WO2024016576A1 - Catalyseur d'hydrogénation sélective pour alcynes et son procédé de préparation - Google Patents

Catalyseur d'hydrogénation sélective pour alcynes et son procédé de préparation Download PDF

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WO2024016576A1
WO2024016576A1 PCT/CN2022/139263 CN2022139263W WO2024016576A1 WO 2024016576 A1 WO2024016576 A1 WO 2024016576A1 CN 2022139263 W CN2022139263 W CN 2022139263W WO 2024016576 A1 WO2024016576 A1 WO 2024016576A1
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catalyst
solution
semi
preparation
palladium
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谭都平
向永生
张峰
谢元
车春霞
韩伟
温翯
韩迎红
杨博
边虎
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中国石油天然气股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • 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
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/55—Cylinders or rings
    • 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
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J35/64—Pore diameter
    • 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
    • B01J35/66—Pore distribution
    • B01J35/69—Pore distribution bimodal
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/04—Ethylene
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
    • C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond

Definitions

  • the invention relates to an alkyne selective hydrogenation catalyst and a preparation method thereof, and belongs to the technical field of catalyst preparation.
  • Ethylene obtained by steam cracking of petroleum hydrocarbons contains acetylene with a mass fraction of 0.2%-2.5%.
  • acetylene in ethylene reduces the activity of the polymerization catalyst and affects the physical properties of the polymer, so it must be removed.
  • selective hydrogenation is commonly used in industry to remove acetylene from ethylene, and the catalysts used are mainly precious metal catalysts such as Pd, Pt, and Au.
  • the catalyst In order to ensure that the ethylene generated by acetylene hydrogenation and the original ethylene in the raw material do not continue to be hydrogenated to generate ethane, causing ethylene loss, the catalyst must have high hydrogenation selectivity to obtain better economic benefits.
  • the hydrogenation after carbon dioxide is based on the content of acetylene. Calculate the required hydrogen and add the hydrogenation materials.
  • the molar ratio of hydrogen to acetylene generally does not exceed 2. It is precisely because of the lack of hydrogen that the hydrogenation dimerization reaction of acetylene easily occurs. , generating a carbon four fraction, which is further polymerized to form an oligomer with a wider molecular weight, commonly known as "green oil". Green oil is adsorbed on the surface of the catalyst and further forms coking, blocking the catalyst pores and preventing the reactants from diffusing to the active center surface of the catalyst, resulting in a decrease in catalyst activity.
  • CN200810119385.8 discloses a non-noble metal supported selective hydrogenation catalyst and its preparation method and application, including a carrier and a main active component and an auxiliary active component loaded on the carrier, wherein the main active component is Ni, and the co-active component is selected from at least one of Mo, La, Ag, Bi, Cu, Nd, Cs, Ce, Zn and Zr.
  • the main active component and the co-active component are both amorphous. It exists in a state form, the average particle size is ⁇ 10 nm, the carrier is a non-oxidizing porous material; and the catalyst is prepared by a micro-emulsification method.
  • CN200810114744.0 discloses an unsaturated hydrocarbon selective hydrogenation catalyst and its preparation method.
  • This catalyst uses alumina as a carrier and palladium as an active component.
  • alumina as a carrier
  • palladium as an active component.
  • the catalysts prepared by the above methods all use catalysts with a single distribution of pore sizes. During the fixed bed reaction process, they are affected by internal diffusion and have poor selectivity. A carrier with bimodal pore distribution ensures high catalyst activity. At the same time, the existence of large pores can reduce the impact of internal diffusion and improve catalyst selectivity.
  • CN101433842A discloses a hydrogenation catalyst, which is characterized in that the catalyst has a bimodal pore distribution. The maximum radius of the small pore part is 2-50nm, and the maximum radius of the large pore part is 100-500nm. Since the catalyst has a bimodal pore distribution, , which not only has good hydrogenation activity, but also has good selectivity and large ethylene increment.
  • the formation of green oil and the coking of the catalyst are important factors affecting the service life of the catalyst.
  • the activity, selectivity and service life of the catalyst constitute the overall performance of the catalyst.
  • the methods listed above may provide better ways to improve the activity and selectivity of the catalyst, but they do not solve the problem of the catalyst being prone to coking, or the problem that the catalyst is prone to coking. It easily generates green oil and coking problems, but does not solve the problem of selectivity.
  • a carrier with a macroporous structure can improve selectivity, larger molecules generated by polymerization and chain growth reactions can easily accumulate in the macropores of the carrier, causing coking and deactivation of the catalyst and affecting the service life of the catalyst.
  • part of the active center is not located close to the catalyst surface, resulting in poor catalyst selectivity and large ethylene loss during hydrogenation.
  • the object of the present invention is to provide an acetylene selective hydrogenation catalyst and a preparation method, which are suitable for an acetylene selective hydrogenation process involving CO.
  • the present invention provides a selective hydrogenation catalyst, wherein the active components of the catalyst contain Pd and Ag. Based on the mass of the carrier being 100%, the content of Pd is 0.045-0.075%, and the content of Ag is 0.045-0.075%. 0.06-0.12%;
  • the catalyst contains an organic cage, which is located on the outer surface of the catalyst.
  • the size of the organic cage is 2.7-3.6 nm.
  • the Pd is loaded in the organic cage, and Ag is located in the middle or bottom of the Pd active center.
  • the catalyst of the present invention synthesizes organic cages with a regular structure in situ on the outer surface of the carrier.
  • the size of the cages is 2.7-3.6 nm, and active components are loaded in these organic cages.
  • the size of the active center is also uniform, which can not only meet the activity needs, but also does not have an overly large active center. The probability of adsorbing olefins and CO at the same time during acetylene hydrogenation is greatly reduced.
  • Ag can form an alloy with Pd to improve the selectivity of acetylene hydrogenation.
  • Ag has two functions: one is that silver atoms separate palladium atoms and increase the spatial distance between adsorbed acetylene molecules. The distance between the corresponding reaction intermediates after hydrogenation of acetylene is larger, which prevents them from forming strongly adsorbed species of acetylene and makes it difficult for intermediate-vinyl coupling to occur, thus reducing the formation of green oil. This is called geometry.
  • the second effect is that the S electrons in the outer layer of silver enter the empty orbit of palladium and reduce the adsorption of palladium on ethylene, which is called electron effect.
  • reaction material contains CO, due to its competitive adsorption relationship with acetylene, it can reduce the probability of strong adsorption of acetylene and play the above-mentioned geometric role. Therefore, Ag can not be exposed to the outer surface of the catalyst, but it will improve the selection of the catalyst. Physically, the electronic role of silver is still needed, so silver can be present inside or at the bottom of the active center of the catalyst.
  • the specific surface area of the catalyst is 15-30 m 2 /g.
  • the carrier of the catalyst is alumina or mainly alumina.
  • the crystal form of the alumina in the carrier can be ⁇ , ⁇ crystal form or a mixed crystal form thereof; the alumina in the catalyst carrier accounts for more than 80%.
  • the support also contains other metal oxides, such as magnesium oxide and/or titanium oxide.
  • the invention also provides a preparation method for the above catalyst, which mainly includes the following processes:
  • a polar polymer is formed in the carrier, which occupies 80-95% of the pore volume of the carrier;
  • step (3) Load the palladium active component in the organic cage, dry and then bake; decompose the polar polymer formed in step (1);
  • the above preparation method includes the following specific steps:
  • the molar ratio of aromatic diamine compounds to tris(4-formylphenyl)amine is 1.2-2.5:1, and the mass ratio of tris(4-formylphenyl)amine to haloacetic acid is 2000-6000: 1;
  • step (1) Immerse the second semi-finished catalyst in the alcohol solution, drop the first solution of the palladium precursor into the mixture of the second semi-finished catalyst and alcohol while stirring, then add the reducing agent dropwise, heat and stir until the surface of the second semi-finished catalyst no longer changes color. , pour off the solution, wash with deionized water, dry, and roast at a temperature where the polymer formed in step (1) can decompose, to obtain a third semi-finished catalyst;
  • the mass ratio of the total mass of the organic palladium salt and tris(4-formylphenyl)amine described in step (3) and step (5) is 2-14 :1.
  • step (4) is performed before step (3), and step (3) and step (5) are combined.
  • the present invention in order to obtain a catalyst with uniform active center size, the present invention first prepares an organic cage, and then loads the active component palladium in the organic cage.
  • the catalyst thus prepared has an active center of The scale is also in the range of 2.7-3.6nm, which can avoid the formation of two vinyl groups on one active center during the hydrogenation reaction, or the simultaneous adsorption of CO and ethylene.
  • the synthesized organic cage will be evenly distributed on the carrier, and the loaded catalyst active components will also be evenly distributed in all parts of the catalyst, and can only be used for full hydrogenation without considering selectivity. , or homogeneous hydrogenation without diffusion limitations, cannot be used for gas-phase selective hydrogenation.
  • the present invention uses other media to occupy the pores inside the carrier in advance, so that the organic cage is synthesized in the pores close to the outer surface.
  • the active component Pd is distributed among the organic cages. Within the range, and the size of the active center is also within the appropriate range of 2.7-3.6nm, it can be suitable for gas-phase selective hydrogenation reactions, especially the selective hydrogenation process of carbon dioxide fractions.
  • the present invention does not limit the specific types of monomers used to synthesize organic cages, as long as the size of the synthesized organic cages is between 2.7-3.6 nm.
  • the hydrophilic polymerizable monomer is a monomer containing a carbonyl group and/or a carboxyl group and capable of polymerization or condensation reaction, and more preferably includes lactic acid, acrylic acid or formaldehyde.
  • the certain temperature in step (1) refers to the temperature at which the thermal condensation reaction or bulk polymerization of the monomer occurs, which varies depending on the monomer, and is generally 80-200°C.
  • the carrier in step (1) may be spherical, cylindrical, clover-shaped, four-leaf clover-shaped, etc.
  • the decomposition temperature of the polymer formed from the hydrophilic polymerizable monomer is lower than 450°C, more preferably lower than 420°C.
  • the aromatic hydrocarbon diamines are tetraphenylenediamine or derivatives with substituents on its benzene ring, preferably p-tetraphenylenediamine.
  • Amine or its derivative with a substituent on the benzene ring, the substituent is preferably a halogen or an alkyl group.
  • haloacetic acid is a catalyst for the reaction of tris(4-formylphenyl)amine and aromatic diamine compounds.
  • the haloacetic acid is fluoroacetic acid.
  • an alkyl halide is the solvent required for the reaction.
  • the alkyl halide includes an alkyl fluoride, an alkyl chloride or an alkyl bromide, and more preferably a methyl halide or an alkyl halide.
  • ethane dichloroethane or chloroform is more preferred.
  • the organic palladium salt includes palladium acetate or palladium acetylacetonate
  • the organic solvent is chloroform
  • the organic solvent is one of chloroform, methylene chloride and glacial acetic acid. one or a combination of two or more.
  • the alcohol includes ethanol or methanol, more preferably ethanol.
  • the reducing agent is a reducing compound, more preferably methanol, formaldehyde, formic acid, ethanol, acetaldehyde , one or a combination of two or more of hydrazine hydrate.
  • the soluble silver salt is a silver salt soluble in water or an organic solvent, more preferably a silver nitrate soluble in water and/or a silver salt soluble in water.
  • Ag is supported by a solution method, such as a saturated impregnation method.
  • step (5) after loading Ag in step (4), Pd is loaded in step (5), and then can be calcined to form an oxidized state catalyst, or can be directly reduced to form a reduced state catalyst.
  • the invention also provides a carbon dioxide fraction selective hydrogenation process using crude hydrogen as the hydrogen source, which is carried out using the above catalyst.
  • the catalyst provided by the invention has the following characteristics: since palladium is loaded in an organic cage, limited by the physical size of the cage, the largest size of the active center composed of palladium is the size of the cage, reducing the activity with an aggregation size greater than 3.0 nm. center. This size meets the activity requirements for acetylene selectivity, but the probability of forming two vinyl groups at the same time in an active center or the simultaneous adsorption of CO and olefins is greatly reduced, reducing the probability of hydroformylation reaction and delaying catalyst deactivation. rate, the yield of butene can be reduced to less than 1/2 of that of traditional catalysts, and the production of oxygenated compounds such as aldehydes is also significantly reduced.
  • the organic cage is located on the outer surface of the catalyst, which avoids the impact of internal diffusion limitation on the catalytic reaction, and the catalyst has good selectivity.
  • the use of the catalyst of the present invention can reduce the production of carbon four by-products, and hydrogenation of the carbonyl group of oxygen-containing compounds reduces the production of macromolecular oxygen-containing compounds.
  • the catalyst prepared by this method does not even need to be regenerated. Even if it is regenerated, the catalyst can be regenerated below 450°C, thereby not destroying the organic cage structure, ensuring good performance in the hydrogenation process, and greatly extending the catalyst life.
  • Figure 1 shows the pore size of the organic cage synthesized in Example 1 measured by the BET method.
  • BET measuring instrument manufactured by Mack Company in the United States, measures the specific surface area and pore size distribution.
  • the contents of Pd and Ag in the catalyst were measured on the A240FS atomic absorption spectrometer.
  • Agilent 7890A gas chromatograph measured hydrogen, acetylene content and butene content at the reactor outlet and inlet.
  • the weight of the catalyst was measured using a 0.1 mg electronic balance.
  • Tris(4-formylphenyl)amine Tris(4-formylphenyl)amine, dichloroacetic acid, dichloroethane, diphenyldiamine, hydrazine hydrate, ethanol, methanol, acetic acid, formic acid, formaldehyde, lactic acid, acrylic acid, palladium acetate, palladium acetylacetonate , silver nitrate, analytical grade, Shanghai Sinopharm Group Company; alumina, Shandong Aluminum Group Company.
  • This embodiment provides a catalyst, wherein:
  • Catalyst carrier Commercially available spherical alumina carrier is used, with a diameter of 4mm. After roasting at 1080°C for 4 hours, the pore volume was 0.55m 3 /g and the specific surface area was 30m 2 /g. Weigh 100g of the carrier.
  • the pore size results of the organic cage synthesized in Example 1 measured by the BET method are shown in Figure 1. As can be seen from Figure 1, the maximum pore diameter is 3.53nm and the minimum pore diameter is 2.91nm.
  • Atomic absorption spectrometry determined that in the catalyst prepared in Example 1, the Pd content was 0.045% and the Ag content was 0.07%.
  • This comparative example provides a catalyst in which:
  • Catalyst carrier The carrier used in Example 1 was used.
  • Catalyst preparation The preparation process conditions are the same as those in Example 1, except that silver is not supported;
  • the Pd content in the catalyst prepared in Comparative Example 1 was determined by atomic absorption spectrometry to be 0.045%.
  • This embodiment provides a catalyst, wherein:
  • Carrier Commercially available spherical alumina carrier is used, with a diameter of 3mm. After roasting at 1150°C for 4 hours, the water absorption pore volume was 0.65m 3 /g, and the specific surface area was 15.07m 2 /g. Weigh 100g of the carrier.
  • Atomic absorption spectrometry determined that in the catalyst prepared in Example 2, the Pd content was 0.05% and the Ag content was 0.06%.
  • This comparative example provides a catalyst in which:
  • Carrier The same carrier as in Example 2 was used.
  • Catalyst preparation The preparation conditions are the same as Example 2, except that all palladium is supported in step (3);
  • Atomic absorption spectrometry determined that in the catalyst prepared in Comparative Example 2, the Pd content was 0.05% and the Ag content was 0.06%.
  • This embodiment provides a catalyst, wherein:
  • Carrier A commercially available spherical alumina-titanium oxide carrier is used, with a titanium oxide content of 20% and a diameter of 4mm. After roasting at 1105°C for 4 hours, the pore volume was 0.50m 3 /g and the specific surface area was 25.14m 2 /g. Weigh 100g of the carrier.
  • Atomic absorption spectrometry determined that in the catalyst prepared in Example 3, the Pd content was 0.065% and the Ag content was 0.1%.
  • This comparative example provides a catalyst in which:
  • Carrier The same carrier as in Example 3 was used.
  • Catalyst preparation The catalyst preparation conditions are the same as those in Example 3, except that the tris(4-formylphenyl)amine in Comparative Example 3 is 4 times higher than that in Example 3;
  • Atomic absorption spectrometry determined that in the catalyst prepared in Comparative Example 3, the Pd content was 0.065% and the Ag content was 0.1%.
  • This embodiment provides a catalyst, wherein:
  • Carrier Commercially available tooth ball type alumina-magnesium oxide carrier is used, with a magnesium oxide content of 5% and a diameter of 3mm. After roasting at 1135°C for 4 hours, the pore volume was 0.55m 3 /g and the specific surface area was 22.39m 2 /g. Weigh 100g of the carrier.
  • Atomic absorption spectrometry determined that in the catalyst prepared in Example 4, the Pd content was 0.075% and the Ag content was 0.12%.
  • This comparative example provides a catalyst in which:
  • the catalyst carrier is the same as in Example 4.
  • Catalyst preparation The difference between this comparative example and Example 4 is that there is no step (1).
  • Atomic absorption spectrometry determined that in the catalyst prepared in Comparative Example 4, the Pd content was 0.075% and the Ag content was 0.12%.
  • This embodiment provides a catalyst, wherein:
  • Carrier A spherical alumina-magnesium oxide carrier is used, with a magnesium oxide content of 10% and a diameter of 3mm. After roasting at 1100°C for 4 hours, the pore volume was 0.53m 3 /g and the specific surface area was 28.68m 2 /g. Weigh 100g of the carrier.
  • the atomic absorption spectrometry method determined that in the catalyst prepared in Example 5, the Pd content was 0.07% and the Ag content was 0.09%.
  • This comparative example provides a catalyst, in which the catalyst carrier is the same as in Example 5, except that the catalyst is prepared using a traditional method.
  • Atomic absorption spectrometry determined that in the catalyst prepared in Comparative Example 5, the Pd content was 0.07% and the Ag content was 0.09%.
  • This embodiment provides a catalyst, wherein:
  • Carrier A commercially available spherical carrier is used, with 95% alumina, 5% titanium oxide content, and a diameter of 3 mm. After roasting at 1090°C for 4 hours, the pore volume was 0.48m 3 /g and the specific surface area was 30.13m 2 /g. Weigh 100g of the carrier.
  • the atomic absorption spectrometry method determined that in the catalyst prepared in Example 6, the Pd content was 0.065% and the Ag content was 0.11%.
  • This comparative example provides a catalyst in which:
  • Carrier Use the same carrier as Example 6. The difference from Example 6 is that phenylenediamine with the same mole number as 3-methyltetraphenylenediamine is used and prepared with tris(4-formylphenyl)amine. Organic cage.
  • Atomic absorption spectrometry determined that in the catalyst prepared in Comparative Example 6, the Pd content was 0.065% and the Ag content was 0.11%.
  • This embodiment provides a catalyst, wherein:
  • Carrier Commercially available spherical alumina carrier is used, with a diameter of 4mm. After roasting at 1135°C for 4 hours, the water absorption pore volume was 0.60m 3 /g, and the specific surface area was 21.75m 2 /g. Weigh 100g of the carrier.
  • Atomic absorption spectrometry determined that in the catalyst prepared in Example 7, the Pd content was 0.06% and the Ag content was 0.12%.
  • This comparative example provides a catalyst in which:
  • Carrier The same carrier as in Example 7 was used.
  • Catalyst preparation The preparation conditions are the same as Example 7, except that the calcination temperature in step (3) is 600°C.
  • Atomic absorption spectrometry determined that in the catalyst prepared in Comparative Example 7, the Pd content was 0.06% and the Ag content was 0.12%.
  • the loading volume of the catalyst in the fixed bed section reactor is 100 mL (record the weight), the filler is 50 mL, the reaction material space velocity is 4000/h, the operating pressure is 2.5 MPa, the hydrogen-to-yne ratio is 1.5, and the reactor inlet temperature is 75°C.
  • Catalyst reduction hydrogen flow rate 10 liters/hour, constant temperature 130°C for 4 hours.
  • the initial selectivity is the selectivity measured 24 hours after the reactor is fed.
  • the initial activity is the activity (acetylene conversion rate) measured 24 hours after the reactor is fed.
  • the reaction material composition is as follows:
  • Comparative Example 1 Compared with Example 1, the selectivity in Comparative Example 1 is at least 5 percentage points lower due to the absence of loaded silver.
  • Comparative Example 4 the polar polymer was not synthesized in the carrier in advance.
  • the synthesis reaction of the organic cage was carried out at all parts inside the carrier.
  • the active center for loading palladium was also located at all parts inside the carrier and was limited by the diffusion of reaction molecules. Its activity selectivity is worse than that of Example 4.
  • Comparative Example 5 the catalyst was prepared by a traditional method. Since silver occupied part of the outer surface of the active center, the catalyst activity was reduced. The situation is similar to that of Comparative Example 2.
  • CO Under the condition that CO participates in the reaction, CO can be adsorbed on palladium atoms and form competitive adsorption with acetylene, which reduces the probability of forming multiple vinyl groups at the same active center at the same time, objectively reducing the amount of green oil produced and improving The role of selectivity.
  • CO may still form strong adsorption and formylation reactions may occur.
  • the electronic effect after the silver and palladium form an alloy can be used. That is, the S electrons of silver first enter the outer empty orbit of palladium. At this time, there is no need to expose silver. outside the active center.
  • the catalyst of the present invention has a significantly reduced loading capacity of precious metal palladium, the production of green oil is also reduced, and the catalyst operation cycle is extended.

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Abstract

L'invention concerne un catalyseur d'hydrogénation sélective pour alcynes et son procédé de préparation. Le catalyseur contient au moins les composants actifs suivants : Pd et Ag. Sur la base de la masse d'un support qui est de 100 %, la teneur en Pd est de 0,045 à 0,075 %, et la teneur en Ag est de 0,06 à 0,12 %. Le catalyseur contient une cage organique située sur la surface externe du catalyseur ; la taille de la cage organique est de 2,7 à 3,6 nm ; Pd est chargé dans la cage organique ; et l'Ag est situé au milieu ou au fond d'un centre actif de Pd. Lorsque le catalyseur de la présente invention est appliqué à un procédé d'hydrogénation sélective d'une fraction C2, le rendement de butène peut être réduit au moitié ou moins d'un catalyseur classique, et la production de composés contenant de l'oxygène tels que des aldéhydes est également significativement réduite.
PCT/CN2022/139263 2022-07-19 2022-12-15 Catalyseur d'hydrogénation sélective pour alcynes et son procédé de préparation WO2024016576A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101884921A (zh) * 2009-05-15 2010-11-17 中国石油天然气股份有限公司 一种钯—银系负载型加氢催化剂
US20180290949A1 (en) * 2016-05-23 2018-10-11 Petrochina Company Limited Palladium-Based Supported Hydrogenation Catalyst, And Preparation Method And Application Thereof
CN110841635A (zh) * 2019-12-04 2020-02-28 天津金玺科技发展有限公司 高分散Pd-Ag负载型乙炔氢化催化剂及其制备方法
CN112675869A (zh) * 2019-10-17 2021-04-20 中国石油天然气股份有限公司 一种碳二馏分炔烃选择加氢催化剂
CN114160196A (zh) * 2021-12-24 2022-03-11 兰州大学 一种钯团簇催化剂的制备方法及其应用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101884921A (zh) * 2009-05-15 2010-11-17 中国石油天然气股份有限公司 一种钯—银系负载型加氢催化剂
US20180290949A1 (en) * 2016-05-23 2018-10-11 Petrochina Company Limited Palladium-Based Supported Hydrogenation Catalyst, And Preparation Method And Application Thereof
CN112675869A (zh) * 2019-10-17 2021-04-20 中国石油天然气股份有限公司 一种碳二馏分炔烃选择加氢催化剂
CN110841635A (zh) * 2019-12-04 2020-02-28 天津金玺科技发展有限公司 高分散Pd-Ag负载型乙炔氢化催化剂及其制备方法
CN114160196A (zh) * 2021-12-24 2022-03-11 兰州大学 一种钯团簇催化剂的制备方法及其应用

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