CN107649148A - A kind of preparation method and application using multi-walled carbon nanotube as the carrier loaded auxiliary agent Pt Ni base catalyst being modified - Google Patents
A kind of preparation method and application using multi-walled carbon nanotube as the carrier loaded auxiliary agent Pt Ni base catalyst being modified Download PDFInfo
- Publication number
- CN107649148A CN107649148A CN201711018078.6A CN201711018078A CN107649148A CN 107649148 A CN107649148 A CN 107649148A CN 201711018078 A CN201711018078 A CN 201711018078A CN 107649148 A CN107649148 A CN 107649148A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carbon nanotube
- walled carbon
- nitrobenzene
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 239000002048 multi walled nanotube Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 title claims abstract description 12
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000007513 acids Chemical class 0.000 claims abstract description 3
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 229910002845 Pt–Ni Inorganic materials 0.000 claims description 13
- 239000000706 filtrate Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 238000002604 ultrasonography Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical class CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 9
- 238000006073 displacement reaction Methods 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000004587 chromatography analysis Methods 0.000 claims description 8
- 239000002608 ionic liquid Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- -1 N- butyl-pyridinium tetrafluoroborates Chemical class 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000006396 nitration reaction Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 238000011001 backwashing Methods 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 abstract description 50
- 238000000034 method Methods 0.000 abstract description 18
- 238000013019 agitation Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000005530 etching Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 239000003814 drug Substances 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 229960005489 paracetamol Drugs 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 2
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004176 ammonification Methods 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000988 sulfur dye Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- IMPPGHMHELILKG-UHFFFAOYSA-N 4-ethoxyaniline Chemical compound CCOC1=CC=C(N)C=C1 IMPPGHMHELILKG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 1
- CKRZKMFTZCFYGB-UHFFFAOYSA-N N-phenylhydroxylamine Chemical compound ONC1=CC=CC=C1 CKRZKMFTZCFYGB-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- 229910002846 Pt–Sn Inorganic materials 0.000 description 1
- 229930003451 Vitamin B1 Natural products 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000003444 anaesthetic effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000003907 antipyretic analgesic agent Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- FEJKLNWAOXSSNR-UHFFFAOYSA-N benorilate Chemical compound C1=CC(NC(=O)C)=CC=C1OC(=O)C1=CC=CC=C1OC(C)=O FEJKLNWAOXSSNR-UHFFFAOYSA-N 0.000 description 1
- 229960004277 benorilate Drugs 0.000 description 1
- RFXSFVVPCLGHAU-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1.OC1=CC=CC=C1 RFXSFVVPCLGHAU-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- KNHUKKLJHYUCFP-UHFFFAOYSA-N clofibrate Chemical compound CCOC(=O)C(C)(C)OC1=CC=C(Cl)C=C1 KNHUKKLJHYUCFP-UHFFFAOYSA-N 0.000 description 1
- 229960001214 clofibrate Drugs 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- KBOPZPXVLCULAV-UHFFFAOYSA-N mesalamine Chemical compound NC1=CC=C(O)C(C(O)=O)=C1 KBOPZPXVLCULAV-UHFFFAOYSA-N 0.000 description 1
- 229960004963 mesalazine Drugs 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- VCRYGHPVKURQMM-UHFFFAOYSA-N methane;platinum Chemical compound C.[Pt] VCRYGHPVKURQMM-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 125000005184 naphthylamino group Chemical class C1(=CC=CC2=CC=CC=C12)N* 0.000 description 1
- 229960003966 nicotinamide Drugs 0.000 description 1
- 235000005152 nicotinamide Nutrition 0.000 description 1
- 239000011570 nicotinamide Substances 0.000 description 1
- LQNUZADURLCDLV-IDEBNGHGSA-N nitrobenzene Chemical group [O-][N+](=O)[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 LQNUZADURLCDLV-IDEBNGHGSA-N 0.000 description 1
- MXFJRKYYYAKTIS-UHFFFAOYSA-N nitrobenzene;sulfuric acid Chemical compound OS(O)(=O)=O.[O-][N+](=O)C1=CC=CC=C1 MXFJRKYYYAKTIS-UHFFFAOYSA-N 0.000 description 1
- 230000009935 nitrosation Effects 0.000 description 1
- 238000007034 nitrosation reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- DURULFYMVIFBIR-UHFFFAOYSA-N practolol Chemical compound CC(C)NCC(O)COC1=CC=C(NC(C)=O)C=C1 DURULFYMVIFBIR-UHFFFAOYSA-N 0.000 description 1
- 229960001749 practolol Drugs 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229960003495 thiamine Drugs 0.000 description 1
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 235000010374 vitamin B1 Nutrition 0.000 description 1
- 239000011691 vitamin B1 Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/892—Nickel and noble metals
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The present invention discloses a kind of preparation method and application using multi-walled carbon nanotube as the carrier loaded auxiliary agent Pt Ni base catalyst being modified.The acid of the invention that first carried out with nitric-sulfuric acid to multi-walled carbon nanotube is modified, then using it as carrier, by multi-walled carbon nanotube, six water chloroplatinic acids and six water nickel nitrates 5 10:0.1‑0.5:5 10 mass ratio adds the precursor salt of platinum, nickel to it, adds deionized water, is dried after ultrasonic agitation, is then calcined and is reduced, and obtains final required catalyst Pt Ni/MWCNT.The catalyst cost of the present invention is low, economical and effective, universality be strong, environment-friendly, not etching apparatus and good cycle, greater activity and the selectivity of higher para-aminophenol can be had under relatively mild reaction conditions by being prepared applied to the step hydrogenation-rearrangement of nitrobenzene one when in the technique of para-aminophenol, improve working condition, production cost is reduced, improves product quality.
Description
Technical field
It is more particularly to a kind of to be modified by carrier loaded auxiliary agent Pt of multi-walled carbon nanotube the present invention relates to field of material preparation
Ni base catalyst preparation method and application.
Background technology
Para-aminophenol (hereinafter referred to as PAP) is today's society a kind of important industrial chemicals and organic intermediate, at present
It is widely used in medicine, dyestuff, rubber and photography industry etc..In China, PAP is mainly used in pharmaceuticals industry, among medicine
Body, PAP can be used for synthesis paracetamol (acamol), benoral, clofibrate, vitamin B1, practolol, complexing agent
The consumption of the medicines such as niacinamide, sal phenol, 6- oxyquinolines, wherein paracetamol is maximum.The 1970s scientific research personnel
It was found that the prosperity such as harmful components, American and Britain, day can be resolved into vivo by taking the antipyretic analgesic such as antifebrin and phenetidine medicine
Country forbids producing, therefore the demand of paracetamol greatly increases.It is mainly used in synthesizing sulfur dye, azo in dye industry
Dyestuff, acid dyes and fur dyes, synthesize as azo dyes and the intermediate 5-aminosalicylic acid of sulfur dye, in China
Proportion is few.It is mainly used in synthesizing p phenylenediamine type antioxidant 4020,4030 etc. in rubber industry, due to this kind of age resistor
It is less toxic, the efficient, product of low stain recognized in the world, so be considered as now most promising route, and
Naphthylamines class and thiazoles age resistor will gradually be substituted.PAP can be also used for photographic developer simultaneously can make wood stain again, also
It may be used as chemical reagent, anesthetic etc..Since at the beginning of 21 century, world's PAP yield is main with average annual 5% speed increase
It is the U.S., France, Japan and Germany to want producing country, wherein it is maximum with U.S.'s yield, and Asia is maximum with Japanese yield.And
A few years from now on countries in the world will be increased PAP consumption figure with annual 8-10% speed.
The production technology of para-aminophenol has following several at present：1st, p-nitrophenol reducing process, but the process recovery ratio
Low, environmental pollution is larger, and product purity cannot be guaranteed；2nd, para-nitrochloro-benzene in the basic conditions pressurized hydrolysis be acidified again for pair
Nitrophenol, it is similar with p-nitrophenol reducing process the shortcomings that the process route；3rd, using phenol as raw material, then by nitrosation
Either halogenation ammonification or coupling the methods of produce para-aminophenol, the process consumption of raw materials is big；4th, using p-phenylenediamine as
Raw material hydrolyzes to obtain para-aminophenol at a certain temperature, but the process byproducts hydroquinones needs to separate；5th, with to benzene
Diphenol is raw material, and aliphatic ether makees solvent, ammoniacal liquor ammonification is used under inert gas shielding, the method cost is higher, and technological requirement is tight
Lattice, post processing are complicated；6th, nitrobenzene method, this method in 20th century mid-term be just suggested, the process include hydrogenation of chloronitrobenzene generation
Then phenylhydroxylamine enters rearrangement and obtains para-aminophenol in acid condition, accessory substance is aniline, this method cost of material
It is low, environmental pollution is small, is easy to industrial production, be presently preferred technique.
Due to the plurality of advantages of the step hydrogenation synthesis para-aminophenol of nitrobenzene one, increasing people begin to focus on the work
Skill production method.Chinese patent CN1283612A discloses support type Pt/ gama-alumina-MEO catalyst, under the conditions of sulfuric acid
Nitrobenzene catalytic reaction is carried out, the load capacity of active component is 0.5-5%, although the selectivity of para-aminophenol can reach
70%, the reaction is carried out under sulfuric acid system, it is necessary to and, cause inconvenience to product separation, together in being carried out with alkaline matter
When can produce some waste water, environmental pollution is more serious, also has certain corrosiveness to catalyst, catalyst preparation is more
Complicated and dosage is larger, and product cost is higher, and metal oxidation waste content is big, is used for medicinal purpose it is difficult to work as.Chinese patent CN
103553943A is disclosed under the conditions of carbon dioxide and water system with Pt/C, Pt-Sn/Al2O3、Pd-CaCO3-PbO/PbAC2Deng
A series of catalyst, under hydrogen 0.3-5MPa pressure, carbon dioxide 0.5-10MPa pressure, at a temperature of 80-170 DEG C, during reaction
Between 0.5-12h, selectivity is in 5-70% or so, but the reaction hydrogen, pressure carbon dioxide are larger, and reaction temperature is high, reaction
Time is longer, requires very high to reaction unit, catalyst preparation is complicated and catalyst activity component content is higher, is urged using platinum charcoal
The duct of activated carbon is deep if agent, unfavorable to the desorption of product.United States Patent (USP) US 6028227 discloses to be handed over ion
Change resin and Pt-S/C while use, in 80 DEG C of reaction pressure 20-27atm, reaction temperature conditions after nitrobenzene is mixed with water
Lower carry out catalytic hydrogenation, but PAP yields are only 13.9%.(the Takayuki Komatsu, Tatsuo such as Takayuki
Hirose.Applied Catalysis A:General,2004,276:95-102) using Pt/ZSM-5 as double-function catalyzing
Agent, using catalyzed gas hydrogenation synthesis para-aminophenol, the environment of reaction is more strict, the conversion ratio 40.5% of nitrobenzene, choosing
Selecting property is 42%.
In summary, the yield of process above route nitrobenzene is not very high that some process route reaction conditions are more severe
Carve.Want the yield of raising para-aminophenol, mainly start with from the selectivity of the para-aminophenol of the conversion ratio of nitrobenzene, therefore grind
Studying carefully the step hydrogenation-rearrangement of suitable nitrobenzene one that a kind of cost is low, performance is good, recycling rate is high, to directly generate para-aminophenol anti-
The catalyst answered has critically important researching value and application prospect.
The content of the invention
The technical problems such as the not high, severe reaction conditions of yield of para-aminophenol for prior art, the present invention provide
A kind of preparation method and application using multi-walled carbon nanotube as the carrier loaded auxiliary agent Pt Ni base catalyst being modified.
The technical scheme is that：
A kind of Ni base catalyst being modified using multi-walled carbon nanotube as carrier loaded auxiliary agent Pt, is designated as Pt-Ni/MWCNT, its
Preparation method comprises the following steps：
(1) 1 is pressed:10-20g/ml solid-liquid mass volume ratio is that respective volume is added in MWCNT to multi-walled carbon nanotube
Nitric-sulfuric acid, at 80-120 DEG C, constant temperature return stirring 12-24 hours, the CNT deionized water after sour modification
Wash repeatedly untill filtrate is in neutrality；
(2) using step (1) resultant multi-wall CNT as carrier, by multi-walled carbon nanotube, six water chloroplatinic acids and six water nitre
Sour nickel 5-10:0.1-0.5:5-10 mass ratio adds platinum, the precursor salt of nickel, deionized water is added, then 20~40
0.5~3h is stirred by ultrasonic with Ultrasound Instrument under the conditions of DEG C, is transferred in round-bottomed flask, 8~12h is stirred under the conditions of 20~40 DEG C,
The stirring liquid is placed in air dry oven, 2~4h is first dried at 70~90 DEG C, 100~120 DEG C is then heated to and continues to do
Dry 5~10h, natural cooling are down to room temperature, are then ground to obtain black powder catalyst；
(3) black powder catalyst obtained by step (2) is first calcined 2~6h at 200~500 DEG C, then 200~
2~6h of hydrogen reducing under the conditions of 500 DEG C, you can obtain catalyst Pt-Ni/MWCNT.
Further, in step (1), nitric-sulfuric acid is by concentrated nitric acid and the concentrated sulfuric acid 3:1 volume ratio is prepared.
Further, in step (3), the atmosphere of roasting is ＞ 99% High Purity Nitrogen, and it is 30~100mL/ to be passed through flow
Min, it is optimal to keep one bubble each second, and using temperature programming, heating rate is 2~8 DEG C/min.
Further, in step (3), hydrogen is ＞ 99% High Purity Hydrogen, and it is 30~100mL/min to be passed through flow.
The catalyst that above-mentioned preparation method obtains is prepared in the step hydrogenation-rearrangement of nitrobenzene one in para-aminophenol reaction
Using comprising the following steps：
Pt-Ni/MWCNT catalyst is added in autoclave, adds the ionic liquid that mass fraction is 5~20%
The aqueous solution is solvent, then adds nitrobenzene and cetyl trimethylammonium bromide, the addition of catalyst is nitrobenzene quality
5~15%, the amount ratio of ionic liquid aqueous solution and nitrobenzene is 10-35mL：0.08~0.12g, is put into magneton, and sealing is high
Kettle is pressed, with air in nitrogen displacement kettle 2~5 times, 1~3h is then disperseed under ultrasound condition, kettle is evacuated to vacuum by vavuum pump, is risen
Temperature react 3~6 hours under stirring condition to pressurized with hydrogen after 80~120 DEG C, is passed through to 0.8~1.2MPa, terminates general after reaction
Reaction mixture filters, the content liquid-phase chromatographic analysis of each material in filtrate.
Further, described ionic liquid aqueous solution is 1- butyl -3- methylimidazole dihydric phosphates, N, N, N- front threes
One or both of base-N- sulphur butyls-disulfate, the N- butyl-pyridinium tetrafluoroborates aqueous solution formed above.
The beneficial effects of the present invention are：
(1) present invention prepares the Ni base catalyst (Pt- of carbon multi-wall nano tube loaded auxiliary agent Pt modifications using hydrogen reduction method
Ni/MWCNT the viewpoint of nitrobenzene liquid-phase hydrogenatin reaction) is carried out.Pt introducing can be by Pt, the metal synergy between Ni
The also proper energy of Ni presomas is effectively reduced, decentralization of the W metal nano-particle in carbon nano tube surface is greatly facilitated, enters
And promote more Ni0+Formation.Multi-walled carbon nanotube can effectively suppress mass transfer and hinder effect because of its unique meso-hole structure
Should, and there is big specific area, catalyst can be greatly improved in its Dispersion on surface, these advantages by being advantageous to raising activearm
Hydrogenation activity.
(2) catalyst of the invention is used for hydrogenation of chloronitrobenzene and prepares para-aminophenol reaction, using mass fraction for 5~
20% ionic liquid aqueous solution such as 1- butyl -3- methylimidazole dihydric phosphates, N, N, N- trimethyls-N- sulphur butyls-sulfuric acid
The solvent as reaction system such as hydrogen salt, N- butyl-pyridinium tetrafluoroborates, the introducing of acidic ion liquid, it is whole reactant
System introduces substantial amounts of acidic site, is more beneficial for being lifted the selectivity of para-aminophenol.
(3) catalyst cost of the invention is low, and economical and effective, universality be strong, environment-friendly, not etching apparatus and cyclicity
Can be good, can be under relatively mild reaction conditions when being prepared applied to the step hydrogenation-rearrangement of nitrobenzene one in the technique of para-aminophenol
Selectivity with greater activity and higher para-aminophenol, improve working condition, reduce production cost, improve product matter
Amount.
(4) present invention gained catalyst activity is high, and preparation process is simple, and is easy to separate from reaction solution, overcomes existing
There are the technical problems such as catalytic mechanical low intensity in technology, easy spontaneous combustion, separation difficulty, while use it for reacting, it also avoid
The serious equipment corrosion and largely handle waste water that the use of a large amount of inorganic acids is brought, in addition, also having, the rate of recovery is high, circulation
The advantages that using effect is good.
Embodiment
With reference to specific embodiment, the present invention will be further described, but the present invention is not limited thereto.
Embodiment 1
First according to concentrated nitric acid and the concentrated sulfuric acid 3:1 volume ratio prepares nitric-sulfuric acid.5g multi-walled carbon nanotubes are taken to be placed in 150mL
In round-bottomed flask, by 1:15g/ml solid-liquid mass volume ratio adds the nitric-sulfuric acid 75mL of respective volume, permanent at 100 DEG C
Warm return stirring 16 hours.CNT after nitration mixture modification is washed untill filtrate is in neutrality repeatedly with deionized water.
The multi-walled carbon nanotube carrier of the above-mentioned preparations of 1g is taken, adds six water chloroplatinic acid 0.0218g, adds six water nickel nitrates
0.99g, above-mentioned three kinds of materials are respectively put into 100ml beakers, then add 25ml deionized waters respectively, used under the conditions of 25 DEG C
1h is stirred by ultrasonic in Ultrasound Instrument, is transferred in 100ml round-bottomed flasks, 10h is stirred under the conditions of 25 DEG C, the stirring liquid is poured into
Air dry oven is put into 100ml beakers, first 80 DEG C of dry 3h, then heat to 110 DEG C and continue to dry 8h, natural cooling is down to
Room temperature, then it is ground the i.e. available Ni base catalyst being modified using multi-walled carbon nanotube as carrier loaded auxiliary agent Pt；Will be with
On obtained black powder catalyst be placed in quartz boat, be put into the quartz ampoule in vacuum tube furnace, with 50mL/min stream
Amount is passed through purity ＞ 99% High Purity Nitrogen, and it is optimal to keep one bubble each second, then with 5 DEG C/min per minute speed liter
Temperature is calcined 4 hours at 350 DEG C of constant temperature, then closed nitrogen, then be passed through purity ＞ with 50mL/min flow to 350 DEG C
99% High Purity Hydrogen, the hydrogen reducing 4h under the conditions of 350 DEG C of constant temperature, after reduction terminates, finally hydrogen is closed, it is cold to open nitrogen
But it can obtain catalyst (Pt-Ni/MWCNT) to room temperature.
Embodiment 2
Weigh the gained Pt-Ni/MWCNT catalyst of 0.1g embodiments 1 to be placed in pyroreaction kettle 100mL liners, add
25mL mass fraction be 15% 1- butyl -3- methylimidazole biphosphate saline solutions, 1.0g nitrobenzene, 0.03g 16
Alkyl trimethyl ammonium bromide, is put into magneton, sealing autoclave, with air in nitrogen displacement kettle 3 times, then under ultrasound condition point
1h is dissipated, kettle is evacuated to vacuum, then reactor is placed in oil bath by vavuum pump.After 95 DEG C of reaction temperatures of setting are raised to, lead to
Enter pressurized with hydrogen to 1.0MPa, open magnetic agitation, reaction timing starts.After reacting 4h, natural cooling cools, each thing in filtrate
The content liquid-phase chromatographic analysis of matter.The conversion ratio of nitrobenzene is 94.78%, and the selectivity of para-aminophenol is 53.68%.
Embodiment 3
Weigh the gained Pt-Ni/MWCNT catalyst of 0.1g embodiments 1 to be placed in pyroreaction kettle 100mL liners, add
25mL mass fraction be 15% 1- butyl -3- methylimidazole biphosphate saline solutions, 1.0g nitrobenzene, 0.03g 16
Alkyl trimethyl ammonium bromide, is put into magneton, sealing autoclave, with air in nitrogen displacement kettle 3 times, then under ultrasound condition point
1h is dissipated, kettle is evacuated to vacuum, then reactor is placed in oil bath by vavuum pump.After 105 DEG C of reaction temperatures of setting are raised to, lead to
Enter pressurized with hydrogen to 1.0MPa, open magnetic agitation, reaction timing starts.After reacting 4h, natural cooling cools, each thing in filtrate
The content liquid-phase chromatographic analysis of matter.The conversion ratio of nitrobenzene is 99.72%, and the selectivity of para-aminophenol is 61.83%.
Embodiment 4
Weigh the gained Pt-Ni/MWCNT catalyst of 0.1g embodiments 1 to be placed in pyroreaction kettle 100mL liners, add
25mL mass fraction be 15% 1- butyl -3- methylimidazole biphosphate saline solutions, 1.0g nitrobenzene, 0.03g 16
Alkyl trimethyl ammonium bromide, is put into magneton, sealing autoclave, with air in nitrogen displacement kettle 3 times, then under ultrasound condition point
1h is dissipated, kettle is evacuated to vacuum, then reactor is placed in oil bath by vavuum pump.After 115 DEG C of reaction temperatures of setting are raised to, lead to
Enter pressurized with hydrogen to 1.0MPa, open magnetic agitation, reaction timing starts.After reacting 4h, natural cooling cools, each thing in filtrate
The content liquid-phase chromatographic analysis of matter.The conversion ratio of nitrobenzene is 100%, and the selectivity of para-aminophenol is 52.97%.
Embodiment 5
Catalyst in embodiment 2,3,4 is centrifuged from reaction mixture and come out, with deionized water, absolute ethyl alcohol
Washing repeatedly, at 100 DEG C after vacuum drying, is collected standby.Weighing the above-mentioned Pt-Ni/MWCNT catalyst of 0.1g, to be placed in high temperature anti-
To answer in kettle 100mL liners, the mass fraction for adding 25mL is 15% 1- butyl -3- methylimidazole biphosphate saline solutions,
1.0g nitrobenzene, 0.03g cetyl trimethylammonium bromides, it is put into magneton, sealing autoclave, with air 3 in nitrogen displacement kettle
It is secondary, 1h is then disperseed under ultrasound condition, kettle is evacuated to vacuum, then reactor is placed in oil bath by vavuum pump.Set when being raised to
After 105 DEG C of fixed reaction temperatures, pressurized with hydrogen is passed through to 1.0MPa, opens magnetic agitation, reaction timing starts.After reacting 4h,
Natural cooling cools, the content liquid-phase chromatographic analysis of each material in filtrate.The conversion ratio of nitrobenzene is 98.79%, to amino
The selectivity of phenol is 60.97%.
According to above step, weigh 0.1g secondary cycle Pt-Ni/MWCNT catalyst and be placed in pyroreaction kettle 100mL
In lining, 25mL 15%1- butyl -3- methylimidazole biphosphate saline solutions, 1.0g nitrobenzene, 0.03g cetyls are added
Trimethylammonium bromide, is put into magneton, sealing autoclave, with air in nitrogen displacement kettle 3 times, then disperses under ultrasound condition
Kettle is evacuated to vacuum, then reactor is placed in oil bath by 1h, vavuum pump.After 105 DEG C of reaction temperatures of setting are raised to, it is passed through
Pressurized with hydrogen opens magnetic agitation, reaction timing starts to 1.0MPa.After reacting 4h, natural cooling cooling, by reaction mixture
Filter, the content liquid-phase chromatographic analysis of each material in filtrate.The conversion ratio of nitrobenzene is 94.65%, the choosing of para-aminophenol
Selecting property is 58.11%.
Comparative example 1
Weigh the above-mentioned Pt-Ni/MWCNT catalyst of 0.1g to be placed in pyroreaction kettle 100mL liners, 1.0g nitrobenzene,
0.03g cetyl trimethylammonium bromides, are put into magneton, sealing autoclave, with air in nitrogen displacement kettle 3 times, then super
Disperse 1h under the conditions of sound, kettle is evacuated to vacuum, then reactor is placed in oil bath by vavuum pump.It is anti-when being raised to 105 DEG C of setting
After answering temperature, pressurized with hydrogen is passed through to 1.0MPa, opens magnetic agitation, reaction timing starts.After reacting 4h, natural cooling drop
Temperature, the content liquid-phase chromatographic analysis of each material in filtrate.The conversion ratio of nitrobenzene is 95.12%, the selection of para-aminophenol
Property is 6.97%.
Comparative example 2
First according to concentrated nitric acid and the concentrated sulfuric acid 3:1 volume ratio prepares nitric-sulfuric acid.5g multi-walled carbon nanotubes are taken to be placed in 150mL
In round-bottomed flask, by 1:15g/ml solid-liquid mass volume ratio adds the nitric-sulfuric acid 75mL of respective volume, permanent at 100 DEG C
Warm return stirring 16 hours.CNT after nitration mixture modification is washed untill filtrate is in neutrality repeatedly with deionized water.
The multi-walled carbon nanotube carrier of the above-mentioned preparations of 1g is taken, six water nickel nitrate 0.99g is added, above two material is distinguished
It is put into 100ml beakers, then adds 25ml deionized waters respectively, 1h is stirred by ultrasonic with Ultrasound Instrument under the conditions of 25 DEG C, is transferred to
In 100ml round-bottomed flasks, 10h is stirred under the conditions of 25 DEG C, the stirring liquid is poured into 100ml beakers and is put into air dry oven,
First 80 DEG C of dry 3h, then heat to 110 DEG C and continue to dry 8h, and natural cooling is down to room temperature, are then ground i.e. available
Using multi-walled carbon nanotube as carrier loaded Ni bases catalyst；Black powder catalyst derived above is placed in quartz boat, put
Enter in the quartz ampoule in vacuum tube furnace, purity ＞ 99% High Purity Nitrogen is passed through with 50mL/min flow, kept for each second one
Individual bubble is optimal, is then warming up to 350 DEG C with 5 DEG C/min per minute speed, is calcined 4 hours at 350 DEG C of constant temperature, then
Nitrogen is closed, then purity ＞ 99% High Purity Hydrogen is passed through with 50mL/min flow, the hydrogen reducing under the conditions of 350 DEG C of constant temperature
4h, after reduction terminates, finally hydrogen is closed, opening nitrogen is cooled to room temperature and can obtain catalyst (Ni/MWCNT).
Weigh the above-mentioned Ni/MWCNT catalyst of 0.1g to be placed in pyroreaction kettle 100mL liners, add the 15% of 25mL
1- butyl -3- methylimidazole biphosphate saline solutions, 1.0g nitrobenzene, 0.03g cetyl trimethylammonium bromides, are put into magnetic
Son, sealing autoclave, with air in nitrogen displacement kettle 3 times, 1h is then disperseed under ultrasound condition, kettle is evacuated to very by vavuum pump
Sky, then reactor is placed in oil bath.After 105 DEG C of reaction temperatures of setting are raised to, pressurized with hydrogen is passed through to 1.0MPa, is opened
Magnetic agitation is opened, reaction timing starts.After reacting 4h, natural cooling cools, the content of each material liquid chromatogram point in filtrate
Analysis.The conversion ratio of nitrobenzene is 82.97%, and the selectivity of para-aminophenol is 26.51%.
Claims (6)
1. a kind of preparation method using multi-walled carbon nanotube as the carrier loaded auxiliary agent Pt Ni base catalyst being modified, its feature exists
In the catalyst is designated as Pt-Ni/MWCNT, and preparation method comprises the following steps：
(1) 1 is pressed:10-20g/ml solid-liquid mass volume ratio, it is the nitre that respective volume is added in MWCNT to multi-walled carbon nanotube
Sulphur nitration mixture, at 80-120 DEG C, constant temperature return stirring 12-24 hours, the CNT deionized water after sour modification is anti-
After backwashing is washed untill filtrate is in neutrality；
(2) using step (1) resultant multi-wall CNT as carrier, by multi-walled carbon nanotube, six water chloroplatinic acids and six water nickel nitrates
5-10:0.1-0.5:5-10 mass ratio adds platinum, the precursor salt of nickel, deionized water is added, then in 20~40 DEG C of bars
0.5~3h is stirred by ultrasonic with Ultrasound Instrument under part, is transferred in round-bottomed flask, 8~12h is stirred under the conditions of 20~40 DEG C, by this
Stirring liquid is placed in air dry oven, and 2~4h is first dried at 70~90 DEG C, is then heated to 100~120 DEG C and is continued to dry 5
~10h, natural cooling are down to room temperature, are then ground to obtain black powder catalyst；
(3) black powder catalyst obtained by step (2) is first calcined 2~6h at 200~500 DEG C, then at 200~500 DEG C
Under the conditions of 2~6h of hydrogen reducing, you can obtain catalyst Pt-Ni/MWCNT.
2. the Ni base catalyst according to claim 1 being modified using multi-walled carbon nanotube as carrier loaded auxiliary agent Pt, it is special
Sign is, in step (1), nitric-sulfuric acid is by concentrated nitric acid and the concentrated sulfuric acid 3:1 volume ratio is prepared.
3. the Ni base catalyst according to claim 1 being modified using multi-walled carbon nanotube as carrier loaded auxiliary agent Pt, it is special
Sign is, in step (3), the atmosphere of roasting is purity ＞ 99% High Purity Nitrogen, and it is 30~100mL/min to be passed through flow, is kept
Each second, one bubble was optimal, and using temperature programming, heating rate is 2~8 DEG C/min.
4. the Ni base catalyst according to claim 1 being modified using multi-walled carbon nanotube as carrier loaded auxiliary agent Pt, it is special
Sign is, in step (3), hydrogen is purity ＞ 99% High Purity Hydrogen, and it is 30~100mL/min to be passed through flow.
5. the catalyst that the preparation method described in any one of Claims 1-4 obtains is in the preparation pair of the step hydrogenation-rearrangement of nitrobenzene one
Application in amino-phenol reaction, it is characterised in that comprise the following steps：
Pt-Ni/MWCNT catalyst is added in autoclave, it is water-soluble to add the ionic liquid that mass fraction is 5~20%
Liquid is solvent, then adds nitrobenzene and cetyl trimethylammonium bromide, the addition of catalyst for nitrobenzene quality 5~
15%, the amount ratio of ionic liquid aqueous solution and nitrobenzene is 10-35mL：0.08~0.12g, is put into magneton, sealing autoclave,
With air in nitrogen displacement kettle 2~5 times, 1~3h is then disperseed under ultrasound condition, kettle is evacuated to vacuum, is warming up to by vavuum pump
After 80~120 DEG C, pressurized with hydrogen is passed through to 0.8~1.2MPa, is reacted 3~6 hours under stirring condition, and terminating will reaction after reaction
Mixed liquor filters, the content liquid-phase chromatographic analysis of each material in filtrate.
6. application according to claim 5, it is characterised in that described ionic liquid aqueous solution is 1- butyl -3- methyl
Imidazoles dihydric phosphate, N, N, N- trimethyls-N- sulphur butyls-disulfate, one kind in N- butyl-pyridinium tetrafluoroborates or
The aqueous solution of two or more formation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711018078.6A CN107649148A (en) | 2017-10-26 | 2017-10-26 | A kind of preparation method and application using multi-walled carbon nanotube as the carrier loaded auxiliary agent Pt Ni base catalyst being modified |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711018078.6A CN107649148A (en) | 2017-10-26 | 2017-10-26 | A kind of preparation method and application using multi-walled carbon nanotube as the carrier loaded auxiliary agent Pt Ni base catalyst being modified |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107649148A true CN107649148A (en) | 2018-02-02 |
Family
ID=61095046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711018078.6A Pending CN107649148A (en) | 2017-10-26 | 2017-10-26 | A kind of preparation method and application using multi-walled carbon nanotube as the carrier loaded auxiliary agent Pt Ni base catalyst being modified |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107649148A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108993536A (en) * | 2018-07-25 | 2018-12-14 | 河南大学 | A kind of palladium grown in conductive substrates-nickel cobalt sulphur composite nano tube array elctro-catalyst and preparation method thereof, application |
| CN109395719A (en) * | 2018-11-05 | 2019-03-01 | 江苏大学 | A method of in multi-wall carbon nano-tube pipe surface controllable load noble metal nanometer material |
| CN109453787A (en) * | 2018-12-06 | 2019-03-12 | 章立兰 | It can be with efficient-decomposition formaldehyde, the MWCNT supporting Pt Fe-TiO of toluene2The preparation method of catalyst |
| CN111514906A (en) * | 2020-05-11 | 2020-08-11 | 云南大学 | Magnetic platinum-based catalyst, preparation method and application |
| CN112108139A (en) * | 2020-09-29 | 2020-12-22 | 西安凯立新材料股份有限公司 | Catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation and preparation method thereof |
| CN113244946A (en) * | 2021-05-18 | 2021-08-13 | 湘潭大学 | Modified sepiolite molecular sieve supported nickel-based catalyst, and preparation method and application thereof |
| CN113304785A (en) * | 2021-06-04 | 2021-08-27 | 南京工业大学 | Preparation method of p-nitrophenol hydrogenation catalyst |
| CN115254188A (en) * | 2022-05-07 | 2022-11-01 | 贵州大学 | Method for preparing amphiphilic composite catalyst Pd @ IL/CNT-COOH by one-pot method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101176852A (en) * | 2007-12-12 | 2008-05-14 | 河北工业大学 | Catalyzer for synthesizing p-aminophenol by nitrobenzene catalytic hydrogenation as well as method for preparing and applying the same |
| CN101531614A (en) * | 2009-04-14 | 2009-09-16 | 大连理工大学 | Method for preparing aromatic hydroxylamine through selective hydrogenation of aromatic nitro compound with nano Pt/C catalyst |
| CN103157494A (en) * | 2013-04-01 | 2013-06-19 | 河北师范大学 | Method of synthesizing Pt-Ni catalyst material by hydrothermal method |
| CN103553943A (en) * | 2013-11-17 | 2014-02-05 | 大连理工大学 | Method for preparing para amino phenol by virtue of nitrobenzene hydrogenation |
| CN105655607A (en) * | 2016-02-01 | 2016-06-08 | 中国科学院福建物质结构研究所 | High-platinum base-loaded carbon nano tube nanocatalyst and preparation method thereof |
| CN106040278A (en) * | 2016-06-12 | 2016-10-26 | 湘潭大学 | Preparation method and application of Pd-Ni bimetallic catalyst supported by N-doped acid-activated sepiolite |
-
2017
- 2017-10-26 CN CN201711018078.6A patent/CN107649148A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101176852A (en) * | 2007-12-12 | 2008-05-14 | 河北工业大学 | Catalyzer for synthesizing p-aminophenol by nitrobenzene catalytic hydrogenation as well as method for preparing and applying the same |
| CN101531614A (en) * | 2009-04-14 | 2009-09-16 | 大连理工大学 | Method for preparing aromatic hydroxylamine through selective hydrogenation of aromatic nitro compound with nano Pt/C catalyst |
| CN103157494A (en) * | 2013-04-01 | 2013-06-19 | 河北师范大学 | Method of synthesizing Pt-Ni catalyst material by hydrothermal method |
| CN103553943A (en) * | 2013-11-17 | 2014-02-05 | 大连理工大学 | Method for preparing para amino phenol by virtue of nitrobenzene hydrogenation |
| CN105655607A (en) * | 2016-02-01 | 2016-06-08 | 中国科学院福建物质结构研究所 | High-platinum base-loaded carbon nano tube nanocatalyst and preparation method thereof |
| CN106040278A (en) * | 2016-06-12 | 2016-10-26 | 湘潭大学 | Preparation method and application of Pd-Ni bimetallic catalyst supported by N-doped acid-activated sepiolite |
Non-Patent Citations (3)
| Title |
|---|
| 唐立等: "硝基苯加氢合成对氨基苯酚的催化剂研究进展", 《化学世界》 * |
| 杨颖等: "《碳纳米管的结构、性能、合成及其应用》", 31 August 2013 * |
| 熊亮等: "Pt-Ni 合金/多壁碳纳米管作为直接甲醇燃料电池阳极材料", 《材料热处理技术》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108993536A (en) * | 2018-07-25 | 2018-12-14 | 河南大学 | A kind of palladium grown in conductive substrates-nickel cobalt sulphur composite nano tube array elctro-catalyst and preparation method thereof, application |
| CN108993536B (en) * | 2018-07-25 | 2021-01-29 | 河南大学 | Palladium-nickel-cobalt-sulfur composite nanotube array electrocatalyst growing on conductive substrate and preparation method and application thereof |
| CN109395719A (en) * | 2018-11-05 | 2019-03-01 | 江苏大学 | A method of in multi-wall carbon nano-tube pipe surface controllable load noble metal nanometer material |
| CN109453787A (en) * | 2018-12-06 | 2019-03-12 | 章立兰 | It can be with efficient-decomposition formaldehyde, the MWCNT supporting Pt Fe-TiO of toluene2The preparation method of catalyst |
| CN111514906A (en) * | 2020-05-11 | 2020-08-11 | 云南大学 | Magnetic platinum-based catalyst, preparation method and application |
| CN112108139A (en) * | 2020-09-29 | 2020-12-22 | 西安凯立新材料股份有限公司 | Catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation and preparation method thereof |
| CN113244946A (en) * | 2021-05-18 | 2021-08-13 | 湘潭大学 | Modified sepiolite molecular sieve supported nickel-based catalyst, and preparation method and application thereof |
| CN113304785A (en) * | 2021-06-04 | 2021-08-27 | 南京工业大学 | Preparation method of p-nitrophenol hydrogenation catalyst |
| CN113304785B (en) * | 2021-06-04 | 2022-08-09 | 南京工业大学 | Preparation method of p-nitrophenol hydrogenation catalyst |
| CN115254188A (en) * | 2022-05-07 | 2022-11-01 | 贵州大学 | Method for preparing amphiphilic composite catalyst Pd @ IL/CNT-COOH by one-pot method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107649148A (en) | A kind of preparation method and application using multi-walled carbon nanotube as the carrier loaded auxiliary agent Pt Ni base catalyst being modified | |
| CN107715873A (en) | A kind of preparation method and application using metal-organic framework materials as the carrier loaded La Pt base catalyst being modified | |
| CN100594210C (en) | Process for synthesizing p-aminophenol by nitrobenzene catalytic hydrogenation | |
| CN104844461A (en) | Synthetic process for amino aromatic hydrocarbon compound | |
| CN106423204A (en) | Method using graphene loaded palladium-nickel nano alloy to catalytically reduce nitro-aromatic compounds | |
| CN105669464A (en) | Application of metal-free hydrogenation catalyst in catalyzing hydrogenation reaction of nitrobenzene and derivatives thereof | |
| CN113563201B (en) | Method for continuously and efficiently synthesizing 3, 4-dichloroaniline based on fixed bed microreactor | |
| CN105601588B (en) | The synthetic method of N- hydroxyethyl piperazine coproduction piperazines | |
| CN109433239A (en) | A kind of preparation method and application for the platinum carbon catalyst that Fe-N is modified | |
| CN101531596A (en) | Preparation method for dinitrotoluene | |
| CN100455559C (en) | Method for reduced preparation of arylamine from aromatic nitro compound | |
| CN104844462A (en) | Synthesis process of dimido dipheny compound | |
| CN101440040B (en) | Process for synthesizing p-aminophenol by catalytic hydrogenation of nitrobenzene | |
| CN106749059A (en) | The preparation method of chloride benzotriazole ultraviolet absorbent | |
| CN104447379A (en) | Preparation method of methanamide | |
| CN109608355A (en) | A kind of synthesis technology of 2- amino -4- acetyl-anisidine | |
| CN105749954B (en) | A kind of no catalytic hydrogenation and its application for being catalyzed 1,5- dinitronaphthalene hydrogenation reactions | |
| CN112707822A (en) | Method for preparing 2, 4-dinitrochlorobenzene by one-step adiabatic continuous nitration of chlorobenzene | |
| CN105268450B (en) | The catalyst that a kind of hydrogenation catalyst synthesizes the method for the disulfonate sodium of 8 amino, 1 naphthols 3,6 and its used | |
| CN107694610B (en) | A kind of phase transfer catalyst and preparation method thereof for cyclohexanol synthesizing cyclohexanone | |
| CN105859574A (en) | Synthesis method of 2-amino-5-chloro-N,3-dimethylbenzamide | |
| CN103193660B (en) | Synthetic method of 4-alkoxy phenylamine compound | |
| CN109400482A (en) | A kind of method that toluene green nitration prepares para-nitrotoluene | |
| CN105801376B (en) | Silica gel supported imidazole ion liquid is catalyzed the production method of benzene direct oxidation phenol | |
| CN108003031A (en) | A kind of method for preparing nitro compound using graphene catalysis nitrogen dioxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180202 |