CN116037084A - Alkyne selective hydrogenation catalyst and preparation method and application thereof - Google Patents

Alkyne selective hydrogenation catalyst and preparation method and application thereof Download PDF

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Publication number
CN116037084A
CN116037084A CN202111260277.4A CN202111260277A CN116037084A CN 116037084 A CN116037084 A CN 116037084A CN 202111260277 A CN202111260277 A CN 202111260277A CN 116037084 A CN116037084 A CN 116037084A
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groups
powder
catalyst
alumina carrier
acid
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毛祖旺
乐毅
王骞阅
杨晨熹
易水生
张立岩
刘海江
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B01J23/04—Alkali 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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

Abstract

The invention provides an alkyne selective hydrogenation catalyst and a preparation method thereof. In the preparation process of the alumina carrier, a certain amount of alpha-Al is added 2 O 3 Powder, alpha-Al used 2 O 3 The particle size, impurity content and the like of the powder are required to meet certain conditions. The prepared alumina carrier has the advantages of low bulk density, high water absorption, large pore volume and large average pore diameter. Because the pore volume of the alumina carrier is increased and the water absorption rate is increased, the active metal Pd can be more uniformly distributed on the surface of the alumina carrier, thereby forming a Pd catalyst with high dispersity, and meanwhile, because the pore diameter is increased, the alkene generated by alkyne selective hydrogenation can be more rapidly diffused, thereby avoiding the alkane from being excessively hydrogenated and having better selectivity.

Description

Alkyne selective hydrogenation catalyst and preparation method and application thereof
Technical Field
The invention belongs to the field of catalysts, and particularly relates to an alkyne selective hydrogenation catalyst, and a preparation method and application thereof.
Background
In an ethylene production device, pyrolysis gas is subjected to rectification separation to obtain a carbon two-fraction rich in ethylene, ethane and acetylene, and a carbon three-fraction rich in propane, propylene, propyne and propadiene (commonly referred to as MAPD) which are impurities in the carbon two-and carbon three-fraction, so that the consumption of a subsequent polymerization catalyst is increased, and the performance of a polymer product is affected. The alkyne is removed in a selective hydrogenation mode in industry, and meanwhile, the yield of alkene can be increased, and the resource utilization rate is improved.
The general alkyne selective hydrogenation catalyst is a supported metal catalyst and consists of a carrier, a main active component and an auxiliary active component. The common carrier is alumina with different structures and different specific surface areas, the main active component is Pd metal with hydrogenation catalytic activity, and the auxiliary active component is Cu, ag, au and the like. The preparation method mainly adopts an impregnation-roasting method, namely, a solution containing active components (mostly saline solution) is fully contacted with a prepared carrier, so that the active components are loaded on the carrier, and the carrier is roasted at high temperature after being dried, so that metal salts are decomposed into corresponding oxides. The active components in the calcined catalyst are usually present in the form of oxides and are reduced with hydrogen for hydrogenation reactions.
In the preparation process of the catalyst, the physical properties and microstructure of the alumina carrier have great influence on the performance of the catalyst, and many related researches have been carried out. Chinese patent CN101062483a discloses a method for preparing a catalyst using porous metal as a carrier, after forming a dense oxide layer on the surface of the porous metal, coating a sol of inorganic oxide, drying and roasting to form a carrier intermediate layer, and then loading a metal active component.
Chinese patent CN106669850a discloses a preparation method of alumina carrier, which uses chloroaluminate modified pseudo-boehmite as raw material, and adds boric acid or phosphoric acid compound, alkyl chloride and binder, and then extrusion-forming-drying and roasting are carried out after uniform mixing to obtain macroporous alumina carrier. The carrier prepared by the method has larger pore diameter and pore volume and double pore distribution.
U.S. patent No. 6794552 discloses a method for modifying an alumina carrier, which uses molten zinc nitrate or magnesium nitrate to impregnate a hot alumina carrier, forms a Zn-Al or Mg-Al spinel structure on the surface of the alumina carrier, and loads metal active components such as Pd.
The existing technical scheme for improving the performance of alkyne selective hydrogenation catalyst by optimizing the preparation method of the alumina carrier has the defects of long and complex preparation flow and high production cost, and the physical properties of different batches of alumina carriers are not stable enough, so that the catalyst performance is unstable. The alkyne selective hydrogenation catalyst with simple preparation method, small performance fluctuation and better selectivity still needs to be developed.
Disclosure of Invention
In order to solve the technical problems, the invention provides an alkyne selective hydrogenation catalyst which is prepared by an improved alumina carrier preparation method. During the preparation of the alumina carrier, addAn amount of alpha-Al 2 O 3 Powder, alpha-Al used 2 O 3 The particle size, impurity content and the like of the powder are required to meet certain conditions. The prepared alumina carrier has the advantages of low bulk density, high water absorption, large pore volume and large average pore diameter. Because the pore volume of the alumina carrier is increased and the water absorption rate is increased, the active metal Pd can be more uniformly distributed on the surface of the alumina carrier, so that a Pd catalyst with high dispersity is formed, meanwhile, because the average pore diameter is increased, the alkene generated by alkyne selective hydrogenation can be more rapidly diffused, the alkane is prevented from being formed by excessive hydrogenation, and the selectivity is better.
One of the purposes of the invention is to provide an alkyne selective hydrogenation catalyst which comprises a main active component Pd, an optional auxiliary metal active component and an alumina carrier, wherein the alumina carrier has water absorption of 40-70%, pore volume of 0.6-0.9 ml/g and most probable pore diameter of 0.100-0.300 mu m.
Preferably, the metal-assisted active component is selected from at least one of Ag, bi, cu, au, pb, zn, ga, preferably Ag, bi, zn, ga;
in the catalyst, the content of Pd as the main active component is 0.02-0.3%, and the content of the auxiliary metal active component is 0-0.6%, preferably 0-0.3%;
the water absorption rate of the alumina carrier is 50-65%, the pore volume is 0.63-0.8 ml/g, and the most probable pore diameter is 0.120-0.250 mu m;
the specific surface area of the alumina carrier is 5-120 m 2 Per gram, bulk density of 0.3-0.9 g/ml, strength of 20-200 Nm; preferably, the specific surface area of the alumina carrier is 20-100 m 2 Per gram, bulk density of 0.5-0.8 g/ml, strength of 30-100 Nm;
the alumina carrier also contains 0.01-1wt% of alkali metal element, alkaline earth metal element and/or rare earth metal element, so as to further improve the strength, specific surface area, pore volume and the like. Wherein the alkali metal element is at least one of Na, K and Li; the alkaline earth metal element is at least one selected from Mg and Ca; the rare earth metal element is selected from at least one of La, ce, pr, Y, preferably selected from at least one of La and Ce.
The second object of the present invention is to provide a method for preparing the alkyne selective hydrogenation catalyst, which comprises loading components including the main active component Pd and the auxiliary metal active component on the alumina carrier to obtain the alkyne selective hydrogenation catalyst, and preferably, the preparation method specifically comprises: immersing the components containing the alumina carrier into a metal compound solution containing Pd compounds and auxiliary metal compounds, and drying and roasting to obtain the alkyne selective hydrogenation catalyst.
In particular, the method comprises the steps of,
the Pd compound is selected from soluble compounds of metal Pd, preferably at least one selected from palladium nitrate, palladium chloride and palladium acetate;
the auxiliary metal compound is at least one selected from the group consisting of Ag, bi, cu, au, pb, zn, ga chloride, nitrate and acetate, preferably Ag, bi, zn, ga chloride and nitrate;
the amount of the metal compound solution is 40 to 90%, preferably 40 to 70%, of the amount of the alumina carrier in terms of saturated water absorption of the alumina carrier.
In the above preparation method, the metal compound solution may be supported on the carrier by impregnation means commonly used in the art, such as spraying, isovolumetric impregnation, supersaturation impregnation, or the like. When a plurality of metal-assisting active components are loaded, a one-step loading method can be adopted, and a step loading method can also be adopted. A one-step loading method is used for preparing mixed solution of two or more metal-assisting active components, and then the mixed solution is loaded on a carrier by the one-step method; the step-by-step loading method is to prepare solutions of several active component precursors respectively and load the solutions on the carrier respectively, and the next loading is carried out after drying and roasting are needed after each loading.
In the preparation method, the drying and roasting conditions are not particularly required, and the drying and roasting conditions commonly used in the field can be adopted, preferably, the drying temperature is 40-150 ℃ and the drying time is 4-48 hours; preferably, the drying temperature is 50-120 ℃ and the drying time is 8-24 hours; the roasting time varies according to the content of the metal active component, the content of the metal active component is increased, and the roasting time can be correspondingly increased, specifically, the roasting time is 2-15 hours, preferably 3-9 hours; the roasting temperature is 300-500 ℃.
In the preparation method, the preparation method of the alumina carrier comprises the steps of powder mixing, kneading molding, drying and roasting, and specifically comprises the following steps:
step 1, uniformly mixing components including alumina powder and additives to obtain powder to be kneaded;
step 2, adding an acidic aqueous solution into the powder to be kneaded for kneading and molding;
and step 3, drying and roasting the kneaded product to obtain the alumina carrier.
In the step 1, the alumina powder comprises pseudo-boehmite powder and alpha-Al 2 O 3 Powder, and optionally alumina trihydrate powder and/or fast deoxidizing aluminum powder.
Wherein the pseudo-boehmite powder can be common pseudo-boehmite, preferably the specific surface area of the pseudo-boehmite powder is 200-300 m 2 Per gram, pore volume of 0.5-1.2 ml/g and bulk density of 0.2-0.4 g/ml.
The alpha-Al 2 O 3 The powder can be obtained by roasting high-purity aluminum hydroxide at a temperature of above 1300deg.C, and fluorine-containing compound can be added during roasting to form flaky alumina particles 2 O 3 The F content in the powder is not more than 0.1%; the alpha-Al 2 O 3 The powder can also be obtained by roasting pseudo-boehmite powder used for molding, and the roasting temperature is higher than 1300 ℃. Preferably, the alpha-Al 2 O 3 alpha-Al in the powder 2 O 3 The content is more than 95%, the particle diameter of the powder is 2-100 mu m, and the mass content of Na, fe and Si is less than 0.1%. The alpha-Al 2 O 3 The powder is 5-30wt%, preferably 5-20wt% of the total weight of the alumina powder.
The aluminum oxide trihydrate and the aluminum oxide rapid deoxidization can be prepared from common components, for example, aluminum oxide trihydrate powder can be at least one of gibbsite, bayerite and nordstranite, and the aluminum oxide rapid deoxidization powder is prepared by rapid dehydration of aluminum hydroxide, wherein the mass content of Na and Fe is less than 0.1%; the weight of the alumina powder body of the trihydrate accounts for 0-10% of the total weight of the alumina powder body; the mass of the rapid deoxidized aluminum powder accounts for 0-10% of the total mass of the aluminum oxide powder.
In the step 1, the additive is at least one selected from silicon-containing compounds and forming pore-forming auxiliary agents, and the dosage of the additive is 0-20% of the total mass of the alumina carrier, preferably 0-10%. Wherein the silicon-containing compound is selected from water-insoluble silicon-containing compounds, preferably at least one of dry silica gel, nano silica and silicon carbide; among them, the average particle size of the nano silicon oxide and the dry silica gel is preferably less than 120nm. The shaping pore-forming auxiliary agent is at least one of natural organic matters, high molecular polymers and decomposable alkaline compounds, preferably at least one of sesbania powder, starch, methyl cellulose, hydroxypropyl methyl cellulose, sodium hydroxymethyl cellulose, polyethylene microspheres, polystyrene, polyethylene oxide, polyethylene glycol, polyvinyl alcohol, sodium polyacrylate, polyethylene glycol, polyacrylate acrylic acid, urea, methylamine, ethylenediamine, ammonium carbonate and ammonium bicarbonate; one skilled in the art can empirically select one or more shaping pore-forming aids.
In the step 2, the acid in the acidic aqueous solution is at least one selected from organic acid, inorganic acid and acidic salt compound, preferably at least one selected from hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, citric acid and ammonium dihydrogen phosphate; the mass percentage concentration of the acid in the acidic aqueous solution is 0.1-10%, preferably 0.1-5%. The weight ratio of the acidic aqueous solution to the powder to be kneaded is 0.5-5: 1, preferably 0.6 to 2:1. the amount of acid in the acidic aqueous solution can be adjusted by those skilled in the art based on the plasticity of the kneaded dough and the specific surface area, strength, bulk density and the like of the carrier after high-temperature firing.
Soluble auxiliary agents are also added into the acidic aqueous solution, and the soluble auxiliary agents are selected from at least one of alkali metal compounds, alkaline earth metal compounds and rare earth metal compounds. Wherein the alkali metal compound is selected from inorganic salt compounds of metals Na, K and Li, preferably at least one selected from nitrate and chloride of metals Na, K and Li; the alkaline earth metal compound is selected from inorganic salt compounds of metal Mg and Ca, preferably at least one of nitrate and chloride of metal Mg and Ca; the rare earth metal compound is selected from at least one of soluble rare earth metal salt compounds, preferably selected from nitrate and chloride of La, ce, pr, Y, more preferably selected from nitrate and chloride of La and Ce; the metal in the soluble auxiliary agent accounts for 0 to 1.35 percent, preferably 0 to 0.9 percent of the total usage of the alumina powder in terms of the mass percent of metal elements.
In the step 3, the drying temperature is 60-150 ℃ and the drying time is 3-48 hours; the roasting temperature is 800-1200 ℃ and the roasting time is 3-48 hours; in the roasting process, the temperature rising rate is 30-150 ℃/h at the temperature below 500 ℃, and the temperature rising rate is 100-280 ℃/h at the temperature above 500 ℃.
The invention also provides the alkyne selective hydrogenation catalyst or the alkyne selective hydrogenation catalyst prepared by the preparation method, which is used for alkyne hydrogenation reaction.
According to a specific embodiment of the present invention, the catalyst is reduced prior to use, preferably under the following conditions: the reducing atmosphere is an atmosphere with the hydrogen content not lower than 50%, the reducing reaction temperature is 80-200 ℃, and the reducing reaction time is 2-12 h;
when the catalyst is used for the selective hydrogenation reaction of the carbon two fractions, the percentage content of acetylene in the carbon two fractions is 1.0-5.0%, the reaction temperature is 20-120 ℃, and the reaction airspeed is 3000-12000 h -1 The method comprises the steps of carrying out a first treatment on the surface of the Or alternatively, the first and second heat exchangers may be,
when the catalyst is used for the selective hydrogenation reaction of the carbon three-fraction, the percentage content of propyne and propadiene in the carbon three-fraction is 1.0-5.0%, the reaction temperature is 30-70 ℃, and the reaction space velocity is high20 to 120 hours -1 。
In the invention, alpha-Al is added in the preparation process of the alumina carrier 2 O 3 The powder can obtain the alumina carrier with larger pore volume, pore diameter and water absorption and smaller bulk density. On the alumina carrier, pd active components, ag, au, zn and other auxiliary active components are loaded, and the alkyne selective hydrogenation catalyst with stable performance and better selectivity can be obtained through proper baking and roasting steps.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The test instruments and test conditions used in the examples are as follows:
the specific surface area is measured by adopting a nitrogen physical adsorption BET method;
bulk density is calculated by measuring the mass of 100mL of alumina carrier, and average value is obtained after each sample is measured for 3 times;
pore volume and the most probable pore diameter are measured by mercury intrusion method, and are carried out by referring to the pore volume measuring method of the common alumina carrier;
the strength is measured by a universal particle strength measuring instrument, and the average value of 20 particle carrier measurement results is taken;
the water absorption is obtained by taking 20g of alumina carrier, immersing in water for 10 minutes, taking out, draining off surface water, and measuring weight increment.
Example 1
The preparation method of the alumina carrier comprises the following steps: 180g of pseudo-boehmite powder and 20g of alpha-Al are weighed 2 O 3 The powder, 8g sesbania powder and 10g starch are mixed uniformly in a mixer and transferred into a kneader. Wherein the specific surface area of the pseudo-boehmite powder is 252.4m 2 Per g, pore volume 0.944ml/g, bulk density 0.33g/ml; alpha-Al 2 O 3 The powder is obtained by roasting pseudo-boehmite at 1400℃, and the alpha-Al thereof 2 O 3 The content is 98.0%, the average grain diameter is 5 μm, and the mass content of Na, fe and Si is less than 0.01%. 2.00g of concentrated nitric acid, 2.00g of acetic acid and 1.517g of lanthanum nitrate are weighed and added into 200g of deionized water to prepare a mixed solution. Adding the mixed solution into the uniformly mixed powder, fully kneading, extruding, molding and granulating to obtain 4-6 mm-diameter tooth spherical particles. Baking at 120deg.C for 12hr, and baking at 1175deg.C for 6hr, wherein the heating rate is controlled at 100deg.C/hr below 600deg.C and 200deg.C/hr above 500deg.C to obtain alumina carrier with La load of 0.35%.
Active metal loading method: 5mL of palladium nitrate solution containing 10mg Pd/mL is weighed, 0.079g of silver nitrate is added to the palladium nitrate solution, diluted to 58mL with deionized water, and sprayed onto 100g of alumina carrier. The sprayed sample was dried at 120℃for 6 hours and calcined at 500℃for 8 hours to obtain a catalyst S1 having a Pd content of 0.05 mass% and an Ag content of 0.05 mass%.
Example 2
The preparation method of the alumina carrier comprises the following steps: 150g of pseudo-boehmite powder and 50g of alpha-Al are weighed 2 O 3 Powder, 6g of sesbania powder, 5g of starch and 3g of crosslinked polyethylene microspheres with the particle size of about 40 microns are uniformly mixed in a mixer and transferred into a kneader. Wherein the specific surface area of the pseudo-boehmite powder is 252.4m 2 Per g, pore volume 0.944ml/g, bulk density 0.33g/ml; alpha-Al 2 O 3 The powder is obtained by roasting pseudo-boehmite at 1500℃, and the alpha-Al thereof 2 O 3 The content is 99.5%, the average grain diameter is 12 μm, and the mass content of Na, fe and Si is less than 0.01%. 3.00g of concentrated nitric acid, 1.745g of cerium nitrate, was weighed and added to 200g of deionized water to prepare a mixed solution. Adding the mixed solution into the uniformly mixed powder, fully kneading, extruding, molding and granulating to obtain 4-6 mm-diameter tooth spherical particles. The drying conditions are the same as in example 1, the roasting temperature raising process is the same as in example 1, the roasting temperature is 1165 ℃, and the alumina carrier with Ce loading of 0.40% is obtained.
Active metal loading method: 5mL of palladium nitrate solution containing 10mg Pd/mL is measured, diluted to 58mL by deionized water, sprayed onto 100g of alumina carrier, dried at 120 ℃ for 6h and baked at 500 ℃ for 8h, and the Pd-containing catalyst precursor is obtained. 0.110g of silver nitrate and 0.045g of zinc nitrate were weighed, a 58mL solution was prepared using deionized water, sprayed onto 100g of the Pd-containing catalyst precursor prepared above, and dried at 120℃for 6 hours and calcined at 500℃for 8 hours to obtain catalyst S2 having a Pd content of 0.05 mass%, an Ag content of 0.07 mass% and a Zn content of 0.01 mass%.
Example 3:
the preparation method of the alumina carrier comprises the following steps: 170g of pseudo-boehmite powder and 20g of alpha-Al are weighed 2 O 3 Powder, 10g of alumina trihydrate powder, 6g of sesbania powder and 5g of urea are uniformly mixed in a mixer and transferred into a kneader. Wherein the specific surface area of the pseudo-boehmite powder is 257.9m 2 Per gram, pore volume of 1.16ml/g, bulk density of 0.23g/ml; alpha-Al 2 O 3 The powder is obtained by roasting high-purity aluminum hydroxide at 1500 ℃, the average grain diameter of the powder is 75 mu m, and the alpha-Al 2 O 3 99.5% of Na, fe and Si, and about 0.05% of Si. The same as in example 1. 2.00g of concentrated nitric acid, 1g of acetic acid and 1.517g of lanthanum nitrate are weighed and added into 190g of deionized water to prepare a mixed solution. Adding the mixed solution into the uniformly mixed powder, fully kneading, extruding, molding and granulating to obtain 4-6 mm-diameter tooth spherical particles. The drying conditions were the same as in example 1, and the calcination procedure was the same as in example 1, at 1180℃to give an alumina support having a La loading of 0.35%.
Active metal loading method: 5mL of palladium nitrate solution containing 10mg Pd/mL is measured, diluted to 58mL by deionized water, sprayed onto 100g of alumina carrier, dried at 120 ℃ for 6h and baked at 500 ℃ for 8h, and the Pd-containing catalyst precursor is obtained. 0.146g of chloroauric acid was weighed, prepared into 58mL of solution using deionized water, sprayed onto 100g of the Pd-containing catalyst precursor prepared above, dried at 120℃for 6 hours and calcined at 500℃for 8 hours to obtain catalyst S3 having a Pd content of 0.05 mass% and an Au content of 0.07 mass%.
Example 4:
the preparation method of the alumina carrier comprises the following steps: 170g of pseudo-boehmite powder and 20g of alpha-Al are weighed 2 O 3 Powder, 10g of quick deoxidized aluminum powder, 6g of sesbania powder and 6g of starch are uniformly mixed in a mixer and transferred into a kneader. Wherein the physical properties of the pseudo-boehmite powder are the same as those of the pseudo-boehmite powderExample 1; alpha-Al 2 O 3 The powder is obtained by roasting high-purity aluminum hydroxide at 1500 ℃, ammonium fluoride is added in the roasting process, and the formed alpha-Al 2 O 3 The powder crystal grain is in the shape of flake, the average grain diameter is 51 mu m, and the alpha-Al 2 O 3 99.5% of Na, fe and Si, and about 0.05% of Si. 2.00g of concentrated nitric acid, 1g of acetic acid and 8.936g of magnesium nitrate were weighed and added to 190g of deionized water to prepare a mixed solution. Adding the mixed solution into the uniformly mixed powder, fully kneading, extruding, molding and granulating to obtain 4-6 mm-diameter tooth spherical particles. The drying conditions were the same as in example 1, and the calcination procedure was the same as in example 1, at 1180℃to give an alumina support having an Mg loading of 0.60%.
Active metal loading method: 5mL of palladium nitrate solution containing 10mg Pd/mL is measured, diluted to 58mL by deionized water, 0.079g of silver nitrate is added, the mixture is sprayed on 100g of alumina carrier, and the mixture is dried at 120 ℃ for 6h and baked at 500 ℃ for 8h to obtain a Pd-containing catalyst precursor. 0.052g of gallium nitrate is weighed, 58mL of solution is prepared by using deionized water, a small amount of dilute nitric acid can be added to promote dissolution, the solution is sprayed onto 100g of Pd-containing catalyst precursor prepared above, and the catalyst is dried at 120 ℃ for 6 hours and baked at 500 ℃ for 8 hours to obtain catalyst S4, wherein the Pd content is 0.05 mass%, the Ag content is 0.04 mass% and the Ga content is 0.01 mass%.
Comparative example 1:
the preparation method of the alumina carrier comprises the following steps: 200g of pseudo-boehmite powder, 8g of sesbania powder and 4g of starch are weighed, uniformly mixed in a mixer and transferred into a kneader. Wherein the specific surface area of the pseudo-boehmite powder is 189.9m 2 Per g, pore volume 0.804ml/g, bulk density 0.25g/ml. 2.80g of concentrated nitric acid was weighed and added to 200g of deionized water to prepare a mixed solution. Adding the mixed solution into the uniformly mixed powder, fully kneading, extruding, molding and granulating to obtain 4-6 mm-diameter tooth spherical particles. The drying conditions were the same as in example 1, and the calcination procedure was the same as in example 1, at 1195℃to obtain an alumina carrier.
Active metal loading method: 5mL of palladium nitrate solution containing 10mg Pd/mL is weighed, 0.016g of silver nitrate is weighed and added to the palladium nitrate solution, deionized water is used for diluting to 58mL, and the solution is sprayed onto 100g of alumina carrier. The sprayed sample was dried at 120℃for 6 hours and calcined at 500℃for 8 hours to obtain catalyst D1 having a Pd content of 0.05 mass% and an Ag content of 0.01 mass%.
Comparative example 2:
the preparation method of the alumina carrier comprises the following steps: 190g of pseudo-boehmite powder and 10g of alpha-Al are weighed 2 O 3 The powder, 8g sesbania powder and 4g starch are mixed uniformly in a mixer and transferred into a kneader. Wherein the physical properties of the pseudo-boehmite powder are the same as those of comparative example 1, alpha-Al 2 O 3 The powder is obtained by roasting common aluminum hydroxide at 1300 ℃, and the average grain diameter of the powder is 4 mu m, alpha-Al 2 O 3 93.9%, si 0.2%, na and Fe 0.1%. 2.80g of concentrated nitric acid was weighed and added to 200g of deionized water to prepare a mixed solution. Adding the mixed solution into the uniformly mixed powder, fully kneading, extruding, molding and granulating to obtain 4-6 mm-diameter tooth spherical particles. The baking conditions were the same as in comparative example 1 to obtain an alumina carrier.
Active metal loading method: as in comparative example 1.
Experimental example 1:
the S1-S4 and D1-D2 catalysts are subjected to a carbon two-selective hydrogenation evaluation experiment, and the reaction conditions are as follows:
5ml of the catalyst was charged into a 316L stainless steel reaction tube, and after the substitution with nitrogen, the reaction materials were introduced into the reactor. The composition (mole fraction) of the reaction raw materials is as follows: hydrogen 0.6%, acetylene 0.4%, ethane 6.56%, ethylene 92.44%. The reaction pressure is 1MPa, the reaction temperature is 90 ℃, and the reaction space velocity is 8000hr -1 . The experimental results are shown in table 1.
TABLE 1 catalytic reactivity of the catalysts obtained in examples 1 to 4 and comparative examples 1 to 2
Selectivity (%) Reactor outlet acetylene content (μg/g)
S1 53 55
S2 58 42
S3 47 60
S4 56 46
D1 35 79
D2 40 68
Example 5:
the preparation method of the alumina carrier comprises the following steps: as in example 1.
Active metal loading method: 25mL of palladium nitrate solution containing 10mg Pd/mL was measured, diluted to 58mL with deionized water, and sprayed onto 100g alumina support. The sprayed sample was dried at 120℃for 6 hours and calcined at 550℃for 8 hours to give catalyst S5 having a Pd content of 0.25% by mass.
Example 6:
the preparation method of the alumina carrier comprises the following steps: 188g of pseudo-boehmite powder, 12 g ofgα-Al 2 O 3 The powder, 8g sesbania powder, 2g cellulose and 3g ammonium carbonate are mixed uniformly in a mixer and transferred into a kneader. Wherein the specific surface area of the pseudo-boehmite powder is 245.7m 2 Per g, pore volume 0.869ml/g, bulk density 0.22g/ml; alpha-Al 2 O 3 The powder was the same as in example 1. 1.00g of concentrated nitric acid, 3g of acetic acid and 0.365g of potassium nitrate were weighed and added to 200g of deionized water to prepare a mixed solution. Adding the mixed solution into the uniformly mixed powder, fully kneading, extruding, molding and granulating to obtain 4-6 mm-diameter tooth spherical particles. The conditions for baking and roasting were the same as in example 1 to obtain an alumina carrier having a K loading of 0.10%.
Active metal loading method: 25mL of palladium nitrate solution containing 10mg Pd/mL is measured, diluted to 58mL by deionized water, sprayed onto 100g of alumina carrier, dried at 120 ℃ for 6h and baked at 550 ℃ for 8h, thus obtaining Pd-containing catalyst precursor. 0.209g of chloroauric acid was weighed, prepared into 58mL of solution using deionized water, sprayed onto 100g of the Pd-containing catalyst precursor prepared above, dried at 120℃for 6 hours, and calcined at 550℃for 8 hours to obtain catalyst S6 having a Pd content of 0.25 mass% and an Au content of 0.1 mass%.
Example 7:
the preparation method of the alumina carrier comprises the following steps: same as in example 4.
Active metal loading method: 25mL of palladium nitrate solution containing 10mg Pd/mL is measured, diluted to 58mL by deionized water, sprayed onto 100g of alumina carrier, dried at 120 ℃ for 6h and baked at 550 ℃ for 8h, thus obtaining Pd-containing catalyst precursor. 0.259g of gallium nitrate is weighed, 58mL of solution is prepared by using deionized water, a small amount of dilute nitric acid can be added to promote dissolution, the solution is sprayed onto 100g of Pd-containing catalyst precursor prepared above, and the catalyst is dried at 120 ℃ for 6 hours and baked at 500 ℃ for 8 hours to obtain a catalyst S7, wherein the Pd content is 0.25 mass percent and the Ga content is 0.05 mass percent.
Comparative example 3:
the preparation method of the alumina carrier comprises the following steps: as in comparative example 1.
Active metal loading method: 35mL of palladium nitrate solution containing 10mg Pd/mL was measured, diluted to 58mL with deionized water, and sprayed onto 100g alumina support. The sprayed sample was dried at 120℃for 6 hours and calcined at 550℃for 8 hours to give catalyst D3 having a Pd content of 0.35% by mass.
Experimental example 2:
the catalysts S5 to S7 and D3 were subjected to a carbon three-fraction propyne and propadiene selective hydrogenation side stream experiment under the following reaction conditions, 92ml of the catalyst was charged into a stainless steel tube reactor, and after the catalyst was replaced with nitrogen, the reaction raw materials were charged with hydrogen and then introduced into the reactor. The composition (mole fraction) of the reaction raw materials is 4.99% of propane, 92.3% of propylene, 1.19% of allene and 1.39% of propyne, the content ratio of hydrogen to alkyne is about 1.4-1.6, and the experimental airspeed is 70h -1 After 100hr of reaction, the reaction results are shown in Table 2 below:
TABLE 2 catalytic Properties of the catalysts obtained in examples 5 to 7 and comparative example 3
Catalyst MAPD conversion (%) MAPD Selectivity (%)
S5 99.1 71
S6 98.7 74
S7 99.5 75
D3 97.4 63
The physical properties of the alumina carriers used in the above examples and comparative examples are shown in Table 3 below:
TABLE 3 physical Property data of alumina supports in examples and comparative examples
Figure BDA0003325314840000131
According to the physical property data table of the alumina carrier, the S1-S4 and S6 alumina carriers prepared by the method have high water absorption rate, large pore volume and large most probable pore diameter, and the specific surface area of the S1-S4 and S6 alumina carriers obtained by testing is 20-50 m 2 And/g. Alkyne selective hydrogenation catalysts prepared based on these supports exhibit higher activity and selectivity in both carbon two-cut selective hydrogenation and carbon three-cut selective hydrogenation reactions.

Claims (14)

1. The alkyne selective hydrogenation catalyst comprises a main active component Pd, an optional auxiliary metal active component and an alumina carrier, wherein the alumina carrier has water absorption of 40-70%, pore volume of 0.6-0.9 ml/g and most probable pore diameter of 0.100-0.300 mu m.
2. The catalyst of claim 1, wherein the catalyst is,
the auxiliary metal active component is selected from at least one of Ag, bi, cu, au, pb, zn, ga, preferably Ag, bi, zn, ga; and/or the number of the groups of groups,
in the catalyst, the content of the main active component Pd is 0.02-0.3% by mass percent; and/or the number of the groups of groups,
the content of the auxiliary metal active component in the catalyst is 0 to 0.6 percent by mass percent; preferably 0 to 0.3%.
3. The catalyst of claim 1, wherein the catalyst is,
the water absorption rate of the alumina carrier is 50-65%, the pore volume is 0.63-0.8 ml/g, and the most probable pore diameter is 0.120-0.250 mu m; and/or the number of the groups of groups,
the specific surface area of the alumina carrier is 5-120 m 2 Per gram, bulk density of 0.3-0.9 g/ml, strength of 20-200 Nm; preferably, the specific surface area of the alumina carrier is 20-100 m 2 Per gram, bulk density of 0.5-0.8 g/ml and strength of 30-100 Nm.
4. The catalyst of claim 1, wherein the catalyst is,
the alumina carrier also contains 0.01 to 1 weight percent of alkali metal element, alkaline earth metal element and/or rare earth metal element; preferably, the alkali metal element is at least one of Na, K and Li; the alkaline earth metal element is at least one selected from Mg and Ca; the rare earth metal element is at least one selected from La, ce, pr, Y.
5. A method for preparing an alkyne selective hydrogenation catalyst according to any one of claims 1 to 4, comprising loading components comprising the main active component Pd and the auxiliary metal active component on the alumina carrier to obtain the alkyne selective hydrogenation catalyst, preferably, the preparation method specifically comprises: immersing the components containing the alumina carrier into a metal compound solution containing Pd compounds and auxiliary metal compounds, and drying and roasting to obtain the alkyne selective hydrogenation catalyst.
6. The method according to claim 5, wherein,
the Pd compound is selected from soluble compounds of metal Pd, preferably at least one selected from palladium nitrate, palladium chloride and palladium acetate; and/or the number of the groups of groups,
the auxiliary metal compound is at least one selected from the group consisting of Ag, bi, cu, au, pb, zn, ga chloride, nitrate and acetate, preferably Ag, bi, zn, ga chloride and nitrate; and/or the number of the groups of groups,
the amount of the metal compound solution is 40 to 90%, preferably 40 to 70%, of the amount of the alumina carrier in terms of saturated water absorption of the alumina carrier.
7. The method according to claim 5, wherein,
the drying temperature is 40-150 ℃ and the drying time is 4-48 h; preferably, the drying temperature is 50-120 ℃ and the drying time is 8-24 hours; and/or the number of the groups of groups,
the roasting temperature is 300-500 ℃; and/or the number of the groups of groups,
the roasting time is 2-15 h, preferably 3-9 h.
8. The preparation method of the alumina carrier according to claim 5, wherein the preparation method comprises the steps of powder mixing, kneading molding, drying and roasting, and specifically comprises the following steps:
step 1, uniformly mixing components including alumina powder and additives to obtain powder to be kneaded;
step 2, adding an acidic aqueous solution into the powder to be kneaded for kneading and molding;
and step 3, drying and roasting the kneaded product to obtain the alumina carrier.
9. The method according to claim 8, wherein,
the alumina powder comprises pseudo-boehmite powder and alpha-Al 2 O 3 Powder, and optionally alumina trihydrate powder and/or fast deoxidized aluminum powder; and/or the number of the groups of groups,
the additive is at least one selected from silicon-containing compounds and forming pore-forming auxiliary agents; and/or the number of the groups of groups,
the acid in the acidic aqueous solution is at least one selected from organic acid, inorganic acid and acidic salt compounds, preferably at least one selected from hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, citric acid and ammonium dihydrogen phosphate; and/or the number of the groups of groups,
the mass percentage concentration of the acid in the acidic aqueous solution is 0.1-10%, preferably 0.1-5%; and/or the number of the groups of groups,
the weight ratio of the acidic aqueous solution to the powder to be kneaded is 0.5-5: 1, preferably 0.6 to 2:1, a step of; and/or the number of the groups of groups,
the acidic aqueous solution is further added with a soluble auxiliary agent, preferably, the soluble auxiliary agent is at least one selected from alkali metal compounds, alkaline earth metal compounds and rare earth metal compounds.
10. The method according to claim 9, wherein,
the specific surface area of the pseudo-boehmite powder is 200-300 m 2 Per gram, pore volume of 0.5-1.2 ml/g and bulk density of 0.2-0.4 g/ml; and/or the number of the groups of groups,
the alpha-Al 2 O 3 alpha-Al in the powder 2 O 3 The content is more than 95%, the particle diameter of the powder is 2-100 mu m, and the mass content of Na, fe and Si is less than 0.1%; and/or the number of the groups of groups,
the alpha-Al 2 O 3 The powder is 5-30wt%, preferably 5-20wt% of the total weight of the alumina powder; and/or the number of the groups of groups,
the weight of the alumina powder body of the trihydrate accounts for 0-10% of the total weight of the alumina powder body; and/or the number of the groups of groups,
the mass of the rapid deoxidized aluminum powder is 0-10% of the total mass of the aluminum oxide powder; and/or the number of the groups of groups,
the silicon-containing compound is selected from water-insoluble silicon-containing compounds, preferably at least one of dry silica gel, nano silica and silicon carbide; and/or the number of the groups of groups,
the Si element in the silicon-containing compound is 0 to 1.35 percent of the total weight of the alumina powder, preferably 0 to 0.9 percent; and/or the number of the groups of groups,
the shaping pore-forming auxiliary agent is at least one of natural organic matters, high molecular polymers and decomposable alkaline compounds, preferably at least one of sesbania powder, starch, methyl cellulose, hydroxypropyl methyl cellulose, sodium hydroxymethyl cellulose, polyethylene microspheres, polystyrene, polyethylene oxide, polyethylene glycol, polyvinyl alcohol, sodium polyacrylate, polyethylene glycol, polyacrylate acrylic acid, urea, methylamine, ethylenediamine, ammonium carbonate and ammonium bicarbonate; and/or the number of the groups of groups,
the dosage of the forming pore-forming auxiliary agent is 0-20% of the total mass of the alumina carrier, preferably 0-10%; and/or the number of the groups of groups,
the acid in the acidic aqueous solution is at least one selected from nitric acid, acetic acid, oxalic acid and citric acid; and/or the number of the groups of groups,
the alkali metal compound is selected from inorganic salt compounds of metals Na, K and Li, preferably at least one selected from nitrate and chloride of metals Na, K and Li; and/or the number of the groups of groups,
the alkaline earth metal compound is selected from inorganic salt compounds of metal Mg and Ca, preferably at least one of nitrate and chloride of metal Mg and Ca; and/or the number of the groups of groups,
the rare earth metal compound is selected from soluble rare earth metal salt compounds, preferably at least one selected from nitrate and chloride of La, ce, pr, Y; and/or the number of the groups of groups,
the metal in the soluble auxiliary agent accounts for 0 to 1.35 percent, preferably 0 to 0.9 percent of the total usage of the alumina powder in terms of the mass percent of metal elements.
11. The method according to claim 8, wherein,
the drying temperature is 60-150 ℃ and the drying time is 3-48 hours; and/or the number of the groups of groups,
the roasting temperature is 800-1200 ℃ and the roasting time is 3-48 hours; and/or the number of the groups of groups,
in the roasting process, the temperature rising rate is 30-150 ℃/h at the temperature below 500 ℃, and the temperature rising rate is 100-280 ℃/h at the temperature above 500 ℃.
12. The alkyne selective hydrogenation catalyst according to any one of claims 1 to 4 or the alkyne selective hydrogenation catalyst prepared by the preparation method according to any one of claims 5 to 11 for use in alkyne selective hydrogenation reactions.
13. The catalyst of claim 12, wherein the catalyst is,
the catalyst is reduced before use, preferably the reduction conditions are: the reducing atmosphere is the atmosphere with the hydrogen content not lower than 50 percent, the reducing reaction temperature is 80-200 ℃, and the reducing reaction time is 2-12 h.
14. The catalyst of claim 12, wherein the catalyst is,
when the catalyst is used for the selective hydrogenation reaction of the carbon two fractions, the percentage content of acetylene in the carbon two fractions is 1.0-5.0%, the reaction temperature is 20-120 ℃, and the reaction airspeed is 3000-12000 h -1 The method comprises the steps of carrying out a first treatment on the surface of the Or alternatively, the first and second heat exchangers may be,
when the catalyst is used for the selective hydrogenation reaction of the carbon three-fraction, the percentage content of propyne and propadiene in the carbon three-fraction is 1.0-5.0%, the reaction temperature is 30-70 ℃, and the reaction space velocity is 20-120 h -1 。
CN202111260277.4A 2021-10-28 2021-10-28 Alkyne selective hydrogenation catalyst and preparation method and application thereof Pending CN116037084A (en)

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