CN106345508B - A kind of catalyst and its preparation method and application for alkynol selective hydrogenation - Google Patents
A kind of catalyst and its preparation method and application for alkynol selective hydrogenation Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 116
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 19
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000005253 cladding Methods 0.000 claims abstract description 11
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 10
- 239000000470 constituent Substances 0.000 claims abstract description 9
- 229910000905 alloy phase Inorganic materials 0.000 claims abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000001257 hydrogen Substances 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 9
- 239000003610 charcoal Substances 0.000 claims description 8
- 150000002085 enols Chemical class 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 229910003244 Na2PdCl4 Inorganic materials 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- USDAQJSRGJCNNX-JJKGCWMISA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanamide;sulfuric acid Chemical compound OS(O)(=O)=O.NC(=O)[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO USDAQJSRGJCNNX-JJKGCWMISA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 3
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011425 bamboo Substances 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 1
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 125000000914 phenoxymethylpenicillanyl group Chemical group CC1(S[C@H]2N([C@H]1C(=O)*)C([C@H]2NC(COC2=CC=CC=C2)=O)=O)C 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 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 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229930003427 Vitamin E Natural products 0.000 abstract description 2
- 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 abstract description 2
- 229940046009 vitamin E Drugs 0.000 abstract description 2
- 235000019165 vitamin E Nutrition 0.000 abstract description 2
- 239000011709 vitamin E Substances 0.000 abstract description 2
- 235000021466 carotenoid Nutrition 0.000 abstract 1
- 150000001747 carotenoids Chemical class 0.000 abstract 1
- 239000003205 fragrance Substances 0.000 abstract 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 18
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 18
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 101150003085 Pdcl gene Proteins 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 11
- 238000001354 calcination Methods 0.000 description 10
- 238000004090 dissolution Methods 0.000 description 10
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 229910052797 bismuth Inorganic materials 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 7
- CHVZQMAANSUXJU-JJKGCWMISA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanamide;hydrochloride Chemical group Cl.NC(=O)[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO CHVZQMAANSUXJU-JJKGCWMISA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 238000006356 dehydrogenation reaction Methods 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 description 5
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 description 5
- 229930007744 linalool Natural products 0.000 description 5
- 235000013311 vegetables Nutrition 0.000 description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011981 lindlar catalyst Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- FUDNBFMOXDUIIE-UHFFFAOYSA-N 3,7-dimethylocta-1,6-diene Chemical compound C=CC(C)CCC=C(C)C FUDNBFMOXDUIIE-UHFFFAOYSA-N 0.000 description 2
- JQZGUQIEPRIDMR-UHFFFAOYSA-N 3-methylbut-1-yn-1-ol Chemical compound CC(C)C#CO JQZGUQIEPRIDMR-UHFFFAOYSA-N 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910003445 palladium oxide Inorganic materials 0.000 description 2
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FQTLCLSUCSAZDY-UHFFFAOYSA-N (+) E(S) nerolidol Natural products CC(C)=CCCC(C)=CCCC(C)(O)C=C FQTLCLSUCSAZDY-UHFFFAOYSA-N 0.000 description 1
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229920000914 Metallic fiber Polymers 0.000 description 1
- FQTLCLSUCSAZDY-ATGUSINASA-N Nerolidol Chemical compound CC(C)=CCC\C(C)=C\CC[C@](C)(O)C=C FQTLCLSUCSAZDY-ATGUSINASA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- YNCZNSWQAGQAJY-UHFFFAOYSA-N but-2-yne-1,1-diol Chemical compound CC#CC(O)O YNCZNSWQAGQAJY-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- WASNIKZYIWZQIP-AWEZNQCLSA-N nerolidol Natural products CC(=CCCC(=CCC[C@@H](O)C=C)C)C WASNIKZYIWZQIP-AWEZNQCLSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- -1 wire mesh Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/644—Arsenic, antimony or bismuth
- B01J23/6447—Bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The catalyst and its preparation method and application that the invention discloses a kind of for alkynol selective hydrogenation, the catalyst includes carrier and active constituent, the active constituent includes the alloy phase that Pd and Pd-Zn is formed, and the carrier is the ZnO of nitrogen-doped carbon material cladding.The catalyst is used for C5‑C20When the hydrogenating reduction of chain alkynol, there is preferable conversion ratio and selectivity, can be used in the synthesis process of vitamin E, carotenoid and fragrance.
Description
Technical field
The invention belongs to organic synthesis fields, and in particular to one kind is used for C5-C20Chain alkynol selective hydration is C5-C20
Catalyst of alkenols and preparation method and application.
Background technique
It is the important process in fine chemistry industry that alkynol, which is selectively hydrogenated to enol, as vitamin E chemical synthesis during
It is related to the synthesis of several important intermediates, such as linalool, nerolidol, different vegetable alcohol, the synthesis of these intermediates is used
To selective hydrocatalyst.Palladium metal shows good activity and selectivity in alkynol selective hydrogenation process.
Industrial alkynol enol process master catalyst to be applied is Lin Dela (Lindlar) catalyst at present, this is urged
Agent is using calcium carbonate or barium sulfate as carrier, carried metal Pd, while metal Pb is added and plays poisoning effect, to improve catalyst
Selectivity.Patent CN 104394988A discloses a kind of preparation method of novel Lindlar catalyst, and the catalyst is main
It is the selectivity by controlling the partial size of calcium carbonate carrier (being greater than 10um) Lai Tigao catalyst.But getting over environmental legislation
Carry out stringenter, the processing presence very hang-up of Pb metal in decaying catalyst, and heel rate is higher.Patent CN1151725A is public
A kind of method for having opened selective hydrogenation of butine diol to butene diol, the catalyst carrier are mainly to carry with δ-aluminium oxide
Body, Pd and Zn or Cu or Ag obtain catalyst after reduction with certain proportion dip loading, which avoids adding for metal Pb
Enter, and the selectivity height and by-products content of butynediols are low.Patent CN103406121A discloses a kind of charcoal load palladium oxide
Catalyst and its preparation method and application, the catalyst form hydration oxygen using active carbon as carrier, by adjusting pH value with lye
Change palladium colloidal solution, after impregnation for a period of time, then with lye adjust maceration extract pH value, continue time of infusion
Afterwards, filtration washing obtains charcoal and carries palladium oxide catalyst, the catalyst is anti-in Isosorbide-5-Nitrae-butynediols Isosorbide-5-Nitrae-butylene glycol to neutrality
It is shown in answering higher selectivity (99%), and palladium metal is easy to recycle.Both the above catalyst primarily directed to
Specific alkynol reactant, therefore above have certain limitation in application.
Patent CN101616733A discloses a kind of Structured catalysts, using metallic fiber SMF as carrier, first loading ZnO,
Palladium nano-particles are impregnated again, catalyst selectivity with higher (95%), but preparation process is more complex, and catalyst holds
Easy in inactivation is used for kettle although catalyst activity can be substantially returned to fresh catalyst level by regenerated mode
It is unfavorable for operating in formula reaction.
In conclusion the active component of alkynol selective hydrocatalyst is mainly metal Pd, carrier can choose activity
Charcoal, aluminum oxide, wire mesh, calcium carbonate, barium sulfate, silica etc., inhibitor is mainly from Pb, Ag, Bi, Mn, Zn, Cu
It is selected in equal metals.The improvement of catalyst mainly changes enol and alkanol in the rate of catalyst surface adsorption desorption, so that alkynes
The enol that alcohol is hydrogenated to can quickly leave catalyst surface, be hydrogenated to alkanol without being to continue with.At present in publication
Catalyst has plenty of for the problem that a kind of specific alkynol is effective, has plenty of there are metal recovery, there is presently no one kind
It can be applicable in different carbon chain lengths alkynol selective hydrocatalyst, and can be realized what the metal in catalyst was easily recycled
It is environmentally friendly simultaneously.
Summary of the invention
The catalyst and its preparation method and application that the object of the present invention is to provide a kind of for alkynol selective hydrogenation, should
Catalyst does not contain Pb, in C5-C20Shown in chain alkynol selective hydrogenation process excellent activity (conversion ratio reach 99.5% with
On) and selectivity, and may be implemented repeatedly to apply, the Pd metal in catalyst is easy recycling.
A kind of catalyst for alkynol selective hydrogenation, including carrier and active constituent, the active constituent include
The alloy phase that Pd and Pd-Zn is formed, the carrier are the ZnO of N doping Carbon Materials cladding.
Catalyst of the invention does not contain metal Pb, reduces the pollution in catalyst recovery process to environment, simultaneously
Conversion ratio with higher and selectivity；And be conducive to the recycling of Pd metal using the ZnO of N doping Carbon Materials cladding as carrier
It utilizes.
Preferably, the X is selected from one of Bi, Mn, Ag also containing ingredient X is inhibited in the active constituent.
At this point, the structure that there is the catalyst following chemical formula to indicate: PdX/CN@ZnO.
As a further preference, the molar ratio Pd:X=10:1-30:0, Pd of active constituent Pd and X and N doping raw material of wood-charcoal
The mass ratio for expecting the ZnO carrier of cladding is 0.1%-5%, and Pd herein includes Pd present in single-phase Pd and alloy phase.
Preferably, the mass ratio of N:C:ZnO is 1:6:7-3:1 in the ZnO carrier of the N doping Carbon Materials cladding:
15。
In the catalyst, the partial size of the carrier is 150-250 mesh, and the partial size of Pd is 2-20nm, catalyst
Specific surface area 10-1000m2/g。
Specific preparation process is as follows for above-mentioned catalyst:
(1) aqueous solution in nitrogenous charcoal source and ZnO powder are stirred at 150-200 DEG C, moisture is evaporated, obtained mixing
Solid under nitrogen protection, is calcined under the conditions of 400-600 DEG C, obtains the ZnO carrier of N doping Carbon Materials cladding；
(2) palladium source, stabilizer and inhibitor (when wherein, needing to inhibit ingredient, inhibitor is added herein, otherwise, is not required to
Inhibitor is added) it is dissolved in the water, it stirs, is heated to 90-120 DEG C and constant temperature 1-3h, lead to hydrogen reducing after being down to room temperature
0.5-1h obtains palladium colloidal sol；
(3) by carrier impregnation that step (1) obtains in the palladium colloidal sol that step (2) obtains 2-24h, then at 60-120 DEG C
Lower drying, obtains catalyst crude product；
(4) the catalyst crude product that step (3) obtains is placed in furnace, is warming up to 300-600 DEG C per minute with 10-30 DEG C,
Then 1-3h is restored under hydrogen atmosphere, obtains catalyst；
The nitrogenous charcoal source is aminoglucose hydrochloride, aminoglucose sulfate, melamine, urea and bamboo
One of.
The palladium source is PdCl2, Pd (NO3)2, Na2PdCl4, Pd (CH3COO)2One of；
The stabilizer is PVP, PVA, sodium citrate, one of ammonium molybdate；
The inhibitor is Bi (NO3)3, MnCl2, AgNO3One of；
The partial size of the catalyst carrier of this method preparation is 150-250 mesh, and the partial size of Pd is 2-20nm, the ratio table of catalyst
Area 10-1000m2/g；Mainly mutually exist with palladium simple substance with Pd-Zn alloy, TEM electron microscope is shown in Fig. 1.
The present invention also provides the catalyst described in one kind to prepare the application in enol in highly selective hydrogenation of alkinols, by alkynes
In alcohol (Formulas I), solvent and the catalyst investment reactor, selective hydrogenation is carried out under an atmosphere of hydrogen, reaction is finished,
Cool down simultaneously filtration catalytic agent, obtains corresponding enol (Formula II), reaction process is as follows:
Wherein R indicates that carbon atom number is alkyl (such as methyl butynol, dehydrogenation linalool, the dehydrogenation different vegetable alcohol of 1-16
Deng), for different reactants, by controlling the preparation process of catalyst, the conversion ratio of catalyst is selected up to 99.5% or more
Selecting property is 95% or more.
Wherein, the alkyl includes alkyl, alkenyl or alkynyl, preferably alkyl or alkenyl.
The solvent is the common solvent of this field hydrogenation reaction, and those skilled in the art can be according to existing knowledge
It is selected, generally polar solvent, such as alcoholic solvent and water etc..
The catalyst being obtained by filtration can be applied, and test result shows after repeatedly applying, the activity of catalyst
It is substantially reduced with selectivity nothing.
Compared with the existing technology, the catalyst be mainly characterized by reduce catalyst recovery process without containing metal Pb
In pollution to environment, and be conducive to using the ZnO of N doping Carbon Materials cladding as carrier the recycling of Pd metal.Simultaneously should
Catalyst is in C5-C20Highly selective and high stability is shown in the selective hydrogenation process of alkynol, advantageously reduces catalyst
Cost.
Detailed description of the invention
The TEM that Fig. 1 is catalyst A schemes；
Fig. 2 catalyst A applies situation in methyl butynol hydrogenation reaction, and wherein ordinate is reaction selectivity, horizontal
Coordinate is to apply number.
The present invention is further illustrated combined with specific embodiments below.
Specific embodiment
Following embodiment is for further illustrating the present invention, but the present invention is not limited only to these embodiments.
Embodiment 1
The preparation of catalyst: being added 3g aminoglucose hydrochloride in 50mL flask, and 2g is added in 25mL water stirring and dissolving
ZnO powder, in oil bath pan 150 DEG C stir it is dry.It stirs after doing and is ground to powder.Lead to nitrogen calcining in tube furnace, 10 DEG C/min rises to
It 550 DEG C, constant temperature 2h, is then ground uniformly, obtained CN@ZnO complex carrier, kept dry, wherein N:C:ZnO=1:6:10
(mass ratio).
0.05g PVP (polyvinylpyrrolidone) dissolution, PVP and PdCl are added in 25ml water2Molar ratio be 10:1,
It is 0.5%PdCl that prepared mass percent concentration in advance, which is added dropwise,2Solution and 0.1%Bi (NO3)3Mole of solution, Pd and Bi
Than for 10:1, being heated to 100 DEG C, 3h is kept.It is down to room temperature (20-25 DEG C) to lead to afterwards hydrogen 2 hours, then be washed with deionized
It obtains palladium colloidal sol 3 times, is then transferred in beaker, the above-mentioned composite material carrier of 0.5g is added, 12h is stirred at room temperature, spends
Ion water washing 3 times, 60 DEG C of dry 12h.Lead to hydrogen reducing in tube furnace, 10 DEG C/min rises to 500 DEG C, keeps 3h, obtains
Catalyst A obtains specific surface area of catalyst in 15g/m2, catalyst particle size 200-250 mesh, Pd particle size is in 15-20nm.
Embodiment 2
The preparation of catalyst: being added 3.0g bamboo powder in 50mL flask, and 1.5g ZnO is added in 25mL water stirring and dissolving,
In oil bath pan 150 DEG C stir it is dry.It stirs after doing and is ground to powder, nitrogen calcining is led in tube furnace, 10 DEG C/min rises to 550 DEG C, keeps
Then 2h is ground uniformly, obtained CN@ZnO complex carrier, kept dry, wherein N:C:ZnO=1:6:7 (mass ratio).
0.1g PVP dissolution, PVP and PdCl are added in 15mL water2Molar ratio be 20:1, be added dropwise in advance it is prepared
0.5%PdCl2Solution and 0.1%Bi (NO3)3The molar ratio of solution, Pd and Bi are 10:1, are heated to 105 DEG C, keep 3h.It is down to
Room temperature (20-25 DEG C) is led to hydrogen 2 hours afterwards, and then deionized water washs 3 times and obtains palladium colloidal sol, is then transferred to beaker
In, the above-mentioned composite material carrier of 0.5g is added, 12h is stirred at room temperature, is washed with deionized 3 times, 120 DEG C of dry 12h.In tubular type
Lead to hydrogen reducing in furnace, 10 DEG C/min rises to 600 DEG C, keeps 3h, obtains catalyst B.Specific surface area of catalyst is obtained in 450g/
m2, catalyst particle size 150-200 mesh, Pd particle size is in 15-20nm.
Embodiment 3
The preparation of catalyst: being added 3.0g melamine in 50mL flask, and 1.5g is added in 25mL water stirring and dissolving
ZnO, in oil bath pan 170 DEG C stir it is dry.It stirs after doing and is ground to powder, nitrogen calcining is led in tube furnace, 10 DEG C/min rises to 550
DEG C, 2h is kept, is then ground uniformly, CN@ZnO complex carrier, kept dry is made.Wherein N:C:ZnO=2.5:1:7
(mass ratio).
0.1g PVA (polyvinyl alcohol) dissolution, PVA and PdCl are added in 10ml water2Molar ratio be 10:1, be added dropwise pre-
First prepared 1.0%PdCl2Solution and 0.034%AgNO3The molar ratio of solution, Pd and Ag are 30:1, are heated to 100 DEG C, are protected
Hold 3h.It is down to room temperature (20-25 DEG C) to lead to afterwards hydrogen 2 hours, is then washed with deionized 3 times and obtains palladium colloidal sol, then by it
It is transferred in beaker, the above-mentioned composite material carrier of 0.5g is added, 12h is stirred at room temperature, is washed with deionized 3 times, 120 DEG C of dryings
12h.Lead to hydrogen reducing in tube furnace, 10 DEG C/min rises to 400 DEG C, keeps 3h, obtains catalyst C.It obtains catalyst and compares table
Area is in 50g/m2, catalyst particle size 200-250 mesh, Pd particle size is in 15-20nm.
Embodiment 4
The preparation of catalyst: being added 3.0g urea in 50mL flask, and 1.5g ZnO is added in 25mL water stirring and dissolving,
In oil bath pan 170 DEG C stir it is dry.It stirs after doing and is ground to powder, nitrogen calcining is led in tube furnace, 10 DEG C/min rises to 550 DEG C, keeps
Then 2h is ground uniformly, obtained CN@ZnO complex carrier, kept dry, wherein N:C:ZnO=3:1:7 (mass ratio).
0.03g ammonium molybdate is added in 10ml water to dissolve, the molar ratio of Mo and Pd are 10:1, are added dropwise prepared in advance
2.0%PdCl2Solution is heated to 100 DEG C, keeps 3h.It is down to room temperature (20-25 DEG C) to lead to afterwards hydrogen 2 hours, then uses deionization
It obtains palladium colloidal sol water washing 3 times, is then transferred in beaker, the above-mentioned composite material carrier of 0.5g is added, is stirred at room temperature
12h is washed with deionized 3 times, 120 DEG C of dry 12h.Lead to hydrogen reducing in tube furnace, 30 DEG C/min rises to 500 DEG C, protects
3h is held, catalyst D is obtained.
Embodiment 5
The preparation of catalyst: being added 3.0g aminoglucose sulfate in 50mL flask, and 25mL water stirring and dissolving is added
3.0g ZnO, in oil bath pan 150 DEG C stir it is dry.It stirs after doing and is ground to powder, nitrogen calcining is led in tube furnace, 30 DEG C/min rises to
600 DEG C, then holding 3h is ground uniformly, obtained CN@ZnO complex carrier, kept dry, wherein N:C:ZnO=1:6:15
(mass ratio).
0.02g PVA dissolution, PVA and PdCl are added in 15ml water2Molar ratio be 5:1, be added dropwise in advance it is prepared
0.2%Na2PdCl4Solution and 0.02%Bi (NO3)3The molar ratio of solution, Pd and Bi are 20:1, are heated to 110 DEG C, keep 3h.
It is down to room temperature (20-25 DEG C) to lead to afterwards hydrogen 0.5 hour, is then washed with deionized 3 times and obtains palladium colloidal sol, then shifted
Into beaker, the above-mentioned composite material carrier of 0.5g is added, 12h is stirred at room temperature, is washed with deionized 3 times, 60 DEG C of dry 12h.
Lead to hydrogen reducing in tube furnace, 20 DEG C/min rises to 600 DEG C, keeps 3h, obtains catalyst E.
Specific surface area of catalyst is obtained in 30g/m2, catalyst particle size 200-250 mesh, Pd particle size is in 2-10nm.
Embodiment 6
The preparation of catalyst: being added 3.0g aminoglucose sulfate in 50mL flask, and 25ml water stirring and dissolving is added
1.5g ZnO, in oil bath pan 150 DEG C stir it is dry.It stirs after doing and is ground to powder, nitrogen calcining is led in tube furnace, 30 DEG C/min rises to
600 DEG C, then holding 3h is ground uniformly, obtained CN@ZnO complex carrier, kept dry, wherein N:C:ZnO=1:6:7
(mass ratio).
0.02g PVP dissolution, PVP and PdCl are added in 10ml water2Molar ratio be 10:1, be added dropwise in advance it is prepared
0.2%Na2PdCl4Solution is heated to 120 DEG C, keeps 3h.It is down to room temperature (20-25 DEG C) to lead to afterwards hydrogen 0.5 hour, then spend
It obtains palladium colloidal sol ion water washing 3 times, is then transferred in beaker, the above-mentioned composite material carrier of 0.5g is added, room temperature is stirred
12h is mixed, is washed with deionized 3 times, 120 DEG C of dry 12h.Leading to hydrogen reducing in tube furnace, 10 DEG C/min rises to 600 DEG C,
3h is kept, catalyst F is obtained.
Embodiment 7
The preparation of catalyst: being added 3.0g aminoglucose hydrochloride in 50mL flask, and 25mL water stirring and dissolving is added
2.0g ZnO, in oil bath pan 150 DEG C stir it is dry.It stirs after doing and is ground to powder, nitrogen calcining is led in tube furnace, 30 DEG C/min rises to
600 DEG C, then holding 3h is ground uniformly, obtained CN@ZnO complex carrier, kept dry, wherein N:C:ZnO=1:6:10
(mass ratio).
0.02g PVP dissolution, PVP and PdCl are added in 10mL water2Molar ratio be 5:1, be added dropwise in advance it is prepared
0.1%Na2PdCl4Solution and 0.01%Bi (NO3)3The molar ratio of solution, Pd and Bi are 20:1, are heated to 120 DEG C, keep 3h.
It is down to room temperature (20-25 DEG C) to lead to afterwards hydrogen 0.5 hour, is then washed with deionized 3 times and obtains palladium colloidal sol, then shifted
Into beaker, the above-mentioned composite material carrier of 0.5g is added, 12h is stirred at room temperature, is washed with deionized 3 times, 120 DEG C of dry 12h.
Lead to hydrogen reducing in tube furnace, 20 DEG C/min rises to 600 DEG C, keeps 3h, obtains catalyst G.Obtain specific surface area of catalyst
In 20g/m2, catalyst particle size 200-250 mesh, Pd particle size is in 10-15nm.
Embodiment 8
The preparation of catalyst: being added 3.0g aminoglucose hydrochloride in 50mL flask, and 25mL water stirring and dissolving is added
2.0g ZnO, in oil bath pan 180 DEG C stir it is dry.It stirs after doing and is ground to powder, nitrogen calcining is led in tube furnace, 30 DEG C/min rises to
600 DEG C, then holding 3h is ground uniformly, obtained CN@ZnO complex carrier, kept dry, wherein N:C:ZnO=1:6:10
(mass ratio).
0.06g PVP dissolution, PVP and PdCl are added in 25mL water2Molar ratio be 5:1, be added dropwise in advance it is prepared
0.3%PdCl2Solution and 0.01%MnCl2The molar ratio of solution, Pd and Mn are 15:1, are heated to 120 DEG C, keep 3h.It is down to room
Warm (20-25 DEG C) leads to hydrogen 0.5h afterwards, is then washed with deionized 3 times and obtains palladium colloidal sol, is then transferred in beaker,
The above-mentioned composite material carrier of 0.5g is added, 12h is stirred at room temperature, is washed with deionized 3 times, 120 DEG C of dry 12h.In tube furnace
In lead to hydrogen reducing, 20 DEG C/min rises to 600 DEG C, keeps 3h, obtains catalyst H.
Comparative catalyst
Embodiment 9 is by commercially available Lindlar catalyst catalyst I as a comparison.
Embodiment 10
3g aminoglucose hydrochloride is added in 50ml flask, 25mL water stirring and dissolving is stirred for 150 DEG C in oil bath pan
It is dry.It stirs after doing and is ground to powder.Lead to nitrogen calcining in tube furnace, 10 DEG C/min rises to 550 DEG C, then constant temperature 2h is ground
Uniformly, CN complex carrier, kept dry is made.PVP dissolution is added in 25ml water, prepared 0.5%PdCl in advance is added dropwise2
Solution, PVP and PdCl2Molar ratio be 10:1, be heated to 100 DEG C, keep 3h.Being down to room temperature (20-25 DEG C), logical hydrogen 2 is small afterwards
When, water washing 3 times after having restored is then transferred in beaker, and the above-mentioned carrier of 0.5g is added, 12h is stirred at room temperature, spend from
Sub- water washing 3 times, 60 DEG C of dry 12h.Lead to hydrogen reducing in tube furnace, 10 DEG C/min rises to 500 DEG C, keeps 3h, obtains pair
Than catalyst J.
Embodiment 11
PVP dissolution is added in 25ml water, prepared 0.5%PdCl in advance is added dropwise2Solution, PVP and PdCl2Mole
Than for 10:1, being heated to 100 DEG C, 3h is kept.It is down to room temperature (20-25 DEG C) to lead to afterwards hydrogen 2 hours, water washing 3 times after having restored,
It is then transferred in beaker, 0.5g ZnO carrier is added, 12h is stirred at room temperature, is washed with deionized 3 times, 60 DEG C of dryings
12h.Lead to hydrogen reducing in tube furnace, 10 DEG C/min rises to 500 DEG C, keeps 3h, obtains comparative catalyst K.
Embodiment 12
3g aminoglucose hydrochloride is added in 50ml flask, 25mL water stirring and dissolving is stirred for 150 DEG C in oil bath pan
It is dry.It stirs after doing and is ground to powder.Lead to nitrogen calcining in tube furnace, 10 DEG C/min rises to 550 DEG C, then constant temperature 2h is ground
Uniformly, CN carrier, kept dry is made.PVP dissolution is added in 25ml water, prepared 0.5%PdCl in advance is added dropwise2Solution
With 1% Zn (NO3)2, PVP and PdCl2Molar ratio be 10:1, be heated to 100 DEG C, keep 3h.It is down to room temperature (20-25 DEG C)
Lead to afterwards hydrogen 2 hours, water washing 3 times, is then transferred in beaker after having restored, and the above-mentioned CN carrier of 0.5g, room temperature is added
12h is stirred, is washed with deionized 3 times, 60 DEG C of dry 12h.Leading to hydrogen reducing in tube furnace, 10 DEG C/min rises to 500 DEG C,
3h is kept, comparative catalyst L is obtained.
Catalyst performance evaluation:
(1) 2- methyl -3- butyne-2-alcohol selective hydrogenation 2-M3BOL reacts
Catalyst 0.4g, 2- methyl -3- butyne-2-alcohol 150g and water 50g are added in 500ml autoclave.Autoclave is successive
It is replaced 3 times with nitrogen, hydrogen.It is continuously passed through hydrogen and keeps Hydrogen Vapor Pressure 1.0-2.0MPa, control reaction temperature in 60-80
℃.Sampling analysis product forms after reaching reaction end.Then cool down, filter to isolate catalyst, Fig. 2 gives catalyst A
Recycled situation in the reaction, wherein abscissa is to apply number, and ordinate is selectivity, is urged as can be seen from Figure 2
After 80 times are applied, selectivity nothing is substantially reduced agent.
(2) dehydrogenation linalool selective hydrogenation linalool (3,7- dimethyl -1,6- octadiene -3- alcohol) reacts
Catalyst 0.4g, dehydrogenation linalool 100g and ethyl alcohol 100g are added in 500ml autoclave.Autoclave successively uses nitrogen
Gas, hydrogen are replaced 3 times.It is continuously passed through hydrogen and keeps Hydrogen Vapor Pressure 1.0-2.0MPa, control reaction temperature at 30-50 DEG C.It reaches
Sampling analysis product forms after to reaction end.Then cool down, filter to isolate catalyst, catalyst is recyclable to be applied.
(3) dehydrogenation different vegetable alcohol selective hydrogenation different vegetable alcohol (3,7,11,15- tetramethyl-cetene -3- alcohol)
Reaction
Catalyst 0.4g, dehydrogenation different vegetable alcohol 100g and ethyl alcohol 100g are added in 500ml autoclave.Autoclave successively uses nitrogen
Gas, hydrogen are replaced 3 times.It is continuously passed through hydrogen and keeps Hydrogen Vapor Pressure 1.0-2.0MPa, control reaction temperature at 60-85 DEG C.It reaches
Sampling analysis product forms after to reaction end.Then cool down, filter to isolate catalyst, catalyst is recyclable to be applied.
Three of the above is reacted, when the content of reactant alkynol is down to 0.3% or less, stops reaction, sampling analysis.
Specific reaction result is shown in Table 1.
The reaction evaluating result of 1 catalyst of table
Table 1 the result shows that, it is similar or more that commercially available Lindlar catalyst can achieve using the catalyst of the application
Good activity and selectivity, but the application is not needed using Pb as composition is inhibited, to more environment-friendly.And individual CN
Complex carrier or ZnO carrier are all unable to reach satisfied activity and/or selectivity, even if being doped into Zn in active constituent.
Claims (11)
1. a kind of catalyst for alkynol selective hydrogenation, including carrier and active constituent, which is characterized in that the activity
Ingredient includes the alloy phase that Pd and Pd-Zn is formed, and the carrier is the ZnO of N doping Carbon Materials cladding；
The preparation method of the catalyst, comprising the following steps:
(1) aqueous solution in nitrogenous charcoal source and ZnO are sufficiently stirred at 150-200 DEG C, then moisture is evaporated, obtained mixing is solid
Body under nitrogen protection, is calcined under the conditions of 400-600 DEG C, obtains the ZnO carrier of N doping Carbon Materials cladding；
(2) palladium source and stabilizer are dissolved in the water, stir, is heated to 90-120 DEG C and constant temperature 1-3h, hydrogen is led to after cooling
0.5-1h is restored, palladium colloidal sol is obtained；
(3) by carrier impregnation that step (1) obtains in the palladium colloidal sol that step (2) obtains 2-24h, then done at 60-120 DEG C
It is dry, obtain catalyst crude product；
(4) the catalyst crude product that step (3) obtains is placed in furnace, is warming up to 300-600 DEG C per minute with 10-30 DEG C, then
1-3h is restored under hydrogen atmosphere, obtains the catalyst.
2. catalyst according to claim 1, which is characterized in that the catalyst has the following structure: PdX/CN@
ZnO；For X as ingredient is inhibited, the X is selected from one of Bi, Mn, Ag.
3. catalyst according to claim 2, which is characterized in that molar ratio Pd:X=10~30 of active constituent Pd and X:
0~1, and X be not 0, Pd and N doping Carbon Materials cladding ZnO carrier mass ratio be 0.1%-5%.
4. catalyst according to claim 1 or 2, which is characterized in that in the ZnO carrier of the N doping Carbon Materials cladding
The mass ratio of N:C:ZnO is 1~3:1~6:7~15.
5. catalyst according to claim 1 or 2, which is characterized in that the partial size of the carrier is 150-250 mesh, activity
The partial size of Pd is 2-20nm in ingredient, and the specific surface area of catalyst is 10-1000m2/g。
6. according to catalyst according to any one of claims 1 to 3, which is characterized in that the nitrogenous charcoal source is amino Portugal
One of grape sugar hydrochloride, aminoglucose sulfate, melamine, urea and bamboo.
7. according to catalyst according to any one of claims 1 to 3, which is characterized in that the palladium source is PdCl2、Pd
(NO3)2、Na2PdCl4、Pd(CH3COO)2One of.
8. according to catalyst according to any one of claims 1 to 3, which is characterized in that the stabilizer be PVP,
One of PVA, sodium citrate, ammonium molybdate.
9. according to catalyst according to any one of claims 1 to 3, which is characterized in that in step (2), palladium source is being added
While with stabilizer, it is additionally added inhibitor.
10. catalyst according to claim 9, which is characterized in that the inhibitor is Bi (NO3)3、MnCl2、AgNO3
One of.
11. a kind of catalyst as claimed in any one of claims 1 to 5 prepares answering in enol in highly selective hydrogenation of alkinols
With, which is characterized in that by alkynol, solvent shown in Formulas I and the catalyst investment reactor, carry out under an atmosphere of hydrogen
Selective hydrogenation, reaction are finished, and cool down simultaneously filtration catalytic agent, obtain enol shown in corresponding Formula II:
Wherein R indicates that carbon atom number is the alkyl of 1-16.
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| CN109289886B (en) * | 2018-08-31 | 2019-09-24 | 浙江新和成股份有限公司 | PdIn alloy catalyst and preparation method thereof, application |
| US10737250B2 (en) | 2018-08-31 | 2020-08-11 | Zhejiang Nhu Company Ltd. | PdIn alloy catalyst, method for manufacturing PdIn alloy catalyst and application thereof |
| CN109317175B (en) * | 2018-09-07 | 2020-04-10 | 浙江大学 | Selective hydrogenation catalyst for alkynol and preparation method and application thereof |
| CN109382100A (en) * | 2018-11-12 | 2019-02-26 | 大连理工大学 | A kind of selection plus hydrogen obtain compound catalyst and preparation method thereof between the zinc-containing metal of 1,4- butylene glycol |
| CN110743590B (en) * | 2019-10-21 | 2023-01-24 | 西安凯立新材料股份有限公司 | High-selectivity catalyst for synthesizing vitamin A intermediate and preparation method thereof |
| CN114249629B (en) * | 2021-12-24 | 2023-05-26 | 兰州大学 | Method for synthesizing enol by selective catalytic hydrogenation of alkynol |
| CN115212905B (en) * | 2022-06-29 | 2024-06-04 | 浙江新和成股份有限公司 | Alkynol selective hydrogenation catalyst and preparation method and application thereof |
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Effective date of registration: 20200102 Address after: 312500, No. 418, West Avenue, Qixing street, Xinchang County, Shaoxing, Zhejiang Co-patentee after: Zhejiang University Patentee after: Zhejiang Xinhecheng Co., Ltd. Co-patentee after: Shandong Xin He Cheng vitamin Co., Ltd. Address before: 312500, No. 418, West Avenue, Qixing street, Xinchang County, Shaoxing, Zhejiang Co-patentee before: Zhejiang University Patentee before: Zhejiang Xinhecheng Co., Ltd. |
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