WO2020042524A1 - PdIn合金催化剂及其制备方法、应用 - Google Patents

PdIn合金催化剂及其制备方法、应用 Download PDF

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WO2020042524A1
WO2020042524A1 PCT/CN2019/070893 CN2019070893W WO2020042524A1 WO 2020042524 A1 WO2020042524 A1 WO 2020042524A1 CN 2019070893 W CN2019070893 W CN 2019070893W WO 2020042524 A1 WO2020042524 A1 WO 2020042524A1
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nitrogen
metal
porous carbon
doped porous
alloy catalyst
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PCT/CN2019/070893
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English (en)
French (fr)
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王勇
于丽丽
马啸
毛建拥
王哲
毛善俊
李建清
陈钢
李浩然
陈志荣
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浙江新和成股份有限公司
浙江大学
山东新和成药业有限公司
山东新和成维生素有限公司
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Priority to DE112019000031.4T priority Critical patent/DE112019000031T5/de
Priority to US16/558,125 priority patent/US10737250B2/en
Publication of WO2020042524A1 publication Critical patent/WO2020042524A1/zh

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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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/392—Metal surface area
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/644—Arsenic, antimony or bismuth
    • B01J23/6445—Antimony
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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
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
    • 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
    • B01J35/615—100-500 m2/g
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/035—Precipitation on carriers
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the invention relates to the technical field of catalysts, in particular to a PdIn alloy catalyst and a preparation method and application thereof.
  • Vitamins are trace organic substances that must be obtained from food in order to maintain the normal physiological functions of living organisms. They play an important role in human growth, metabolism, and development.
  • the proportion of synthetic vitamins in vitamin production has increased year by year, and the selective hydrogenation of alkynyl alcohols is one of the most important reactions in vitamin production.
  • Supported Pd catalysts are more commonly used in this reaction.
  • the catalyst for hydrogenation of alkynyl alcohol in industrial production is mainly Lindlar catalyst.
  • Lindlar catalyst still has many problems such as high toxicity, poor stability of water phase, insufficient selectivity, etc. It is urgent to develop a more efficient and stable catalyst for selective hydrogenation of alkynyl alcohol.
  • Pd-based alloy catalysts have received widespread attention in the field of hydrogenation of alkynyl alcohols, especially Pd-based alloy catalysts obtained by reducing high-temperature hydrogen when a reducible oxide is used as a carrier.
  • such catalysts usually have problems such as low specific surface area, and the formation of these alloys will reduce the exposed Pd sites to varying degrees, thereby reducing catalytic activity.
  • Carbon material has a large specific surface area and is easy to regulate and control. It is an ideal catalyst support.
  • nitrogen-doped carbon materials have some unique advantages. For example, nitrogen doping changes the local electronic structure of the carbon material, which is conducive to the dispersion of precious metal nanoparticles. It can improve the activity and stability of the catalyst.
  • the present invention provides a PdIn alloy catalyst, a preparation method thereof and related applications.
  • the corners and corners of Pd metal are occupied by In metal, thereby achieving selective poisoning. Therefore, the PdIn alloy catalyst has an excellent catalytic effect.
  • the invention provides a PdIn alloy catalyst.
  • the PdIn alloy catalyst includes a support and a Pd metal supported on the support.
  • the support is a nitrogen-doped porous carbon composite material having multiple channels, and the Pd metal is distributed in the channels.
  • the nitrogen-doped porous carbon composite material includes a nitrogen-doped porous carbon material, indium oxide, and metal In exposed through the pores, and the indium oxide is uniformly distributed in the nitrogen-doped porous carbon material.
  • the metal In selectively occupies the corners of the Pd metal.
  • the dispersion degree of the Pd metal in the nitrogen-doped porous carbon composite material is 70% to 95%.
  • the mass fraction of the Pd metal in the composite catalyst is 0.1% to 10%; the mass fraction of the indium oxide and metal In in the composite catalyst is 2% to 30%;
  • the mass fraction of the nitrogen-doped porous carbon material in the composite catalyst is 60% to 97.9%, and the mass fraction of the nitrogen element in the nitrogen-doped porous carbon material is 0.5% to 15%.
  • the invention also provides a method for preparing a PdIn alloy catalyst, which comprises the following steps:
  • the nitrogen-doped porous carbon composite material includes a nitrogen-doped porous carbon material and indium oxide, and the indium oxide is uniformly distributed in the nitrogen-doped porous material. Carbon material and part of indium oxide is exposed through the channel;
  • Hydrogen reduction is performed on the nitrogen-doped porous carbon composite material after the first calcination.
  • indium oxide is reduced to metal In, and metal In selectively occupies the corners of the Pd metal. Bit.
  • the method for preparing the nitrogen-doped porous carbon composite material in step 1) is as follows:
  • the mixture is subjected to a second calcination under an inert atmosphere at 500 ° C. to 1200 ° C. to obtain a nitrogen-doped porous carbon composite material having a plurality of pore channels.
  • the Pd metal precursor in the Pd metal precursor solution is at least one of PdCl 2 , H 2 PdCl 4 , Pd (NO 3 ) 2 , and Pd (NH 3 ) 4 (NO 3 ) 2 .
  • the calcination temperature is 200 ° C to 500 ° C
  • the heating rate is 1 ° C / min to 20 ° C / min
  • the time is 1 minute to 240 minutes
  • the process of hydrogen reduction The medium temperature is 50 degrees Celsius to 500 degrees Celsius
  • the heating rate is 1 degree Celsius / minute to 20 degrees Celsius / minute
  • the time is 1 minute to 360 minutes
  • the hydrogen flow rate is 20 ml / minute to 200 ml / minute.
  • the nitrogen-containing biomass is at least one of bamboo, chitin, carboxymethyl chitin, chitosan, carboxymethyl chitosan, and glucosamine hydrochloride.
  • the mass ratio of the indium nitrate to the nitrogen-containing biomass in step b) is (0.05-2): 1.
  • the calcining time in the second calcining process is 0.1 hour to 5 hours.
  • the metal In selectively occupying the corners of the Pd metal means that after the indium oxide exposed through the channel is reduced, the metal In will be formed, and the metal In will migrate to the surface of the Pd nanoparticle, and will preferentially occupy the Pd metal.
  • the coordination number is lower and the corner corners are relatively unsaturated, thus achieving selective poisoning of Pd metal.
  • the selective poisoning gives the PdIn alloy catalyst a unique catalytic effect in selective hydrogenation.
  • carbonate ions or bicarbonate ions in the porogen can react with indium ions in the indium nitrate to obtain a metal precipitate.
  • the metal precipitates are uniformly distributed; on the other hand, the porogen and the metal precipitates can be decomposed in the subsequent calcination process, and the generated gas can promote the formation of multiple pores in the nitrogen-doped porous carbon material.
  • metal precipitates decompose to form nano-sized indium oxide.
  • the indium oxide is finally uniformly distributed in the nitrogen-doped porous carbon material, and a part of the surface is exposed through the pores.
  • the porogen does not need to be excessive relative to the indium nitrate, and the carbonate or oxalate in the porogen is not required. Even if it is transferred to the metal precipitate, the metal precipitate will also decompose, and the generated gas will also form a porosity effect.
  • the In atom in the obtained PdIn alloy catalyst selectively poisons the corner and corner positions of the Pd metal, and is therefore applicable to the selective hydrogenation of alkynyl alcohol.
  • the PdIn alloy catalyst has a large specific surface area, which is also favorable for the adsorption of reactants and has high catalytic activity.
  • the invention also provides an application of a PdIn alloy catalyst in a catalytic hydrogenation reaction, and the PdIn alloy catalyst is used as a catalyst in a selective hydrogenation reaction of an alkynol.
  • the alkynol is 2-methyl-3-butyn-2-ol, 3,7-dimethyl-1-octyn-3-ol, 3,7-dimethyl-6-octyl En-1-yn-3-ol, 3,7,11-trimethyl-1-dodecyn-3-ol, 3,7,11-trimethyl-6-dodecen-1-yne- 3-alcohol, 3,7,11-trimethyl-6,10-dodecadien-1-yn-3-ol, 3,7,11,15-trimethyl-1-hexadecyne- 3-ol, 3-methyl-1- (2,6,6-trimethyl-1-cyclohexen-1-yl) -1-pentene-4-yn-3-ol, and 3,6-di At least one of methyl-8- (2,6,6-trimethyl-1-cyclohexene-1-yl) -2,7-octadiene-4-yne-1,6-diol
  • the PdIn alloy catalyst can be reused multiple times.
  • FIG. 1 is a scanning electron microscope photograph of the nitrogen-doped porous carbon composite material described in Example 1.
  • FIG. 1 is a scanning electron microscope photograph of the nitrogen-doped porous carbon composite material described in Example 1.
  • FIG. 2 is a transmission electron microscope photograph of the nitrogen-doped porous carbon composite material described in Example 1.
  • FIG. 2 is a transmission electron microscope photograph of the nitrogen-doped porous carbon composite material described in Example 1.
  • FIG. 3 is a transmission electron microscope photograph of the PdIn alloy catalyst described in Example 1.
  • FIG. 3 is a transmission electron microscope photograph of the PdIn alloy catalyst described in Example 1.
  • FIG. 4 is an X-ray photoelectron spectrum of the PdIn alloy catalyst described in Example 1.
  • FIG. 4 is an X-ray photoelectron spectrum of the PdIn alloy catalyst described in Example 1.
  • FIG. 5 is a schematic structural diagram of a selective hydrogenation reaction using a PdIn alloy catalyst according to the present invention.
  • the invention provides a method for preparing a PdIn alloy catalyst.
  • the preparation method includes the following steps:
  • the nitrogen-doped porous carbon composite material includes a nitrogen-doped porous carbon material and indium oxide, and the indium oxide is uniformly distributed in the nitrogen-doped porous material. A part of the indium oxide in the carbon material is exposed through the channel;
  • Hydrogen reduction is performed on the nitrogen-doped porous carbon composite material after the first calcination.
  • indium oxide exposed through the channel is reduced to metal In, and the metal In is selectively Occupying the corners of the Pd metal to achieve recombination with the Pd metal.
  • step S1 the method for preparing the nitrogen-doped porous carbon composite material is as follows:
  • the mixture is subjected to a second calcination under an inert atmosphere at 500 ° C. to 1200 ° C. to obtain a nitrogen-doped porous carbon composite material having a plurality of pore channels.
  • the ratio of the indium nitrate to water is not limited.
  • the ratio of the mass of the indium nitrate to the volume of water is (1 g to 10 g): 100 mL.
  • the nitrogen-containing biomass is at least one of bamboo, chitin, carboxymethyl chitin, chitosan, carboxymethyl chitosan, and glucosamine hydrochloride.
  • the nitrogen-containing biomass contains a nitrogen element and a carbon element, and serves as a nitrogen source and a carbon source.
  • the nitrogen-containing biomass is insoluble in water.
  • the indium nitrate reacts with a part of the porogen to form a precipitate.
  • the precipitate is formed by carbonate ions and metal ions.
  • Another part of the excess porogen is decomposed in the subsequent calcination process to generate a gas, which can play a role of pore formation, and a plurality of pore channels are formed in the nitrogen-doped porous carbon material.
  • the mass ratio of the indium nitrate to the nitrogen-containing biomass may be (0.05-2): 1, and preferably, the mass ratio of the indium nitrate to the nitrogen-containing biomass is (0.5-2): 1.
  • stirring was continued for 0.1 to 10 hours.
  • the obtained mixture is actually a suspension, in which the resulting precipitate and nitrogen-containing biomass are insoluble in the solvent, but are uniformly distributed in the mixture, and the mixture is a suspension.
  • the mixture is dried, and a specific drying process may be: drying at a temperature of 60 degrees Celsius to 180 degrees Celsius.
  • the time for the second calcination may be 0.1 to 5 hours.
  • the specific second calcination process is as follows: the temperature is raised to 500 ° C. to 1200 ° C. at 2 ° C./min to 30 ° C./min, and calcined at 500 ° C. to 1200 ° C. for 0.1 h to 5 h; finally, the temperature is naturally reduced to room temperature.
  • the temperature of the second calcination is 600 ° C to 900 ° C.
  • the loading amount (ie, mass fraction) of the Pd metal in the PdIn alloy catalyst can be adjusted without limitation; specifically, the mass of the Pd precursor in the Pd precursor solution can be adjusted or A molar amount is achieved.
  • a method for forming Pd metal in the pores of the nitrogen-doped porous carbon composite material is as follows: immersing the nitrogen-doped porous carbon composite material in a Pd metal precursor solution; and immersing the nitrogen-doped porous carbon composite material The first calcination and hydrogen reduction are sequentially performed, and Pd metal is formed in the pores of the nitrogen-doped porous carbon composite material.
  • the calcination temperature during the first calcination process is 200 degrees Celsius to 500 degrees Celsius, the heating rate is 1 degree Celsius / minute to 20 degrees Celsius / minute, and the time is 1 minute to 240 minutes; the temperature during the hydrogen reduction is 150 degrees Celsius to 500 degrees Celsius, heating rate is 1 degree Celsius / minute to 20 degrees Celsius / minute, time is 1 minute to 360 minutes, and hydrogen flow rate is 20 ml / minute to 200 ml / minute.
  • the calcination temperature is 300 degrees Celsius to 500 degrees Celsius, the heating rate is 5 degrees Celsius / minute to 10 degrees Celsius / minute, and the time is 60 minutes to 120 minutes; during the hydrogen reduction process, the temperature is 200 degrees Celsius to 400 degrees Celsius, and the temperature is increased.
  • the rate is 5 degrees Celsius / minute to 10 degrees Celsius / minute, the time is 60 minutes to 180 minutes, and the hydrogen flow rate is 40 ml / minute to 100 ml / minute.
  • the Pd metal precursor in the Pd metal precursor solution may be at least one of PdCl 2 , H 2 PdCl 4 , Pd (NO 3 ) 2 , and Pd (NH 3 ) 4 (NO 3 ) 2 .
  • the invention also provides a PdIn alloy catalyst.
  • the PdIn alloy catalyst includes a support and a Pd metal supported on the support.
  • the support is a nitrogen-doped porous carbon composite material having a plurality of channels.
  • the Pd metal is distributed in the channels, and the nitrogen-doped porous carbon.
  • the composite material includes a nitrogen-doped porous carbon material, indium oxide, and metal In exposed through the pores, the indium oxide is uniformly distributed in the nitrogen-doped porous carbon material, and the metal In selectively occupies the Pd
  • the corners and corners of the metal are combined with the Pd metal. That is, only the exposed portion of indium oxide (In 2 O 3 ) is reduced to form In, and the unexposed portion is not reduced.
  • the degree of dispersion of the Pd metal in the nitrogen-doped porous carbon composite material is 70% to 95%.
  • the dispersion degree of the Pd metal in the nitrogen-doped porous carbon composite material is 70% to 80%.
  • the mass fraction of the Pd metal in the composite catalyst is 0.1% to 10%; the mass fraction of the indium oxide and metal In in the composite catalyst is 2% to 30%; the nitrogen doping
  • the mass fraction of the porous carbon material in the composite catalyst is 60% to 97.9%, and the mass fraction of the nitrogen element in the nitrogen-doped porous carbon material is 0.5% to 15%.
  • the present invention also provides an application of a PdIn alloy catalyst in a catalytic hydrogenation reaction.
  • the PdIn alloy catalyst is used as a catalyst in the selective hydrogenation reaction of alkynyl alcohol.
  • Alkynols are 2-methyl-3-butyn-2-ol, 3,7-dimethyl-1-octyn-3-ol, 3,7-dimethyl-6-octene-1-yne -3-ol, 3,7,11-trimethyl-1-dodecyn-3-ol, 3,7,11-trimethyl-6-dodecen-1-ol-3-ol, 3 , 7,11-trimethyl-6,10-dodecadien-1-yn-3-ol, 3,7,11,15-trimethyl-1-hexadecyn-3-ol, 3 -Methyl-1- (2,6,6-trimethyl-1-cyclohexen-1-yl) -1-pentene-4-yn-3-ol and 3,6
  • Atomic emission spectroscopy was used to test the actual loading of Pd in the PdIn alloy catalyst, and the result was 0.59%. This is basically consistent with the theoretical load of Pd.
  • FIG. 1 A scanning electron microscope test was performed on the nitrogen-doped porous carbon composite material, and the results are shown in FIG. 1. It can be seen from FIG. 1 that a rich channel structure can be clearly observed.
  • the CO titration method (Note: The CO titration method is a carbon monoxide adsorption test for the dispersion of Pd metal) was used to test the dispersion and specific surface area of Pd of the PdIn alloy catalyst.
  • the test result was: the dispersion of Pd was 73% ;
  • the specific surface area of the PdIn alloy catalyst was 113.7 m 2 g -1 .
  • the method for preparing the PdIn alloy catalyst of Example 2 is basically the same as the method of Example 1, except that the nitrogen-containing biotin is carboxymethyl chitosan.
  • FIG. 4 Please refer to FIG. 4 for the reaction structural formula of the hydrogenation reaction in the following examples.
  • the PdIn alloy catalyst catalyzes the selective hydrogenation of 2-methyl-3-butyne-2-ol (I), as follows:
  • a 50 mL high-pressure reaction kettle was used; 50 mg of the PdIn alloy catalyst obtained in Example 1 was added; the substrate 2-methyl-3-butyn-2-ol 20 mmol; ethanol 5 mL; hydrogen 1 MPa; reaction temperature 30 ° C; reaction time 2 h.
  • the conversion of 2-methyl-3-butyne-2-ol (I) was 100%, and the selectivity of 2-methyl-3-butene-2-ol (II) was 98%.
  • Comparative Examples 1 and 2 are further provided. Comparative Examples 1 and 2 are Pd / Al 2 O 3 and Pd / ZnO catalysts prepared by conventional impregnation methods, respectively. The conversion and selectivity of the Pd / Al 2 O 3 catalyst were 100% and 72%, respectively, while the conversion and selectivity of the Pd / ZnO catalyst were 15% and 99%, respectively. It can be seen that the highly dispersed PdIn alloy catalyst prepared in Example 1 greatly improved the selectivity while maintaining the catalyst activity.
  • the PdIn alloy catalyst catalyzes the selective hydrogenation of 3,7-dimethyl-1-octyn-3-ol (III), as follows:
  • a 50 mL autoclave was used; 50 mg of the PdIn alloy catalyst of Example 1 was added; substrate 3,7-dimethyl-1-octyn-3-ol (III) 20 mmol; ethanol 5 mL; hydrogen 1 MPa; reaction temperature 30 ° C; The reaction time is 2h.
  • the conversion of 3,7-dimethyl-1-octyn-3-ol (III) was 100%, and the selectivity of 3,7-dimethyl-1-octen-3-ol (IV) was 98%.
  • the PdIn alloy catalyst catalyzes the selective hydrogenation of 3,7-dimethyl-6-octen-1-yn-3-ol (V), as follows:
  • the PdIn alloy catalyst catalyzes the selective hydrogenation of 3,7,11-trimethyl-1-dodecyn-3-ol (VII), as follows:
  • the PdIn alloy catalyst catalyzes the selective hydrogenation of 3,7,11-trimethyl-6-dodecen-1-yn-3-ol (IX), as follows:
  • the PdIn alloy catalyst catalyzes the selective hydrogenation of 3,7,11-trimethyl-6,10-dodecadien-1-yn-3-ol (XI), as follows:
  • a 50 mL autoclave was used; 50 mg of the PdIn alloy catalyst of Example 1 was added; the substrate 3,7,11-trimethyl-6,10-dodecadiene-1-yne-3-ol (XI) 15 mmol; Ethanol 5mL; hydrogen 1MPa; reaction temperature 30 ° C; reaction time 2h.
  • 3,7,11-trimethyl-6,10-dodecadien-1-yn-3-ol (XI) conversion rate is 100%, 3,7,11-trimethyl-1,6, 10-Dodecanetrien-3-ol (X) has a selectivity of 98%.
  • the PdIn alloy catalyst catalyzes the selective hydrogenation of 3,7,11,15-trimethyl-1-hexadecyn-3-ol (XIII), as follows:
  • a 50 mL autoclave was used; 50 mg of the PdIn alloy catalyst of Example 1 was added; substrate 3,7,11,15-trimethyl-1-hexadecyn-3-ol (XIII) 20 mmol; ethanol 5 mL; hydrogen 1 MPa; The reaction temperature is 30 ° C; the reaction time is 2h. 3,7,11,15-trimethyl-1-hexadecyn-3-ol (XIII) conversion is 100%, 3,7,11,15-trimethyl-1-hexadecene-3- Alcohol (XIV) selectivity is 98%.
  • PdIn alloy catalyst catalyzes the selectivity of 3-methyl-1- (2,6,6-trimethyl-1-cyclohexen-1-yl) -1-pentene-4-yn-3-ol (XV)
  • the hydrogenation reaction is as follows:
  • PdIn alloy catalyst for the selective hydrogenation of 2-methyl-3-butyne-2-ol (I) is as follows:

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Abstract

本发明提供一种PdIn合金催化剂，所述PdIn合金催化剂包含载体以及负载于所述载体的Pd金属，所述载体为具有多个孔道的氮掺杂多孔碳复合材料，所述氮掺杂多孔碳复合材料包含氮掺杂多孔碳材料、氧化铟以及通过该孔道而暴露的金属In，所述氧化铟均匀分布于所述氮掺杂多孔碳材料中，所述Pd金属的边角位选择性地被金属In占据。本发明还提供一种PdIn合金催化剂的制备方法及其应用。

Description

PdIn合金催化剂及其制备方法、应用
相关申请
本申请要求2018年8月31日申请的，申请号为201811010568.6，名称为“PdIn合金催化剂及其制备方法、应用”的中国专利申请的优先权，在此将其全文引入作为参考。
技术领域
本发明涉及催化剂技术领域，特别是涉及PdIn合金催化剂及其制备方法、应用。
背景技术
维生素是为维持生命体正常的生理功能而必须从食物中获得的一类微量有机物质，在人体生长、代谢、发育过程中发挥着重要的作用。合成维生素在维生素生产中占据的比重逐年增长，而炔醇类物质的选择性加氢反应是维生素生产中最为重要的反应之一。负载型Pd催化剂在该反应中较为常用。目前在工业生产中炔醇加氢反应的催化剂主要是Lindlar催化剂。但是Lindlar催化剂仍存在毒性大、水相稳定性差、选择性不足等许多问题，急需开发一种更为高效、稳定的炔醇选择性加氢反应催化剂。
近期Pd基合金催化剂在炔醇加氢反应领域受到广泛关注，尤其以可还原氧化物为载体时高温氢气还原得到的Pd基合金催化剂。但是这类催化剂通常存在比表面积低等问题，而且这些合金的形成会不同程度的减少表面暴露的Pd位点，从而降低催化活性。炭材料比表面积大且易于调控，是一种理想的催化剂载体。相比于普通的炭材料，氮掺杂炭材料则有着一些独特的优势，比如氮掺杂改变了炭材料的局域电子结构，有利于贵金属纳米颗粒的分散，通过氮和金属之间的相互作用提高催化剂的活性及稳定性等。但是如何结合两种载体的优势制备独特性能的金属氧化物复合的氮掺杂多孔炭负载的高分散Pd基合金催化剂仍面临巨大的挑战。近期，Wang等(J.Catal.2017，350，13-20)以Pd颗粒的边角位是造成炔醇过加氢这一理论为基础，开发了一种PdZn/CN@ZnO催化剂，虽然Zn毒化了Pd的边角位，但是这种毒化作用并不是选择性的，Zn也会占据平面位，造成催化剂活性的下降。因此如何形成边角位选择性被毒化的Pd基合金也是该领域面临的难题之一。
发明内容
针对上述问题，本发明提供一种PdIn合金催化剂及其制备方法及相关应用。所得到的PdIn合金催化剂中Pd金属的边角位被In金属占据，而实现选择性毒化，因而该PdIn合 金催化剂具有优异的催化效果。
本发明提供一种PdIn合金催化剂，所述PdIn合金催化剂包含载体以及负载于所述载体的Pd金属，所述载体为具有多个孔道的氮掺杂多孔碳复合材料，Pd金属分布于所述孔道中，所述氮掺杂多孔碳复合材料包含氮掺杂多孔碳材料、氧化铟以及通过该孔道而暴露的金属In，所述氧化铟均匀分布于所述氮掺杂多孔碳材料中，所述金属In选择性地占据所述Pd金属的边角位。
优选的，所述Pd金属在所述氮掺杂多孔碳复合材料中的分散度为70％～95％。
优选的，所述Pd金属在所述复合催化剂所占的质量分数为0.1％～10％；所述氧化铟以及金属In在所述复合催化剂所占的质量分数为2％～30％；所述氮掺杂多孔碳材料在所述复合催化剂所占的质量分数为60％～97.9％，其中所述氮掺杂多孔碳材料中氮元素的质量分数为0.5％～15％。
本发明还提供一种PdIn合金催化剂的制备方法，其包含以下步骤：
1)提供具有多个孔道的氮掺杂多孔碳复合材料，其中所述氮掺杂多孔碳复合材料包含氮掺杂多孔碳材料以及氧化铟，所述氧化铟均匀分布于所述氮掺杂多孔碳材料中并且部分氧化铟通过该孔道而暴露；
2)将所述氮掺杂多孔碳复合材料浸渍于Pd金属前驱体溶液中；
3)对浸渍后的氮掺杂多孔碳复合材料进行第一煅烧，使Pd金属前驱体溶液中的Pd金属前驱体转化为Pd金属，Pd金属分布于所述孔道中；
4)对经过第一煅烧后的氮掺杂多孔碳复合材料进行氢气还原，其中，在氢气还原过程中，氧化铟被还原为金属In，并且金属In选择性地占据所述Pd金属的边角位。
优选的，步骤1)中所述氮掺杂多孔碳复合材料的制备方法具体如下：
a)将硝酸铟溶于水中，得到预混物；
b)依次向所述预混物中加入含氮生物质及致孔剂，并使所述硝酸铟与致孔剂进行反应，得到含金属沉淀物的混合物，其中所述致孔剂为碳酸氢铵、碳酸铵、草酸铵、草酸氢胺、草酸中的至少一种，所述硝酸铟与致孔剂的摩尔比为1∶(1～20)；以及
c)将所述混合物于500摄氏度～1200摄氏度在惰性氛围下进行第二煅烧，得到具有多个孔道的氮掺杂多孔碳复合材料。
优选的，所述Pd金属前驱体溶液中的Pd金属前驱体为PdCl 2、H 2PdCl 4、Pd(NO 3) 2、Pd(NH 3) 4(NO 3) 2中的至少一种。
优选的，步骤3)所述第一煅烧过程中，煅烧温度为200摄氏度～500摄氏度，升温速率为1摄氏度/分钟～20摄氏度/分钟，时间为1分钟～240分钟；所述氢气还原的过程中温度为 50摄氏度～500摄氏度，升温速率为1摄氏度/分钟～20摄氏度/分钟，时间为1分钟～360分钟，氢气流速为20毫升/分钟～200毫升/分钟。
优选的，步骤b)，所述含氮生物质为竹子、甲壳素、羧甲基甲壳素、壳聚糖、羧甲基壳聚糖、氨基葡萄糖盐酸盐中的至少一种。
优选的，步骤b)中所述硝酸铟与含氮生物质的质量比为(0.05～2)∶1。
优选的，步骤c)中，所述第二煅烧的过程中煅烧时间为0.1小时～5小时。
所述PdIn合金催化剂及其制备方法具有以下优点：
所述金属In选择性地占据所述Pd金属的边角位是指通过该孔道暴露的氧化铟经过还原后会形成金属In，该金属In会向Pd纳米颗粒表面迁移，而会优先占据Pd金属的配位数较低、相对不饱和的边角位，而实现对Pd金属选择性的毒化。该选择性的毒化而赋予该PdIn合金催化剂在选择性加氢中的独特的催化效果。
在制备氮掺杂多孔碳复合材料的过程中：一方面，所述致孔剂中的碳酸根离子或碳酸氢根离子可与所述硝酸铟中的铟离子进行反应，得到金属沉淀物，该金属沉淀物均匀分布；另一方面，所述致孔剂及金属沉淀物可在后续的煅烧过程中发生分解，生成的气体可促使在所述氮掺杂多孔碳材料形成多个孔道。在煅烧过程中，金属沉淀物会分解形成纳米级的氧化铟。该氧化铟最终在所述氮掺杂多孔碳材料中均匀分布，并部分表面通过孔道而暴露。在这里需要说明的是，在所述致孔剂与所述硝酸铟的反应中，所述致孔剂相对于所述硝酸铟并不需要过量，所述致孔剂中的碳酸根或草酸根即使转移至金属沉淀物中，金属沉淀物也同样会发生分解，生成的气体也会形成致孔的效果。
另外，由于氧化铟以纳米颗粒的形式分散于炭材料上，即在孔道中形成的金属In也较为均匀，因此，Pd金属也会高度分散于所述氮掺杂多孔碳材料中，同时也避免了还原过程中Pd金属的聚合团簇。该制备方法工艺简单，易于工业化。
该得到的PdIn合金催化剂中的In原子选择性的毒化Pd金属的边角位，因此在可应用于炔醇的选择性加氢中。另外，PdIn合金催化剂的比表面积大，也利于反应物的吸附，催化活性高。
本发明还提供一种PdIn合金催化剂在催化加氢反应中的应用，所述PdIn合金催化剂在炔醇的选择性加氢反应中作为催化剂。
优选的，所述炔醇为2-甲基-3-丁炔-2-醇、3，7-二甲基-1-辛炔-3-醇、3，7-二甲基-6-辛烯-1-炔-3-醇、3，7，11-三甲基-1-十二炔-3-醇、3，7，11-三甲基-6-十二烯-1-炔-3-醇、3，7，11-三甲基-6，10-十二烷二烯-1-炔-3-醇、3，7，11，15-三甲基-1-十六炔-3-醇、3-甲基-1-(2，6，6-三甲基-1-环己烯-1-基)-1-戊烯-4-炔-3-醇和3，6-二甲基-8-(2，6，6-三甲基-1-环己烯-1-基)-2，7-辛二烯-4-炔-1，6- 二醇中的至少一种。
由于该PdIn合金催化剂中的Pd金属的结构稳定，因此该PdIn合金催化剂可多次重复利用。
附图说明
图1为实施例1所述氮掺杂多孔碳复合材料的扫描电镜照片。
图2为实施例1所述氮掺杂多孔碳复合材料的透射电镜照片。
图3为实施例1所述PdIn合金催化剂的透射电镜照片。
图4为实施例1所述PdIn合金催化剂的X射线光电子能谱图。
图5为本发明采用PdIn合金催化剂进行选择性加氢反应的结构示意图。
具体实施方式
下面将对本发明实施方式中的技术方案进行清楚、完整地描述，显然，所描述的实施方式仅仅是本发明一部分实施方式，而不是全部的实施方式。基于本发明中的实施方式，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施方式，都属于本发明保护的范围。
本发明提供一种PdIn合金催化剂的制备方法。所述制备方法包含以下步骤：
S1，提供具有多个孔道的氮掺杂多孔碳复合材料，其中所述氮掺杂多孔碳复合材料包含氮掺杂多孔碳材料以及氧化铟，所述氧化铟均匀分布于所述氮掺杂多孔碳材料中并部分氧化铟通过该孔道而暴露；
S2，将所述氮掺杂多孔碳复合材料浸渍于Pd金属前驱体溶液中；
S3，对浸渍后的氮掺杂多孔碳复合材料进行第一煅烧，使Pd金属前驱体溶液中的Pd金属前驱体转化为Pd金属，Pd金属分布于所述孔道中；以及
S4，对经过第一煅烧后的氮掺杂多孔碳复合材料进行氢气还原，其中，在氢气还原过程中，通过该孔道而暴露的氧化铟被还原为金属In，并且所述金属In选择性地占据所述Pd金属的边角位而实现与Pd金属复合。
在步骤S1中，所述氮掺杂多孔碳复合材料的制备方法具体如下：
a)将硝酸铟溶于水中，得到预混物；
b)依次向所述预混物中加入含氮生物质及致孔剂，并使所述硝酸铟与致孔剂进行反应，得到含金属沉淀物的混合物，其中所述致孔剂为碳酸氢铵、碳酸铵、草酸铵、草酸氢胺、草酸中的至少一种，所述硝酸铟与致孔剂的摩尔比为1∶(1～20)；以及
c)将所述混合物于500摄氏度～1200摄氏度在惰性氛围下进行第二煅烧，得到具有多个孔道的氮掺杂多孔碳复合材料。
所述硝酸铟与水的比例不做限定。优选的，所述硝酸铟的质量与水的体积的比例为(1g～10g)∶100mL。
所述含氮生物质为竹子、甲壳素、羧甲基甲壳素、壳聚糖、羧甲基壳聚糖、氨基葡萄糖盐酸盐中的至少一种。所述含氮生物质含有氮元素和碳元素，而作为氮源和碳源。所述含氮生物质不溶于水。
所述硝酸铟与部分的所述致孔剂会发生反应，而生成沉淀物。该沉淀物为碳酸根离子与金属离子所形成的。另外一部分过量的致孔剂在后续的煅烧过程中分解而生成气体，该气体可起到致孔的作用，而在所述氮掺杂多孔碳材料中形成多个孔道。所述硝酸铟与含氮生物质的质量比可为(0.05～2)∶1，优选的，所述硝酸铟与含氮生物质的质量比为(0.5～2)∶1。在反应的过程中持续搅拌0.1小时～10小时。所得到的混合物实际为悬浮液，其中生成的沉淀物及含氮生物质是不溶于所述溶剂的，而是均匀分布于所述混合物中，所述混合物为悬浮液。
可以理解，在进行第二煅烧之前，将所述混合物进行干燥，具体的干燥过程可为：在60摄氏度～180摄氏度的温度下干燥。
所述第二煅烧的时间可为0.1小时～5小时。具体的第二煅烧的过程如下：以2℃/min～30℃/min升温至500℃～1200℃，并于500℃～1200℃煅烧0.1h～5h；最后，自然降温到室温。优选的，第二煅烧的温度为600℃～900℃。
在步骤S2中，所述Pd金属在所述PdIn合金催化剂中的负载量(即质量分数)可以调控，不做限定；具体的，可通过调整所述Pd前驱体溶液中Pd前驱体的质量或者摩尔量实现。
在所述氮掺杂多孔碳复合材料的孔道内形成Pd金属的方法如下：将所述氮掺杂多孔碳复合材料浸于Pd金属前驱体溶液中；对浸过后的氮掺杂多孔碳复合材料依次进行第一煅烧、氢气还原，而在所述氮掺杂多孔碳复合材料的孔道内形成Pd金属。所述第一煅烧过程中煅烧的温度为200摄氏度～500摄氏度，升温速率为1摄氏度/分钟～20摄氏度/分钟，时间为1分钟～240分钟；所述氢气还原的过程中温度为150摄氏度～500摄氏度，升温速率为1摄氏度/分钟～20摄氏度/分钟，时间为1分钟～360分钟，氢气流速为20毫升/分钟～200毫升/分钟。优选的，煅烧的温度为300摄氏度～500摄氏度，升温速率为5摄氏度/分钟～10摄氏度/分钟，时间为60分钟～120分钟；所述氢气还原的过程中温度为200摄氏度～400摄氏度，升温速率为5摄氏度/分钟～10摄氏度/分钟，时间为60分钟～180分钟，氢气流速为40毫升/分钟～100毫升/分钟。
所述Pd金属前驱体溶液中的Pd金属前驱体可为PdCl 2、H 2PdCl 4、Pd(NO 3) 2、Pd(NH 3) 4(NO 3) 2中的至少一种。
本发明还提供一种PdIn合金催化剂。所述PdIn合金催化剂包含载体以及负载于所述载体的Pd金属，所述载体为具有多个孔道的氮掺杂多孔碳复合材料，Pd金属分布于所述孔道中，所述氮掺杂多孔碳复合材料包含氮掺杂多孔碳材料、氧化铟以及通过该孔道而暴露的金属In，所述氧化铟均匀分布于所述氮掺杂多孔碳材料中，所述金属In选择性地占据所述Pd金属的边角位而实现与Pd金属复合。也就是说，氧化铟(In 2O 3)仅暴露的部分被还原形成In，而没有暴露的部分没有被还原。
所述Pd金属在所述氮掺杂多孔碳复合材料中的分散度为70％～95％。优选的，所述Pd金属在所述氮掺杂多孔碳复合材料中的分散度为70％～80％。
所述Pd金属在所述复合催化剂所占的质量分数为0.1％～10％；所述氧化铟以及金属In在所述复合催化剂所占的质量分数为2％～30％；所述氮掺杂多孔碳材料在所述复合催化剂所占的质量分数为60％～97.9％，其中所述氮掺杂多孔碳材料中氮元素的质量分数为0.5％～15％。
请参阅图5，本发明还提供一种PdIn合金催化剂在催化加氢反应中的应用。所述PdIn合金催化剂在炔醇的选择性加氢反应中作为催化剂。炔醇为2-甲基-3-丁炔-2-醇、3，7-二甲基-1-辛炔-3-醇、3，7-二甲基-6-辛烯-1-炔-3-醇、3，7，11-三甲基-1-十二炔-3-醇、3，7，11-三甲基-6-十二烯-1-炔-3-醇、3，7，11-三甲基-6，10-十二烷二烯-1-炔-3-醇、3，7，11，15-三甲基-1-十六炔-3-醇、3-甲基-1-(2，6，6-三甲基-1-环己烯-1-基)-1-戊烯-4-炔-3-醇和3，6-二甲基-8-(2，6，6-三甲基-1-环己烯-1-基)-2，7-辛二烯-4-炔-1，6-二醇中的至少一种。
以下将通过实施例对本发明所述PdIn合金催化剂及其应用作进一步的说明。
实施例1
称取1g硝酸铟水合物分散于30mL水，待其溶解后加入3g羧甲基甲壳素，搅拌1小时。随后缓慢加入3g碳酸氢铵，搅拌1小时后升温至80℃，搅拌至干燥；然后，转移到坩埚中，在氮气炉中进行煅烧，具体的煅烧过程为：以5℃/min升温到1000℃，在1000℃煅烧1h；然后，自然降温到室温。把煅烧后的混合物研磨碎，得到氮掺杂多孔碳复合材料。
称取1g氮掺杂多孔碳复合材料，加入到60mL去离子水中，缓慢滴加1mL 10mg/mL的PdCl2溶液，50℃搅拌12h，放入70℃烘箱烘干24h。再于空气中200℃煅烧1h。最后300℃氢气还原1h(氢气流速为50mL/min，升温速率5℃/min)，即可得到PdIn合金催化剂，其中在所述PdIn合金催化剂中金属Pd的理论负载量(所占质量比)为0.6％。
采用原子发射光谱，对PdIn合金催化剂中Pd的实际负载量进行测试，结果为0.59％。这与上述Pd的理论负载量基本一致。
对所述氮掺杂多孔碳复合材料进行扫描电镜测试，结果见图1。由图1可见，可以明显观察到丰富的孔道结构。对所述氮掺杂多孔碳复合材料进行透射电镜测试，结果见图2。由图2可见，氧化铟均匀分散在氮掺杂多孔碳复合材料中。。
对所述PdIn合金催化剂进行高倍率的透射电镜测试，结果见图3。由图3可见，Pd颗粒的边角位被In部分占据。
对所述PdIn合金催化剂进行X射线光电子能谱测试，结果见图4。由图4可见，该PdIn合金催化剂催化剂中包含金属态的In 0。
采用CO滴定的方法(备注：CO滴定方法是一氧化碳吸附测试Pd金属的分散度实验)对所述PdIn合金催化剂的Pd的分散度及比表面积进行测试，测试结果为：Pd的分散度为73％；PdIn合金催化剂的比表面积为113.7m 2g -1。
实施例2
称取1g硝酸铟水合物分散于30mL水，待其溶解后加入3g羧甲基壳聚糖，搅拌1小时。随后缓慢加入3g碳酸氢铵，搅拌1小时后升温至80℃，搅拌至干燥；然后，转移到坩埚中，在氮气炉中进行煅烧，具体的煅烧过程为：以5℃/min升温到1000℃，在1000℃煅烧1h；然后，自然降温到室温。把煅烧后的混合物研磨碎，得到氮掺杂多孔碳复合材料。
称取1g氮掺杂多孔碳复合材料，加入到60mL去离子水中，缓慢滴加1mL 10mg/mL的PdCl 2溶液，50℃搅拌12h，放入70℃烘箱烘干24h。再于空气中200℃煅烧1h，最后300℃氢气还原1h(氢气流速为50mL/min，升温速率5℃/min)即可得到PdIn合金催化剂。
实施例2的PdIn合金催化剂的制备方法与实施例1的方法基本相同，不同之处在于，含氮生物素为羧甲基壳聚糖。
采用CO滴定的方法测试所得到的PdIn合金催化剂中Pd的分散度，结果为：Pd的分散度为77％。该PdIn合金催化剂的比表面积为126.6m 2g -1。
以下实施例加氢反应的反应结构式请参见图4。
实施例3
PdIn合金催化剂催化2-甲基-3-丁炔-2-醇(I)选择性加氢反应，具体如下：
采用50mL高压反应釜；加入实施例1得到的PdIn合金催化剂50mg；底物2-甲基-3-丁炔-2-醇20mmol；乙醇5mL；氢气1MPa；反应温度30℃；反应时间2h。2-甲基-3-丁炔-2- 醇(I)转化率为100％，2-甲基-3-丁烯-2-醇(II)选择性为98％。
进一步提供对比例1和对比例2。对比例1和对比例2分别为传统浸渍法制备的Pd/Al 2O 3和Pd/ZnO催化剂。Pd/Al 2O 3催化剂的转化率和选择性分别为100％和72％，而Pd/ZnO催化剂的转化率和选择性分别为15％和99％。由此可见，实施例1中制备的高分散PdIn合金催化剂在维持催化剂活性的同时大大提升了选择性。
实施例4
PdIn合金催化剂催化3，7-二甲基-1-辛炔-3-醇(III)选择性加氢反应，具体如下：
采用50mL高压反应釜；加入实施例1的PdIn合金催化剂50mg；底物3，7-二甲基-1-辛炔-3-醇(III)20mmol；乙醇5mL；氢气1MPa；反应温度30℃；反应时间2h。3，7-二甲基-1-辛炔-3-醇(III)转化率为100％，3，7-二甲基-1-辛烯-3-醇(IV)选择性为98％。
实施例5
PdIn合金催化剂催化3，7-二甲基-6-辛烯-1-炔-3-醇(V)选择性加氢反应，具体如下：
采用50mL高压反应釜；加入实施例1的PdIn合金催化剂50mg；底物3，7-二甲基-6-辛烯-1-炔-3-醇(V)20mmol；乙醇5mL；氢气1MPa；反应温度30℃；反应时间2h。3，7-二甲基-6-辛烯-1-炔-3-醇(V)转化率为100％，3，7-二甲基-1，6-辛二烯-3-醇(VI)选择性为98％。
实施例6
PdIn合金催化剂催化3，7，11-三甲基-1-十二炔-3-醇(VII)选择性加氢反应，具体如下：
采用50mL高压反应釜；加入实施例1的PdIn合金催化剂50mg；底物3，7，11-三甲基-1-十二炔-3-醇(VII)20mmol；乙醇5mL；氢气1MPa；反应温度30℃；反应时间2h。3，7，11-三甲基-1-十二炔-3-醇(VII)转化率为100％，3，7，11-三甲基-1-十二烯-3-醇(VIII)选择性为98％。
实施例7
PdIn合金催化剂催化3，7，11-三甲基-6-十二烯-1-炔-3-醇(IX)选择性加氢反应，具体如下：
采用50mL高压反应釜；加入实施例1的PdIn合金催化剂50mg；底物3，7，11-三甲基-6-十二烯-1-炔-3-醇(IX)20mmol；乙醇5mL；氢气1MPa；反应温度30℃；反应时间2h。3，7，11-三甲基-6-十二烯-1-炔-3-醇(IX)转化率为100％，3，7，11-三甲基-1，6-十二烷二烯-3-醇 (X)选择性为98％。
实施例8
PdIn合金催化剂催化3，7，11-三甲基-6，10-十二烷二烯-1-炔-3-醇(XI)选择性加氢反应，具体如下：
采用50mL高压反应釜；加入实施例1的PdIn合金催化剂50mg；底物3，7，11-三甲基-6，10-十二烷二烯-1-炔-3-醇(XI)15mmol；乙醇5mL；氢气1MPa；反应温度30℃；反应时间2h。3，7，11-三甲基-6，10-十二烷二烯-1-炔-3-醇(XI)转化率为100％，3，7，11-三甲基-1，6，10-十二烷三烯-3-醇(X)选择性为98％。
实施例9
PdIn合金催化剂催化3，7，11，15-三甲基-1-十六炔-3-醇(XIII)选择性加氢反应，具体如下：
采用50mL高压反应釜；加入实施例1的PdIn合金催化剂50mg；底物3，7，11，15-三甲基-1-十六炔-3-醇(XIII)20mmol；乙醇5mL；氢气1MPa；反应温度30℃；反应时间2h。3，7，11，15-三甲基-1-十六炔-3-醇(XIII)转化率为100％，3，7，11，15-三甲基-1-十六烯-3-醇(XIV)选择性为98％。
实施例10
PdIn合金催化剂催化3-甲基-1-(2，6，6-三甲基-1-环己烯-1-基)-1-戊烯-4-炔-3-醇(XV)选择性加氢反应，具体如下：
采用50mL高压反应釜；加入实施例7的PdIn合金催化剂50mg；底物3-甲基-1-(2，6，6-三甲基-1-环己烯-1-基)-1-戊烯-4-炔-3-醇(XV)10mmol；乙醇5mL；氢气1MPa；反应温度30℃；反应时间2h。3-甲基-1-(2，6，6-三甲基-1-环己烯-1-基)-1-戊烯-4-炔-3-醇(XV)转化率为100％，3-甲基-1-(2，6，6-三甲基-1-环己烯-1-基)-1，4-戊二烯-3-醇(XVI)选择性为98％。
实施例11
PdIn合金催化剂催化3，6-二甲基-8-(2，6，6-三甲基-1-环己烯-1-基)-2，7-辛二烯-4-炔-1，6-二醇(XVII)选择性加氢反应，具体如下：
采用50mL高压反应釜；加入实施例1的PdIn合金催化剂50mg；底物3，6-二甲基-8-(2，6，6-三甲基-1-环己烯-1-基)-2，7-辛二烯-4-炔-1，6-二醇(XVII)10mmol；乙醇5mL；氢气 1MPa；反应温度30℃；反应时间2h。3，6-二甲基-8-(2，6，6-三甲基-1-环己烯-1-基)-2，7-辛二烯-4-炔-1，6-二醇(XVI)转化率为100％，3，6-二甲基-8-(2，6，6-三甲基-1-环己烯-1-基)-2，4，7-辛三烯-1，6-二醇(XVIII)选择性为98％。
实施例12
PdIn合金催化剂催化2-甲基-3-丁炔-2-醇(I)选择性加氢反应的套用性能，具体如下：
采用50mL高压反应釜；加入实施例1的PdIn合金催化剂50mg；底物2-甲基-3-丁炔-2-醇(I)50mg；加入底物2-甲基-3-丁炔-2-醇(I)20mmol；乙醇5mL；氢气1MPa；反应温度30℃；反应时间2h。反应后催化剂通过离心取出，用乙醇洗涤3次，40℃真空干燥后继续用于2-甲基-3-丁炔-2-醇(I)选择性加氢反应。套用结果见表1，可以发现该PdIn合金催化剂性能稳定，套用15次后，活性和选择性依然可以保持。
表1
Figure PCTCN2019070893-appb-000001
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (12)

  1. 一种PdIn合金催化剂，其特征在于，所述PdIn合金催化剂包含载体以及负载于所述载体的Pd金属，所述载体为具有多个孔道的氮掺杂多孔碳复合材料，Pd金属分布于所述孔道中，所述氮掺杂多孔碳复合材料包含氮掺杂多孔碳材料、氧化铟以及通过该孔道而暴露的金属In，所述氧化铟均匀分布于所述氮掺杂多孔碳材料中，所述金属In选择性地占据所述Pd金属的边角位。
  2. 如权利要求1所述的PdIn合金催化剂，其特征在于，所述Pd金属在所述氮掺杂多孔碳复合材料中的分散度为70％～95％。
  3. 如权利要求1所述的PdIn合金催化剂，其特征在于，所述Pd金属在所述复合催化剂所占的质量分数为0.1％～10％；所述氧化铟以及金属In在所述复合催化剂所占的质量分数为2％～30％；所述氮掺杂多孔碳材料在所述复合催化剂所占的质量分数为60％～97.9％，其中所述氮掺杂多孔碳材料中氮元素的质量分数为0.5％～15％。
  4. 一种PdIn合金催化剂的制备方法，其特征在于，其包含以下步骤：
    1)提供具有多个孔道的氮掺杂多孔碳复合材料，其中所述氮掺杂多孔碳复合材料包含氮掺杂多孔碳材料以及氧化铟，所述氧化铟均匀分布于所述氮掺杂多孔碳材料中并部分氧化铟通过该孔道而暴露；
    2)将所述氮掺杂多孔碳复合材料浸渍于Pd金属前驱体溶液中；
    3)对浸渍后的氮掺杂多孔碳复合材料进行第一煅烧，使Pd金属前驱体溶液中的Pd金属前驱体转化为Pd金属，Pd金属分布于所述孔道中；
    4)对经过第一煅烧后的氮掺杂多孔碳复合材料进行氢气还原，其中，在氢气还原过程中，通过该孔道而暴露的氧化铟被还原为金属In，并且所述金属In选择性地占据所述Pd金属的边角位而实现与Pd金属复合。
  5. 如权利要求4所述的PdIn合金催化剂的制备方法，其特征在于，步骤1)中所述氮掺杂多孔碳复合材料的制备方法具体如下：
    a)将硝酸铟溶于水中，得到预混物；
    b)依次向所述预混物中加入含氮生物质及致孔剂，并使所述硝酸铟与致孔剂进行反应，得到含金属沉淀物的混合物，其中所述致孔剂为碳酸氢铵、碳酸铵、草酸铵、草酸氢胺、草酸中的至少一种，所述硝酸铟与致孔剂的摩尔比为1∶(1～20)；以及
    c)将所述混合物于500摄氏度～1200摄氏度在惰性氛围下进行第二煅烧，得到具有多个孔道的氮掺杂多孔碳复合材料。
  6. 如权利要求4所述的PdIn合金催化剂的制备方法，其特征在于，所述Pd金属前驱体 溶液中的Pd金属前驱体为PdCl 2、H 2PdCl 4、Pd(NO 3) 2、Pd(NH 3) 4(NO 3) 2中的至少一种。
  7. 如权利要求4所述的PdIn合金催化剂的制备方法，其特征在于，步骤3)所述第一煅烧过程中，煅烧温度为200摄氏度～500摄氏度，升温速率为1摄氏度/分钟～20摄氏度/分钟，时间为1分钟～240分钟；所述氢气还原的过程中温度为50摄氏度～500摄氏度，升温速率为1摄氏度/分钟～20摄氏度/分钟，时间为1分钟～360分钟，氢气流速为20毫升/分钟～200毫升/分钟。
  8. 如权利要求5所述的PdIn合金催化剂的制备方法，其特征在于，步骤b)，所述含氮生物质为竹子、甲壳素、羧甲基甲壳素、壳聚糖、羧甲基壳聚糖、氨基葡萄糖盐酸盐中的至少一种。
  9. 如权利要求5所述的PdIn合金催化剂的制备方法，其特征在于，步骤b)中所述硝酸铟与含氮生物质的质量比为(0.05～2)∶1。
  10. 如权利要求5所述的PdIn合金催化剂的制备方法，其特征在于，步骤c)中，所述第二煅烧的过程中煅烧时间为0.1小时～5小时。
  11. 一种如权利要求1～3所述PdIn合金催化剂在催化加氢反应中的应用，其特征在于，所述PdIn合金催化剂在炔醇的选择性加氢反应中作为催化剂。
  12. 如权利要求11所述PdIn合金催化剂在催化加氢反应中的应用，其特征在于，所述炔醇为2-甲基-3-丁炔-2-醇、3，7-二甲基-1-辛炔-3-醇、3，7-二甲基-6-辛烯-1-炔-3-醇、3，7，11-三甲基-1-十二炔-3-醇、3，7，11-三甲基-6-十二烯-1-炔-3-醇、3，7，11-三甲基-6，10-十二烷二烯-1-炔-3-醇、3，7，11，15-三甲基-1-十六炔-3-醇、3-甲基-1-(2，6，6-三甲基-1-环己烯-1-基)-1-戊烯-4-炔-3-醇和3，6-二甲基-8-(2，6，6-三甲基-1-环己烯-1-基)-2，7-辛二烯-4-炔-1，6-二醇中的至少一种。
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