL, adjusted to pH 5.0 with 2mol/L aqueous ammonia, and then diluted to 65 mL. Weighing the Al2O3100g of the carrier, to which the prepared solution was sprayed. The sample was dried at 120 ℃ for 6h and then decomposed in a tube furnace with air at 450 ℃ for 6h to give an intermediate sample with a Pd content of 0.3 wt%.
Weighing Pb (NO)3)20.48g, dissolved in 65mL of deionized water and sprayed onto 100g of the above intermediate sample. The sample was dried at 120 ℃ for 6 hours and decomposed at 450 ℃ for 6 hours by introducing air into a tube furnace to obtain a catalyst A3 having a Pd content of 0.3 wt% and a Pb content of 0.3 wt%.
[ example 4 ]
Pd (NO) was measured at a concentration of 25mgPd/ml3)2The solution is 12mL in volume,dilute to 65mL using deionized water. Then adding Pb (NO)3)20.48g of Al prepared in example 3 was weighed2O3100g of the carrier, to which the prepared solution was sprayed. The sample was dried at 120 ℃ for 6 hours and decomposed at 450 ℃ for 6 hours by introducing air into a tube furnace to obtain a catalyst A4 having a Pd content of 0.3 wt% and a Pb content of 0.3 wt%.
[ example 5 ]
2.00g of concentrated nitric acid, 2.00g of acetic acid, 0.30g of 60% polytetrafluoroethylene concentrated dispersion and 3.03g of lanthanum nitrate hexahydrate are weighed and added into 180g of deionized water to prepare a mixed solution. 190g of pseudo-boehmite powder, 10g of alumina trihydrate, 8g of sesbania powder, 2g of hydroxymethyl cellulose and 3g of ammonium carbonate are weighed, mixed uniformly in a mixer and transferred into a kneader. Slowly adding the mixed solution, fully kneading, extruding, molding and granulating to obtain particles with the particle size of 4-6 mm. Oven drying at 140 deg.C for more than 9hr, and calcining at 1135 deg.C for 6hr to obtain alumina carrier with fluorine loading of about 0.1% and La loading of about 0.7%.
PdCl with a concentration of 25mgPd/mL is measured2The solution was diluted to 12mL with deionized water to 50mL, adjusted to pH 3.0 with 1mol/L NaOH solution, and then diluted to 62 mL. Weighing the Al2O3100g of the support, onto which the PdCl thus prepared was sprayed2And (3) solution. The sample was dried at 120 ℃ for 6h and decomposed at 450 ℃ for 6h by passing air through a tube furnace to give catalyst A5 having a Pd content of 0.3 wt%.
Weighing Pb (NO)3)20.48g, dissolved in 65mL of deionized water and sprayed onto 100g of the above intermediate sample. The sample was dried at 120 ℃ for 6 hours and decomposed at 450 ℃ for 6 hours by introducing air into a tube furnace to obtain a catalyst A5 having a Pd content of 0.3 wt% and a Pb content of 0.3 wt%.
[ example 6 ]
3.00g of concentrated nitric acid and 0.73g of potassium nitrate were weighed and added to 200g of deionized water to prepare a mixed solution. 200g of pseudo-boehmite powder, 6g of sesbania powder, 6g of starch and 1.04g of K-value 72-71 polyvinyl chloride powder are weighed, mixed uniformly in a mixer and transferred into a kneader. Slowly adding the mixed solution, fully kneading, extruding, molding and granulating to obtain particles with the particle size of 4-6 mm. Drying at 120 deg.C for more than 12hr, calcining at 1135 deg.C for 6hr, wherein the temperature rise rate is controlled at 100 deg.C/hr below 600 deg.C and 200 deg.C/hr above 600 deg.C, and naturally cooling to room temperature to obtain alumina carrier S6 with chlorine loading of about 0.4% and K loading of about 0.2%.
PdCl with a concentration of 25mgPd/ml is measured28mL of the solution was diluted to 50mL with deionized water, the pH was adjusted to 3.0 with 2mol/L aqueous ammonia, and the solution was diluted to 58 mL. Weighing the Al2O3100g of the support, onto which the PdCl thus prepared was sprayed2And (3) solution. The sample was dried at 120 ℃ for 6h and decomposed at 450 ℃ for 6h by passing air through a tube furnace to give catalyst A6 having a Pd content of 0.2 wt%.
Weighing Pb (NO)3)20.16g, dissolved in 65mL of deionized water, was sprayed onto the 100g of intermediate sample. The sample was dried at 120 ℃ for 6 hours and decomposed at 450 ℃ for 6 hours by introducing air into a tube furnace to obtain a catalyst A6 having a Pd content of 0.2 wt% and a Pb content of 0.1 wt%.
Comparative example 1
3.00g of concentrated nitric acid is weighed and added into 190g of deionized water to prepare a mixed solution. 200g of pseudo-boehmite powder, 8g of sesbania powder and 4g of starch are weighed, mixed uniformly in a mixer and transferred into a kneader. Slowly adding the mixed solution, fully kneading, extruding, molding and granulating to obtain particles with the particle size of 4-6 mm. Oven drying at 120 deg.C for more than 12hr, calcining at 1195 deg.C for 6hr, controlling heating rate at 300 deg.C/hr, and naturally cooling to room temperature to obtain alumina carrier.
PdCl with a concentration of 25mgPd/ml is measured2The solution was diluted to 35mL with deionized water, adjusted to pH 3.0 with 1mol/L NaOH solution, and then diluted to 45 mL. Weighing the Al2O3100g of the carrier, to which the prepared solution was sprayed. The sample was dried at 120 ℃ for 6h and then decomposed in a tube furnace with air at 450 ℃ for 6h to give an intermediate sample with a Pd content of 0.3 wt%.
Weighing Pb (NO)3)2 0.16g，Dissolved in 45mL of deionized water and sprayed onto 100g of the above-mentioned intermediate sample. The sample was dried at 120 ℃ for 6 hours and decomposed at 450 ℃ for 6 hours by introducing air into a tube furnace to obtain catalyst B1 having a Pd content of 0.3 wt% and a Pb content of 0.1 wt%.
Comparative example 2
The procedure of example 1 was repeated except that: when the alumina carrier is prepared, 1.25g of trifluoroethanol is not adopted, and the process of loading the catalytic component is the same under the same conditions, so that the catalyst is obtained.
Comparative example 3
The procedure of example 1 was repeated except that: 2.24g of potassium fluoride is adopted to replace 1.25g of trifluoroethanol (the fluorine content of the trifluoroethanol is the same as that of the trifluoroethanol), and the process of loading the catalytic component is the same under the same other conditions, so that the catalyst is obtained.
Comparative example 4
The procedure of example 1 was repeated except that (2.24g of potassium fluoride and 1.7g of ethyl acetate) was used in place of 1.25g of trifluoroethanol (both having the same fluorine content), and the same conditions were used for the same procedure for supporting the catalytic component, to obtain a catalyst.
Comparative example 5
The procedure of example 1 was repeated except that 1.427g of ammonium fluoride was used in place of 1.25g of trifluoroethanol (both having the same fluorine content), and the procedure for supporting the catalytic component was the same, except that the conditions were the same, to obtain a supported metal catalyst.
[ Experimental example ]
The above catalyst was evaluated by selective hydrogenation alkyne removal reaction with mixed C4 under the following reaction conditions:
fixed bed reactor, catalyst loading 200mL, reaction pressure 1.2MPaG, reactor inlet temperature 40 ℃. The composition (mole fraction) of the reaction feed was 1.85% of Vinylacetylene (VA), 0.20% of Ethylacetylene (EA), 51.23% of 1, 3-Butadiene (BD), and the balance butane/butene and a small amount of 1, 2-butadiene. The space velocity of the experimental liquid is 16h-1. The results of the reaction after 8hr are shown in Table 1 below.
The experimental result shows that the selectivity of the catalyst prepared by the method is far higher than that of a comparative example when the catalyst is used for the selective hydrogenation reaction of the carbon-tetrayne to generate the 1, 3-butadiene.
TABLE 1 catalytic reaction Properties
Figure BDA0002499762160000151

Claims (15)

1. A supported metal catalyst comprises an alumina carrier, a catalytic component Pd and a promoter component, wherein the catalytic component Pd and the promoter component are loaded on the surface of the alumina carrier; a halogen element is added into the alumina carrier, the weight ratio of the halogen element to the alumina carrier is (0.01-3): 100, and the promoter component is selected from at least one of Sn, Pb, Co, Ni, IVB group and VB group; at least one of La, Ce, Pr, Li, K and Ba elements is optionally contained in the alumina carrier.
2. The supported metal catalyst of claim 1,
the weight ratio of the catalytic component Pd to the alumina carrier is (0.005-2): 100; and/or
The promoter component is selected from at least one of Sn, Pb, Co, Ni, Ti, Zr and V, and more preferably, the weight ratio of the promoter component to the alumina carrier is (0.01-10): 100.
3. The supported metal catalyst of claim 1,
the specific surface area of the alumina carrier is 5-150 m2(ii)/g, bulk density of 0.3-0.9 g/mL, pore volume of 0.25-1.00 mL/g; and/or
The alumina carrier contains fluorine and/or chlorine; preferably, the weight ratio of the fluorine element to the carrier is (0.01-1): 100, and the weight ratio of the chlorine element to the carrier is (0.01-2): 100; and/or
The alumina carrier optionally contains Si element, and the weight ratio of the Si element to the carrier is (0-1.5): 100; and/or
The mass ratio of at least one of La, Ce, Pr, Li, K and Ba elements to the carrier is (0-1.5): 100.
4. A method for preparing a supported metal catalyst, preferably for preparing a supported metal catalyst according to any one of claims 1 to 3, comprising the steps of:
step 1, mixing powdery raw materials;
step 2, adding an acidic aqueous solution into the powdery raw materials, and then kneading and molding;
step 3, adding halogen-containing organic matters, preferably fluorine-containing and/or chlorine-containing organic matters into the powdery raw materials in the step 1 and/or into the acidic aqueous solution in the step 2 and/or during kneading and molding;
step 4, drying and roasting to obtain the alumina carrier;
and 5, loading the catalytic component Pd and the cocatalyst component on the alumina carrier obtained in the step 3, and drying and roasting to obtain the supported metal catalyst.
5. The production method according to claim 4,
the amount of the fluorine-containing organic matter is 0.01-1 wt%, preferably 0.05-0.8 wt% of the total amount of the powdery raw materials, wherein the amount of the fluorine-containing organic matter is calculated by the weight of fluorine element in the fluorine-containing organic matter; and/or
The dosage of the chlorine-containing organic matter is 0.01-2 wt%, preferably 0.05-1 wt%, and more preferably 0.01-1 wt% of the total dosage of the powdery raw materials, wherein the dosage of the chlorine-containing organic matter is based on the weight of chlorine element in the chlorine-containing organic matter; and/or
The catalytic component Pd accounts for 0.005-2 wt% of the total weight of the alumina carrier; and/or
The cocatalyst component accounts for 0.01-10 wt% of the total weight of the alumina carrier. .
6. The method according to claim 4, wherein the fluorine-containing and/or chlorine-containing organic substance is at least one selected from the group consisting of a fluorine-containing and/or chlorine-containing polymer, a suspension of a fluorine-containing and/or chlorine-containing polymer, and a fluorine-containing and/or chlorine-containing organic compound;
preferably, when the fluorine-containing and/or chlorine-containing organic matter is a fluorine-containing and/or chlorine-containing polymer, it is added to the powdery raw material; when the fluorine-containing and/or chlorine-containing organic matter is a fluorine-containing and/or chlorine-containing polymer suspension, adding the fluorine-containing and/or chlorine-containing organic matter into the acidic aqueous solution; when the fluorine-containing and/or chlorine-containing organic compound is a fluorine-containing and/or chlorine-containing organic compound, adding the fluorine-containing and/or chlorine-containing organic compound into the acidic aqueous solution.
7. The production method according to claim 6,
the fluorine-containing and/or chlorine-containing polymer is selected from one or more of polytetrafluoroethylene, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/ethylene copolymer, polyvinylidene fluoride, polyvinyl fluoride, polychlorotrifluoroethylene, chlorotrifluoroethylene/ethylene copolymer, polyvinyl chloride, polyvinylidene chloride, chlorinated polypropylene, chlorinated polyethylene and vinyl chloride/vinylidene chloride copolymer; preferably, the fluorine-and/or chlorine-containing polymer has a particle diameter of less than 100 μm, preferably less than 50 μm; and/or
The fluorine-and/or chlorine-containing polymer suspension is selected from, but not limited to, polytetrafluoroethylene suspensions; and/or
The fluorine-containing and/or chlorine-containing organic compound is a water-soluble organic compound containing fluorine and/or chlorine elements, and preferably, the fluorine-containing and/or chlorine-containing organic compound is selected from at least one of, but not limited to, tetrafluoropropanol, trifluoroethanol, trifluoroacetal, chloroacetic acid, dichloroacetic acid, trichloroacetic acid and trichloroethanol.
8. The preparation method according to any one of claims 4 to 7, wherein in step 1, the powdery raw materials comprise alumina powder, an optional Si-containing compound and an optional formed pore-forming agent, wherein the alumina powder is selected from pseudo-boehmite powder and optional other alumina powder; preferably, the other alumina powder is selected from at least one of trihydrate alumina powder, fast deoxidized alumina powder and composite phase alumina powder; more preferably:
the amount of the alumina trihydrate accounts for 0-30 wt% of the total amount of the alumina powder; and/or
The dosage of the fast deoxidized aluminum powder accounts for 0-30 wt% of the total dosage of the aluminum oxide powder; and/or
The amount of the composite phase alumina is 0-30 wt% of the total amount of the alumina powder.
9. The preparation method according to claim 8, wherein the forming pore-forming agent is at least one selected from sesbania powder, starch, cellulose, high molecular polymer and decomposable alkaline substances, preferably, the forming pore-forming agent is used in an amount of 0-20 wt% of the total amount of the alumina powder; more preferably:
the cellulose is at least one selected from methylcellulose, hydroxypropyl methylcellulose and sodium hydroxymethyl cellulose; and/or the high molecular polymer is selected from at least one of polyethylene microspheres, polystyrene, polyethylene oxide, polyethylene glycol, polyvinyl alcohol, sodium polyacrylate, polyethylene glycol and polyacrylate acrylic acid; and/or the decomposable alkaline substance is selected from at least one of urea, methylamine, ethylenediamine, ammonium carbonate and ammonium bicarbonate.
10. The production method according to claim 8, wherein the Si-containing compound is a water-insoluble Si-containing compound, preferably at least one selected from the group consisting of dry silica gel, nano-silica, and silicon carbide; preferably, the Si-containing compound is used in an amount of 0 to 1.5 wt% based on the total amount of the alumina powder, wherein the Si-containing compound is used in an amount based on the weight of Si element therein.
11. The production method according to claim 8, wherein, in step 2,
the acidic aqueous solution is selected from at least one of hydrochloric acid aqueous solution, nitric acid aqueous solution, sulfuric acid aqueous solution, acetic acid aqueous solution, oxalic acid aqueous solution, citric acid aqueous solution, phosphoric acid aqueous solution and ammonium dihydrogen phosphate aqueous solution, and preferably from at least one of nitric acid aqueous solution, acetic acid aqueous solution, oxalic acid aqueous solution and citric acid aqueous solution; and/or
The weight ratio of the acidic aqueous solution to the powdery raw material is (0.5-5): 1, preferably (0.6-2): 1; and/or
Adding a soluble auxiliary agent into the acidic aqueous solution, wherein the soluble auxiliary agent is selected from at least one inorganic substance of La, Ce, Pr, Li, K and Ba, preferably, the soluble auxiliary agent is selected from at least one nitric compound and/or oxide of La, Ce, Pr, Li, K and Ba, more preferably, the amount of the soluble auxiliary agent is 0-1.5 wt% of the total amount of the alumina powder, and the amount of the soluble auxiliary agent is calculated by the weight of La, Ce, Pr, Li, K or Ba.
12. The production method according to claim 8, wherein, in step 4,
the drying temperature is 60-150 ℃, and preferably 80-150 ℃; the drying time is 3-48 hours, preferably 5-25 hours; and/or
The roasting temperature is 800-1200 ℃, and preferably 1000-1200 ℃; the roasting time is 3-48 hours, preferably 4-10 hours.
13. The production method according to claim 8, wherein, in step 5,
the drying is carried out for 5-48 h at 50-200 ℃, preferably for 5-24 h at 50-120 ℃; and/or
The roasting is carried out for 2-10 h at 300-600 ℃, preferably for 4-8 h at 400-500 ℃.
14. A supported metal catalyst obtained by the production method according to any one of claims 4 to 13.
15. The use of the supported metal catalyst of any one of claims 1 to 3 or the supported metal catalyst of claim 14 for a carbo-tetra liquid phase selective hydrogenation alkyne removal reaction.
CN202010428855.XA 2020-05-20 2020-05-20 Supported metal catalyst and preparation method and application thereof Active CN113694941B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010428855.XA CN113694941B (en) 2020-05-20 2020-05-20 Supported metal catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010428855.XA CN113694941B (en) 2020-05-20 2020-05-20 Supported metal catalyst and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN113694941A true CN113694941A (en) 2021-11-26
CN113694941B CN113694941B (en) 2024-05-07

Family

ID=78645454

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010428855.XA Active CN113694941B (en) 2020-05-20 2020-05-20 Supported metal catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113694941B (en)

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN87103074A (en) * 1986-04-29 1988-11-09 国际壳牌研究有限公司 The method for preparing silver-containing catalyst
CA1292974C (en) * 1987-04-03 1991-12-10 Gosse Boxhoorn Process for the preparation of a silver-containing catalyst
CN1295880A (en) * 1999-11-12 2001-05-23 中国石化集团齐鲁石油化工公司 Selective hydrogenation catalyst for alkyne and diene
CN101255358A (en) * 2008-04-17 2008-09-03 中国石油天然气集团公司 Selective hydrogenation catalyst and preparation method thereof
CN101875009A (en) * 2009-04-29 2010-11-03 中国石油化工股份有限公司 C3 fraction selective hydrogenation catalyst and preparation method thereof
CN102206131A (en) * 2011-04-07 2011-10-05 中国石油天然气股份有限公司 Selective hydrogenation method for C2 fraction
CN102989452A (en) * 2011-09-09 2013-03-27 中国石油天然气股份有限公司 C2 front-end hydrogenation catalyst containing composite carrier and preparation method
CN103962161A (en) * 2013-01-30 2014-08-06 中国石油天然气股份有限公司 Continuous reforming catalyst and preparation method thereof
CN105727992A (en) * 2014-12-12 2016-07-06 中国石油天然气股份有限公司 Pd-Ni-series supported hydrogenation catalyst
CN105749910A (en) * 2014-12-19 2016-07-13 中国石油天然气股份有限公司 Palladium-lead based loaded hydrogenation catalyst
CN106311353A (en) * 2015-07-02 2017-01-11 中国石油化工股份有限公司 Alpha-alumina support, corresponding silver catalyst and application
CN109718762A (en) * 2017-10-27 2019-05-07 中国石油化工股份有限公司 It is the method for the selective hydrogenation of catalyst of ethylene and preparation method thereof and acetylene for selective hydrogenation of acetylene

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN87103074A (en) * 1986-04-29 1988-11-09 国际壳牌研究有限公司 The method for preparing silver-containing catalyst
CA1292974C (en) * 1987-04-03 1991-12-10 Gosse Boxhoorn Process for the preparation of a silver-containing catalyst
CN1295880A (en) * 1999-11-12 2001-05-23 中国石化集团齐鲁石油化工公司 Selective hydrogenation catalyst for alkyne and diene
CN101255358A (en) * 2008-04-17 2008-09-03 中国石油天然气集团公司 Selective hydrogenation catalyst and preparation method thereof
CN101875009A (en) * 2009-04-29 2010-11-03 中国石油化工股份有限公司 C3 fraction selective hydrogenation catalyst and preparation method thereof
CN102206131A (en) * 2011-04-07 2011-10-05 中国石油天然气股份有限公司 Selective hydrogenation method for C2 fraction
CN102989452A (en) * 2011-09-09 2013-03-27 中国石油天然气股份有限公司 C2 front-end hydrogenation catalyst containing composite carrier and preparation method
CN103962161A (en) * 2013-01-30 2014-08-06 中国石油天然气股份有限公司 Continuous reforming catalyst and preparation method thereof
CN105727992A (en) * 2014-12-12 2016-07-06 中国石油天然气股份有限公司 Pd-Ni-series supported hydrogenation catalyst
CN105749910A (en) * 2014-12-19 2016-07-13 中国石油天然气股份有限公司 Palladium-lead based loaded hydrogenation catalyst
CN106311353A (en) * 2015-07-02 2017-01-11 中国石油化工股份有限公司 Alpha-alumina support, corresponding silver catalyst and application
CN109718762A (en) * 2017-10-27 2019-05-07 中国石油化工股份有限公司 It is the method for the selective hydrogenation of catalyst of ethylene and preparation method thereof and acetylene for selective hydrogenation of acetylene

Also Published As

Publication number Publication date
CN113694941B (en) 2024-05-07

Similar Documents

Publication Publication Date Title
JP4339681B2 (en) Selective hydrogenation catalyst for selective hydrogenation of unsaturated olefins and use thereof
US7288686B2 (en) Hydrogenation catalyst and hydrogenation process
CN101293208B (en) Reforming catalyst and preparation method thereof
CN108927173B (en) Alkyne selective hydrogenation catalyst and preparation method and application thereof
CN107486197B (en) Preparation method of low-carbon alkane dehydrogenation microspherical catalyst
TWI517900B (en) Production of shell catalysts in a coating device
CN113694941A (en) Supported metal catalyst and preparation method and application thereof
CN111686709B (en) Propane dehydrogenation propylene supported catalyst with specific pore structure and preparation method thereof
CA2031429A1 (en) Process for the preparation of vinyl acetate
CN114950471B (en) Nickel-based catalyst, preparation method thereof and application thereof in selective hydrogenation of acetylene in ethylene
US9555397B2 (en) Pre-gold-plating Pd-Au-coated shell catalysts
CN108863706B (en) Selective hydrogenation method for alkyne-containing four-fraction
CN113694944B (en) Palladium selective hydrogenation catalyst for pyrolysis gasoline and preparation method and application thereof
CN113694942B (en) Carbon three-fraction selective hydrogenation catalyst and preparation method thereof
CN109364945B (en) Method for selective hydrogenation of full-fraction pyrolysis gasoline
CN1364855A (en) Selective hydrogenization catalyst and its preparing method and use
CN1295880A (en) Selective hydrogenation catalyst for alkyne and diene
CN109022025B (en) Selective hydrogenation method for full-fraction pyrolysis gasoline
CN113828319A (en) Cu-Zn-M composite oxide catalyst and preparation method and application thereof
KR20170052461A (en) Transition Metal-Noble Metal Complex Oxide Catalysts Prepared by One-Pot for Dehydrogenation and Use Thereof
CN108863699B (en) Method for recycling butadiene through selective hydrogenation of alkyne
CN114682245B (en) Treatment, activation and regeneration method of Ma-Mb metal supported catalyst
CN113663699B (en) Alumina carrier and preparation method thereof
CN113786862B (en) Selective ketene hydrogenation catalyst and preparation method and application thereof
CN110314684B (en) N-heptane isomerization catalyst and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant