CN105833864A - Supported spherical nano particle palladium catalyst and preparation method and application thereof - Google Patents
Supported spherical nano particle palladium catalyst and preparation method and application thereof Download PDFInfo
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- CN105833864A CN105833864A CN201610282146.9A CN201610282146A CN105833864A CN 105833864 A CN105833864 A CN 105833864A CN 201610282146 A CN201610282146 A CN 201610282146A CN 105833864 A CN105833864 A CN 105833864A
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- -1 nitro aromatic amine Chemical class 0.000 claims abstract description 21
- 239000012798 spherical particle Substances 0.000 claims abstract description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 6
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 4
- 244000060011 Cocos nucifera Species 0.000 claims description 4
- 239000010903 husk Substances 0.000 claims description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 2
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 2
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical compound [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000005984 hydrogenation reaction Methods 0.000 description 20
- 238000000034 method Methods 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000004531 microgranule Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 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 description 1
- FYFDQJRXFWGIBS-UHFFFAOYSA-N 1,4-dinitrobenzene Chemical class [O-][N+](=O)C1=CC=C([N+]([O-])=O)C=C1 FYFDQJRXFWGIBS-UHFFFAOYSA-N 0.000 description 1
- LXQOQPGNCGEELI-UHFFFAOYSA-N 2,4-dinitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O LXQOQPGNCGEELI-UHFFFAOYSA-N 0.000 description 1
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 description 1
- LWFUFLREGJMOIZ-UHFFFAOYSA-N 3,5-dinitrosalicylic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O LWFUFLREGJMOIZ-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910017398 Au—Ni Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910021650 platinized titanium dioxide Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B01J35/51—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
Abstract
The invention discloses a supported spherical nano particle palladium catalyst and a preparation method and application thereof .The catalyst is composed of a carrier and an active component supported by the carrier, wherein the carrier is active carbon, alumina, silicon dioxide or titanium dioxide, the active component is elemental palladium, the elemental palladium is a spherical particle in shape, and the particle size ranges from 5 nm to 50 nm .Based on the mass of the carrier, the capacity of the elemental palladium is 0.10-15.0wt% .The application of the catalyst in catalytic hydrogenation reaction of polynitroaromatics shown in formula (I) selectively synthesizing nitro aromatic amine shown in formula (II) is provided .In formula (I), at least two of R1, R2, R3, R4, R5 and R6 are nitryls, and the other groups are independent H, Cl, F, CH3, OH, CH2CH3, NH2, OCH3, OCH2CH3, C6H5, COOH or COOCH3; in formula (II), only one nitryl is reduced into amino, the other groups correspond to the groups in formula (i) in a one-to-one mode and do not change before and after reaction .Please see formula (I) and formula (II) in the description.
Description
(1) technical field
The present invention relates to a kind of support type nano spherical particle palladium catalyst and its preparation method and application, described catalyst can be applied
Catalytic hydrogenation reaction in Polynitroaramatics selectivity synthesis nitro aromatic amine.
(2) technical background
Nitro aromatic amine is the organic synthesis intermediate that a class is important, is widely used in pigment, dyestuff, medicine, pesticide and rubber and helps
The synthesis of the fine chemicals such as agent, resin, sensitive material.At present, nitro aromatic amine is mainly by corresponding many nitro aromatics and thing
Partial reduction is produced.More ripe technique is chemical reduction method.This method uses akali sulphide, iron powder etc. by nitre in acid medium
Base section reduction prepares nitro aromatic amine, and this technological operation is easy, but can produce a large amount of waste residue containing organic poison, the most disposable dirt
Dye is serious.Liquid phase catalytic hydrogenation reducing process because of its have that the three wastes are few, superior product quality and low power consumption and other advantages and receive much concern, be
Article one, eco-friendly friendly process.But, during Polynitroaramatics hydrogenating reduction, although multiple nitryl group leads to
Often having the feature gradually reduced, but the Nitro group reduction course of reaction energy barrier of diverse location difference is less, hydrogenation process is difficult to
Rest on the nitro aromatic amine stage.Therefore, selectivity of catalyst and stability are always Polynitroaramatics selective hydrogenation
React a key technology difficult problem urgently to be resolved hurrily.
In published document report, active constituent or the auxiliary agent with Polynitroaramatics selective hydrogenation performance are mainly
The metals such as Au, Ni, Pd, Pt, Ru, Ir and Se, it is common that be supported on aluminium oxide, silicon dioxide and activated carbon etc. and carry
Support type monometallic or bimetallic catalyst it is prepared as, such as Au/Al on body2O3、Au-Ni/Al2O3、Au/TiO2、Pt/SiO2、
Pt/TiO2、Pt/Al2O3, Pd/C and PVP-Ru/Al2O3Deng.These catalyst all show preferable many nitryl aromatics chemical combination
Thing conversion ratio or nitro aromatic amine selectivity, but be difficult to reach conversion ratio and selectivity is all 100%, i.e. nitro aromatic amine yield is low
In 100%.[Hou Jie, grinding of nitroaniline is prepared in ruthenium-based catalyst paradinitrobenzene compounds selective hydrogenation to open source literature
Study carefully, thesis for the doctorate, 2008.] report, use high-dispersion nano support type Ru/C catalyst prepared by surfactant Protection Code,
Under preferred reaction conditions, selective catalysis 2,4-DNP, 2,4-dinitroaniline and 3,5-dinitrosalicylic acid hydrogenation turns
Rate and nitro aromatic amine selectivity all can reach 100%.But, the nitro aromatic amine of generation is little to stable in reaction system
Stopping, it can quickly continue to be hydrogenated to arylamine, and inconspicuous being difficult to determines reaction end, is only capable of being controlled by theoretical hydrogen-consuming volume
Reaction process.This greatly improves the precision to hydrogenation reaction operational process of craft and the requirement of difficulty, hinder its industry metaplasia
The breakthrough of product technology.
(3) summary of the invention
It is an object of the invention to provide a kind of support type nano spherical particle palladium catalyst and its preparation method and application, described catalysis
Agent can be applicable to the catalytic hydrogenation reaction of Polynitroaramatics selectivity synthesis nitro aromatic amine.
For achieving the above object, the present invention adopts the following technical scheme that
The invention provides a kind of support type nano spherical particle palladium catalyst, described catalyst is by carrier and is supported on carrier
Active component forms, and described carrier is activated carbon, aluminium oxide, silicon dioxide or titanium dioxide, and described active component is simple substance palladium,
The pattern of described simple substance palladium is subsphaeroidal particle, and particle diameter is between 5～50nm；Based on carrier quality, bearing of simple substance palladium
Carrying capacity is 0.10～15.0wt%.
Further, in described catalyst, based on carrier quality, the load capacity of simple substance palladium is preferably 0.5～10.0wt%.
Further, in described catalyst, palladium particle diameter is preferably between 8～45nm.
Further, described carrier is activated carbon, and its ash is 0.01～5.0wt%, and specific surface area is 500～2000m2/ g, hole
Appearance is 0.4～1.5mL/g；The material of described activated carbon can be coconut husk or wooden.
Further, described carrier is aluminium oxide, silicon dioxide or titanium dioxide, and its specific surface area is 100～800m2/ g, hole
Appearance is 0.2～1.0mL/g.
Present invention also offers the preparation method of described support type nano spherical particle palladium catalyst, described preparation method is by following step
Suddenly carry out:
A () takes carrier and is dried dehydration；
B () palladium liquid is prepared；Palladous chloride. or Palladous nitrate. are dissolved in ammonia, are stirred at room temperature to being completely dissolved, obtain palladium liquid；
C () carrier through step (a) drying and dehydrating is immersed in the ethylene glycol of-10.0～0.0 DEG C or mass content is not less than
In the glycol water of 50%, stir to constant temperature, instill the palladium liquid that the step (b) of amount corresponding with load capacity obtains, with
And for palladium ion being reduced to the reducing agent of simple substance palladium, continue stirring to being thoroughly mixed and maintain the temperature at-10.0～0.0 DEG C；
Then this serosity is sealed up for safekeeping in closed pressure resistant container, and displaced air is filled with chemically inactive gas, first with 0.01～2.0 DEG C/h
Programming rate be warming up to 50～100 DEG C, then be warming up to 150～500 DEG C by 2.0～10 DEG C/h, constant temperature 1～10 at a temperature of final temperature
My god；Afterwards, opening closed pressure resistant container, filter serosity, filter cake is washed with deionized to without chloride ion or nitrate ion,
Seal up for safekeeping after vacuum drying, obtain support type nano spherical particle palladium catalyst.
Further, in preparation method step (a) of the present invention, it is recommended that described carrier carries out vacuum at 100～150 DEG C to be done
Dry dehydration 1～10h.
Further, the ammonia concn described in step (b) is preferably 25～28wt%, and its consumption is theoretical for dissolving palladium metal
1.0～5.0 times of consumption.
Further, the volumetric usage of ethylene glycol described in step (c) or glycol water is with the quality of carrier after drying and dehydrating
It is calculated as 2～10mL/g；
Further, in step (c), the inventory of described palladium liquid is calculated as drying and dehydrating rear bearing with the quality of wherein palladium metal element
The 0.10%～15.0% of weight, preferably 0.5%～10.0%.
Further, reducing agent described in step (c) is preferably ascorbic acid, ethylene glycol, ethanol or glucose；Described reduction
The amount of the material of agent is 1.0～100 times of the amount of the theoretical material of palladium metal element in palladium liquid, preferably 1.5～80 times.
Further, chemically inactive gas described in step (c) be not with the gas of reaction system generation chemical reaction, be preferably
Nitrogen, argon, helium, carbon dioxide or the mixed gas of their arbitrary proportions, pressure is 0.1～3.0MPa.
Further, in step (c), it is recommended that vacuum drying temperature is 25～120 DEG C, the time is 2～5h.
Invention further provides described support type nano spherical particle palladium catalyst at the many nitro aromatics shown in formula (I)
Application in the catalytic hydrogenation reaction of the nitro aromatic amine shown in a compound selective synthesizing accepted way of doing sth (II)；
In formula (I), R1、R2、R3、R4、R5、R6In at least two be nitro, remaining group each stand alone as H,
Cl、F、CH3、OH、CH2CH3、NH2、OCH3、OCH2CH3、C6H5, COOH or COOCH3；Formula (II)
In, only a nitro is reduced to amino, and other groups keep constant before and after one_to_one corresponding in formula (I), and reaction.
Further, the compound shown in formula (I) is selected from one of following:
Concrete, described application is: by compound shown in formula (I), solvent and described support type nano spherical particle palladium chtalyst
Agent puts in high-pressure hydrogenation reactor, closed reactor, with opening stirring after hydrogen exchange air, temperature be 20～100 DEG C,
Hydrogen Vapor Pressure is to carry out catalytic hydrogenation reaction under conditions of 0.1～3.0MPa；When Hydrogen Vapor Pressure no longer declines in 5 minutes, stop
Stirring, hydrogenation liquid is post-treated obtains compound shown in product formula (II).
In described application process, it is recommended that compound shown in described formula (I) and described support type nano spherical particle palladium catalyst
The mass ratio that feeds intake is 100:0.1～4, preferably 100:0.2～2.0.
In described application process, preferable reaction temperature is 25～80 DEG C, and preferably Hydrogen Vapor Pressure is 0.2～2.5MPa.
Described application can also be carried out in fixed bed, method particularly includes: catalyst carrier is chosen for graininess, a size of reacts
Less than the 1/10 of pipe diameter.During reaction, use micro pump that compound shown in formula (I) and solvent are squeezed into vaporizer, use matter
Amount effusion meter controls hydrogen flowing quantity, is sufficiently mixed, subsequently into equipped with support type nano spherical particle palladium catalyst in mixing tube
Fixed bed reactors.Tail gas is cooled, gas-liquid separation, obtain compound shown in product i.e. formula (II) after Liquid liquid Separation.Instead
During should, chromatograph be used to be analyzed mutually Organic substance monitoring reaction process.
In described fixed bed reaction, hydrogen is 0.05～10*10 with the gas space velocity of Polynitroaramatics sum4h-1, hydrogen
Gas and Polynitroaramatics mol ratio are 30～100:1.
In described fixed bed reaction, temperature is 25～100 DEG C, and Hydrogen Vapor Pressure is 0.1～3.0MPa.
Shown in described formula (I), compound carries out hydrogenation reaction in a solvent, applicable solvent be methanol, ethanol, water, positive third
The mixed solvent of one or more arbitrary proportions in alcohol, isopropanol, n-butyl alcohol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol,
Recommend the volumetric usage of described solvent with the quality of compound shown in substrate formula (I) be calculated as 0.5～15mL/g, preferably 1～
10mL/g。
When carrying out hydrogenation reaction in a kettle., the method for described hydrogenation liquid post processing is: hydrogenation liquid filters to isolate catalyst,
Filtrate i.e. obtains product after vacuum distillation recovered solvent and dehydration；Further, in last handling process, the catalysis that hydrogenation liquid is filtrated to get
Agent filter cake may return to reactor to carry out catalyst and applies mechanically.When carrying out hydrogenation reaction in fixed bed, described hydrogenation liquid post processing
Method be: after and gas-liquid separation cooled through the tail gas of beds, obtain hydrogenation liquid similar in identical reaction kettle, after
Continuous processing method is carried out successively, obtains compound shown in product formula (II).
Compared with prior art, beneficial effects of the present invention is embodied in:
(1) the active component palladium particle almost spherical on support type nano spherical particle palladium catalyst surface of the present invention, size,
Regular appearance is homogeneous, and size concentrates on 8～45nm, is particularly well-suited to Polynitroaramatics selective catalytic hydrogenation；
(2) support type nano spherical particle palladium catalyst of the present invention, not only hydrogenation conversion and nitro aromatic amine selectivity all up to
To 100%.And, reaction end is prone to judge, can rest on the nitro aromatic amine stage of generation, can be satisfied with industry completely
Change production requirement；
(3) catalyst of the present invention recycles process condition gentleness, good stability, applies mechanically often；
(4) method for preparing catalyst of the present invention is simple, easy and simple to handle.
In sum, particle almost spherical during catalyst of the present invention application, size, regular appearance are homogeneous, and size is the suitableeest
Close the selective hydrogenation of Polynitroaramatics, higher reaction rate can be kept, can reach again hydrogenation reaction conversion ratio
100%, nitro aromatic amine selectivity 100%, and reaction end be prone to judge, possess the technical conditions of industrialized production, have
The most progressive.
(4) accompanying drawing explanation
Fig. 1 is the TEM figure of the catalyst that the embodiment of the present invention 1 prepares.
Fig. 2 is the TEM figure of the catalyst that the embodiment of the present invention 8 prepares.
Fig. 3 is the TEM figure of the catalyst that comparative example 1 of the present invention prepares.
Fig. 4 is the TEM figure of the catalyst that comparative example 2 of the present invention prepares.
Fig. 5 is the reaction mechanism mechanism of reaction figure of the embodiment of the present invention 16.
(5) detailed description of the invention
Further illustrate technical scheme with specific embodiment below, but protection scope of the present invention is not limited to this.
Embodiment 1～embodiment 15
Provide catalyst activity constituent content, proportioning and preparation condition (as shown in table 1) thereof.
The concrete preparation process of catalyst is following (as a example by embodiment 1):
1) by coconut husk preparing active carbon in 120 DEG C of vacuum dehydration 3h；
2) being dissolved in by Palladous chloride. in strong aqua ammonia (25～28wt%), consumption is just to dissolve to get final product (the 1.0 of theoretical amount
Times), it is stirred at room temperature to being completely dissolved, then dilute is configured to the palladium liquid that concentration is 0.05g/ml.
3) take ethylene glycol solution that 25ml mass content is 80% in 100ml Hydrothermal Synthesis still, control temperature and be-8.0 DEG C.
After the 10g activated carbon through vacuum dehydration is poured in synthesis reactor, stir to slurry temperature arrive-8.0 DEG C；Instill 10ml
Above-mentioned prepared palladium liquid and 1.0ml ethylene glycol, stir and arrive-8.0 DEG C to slurry temperature, close still, pour nitrogen after displaced air
To 0.5MPa；Heating schedule is set:Open synthesis reactor, filter
Serosity, filter cake is washed with deionized to without chloride ion, seals up for safekeeping after 80 DEG C of vacuum drying 3h, obtains that described support type is spherical to be received
Rice corpuscles palladium catalyst.Load capacity is 5%, Pd nano particle 10～35nm.
Comparative example 1
Conventional carbon-carried palladium catalyst preparation method: be 1350m by specific surface area2/ g, pore volume are 0.65mL/g, ash is 3.5%
Coconut husk preparing active carbon is in 120 DEG C of vacuum dehydration 3h；Pipette chlorine palladium acid solution (the wherein hydrochloric acid that 10mL concentration is 0.05g/mL
Concentration 0.1mol/L) in 50mL deionized water, making its pH value with hydrochloric acid regulation is 0.8；Then will be through vacuum dehydration
10g activated carbon be dipped in palladium liquid, 80 DEG C be sufficiently stirred for impregnate 5h, with sodium hydroxide regulation pH value to 8～10；After half an hour,
Dropping 2.5mL hydrazine hydrate, 35 DEG C of reductase 12 h.Being down to room temperature afterwards, reaction system filters, filter cake be washed with deionized in
Property, 105 DEG C of drying and dehydrating 3h, obtain simple substance supported palladium catalyst.Mean size through high power transmissioning electric mirror determining palladium microgranule
For 6nm, pattern is irregular.
Comparative example 2
Prepared by catalyst preparation process method as disclosed in Chinese patent [CN1817455A], palladium load capacity is 2.0%.
Concrete preparation method is:
Weighing 10g activated carbon, the specific surface area of activated carbon is 1200m2/ g, it is 2.5mol/L that activated carbon is immersed in 120 milliliters of concentration
KI solution in 6 hours, filter, be washed with deionized to without iodide ion detection.Then the activated carbon of process is configured to temperature
Spend the 100mL serosity of 80 DEG C, be slowly added dropwise the H of 4 milliliters2PdCl4Solution (Pd content is 0.05g/mL), stirs 6h, then uses
The NaOH solution regulation solution ph of 10% is to alkalescence (pH=8), and cools the temperature to room temperature, filters, and deionization is washed
Wash to neutrality.Unreduced catalyst is configured at 30 DEG C the serosity of 150mL, is then slowly added dropwise 85% water of 2 milliliters
Close hydrazine solution, continue stirring 2 hours.Catalyst after reduction is through filtering, and deionized water wash, to neutral, finally exists in room temperature
Through preliminarily dried in air, seal and preserve.Being 25nm through the mean size of high power transmissioning electric mirror determining palladium microgranule, pattern is not advised
Then.
Embodiment 16～32 is that the catalyst that above-described embodiment 1～15, comparative example 1～2 preparation method prepare is applied to many nitros virtue
The example of aroma compounds selectivity synthesis nitro aromatic amine catalytic hydrogenation reaction.Its catalytic performance result is as shown in table 2.
Embodiment 16～32
By 50g meta-dinitro-benzent, 100ml methanol and 0.5g embodiment 1～15 or the loaded catalyst of comparative example 1～2 preparation add
In 500mL autoclave, close reactor, displace air in reactor with nitrogen, then use hydrogen exchange nitrogen, open
Opening stirring, agitation revolution 1000r/min, maintenance reaction temperature 25～70 DEG C, Hydrogen Vapor Pressure 1.0～1.5MPa reacts.Work as hydrogen
Gas no longer declined in 5 minutes, was considered as reaction terminating, stopped reaction, filtering catalyst.Filtrate is through point water and the decompression steaming of being separated
It is product, through chromatographic quantitative analysis (molar percentage) after evaporating dehydration.
Embodiment 33
Choosing the catalyst of embodiment 10 preparation, carrier granular is chosen for 0.5-1.0mm, 8cm in fixed bed.Hydrogen and
The gas space velocity of dinitro benzene sum is 2.0*104h-1, hydrogen and meta-dinitro-benzent mol ratio are 40:1；Temperature is 70 DEG C, hydrogen
Atmospheric pressure is 2.0MPa.Product is all 100% through chromatography, conversion ratio and selectivity.
Embodiment 34
Choosing the catalyst of embodiment 15 preparation, carrier granular is chosen for 0.5-1.0mm, 8cm in fixed bed.Hydrogen and
The gas space velocity of dinitro benzene sum is 0.5*104h-1, hydrogen and meta-dinitro-benzent mol ratio are 40:1；Temperature is 60 DEG C, hydrogen
Atmospheric pressure is 2.0MPa.Product is all 100% through chromatography, conversion ratio and selectivity.
Table 2 embodiment 1～15 and the catalytic performance result of comparative example 1～2 prepared catalyst
The embodiment 35～44 hydrogenation catalyst prepared by embodiment 1 synthesizes corresponding nitre at Polynitroaramatics catalytic hydrogenation
Catalytic performance in base arylamine reaction, its result is as shown in table 3.
The catalyst prepared by table 3 embodiment 1 catalytic performance in Polynitroaramatics catalytic hydrogenation synthesizes the reaction of corresponding nitro aromatic amine
Embodiment 45
Embodiment 45 is under the operating condition of embodiment 16, and the catalyst prepared by embodiment 1 is at meta-dinitro-benzent catalytic hydrogenation
Applying mechanically experimental conditions in reaction, its result is as shown in table 4.
Table 4 embodiment 1 prepared catalyst synthesizing nitryl aniline reaction apply mechanically experimental result
Claims (10)
1. a support type nano spherical particle palladium catalyst, it is characterised in that: described catalyst is by carrier and the active component being supported on carrier
Composition, described carrier is activated carbon, aluminium oxide, silicon dioxide or titanium dioxide, and described active component is simple substance palladium, and the pattern of described simple substance palladium is
Spheroidal particle, particle diameter is between 5-50nm；Based on carrier quality, the load capacity of simple substance palladium is 0.10wt%～15.0wt%.
2. support type nano spherical particle palladium catalyst as claimed in claim 1, it is characterised in that: described carrier is activated carbon, and its ash is
0.01wt%～5.0wt%, specific surface area is 500～2000m2/ g, pore volume is 0.4～1.5mL/g；The material of described activated carbon can be coconut husk or wooden.
3. support type nano spherical particle palladium catalyst as claimed in claim 1, it is characterised in that: described carrier is aluminium oxide, silicon dioxide
Or titanium dioxide, its specific surface area is 100～800m2/ g, pore volume is 0.2～1.0mL/g.
4. the support type nano spherical particle palladium catalyst as described in one of claims 1 to 3, it is characterised in that: in described catalyst, based on load
Weight, the load capacity of simple substance palladium is 0.5wt%～10.0wt%.
5. the support type nano spherical particle palladium catalyst as described in one of claims 1 to 3, it is characterised in that: in described catalyst, palladium particle
Particle diameter is between 8-45nm.
6. a preparation method for support type nano spherical particle palladium catalyst as claimed in claim 1, described preparation method is entered as follows
OK:
A () takes carrier and is dried dehydration；
B () palladium liquid is prepared；Palladous chloride. or Palladous nitrate. are dissolved in ammonia, are stirred at room temperature to being completely dissolved, obtain palladium liquid；
(c) carrier through step (a) drying and dehydrating is immersed in the ethylene glycol of-10.0～0.0 DEG C or mass content be not less than 50% ethylene glycol water
In solution, stir the palladium liquid obtained to the step (b) instilling amount corresponding with load capacity after constant temperature and for palladium ion being reduced to simple substance palladium
Reducing agent, continues stirring to being thoroughly mixed and maintain the temperature at-10.0～0.0 DEG C DEG C；Then this serosity is sealed up for safekeeping in closed pressure resistant container, and replace
Air is filled with chemically inactive gas, is first warming up to 50-100 DEG C with the programming rate of 0.01～2.0 DEG C/h, then is warming up to 150-500 DEG C by 2.0-10 DEG C/h,
Constant temperature 1-10 days at a temperature of final temperature；Afterwards, opening closed pressure resistant container, filter serosity, filter cake is washed with deionized to without chloride ion or nitrate anion
Ion, seals up for safekeeping after vacuum drying, obtains spherical Pd nano particle loaded catalyst.
7. preparation method as claimed in claim 6, it is characterised in that: reducing agent described in step (c) is ascorbic acid, ethylene glycol, ethanol
Or glucose, the amount of the material of described reducing agent is 1.0～100 times of the amount of the theoretical material of palladium metal element in palladium liquid.
8. preparation method as claimed in claim 6, it is characterised in that: described chemically inactive gas is nitrogen, argon, helium, carbon dioxide
Or the mixed gas of they arbitrary proportions, pressure is 0.1～3.0MPa.
9. support type nano spherical particle palladium catalyst as claimed in claim 1 is at the Polynitroaramatics selectivity synthesis shown in formula (I)
Application in the catalytic hydrogenation reaction of the nitro aromatic amine shown in formula (II)；
In formula (I), R1、R2、R3、R4、R5、R6In at least two be nitro, remaining group each stands alone as H, Cl, F, CH3、
OH、CH2CH3、NH2、OCH3、OCH2CH3、C6H5, COOH or COOCH3；In formula (II), only a nitro is reduced to
Amino, other groups keep constant before and after one_to_one corresponding in formula (I), and reaction.
Apply the most as claimed in claim 9, it is characterised in that: the compound shown in formula (I) is selected from one of following:
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| CN106311182A (en) * | 2016-10-18 | 2017-01-11 | 江苏理工学院 | Preparation method and application of ultrafine chelated fibers |
| EP3207991A1 (en) * | 2016-02-17 | 2017-08-23 | Korea Institute of Energy Research | Direct synthesis method of nanostructured catalyst particles on various supports and catalyst structure produced by the same |
| CN109395721A (en) * | 2017-08-16 | 2019-03-01 | 王学彬 | Load type palladium catalyst and preparation method thereof |
| US10384201B2 (en) | 2016-02-17 | 2019-08-20 | Korea Institute Of Energy Research | Direct synthesis method of nanostructured catalyst particles on various supports and catalyst structure produced by the same |
| CN110743590A (en) * | 2019-10-21 | 2020-02-04 | 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 |
| CN111995503A (en) * | 2019-05-27 | 2020-11-27 | 华东师范大学 | Ethylene glycol monobutyl ether synthesis method, supported palladium catalyst and application thereof |
| CN115504892A (en) * | 2022-11-09 | 2022-12-23 | 浙江工业大学 | Method for synthesizing procaine by continuous catalytic hydrogenation |
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| EP3207991A1 (en) * | 2016-02-17 | 2017-08-23 | Korea Institute of Energy Research | Direct synthesis method of nanostructured catalyst particles on various supports and catalyst structure produced by the same |
| US10384201B2 (en) | 2016-02-17 | 2019-08-20 | Korea Institute Of Energy Research | Direct synthesis method of nanostructured catalyst particles on various supports and catalyst structure produced by the same |
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| CN109395721A (en) * | 2017-08-16 | 2019-03-01 | 王学彬 | Load type palladium catalyst and preparation method thereof |
| CN111995503A (en) * | 2019-05-27 | 2020-11-27 | 华东师范大学 | Ethylene glycol monobutyl ether synthesis method, supported palladium catalyst and application thereof |
| CN111995503B (en) * | 2019-05-27 | 2022-10-25 | 华东师范大学 | Ethylene glycol monobutyl ether synthesis method, supported palladium catalyst and application thereof |
| CN110743590A (en) * | 2019-10-21 | 2020-02-04 | 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 |
| 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 |
| CN115504892A (en) * | 2022-11-09 | 2022-12-23 | 浙江工业大学 | Method for synthesizing procaine by continuous catalytic hydrogenation |
| CN115504892B (en) * | 2022-11-09 | 2023-04-07 | 浙江工业大学 | Method for synthesizing procaine by continuous catalytic hydrogenation |
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