CN112452340A - Catalyst for preparing propylene by selective hydrogenation of propyne, and preparation method and application thereof - Google Patents

Catalyst for preparing propylene by selective hydrogenation of propyne, and preparation method and application thereof Download PDF

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CN112452340A
CN112452340A CN202011320829.1A CN202011320829A CN112452340A CN 112452340 A CN112452340 A CN 112452340A CN 202011320829 A CN202011320829 A CN 202011320829A CN 112452340 A CN112452340 A CN 112452340A
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catalyst
temperature
propyne
metal
carrier
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CN112452340B (en
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罗军
杨卫东
高军
田俊凯
范昌海
陆朝阳
亓虎
李亚萍
周轶
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Zhejiang Satellite Energy Co ltd
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth 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
    • B01J23/38—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
    • B01J23/56—Platinum group metals
    • B01J23/60—Platinum group metals with zinc, cadmium or mercury
    • 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
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    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/56—Platinum group metals
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    • C07—ORGANIC CHEMISTRY
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    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with alkali- or alkaline earth metals or beryllium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
    • 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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Abstract

The invention relates to a preparation method of a catalyst, in particular to a catalyst for preparing propylene by selective hydrogenation of propine, a preparation method and application thereof, belonging to the technical field of organic chemistry. The catalyst for preparing propylene by selective hydrogenation of propyne is a supported noble metal catalyst, and the catalyst uses gamma-Al2O3Is the main component of the catalyst carrier, and MgO is adhered to the surface of the carrier to form a composite metal oxygen compound carrier; one or more of noble metals Ru, Pd and Pt are used as main active ingredients, and the content of the noble metals is 0.1-3.0 wt% based on the weight content of the final catalyst; one or more of non-noble metals Cu, Zn and CoAnd modifying the noble metal as an auxiliary metal, wherein the molar ratio of the noble metal to the non-noble metal is 1: 1-10.

Description

Catalyst for preparing propylene by selective hydrogenation of propyne, and preparation method and application thereof
Technical Field
The invention relates to a preparation method of a catalyst, in particular to a catalyst for preparing propylene by selective hydrogenation of propine, a preparation method and application thereof, belonging to the technical field of organic chemistry.
Background
The propylene is the second basic chemical raw material of the petrochemical industry, the dosage of the propylene is second to that of the ethylene, the largest dosage of the propylene is used for producing the polypropylene, and in addition, the propylene can be used for producing acrylonitrile, isopropanol, phenol, acetone, butanol, octanol, acrylic acid and esters thereof, and preparing propylene oxide, propylene glycol, epichlorohydrin, synthetic glycerol and the like. The main process routes for producing propylene at present comprise: steam cracking process, catalytic cracking process, coal-to-olefin process, olefin disproportionation process and propane dehydrogenation process. With the trend of the propane dehydrogenation process technology towards maturity and the large-scale application of new energy shale gas, the process for preparing propylene by propane dehydrogenation has strong advantages, causes numerous investments of companies at home and abroad, and becomes a hot spot for the development of petrochemical industry in recent years.
The catalytic dehydrogenation of propane to produce propylene is an endothermic reaction requiring the provision of large amounts of heat, and the reaction is often accompanied by over-dehydrogenation of propane to produce propyne (MA) and Propadiene (PD). MAPD is a precursor of catalytic dehydrogenation catalyst poison coke, and when the catalyst coke enters the reactor again along with circulating propane, the phenomena of catalyst coking and reactor internal and external net blockage are easily caused; MAPD affects propylene polymerization and results in unacceptable polypropylene product when it comes with product propylene to downstream polypropylene plants. MAPD boiling point is very close to that of propane and propylene, and is difficult to remove from cryogenic separation unit and fractionating tower unit, so that after the liquid-phase product is discharged from cryogenic separation unit, hydrogenation equipment (SHP) must be added to make trace MAPD (MAPD) (About 100 ppm) is hydrogenated and converted into propylene, and the product yield is increased. The most applied catalyst on the SHP device in the present propane dehydrogenation process for producing propylene is Pd/Al2O3The catalyst shows good selective hydrogenation performance, but the catalytic performance of the catalyst is limited, and MAPD can not be well converted into propylene when the abnormal process condition MAPD exceeds the standard; if the liquid hourly space velocity is selected to increase the conversion of MAPD, propylene is easy to generate propane by catalytic hydrogenation, and product loss is caused.
Disclosure of Invention
The invention aims to provide a catalyst for preparing propylene by selective hydrogenation of propyne, which solves the problems of narrow reaction range, easy carbon deposition of the catalyst, poor catalyst selectivity and the like in the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a catalyst for preparing propylene by selective hydrogenation of propyne is a supported noble metal catalyst
With gamma-Al2O3Is the main component of the catalyst carrier, and MgO is adhered to the surface of the carrier to form a composite metal oxygen compound carrier;
one or more of noble metals Ru, Pd and Pt are used as main active ingredients, and the content of the noble metals is 0.1-3.0 wt% based on the weight content of the final catalyst;
one or more of non-noble metals Cu, Zn and Co are used as auxiliary metals to modify noble metals, and the molar ratio of the noble metals to the non-noble metals is 1: 1-10.
According to the invention, the selective hydrogenation catalyst with low noble metal loading, high dispersity and high mechanical strength is prepared by using noble metals Ru, Pd and Pt as main active components and a composite metal oxide compound as a carrier through an isometric impregnation method. The catalyst is used for preparing propylene by MAPD selective hydrogenation, the conversion rate and the selectivity of the catalyst are high, and the industrial application value is high.
The supported noble metal catalyst provided by the invention can effectively solve the defects of narrow reaction range, easy carbon deposition of the catalyst, poor catalyst selectivity and the like of the catalytic hydrogenation catalyst in the SHP device in the existing process for producing propylene by propane dehydrogenation.
Preferably, the amount of MgO supported is 5 to 30 wt%. The preferable weight percentage is 10-20%, and the catalyst carrier has more weak acid sites in the loading range, so that the catalyst carrier is more beneficial to the activation of hydrogen molecules, the timely desorption of propylene and the like.
Preferably, the MgO precursor is a 10-60 wt% magnesium nitrate aqueous solution. Further preferred is a 30wt% aqueous solution of magnesium nitrate.
A preparation method of a catalyst for preparing propylene by selective hydrogenation of propyne comprises the following steps:
（1）γ-Al2O3drying at 80-150 ℃ for 10-20 h, and dropwise adding the MgO precursor aqueous solution to the dried gamma-Al under stirring2O3Dipping, dehydrating, drying and roasting to obtain a composite oxygen compound carrier;
(2) dissolving noble metal salt and non-noble metal salt in dilute hydrochloric acid water solution to obtain mixed metal dipping solution;
(3) slowly dripping the mixed metal impregnation solution obtained in the step (2) onto the composite oxygen compound carrier obtained in the step (1) under stirring, and carrying out impregnation, washing, separation, drying and roasting to obtain a catalyst precursor;
(4) and (4) reducing the noble metal oxide in the catalyst precursor in the step (3) into a metal simple substance by using hydrogen, so that the catalyst has catalytic activity and performs catalytic reaction. The catalyst activation in step (4) is generally carried out in a tubular fixed bed during the selective hydrogenation of propyne to propylene. The concentration of dilute hydrochloric acid is generally about 1.0 mmol/L.
Preferably, in the step (1) and the step (3), the dipping time is 12-24 h, the drying temperature is 80-120 ℃, the drying time is 6-12 h, and the roasting condition is as follows: the heating rate is as follows: 5-12 ℃/min, raising the temperature from room temperature to 450-750 ℃, and keeping the temperature for 2-6 h.
Preferably, in the step (3), the washing step is specifically: the catalyst solution was washed with deionized water to be neutral and free of chloride ions.
Use of the catalyst of claim 1 for the selective catalytic hydrogenation of propyne to propylene.
Preferably, the liquid hourly space velocity is 20 +/-5 h-1In the case of the catalyst, the amount of the catalyst is 100 to 1000 mg. Most preferably 300mg (when the liquid hourly space velocity is 20 +/-2 h)-1Time).
Preferably, the method comprises the steps of:
loading the catalyst into a tubular fixed bed reactor, filling quantitative catalyst in a constant temperature area in the middle of the tubular fixed bed, filling the rest space with quartz sand, connecting the fixed tubes completely and airtightly, starting temperature programming, firstly increasing the temperature to 300-600 ℃ at a temperature rise rate of 5 +/-1 ℃/min, keeping the temperature for 2-5 h, keeping the hydrogen pressure at 0.5-3 MPa, activating the catalyst, and cooling the tubular fixed bed reactor to room temperature after the catalyst is completely reduced; and then conveying the mixture of the propyne and the cyclohexane to a tubular fixed bed reactor to perform hydrogenation reaction with hydrogen.
Preferably, the hydrogenation reaction conditions are as follows: reaction temperature: the hydrogen pressure is as follows at 30-80 ℃: 0.5-3 MPa, the molar concentration of the propyne in the cyclohexane is 0.01-1.0%, the molar ratio of the hydrogen to the propyne is 1.1-1.5, and the hourly space velocity (LHSV) of the reaction liquid is as follows: 10 to 30 hours-1。
Compared with the prior art, the catalyst has the advantages that:
1. with commercially available shaped gamma-Al2O3The composite oxygen compound carrier synthesized by the method has more weak acid sites, is more favorable for dissociation of a hydrocarbon single bond, and promotes hydrogen molecule activation, electron transfer and propylene desorption; dispersing the catalyst active metal; reduce the carbon deposit on the surface of the catalyst.
2. The non-noble metal Co has an important modification effect on the noble metal Pd, can change the electron cloud state, the dispersity and the microstructure of the metal Pd, promotes the desorption of the propylene and improves the selectivity of the propylene.
3. The catalyst has high selective hydrogenation performance, high process fluctuation resistance, high stability, high mechanical strength and good industrial application prospect.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.
In the present invention, all parts and percentages are by weight, unless otherwise specified, and the equipment and materials used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
The reagents used in the following examples, unless otherwise specified, were purchased from conventional biochemical reagent stores.
Since Propadiene (PD) is extremely unstable and difficult to prepare and use in large quantities in the laboratory, in the present invention, the catalyst performance test evaluation was carried out using propyne (MA) dissolved in cyclohexane as a reaction substrate model, and the molar concentrations of the reactants propyne were: 0.01 to 1.0%.
In the catalyst of the present invention, the catalyst carrier: gamma-Al2O3The synthesis can be carried out by using the existing commercial products or the laboratory according to the existing technology.
The concentration of the dilute hydrochloric acid solution described in the following examples was 1.0 mmol/L.
Example 1
A preparation method of a catalyst for preparing propylene by selective hydrogenation of propyne comprises the following specific steps:
1. accurately weighing 5g of dried gamma-Al2O3(the particle is about 30 meshes), placing the mixture into a 250mL beaker, weighing a certain amount of 30wt% magnesium nitrate solution according to the load of MgO of 10wt%, slowly adding the mixture into the beaker with stirring, soaking and aging for 24h, placing the beaker into an oven, drying the beaker at the constant temperature of 120 ℃ for 12h, and finally placing the beaker into the oven, drying the beaker at the constant temperature of 120 ℃ for 12hTransferring the bulk precursor into a crucible, placing the crucible in a muffle furnace for roasting, heating the crucible to 650 ℃ from room temperature at a heating rate of 5 ℃/min, keeping the temperature for 4 hours, cooling the crucible to room temperature to obtain a composite catalyst carrier, and placing the composite catalyst carrier in a closed dryer for later use.
2. Accurately weighing 3g of the composite catalyst carrier, and placing the composite catalyst carrier in a 100mL beaker; according to the loading amounts of metal palladium and metal cobalt: 0.3wt%, accurately weighing solid PdCl2And CoCl2·6H2Dissolving O (the molar ratio of metal platinum to metal cobalt is 1: 5) in a dilute hydrochloric acid solution, ultrasonically dissolving for 30min in an ultrasonic instrument, slowly adding 3g of the composite catalyst carrier into a beaker, stirring while adding, carrying out equal-volume soaking and aging for 24h, then carrying out suction filtration, washing with deionized water until the solution is neutral, and using AgNO to wash3Detecting that no white precipitate exists in the washing solution, placing the beaker in an oven for drying at the constant temperature of 120 ℃ for 12h, finally transferring the catalyst precursor into a crucible, placing the crucible in a muffle furnace for roasting, raising the temperature from room temperature to 650 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2h, reducing the temperature to room temperature to obtain the catalyst to be activated, and placing the catalyst in a closed dryer for later use.
Accurately weighing 0.3g of catalyst to be activated, tabletting and crushing the catalyst to be activated, putting the catalyst into a constant-temperature area of a tubular fixed bed reactor, filling the rest space with quartz sand, connecting the fixed tubes completely and airtightly, starting temperature programming, raising the temperature to 300 ℃ at the rate of 5 ℃/min, keeping the temperature for 3 hours, keeping the hydrogen pressure at 1MPa, activating the prepared catalyst, and cooling the tubular fixed bed reactor to room temperature after the catalyst is completely reduced; at the reaction temperature: 50 ℃, hydrogen pressure: 2MPa, the molar concentration of propyne in cyclohexane is: 0.1%, the molar ratio of the injected amount of hydrogen to the propyne is as follows: 1.1:1, reaction Liquid Hourly Space Velocity (LHSV) is: 20h-1And then, conveying the mixture of the propyne and the cyclohexane to a tubular fixed bed reactor through a high-pressure constant-current micro pump to react with hydrogen, collecting liquid products at intervals of 1h after the preset reaction condition is achieved, analyzing the liquid products by using a gas chromatograph, sampling for multiple times in parallel, taking an average value of the liquid products, and calculating the conversion rate and the selectivity under the current reaction working condition.
Example 2
With metallic ruthenium (RuCl)3) The procedure was otherwise the same as in example 1, except that palladium metal in example 1 was replaced.
Example 3
With platinum (K) metal2PtCl6) The procedure was otherwise the same as in example 1, except that palladium metal in example 1 was replaced.
Example 4
With metallic copper (CuCl)2·2H2O) instead of the metallic cobalt in example 1, the other steps are the same as in example 1.
Example 5
With metallic zinc (ZnCl)2) The procedure was otherwise the same as in example 1, except that the metallic cobalt in example 1 was replaced.
Example 6
The procedure of example 1 was repeated except that the molar ratio of platinum metal to cobalt metal in example 1 was 1:1 instead of 1: 5.
Example 7
The procedure of example 1 was repeated except that the molar ratio of platinum metal to cobalt metal in example 1 was 1:10 instead of 1: 5.
Example 8
The procedure of example 1 was repeated except that the MgO supporting amount was 20wt% instead of 10wt% in example 1.
Example 9
The procedure of example 1 was repeated except that the MgO supporting amount was 30wt% instead of 10wt% in example 1.
Example 10
The procedure of example 1 was otherwise the same except that the molar concentration of propyne in cyclohexane was 0.01% instead of 0.1% in example 1.
Example 11
The procedure of example 1 was repeated except that the molar concentration of propyne in cyclohexane was 1% instead of 0.1% in cyclohexane in example 1.
Comparative example 1
Accurately weighing 3g of dried gamma-Al2O3(particles are about 30 meshes), and the mixture is placed in a 100mL beaker; according to the loading amounts of metal palladium and metal cobalt: 0.3wt%, accurately weighing solid PdCl2And CoCl2·6H2Dissolving O (the molar ratio of metal platinum to metal cobalt is 1: 5) in a dilute hydrochloric acid solution, ultrasonically dissolving for 30min in an ultrasonic instrument, slowly adding 3g of the composite catalyst carrier into a beaker, stirring while adding, carrying out equal-volume soaking and aging for 24h, then carrying out suction filtration, washing with deionized water until the solution is neutral, and using AgNO to wash3Detecting that no white precipitate exists in the washing solution, placing the beaker in an oven for drying at the constant temperature of 120 ℃ for 12h, finally transferring the catalyst precursor into a crucible, placing the crucible in a muffle furnace for roasting, raising the temperature from room temperature to 650 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2h, reducing the temperature to room temperature to obtain the catalyst to be activated, and placing the catalyst in a closed dryer for later use.
Accurately weighing 0.3g of catalyst to be activated, tabletting and crushing the catalyst to be activated, putting the catalyst into a constant-temperature area of a tubular fixed bed reactor, filling the rest space with quartz sand, connecting the fixed tubes completely and airtightly, starting temperature programming, raising the temperature to 300 ℃ at the rate of 5 ℃/min, keeping the temperature for 3 hours, keeping the hydrogen pressure at 1MPa, activating the prepared catalyst, and cooling the tubular fixed bed reactor to room temperature after the catalyst is completely reduced; at the reaction temperature: 50 ℃, hydrogen pressure: 2MPa, the molar concentration of propyne in cyclohexane is: 0.1%, the molar ratio of the injected amount of hydrogen to the propyne is as follows: 1.1:1, reaction Liquid Hourly Space Velocity (LHSV) is: 20h-1And then, conveying the mixture of the propyne and the cyclohexane to a tubular fixed bed reactor through a high-pressure constant-current micro pump to react with hydrogen, collecting liquid products at intervals of 1 hour after the preset reaction conditions are reached, and sampling and analyzing the liquid products.
Comparative example 2
Accurately weighing 3g of dried MgO (commercially available, chemical grade), and placing in a 100mL beaker; according to the loading amounts of metal palladium and metal cobalt: 0.3wt%, accurately weighing solid PdCl2And CoCl2·6H2Dissolving O (molar ratio of metal platinum to metal cobalt is 1: 5) in dilute hydrochloric acid solution, and ultrasonically dissolving in ultrasonic instrument for 30min, slowly adding 3g of the composite catalyst carrier into a beaker, stirring while adding, carrying out equal-volume soaking and aging for 24 hours, then carrying out suction filtration, washing with deionized water until the solution is neutral, and using AgNO to soak and age3Detecting that no white precipitate exists in the washing solution, placing the beaker in an oven for drying at the constant temperature of 120 ℃ for 12h, finally transferring the catalyst precursor into a crucible, placing the crucible in a muffle furnace for roasting, raising the temperature from room temperature to 650 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2h, reducing the temperature to room temperature to obtain the catalyst to be activated, and placing the catalyst in a closed dryer for later use.
Accurately weighing 0.3g of catalyst to be activated, tabletting and crushing the catalyst to be activated, putting the catalyst into a constant-temperature area of a tubular fixed bed reactor, filling the rest space with quartz sand, connecting the fixed tubes completely and airtightly, starting temperature programming, raising the temperature to 300 ℃ at the rate of 5 ℃/min, keeping the temperature for 3 hours, keeping the hydrogen pressure at 1MPa, activating the prepared catalyst, and cooling the tubular fixed bed reactor to room temperature after the catalyst is completely reduced; at the reaction temperature: 50 ℃, hydrogen pressure: 2MPa, the molar concentration of propyne in cyclohexane is: 0.1%, the molar ratio of the injected amount of hydrogen to the propyne is as follows: 1.1:1, reaction Liquid Hourly Space Velocity (LHSV) is: 20h-1And then, conveying the mixture of the propyne and the cyclohexane to a tubular fixed bed reactor through a high-pressure constant-current micro pump to react with hydrogen, collecting liquid products at intervals of 1 hour after the preset reaction conditions are reached, and sampling and analyzing the liquid products.
Comparative example 3
Accurately weighing 5g of dried gamma-Al2O3(particles are about 30 meshes), and the particles are placed in a 250mL beaker, and the loading of MgO is as follows: and (2) calculating by 10wt%, weighing 30wt% magnesium nitrate solution with a certain mass, slowly adding the magnesium nitrate solution into a carrier beaker while stirring, soaking and aging for 24h, then placing the beaker into an oven for drying at the constant temperature of 120 ℃ for 12h, finally transferring the carrier precursor into a crucible, placing the crucible into a muffle furnace for roasting, raising the temperature from room temperature to 650 ℃ at the constant temperature of 5 ℃/min, keeping the temperature for 4h, reducing the temperature to room temperature to obtain a composite catalyst carrier, and placing the composite catalyst carrier into a closed dryer for later use.
Accurately weighing 3g of composite catalyst carrier, and placing 10 g of composite catalyst carrier0mL beaker; according to the loading amount of metal palladium: 0.3wt%, accurately weighing solid PdCl2Dissolving in dilute hydrochloric acid solution, ultrasonic dissolving in ultrasonic instrument for 30min, slowly adding 3g of composite catalyst carrier into beaker, stirring while adding, soaking and aging for 24h in equal volume, suction filtering, washing with deionized water until the solution is neutral, and adding AgNO3Detecting that no white precipitate exists in the washing solution, placing the beaker in an oven for drying at the constant temperature of 120 ℃ for 12h, finally transferring the catalyst precursor into a crucible, placing the crucible in a muffle furnace for roasting, raising the temperature from room temperature to 650 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2h, reducing the temperature to room temperature to obtain the catalyst to be activated, and placing the catalyst in a closed dryer for later use.
Accurately weighing 0.3g of catalyst to be activated, tabletting and crushing the catalyst to be activated, putting the catalyst into a constant-temperature area of a tubular fixed bed reactor, filling the rest space with quartz sand, connecting the fixed tubes completely and airtightly, starting temperature programming, raising the temperature to 300 ℃ at the rate of 5 ℃/min, keeping the temperature for 3 hours, keeping the hydrogen pressure at 1MPa, activating the prepared catalyst, and cooling the tubular fixed bed reactor to room temperature after the catalyst is completely reduced; at the reaction temperature: 50 ℃, hydrogen pressure: 2MPa, the molar concentration of propyne in cyclohexane is: 0.1%, the molar ratio of the injected amount of hydrogen to the propyne is as follows: 1.1:1, reaction Liquid Hourly Space Velocity (LHSV) is: 20h-1And then, conveying the mixture of the propyne and the cyclohexane to a tubular fixed bed reactor through a high-pressure constant-current micro pump to react with hydrogen, collecting liquid products at intervals of 1 hour after the preset reaction conditions are reached, and sampling and analyzing the liquid products.
Performance testing
Qualitative and quantitative analysis of the liquid products of examples 1 to 11 and comparative examples 1 to 3 was performed by gas chromatography, and the conversion of propynes, selectivity and yield of propylene were calculated, and the results are shown in table 1.
TABLE 1 hydrogenation of propyne results for examples 1 to 11 and comparative examples 1 to 3
Serial number Propyne conversion/%) Propylene selectivity/%) Propylene yield/%
Example 1 99.6 87.2 86.9
Example 2 85.1 70.8 60.3
Example 3 99.8 82.4 82.2
Example 4 97.0 83.1 80.6
Example 5 98.2 78.7 77.3
Example 6 99.5 81.5 81.1
Example 7 90.7 88.4 80.2
Example 8 99.8 90.0 89.8
Example 9 98.3 85.9 84.4
Example 10 99.4 85.5 85.0
Example 11 97.0 88.6 85.9
Comparative example 1 99.2 74.0 73.4
Comparative example 2 86.1 67.9 58.5
Comparative example 3 99.4 68.0 67.6
Table 1 shows that the noble metal Pd is used as the main active component, the metal Co is used as the auxiliary agent, and the gamma-Al is used as the auxiliary agent2O3And the MgO composite oxygen compound is used as a carrier, and the prepared supported catalyst has higher catalytic activity and selectivity for the reaction of preparing propylene by selectively hydrogenating propyne, has strong process fluctuation resistance and shows good industrial application value. gamma-Al2O3The catalyst has higher mechanical strength and carbon deposit resistance due to the interaction with MgO, and the addition of the metal Co changes the valence state and the electron cloud state of the noble metal Pd, so that the metal Pd particles are dispersed more uniformly, and the timely desorption of propylene is promoted.
The invention is characterized in that the catalyst prepared by the invention is used for selective hydrogenation reaction of propyne, the main product is propylene, the byproduct is propane, and the propane can be separated by a rectifying tower during industrial production, so that the propane can be recycled.
The embodiments are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same or similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The catalyst for preparing propylene by selective hydrogenation of propyne, the preparation method and the application thereof provided by the invention are described in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims (10)

1. A catalyst for preparing propylene by selective hydrogenation of propyne is characterized in that: the catalyst is a supported noble metal catalyst, and the catalyst
With gamma-Al2O3Is the main component of the catalyst carrier, and MgO is adhered to the surface of the carrier to form a composite metal oxygen compound carrier;
one or more of noble metals Ru, Pd and Pt are used as main active ingredients, and the content of the noble metals is 0.1-3.0 wt% based on the weight content of the final catalyst;
one or more of non-noble metals Cu, Zn and Co are used as auxiliary metals to modify noble metals, and the molar ratio of the noble metals to the non-noble metals is 1: 1-10.
2. The carbon-based fertilizer according to claim 1, characterized in that: the load amount of MgO is 5-30 wt%.
3. The carbon-based fertilizer according to claim 1, characterized in that: the MgO precursor is 10-60 wt% of magnesium nitrate aqueous solution.
4. A preparation method of a catalyst for preparing propylene by selective hydrogenation of propyne is characterized by comprising the following steps:
（1）γ-Al2O3drying at 80-150 ℃ for 10-20 h, and dropwise adding the MgO precursor aqueous solution to the dried gamma-Al under stirring2O3Dipping, dehydrating, drying and roasting to obtain a composite oxygen compound carrier;
(2) dissolving noble metal salt and non-noble metal salt in dilute hydrochloric acid water solution to obtain mixed metal dipping solution;
(3) slowly dripping the mixed metal impregnation solution obtained in the step (2) onto the composite oxygen compound carrier obtained in the step (1) under stirring, and carrying out impregnation, washing, separation, drying and roasting to obtain a catalyst precursor;
(4) and (4) reducing the noble metal oxide in the catalyst precursor in the step (3) into a metal simple substance by using hydrogen, so that the catalyst has catalytic activity and performs catalytic reaction.
5. The method of claim 4, wherein: in the step (1) and the step (3), the dipping time is 12-24 h, the drying temperature is 80-120 ℃, the drying time is 6-12 h, and the roasting condition is as follows: the heating rate is as follows: 5-12 ℃/min, raising the temperature from room temperature to 450-750 ℃, and keeping the temperature for 2-6 h.
6. The method of claim 4, wherein: in the step (3), the washing step is specifically: the catalyst solution was washed with deionized water to be neutral and free of chloride ions.
7. Use of the catalyst of claim 1 for the selective catalytic hydrogenation of propyne to propylene.
8. The use according to claim 7, wherein the catalyst is present in an amount of 100 to 1000 mg.
9. Use according to claim 7, characterized in that the method comprises the following steps:
loading the catalyst into a tubular fixed bed reactor, filling quantitative catalyst in a constant temperature area in the middle of the tubular fixed bed, filling the rest space with quartz sand, connecting the fixed tubes completely and airtightly, starting temperature programming, firstly increasing the temperature to 300-600 ℃ at a temperature rise rate of 5 +/-1 ℃/min, keeping the temperature for 2-5 h, keeping the hydrogen pressure at 0.5-3 MPa, activating the catalyst, and cooling the tubular fixed bed reactor to room temperature after the catalyst is completely reduced; and then conveying the mixture of the propyne and the cyclohexane to a tubular fixed bed reactor to perform hydrogenation reaction with hydrogen.
10. The use according to claim 9, characterized in that the hydrogenation reaction conditions are: reaction temperature: hydrogen pressure at 30-80 deg.CThe force is: 0.5-3 MPa, the molar concentration of the propyne in the cyclohexane is 0.01-1.0%, the molar ratio of the hydrogen to the propyne is 1.1-1.5, and the hourly space velocity (LHSV) of the reaction liquid is as follows: 10 to 30 hours-1。
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