CN106311274A - Magnetic nanoparticles catalyst used for p-nitrophenol of catalysis hydrogenation and preparing method and application thereof - Google Patents
Magnetic nanoparticles catalyst used for p-nitrophenol of catalysis hydrogenation and preparing method and application thereof Download PDFInfo
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- CN106311274A CN106311274A CN201610614386.4A CN201610614386A CN106311274A CN 106311274 A CN106311274 A CN 106311274A CN 201610614386 A CN201610614386 A CN 201610614386A CN 106311274 A CN106311274 A CN 106311274A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000006555 catalytic reaction Methods 0.000 title abstract description 7
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 7
- 239000002122 magnetic nanoparticle Substances 0.000 title abstract 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- 230000009467 reduction Effects 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 239000011943 nanocatalyst Substances 0.000 claims description 28
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 23
- 239000008187 granular material Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052681 coesite Inorganic materials 0.000 claims description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims description 11
- 229910052682 stishovite Inorganic materials 0.000 claims description 11
- 229910052905 tridymite Inorganic materials 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 230000005070 ripening Effects 0.000 claims description 6
- 150000003303 ruthenium Chemical class 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 4
- 229940038773 trisodium citrate Drugs 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- VJVWNPYNKXNTJV-UHFFFAOYSA-K [Ru+3].I(=O)(=O)[O-].I(=O)(=O)[O-].I(=O)(=O)[O-] Chemical compound [Ru+3].I(=O)(=O)[O-].I(=O)(=O)[O-].I(=O)(=O)[O-] VJVWNPYNKXNTJV-UHFFFAOYSA-K 0.000 claims description 2
- SPDCFZAAMSXKTK-UHFFFAOYSA-N acetic acid;ruthenium Chemical compound [Ru].CC(O)=O SPDCFZAAMSXKTK-UHFFFAOYSA-N 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 2
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- 238000007654 immersion Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 239000013049 sediment Substances 0.000 claims 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000005408 paramagnetism Effects 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- 239000012153 distilled water Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 23
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 22
- 239000000047 product Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- 238000006392 deoxygenation reaction Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000002955 isolation Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000010757 Reduction Activity Effects 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- OEHNVKBOQOXOJN-UHFFFAOYSA-N 2-(4-nitrophenyl)phenol Chemical compound OC1=CC=CC=C1C1=CC=C([N+]([O-])=O)C=C1 OEHNVKBOQOXOJN-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- PIVQQUNOTICCSA-UHFFFAOYSA-N ANTU Chemical compound C1=CC=C2C(NC(=S)N)=CC=CC2=C1 PIVQQUNOTICCSA-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000001195 anabolic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 230000008033 biological extinction Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- UWQSRFYTPSKUPO-UHFFFAOYSA-N iron 2-nitrophenol Chemical compound [Fe].[N+](=O)([O-])C1=C(C=CC=C1)O UWQSRFYTPSKUPO-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229960005489 paracetamol Drugs 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 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
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- OVYWMEWYEJLIER-UHFFFAOYSA-N quinolin-6-ol Chemical compound N1=CC=CC2=CC(O)=CC=C21 OVYWMEWYEJLIER-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 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
- 238000012430 stability testing Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910003158 γ-Al2O3 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
- B01J23/8906—Iron and noble metals
-
- 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
- B01J35/33—Electric or magnetic properties
-
- 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
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the field of catalyst, and in particular relates to a magnetic nanoparticle catalyst used for p-nitrophenol of catalysis hydrogenation and a preparing method and an application thereof. The catalyst uses magnetic nanoparticle Fe3O4 as catalyst core, mesoporous silica is covered on the surface of magnetic nanoparticle Fe3O4, mesoporous silica serves as vector, and active component Ru is loaded on the vector through an impregnation reduction method, wherein the loading capacity of the active component Ru is 0.1-5% of total mass of magnetic nanoparticle catalyst. The magnetic nanoparticle catalyst prepared has good paramagnetism, extremely high catalytic activity, hydrogenation reaction of p-nitrophenol can happen at a relatively low temperature of 0-30 DEG C and with relatively low dosage of catalyst, meanwhile, the catalyst cam keep activity within 25 times of repeated use and basically keep activity soaking in solution of pH 6-13 for long time (45d).
Description
Technical field
The invention belongs to catalyst field, relate to a kind of paranitrophenol catalytic hydrogenation magnetic nano-catalyst
And its preparation method and application.
Background technology
Para-aminophenol is a kind of widely used organic synthesis intermediate, is widely used in medicine, dyestuff, rubber, photograph
In field.Pharmaceuticals industry is the major consumers field of para-aminophenol, is mainly used in synthesis acetaminophen, benorylate, ANTU
Bright, vitamin B1,6-hydroxyquinoline, complexing agent nicotiamide, practolol etc..It is right that the production method of current para-aminophenol mainly has
Nitrophenol iron powder reducing method, Nitrobenzol catalytic hydrogenation method, Nitrobenzol electrolytic reduction, paranitrophenol catalytic hydrogenating reduction method
Four kinds.Nitrobenzol catalytic hydrogenation method is with Nitrobenzol as raw material, and catalytic hydrogenating reduction in acid medium, the method noble metal reclaims
Cost is high, and recycling rate of waterused is low, and there are aniline and other impurity on a small quantity in product.Nitrobenzol electrolytic reduction is to reactor
Design and process regulation have higher technology requirement, and energy consumption is higher, domestic unrealized industrialization.Paranitrophenol iron powder is also
Former method is the main production process of current domestic para-aminophenol, and this method process route is longer, and production cost is high, product quality
Difference, metal ion content is higher, and because a large amount of scums cause environmental pollution serious, most developed countries have eliminated the method.Right
Nitrophenol catalytic hydrogenation method technique is simple, and product quality is high, and three waste discharge is substantially reduced compared with other techniques, environmental pollution
Little, and product is more suitable for pharmaceuticals industry, has broad based growth prospect.
Paranitrophenol liquid phase catalytic hydrogenation generally uses skeleton nickel as catalyst, but it exists easy in inactivation, conversion ratio
The problem of the highest and poor selectivity, the problem such as the design of reaction unit, catalyst separation be always its realize industrialized mainly
Obstacle, the relative deficiency and the research of this respect seems.During paranitrophenol catalytic hydrogenation prepares para-aminophenol, hydrogen
The selection changing catalyst is the most key, and the catalyst of high activity and stability can improve para-aminophenol productivity and quality, fall
Low production cost.Paranitrophenol catalytic hydrogenation disclosed in current patent prepares the catalyst of para-aminophenol mainly two
Class.One class is unsupported catalyst, including skeleton nickel and nano nickel；Another kind of is that nickel or precious metal palladium, platinum even load type are urged
Agent, used carrier mainly has α-Al2O3、γ-Al2O3、SiO2, molecular sieve, TiO2、MgO、CeO2, activated carbon etc..Patent
CN101007275, CN101693201A, CN101693212A refer to the preparation method of loaded catalyst, and for right
Nitrophenol catalytic hydrogenation prepares para-aminophenol.These catalyst have in use been directed to separate difficulty with product
Problem, use cost is higher.Patent CN10209126A refer to the preparation method of supported catalyst film, although separates and relatively holds
Easily, but due between its active component and film adhesion weak, film and the restriction of substrate contact area etc. cause applying limited.Patent
CN105126869A refer to Ni/Ag/Fe3O4Complex catalyst prepares para-aminophenol, owing to it is only fixed by complexing
Active component, catalyst recycling rate of waterused is relatively low, poor stability.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, it is therefore intended that provide a kind of paranitrophenol catalytic hydrogenation magnetic
Property nanocatalyst and its preparation method and application.
For achieving the above object, the technical solution adopted in the present invention is:
A kind of paranitrophenol catalytic hydrogenation magnetic nano-catalyst, is with magnetic Nano Fe3O4Granule is as catalyst
Kernel, at magnetic Nano Fe3O4The coating mesoporous silicon dioxide of particle surface, using mesoporous silicon oxide as carrier, by dipping also
Former method makes active component Ru be supported on carrier.
In such scheme, the load capacity of described active component Ru is the 0.1～5% of magnetic nano-catalyst gross mass.
The preparation method of above-mentioned paranitrophenol catalytic hydrogenation magnetic nano-catalyst, comprises the steps:
(1) coprecipitation reaction synthesizing magnetic nanometer Fe is used3O4Granule: by Fe2+Salt and Fe3+Salt mixes, stirring at normal temperature bar
Under part, rapidly join the OH of excess-, after having reacted, add appropriate trisodium citrate, be heated to uniform temperature ripening, then
Collection precipitates, washs, is vacuum dried, and obtains magnetic Nano Fe3O4Granule；
(2) mesoporous SiO2Coated magnetic nanometer Fe3O4Granule: take magnetic Nano Fe3O4Granule is scattered in ethanol water
Anabolic reaction system, under mechanical agitation, adds template, base catalyst to reaction system, is warming up to 35 DEG C, is slowly added dropwise
The ethanol solution of tetraethoxysilane (TEOS), continues after dripping stirring reaction a period of time, Magnet separation solid particle, so
Rear employing ion exchange removes template, more scrubbed, dried, obtains coating mesoporous SiO2Magnetic Nano Fe3O4?
Grain；
(3) load of active component Ru: take a certain amount of coating mesoporous SiO2Magnetic Nano Fe3O4Granule ultrasonic disperse in
In methanol solution, add ruthenium salt, reaction 2～5h is stirred at room temperature, be subsequently placed under condition of ice bath dropping reducing agent, continue stirring anti-
Answering 2～5h, with Magnet separation solid, solid is the most scrubbed, i.e. obtain magnetic nano-catalyst after vacuum drying.
In such scheme, step (1) described Fe2+With Fe3+Mol ratio be 1:2.
In such scheme, the time of step (1) described reaction is 0.5～1h, and the temperature of described ripening is 70～100 DEG C,
Time is 0.5～3h.
In such scheme, described template is cetyl trimethylammonium bromide or hexadecyltrimethylammonium chloride, institute
State addition is reaction system quality 0.1%～the 5% of template.
In such scheme, described base catalyst is ammonia or sodium hydroxide solution, and the addition of described base catalyst is anti-
Answer the 1%～5% of system volume.
In such scheme, the dripping quantity of tetraethoxysilane described in step (2) be reaction system volume for 1%～
5%, continue stirring reaction 3～10h after dripping.
In such scheme, described ion exchange removes the method for template and is: by the solid particle dispersions of separation in second
In alcoholic solution, add NH4NO3It is heated to 60 DEG C of backflows 0.5～2h, repeats 2～3 times.
In such scheme, described ruthenium salt is ruthenium trichloride, acetic acid ruthenium, iodate ruthenium or carbonyl ruthenic chloride.
In such scheme, with every gram of coating mesoporous SiO2Magnetic Nano Fe3O4On the basis of granule, the addition of described ruthenium salt
Amount is 0.3～5mmol.
In such scheme, described reducing agent is containing BH- 4Solution or hydrazine hydrate, described BH- 4It is 1.2 with the mol ratio of Ru
～10:1, described hydrazine hydrate is 1.5～10:1 with the mol ratio of Ru.
In such scheme, described containing BH- 4Solution in BH- 4Concentration be 0.06～0.25mol/L.
The present invention uses following two kind method of testing to carry out activity rating:
(1) active testing under sodium borohydride effect: take the p-nitrophenyl phenol solution of certain volume, detect with Uv-vis
The scanning curve of 500～250nm；Add NaBH4After aqueous solution stirs, sampling scans in the range of 500～250nm；Add
Enter the aqueous catalyst solution of certain volume ultrasonic disperse, start simultaneously at timing, at interval of a period of time sampling detection 500-250nm
Scanning curve；The reperformance test method of catalyst: used sample Magnet is isolated from reacted mixture
Come, respectively with deionized water and washing with alcohol 2～3 times, continue under the same conditions to test its catalytic reduction activity.
(2) catalytic hydrogenation test: reaction is carried out in autoclave, weighing quantitative paranitrophenol, to be dissolved in ethanol water-soluble
Liquid, adds quantitative magnetic nano-catalyst stirring, autoclave evacuation the most first then passes to high pressure hydrogen reduction
Paranitrophenol, changes pressure and response time, detects the extinction of product after stopped reaction with ultraviolet-uisible spectrophotometer
The change of degree, and calculate conversion ratio according to para-aminophenol standard curve；Catalytic hydrogenating reduction is carried out in neutral conditions,
The summit of product para-aminophenol superposes at 317nm with reactant, it is impossible to judge conversion ratio and productivity, adds before detection every time
Enter after quantitative sodium hydroxide solution adjusts pH and detect absorbance；Unit interval unit mass catalyst institute is calculated according to conversion ratio
The quality consumed represents the catalysis activity of catalyst.
Beneficial effects of the present invention:
(1) magnetic nano-catalyst prepared by the present invention has the paramagnetism of excellence, in the absence of a magnetic field can be equal
Even dispersion suspends in the solution so that active center is more abundant with contacting of substrate, can be rapidly from instead under externally-applied magnetic field
Answer system to separate, can effectively solve catalyst and separate the problem of difficulty with product, simplify production technology and equipment investment；
(2) magnetic nano-catalyst prepared by the present invention is using the coating mesoporous silicon dioxide of magnetic core as carrier loaded work
Property metal component, substantially increase utilization rate and the load stability of active component, mesoporous silicon oxide be coated on effectively guarantor
The fully dispersed of big specific surface area, beneficially active component and its contacting with substrate is provided while protecting magnetic core；Urge
Agent is reused 25 activity and is basically unchanged, and soaks (45d) catalysis activity for a long time the most not in the solution of pH=6～13
Become；
(3) load capacity of active component Ru of the present invention is 0.1～5wt%, and catalysis activity is high, traditional handicraft p-nitrophenyl
Phenol liquid phase catalytic hydrogenation reaction temperature is 70～110 DEG C, and catalyst amount is 2%～15% relative to substrate quality, the present invention
At lower temperature conditions 0～30 DEG C, just have the highest catalytic hydrogenation activity, catalyst amount be only substrate quality 0.5%～
4%, reaction can occur in a mild condition, etoh solvent aqueous solution, it is not necessary to adds acid and surfactant, post processing
Technique is simple.
Accompanying drawing explanation
Fig. 1 is the magnetic Nano Fe prepared by the present invention3O4Granule, the magnetization curve figure of magnetic nano-catalyst.
Fig. 2 is schematic diagram before and after the magnetic nano-catalyst Magnetic Isolation prepared by the present invention, and wherein (a) is magnetic Nano
Catalyst is evenly dispersed in the state in reaction system, and (b) is under additional the action of a magnetic field, and magnetic nano-catalyst is by magnetic
The state of reaction system after separation.
Fig. 3～Fig. 5 is the transmission electron microscope picture of the magnetic nano-catalyst prepared by the present invention.
Detailed description of the invention
In order to be more fully understood that the present invention, it is further elucidated with present disclosure below in conjunction with embodiment, but the present invention
Content is not limited solely to the following examples.
Embodiment 1
A kind of paranitrophenol catalytic hydrogenation magnetic nano-catalyst, is prepared via a method which to obtain:
(1) coprecipitation reaction synthesizing magnetic nanometer Fe is used3O4Granule: take 160mL deoxygenation deionized water under argon shield
In 500mL there-necked flask, add the anhydrous FeCl of 3.88g3(0.0239mol), 3.34g FeSO is added after dissolving4·7H2O
(0.012mol), 100mL deoxygenation deionized water, mechanical agitation 30min are added；Weigh 4.32g NaOH (0.108mol) to be dissolved in
In 30mL deoxygenation deionized water, constant voltage quickly instills in there-necked flask；After reacting 1h under room temperature, add trisodium citrate 1.5g
(0.0051mol), and ripening 30min at 90 DEG C, the magnetic Nano Fe of carboxyl modified is collected with Magnet3O4Granule；Deionized water
Rinsing 3～4 times, after pH 7～8, then with alcohol flushing 2～3 times, sucking filtration is placed in vacuum drying oven and is dried 24h, puts into dry
Dry device seals and saves backup.
(2) mesoporous SiO2Coated magnetic nanometer Fe3O4Granule: take Fe3O4(0.500g) ultrasonic 10min is scattered in 15mL ethanol
With in 35mL distilled water mixed liquor, after adding CTAB (0.20g) and 1mL ammonia stirring 30min, it is warming up to 35 DEG C；With peristaltic pump with
Flow velocity dropping TEOS ethanol (2mLTEOS the is dissolved in 8ml ethanol) solution of 0.2mL/min, continues stirring 6h after dripping；Use Magnet
Separate solid particle, the magnetic retention granule of separation is scattered in 60mL ethanol solution, add NH4NO3(0.10g,
0.62mmol) it is heated at 60 DEG C the 0.5h that refluxes, is repeated twice, with the AgNO of 0.1mol/L3Solution detection is steamed without using after precipitation
Distilled water is washed 3 times, is vacuum dried, obtains mesoporous SiO under room temperature2Coated magnetic nanometer Fe3O4Granule, is carrier granular.
(3) weighing carrier granular 0.30g, in 30mL methanol, ultrasonic disperse 5min, mechanical agitation, weigh ruthenium trichloride
0.1234g adds in the carrier granular stirred, and continues stirring 3h, then drip sodium borohydride under condition of ice bath after adding
Aqueous solution (0.1350g is dissolved in 6ml distilled water), after dripping off continue stirring 2h, proceed to for three times very by distilled water and washing with alcohol
Empty drying baker normal temperature drying 24h i.e. obtains paranitrophenol catalytic hydrogenation magnetic nano-catalyst.
Take paranitrophenol (2.08mM, 20mL) and add in there-necked flask, take 0.2mL solution with liquid-transfering gun and add 3mL stone
In English cuvette, add and after 2.8mL distilled water stirs, scan the ultraviolet absorptivity at 500～250nm, add NaBH4
After (131mg is dissolved in 9mL distilled water) solution stirring is uniform, take the same method detection ultraviolet light absorption curve of 0.2mL sample.Take
The magnetic nano-catalyst 1mg ultrasonic disperse of embodiment 1 preparation, in the distilled water of 1mL, starts meter while adding catalyst
Time, certain interval of time sampling detection absorbance.In test result shows 25s, paranitrophenol conversion ratio reaches 98.4%, produces
Product yield 98.1%.Test and used Magnet separating catalyst particles afterwards, with distilled water wash 2～3 times, be then dispersed in
1mL distilled water, tests the reactivity of its catalysis reduction paranitrophenol in the case of other conditions are constant.Through 25 circulations
After, paranitrophenol conversion ratio 98.3% in 180s, product yield 98%.
The magnetic nano-catalyst 1mg of Example 1 preparation is placed in the aqueous solution of 10mL difference pH respectively, and pH is respectively
6,7,8,9,10,11,12,13, after placing 45 days, Magnetic Isolation, it is washed with distilled water to neutrality, adds 1ml distilled water, ultrasonic
Dispersion.Test each sample catalytic reduction activity respectively by similarity condition, result shows, it is right that all samples all can make in 30s
The conversion ratio of nitrophenol reaches 98.4%, product yield 98%.
Weigh paranitrophenol 0.7833g and be dissolved in 130ml ethanol and the mixed solvent of 20ml distilled water, add embodiment 1
The magnetic nano-catalyst 0.03g of preparation, adds solution in autoclave, evacuation after sealing (also can first blow with nitrogen sweep, then
Sweep with hydrogen and blow), it is filled with hydrogen, pressure 2.0Mpa, temperature 20 DEG C, mechanical agitation rotating speed is set to 150r/min, response time
3.5h.Detecting absorbance after having reacted and calculate conversion ratio, result shows that conversion ratio is 79.28%, is calculated hydrogenation rate
For 127.5mmol/ (h g).
By catalyst Magnetic Isolation, with distilled water wash 3～4 times, continue test catalytic hydrogenation reaction activity, other reactions
Condition is identical, and after 10 times circulate, the conversion ratio recording paranitrophenol is 79.45%, and hydrogenation rate is 127.8mmol/
(h·g)。
Embodiment 2
A kind of paranitrophenol catalytic hydrogenation magnetic nano-catalyst, is prepared via a method which to obtain:
(1) taking 80mL deoxygenation deionized water in there-necked flask, device is passed through argon shield, adds 1.50g anhydrous
FeCl3, after dissolving, add 1.29g FeSO4·7H2O, adds 30mL deoxygenation deionized water, mechanical agitation 30min；Weigh
1.58g NaOH is dissolved in 20mL deoxygenation deionized water, and constant voltage quickly instills in there-necked flask；After stirring 0.5h under room temperature, add
Trisodium citrate 0.7g, and ripening 45min at 80 DEG C, use magnetic Nano Fe3O4Granule；Deionized water rinsing 3～4 times, pH7
～after 8, then with alcohol flushing 2～3 times, sucking filtration is placed in vacuum drying oven and is dried 24h, put into exsiccator seals preserve standby
With.
(2) Fe is taken3O4(0.80g), during ultrasonic 8min is scattered in 20mL ethanol and 45mL distilled water mixed liquor, CTAB is added
(0.15g) and it is warming up to 35 DEG C after 2mL ammonia stirring 30min；TEOS ethanol is dripped with the flow velocity of 0.2mL/min molten with peristaltic pump
Liquid (2.5mL TEOS is dissolved in 10ml ethanol), continues stirring 3h after dripping；By Magnet separation solid particle, the magnetic that will separate
Solid particle dispersions, in 50mL ethanol solution, adds NH4NO3(0.10g) it is heated at 60 DEG C the 0.5h that refluxes, is repeated twice,
With the AgNO of 0.1mol/L3Solution detection, without using distilled water wash 3 times after precipitation, is vacuum dried under room temperature, obtains mesoporous SiO2Bag
Cover magnetic Nano Fe3O4Granule, is carrier granular.
(3) weighing carrier granular 0.50g, in 40mL methanol, ultrasonic disperse 5min, mechanical agitation, weigh ruthenium trichloride
0.22g adds in the carrier granular stirred, and continues stirring 3h, then drip hydrazine hydrate solution under condition of ice bath after adding
(0.46ml is dissolved in 4ml distilled water), continues stirring 3h, proceeds to vacuum drying oven three times by distilled water and washing with alcohol normal after dripping off
Temperature is dried 24h and i.e. obtains catalyst.
By the method test catalyst activity that embodiment 1 is identical.In test result shows 23s, paranitrophenol converts
Rate reaches 99.1%, product yield 98.7%.Test and used Magnet separating catalyst particles afterwards, with distilled water wash 2～3
Secondary, it is then dispersed in 1mL distilled water, the reaction testing its catalysis reduction paranitrophenol in the case of other conditions are constant is lived
Property, result shows, after 25 times circulate, and paranitrophenol conversion ratio 98.4% in 135s, product yield 98.1%.
Catalyst stability testing method in different pH solution is same as in Example 1, respectively the magnetic of Example 2 preparation
Property nanocatalyst 1mg is placed in the aqueous solution of 10mL difference pH value, after placing 45 days, and Magnetic Isolation, it is washed with distilled water to
Neutrality, adds 1ml distilled water, ultrasonic disperse.Each sample catalytic reduction activity, result is tested respectively by embodiment 1 similarity condition
Showing, all samples all can make the conversion ratio of paranitrophenol reach 98.2% in 30s, product yield 98%.
Weigh paranitrophenol 0.7833g and be dissolved in 130ml ethanol and the mixed solvent of 20ml distilled water, add embodiment 2
The magnetic nano-catalyst 0.02g of preparation, adds solution in autoclave, is passed through hydrogen exchange 3～4 times, is filled with hydrogen, pressure
2.0Mpa, reaction temperature 20 DEG C, mechanical agitation rotating speed is 150r/min, response time 4h.Absorbance meter is detected after having reacted
Calculating conversion ratio, result shows that conversion ratio is 82.45%, and being calculated hydrogenation rate is 174.1mmol/ (h g).By catalyst
Magnetic Isolation, with distilled water wash 3～4 times, continues test catalytic hydrogenation reaction activity, and other reaction conditions are identical, through 10
After secondary circulation, the conversion ratio of the paranitrophenol of survey is 81.75%, and hydrogenation rate is 172.6mmol/ (h g).
Obviously, above-described embodiment is only by clearly demonstrating made example, and not restriction to embodiment.Right
For those of ordinary skill in the field, can also make on the basis of the above description other multi-form change or
Variation.Here without also cannot all of embodiment be given exhaustive.And the obvious change therefore amplified or change
Within moving still in the protection domain of the invention.
Claims (10)
1. a paranitrophenol catalytic hydrogenation magnetic nano-catalyst, it is characterised in that be with magnetic Nano Fe3O4Granule
As catalyst kernel, at magnetic Nano Fe3O4The coating mesoporous silicon dioxide of particle surface, using mesoporous silicon oxide as carrier,
Active component Ru is made to be supported on carrier by immersion reduction method.
Paranitrophenol catalytic hydrogenation magnetic nano-catalyst the most according to claim 1, it is characterised in that described work
Load capacity is magnetic nano-catalyst gross mass the 0.1 ~ 5% of property component Ru.
3. the preparation method of the arbitrary described paranitrophenol catalytic hydrogenation magnetic nano-catalyst of claim 1 ~ 2, it is special
Levy and be, comprise the steps:
(1) coprecipitation reaction synthesizing magnetic nanometer Fe is used3O4Granule: by Fe2+Salt and Fe3+Salt mixes, under the conditions of stirring at normal temperature,
Rapidly join the OH of excess-, after having reacted, add appropriate trisodium citrate, be heated to uniform temperature ripening, it is heavy then to collect
Form sediment, wash, be vacuum dried, obtain magnetic Nano Fe3O4Granule；
(2) mesoporous SiO2Coated magnetic nanometer Fe3O4Granule: take magnetic Nano Fe3O4Granule is scattered in ethanol water composition
Reaction system, under mechanical agitation, adds template, base catalyst to reaction system, is warming up to 35 DEG C, is slowly added dropwise tetrem
The ethanol solution of TMOS, continues stirring reaction a period of time, Magnet separation solid particle, then uses ion after dripping
Exchange process removes template, more scrubbed, dried, obtains coating mesoporous SiO2Magnetic Nano Fe3O4Granule；
(3) load of active component Ru: take a certain amount of coating mesoporous SiO2Magnetic Nano Fe3O4Granule ultrasonic disperse is in methanol
In solution, add ruthenium salt, reaction 2 ~ 5h be stirred at room temperature, be subsequently placed under condition of ice bath dropping reducing agent, continue stirring reaction 2 ~
5h, with Magnet separation solid, solid is the most scrubbed, i.e. obtain magnetic nano-catalyst after vacuum drying.
Preparation method the most according to claim 3, it is characterised in that Fe described in step (1)2+With Fe3+Mol ratio be
1:2；The time of described reaction is 0.5 ~ 1h, and the temperature of described ripening is 70 ~ 100 DEG C, and the time is 0.5 ~ 3 h.
Preparation method the most according to claim 3, it is characterised in that described template is cetyl trimethylammonium bromide
Or hexadecyltrimethylammonium chloride, the addition of described template is the 0.1% ~ 5% of reaction system quality.
Preparation method the most according to claim 3, it is characterised in that described base catalyst be ammonia or sodium hydroxide molten
Liquid, the addition of described base catalyst is the 1% ~ 5% of reaction system volume.
Preparation method the most according to claim 3, it is characterised in that the dropping of tetraethoxysilane described in step (2)
Amount for reaction system volume for 1% ~ 5%, after dripping continue stirring reaction 3 ~ 10 h.
Preparation method the most according to claim 3, it is characterised in that described ruthenium salt is ruthenium trichloride, acetic acid ruthenium, iodate
Ruthenium or carbonyl ruthenic chloride.
Preparation method the most according to claim 3, it is characterised in that with every gram of coating mesoporous SiO2Magnetic Nano Fe3O4
On the basis of granule, the addition of described ruthenium salt is 0.3 ~ 5mmol.
Preparation method the most according to claim 3, it is characterised in that described reducing agent is containing BH- 4Solution or hydration
Hydrazine, described BH- 4Being 1.2 ~ 10:1 with the mol ratio of Ru, described hydrazine hydrate is 1.5 ~ 10:1 with the mol ratio of Ru.
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| CN110813312A (en) * | 2019-11-08 | 2020-02-21 | 珠海格力电器股份有限公司 | Magnetic nano composite material and preparation method and application thereof |
| CN113072452A (en) * | 2021-04-01 | 2021-07-06 | 九江善水科技股份有限公司 | Method for catalytically synthesizing o-aminophenol |
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