CN109092326A - 一种核壳状钨酸镍微球负载钯催化剂及其制备方法和应用 - Google Patents
一种核壳状钨酸镍微球负载钯催化剂及其制备方法和应用 Download PDFInfo
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- CN109092326A CN109092326A CN201810709348.6A CN201810709348A CN109092326A CN 109092326 A CN109092326 A CN 109092326A CN 201810709348 A CN201810709348 A CN 201810709348A CN 109092326 A CN109092326 A CN 109092326A
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- nickel
- palladium catalyst
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- tungstate
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 108
- QLTKZXWDJGMCAR-UHFFFAOYSA-N dioxido(dioxo)tungsten;nickel(2+) Chemical compound [Ni+2].[O-][W]([O-])(=O)=O QLTKZXWDJGMCAR-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 53
- 239000011806 microball Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- 239000004005 microsphere Substances 0.000 claims abstract description 16
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004202 carbamide Substances 0.000 claims abstract description 13
- 229960001484 edetic acid Drugs 0.000 claims abstract description 13
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000002815 nickel Chemical class 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 239000010937 tungsten Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 42
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- 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 14
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 9
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 8
- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910001453 nickel ion Inorganic materials 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- -1 tungsten ion Chemical class 0.000 claims description 2
- 239000002211 L-ascorbic acid Substances 0.000 claims 1
- 235000000069 L-ascorbic acid Nutrition 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 238000006555 catalytic reaction Methods 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 4
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000011258 core-shell material Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 3
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 10
- 229910000510 noble metal Inorganic materials 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- 239000010970 precious metal Substances 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 2
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- OSCBARYHPZZEIS-UHFFFAOYSA-N phenoxyboronic acid Chemical class OB(O)OC1=CC=CC=C1 OSCBARYHPZZEIS-UHFFFAOYSA-N 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
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- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明涉及一种核壳状钨酸镍微球负载钯催化剂及其制备方法和应用,主要以钨酸钠与可溶性镍盐为原料,并添加乙二胺四乙酸和尿素为合成助剂,通过水热方法制备钨酸镍,对镍钨比、助剂加入量、水热温度、水热时间及后续的焙烧过程进行控制,得到核壳结构的钨酸镍微球,呈现多级孔结构,主要含有10nm以下的介孔和50nm左右的大孔,其介孔孔径在2‑10nm范围内可调。催化剂的活性组分钯能在微球载体表面高度分散,而且可以控制钯主要分布在微球载体的外壳层,钯用量小,催化活性高;镍和钨在催化反应中发生一定程度的价态变化,参与氧化还原过程,促进了催化活性提高;钯负载牢固,不易流失,催化剂具有良好的循环使用性能。
Description
技术领域
本发明属于催化材料技术领域,具体涉及一种核壳状钨酸镍微球负载钯催化剂及其制备方法和应用。
背景技术
贵金属催化剂是工业催化领域里一类重要的催化剂,在加氢、脱氢、氧化等反应体系中有着广泛应用。由于贵金属催化剂成本较高,一般需将其负载以减少其用量,降低成本。同时,高分散的负载能够暴露贵金属某些特定的晶面,从而有效地提高催化剂的活性和选择性。为了得到高性能的贵金属催化剂,其载体的选择尤为重要。负载贵金属催化剂的常规载体包括氧化硅、氧化铝、分子筛、碳材料等,除此之外,一些复合氧化物及具有特殊孔结构的新型多孔材料负载贵金属催化剂后,也对某些反应表现出良好的活性。如专利CN105618033A公开了一种介孔γ-Al2O3高分散负载钯催化剂的制备方法,将钯纳米粒子分散于γ-Al2O3的蠕虫状孔道结构中,据称所得催化剂具有高分散性、高比表面积以及高稳定性的优点。专利CN1446635A报道了一种基于纳米碳纤维为载体的负载钯催化剂,能有效地催化一氧化碳与亚硝酸甲酯反应生成草酸二甲酯。专利CN107029799A公开了一种包覆型磁性纳米Fe3O4负载钯催化剂的制备方法,该催化剂在甘油制备乳酸的反应中表现出高活性。金属有机框架材料也被用来负载贵金属催化剂,如Yufen Yang等(ACSAppl.Mater.Interfaces,2014,6:18163-18171)及Feilong Li等(CrystEngComm,2016,18:1760-1767)所报道,这类载体的特殊孔道结构能够对某些反应表现出分子选择性催化效果。有些载体由于自身的氧化还原性,能够影响贵金属表面的电子转移,起到助催化的作用。一些研究表明,稀土氧化物作为贵金属载体,针对一些氧化反应能够促进催化剂活性的提高,如氧化铈因其具有强的氧化还原性,高的储放氧能力和氧移动性而被较多的研究,Zong hu等(ACS Catalysis,2016,6:2265-2279)的研究表明将Pd/CeO2催化剂用于CO氧化反应中,氧化铈特定晶面的暴露对氧空位形成及表面氧的移动产生影响,从而提高了催化性能。
总的来看,负载贵金属催化剂需要满足如下一些要求:首先载体要对贵金属活性组分起到良好的支撑和分散的作用,小粒径的金属活性组分具有的表面效应和小尺寸效应能使其表现出独特的催化性能;其次,负载的贵金属活性组分要有足够的结构稳定性,应避免在反应过程中的流失、团聚等,保持良好的耐受性;针对具体反应类型,有时还需要载体与活性组分之间存在适宜的相互作用从而有利于促进反应的进行;另外,贵金属活性组分的用量、载体的制备成本以及负载过程的难易程度也是需要考虑的问题。因此,开发更加实用的高活性、高稳定性的新型负载贵金属催化剂仍是催化剂制备领域的一个研究热点。
发明内容
为了解决现有技术缺点和不足,本发明的目的是提供一种新型的负载贵金属催化剂及其制备方法和应用,具体的是一种以核壳状钨酸镍微球为载体负载钯催化剂及其制备方法,本发明的另一目的在于提供上述核壳状钨酸镍微球负载钯催化剂在催化烯烃加氢、醛加氢及suzuki偶联反应中的应用。
本发明目的通过以下技术方案实现:
一种核壳状钨酸镍微球负载钯催化剂的制备方法,包括如下制备步骤:
(1)配制体积分数为30%-85%的乙二醇水溶液;
(2)将一定量可溶性镍盐加至一定量乙二醇水溶液中至完全溶解,然后加入一定量乙二胺四乙酸,在30-90℃下恒温搅拌0.5-3小时,得到溶液A;
(3)将一定量钨酸钠加至一定量乙二醇水溶液中,搅拌至完全溶解,得到溶液B;
(4)在保持搅拌情况下,将溶液B逐滴加至溶液A中,然后加入一定量尿素,并继续搅拌0.1-3小时;
(5)将溶液A和溶液B的混合溶液转入水热反应釜中,在120-210℃下水热反应0.5-36小时;水热反应结束后,将所得产物过滤,滤饼经去离子水洗涤并干燥后,在空气气氛中焙烧1-6小时,得到核壳状钨酸镍微球载体;
(6)将一定量钨酸镍微球载体加入体积分数为40%的乙醇水溶液中,加热回流2小时,然后冷却至室温,向其加入一定量0.01-0.05mol/L的氯化钯溶液搅拌1-6小时,再加入一定量0.1mol/L的抗坏血酸溶液,搅拌1小时后,经离心、干燥后得到钨酸镍微球负载钯催化剂。
优选地,步骤(2)中,所述可溶性镍盐包括硝酸镍、氯化镍、醋酸镍、硫酸镍中的一种。
优选地,步骤(2)中,乙二胺四乙酸的摩尔数为镍离子摩尔数的0.2-1倍。
优选地,步骤(3)中,按照钨离子与镍离子摩尔比为0.5-1,加入钨酸钠。
优选地,步骤(4)中,加入尿素的摩尔数为镍离子摩尔数的0.5-3倍。
优选地,步骤(5)中,水热产物的焙烧温度为150-550℃。
优选地,步骤(6)中,加入氯化钯溶液与40%乙醇水溶液体积比为1:40-1:70,,加入的抗坏血酸的摩尔数为氯化钯摩尔数的2-10倍。
优选地,步骤(2)、(3)、(6)中,所述乙醇水溶液的用量并没有特别的限定,只要其能够使得反应顺利进行即可。
一种核壳状钨酸镍微球负载钯催化剂,由以上步骤所述方法制备得到。
所述的核壳状钨酸镍微球负载钯催化剂可用于催化烯烃加氢、醛加氢及suzuki偶联反应。
本发明的制备方法及所得到的产物具有如下优点及有益效果:
(1)本发明以钨酸钠与可溶性镍盐为原料,并添加乙二胺四乙酸和尿素为合成助剂,通过水热方法制备钨酸镍,对镍钨比、助剂加入量、水热温度、水热时间及后续的焙烧过程进行控制,得到核壳结构的钨酸镍微球,呈现多级孔结构,主要含有10nm以下的介孔和50nm左右的大孔,其介孔孔径在2-10nm范围内可调。
(2)本发明提出的以核壳状钨酸镍微球为载体负载钯催化剂的活性组分钯能在微球载体表面高度分散,而且可以控制钯主要分布在微球载体的外壳层,钯用量小,催化活性高;镍和钨在催化反应中发生一定程度的价态变化,参与氧化还原过程,促进了催化活性提高;钯负载牢固,不易流失,催化剂具有良好的循环使用性能。
(3)本发明提出的核壳状钨酸镍微球负载钯催化剂能高效催化烯烃加氢、醛加氢等反应,对其它加氢反应及suzuki偶联反应等也有良好的催化活性。
(4)本发明的制备方法简单,制备成本低廉,具有良好的实际应用价值。
附图说明
图1为实施例1中钨酸镍微球载体的X射线衍射图。
图2为实施例1中钨酸镍微球载体的扫描电镜照片。
图3为实施例1中钨酸镍微球载体的孔径分布图。
图4为实施例1中钨酸镍微球负载钯催化剂的透射电镜照片。
图5为对比例1中钨酸镍载体的X射线衍射图。
图6为对比例1中钨酸镍载体的扫描电镜照片。
图7为对比例2中钨酸镍载体的X射线衍射图。
图8为对比例2中钨酸镍载体的扫描电镜照片。
图9为对比例3中钨酸镍载体的X射线衍射图。
图10为对比例3中钨酸镍载体的扫描电镜照片。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述,但本发明的实施方式不限于此。
实施例1
(1)配制乙二醇的体积分数为70%的乙二醇水溶液;
(2)称取0.015mol硝酸镍加至40mL乙二醇水溶液中,搅拌至完全溶解,再加入0.0075mol乙二胺四乙酸,在30℃下恒温搅拌0.5小时,得到溶液A;
(3)称取0.01mol钨酸钠加至20mL乙二醇水溶液中,搅拌至完全溶解,得到溶液B;
(4)在保持搅拌情况下,将溶液B逐滴加至溶液A中,然后加入0.015mol尿素,继续搅拌0.5小时;
(5)然后将上述A和B混合溶液转入水热反应釜中,在150℃下水热反应12小时。水热反应结束后,将所得产物过滤,滤饼经去离子水洗涤并干燥后,在空气气氛中450℃下焙烧3小时,得到钨酸镍微球,其X射线衍射图、扫描电镜照片及孔径分布图分别如附图1、附图2和附图3所示;
(6)取上述制备好的钨酸镍微球载体0.5g加入100mL乙醇体积分数为40%的乙醇水溶液中,加热回流2小时,然后冷却至室温,向其加入0.02mol/L的氯化钯溶液2.4mL,搅拌1小时,再加入0.1mol/L的抗坏血酸溶液1.9mL,搅拌1小时后,经离心、干燥后,得到钯负载量约为1%的钨酸镍微球负载钯催化剂,其透射电镜照片如附图4所示,钨酸镍微球载体负载钯后,其核壳状结构得到良好的保持。
(7)取0.1克钨酸镍微球负载钯催化剂,将其加到100毫升乙醇中,充分分散以后,再加入10毫摩尔苯乙烯,通入氢气,保持搅拌在室温下反应,反应时间1小时,苯乙烯转化率达到100%,乙苯的选择性为100%。
在本发明提出的核壳状钨酸镍微球的制备方法中,乙二胺四乙酸与尿素的联合作用对于其核壳状形貌以及多级孔结构的形成具有重要影响,继而对其负载钯后的催化效果产生影响。下面通过几个对比例予以说明。
对比例1
(1)称取0.01mol硝酸镍加至40mL水中,搅拌至完全溶解,得到溶液A;
(2)称取0.01mol钨酸钠加至20mL水中,搅拌至完全溶解,得到溶液B;
(3)在保持搅拌情况下,将溶液B逐滴加至溶液A中;
(4)然后将上述A和B混合溶液转入水热反应釜中,在150℃下水热反应12小时。水热反应结束后,将所得产物过滤,滤饼经去离子水洗涤并干燥后,在空气气氛中450℃下焙烧3小时,得到钨酸镍产品,其X射线衍射图、扫描电镜照片分别如附图5、附图6所示。
在不加乙二胺四乙酸和尿素、以水为溶剂的条件下,通过水热法制备的产品虽然在组成上为单一相的钨酸镍,但是其形貌为不规则块状,不存在大量的介孔结构,采用与实施例1相同的方法,将其用来负载钯,并进行苯乙烯加氢反应,反应进行1小时,苯乙烯的转化率仅为9.1%。
对比例2
除了在步骤(4)中不加尿素外,其它制备步骤与实施例1相同。所得钨酸镍产品,其X射线衍射图、扫描电镜照片分别如附图7、附图8所示。在不加尿素的情况下,产物除存在钨酸镍主物相外,有明显的杂相出现,从形貌上看虽有成球趋势,但大小不均一,且不存在核壳状结构。采用与实施例1相同的方法,将其用来负载钯,并进行苯乙烯加氢反应,反应进行1小时,苯乙烯的转化率为73.2%。
对比例3
除了在步骤(2)中不加乙二胺四乙酸外,其它制备步骤与实施例1相同。所得钨酸镍产品,其X射线衍射图、扫描电镜照片分别如附图9、附图10所示。在不加乙二胺四乙酸的情况下,所得产物在组成上为单一相的钨酸镍,呈现不规则颗粒形貌,无成球趋势。采用与实施例1相同的方法,将其用来负载钯,并进行苯乙烯加氢反应,反应进行1小时,苯乙烯的转化率为55.6%。
实施例2
(1)配制乙二醇的体积分数为30%的乙二醇水溶液;
(2)称取0.01mol硝酸镍加至40mL乙二醇水溶液中,搅拌至完全溶解,再加入0.01mol乙二胺四乙酸,在90℃下恒温搅拌1小时,得到溶液A;
(3)称取0.005mol钨酸钠加至20mL乙二醇水溶液中,搅拌至完全溶解,得到溶液B;
(4)在保持搅拌情况下,将溶液B逐滴加至溶液A中,然后加入0.005mol尿素,继续搅拌0.1小时;
(5)然后将上述A和B混合溶液转入水热反应釜中,在120℃下水热反应36小时。水热反应结束后,将所得产物过滤,滤饼经去离子水洗涤并干燥后,在空气气氛中550℃下焙烧1小时,得到钨酸镍微球载体,其形貌结构与实施例1所得钨酸镍微球相近;
(6)取上述制备好的钨酸镍微球载体0.5g加入50mL乙醇体积分数为40%的乙醇水溶液中,加热回流2小时,然后冷却至室温,向其加入0.02mol/L的氯化钯溶液1.2mL,搅拌2小时,再加入0.1mol/L的抗坏血酸溶液0.5mL,搅拌1小时后,经离心、干燥后,得到钯负载量约为0.5%的钨酸镍微球负载钯催化剂。
(7)取0.1克实施例1-3中的钨酸镍微球负载钯催化剂,将其加到100毫升乙醇中,充分分散以后,再加入10毫摩尔苯乙烯,通入氢气,保持搅拌在室温下反应,反应时间3小时,苯乙烯转化率达到100%,乙苯的选择性为100%。
实施例3
(1)配制乙二醇的体积分数为85%的乙二醇水溶液;
(2)称取0.025mol氯化镍加至40mL乙二醇水溶液中,搅拌至完全溶解,再加入0.005mol乙二胺四乙酸,在50℃下恒温搅拌3小时,得到溶液A;
(3)称取0.025mol钨酸钠加至20mL乙二醇水溶液中,搅拌至完全溶解,得到溶液B;
(4)在保持搅拌情况下,将溶液B逐滴加至溶液A中,然后加入0.015mol尿素,继续搅拌3小时;
(5)然后将上述A和B混合溶液转入水热反应釜中,在210℃下水热反应0.5小时。水热反应结束后,将所得产物过滤,滤饼经去离子水洗涤并干燥后,在空气气氛中150℃下焙烧6小时,得到钨酸镍微球载体,其形貌结构与实施例1所得钨酸镍微球相近。
(6)取上述制备好的钨酸镍微球载体0.5g加入200mL乙醇体积分数为40%的乙醇水溶液中,加热回流2小时,然后冷却至室温,向其加入0.02mol/L的氯化钯溶液3mL,搅拌2小时,再加入0.1mol/L的抗坏血酸溶液6mL,搅拌1小时后,经离心、干燥后,得到钯负载量约为1.25%的钨酸镍微球负载钯催化剂。
(7)取0.1克钨酸镍微球负载钯催化剂,将其加到50毫升乙醇中,充分分散以后,再加入5毫摩尔苯甲醛,通入氢气,保持搅拌在60℃下反应,反应时间3小时,苯甲醛转化率为91.6%,苯甲醇的选择性为99.0%。
实施例4
将实施例1使用后的催化剂通过离心回收,采用与实施例1相同的加氢反应条件,进行多次循环实验,结果如下表所示。经过六次循环实验后,苯乙烯的转化率仍保持在99%以上,乙苯的选择性为100%,体现出催化剂具有良好的循环使用性能。
实施例5
采用与实施例1中相同的催化剂,以碘苯和苯硼酸为原料进行Suzuki反应。将2毫摩尔碘苯、2.4毫摩尔苯硼酸、50毫克钨酸镍微球负载钯催化剂加至6毫升的50%(体积分数)乙醇水溶液中,再加入4毫摩尔碳酸钾,在75℃下搅拌反应3小时,联苯收率达到95.3%。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
1.一种核壳状钨酸镍微球负载钯催化剂的制备方法,其特征在于,包括如下步骤:
(1)配制体积分数为30%-85%的乙二醇水溶液;
(2)将一定量可溶性镍盐加至一定量乙二醇水溶液中至完全溶解,然后加入一定量乙二胺四乙酸,在30-90℃下恒温搅拌0.5-3小时,得到溶液A;
(3)将一定量钨酸钠加至一定量乙二醇水溶液中,搅拌至完全溶解,得到溶液B;
(4)在保持搅拌情况下,将溶液B逐滴加至溶液A中,然后加入一定量尿素,并继续搅拌0.1-3小时;
(5)将溶液A和溶液B的混合溶液转入水热反应釜中,在120-210℃下水热反应0.5-36小时;水热反应结束后,将所得产物过滤,滤饼经去离子水洗涤并干燥后,在空气气氛中焙烧1-6小时,得到核壳状钨酸镍微球载体;
(6)将一定量钨酸镍微球载体加入体积分数为40%的乙醇水溶液中,加热回流2小时,然后冷却至室温,向其加入一定量0.01-0.05mol/L的氯化钯溶液搅拌1-6小时,再加入一定量0.1mol/L的抗坏血酸溶液,搅拌1小时后,经离心、干燥后得到钨酸镍微球负载钯催化剂。
2.根据权利要求1所述的一种核壳状钨酸镍微球负载钯催化剂的制备方法,其特征在于:步骤(2)中,所述可溶性镍盐包括硝酸镍、氯化镍、醋酸镍、硫酸镍中的一种。
3.根据权利要求1所述的一种核壳状钨酸镍微球负载钯催化剂的制备方法,其特征在于:步骤(2)中,乙二胺四乙酸的摩尔数为镍离子摩尔数的0.2-1倍。
4.根据权利要求1所述的一种核壳状钨酸镍微球负载钯催化剂的制备方法,其特征在于:步骤(3)中,按照钨离子与镍离子摩尔比为0.5-1,加入钨酸钠。
5.根据权利要求1所述的一种核壳状钨酸镍微球负载钯催化剂的制备方法,其特征在于:步骤(4)中,加入尿素的摩尔数为镍离子摩尔数的0.5-3倍。
6.根据权利要求1所述的一种核壳状钨酸镍微球负载钯催化剂的制备方法,其特征在于:步骤(5)中,水热产物的焙烧温度为150℃-550℃。
7.根据权利要求1所述的一种核壳状钨酸镍微球负载钯催化剂的制备方法,其特征在于:步骤(6)中,加入氯化钯溶液与40%乙醇水溶液体积比为1:40-1:70,,加入的抗坏血酸的摩尔数为氯化钯摩尔数的2-10倍。
8.根据权利要求1所述的一种核壳状钨酸镍微球负载钯催化剂的制备方法,其特征在于:步骤(2)、(3)、(6)中,所述乙醇水溶液的用量并没有特别的限定,只要其能够使得反应顺利进行即可。
9.一种核壳状钨酸镍微球负载钯催化剂,其特征在于:所述核壳状钨酸镍微球负载钯催化剂通过权利要求1-7中任一项所述的核壳状钨酸镍微球负载钯催化剂的制备方法制备得到。
10.一种根据权利要求9所述核壳状钨酸镍微球负载钯催化剂的应用,其特征在于:所述的核壳状钨酸镍微球负载钯催化剂用于催化烯烃加氢、醛加氢及suzuki偶联反应。
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