CN114100653B - Nitride supported palladium catalyst and preparation method and application thereof - Google Patents
Nitride supported palladium catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN114100653B CN114100653B CN202010896109.3A CN202010896109A CN114100653B CN 114100653 B CN114100653 B CN 114100653B CN 202010896109 A CN202010896109 A CN 202010896109A CN 114100653 B CN114100653 B CN 114100653B
- Authority
- CN
- China
- Prior art keywords
- nitride
- palladium
- catalyst
- supported
- palladium catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 70
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002105 nanoparticle Substances 0.000 claims abstract description 22
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 21
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 21
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 cobalt nitride Chemical class 0.000 claims abstract description 11
- 229910052582 BN Inorganic materials 0.000 claims abstract description 8
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 8
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 claims abstract description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 38
- 239000008247 solid mixture Substances 0.000 claims description 30
- 238000001354 calcination Methods 0.000 claims description 20
- 239000005711 Benzoic acid Substances 0.000 claims description 19
- 239000012696 Pd precursors Substances 0.000 claims description 19
- 235000010233 benzoic acid Nutrition 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001704 evaporation Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 230000003993 interaction Effects 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- 238000003756 stirring Methods 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 101150003085 Pdcl gene Proteins 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000013112 stability test Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- FPIQZBQZKBKLEI-UHFFFAOYSA-N ethyl 1-[[2-chloroethyl(nitroso)carbamoyl]amino]cyclohexane-1-carboxylate Chemical compound ClCCN(N=O)C(=O)NC1(C(=O)OCC)CCCCC1 FPIQZBQZKBKLEI-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon 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
- C07C2601/14—The ring being saturated
Abstract
The invention relates to the technical field of catalysts, in particular to a nitride supported palladium catalyst and a preparation method and application thereof. The nitride supported palladium catalyst comprises a nitride and palladium nano-particles supported on the nitride; the nitride is cobalt nitride, silicon nitride, boron nitride or zirconium nitride. According to the invention, nitride is used as a carrier, so that a chemical bond with strong interaction with metal palladium can be formed, and the stability of the palladium catalyst is improved, thereby prolonging the service life of the catalyst; in addition, the strong interaction between the metal palladium nano-particles and the nitride carrier is beneficial to the uniform dispersion of the palladium nano-particles, so that the activity of the catalyst is improved; the nitride-supported palladium catalyst provided by the invention has the advantages that the nitride carrier and the palladium nano particles are mutually coordinated, and the catalyst has good activity and higher selectivity of the cyclohexanecarboxylic acid.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a nitride supported palladium catalyst and a preparation method and application thereof.
Background
Cyclohexanecarboxylic acid is an important organic intermediate for the synthesis of pharmaceuticals. At present, the selective hydrogenation of benzoic acid is mainly used for synthesizing the cyclohexanecarboxylic acid. However, aromatic ring hydrogenation requires more severe conditions than other functional group hydrogenation (c= O, C =c and c=n), because of the need to overcome the high resonance energy of the benzene ring. It has been found that molten benzoic acid can be hydrogenated to form cyclohexanecarboxylic acid on a carbon-containing noble metal catalyst without the need for any solvent. Unfortunately, these reactions all need to be carried out at high pressure and high temperature. Therefore, there is an urgent need to prepare a high-efficiency and environment-friendly benzoic acid selective hydrogenation catalyst under mild reaction conditions.
In recent years, researchers have found Pd useful in selective hydrogenation reactions. The activity of the catalyst can be controlled by changing the Pd catalyst support material. For example, human MgO (Claus, P.; berndt, H.; mohr, C.; radnik, J.; shin, E. -J.; keane, M.A., J.Catal.2000,192, 88-97.;) Al.) 2 O 3 (Cervantes, G.G.; aires, F.C.S.; bertholini, J.; J.Catal.2003,214, 26-32), activated Carbon (Cabiac, A.; delahay, G.; durand, R.; trens, P.; coq, B.; plene, D.; carbon2007,45,3-10), tiO) 2 (Panprantot, J.; kontapakdee, K.; praserthdam, P.; J.Phys.chem.B., 2006,110,8019-8024.) and the like. While carbon materials are common Pd catalyst supports, however, activated carbon supported Pd catalysts are also less active for aromatic ring hydrogenation as reported by Anderson (Anderson, j.a.; athawale, a.; im rie, f.e.; mcKenna, f.m.; mcCue, a.; molyneux, d.; power, k.; shand, m.; wells, R.P.K., J.Catal.2010,270, 9-15) and Pd/AC (activated carbon) converts only 34% of benzoic acid to cyclohexanecarboxylic acid in 24 hours at 85 ℃ under 1bar of hydrogen. In addition, palladium deposited on carbon is easily filtered during catalysis because the interaction of the metal and the carbon surface is weak. Thus, the chemical or catalytic nature of carbon does not always meet the dramatically increasing demands of catalysis.
Disclosure of Invention
The invention aims to provide a nitride supported palladium catalyst, a preparation method and application thereof, and the nitride supported palladium catalyst has good activity and higher selectivity of cyclohexanecarboxylic acid, and has improved stability due to strong interaction of palladium and nitride, so that the service life of the catalyst is prolonged.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a nitride supported palladium catalyst, which comprises a nitride and palladium nano-particles supported on the nitride; the nitride is cobalt nitride, silicon nitride, boron nitride or zirconium nitride.
Preferably, the palladium nano particles account for 3 to 6 percent of the mass of the nitride.
The invention provides a preparation method of the nitride supported palladium catalyst, which comprises the following steps:
mixing the nitride and the palladium precursor solution, and evaporating to dryness to obtain a solid mixture;
and calcining and reducing the solid mixture in sequence to obtain the nitride supported palladium catalyst.
Preferably, the palladium precursor in the palladium precursor solution is one or more of palladium chloride, potassium hexachloropalladate, palladium acetate, sodium chloropalladate, palladium nitrate, palladium acetylacetonate and ammonium tetrachloropalladate.
Preferably, the evaporating temperature is 80-160 ℃ and the evaporating time is 6-14 h.
Preferably, the calcination is performed in a shielding gas; the calcining temperature is 500-800 ℃ and the calcining time is 2-7 h.
Preferably, the reduction is carried out in hydrogen and/or ammonia; the temperature of the reduction is 200-600 ℃ and the time is 2-5 h.
Preferably, the concentration of the palladium precursor solution is 10mg/mL.
The invention provides an application of the nitride supported palladium catalyst prepared by the scheme or the preparation method of the scheme in preparing the cyclohexanecarboxylic acid by catalyzing benzoic acid hydrogenation.
Preferably, the conditions of the application include: taking water as a solvent, wherein the reaction temperature is 50-200 ℃, and the hydrogen pressure is 0.05-4 MPa; the mass ratio of the benzoic acid to the nitride supported palladium catalyst is (1-4): 1.
the invention provides a nitride supported palladium catalyst, which comprises a nitride and palladium nano-particles supported on the nitride; the nitride is cobalt nitride, silicon nitride, boron nitride or zirconium nitride.
According to the invention, nitride is used as a carrier, and nitrogen can form a chemical bond with strong interaction with metal palladium, so that the stability of the palladium catalyst is improved, and the service life of the catalyst is prolonged; in addition, the strong interaction between the metal palladium nano-particles and the nitride carrier is beneficial to the uniform dispersion of the palladium nano-particles, so that the activity of the catalyst is improved; the nitride-supported palladium catalyst provided by the invention has the advantages that the nitride carrier and the palladium nano particles are mutually coordinated, and the catalyst has good activity and higher selectivity of the cyclohexanecarboxylic acid.
The nitride supported palladium catalyst is used for catalyzing benzoic acid to hydrogenate to prepare the cyclohexanecarboxylic acid, can react at lower temperature and pressure, and is more environment-friendly by using water as a solvent.
Drawings
FIG. 1 is a TEM image of a silicon nitride supported Pd catalyst prepared in example 1;
FIG. 2 is a graph showing the results of the cyclic stability test of the Pd catalyst supported on silicon nitride prepared in example 1;
fig. 3 is a graph showing the results of the cycle stability test of the activated carbon-supported Pd catalyst prepared in comparative example 1.
Detailed Description
The invention provides a nitride supported palladium catalyst, which comprises a nitride and palladium nano-particles supported on the nitride; the nitride is cobalt nitride, silicon nitride, boron nitride or zirconium nitride.
In the present invention, the particle diameter of the palladium nanoparticle is preferably 3 to 10nm, more preferably 4 to 6nm. In the present invention, the nitride is preferably silicon nitride. In the present invention, the mass of the palladium nanoparticle is preferably 3 to 6% of the mass of the nitride, more preferably 4.5 to 5.5%, and still more preferably 5%.
In the present invention, the palladium nanoparticles are uniformly distributed on the surface and/or in the pores of the nitride.
According to the invention, nitride is used as a carrier, so that a chemical bond with strong interaction with metal palladium can be formed, and the stability of the palladium catalyst is improved, thereby prolonging the service life of the catalyst; in addition, the strong interaction between the metal palladium nano-particles and the nitride carrier is beneficial to the uniform dispersion of the palladium nano-particles, so that the activity of the catalyst is improved; the nitride-supported palladium catalyst provided by the invention has the advantages that the nitride carrier and the palladium nano particles are mutually coordinated, and the catalyst has good activity and higher selectivity of the cyclohexanecarboxylic acid.
The invention provides a preparation method of the nitride supported palladium catalyst, which comprises the following steps:
mixing the nitride and the palladium precursor solution, and evaporating to dryness to obtain a solid mixture;
and calcining and reducing the solid mixture in sequence to obtain the nitride supported palladium catalyst.
In the present invention, the raw materials used are commercially available products well known in the art, unless specifically described otherwise.
According to the invention, the nitride and the palladium precursor solution are mixed and then evaporated to dryness, so that a solid mixture is obtained.
In the present invention, the particle size of the nitride is preferably in the nanometer scale, and the present invention has no particular requirement for the source of the nitride, and commercially available products well known in the art may be used. In the present invention, the palladium precursor in the palladium precursor solution is preferably one or more of palladium chloride, potassium hexachloropalladate, palladium acetate, sodium chloropalladate, palladium nitrate, palladium acetylacetonate and ammonium tetrachloropalladate, more preferably palladium chloride. The solvent in the palladium precursor solution is not particularly required, and the solvent which is well known in the art and can be dissolved and can not react with nitride and can be evaporated can be selected according to the type of the palladium precursor. In the present invention, when the palladium precursor is palladium chloride, the solvent is hydrochloric acid and water, and the concentration of the hydrochloric acid is preferably 2M. In the present invention, the concentration of the palladium precursor solution is preferably 10mg/mL. In the present invention, the amounts of the nitride and palladium precursor solutions are determined according to the contents of the nitride and palladium nanoparticles in the nitride-supported palladium catalyst.
The method is preferably to mix the nitride and the palladium precursor solution, stir the mixture for 2 to 8 hours and evaporate the mixture. The stirring rate is not particularly limited in the present invention, and stirring rates well known in the art may be used. The invention uses stirring to disperse the palladium precursor solution uniformly.
In the present invention, the evaporating temperature is preferably 80 to 160 ℃, more preferably 90 to 110 ℃; the drying time is preferably 6 to 14 hours, more preferably 8 to 10 hours. In the present invention, the drying by distillation is preferably performed under stirring conditions to accelerate the drying by distillation. In the evaporating process, palladium ions are adsorbed on nitride.
After the solid mixture is obtained, the solid mixture is calcined and reduced in sequence to obtain the nitride supported palladium catalyst.
In the present invention, the calcination is preferably performed in a protective gas; the shielding gas is preferably nitrogen or an inert gas. In the present invention, the temperature of the calcination is preferably 500 to 800 ℃, more preferably 550 to 650 ℃; the calcination time is preferably 2 to 7 hours, more preferably 3 to 5 hours. The invention utilizes calcination to combine palladium ions with nitride carriers well.
In the present invention, the reduction is preferably carried out in hydrogen and/or ammonia; when the reducing gas adopts hydrogen and ammonia, the invention has no special requirement on the ratio of the hydrogen to the ammonia, and any ratio can be adopted. In the present invention, the temperature of the reduction is preferably 200 to 600 ℃, more preferably 350 to 450 ℃; the time for the reduction is preferably 2 to 5 hours, more preferably 3 to 4 hours. In the reduction process, palladium ions are reduced into metal palladium, and the metal palladium is distributed on the nitride carrier in the form of nano particles and is firmly combined with the nitride carrier.
The invention provides an application of the nitride supported palladium catalyst prepared by the scheme or the preparation method of the scheme in preparing the cyclohexanecarboxylic acid by catalyzing benzoic acid hydrogenation.
In the present invention, the conditions of the application preferably include: taking water as a solvent, wherein the reaction temperature is 50-200 ℃, and the hydrogen pressure is 0.05-4 MPa; the mass ratio of the benzoic acid to the nitride supported palladium catalyst is (1-4): 1. further, the reaction temperature is more preferably 70 to 150 ℃, and most preferably 90 ℃; the hydrogen pressure is more preferably 0.1 to 2MPa, most preferably 0.1MPa; the mass ratio of benzoic acid to the nitride supported palladium catalyst is more preferably (2 to 3): 1, most preferably 2:1. In the present invention, the ratio of benzoic acid to water is preferably (10-13) mg/1 mL, more preferably 10 mg/1 mL.
The nitride supported palladium catalyst, the preparation method and application thereof provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
1) Weigh 1g of PdCl 2 Dissolving in concentrated hydrochloric acid, transferring to a 100mL volumetric flask, and adding deionized water to corresponding scales to prepare a chloropalladite solution with the mass concentration of 10 mg/mL;
2) Mixing 1g of silicon nitride with 85.5mL of the chloropalladite solution in the step 1) (Pd in the chloropalladite solution accounts for 5% of the mass of the silicon nitride), stirring for 4h, and then stirring for 9h at the temperature of 100 ℃ for evaporating to dryness to obtain a solid mixture;
3) And 2) calcining the solid mixture obtained in the step 2) at 600 ℃ for 4 hours under nitrogen, and then reducing the solid mixture at 400 ℃ for 3 hours under hydrogen gas to obtain the silicon nitride supported Pd catalyst.
FIG. 1 is a TEM image of the Pd catalyst supported on silicon nitride prepared in example 1, and it is clear from FIG. 1 that the metal palladium particles are uniformly dispersed, and the particle size is about 5 nm.
Example 2
1) Weigh 1g of PdCl 2 Dissolving in concentrated hydrochloric acid, transferring to a 100mL volumetric flask, and adding deionized water to corresponding scales to prepare a chloropalladite solution with the mass concentration of 10 mg/mL;
2) Mixing 1g of cobalt nitride with 85.5mL of the chloropalladite solution in the step 1) (Pd in the chloropalladite solution accounts for 5% of the mass of the cobalt nitride), stirring for 4h, and then stirring for 9h at the temperature of 100 ℃ for evaporating to dryness to obtain a solid mixture;
3) And 2) calcining the solid mixture obtained in the step 2) at 600 ℃ for 4 hours under nitrogen, and then reducing the solid mixture at 400 ℃ for 3 hours under hydrogen gas to obtain the cobalt nitride supported Pd catalyst.
Example 3
1) Weigh 1g of PdCl 2 Dissolving in concentrated hydrochloric acid, transferring to a 100mL volumetric flask, and adding deionized water to corresponding scales to prepare a chloropalladite solution with the mass concentration of 10 mg/mL;
2) Mixing 1g of boron nitride with 85.5mL of the chloropalladite solution in the step 1) (Pd in the chloropalladite solution accounts for 5% of the mass of the boron nitride), stirring for 4h, and then stirring for 9h at the temperature of 100 ℃ for evaporating to dryness to obtain a solid mixture;
3) And 2) calcining the solid mixture obtained in the step 2) at 600 ℃ for 4 hours under nitrogen, and then reducing the solid mixture at 400 ℃ for 3 hours under hydrogen gas to obtain the boron nitride supported Pd catalyst.
Example 4
1) Weigh 1g of PdCl 2 Dissolving in concentrated hydrochloric acid, transferring to a 100mL volumetric flask, and adding deionized water to corresponding scales to prepare a chloropalladite solution with the mass concentration of 10 mg/mL;
2) Mixing 1g of zirconium nitride with 85.5mL of the chloropalladite solution in the step 1) (Pd in the chloropalladite solution accounts for 5% of the mass of the zirconium nitride), stirring for 4h, and then stirring for 9h at the temperature of 100 ℃ for evaporating to dryness to obtain a solid mixture;
3) And 2) calcining the solid mixture obtained in the step 2) at 600 ℃ for 4 hours under nitrogen, and then reducing the solid mixture at 400 ℃ for 3 hours under hydrogen gas to obtain the zirconium nitride supported Pd catalyst.
Example 5
1) 1g of palladium nitrate is weighed and dissolved in deionized water, transferred to a 100mL volumetric flask, and deionized water is added to corresponding scales to prepare a palladium nitrate solution with the mass concentration of 10 mg/mL;
2) Mixing 1g of silicon nitride with 108.5mL of the palladium nitrate solution in the step 1) (Pd in the palladium nitrate solution accounts for 5% of the mass of the silicon nitride), stirring for 4h, and then stirring for 9h at the temperature of 100 ℃ for evaporating to dryness to obtain a solid mixture;
3) And 2) calcining the solid mixture obtained in the step 2) at 600 ℃ for 4 hours under nitrogen, and then reducing the solid mixture at 400 ℃ for 3 hours under hydrogen gas to obtain the silicon nitride supported Pd catalyst.
Example 6
1) 1g of potassium hexachloropalladate is weighed and dissolved in deionized water, transferred to a 100mL volumetric flask, and deionized water is added to corresponding scales to prepare a potassium hexachloropalladate solution with the mass concentration of 10 mg/mL;
2) Mixing 1g of silicon nitride with 187.3mL of the potassium hexachloropalladate solution in the step 1) (Pd in the potassium hexachloropalladate solution accounts for 5% of the mass of the silicon nitride), stirring for 4h, and then stirring for 9h at the temperature of 100 ℃ to evaporate to obtain a solid mixture;
3) And 2) calcining the solid mixture obtained in the step 2) at 600 ℃ for 4 hours under nitrogen, and then reducing the solid mixture at 400 ℃ for 3 hours under hydrogen gas to obtain the silicon nitride supported Pd catalyst.
Example 7
The difference from example 1 is that the hydrogen reduction of step 3) is changed to ammonia reduction.
Comparative example 1
The only difference from example 1 is that the silicon nitride was replaced with activated carbon, and the specific procedure was as follows:
1) Weigh 1g of PdCl 2 Dissolving in concentrated hydrochloric acid, transferring to a 100mL volumetric flask, and adding deionized water to the corresponding scale to obtain a chloropalladite solution with the mass concentration of 10mg/mL.
2) Mixing 1g of activated carbon with 85.5mL of the chloropalladate solution obtained in the step 1) and stirring for 4h, and then stirring for 9h at the temperature of 100 ℃ and evaporating to dryness to obtain a solid mixture;
3) And 2) calcining the solid mixture obtained in the step 2) at 600 ℃ for 4 hours under nitrogen, and then reducing the solid mixture at 400 ℃ for 3 hours under hydrogen gas to obtain the activated carbon supported Pd catalyst.
Performance testing
10mg of the catalyst prepared in examples 1 to 7 and comparative example 1 was charged in a high-pressure reaction vessel, and 2mL of water was used as a solvent, and the mass ratio of benzoic acid to the silicon nitride supported Pd catalyst was 2: under the condition 1, the benzoic acid is hydrogenated to obtain the cyclohexanecarboxylic acid, and the conversion rate of the benzoic acid and the selectivity of the cyclohexanecarboxylic acid are shown in Table 1.
TABLE 1 conversion to benzoic acid and cyclohexanecarboxylic acid selectivity data for the catalysts prepared in examples 1-7 and comparative example 1
| Numbering device | Benzoic acid conversion | Cyclohexanecarboxylic acid selectivity |
| Example 1 | 98.5％ | 99.2％ |
| Example 2 | 90.1％ | 92.6％ |
| Example 3 | 80.9％ | 91.6％ |
| Example 4 | 89.3％ | 94.5％ |
| Example 5 | 97.2％ | 98.8％ |
| Example 6 | 95.8％ | 97.3％ |
| Example 7 | 98.3％ | 98.9％ |
| Comparative example 1 | 50.7％ | 37.5％ |
As can be seen from the results in Table 1, the catalyst of the present invention has higher benzoic acid conversion rate with nitride as the carrier than the catalyst prepared with activated carbon as the carrier, which indicates that the catalyst of the present invention has better catalytic activity and higher selectivity to cyclohexanecarboxylic acid. In particular, the catalyst prepared by taking silicon nitride as a carrier has better catalytic activity and selectivity.
The catalyst prepared in example 1 was subjected to a cycle stability test, and the results are shown in fig. 2. As can be seen from fig. 2, the conversion of the catalyst was substantially unchanged and maintained around 99.0% after six cycle experiments, indicating good stability.
The catalyst prepared in comparative example 1 was subjected to a cycle stability test, and the results are shown in fig. 3. As can be seen from fig. 3, the conversion of the catalyst was severely reduced (reduced to 20.5%) and the stability was poor after six cycling experiments.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (5)
1. The application of a nitride-supported palladium catalyst in catalyzing benzoic acid to prepare cyclohexanecarboxylic acid is characterized in that the nitride-supported palladium catalyst comprises nitride and palladium nano-particles supported on the nitride; the nitride is cobalt nitride, silicon nitride, boron nitride or zirconium nitride; the palladium nano particles account for 3-6% of the mass of the nitride; the particle size of the palladium nano particles is 3-10 nm;
the preparation method of the nitride supported palladium catalyst comprises the following steps:
mixing the nitride and the palladium precursor solution, and evaporating to dryness to obtain a solid mixture;
calcining and reducing the solid mixture in sequence to obtain a nitride supported palladium catalyst;
the calcination is carried out in a protective gas; the calcining temperature is 500-800 ℃ and the calcining time is 2-7 h;
the reduction is carried out in hydrogen and/or ammonia; the temperature of the reduction is 200-600 ℃ and the time is 2-5 h.
2. The application according to claim 1, wherein the conditions of the application comprise: taking water as a solvent, wherein the reaction temperature is 50-200 ℃, and the hydrogen pressure is 0.05-4 MPa; the mass ratio of the benzoic acid to the nitride supported palladium catalyst is (1-4): 1.
3. the use according to claim 1, wherein the palladium precursor in the palladium precursor solution is one or more of palladium chloride, potassium hexachloropalladate, palladium acetate, sodium chloropalladate, palladium nitrate, palladium acetylacetonate and ammonium tetrachloropalladate.
4. The use according to claim 1, wherein the evaporating temperature is 80-160 ℃ and the time is 6-14 h.
5. The use according to claim 1, wherein the concentration of the palladium precursor solution is 10mg/mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010896109.3A CN114100653B (en) | 2020-08-31 | 2020-08-31 | Nitride supported palladium catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010896109.3A CN114100653B (en) | 2020-08-31 | 2020-08-31 | Nitride supported palladium catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114100653A CN114100653A (en) | 2022-03-01 |
| CN114100653B true CN114100653B (en) | 2024-03-08 |
Family
ID=80359893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010896109.3A Active CN114100653B (en) | 2020-08-31 | 2020-08-31 | Nitride supported palladium catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114100653B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115845904A (en) * | 2023-02-09 | 2023-03-28 | 成都中科凯特科技有限公司 | Preparation method of catalyst and application of catalyst in preparation of hydrogen by catalyzing formic acid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB967919A (en) * | 1961-08-18 | 1964-08-26 | Snia Viscosa | Improved process for preparing hexahydrobenzoic acid |
| CN101628234A (en) * | 2008-07-18 | 2010-01-20 | 赢创德固赛有限责任公司 | Method for producing improved catalyst |
| CN103086878A (en) * | 2013-01-14 | 2013-05-08 | 浙江大学 | Preparation method of cyclohexyl compound by aromatic compound catalytic hydrogenation |
| CN106179440A (en) * | 2016-06-24 | 2016-12-07 | 浙江大学 | N doping multi-stage porous charcoal and its preparation method and application |
| CN109603707A (en) * | 2018-12-26 | 2019-04-12 | 大连海事大学 | A kind of CH4/CO2Low temperature directly synthesizes the device and its synthetic method of C1-C4 alcohol |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6146301B2 (en) * | 2011-03-01 | 2017-06-14 | 三菱瓦斯化学株式会社 | Process for producing alicyclic carboxylic acid and catalyst used in the process |
-
2020
- 2020-08-31 CN CN202010896109.3A patent/CN114100653B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB967919A (en) * | 1961-08-18 | 1964-08-26 | Snia Viscosa | Improved process for preparing hexahydrobenzoic acid |
| CN101628234A (en) * | 2008-07-18 | 2010-01-20 | 赢创德固赛有限责任公司 | Method for producing improved catalyst |
| CN103086878A (en) * | 2013-01-14 | 2013-05-08 | 浙江大学 | Preparation method of cyclohexyl compound by aromatic compound catalytic hydrogenation |
| CN106179440A (en) * | 2016-06-24 | 2016-12-07 | 浙江大学 | N doping multi-stage porous charcoal and its preparation method and application |
| CN109603707A (en) * | 2018-12-26 | 2019-04-12 | 大连海事大学 | A kind of CH4/CO2Low temperature directly synthesizes the device and its synthetic method of C1-C4 alcohol |
Non-Patent Citations (5)
| Title |
|---|
| Boron nitride supported Pd catalysts for the hydrogenation of lactose;Nathalie Meyer et al;Catalysis Today;第241卷;200-207 * |
| F.J. Cadete Santos Aires et al.Pd catalysts supported on silicon nitride for the combustion of methane: Influence of the crystalline and amorphous phases of the support and of the preparation method on the catalytic performances.Catalysis Today.2006,第117卷518-524. * |
| Nathalie Meyer et al.Boron nitride supported Pd catalysts for the hydrogenation of lactose.Catalysis Today.2015,第241卷200-207. * |
| Pd catalysts supported on silicon nitride for the combustion of methane: Influence of the crystalline and amorphous phases of the support and of the preparation method on the catalytic performances;F.J. Cadete Santos Aires et al;Catalysis Today;第117卷;518-524 * |
| 氮杂活性炭负载钯的制备及其在苯甲酸水相加氢中的应用;喻小龙等;湖北大学学报（自然科学版）;第39卷(第1期);19-24 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114100653A (en) | 2022-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101502802B (en) | Preparation method of catalyst for continuous production of succinic anhydride from hydrogenation of maleic anhydride | |
| CN105032424A (en) | Catalyst for selective hydrogenation reaction of aromatic nitrocompound and preparation method of catalyst | |
| CN113797947B (en) | Application of C modified platinum-based catalyst in catalyzing hydrogenation reaction of halogenated nitrobenzene | |
| JPH07507767A (en) | Method and catalyst for partially hydrogenating aromatics to produce cycloolefins | |
| CN113398924A (en) | Metal catalyst and preparation and application thereof | |
| CN110013854A (en) | The preparation and the application in C5/C9 Petropols catalytic hydrogenation of a kind of load-type nickel series catalysts | |
| CN114054061B (en) | Nitrogen-doped carbon-supported palladium catalyst and preparation method and application thereof | |
| CN114471540A (en) | Sub-nano Pt selective hydrogenation catalyst, preparation method and application thereof | |
| CN110813281B (en) | Application of nano-carbon supported cluster-state palladium-based catalyst in preparation of primary amine by catalytic hydrogenation of nitrile compound | |
| CN101049562A (en) | Catalyst for preparing halogeno anilin through catalytic hydrogenation of halogeno nitrobenzene and preparation method | |
| CN111644197A (en) | Catalytic system for preparing aromatic hydrocarbon by low-temperature methane conversion, preparation method and application | |
| CN113731465A (en) | Pd/N-CNTs catalyst, and preparation method and application thereof | |
| CN114100653B (en) | Nitride supported palladium catalyst and preparation method and application thereof | |
| CN113070078B (en) | Rare earth element-doped organic hydrogen storage medium hydrogenation monatomic catalyst and preparation method thereof | |
| CN101993362A (en) | Method for producing oxalic ester through coupling CO | |
| CN115282956A (en) | Titanium dioxide loaded ruthenium metal catalyst and preparation method and application thereof | |
| CN109096029B (en) | Preparation method of isopropyl benzene | |
| CN1061269C (en) | Ni-B amorphous alloy catalyst, its preparing process and application | |
| CN111054384A (en) | Catalyst for organic liquid hydrogen storage material dehydrogenation and preparation method thereof | |
| CN109796305B (en) | Method for preparing cyclohexanol by adopting composite catalyst | |
| CN113751021B (en) | Catalyst for preparing p-aminostyrene by hydrogenation of p-nitrostyrene and preparation method and application thereof | |
| CN113750995B (en) | Titanium dioxide loaded platinum-gallium-indium liquid alloy composite catalyst and preparation method and application thereof | |
| CN113713840B (en) | Cobalt nitride-nickel gallium liquid alloy composite catalyst and preparation method and application thereof | |
| CN113368870B (en) | Sulfur ligand modified monoatomic catalyst and preparation method and application thereof | |
| CN114456055B (en) | Hydrofining method for crude terephthalic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |