CN109529902B - Method for synthesizing vitamin E intermediate under catalysis of high-stability palladium-nickel-carbon catalyst - Google Patents
Method for synthesizing vitamin E intermediate under catalysis of high-stability palladium-nickel-carbon catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 57
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229930003427 Vitamin E Natural products 0.000 title claims abstract description 20
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 235000019165 vitamin E Nutrition 0.000 title claims abstract description 20
- 229940046009 vitamin E Drugs 0.000 title claims abstract description 20
- 239000011709 vitamin E Substances 0.000 title claims abstract description 20
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 109
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 66
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 31
- QIXDHVDGPXBRRD-UHFFFAOYSA-N 2,3,5-trimethylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C(C)=C(C)C1=O QIXDHVDGPXBRRD-UHFFFAOYSA-N 0.000 claims abstract description 28
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004202 carbamide Substances 0.000 claims abstract description 22
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 21
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical compound CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 66
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 56
- 239000000243 solution Substances 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 239000012065 filter cake Substances 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 239000008367 deionised water Substances 0.000 claims description 43
- 229910021641 deionized water Inorganic materials 0.000 claims description 43
- 238000001914 filtration Methods 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 30
- 239000001257 hydrogen Substances 0.000 claims description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims description 29
- 238000002791 soaking Methods 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 150000002815 nickel Chemical class 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 239000012696 Pd precursors Substances 0.000 claims description 16
- 238000004537 pulping Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000006722 reduction reaction Methods 0.000 claims description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 5
- 229940078494 nickel acetate Drugs 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000004280 Sodium formate Substances 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 3
- 235000019254 sodium formate Nutrition 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 239000000543 intermediate Substances 0.000 claims 10
- 238000007036 catalytic synthesis reaction Methods 0.000 claims 7
- 230000000694 effects Effects 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 2
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 239000012018 catalyst precursor Substances 0.000 abstract 1
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 239000002002 slurry Substances 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- 229910000510 noble metal Inorganic materials 0.000 description 8
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007865 diluting Methods 0.000 description 5
- 238000011010 flushing procedure Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229930003231 vitamin Natural products 0.000 description 2
- 239000011782 vitamin Substances 0.000 description 2
- 229940088594 vitamin Drugs 0.000 description 2
- 235000013343 vitamin Nutrition 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron halide Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 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
-
- B01J35/393—
-
- B01J35/394—
-
- 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
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J37/024—Multiple impregnation or coating
-
- 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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
- C07C37/07—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation with simultaneous reduction of C=O group in that ring
Abstract
The invention discloses a method for synthesizing a vitamin E intermediate under the catalysis of a high-stability palladium-nickel-carbon catalyst, which takes palladium-nickel-carbon as the catalyst to catalyze trimethylbenzoquinone to be hydrogenated to synthesize trimethylhydroquinone, wherein the catalyst takes powdered activated carbon as a carrier, the carrier is treated by urea, then dried and cured at high temperature, then auxiliary agent metallic nickel is loaded on the pretreated activated carbon, and the activated carbon loaded with nickel is activated at high temperature; then loading active metal palladium on the nickel carbon to obtain a catalyst precursor; finally, the catalyst is obtained by reducing with a reducing agent. Compared with the prior art, the method of the invention has the advantages of high activity and selectivity of the catalyst, stable performance of the catalyst, good application performance and convenient recycling.
Description
Technical Field
The invention belongs to the technical field of synthesis of vitamin E, and particularly relates to a method for synthesizing a vitamin E intermediate under catalysis of a high-stability palladium-nickel-carbon catalyst.
Background
Vitamin E is one of the essential but not self-synthesized vitamins of human body, plays an important role in regulating the fertility function and the antioxidant function of the human body, and thus becomes one of the three major products in the vitamin industry.
The reduction of trimethylbenzoquinone to trimethylhydroquinone is an important link in the industrial preparation of vitamin E. In the conventional method, the reduction of trimethylbenzoquinone to trimethylhydroquinone is carried out by adding an excess amount of a reducing agent. In the preparation method, due to the addition of excessive reducing agent, the separation and purification process of the product is complicated, and the residual reducing agent can pollute the environment. The catalysts used in the catalytic reduction process can be classified into: non-noble metal catalysts and noble metal catalysts. Among the non-noble metal catalysts are: non-noble metal catalysts such as magnesium chloride-supported silica catalysts, p-benzenesulfonic acid, Raney Ni, carbon-supported cobalt catalysts, magnesium ferrite catalysts, complex iron halide complexes, and the like have been reported as the catalytic reaction. Noble metal catalysts are more and more widely used due to their higher catalytic activity and low requirements on reaction conditions (temperature, pressure). Noble metal catalysts reported in the literature are: palladium carbon and platinum carbon catalysts used for fixed bed reaction, palladium catalysts loaded on treated and modified waste activated carbon, palladium alumina catalysts and the like; in the patent, there are reported an alkali metal-containing aluminosilicate-supported palladium catalyst, a metal organic framework-supported palladium catalyst, and the like. However, the noble metal catalysts generally have the problems of poor catalyst recovery, relatively poor catalytic activity and selectivity, poor recycling performance of the catalysts and the like.
Disclosure of Invention
The invention aims to solve the problems of the prior art and provides a method for catalytically synthesizing a vitamin E intermediate, which has high catalytic activity, good selectivity and good catalyst recycling performance and is convenient to recycle.
The technical scheme for solving the technical problems is as follows: dissolving trimethylbenzoquinone completely in isopropanol, adding a palladium-nickel-carbon catalyst, stirring and reacting for 80-150 min at normal temperature under the hydrogen atmosphere with the pressure of 0.5-1.5 MPa, filtering the reaction solution after the reaction is finished, purifying the filtrate to obtain a vitamin E intermediate, namely trimethylhydroquinone, and washing a filter cake with the isopropanol for repeated use.
In the palladium-nickel-carbon catalyst, the mass fraction of palladium is 3-10%, the mass fraction of nickel is 0.2-4.5%, preferably the mass fraction of palladium is 5%, and the mass fraction of nickel is 1-3%; the catalyst is prepared according to the following steps:
1. adding powdered activated carbon into a urea aqueous solution with the concentration of 3-10 mol/L, soaking for 4-8 h, centrifuging to remove the redundant urea aqueous solution, drying the precipitate at 60-100 ℃ to constant weight, and curing for 3-6 h at 400-700 ℃ in a nitrogen atmosphere to obtain the pretreated activated carbon.
2. Dissolving soluble salt of nickel in deionized water, uniformly stirring to obtain a nickel precursor solution, adding pretreated activated carbon, dipping for 2-6 h under a stirring condition, adding an alkaline compound to adjust the pH value of a dipping system to 7-11, continuously stirring for 1-5 h, filtering, washing a filter cake to be neutral by the deionized water, drying at 60-100 ℃ to constant weight, and activating for 2-6 h at 300-800 ℃ in a hydrogen atmosphere to obtain activated nickel-loaded activated carbon.
3. Dissolving soluble salt of palladium in water, and uniformly stirring to obtain a palladium precursor solution; adding activated nickel-loaded activated carbon into an aqueous solution of an alkaline compound for pulping, heating to 40-70 ℃ under a stirring state, then adding a palladium precursor solution by using a jet pump, carrying out heat preservation and stirring for 2-6 h, then cooling, filtering, pulping a filter cake by using deionized water, adding a reducing agent for reduction, filtering, washing the filter cake by using the deionized water until no chloride ion exists, and drying to obtain the palladium-nickel-carbon catalyst.
In the preparation step 1 of the catalyst, the mass ratio of the powdered activated carbon to the urea aqueous solution is preferably 1: 8-15, wherein the particle size of the powdered activated carbon is 200-400 meshes.
In the step 2 of preparing the catalyst, the soluble salt of nickel is nickel nitrate or nickel acetate.
In the preparation step 3 of the catalyst, the soluble salt of palladium is any one or more of chloropalladic acid, water-soluble palladium chloride and sodium chloropalladite.
In the preparation steps 2 and 3 of the catalyst, the alkaline compound is any one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, wherein the mass fraction of the aqueous solution of the alkaline compound in the step 3 is 1-20%.
In the preparation step 3 of the catalyst, the reducing agent is any one of hydrogen, hydrazine hydrate, formic acid and sodium formate, the reducing temperature of the reducing agent is 60-80 ℃, and the reducing time is 2-4 hours.
In the synthesis method, the ratio of the added mass of the palladium-nickel-carbon catalyst to the volume of the trimethylbenzoquinone is preferably 1g: 10-30 mL.
Compared with the prior art, the invention has the following advantages:
1. the method comprises the steps of soaking activated carbon in a urea aqueous solution to enable urea to be adsorbed on the activated carbon, decomposing the urea adsorbed in the activated carbon into ammonia gas, and carrying out in-situ adsorption on the ammonia gas, so that ammonia molecules are uniformly dispersed in the activated carbon. Then ammonia is decomposed into nitrogen in the high-temperature curing process in the nitrogen atmosphere, so that uniform nitrogen doping of the activated carbon can be realized.
2. According to the invention, soluble nickel salt is loaded on the pretreated activated carbon, and is activated at high temperature in a hydrogen atmosphere, so that the soluble nickel salt is reduced into metallic nickel, and the metallic nickel is firmly loaded on the activated carbon, thus the activity and selectivity of the catalyst are improved, the anti-poisoning performance of the catalyst is improved, and the application performance of the catalyst is improved.
3. The method respectively adsorbs and reduces the noble metal palladium and the assistant metallic nickel, avoids competitive adsorption in the process of simultaneous adsorption, and simultaneously avoids the problem that the same reduction condition can not be simultaneously suitable for two metals with different properties.
4. The preparation method of the catalyst is simple, and the metal particles on the catalyst are small and can be highly dispersed on the carrier. The palladium-nickel-carbon catalyst is used for catalyzing trimethylbenzoquinone to synthesize a vitamin E intermediate through hydrogenation, and the catalyst is high in activity, high in stability, good in repeatability, not easy to agglomerate metal particles after being used for multiple times, and good in application performance.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to these examples.
Example 1
1. Adding 100g of powdery active carbon with the particle size of 200-400 meshes into 1000mL of 5mol/L urea aqueous solution, soaking for 6h, centrifuging in a centrifuge, removing redundant urea aqueous solution in carbon slurry, then placing precipitate in a drying oven, drying for 10 h at 80 ℃ to constant weight, and curing for 4h at 650 ℃ in a nitrogen atmosphere to obtain the pretreated active carbon.
2. Dissolving 4.24g of nickel acetate in 200mL of deionized water, and uniformly stirring to obtain a nickel precursor solution; adding 94.5g of pretreated activated carbon into a nickel precursor solution, soaking for 4h under the stirring condition, adding sodium hydroxide to adjust the pH value of a soaking system to 8.5, continuously stirring for 2h, filtering, washing a filter cake to be neutral by deionized water, placing the filter cake in a drying oven to be dried to constant weight at 80 ℃, and then activating for 3h at 800 ℃ in a hydrogen atmosphere to obtain activated nickel-loaded activated carbon.
3. 13.823g of sodium chloropalladite is dissolved in deionized water, diluted to 200mL by the deionized water and stirred uniformly to obtain a palladium precursor solution; adding activated nickel-loaded activated carbon into 500mL of sodium carbonate aqueous solution with the mass fraction of 1% for pulping, heating to 55 ℃ under the stirring state, adding a palladium precursor solution by using a jet pump, preserving heat, stirring for 2h, cooling, filtering, pulping a filter cake by using deionized water to obtain slurry, introducing hydrogen into the slurry under the stirring state, reducing for 4h at 60 ℃, filtering, washing the obtained filter cake by using deionized water until a silver nitrate solution is checked to be free of chloride ions, drying for 10 hours at 80 ℃ to constant weight to obtain a palladium-nickel-carbon catalyst, wherein the mass percent of palladium in the catalyst is 5%, and the mass percent of nickel is 0.5%.
4. Adding 20mL of trimethylbenzoquinone and 380mL of isopropanol into a high-pressure reaction kettle, stirring until the trimethylbenzoquinone and the isopropanol are completely dissolved, then adding 1g of palladium-nickel-carbon catalyst, replacing air in the high-pressure reaction kettle with nitrogen, replacing the nitrogen with hydrogen, circulating for three times, keeping the hydrogen pressure of 1.0MPa and the stirring speed of 1000 revolutions per minute, reacting at normal temperature for 120min, filtering the reaction solution after the reaction is finished, analyzing the yield of the trimethylhydroquinone by using gas chromatography-mass spectrometry to analyze, flushing a filter cake with the isopropanol, then completely transferring the filter cake into the high-pressure reaction kettle, and adding 20mL of trimethylbenzoquinone and 380mL of isopropanol into the high-pressure reaction kettle for first application. The application step is repeated for 10 times.
Example 2
1. Adding 100g of powdery active carbon with the particle size of 200-400 meshes into 800mL of 6mol/L urea aqueous solution, soaking for 4h, centrifuging in a centrifuge, removing redundant urea aqueous solution in carbon slurry, then placing precipitate in a drying oven, drying for 8h at 80 ℃ to constant weight, and curing for 4h at 680 ℃ in a nitrogen atmosphere to obtain the pretreated active carbon.
2. Dissolving 8.48g of nickel acetate in 200mL of deionized water, and uniformly stirring to obtain a nickel precursor solution; adding 93g of pretreated activated carbon into a nickel precursor solution, soaking for 4.5h under the stirring condition, adding sodium carbonate to adjust the pH value of a soaking system to 8.5, continuously stirring for 3h, filtering, washing a filter cake to be neutral by deionized water, placing the filter cake in a drying oven at 80 ℃ to be dried to constant weight, and then activating for 2.5h at 600 ℃ in a hydrogen atmosphere to obtain activated nickel-loaded activated carbon.
3. Diluting 50mL of 0.1g/mL chloropalladite acid aqueous solution to 200mL by using deionized water, and uniformly stirring to obtain a palladium precursor solution; adding activated nickel-loaded activated carbon into 500mL of 20 mass percent sodium bicarbonate aqueous solution for pulping, heating to 40 ℃ under a stirring state, adding a palladium precursor solution by using a jet pump, carrying out heat preservation and stirring for 6 hours, cooling, filtering, pulping a filter cake by using deionized water to obtain slurry, adding 50mL of formic acid into the slurry under a stirring state, reducing for 2 hours at 70 ℃, filtering, washing the obtained filter cake by using deionized water until no chloride ion is detected in a silver nitrate solution, drying for 10 hours at 80 ℃ to constant weight to obtain the palladium-nickel-carbon catalyst, wherein the mass percent of palladium in the catalyst is 5%, and the mass percent of nickel in the catalyst is 2%.
4. Adding 20mL of trimethylbenzoquinone and 380mL of isopropanol into a high-pressure reaction kettle, stirring until the trimethylbenzoquinone and the isopropanol are completely dissolved, then adding 1g of palladium-nickel-carbon catalyst, replacing air in the high-pressure reaction kettle with nitrogen, then replacing the nitrogen with hydrogen, circulating for three times, keeping the hydrogen pressure at 1.0MPa and the stirring speed at 1000 rpm, reacting at normal temperature for 120min, filtering the reaction solution after the reaction is finished, analyzing the yield of the trimethylhydroquinone by using a gas chromatography-mass spectrometry (GC) for filtrate, completely transferring filter cakes into the high-pressure reaction kettle after the filter cakes are washed with the isopropanol, and adding 20mL of trimethylbenzoquinone and 380mL of isopropanol into the high-pressure reaction kettle for first application. The application step is repeated for 10 times.
Example 3
1. Adding 100g of powdery active carbon with the particle size of 200-400 meshes into 1200mL of 4mol/L urea aqueous solution, soaking for 7h, centrifuging in a centrifuge, removing redundant urea aqueous solution in carbon slurry, then placing precipitate in a drying oven, drying for 9 h at 80 ℃ to constant weight, and curing for 4h at 600 ℃ in a nitrogen atmosphere to obtain the pretreated active carbon.
2. 12.387g of nickel nitrate is dissolved in 200mL of deionized water, and the mixture is uniformly stirred to obtain a nickel precursor solution; adding 92.5g of pretreated activated carbon into a nickel precursor solution, soaking for 4h under the stirring condition, adding sodium bicarbonate to adjust the pH value of a soaking system to 10, continuously stirring for 4h, filtering, washing a filter cake to be neutral by deionized water, placing the filter cake in a drying oven to be dried to constant weight at 80 ℃, and then activating for 3.5h at 500 ℃ in a hydrogen atmosphere to obtain activated nickel-loaded activated carbon.
3. Dissolving 8.33g of water-soluble palladium chloride in deionized water, diluting the solution to 200mL by using the deionized water, and uniformly stirring to obtain a palladium precursor solution; adding activated nickel-loaded activated carbon into 500mL of potassium bicarbonate aqueous solution with the mass fraction of 12% for pulping, heating to 60 ℃ under a stirring state, adding a palladium precursor solution by using a jet pump, preserving heat, stirring for 4 hours, cooling, filtering, pulping a filter cake by using deionized water to obtain slurry, introducing hydrogen into the slurry under the stirring state, reducing for 4 hours at 60 ℃, filtering, washing the obtained filter cake by using deionized water until no chloride ion is detected in a silver nitrate solution, drying for 10 hours at 80 ℃ to constant weight to obtain a palladium-nickel-carbon catalyst, wherein the mass percent of palladium in the catalyst is 5%, and the mass percent of nickel is 2.5%.
4. Adding 20mL of trimethylbenzoquinone and 380mL of isopropanol into a high-pressure reaction kettle, stirring until the trimethylbenzoquinone and the isopropanol are completely dissolved, then adding 1g of palladium-nickel-carbon catalyst, replacing air in the high-pressure reaction kettle with nitrogen, replacing the nitrogen with hydrogen, circulating for three times, keeping the hydrogen pressure of 1.0MPa and the stirring speed of 1000 revolutions per minute, reacting at normal temperature for 120min, filtering the reaction solution after the reaction is finished, analyzing the yield of the trimethylhydroquinone by using gas chromatography-mass spectrometry to analyze, flushing a filter cake with the isopropanol, then completely transferring the filter cake into the high-pressure reaction kettle, and adding 20mL of trimethylbenzoquinone and 380mL of isopropanol into the high-pressure reaction kettle for first application. The application step is repeated for 10 times.
Example 4
1. Adding 100g of powdery active carbon with the particle size of 200-400 meshes into 900mL of 7mol/L urea aqueous solution, soaking for 5.5h, centrifuging in a centrifuge, removing redundant urea aqueous solution in carbon slurry, then placing precipitate in an oven, drying for 11 h at 80 ℃ to constant weight, and curing for 4h at 650 ℃ in a nitrogen atmosphere to obtain the pretreated active carbon.
2. Dissolving 14.86g of nickel nitrate in 200mL of deionized water, and uniformly stirring to obtain a nickel precursor solution; adding 90.5g of pretreated activated carbon into a nickel precursor solution, soaking for 4 hours under the stirring condition, adding sodium hydroxide to adjust the pH value of a soaking system to 10.5, continuously stirring for 4 hours, filtering, washing a filter cake to be neutral by deionized water, placing the filter cake in a drying oven at 80 ℃ to be constant in weight, and then activating for 2.5 hours at 680 ℃ in a hydrogen atmosphere to obtain the activated nickel-loaded activated carbon.
3. Dissolving 8.33g of water-soluble palladium chloride in deionized water, diluting the solution to 200mL by using the deionized water, and uniformly stirring to obtain a palladium precursor solution; adding activated nickel-loaded activated carbon into 800mL of potassium carbonate aqueous solution with the mass fraction of 15% for pulping, heating to 50 ℃ under a stirring state, adding a palladium precursor solution by using a jet pump, preserving heat, stirring for 3 hours, cooling, filtering, pulping a filter cake by using deionized water to obtain slurry, adding 50g of sodium formate into the slurry under the stirring state, reducing for 3 hours at 80 ℃, filtering, washing the obtained filter cake by using the deionized water until no chloride ion is detected in a silver nitrate solution, drying for 10 hours at 80 ℃ to constant weight to obtain a palladium-nickel-carbon catalyst, wherein the mass percent of palladium in the catalyst is 5%, and the mass percent of nickel in the catalyst is 4.5%.
4. Adding 20mL of trimethylbenzoquinone and 380mL of isopropanol into a high-pressure reaction kettle, stirring until the trimethylbenzoquinone and the isopropanol are completely dissolved, then adding 1g of palladium-nickel-carbon catalyst, replacing air in the high-pressure reaction kettle with nitrogen, replacing the nitrogen with hydrogen, circulating for three times, keeping the hydrogen pressure of 1.0MPa and the stirring speed of 1000 revolutions per minute, reacting at normal temperature for 120min, filtering the reaction solution after the reaction is finished, analyzing the yield of the trimethylhydroquinone by using gas chromatography-mass spectrometry to analyze, flushing a filter cake with the isopropanol, then completely transferring the filter cake into the high-pressure reaction kettle, and adding 20mL of trimethylbenzoquinone and 380mL of isopropanol into the high-pressure reaction kettle for first application. The application step is repeated for 10 times.
Example 5
1. Adding 100g of powdery active carbon with the particle size of 200-400 meshes into 1500mL of 3mol/L urea aqueous solution, soaking for 8h, centrifuging in a centrifuge, removing redundant urea aqueous solution in carbon slurry, then placing precipitate in a drying oven, drying for 12 h at 80 ℃ to constant weight, and curing for 6h at 400 ℃ in a nitrogen atmosphere to obtain the pretreated active carbon.
2. Dissolving 7.43g of nickel nitrate in 200mL of deionized water, and uniformly stirring to obtain a nickel precursor solution; adding 94g of pretreated activated carbon into a nickel precursor solution, soaking for 6h under the stirring condition, adding potassium hydroxide to adjust the pH value of a soaking system to 11, continuously stirring for 2h, filtering, washing a filter cake to be neutral by deionized water, placing the filter cake in an oven to be dried to constant weight at 80 ℃, and then activating for 6h at 400 ℃ in a hydrogen atmosphere to obtain the activated nickel-loaded activated carbon.
3. Dissolving 13.82g of sodium chloropalladite in deionized water, diluting the solution to 200mL by using the deionized water, and uniformly stirring to obtain a palladium precursor solution; adding activated nickel-loaded activated carbon into 800mL of 6 mass percent sodium carbonate aqueous solution for pulping, heating to 70 ℃ under a stirring state, adding a palladium precursor solution by using a jet pump, carrying out heat preservation and stirring for 4h, cooling, filtering, pulping a filter cake by using deionized water to obtain slurry, introducing hydrogen into the slurry under a stirring state, reducing for 4h at 60 ℃, filtering, washing the obtained filter cake by using deionized water until a silver nitrate solution is checked to be free of chloride ions, drying for 10 hours at 80 ℃ to constant weight to obtain a palladium-nickel-carbon catalyst, wherein the mass percent of palladium in the catalyst is 5%, and the mass percent of nickel is 1%.
4. Adding 20mL of trimethylbenzoquinone and 380mL of isopropanol into a high-pressure reaction kettle, stirring until the trimethylbenzoquinone and the isopropanol are completely dissolved, then adding 1g of palladium-nickel-carbon catalyst, replacing air in the high-pressure reaction kettle with nitrogen, replacing the nitrogen with hydrogen, circulating for three times, keeping the hydrogen pressure of 1.0MPa and the stirring speed of 1000 revolutions per minute, reacting at normal temperature for 120min, filtering the reaction solution after the reaction is finished, analyzing the yield of the trimethylhydroquinone by using gas chromatography-mass spectrometry to analyze, flushing a filter cake with the isopropanol, then completely transferring the filter cake into the high-pressure reaction kettle, and adding 20mL of trimethylbenzoquinone and 380mL of isopropanol into the high-pressure reaction kettle for first application. The application step is repeated for 10 times.
Example 6
1. Adding 100g of powdery active carbon with the particle size of 200-400 meshes into 1300mL of 10mol/L urea aqueous solution, soaking for 5h, centrifuging in a centrifuge, removing redundant urea aqueous solution in carbon slurry, then placing the precipitate in a drying oven, drying for 11 h at 80 ℃ to constant weight, and curing for 3h at 700 ℃ in a nitrogen atmosphere to obtain the pretreated active carbon.
2. Dissolving 12.72g of nickel acetate in 200mL of deionized water, and uniformly stirring to obtain a nickel precursor solution; adding 94g of pretreated activated carbon into a nickel precursor solution, soaking for 6h under the stirring condition, adding sodium hydroxide to adjust the pH value of a soaking system to 7.5, continuously stirring for 2h, filtering, washing a filter cake to be neutral by deionized water, placing the filter cake in a drying oven at 80 ℃ to dry to constant weight, and then activating for 2h at 300 ℃ in a hydrogen atmosphere to obtain activated nickel-loaded activated carbon.
3. Diluting 50mL of 0.1g/mL chloropalladite acid aqueous solution to 200mL by using deionized water, and uniformly stirring to obtain a palladium precursor solution; adding activated nickel-loaded activated carbon into 1000mL of sodium bicarbonate aqueous solution with the mass fraction of 8% for pulping, heating to 60 ℃ under a stirring state, adding a palladium precursor solution by using a jet pump, carrying out heat preservation stirring for 2h, cooling, filtering, pulping a filter cake by using deionized water to obtain slurry, adding 50mL of formic acid into the slurry under the stirring state, reducing for 2.5h at 70 ℃, filtering, washing the obtained filter cake by using deionized water until a silver nitrate solution is detected to be free of chloride ions, drying for 10 h at 80 ℃ to constant weight to obtain the palladium-nickel-carbon catalyst, wherein the mass percent of palladium in the catalyst is 5%, and the mass percent of nickel in the catalyst is 1%.
4. Adding 20mL of trimethylbenzoquinone and 380mL of isopropanol into a high-pressure reaction kettle, stirring until the trimethylbenzoquinone and the isopropanol are completely dissolved, then adding 1g of palladium-nickel-carbon catalyst, replacing air in the high-pressure reaction kettle with nitrogen, replacing the nitrogen with hydrogen, circulating for three times, keeping the hydrogen pressure of 1.0MPa and the stirring speed of 1000 revolutions per minute, reacting at normal temperature for 120min, filtering the reaction solution after the reaction is finished, analyzing the yield of the trimethylhydroquinone by using gas chromatography-mass spectrometry to analyze, flushing a filter cake with the isopropanol, then completely transferring the filter cake into the high-pressure reaction kettle, and adding 20mL of trimethylbenzoquinone and 380mL of isopropanol into the high-pressure reaction kettle for first application. The application step is repeated for 10 times.
Comparative example 1
Step 1 of example 1 was changed to: adding 100g of powdery activated carbon with the particle size of 200-400 meshes into 1000mL of deionized water, soaking for 6h, centrifuging in a centrifuge, removing excessive water in carbon slurry, then placing the precipitate in an oven, and drying at 80 ℃ to constant weight. Step 2 and step 3 were the same as in example 1 to obtain a palladium-nickel-carbon catalyst.
Comparative example 2
In step 1 of example 1, the precipitate was dried to a constant weight, and then, the palladium-nickel-carbon catalyst was obtained in the same manner as in example 1, except that high-temperature curing in a nitrogen atmosphere was not performed.
Comparative example 3
In example 1, the palladium-carbon catalyst was prepared without the nickel loading process of step 2.
Comparative example 4
In step 2 of example 1, the supported palladium of step 3 was directly carried out without reduction in a hydrogen atmosphere after drying the filter cake to a constant weight.
The results of the experiments in examples 1 to 6 and comparative examples 1 to 4 are shown in Table 1.
TABLE 1 yield of trimethylhydroquinone from trimethylbenzoquinone by hydrogenation in the presence of different catalysts
As can be seen from Table 1, when the catalyst prepared by the method is used for catalyzing the reaction of synthesizing trimethylhydroquinone from trimethylbenzoquinone, the activity and the stability of the catalyst are obviously improved due to doping modification of activated carbon and addition and step-by-step reduction of auxiliary metal nickel, and the catalytic activity is basically unchanged after the catalyst is mechanically used for 10 times.
Claims (9)
1. A method for synthesizing a vitamin E intermediate under the catalysis of a high-stability palladium-nickel-carbon catalyst is characterized by comprising the following steps: completely dissolving trimethylbenzoquinone in isopropanol, adding a palladium-nickel-carbon catalyst, wherein the adding mass of the palladium-nickel-carbon catalyst is 1g: 10-30 mL relative to the volume of the trimethylbenzoquinone, stirring and reacting at normal temperature for 80-150 min under the hydrogen atmosphere with the pressure of 0.5-1.5 MPa, filtering the reaction solution after the reaction is finished, purifying the filtrate to obtain a vitamin E intermediate, namely trimethylhydroquinone, and washing a filter cake with isopropanol for repeated use;
the palladium-nickel-carbon catalyst comprises 3-10% of palladium and 0.2-4.5% of nickel by mass, and is prepared according to the following steps:
(1) adding powdered activated carbon into a urea aqueous solution with the concentration of 3-10 mol/L, soaking for 4-8 h, centrifuging to remove redundant urea aqueous solution, drying the precipitate at 60-100 ℃ to constant weight, and curing for 3-6 h at 400-700 ℃ in a nitrogen atmosphere to obtain pretreated activated carbon;
(2) dissolving soluble salt of nickel in deionized water, uniformly stirring to obtain a nickel precursor solution, adding pretreated activated carbon, dipping for 2-6 h under a stirring condition, adding an alkaline compound to adjust the pH value of a dipping system to 7-11, continuously stirring for 1-5 h, filtering, washing a filter cake to be neutral by the deionized water, drying at 60-100 ℃ to constant weight, and activating for 2-6 h at 300-800 ℃ in a hydrogen atmosphere to obtain activated nickel-loaded activated carbon;
(3) dissolving soluble salt of palladium in water, and uniformly stirring to obtain a palladium precursor solution; adding activated nickel-loaded activated carbon into an aqueous solution of an alkaline compound for pulping, heating to 40-70 ℃ under a stirring state, then adding a palladium precursor solution by using a jet pump, carrying out heat preservation and stirring for 2-6 h, then cooling, filtering, pulping a filter cake by using deionized water, adding a reducing agent for reduction, filtering, washing the filter cake by using the deionized water until no chloride ion exists, and drying to obtain the palladium-nickel-carbon catalyst.
2. The method for the catalytic synthesis of vitamin E intermediates with the highly stable palladium-nickel-carbon catalyst as claimed in claim 1, wherein: in the step (1), the mass ratio of the powdered activated carbon to the urea aqueous solution is 1: 8-15, wherein the particle size of the powdered activated carbon is 200-400 meshes.
3. The method for the catalytic synthesis of vitamin E intermediates with the highly stable palladium-nickel-carbon catalyst as claimed in claim 1, wherein: in the steps (2) and (3), the alkaline compound is any one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate.
4. The method for the catalytic synthesis of vitamin E intermediates with the highly stable palladium-nickel-carbon catalyst as claimed in claim 3, wherein: in the step (3), the mass fraction of the aqueous solution of the alkaline compound is 1-20%.
5. The method for the catalytic synthesis of vitamin E intermediates with the highly stable palladium-nickel-carbon catalyst as claimed in claim 1, wherein: in the step (2), the soluble salt of nickel is nickel nitrate or nickel acetate.
6. The method for the catalytic synthesis of vitamin E intermediates with the highly stable palladium-nickel-carbon catalyst as claimed in claim 1, wherein: in the step (3), the soluble salt of palladium is any one or more of chloropalladic acid, water-soluble palladium chloride and sodium chloropalladite.
7. The method for the catalytic synthesis of vitamin E intermediates with the highly stable palladium-nickel-carbon catalyst as claimed in claim 1, wherein: in the step (3), the reducing agent is any one of hydrogen, hydrazine hydrate, formic acid and sodium formate.
8. The method for the catalytic synthesis of vitamin E intermediates with the highly stable palladium-nickel-carbon catalyst as claimed in claim 7, wherein: in the step (3), the reduction temperature is 60-80 ℃, and the reduction time is 2-4 h.
9. The method for synthesizing the vitamin E intermediate under the catalysis of the high-stability palladium-nickel-carbon catalyst according to any one of claims 1 to 8, wherein the method comprises the following steps: the mass fraction of palladium in the palladium-nickel-carbon catalyst is 5%, and the mass fraction of nickel is 1% -3%.
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