WO2020042526A1 - 复合催化剂及其制备方法、应用 - Google Patents

复合催化剂及其制备方法、应用 Download PDF

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WO2020042526A1
WO2020042526A1 PCT/CN2019/071319 CN2019071319W WO2020042526A1 WO 2020042526 A1 WO2020042526 A1 WO 2020042526A1 CN 2019071319 W CN2019071319 W CN 2019071319W WO 2020042526 A1 WO2020042526 A1 WO 2020042526A1
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nitrogen
porous carbon
composite catalyst
doped porous
metal
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PCT/CN2019/071319
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English (en)
French (fr)
Inventor
王勇
于丽丽
马啸
毛建拥
王哲
毛善俊
唐静思
李浩然
陈志荣
Original Assignee
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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Application filed by 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 filed Critical 浙江新和成股份有限公司
Priority to DE112019000069.1T priority Critical patent/DE112019000069T5/de
Priority to US16/669,524 priority patent/US10668460B2/en
Publication of WO2020042526A1 publication Critical patent/WO2020042526A1/zh

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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
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    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
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    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/464—Rhodium
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/468—Iridium
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    • 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
    • B01J35/393—Metal or metal oxide crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • 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
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems

Definitions

  • the invention relates to the technical field of catalysts, in particular to a composite catalyst and a preparation method and application thereof.
  • the present invention provides a composite catalyst, a preparation method thereof, and related applications.
  • Noble metals are highly dispersed in the obtained composite catalyst, so the composite catalyst has excellent catalytic effect.
  • the invention provides a composite catalyst comprising a support and a precious metal supported on the support, the support is a nitrogen-doped porous carbon composite material, and the nitrogen-doped porous carbon composite material comprises a nitrogen-doped porous carbon.
  • Materials and metal oxides the metal oxides are uniformly distributed in the nitrogen-doped porous carbon material, the nitrogen-doped porous carbon composite material has a plurality of channels, and a part of the surface of the metal oxide passes through the channels
  • the precious metal is tightly combined with the exposed metal oxide to achieve recombination, and the precious metal is at least one of Pd, Pt, Ru, Rh, Ir, and Au.
  • the dispersion degree of the noble metal in the nitrogen-doped porous carbon composite material is 75% to 95%.
  • the mass fraction of the noble metal in the composite catalyst is 0.1% to 10%; the mass fraction of the metal oxide 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 invention also provides a method for preparing a composite catalyst, which comprises the following steps:
  • Nitrogen-containing biomass and a porogen are sequentially added to the premix, and the metal source is reacted with the porogen to obtain a mixture containing a metal precipitate, wherein the porogen is hydrogen carbonate At least one of ammonium, ammonium carbonate, ammonium oxalate, ammonium oxalate, and oxalic acid, and the molar ratio of the metal source to the porogen is 1: (1-20);
  • the mixture is first calcined under an inert atmosphere at 500 degrees Celsius to 1200 degrees Celsius to obtain a nitrogen-doped porous carbon composite material having multiple channels, wherein the nitrogen-doped porous carbon composite material includes nitrogen-doped porous Carbon material and metal oxide, the metal oxide is uniformly distributed in the nitrogen-doped porous carbon material, and a part of the metal oxide is exposed through the pores;
  • a noble metal is formed in the pores of the nitrogen-doped porous carbon composite material, so that the noble metal is tightly bound to oxygen atoms in the exposed metal oxide.
  • step 4 forming a noble metal in the pores of the nitrogen-doped porous carbon composite material is as follows:
  • the impregnated nitrogen-doped porous carbon composite material is sequentially subjected to a second calcination and hydrogen reduction, and a noble metal is formed in the pores of the nitrogen-doped porous carbon composite material.
  • step 4 forming a noble metal in the pores of the nitrogen-doped porous carbon composite material is as follows:
  • the calcination temperature is 200 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 240 minutes
  • the temperature during the hydrogen reduction process is 150 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 reducing agent is at least one of NaBH4, HCOOH, and hydrazine hydrate, and the molar ratio of the reducing agent to the precious metal precursor in the precious metal precursor solution is (1 to 1000): 1.
  • the metal source is cerium nitrate, zirconium nitrate, aluminum nitrate
  • the solvent is water
  • the nitrogen-containing biomass is bamboo, chitin, carboxymethyl chitin, chitosan, and carboxymethyl At least one of a base chitosan and glucosamine hydrochloride.
  • the mass ratio of the metal source to the nitrogen-containing biomass in step 2) is (0.05-2): 1.
  • the calcining time in the first calcining process is 0.1 hour to 5 hours.
  • the carbonate ion or bicarbonate ion in the porogen can react with the metal ion in the metal source to obtain a metal precipitate, and the metal precipitate is uniform. Distribution; on the other hand, the porogen and metal precipitate can be decomposed during the subsequent calcination process, and the generated gas can promote the formation of multiple pores in the nitrogen-doped porous carbon material. During the calcination process, metal precipitates decompose to form nano-scale metal oxides. The metal 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 metal source, and the carbonate or oxalate in the porogen 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 present invention also provides an application of a composite catalyst in a catalytic hydrogenation reaction.
  • the composite catalyst is used as a catalyst in a selective hydrogenation reaction of an unsaturated ketone or a biotin precursor.
  • the structure of the biotin precursor is as follows: :
  • the unsaturated ketone is 6-methyl-5-hepten-2-one, 6,10-dimethyl-5-undecen-2-one, 6,10-dimethyl-5 , 9-undecanedien-2-one, 6,10,14-trimethyl-5-pentadecen-2-one, 6,10,14-trimethyl-5,9-pentadecane At least one of diene-2-one and 6,10,14-trimethyl-5,9,13-pentadecantrien-2-one.
  • the composite 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 composite catalyst described in Example 1.
  • FIG. 3 is a transmission electron microscope photograph of the composite catalyst described in Example 1.
  • FIG. 4 is an X-ray diffraction pattern of the nitrogen-doped porous carbon composite material and the composite catalyst described in Example 1.
  • FIG. 4 is an X-ray diffraction pattern of the nitrogen-doped porous carbon composite material and the composite catalyst described in Example 1.
  • FIG. 5 is a schematic structural diagram of a selective hydrogenation reaction using a composite catalyst according to the present invention.
  • the invention provides a method for preparing a composite catalyst.
  • the preparation method includes the following steps:
  • Nitrogen-containing biomass and a porogen are sequentially added to the premix, and a metal source is reacted with the porogen to obtain a mixture containing a metal precipitate, wherein the porogen is ammonium bicarbonate, At least one of ammonium carbonate, ammonium oxalate, ammonium oxalate, and oxalic acid, and the molar ratio of the metal source to the porogen is 1: (1-20);
  • the mixture is first calcined under an inert atmosphere at 500 degrees Celsius to 1200 degrees Celsius to obtain a nitrogen-doped porous carbon composite material having multiple channels, wherein the nitrogen-doped porous carbon composite material includes a nitrogen-doped porous material.
  • a carbon material and a metal oxide which are uniformly distributed in the nitrogen-doped porous carbon material and a part of the metal oxide is exposed through the channel;
  • a noble metal is formed in the pores of the nitrogen-doped porous carbon composite material, so that the noble metal is tightly bound to oxygen atoms in the exposed metal oxide.
  • the metal source generally selects a metal oxide that can support a noble metal catalyst.
  • the metal source is required to be soluble in the solvent.
  • the metal source may be cerium nitrate, zirconium nitrate, or aluminum nitrate, and the solvent may be water.
  • the ratio of the metal source to the solvent is not limited.
  • the ratio of the mass of the metal source to the volume of the solvent 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 the solvent.
  • the metal source reacts with a portion 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 metal source to the nitrogen-containing biomass may be (0.05-2): 1, and preferably, the mass ratio of the metal source 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.
  • step S2 and before step S3 the mixture is dried, and the specific drying process may be: drying at a temperature of 60 degrees Celsius to 180 degrees Celsius.
  • the first calcination time may be 0.1 to 5 hours.
  • the specific first 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 first calcination temperature is 600 ° C to 900 ° C.
  • the noble metal is at least one of Pd, Pt, Ru, Rh, Ir, and Au.
  • the supported amount (ie, the mass fraction) of the noble metal in the composite catalyst can be controlled without limitation.
  • the process of the impregnation method is as follows: the nitrogen-doped porous carbon composite material is immersed in a precious metal precursor solution; the soaked nitrogen-doped porous carbon composite material is sequentially subjected to a second calcination and hydrogen reduction, and the Noble metals are formed in the pores of the nitrogen-doped porous carbon composite.
  • the calcining temperature in the second calcining 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 in the hydrogen reduction process 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 process of the liquid-phase reduction method is as follows: immersing the nitrogen-doped porous carbon composite material in a precious metal precursor solution; continuing to add a reducing agent to cause the precious metal precursor to react with the reducing agent, and doping the nitrogen Precious metals are formed in the pores of the porous carbon composite.
  • the noble metal precursor in the noble metal precursor solution referred to in the above-mentioned impregnation method and liquid phase reduction method may be PdCl 2 , H 2 PdCl 4 , Pd (NO 3 ) 2 , Pd (NH 3 ) 4 (NO 3 ) 2 , H 2 PtCl 6 ⁇ 6H 2 O, [Pt (NH 3 ) 4 ] (NO 3 ) 2 , Na 2 PtCl 4 ⁇ xH 2 O, H 8 C 14 N 2 Pt, PtCl 4 , Pt (C 5 H 7 O 2 ) 2 , C 10 H 14 O 4 Pt, (NH 4 ) 2 RuCl 6 , RuCl 3 , C 15 H 21 O 6 Ru, H 12 Cl 6 N 3 Rh, RhN 3 O 9 , RhCl 3 ⁇ 3H 2 O , IrCl 3 , Na 2 IrCl 6 ⁇ 6H 2 O, H 2 IrCl 6 ⁇ xH 2 O, [CH
  • the reducing agent in the liquid phase reduction is at least one of NaBH4, HCOOH, and hydrazine hydrate.
  • the molar ratio of the reducing agent to the precious metal precursor solution in the precious metal precursor solution is (1 to 1000): 1.
  • the invention also provides a composite catalyst.
  • the composite catalyst includes a support and a precious metal supported on the support.
  • the support is a nitrogen-doped porous carbon composite material having a plurality of pores.
  • the nitrogen-doped porous carbon composite material includes a nitrogen-doped porous carbon material and a metal. Oxide, the metal oxide is uniformly distributed in the nitrogen-doped porous carbon material, a part of the surface of the metal oxide is exposed through the channel, and the precious metal is tightly combined with the exposed metal oxide to achieve recombination,
  • the noble metal is at least one of Pd, Pt, Ru, Rh, Ir, and Au.
  • the dispersion degree of the noble metal in the nitrogen-doped porous carbon composite material is 75% to 95%.
  • the mass fraction of the precious metal in the composite catalyst is 0.1% to 10%; the mass fraction of the metal oxide in the composite catalyst is 2% to 30%; the nitrogen-doped porous carbon material A mass fraction occupied by the composite catalyst is 60% to 97.9%, and a 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 composite catalyst in a catalytic hydrogenation reaction.
  • the composite catalyst is used as a catalyst in the selective hydrogenation reaction of unsaturated ketone or biotin precursor (X).
  • the unsaturated ketone is 6-methyl-5-hepten-2-one (I), 6,10-dimethyl-5-undecen-2-one (III), 6,10-dimethyl -5,9-undecanedione-2-one (V), 6,10,14-trimethyl-5-pentadecen-2-one (VI), 6,10,14-trimethyl At least 5-5,9-pentadecanedien-2-one (VIII), 6,10,14-trimethyl-5,9,13-pentadecantrien-2-one (IX) One.
  • Atomic emission spectroscopy was used to test the actual loading of Pd in the composite 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.
  • FIG. 3 A transmission electron microscope test was performed on the composite catalyst, and the results are shown in FIG. 3. Comparing FIG. 2 and FIG. 3, it can be seen that the morphology of FIG. 3 is basically unchanged compared to FIG. 2, and it is difficult to see the Pd metal in FIG. 3 because the particle size of the Pd particles is very small, below 1 nm.
  • the CO titration method (Note: The CO titration method is a carbon monoxide adsorption test for the dispersion of precious metals) was used to test the Pd dispersion and specific surface area of the composite catalyst. The test results were: Pd dispersion was 83%; The specific surface area of the catalyst was 135.3 m 2 g -1 .
  • the composite catalyst can be obtained by calcining in air at 300 ° C for 1 hour, and finally reducing the hydrogen at 300 ° C for 1 hour (hydrogen flow rate is 50 mL / min, and the heating rate is 5 ° C / min).
  • the method for preparing the composite catalyst in Example 2 is basically the same as the method in Example 1, except that the nitrogen-containing biotin is chitosan.
  • the composite catalyst can be obtained by reducing the hydrogen at 300 ° C for 1 hour (the hydrogen flow rate is 50 mL / min and the heating rate is 5 ° C / min).
  • CO titration was used to test the dispersion and specific surface area of Pd of the composite catalyst.
  • the test results were: the dispersion of Pd was 79%; the specific surface area of the composite catalyst was 126.8 m 2 g -1 .
  • the composite catalyst can be obtained by reducing the hydrogen at 300 ° C for 1 hour (the hydrogen flow rate is 50 mL / min and the heating rate is 5 ° C / min).
  • CO titration was used to test the dispersion and specific surface area of Pd of the composite catalyst, and the test result was: the dispersion of Pd was 76%.
  • the specific surface area of the composite catalyst was 115.5 m 2 g -1 .
  • CO titration was used to test the dispersion and specific surface area of Pd of the composite catalyst.
  • the test results were: the dispersion of Pd was 89%; the specific surface area of the composite catalyst was 138.7 m 2 g -1 .
  • the composite catalyst can be obtained by reducing the hydrogen at 300 ° C for 1 hour (the hydrogen flow rate is 50 mL / min and the heating rate is 5 ° C / min).
  • CO titration was used to test the dispersion and specific surface area of Pt of the composite catalyst.
  • the test results were: the dispersion of Pt was 91%, and the specific surface area of the catalyst was as high as 133.5 m 2 g -1 .
  • the composite catalyst can be obtained by reducing the hydrogen at 300 ° C for 1 hour (the hydrogen flow rate is 50 mL / min and the heating rate is 5 ° C / min).
  • the method of CO titration was used to test the dispersion and specific surface area of Ru of the composite catalyst.
  • the test result was: the dispersion of Ru was 82%, and the specific surface area of the composite catalyst was 133.9 m 2 g -1 .
  • a CO titration method was used to test the dispersion and specific surface area of Rh of the composite catalyst.
  • the test result was: the dispersion of Rh was 83%; the specific surface area of the composite catalyst was as high as 139.2 m 2 g -1 .
  • a CO titration method was used to test the dispersion and specific surface area of Ir of the composite catalyst.
  • the test result was: the dispersion of Ir was 81%, and the specific surface area of the composite catalyst was 128.4 m 2 g -1 .
  • the composite catalyst can be obtained by reducing the hydrogen at 300 ° C for 1 hour (the hydrogen flow rate is 50 mL / min and the heating rate is 5 ° C / min).
  • CO titration was used to test the dispersity and specific surface area of Au of the composite catalyst.
  • the test result was: the dispersity of Au was 88%, and the specific surface area of the composite catalyst was as high as 137.3 m 2 g -1 .
  • the composite catalyst catalyzes the selective hydrogenation of 6-methyl-5-hepten-2-one (I) as follows:
  • the composite catalyst catalyzes the selective hydrogenation of 6,10-dimethyl-5-undecen-2-one (III) as follows:
  • a 50 mL autoclave was used; 50 mg of the composite catalyst of Example 1 was added; the substrate 6,10-dimethyl-5-undecen-2-one (III) 15 mmol; ethanol 5 mL; hydrogen 2 MPa; reaction temperature 30 ° C; The reaction time is 4h.
  • the 6,10-dimethyl-5-undecen-2-one (III) conversion was 100%, and the 6,10-dimethyl-undecane-2-one (IV) selectivity was 99%.
  • the composite catalyst catalyzes the selective hydrogenation of 6,10-dimethyl-5,9-undecanedione-2-one (V) as follows:
  • the composite catalyst catalyzes the selective hydrogenation of 6,10,14-trimethyl-5-pentadecen-2-one (VI) as follows:
  • the composite catalyst catalyzes the selective hydrogenation of 6,10,14-trimethyl-5,9-pentadecanedien-2-one (VIII) as follows:
  • the composite catalyst catalyzes the selective hydrogenation of 6,10,14-trimethyl-5,9,13-pentadecantrien-2-one (IX) as follows:
  • the composite catalyst catalyzes the selective hydrogenation of 6-methyl-5-hepten-2-one (I) as follows:
  • the composite catalyst catalyzes the selective hydrogenation of 6-methyl-5-hepten-2-one (I) as follows:
  • a 50 mL autoclave was used; 50 mg of the composite catalyst of Example 7 was added; the substrate 6-methyl-5-hepten-2-one (I) 2 mmol; ethanol 5 mL; hydrogen 2 MPa; reaction temperature 40 ° C; reaction time 5 h.
  • the conversion of 6-methyl-5-hepten-2-one (I) was 100%, and the selectivity of 6-methyl-2-heptenone (II) was 97%.
  • the composite catalyst catalyzes the selective hydrogenation of 6-methyl-5-hepten-2-one (I) as follows:
  • a 50 mL autoclave was used; 50 mg of the composite catalyst of Example 8 was added; substrate 6-methyl-5-hepten-2-one (I) 15 mmol; ethanol 5 mL; hydrogen 2 MPa; reaction temperature 30 ° C; reaction time 4 h. 6-methyl-5-hepten-2-one (I) conversion was 100%, and 6-methyl-2-heptanone (II) selectivity was 99%.
  • the composite catalyst catalyzes the selective hydrogenation of 6-methyl-5-hepten-2-one (I) as follows:
  • the composite catalyst catalyzes the selective hydrogenation of 6-methyl-5-hepten-2-one (I) as follows:
  • a 50 mL autoclave was used; 50 mg of the composite catalyst of Example 10 was added; the substrate 6-methyl-5-hepten-2-one (I) 2 mmol; ethanol 5 mL; hydrogen 2 MPa; reaction temperature 50 ° C; reaction time 6 h.
  • the conversion of 6-methyl-5-hepten-2-one (I) was 100%, and the selectivity of 6-methyl-2-heptenone (II) was 97%.
  • the composite catalyst catalyzes the selective hydrogenation of biotin precursor (X), as follows:
  • a 50 mL autoclave was used; 200 mg of the composite catalyst of Example 1 was added; 2 mmol of the substrate biotin precursor (X); 5 mL of ethanol; 2 MPa of hydrogen; a reaction temperature of 40 ° C; and a reaction time of 3 hours.
  • Biotin precursor (X) conversion was 100% and biotin (XI) selectivity was 99%.
  • the composite catalyst catalyzes the selective hydrogenation of biotin precursor (X), as follows:
  • a 50 mL autoclave was used; 200 mg of the composite catalyst of Example 6 was added; 2 mmol of the substrate biotin precursor (X); 5 mL of ethanol; 2 MPa of hydrogen; a reaction temperature of 50 ° C; and a reaction time of 3 hours.
  • Biotin precursor (X) conversion was 100% and biotin (XI) selectivity was 99%.
  • Example 1 A 50 mL autoclave was used; 50 mg of the composite catalyst of Example 1 was added; substrate 6-methyl-5-hepten-2-one (I) 15 mmol; ethanol 5 mL; hydrogen 2 MPa; reaction temperature 30 ° C; reaction time 4 h. After the reaction, the composite catalyst was taken out by centrifugation, washed with ethanol three times, and dried at 40 ° C under vacuum and continued to be used for the reaction.
  • the application results of the composite catalyst are shown in Table 1. The composite catalyst can be applied 60 times repeatedly, with little change in activity and selectivity, and excellent stability.
  • the specific performance of the composite catalyst for the selective hydrogenation of biotin precursor (X) is as follows:
  • a 50 mL autoclave was used; 200 mg of the composite catalyst of Example 1 was added; 2 mmol of the substrate biotin precursor (X); 5 mL of ethanol; 2 MPa of hydrogen; a reaction temperature of 40 ° C; and a reaction time of 3 hours.
  • the composite catalyst was taken out by centrifugation, washed three times with ethanol, and dried at 40 ° C under vacuum and continued to be used for the reaction.
  • the results of the application of the composite catalyst are shown in Table 2.
  • the composite catalyst can be applied 35 times repeatedly with almost no change in activity and selectivity, and has excellent stability.

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Abstract

本发明提供一种复合催化剂，所述复合催化剂包含载体以及负载于所述载体的贵金属，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以及金属氧化物，所述金属氧化物均匀分布于所述氮掺杂多孔碳材料中，所述金属氧化物的部分表面通过该孔道而暴露，所述贵金属与暴露的金属氧化物紧密结合而实现复合，所述贵金属为Pd、Pt、Ru、Rh、Ir、Au中的至少一种。本发明还提供一种复合催化剂的制备方法及其应用。

Description

复合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201811010567.1，名称为“复合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，特别是涉及复合催化剂及其制备方法、应用。
背景技术
生活中用到的各类化学品超过80％是通过特定的催化过程生产获取的。催化过程的核心是催化剂。而多相催化剂因其操作简便等特点而受到广泛关注。作为多相催化剂的重要代表，负载型金属纳米催化剂的应用范围非常广。将活性位金属分散在某一载体上能够使其在达到相同催化效果的前提下大大减少金属的用量。而炭材料具有高导热导电性能和化学稳定性，是一种理想的催化剂载体。贵金属纳米颗粒由于为纳米级别而易团聚，因此当用碳材料负载时，难以实现高度分散。
发明内容
针对上述问题，本发明提供一种复合催化剂及其制备方法及相关应用。所得到的复合催化剂中贵金属高度分散，因而该复合催化剂具有优异的催化效果。
本发明提供一种复合催化剂，所述复合催化剂包含载体以及负载于所述载体的贵金属，所述载体为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以及金属氧化物，所述金属氧化物均匀分布于所述氮掺杂多孔碳材料中，所述氮掺杂多孔碳复合材料具有多个孔道，所述金属氧化物的部分表面通过该孔道而暴露，所述贵金属与暴露的金属氧化物紧密结合而实现复合，所述贵金属为Pd、Pt、Ru、Rh、Ir、Au中的至少一种。
优选的，所述贵金属在所述氮掺杂多孔碳复合材料中的分散度为75％～95％。
优选的，所述贵金属在所述复合催化剂所占的质量分数为0.1％～10％；所述金属氧化物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％。
本发明还提供一种复合催化剂的制备方法，其包含以下步骤：
1)将金属源溶于溶剂中，得到预混物；
2)依次向所述预混物中加入含氮生物质及致孔剂，并使所述金属源与致孔剂进行反应，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，所述金属源与致孔剂的摩尔比为1∶(1～20)；
3)将所述混合物于500摄氏度～1200摄氏度在惰性氛围下进行第一煅烧，得到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金属氧化物，所述金属氧化物均匀分布于所述氮掺杂多孔碳材料中并部分金属氧化物通过该孔道而暴露；
4)在所述氮掺杂多孔碳复合材料的孔道内形成贵金属，而使所述贵金属与暴露的金属氧化物中的氧原子紧密结合。
优选的，步骤4)中在所述氮掺杂多孔碳复合材料的孔道内形成贵金属具体如下：
将所述氮掺杂多孔碳复合材料浸渍于贵金属前驱体溶液中；
对浸渍后的氮掺杂多孔碳复合材料依次进行第二煅烧、氢气还原，而在所述氮掺杂多孔碳复合材料的孔道内形成贵金属。
优选的，步骤4)中在所述氮掺杂多孔碳复合材料的孔道内形成贵金属具体如下：
将所述氮掺杂多孔碳复合材料浸于贵金属前驱体溶液中；
继续加入还原剂，使贵金属前驱体与还原剂进行反应，而在所述氮掺杂多孔碳复合材料的孔道内形成贵金属。
优选的，所述贵金属前驱体溶液中的贵金属前驱体为PdCl 2、H 2PdCl 4、Pd(NO 3) 2、Pd(NH 3) 4(NO 3) 2、H 2PtCl 6·6H 2O、[Pt(NH 3) 4](NO 3) 2、Na 2PtCl 4·xH 2O、H 8C 14N 2Pt、PtCl 4、Pt(C 5H 7O 2) 2、C 10H 14O 4Pt、(NH 4) 2RuCl 6、RuCl 3、C 15H 21O 6Ru、H 12Cl 6N 3Rh、RhN 3O 9、RhCl 3·3H 2O、IrCl 3、Na 2IrCl 6·6H 2O、H 2IrCl 6·xH 2O、[CH 3COCH＝C(O-)CH 3] 3Ir、NaAuCl 4·2H 2O、HAuCl 4·XH 2O、(NH 4)AuCl 4中的至少一种。
优选的，所述第二煅烧过程中，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，所述还原剂为NaBH4、HCOOH、水合肼中的至少一种，所述还原剂与所述贵金属前驱体溶液中的贵金属前驱体的摩尔比例为(1～1000)∶1。
优选的，步骤1)所述金属源为硝酸铈、硝酸锆、硝酸铝，所述溶剂为水，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2)中所述金属源与含氮生物质的质量比为(0.05～2)∶1。
优选的，步骤3)中，所述第一煅烧的过程中煅烧时间为0.1小时～5小时。
所述复合催化剂及其制备方法具有以下优点：
所述致孔剂的作用如下：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金属源中的金属离子进行反应，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金属氧化物。该金属氧化物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金属源的反应中，所述致孔剂相对于所述金属源并不需要过量，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。
在第一煅烧的热处理下，所述贵金属与暴露的金属氧化物之间实现较强的作用结合力。并且，利用金属氧化物的氧空位，贵金属原子也会与金属氧化物实现复合而牢固地负载于载体上。即，由于金属氧化物以纳米颗粒的形式分散于炭材料上，因此，贵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贵金属的聚合团簇。该制备方法工艺简单，通过金属氧化物可促进较多的贵金属复合分散，因此贵金属的负载效率较高。该得到的复合催化剂中的贵金属的比表面积大，利于反应物的吸附，催化活性高。
本发明还提供一种复合催化剂在催化加氢反应中的应用，所述复合催化剂在对不饱和酮或者生物素前体的选择性加氢反应中作为催化剂，所述生物素前体的结构如下：
Figure PCTCN2019071319-appb-000001
优选的，所述不饱和酮为6-甲基-5-庚烯-2-酮、6，10-二甲基-5-十一烯-2-酮、6，10-二甲基-5，9-十一烷二烯-2-酮、6，10，14-三甲基-5-十五烯-2-酮、6，10，14-三甲基-5，9-十五烷二烯-2-酮、6，10，14-三甲基-5，9，13-十五烷三烯-2-酮中的至少一种。
由于该复合催化剂中的贵金属的结构稳定，因此该复合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所述复合催化剂的透射电镜照片。
图4为实施例1所述氮掺杂多孔碳复合材料以及复合催化剂的X-射线衍射图谱。
图5为本发明采用复合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。
本发明提供一种复合催化剂的制备方法。所述制备方法包含以下步骤：
S1，将金属源溶于溶剂中，得到预混物；
S2，依次向所述预混物中加入含氮生物质及致孔剂，并使金属源与致孔剂进行反应，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，所述金属源与致孔剂的摩尔比为1∶(1～20)；
S3，将所述混合物于500摄氏度～1200摄氏度在惰性氛围下进行第一煅烧，得到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金属氧化物，所述金属氧化物均匀分布于所述氮掺杂多孔碳材料中并部分金属氧化物通过该孔道而暴露；以及
S4，在所述氮掺杂多孔碳复合材料的孔道内形成贵金属，而使所述贵金属与暴露的金属氧化物中的氧原子紧密结合。
在步骤S1中，所述金属源一般选择可负载贵金属催化剂的金属氧化物。所述金属源要求能溶于所述溶剂中。所述金属源可选为硝酸铈、硝酸锆、硝酸铝，所述溶剂可选为水。所述金属源与所述溶剂的比例不做限定。优选的，所述金属源的质量与所述溶剂的体积的比例为(1g～10g)∶100mL。
在步骤S2中，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所述溶剂。
所述金属源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。所述金属源与含氮生物 质的质量比可为(0.05～2)∶1，优选的，所述金属源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，在步骤S2之后，步骤S3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。
在步骤S3中，所述第一煅烧的时间可为0.1小时～5小时。具体的第一煅烧的过程如下：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，第一煅烧的温度为600℃～900℃。
在步骤S4中，所述贵金属为Pd、Pt、Ru、Rh、Ir、Au中的至少一种。所述贵金属在所述复合催化剂中的负载量(即，质量分数)可以调控，不做限定。在所述氮掺杂多孔碳复合材料的孔道内形成贵金属的方法可为两种：一种为浸渍法；另一种为液相还原法。
所述浸渍法的过程如下：将所述氮掺杂多孔碳复合材料浸于贵金属前驱体溶液中；对浸过后的氮掺杂多孔碳复合材料依次进行第二煅烧、氢气还原，而在所述氮掺杂多孔碳复合材料的孔道内形成贵金属。所述第二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。
所述液相还原法的过程如下：将所述氮掺杂多孔碳复合材料浸于贵金属前驱体溶液中；继续加入还原剂，使贵金属前驱体与还原剂进行反应，而在所述氮掺杂多孔碳复合材料的孔道内形成贵金属。
上述浸渍法以及液相还原法中所称的贵金属前驱体溶液中的贵金属前驱体可为PdCl 2、H 2PdCl 4、Pd(NO 3) 2、Pd(NH 3) 4(NO 3) 2、H 2PtCl 6·6H 2O、[Pt(NH 3) 4](NO 3) 2、Na 2PtCl 4·xH 2O、H 8C 14N 2Pt、PtCl 4、Pt(C 5H 7O 2) 2、C 10H 14O 4Pt、(NH 4) 2RuCl 6、RuCl 3、C 15H 21O 6Ru、H 12Cl 6N 3Rh、RhN 3O 9、RhCl 3·3H 2O、IrCl 3、Na 2IrCl 6·6H 2O、H 2IrCl 6·xH 2O、[CH 3COCH＝C(O-)CH 3] 3Ir、NaAuCl 4·2H 2O、HAuCl 4·XH 2O、(NH 4)AuCl 4中的至少一种。
上述液相还原中的还原剂为NaBH4、HCOOH、水合肼中的至少一种。所述还原剂与所述贵金属前驱体溶液中的贵金属前驱体的摩尔比例为(1～1000)∶1。
本发明还提供一种复合催化剂。所述复合催化剂包含载体以及负载于所述载体的贵金 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以及金属氧化物，所述金属氧化物均匀分布于所述氮掺杂多孔碳材料中，所述金属氧化物的部分表面通过该孔道而暴露，所述贵金属与暴露的金属氧化物紧密结合而实现复合，所述贵金属为Pd、Pt、Ru、Rh、Ir、Au中的至少一种。所述贵金属在所述氮掺杂多孔碳复合材料中的分散度为75％～95％。
所述贵金属在所述复合催化剂所占的质量分数为0.1％～10％；所述金属氧化物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，本发明还提供一种复合催化剂在催化加氢反应中的应用。所述复合催化剂在对不饱和酮或者生物素前体(X)的选择性加氢反应中作为催化剂。所述不饱和酮为6-甲基-5-庚烯-2-酮(I)、6，10-二甲基-5-十一烯-2-酮(III)、6，10-二甲基-5，9-十一烷二烯-2-酮(V)、6，10，14-三甲基-5-十五烯-2-酮(VI)、6，10，14-三甲基-5，9-十五烷二烯-2-酮(VIII)、6，10，14-三甲基-5，9，13-十五烷三烯-2-酮(IX)中的至少一种。
以下将通过实施例对本发明所述复合催化剂及其应用作进一步的说明。
实施例1
称取1g六水合硝酸铈分散于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0.5g氮掺杂多孔碳复合材料，加入到40mL去离子水中，缓慢滴加0.5mL 10mg/mL的PdCl 2溶液，50℃搅拌12h，放入70℃烘箱烘干24h。再于空气中300℃煅烧1h。最后300℃氢气还原1h(氢气流速为50mL/min，升温速率5℃/min)，即可得到复合催化剂，其中在所述复合催化剂中金属Pd的理论负载量(所占质量比)为0.6％。
采用原子发射光谱，对复合催化剂中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。
对所述复合催化剂进行透射电镜测试，结果见图3。对比图2及图3可见，图3与图2相比，形貌基本没有改变，图3中难以看到Pd金属，这是因为Pd颗粒的粒径非常小，在1纳米以下。
对所述氮掺杂多孔碳复合材料及复合催化剂进行X-射线衍射测试，结果见图4。由图4可见，对应于氮掺杂多孔碳复合材料的曲线a没有Pd的衍射特征峰；对应于所述复合催化剂的曲线b与Pd的标准卡片对比，Pd的特征峰并不明显，这也印证了上述图3所得到的Pd颗粒在1纳米以下的结论。
采用CO滴定的方法(备注：CO滴定方法是一氧化碳吸附测试贵金属的分散度实验)对所述复合催化剂的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83％；复合催化剂的比表面积为135.3m 2g -1。
为了对比，还提供一对比例1。该对比例1的复合催化剂的制备方法中仅将Pd通过CeO 2进行负载，而并不添加羧甲基甲壳素，得到Pd/CeO 2催化剂，该Pd/CeO 2催化剂的比表面积只有5.6m 2g -1。
实施例2
称取1g六水合硝酸铈分散于30mL水，待其溶解后加入3g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0.5g氮掺杂多孔碳复合材料，加入到40mL去离子水中，缓慢滴加0.5mL 10mg/mL的PdCl 2溶液，50℃搅拌12h，放入70℃烘箱烘干24h。再于空气中300℃煅烧1h，最后300℃氢气还原1h(氢气流速为50mL/min，升温速率5℃/min)即可得到复合催化剂。
实施例2复合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，含氮生物素为壳聚糖。
采用CO滴定的方法测试所得到的复合催化剂中Pd的分散度，结果为：Pd的分散度为81％。该复合催化剂的比表面积为147.3m 2g -1。
实施例3
称取1g硝酸锆五水合物分散于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0.5g上述氮掺杂多孔碳复合材料，加入到40mL去离子水中，缓慢滴加0.5mL 浓度为10mg/mL的PdCl2溶液，50℃搅拌12h，放入70℃烘箱烘干24h。再于空气中300℃煅烧1h。最后300℃氢气还原1h(氢气流速为50mL/min，升温速率5℃/min)即可得到复合催化剂。
采用CO滴定的方法对所述复合催化剂的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79％；复合催化剂的比表面积为126.8m 2g -1。
实施例4
称取1g硝酸铝九水合物分散于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0.5g上述氮掺杂多孔碳复合材料，加入到40mL去离子水中，缓慢滴加0.5mL10mg/mL的PdCl 2溶液，50℃搅拌12h，放入70℃烘箱烘干24h。再于空气中300℃煅烧1h。最后300℃氢气还原1h(氢气流速为50mL/min，升温速率5℃/min)即可得到复合催化剂。
采用CO滴定的方法对所述复合催化剂的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76％。该复合催化剂的比表面积为115.5m 2g -1。
实施例5
称取1g六水合硝酸铈分散于30mL水，待其溶解后加入3g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，具体地煅烧过程为：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0.5g上述氮掺杂多孔碳复合材料，加入到60mL去离子水中，缓慢滴加0.5mL浓度为10mg/mL的PdCl2溶液，25℃超声30min。再缓慢滴加10.7mL 2mg/mL的NaBH4溶液，继续超声30min，过滤，用去离子水清洗至中性。最后放入70℃烘箱烘干24h，即可得到复合催化剂。
采用CO滴定的方法对所述复合催化剂的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89％；复合催化剂的比表面积为138.7m 2g -1。
实施例6
称取1g六水合硝酸铈分散于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，具体地煅烧过程为：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0.5g上述氮掺杂多孔碳复合材料，加入到40mL去离子水中，缓慢滴加0.8mL10mg/mL的H 2PtCl 6·6H 2O溶液，50℃搅拌12h，放入70℃烘箱烘干24h。再于空气中300℃煅烧1h。最后300℃氢气还原1h(氢气流速为50mL/min，升温速率5℃/min)即可得到复合催化剂。
采用CO滴定的方法对所述复合催化剂的Pt的分散度及比表面积进行测试，测试结果为：Pt的分散度为91％，该催化剂比表面积高达133.5m 2g -1。
实施例7
称取1g六水合硝酸铈分散于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，具体地煅烧过程为：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0.5g上述氮掺杂多孔碳复合材料，加入到60mL去离子水中，缓慢滴加0.7mL浓度为10mg/mL的RuCl3溶液，50℃搅拌12h，放入70℃烘箱烘干24h。再于空气中300℃煅烧1h。最后300℃氢气还原1h(氢气流速为50mL/min，升温速率5℃/min)即可得到复合催化剂。
采用CO滴定的方法对所述复合催化剂的Ru的分散度及比表面积进行测试，测试结果为：Ru的分散度为82％，该复合催化剂的比表面积为133.9m 2g -1。
实施例8
称取1g六水合硝酸铈分散于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，具体地煅烧过程为：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0.5g上述氮掺杂多孔碳复合材料，加入到60mL去离子水中，缓慢滴加1.1mL浓度为10mg/mL的H 12Cl 6N 3Rh溶液，50℃搅拌12h，放入70℃烘箱烘干24h。再于空气中300℃煅烧1h。最后300℃氢气还原1h(氢气流速为50mL/min，升温速率5℃/min)即可得到复合催化剂。
采用CO滴定的方法对所述复合催化剂的Rh的分散度及比表面积进行测试，测试结果为：Rh的分散度为83％；该复合催化剂的比表面积高达139.2m 2g -1。
实施例9
称取1g六水合硝酸铈分散于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0.5g上述氮掺杂多孔碳复合材料，加入到60mL去离子水中，缓慢滴加0.9mL浓度为10mg/mL的H 2IrCl 6·xH 2O溶液，50℃搅拌12h，放入70℃烘箱烘干24h。再于空气中300℃煅烧1h。最后300℃氢气还原1h(氢气流速为50mL/min，升温速率5℃/min)即可得到复合催化剂。
采用CO滴定的方法对所述复合催化剂的Ir的分散度及比表面积进行测试，测试结果为：Ir的分散度为81％，该复合催化剂的比表面积为128.4m 2g -1。
实施例10
称取1g六水合硝酸铈分散于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0.5g上述氮掺杂多孔碳复合材料，加入到60mL去离子水中，缓慢滴加0.6mL10mg/mL的HAuCl 4·XH 2O溶液，50℃搅拌12h，放入70℃烘箱烘干24h。再于空气中300℃煅烧1h。最后300℃氢气还原1h(氢气流速为50mL/min，升温速率5℃/min)即可得到复合催化剂。
采用CO滴定的方法对所述复合催化剂的Au的分散度及比表面积进行测试，测试结果为：Au的分散度为88％，该复合催化剂的比表面积高达137.3m 2g -1。
以下实施例的具体反应结构式请见图5。
实施例11
复合催化剂催化6-甲基-5-庚烯-2-酮(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得到的复合催化剂50mg；底物6-甲基-5-庚烯 -2-酮(I)15mmol；乙醇5mL；氢气2MPa；反应温度30℃；反应时间4h。6-甲基-5-庚烯-2-酮(I)转化率为100％，6-甲基-2-庚酮(II)选择性为99％。而对比例1的Pd/CeO 2在同样的催化反应条件下，6-甲基-5-庚烯-2-酮(I)转化率仅为68％，6-甲基-2-庚酮(II)选择性为99％。
实施例12
复合催化剂催化6，10-二甲基-5-十一烯-2-酮(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的复合催化剂50mg；底物6，10-二甲基-5-十一烯-2-酮(III)15mmol；乙醇5mL；氢气2MPa；反应温度30℃；反应时间4h。6，10-二甲基-5-十一烯-2-酮(III)转化率为100％，6，10-二甲基-十一烷-2-酮(IV)选择性为99％。
实施例13
复合催化剂催化6，10-二甲基-5，9-十一烷二烯-2-酮(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的复合催化剂50mg；底物6，10-二甲基-5，9-十一烷二烯-2-酮(V)10mmol；乙醇5mL；氢气2MPa；反应温度30℃；反应时间4h。6，10-二甲基-5，9-十一烷二烯-2-酮(V)转化率为100％，6，10-二甲基-十一烷-2-酮(IV)选择性为99％。
实施例14
复合催化剂催化6，10，14-三甲基-5-十五烯-2-酮(VI)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的复合催化剂50mg；底物6，10，14-三甲基-5-十五烯-2-酮(VI)15mmol；乙醇5mL；氢气2MPa；反应温度30℃；反应时间4h。6，10，14-三甲基-5-十五烯-2-酮(VI)转化率为100％，6，10，14-三甲基-十五烷-2-酮(VII)选择性为99％。
实施例15
复合催化剂催化6，10，14-三甲基-5，9-十五烷二烯-2-酮(VIII)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的复合催化剂50mg；底物6，10，14-三甲基-5，9-十五烷二烯-2-酮(VIII)10mmol；乙醇5mL；氢气2MPa；反应温度30℃；反应时间4h。6，10，14-三甲基-5，9-十五烷二烯-2-酮(VIII)转化率为100％，6，10，14-三甲基-十五烷-2-酮(VII)选择性为99％。
实施例16
复合催化剂催化6，10，14-三甲基-5，9，13-十五烷三烯-2-酮(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的复合催化剂50mg；底物6，10，14-三甲基-5，9，13-十五烷三烯-2-酮(IX)5mmol；乙醇5mL；氢气2MPa；反应温度30℃；反应时间3h。6，10，14-三甲基-5，9，13-十五烷三烯-2-酮(IX)转化率为100％，6，10，14-三甲基-十五烷-2-酮(VII)选择性为99％。
实施例17
复合催化剂催化6-甲基-5-庚烯-2-酮(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6的复合催化剂50mg；底物6-甲基-5-庚烯-2-酮(I)4mmol；乙醇5mL；氢气2MPa；反应温度40℃；反应时间4h。6-甲基-5-庚烯-2-酮(I)转化率为100％，6-甲基-2-庚酮(II)选择性为98％。
实施例18
复合催化剂催化6-甲基-5-庚烯-2-酮(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7的复合催化剂50mg；底物6-甲基-5-庚烯-2-酮(I)2mmol；乙醇5mL；氢气2MPa；反应温度40℃；反应时间5h。6-甲基-5-庚烯-2-酮(I)转化率为100％，6-甲基-2-庚酮(II)选择性为97％。
实施例19
复合催化剂催化6-甲基-5-庚烯-2-酮(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8的复合催化剂50mg；底物6-甲基-5-庚烯-2-酮(I)15mmol；乙醇5mL；氢气2MPa；反应温度30℃；反应时间4h。6-甲基-5-庚烯-2-酮(I)转化率为100％，6-甲基-2-庚酮(II)选择性为99％。
实施例20
复合催化剂催化6-甲基-5-庚烯-2-酮(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9的复合催化剂50mg；底物6-甲基-5-庚烯-2-酮(I)15mmol；乙醇5mL；氢气2MPa；反应温度30℃；反应时间4h。6-甲基-5-庚烯-2- 酮(I)转化率为100％，6-甲基-2-庚酮(II)选择性为99％。
实施例21
复合催化剂催化6-甲基-5-庚烯-2-酮(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10的复合催化剂50mg；底物6-甲基-5-庚烯-2-酮(I)2mmol；乙醇5mL；氢气2MPa；反应温度50℃；反应时间6h。6-甲基-5-庚烯-2-酮(I)转化率为100％，6-甲基-2-庚酮(II)选择性为97％。
实施例22
复合催化剂催化生物素前体(X)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的复合催化剂200mg；底物生物素前体(X)2mmol；乙醇5mL；氢气2MPa；反应温度40℃；反应时间3h。生物素前体(X)转化率为100％，生物素(XI)选择性为99％。
实施例23
复合催化剂催化生物素前体(X)选择性加氢反应，具体如下：
采用50mL高压反应釜；加入实施例6的复合催化剂200mg；底物生物素前体(X)2mmol；乙醇5mL；氢气2MPa；反应温度50℃；反应时间3h。生物素前体(X)转化率为100％，生物素(XI)选择性为99％。
实施例24
复合催化剂催化6-甲基-5-庚烯-2-酮(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的复合催化剂50mg；底物6-甲基-5-庚烯-2-酮(I)15mmol；乙醇5mL；氢气2MPa；反应温度30℃；反应时间4h。反应后复合催化剂通过离心取出，用乙醇洗涤3次，40度真空干燥后继续用于反应。复合催化剂的套用结果见表1，该复合催化剂可重复套用60次，活性和选择性几乎没有变化，有着优异的稳定性。
表1
Figure PCTCN2019071319-appb-000002
Figure PCTCN2019071319-appb-000003
实施例25
复合催化剂催化生物素前体(X)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的复合催化剂200mg；底物生物素前体(X)2mmol；乙醇5mL；氢气2MPa；反应温度40℃；反应时间3h。反应后复合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反应。复合催化剂的套用结果见表2，该复合催化剂可重复套用35次，活性和选择性几乎没有变化，有着优异的稳定性。
表2
Figure PCTCN2019071319-appb-000004
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 (14)

  1. 一种复合催化剂，其特征在于，所述复合催化剂包含载体以及负载于所述载体的贵金属，所述载体为具有多个孔道的氮掺杂多孔碳复合材料，包含所述氮掺杂多孔碳复合材料包含氮掺杂多孔碳材料以及金属氧化物，所述金属氧化物均匀分布于所述氮掺杂多孔碳材料中，所述金属氧化物的部分表面通过孔道而暴露，所述贵金属与暴露的金属氧化物紧密结合而实现复合，所述贵金属为Pd、Pt、Ru、Rh、Ir、Au中的至少一种。
  2. 如权利要求1所述的复合催化剂，其特征在于，所述贵金属在所述氮掺杂多孔碳复合材料中的分散度为75％～95％。
  3. 如权利要求1所述的复合催化剂，其特征在于，所述贵金属在所述复合催化剂所占的质量分数为0.1％～10％；所述金属氧化物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. 一种复合催化剂的制备方法，其特征在于，其包含以下步骤：
    1)将金属源溶于溶剂中，得到预混物；
    2)依次向所述预混物中加入含氮生物质及致孔剂，并使所述金属源与致孔剂进行反应，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，所述金属源与致孔剂的摩尔比为1∶(1～20)；
    3)将所述混合物于500摄氏度～1200摄氏度在惰性氛围下进行第一煅烧，得到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金属氧化物，所述金属氧化物均匀分布于所述氮掺杂多孔碳材料中并部分金属氧化物通过该孔道而暴露；
    4)在所述氮掺杂多孔碳复合材料的孔道内形成贵金属，而使所述贵金属与暴露的金属氧化物中的氧原子紧密结合。
  5. 如权利要求4所述的复合催化剂的制备方法，其特征在于，步骤4)中在所述氮掺杂多孔碳复合材料的孔道内形成贵金属具体如下：
    将所述氮掺杂多孔碳复合材料浸渍于贵金属前驱体溶液中；
    对浸渍后的氮掺杂多孔碳复合材料依次进行第二煅烧、氢气还原，而在所述氮掺杂多孔碳复合材料的孔道内形成贵金属。
  6. 如权利要求4所述的复合催化剂的制备方法，其特征在于，步骤4)中在所述氮掺杂多孔碳复合材料的孔道内形成贵金属具体如下：
    将所述氮掺杂多孔碳复合材料浸于贵金属前驱体溶液中；
    继续加入还原剂，使贵金属前驱体与还原剂进行反应，而在所述氮掺杂多孔碳复合材料的孔道内形成贵金属。
  7. 如权利要求5或6所述的复合催化剂的制备方法，其特征在于，所述贵金属前驱体溶液中的贵金属前驱体为PdCl 2、H 2PdCl 4、Pd(NO 3) 2、Pd(NH 3) 4(NO 3) 2、H 2PtCl 6·6H 2O、[Pt(NH 3) 4](NO 3) 2、Na 2PtCl 4·xH 2O、H 8C 14N 2Pt、PtCl 4、Pt(C 5H 7O 2) 2、C 10H 14O 4Pt、(NH 4) 2RuCl 6、RuCl 3、C 15H 21O 6Ru、H 12Cl 6N 3Rh、RhN 3O 9、RhCl 3·3H 2O、IrCl 3、Na 2IrCl 6·6H 2O、H 2IrCl 6·xH 2O、[CH 3COCH＝C(O-)CH 3] 3Ir、NaAuCl 4·2H 2O、HAuCl 4·XH 2O、(NH 4)AuCl 4中的至少一种。
  8. 如权利要求5所述的复合催化剂的制备方法，其特征在于，所述第二煅烧过程中，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。
  9. 如权利要求6所述的复合催化剂的制备方法，其特征在于，所述还原剂为NaBH 4、HCOOH、水合肼中的至少一种，所述还原剂与所述贵金属前驱体溶液中的贵金属前驱体的摩尔比例为(1～1000)∶1。
  10. 如权利要求4所述的复合催化剂的制备方法，其特征在于，步骤1)所述金属源为硝酸铈、硝酸锆、硝酸铝，所述溶剂为水，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。
  11. 如权利要求4所述的复合催化剂的制备方法，其特征在于，步骤2)中所述金属源与含氮生物质的质量比为(0.05～2)∶1。
  12. 如权利要求4所述的复合催化剂的制备方法，其特征在于，步骤3)中，所述第一煅烧的过程中煅烧时间为0.1小时～5小时。
  13. 一种如权利要求1～3所述复合催化剂在催化加氢反应中的应用，其特征在于，所述复合催化剂在对不饱和酮或者生物素前体的选择性加氢反应中作为催化剂，所述生物素前体的结构如下：
    Figure PCTCN2019071319-appb-100001
  14. 如权利要求13所述复合催化剂在催化加氢反应中的应用，其特征在于，所述不饱和酮为6-甲基-5-庚烯-2-酮、6，10-二甲基-5-十一烯-2-酮、6，10-二甲基-5，9-十一烷二烯-2-酮、6，10，14-三甲基-5-十五烯-2-酮、6，10，14-三甲基-5，9-十五烷二烯-2-酮、6，10，14-三甲基-5，9，13- 十五烷三烯-2-酮中的至少一种。
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