CN107469828A - 一种核‑壳结构负载型钨复合催化剂及其制备方法和应用 - Google Patents
一种核‑壳结构负载型钨复合催化剂及其制备方法和应用 Download PDFInfo
- Publication number
- CN107469828A CN107469828A CN201710540001.9A CN201710540001A CN107469828A CN 107469828 A CN107469828 A CN 107469828A CN 201710540001 A CN201710540001 A CN 201710540001A CN 107469828 A CN107469828 A CN 107469828A
- Authority
- CN
- China
- Prior art keywords
- preparation
- sio
- catalyst
- support type
- type tungsten
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 26
- 239000010937 tungsten Substances 0.000 title claims abstract description 26
- 239000011258 core-shell material Substances 0.000 title claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 54
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 27
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 27
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 27
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 27
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 27
- -1 Carbostyril compound Chemical class 0.000 claims abstract description 19
- LISFMEBWQUVKPJ-UHFFFAOYSA-N carbostyril Natural products C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002105 nanoparticle Substances 0.000 claims abstract description 12
- 239000000084 colloidal system Substances 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- 239000003495 polar organic solvent Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000002506 iron compounds Chemical class 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical group NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 150000003141 primary amines Chemical class 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- SGZSJPBASHYOHQ-UHFFFAOYSA-N 2-chloro-5-fluorobenzoyl chloride Chemical class FC1=CC=C(Cl)C(C(Cl)=O)=C1 SGZSJPBASHYOHQ-UHFFFAOYSA-N 0.000 claims description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 3
- MIIPXDMKJATXBI-UHFFFAOYSA-N C(=O)CC[Na] Chemical class C(=O)CC[Na] MIIPXDMKJATXBI-UHFFFAOYSA-N 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 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 2
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 230000002045 lasting effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 230000009849 deactivation Effects 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 208000030507 AIDS Diseases 0.000 description 1
- 206010067484 Adverse reaction Diseases 0.000 description 1
- 102000003915 DNA Topoisomerases Human genes 0.000 description 1
- 108090000323 DNA Topoisomerases Proteins 0.000 description 1
- 206010034133 Pathogen resistance Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 101710183280 Topoisomerase Proteins 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000002924 anti-infective effect Effects 0.000 description 1
- 230000000078 anti-malarial effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 239000003430 antimalarial agent Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001647 drug administration Methods 0.000 description 1
- IDYZIJYBMGIQMJ-UHFFFAOYSA-N enoxacin Chemical compound N1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 IDYZIJYBMGIQMJ-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012678 infectious agent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/398—Egg yolk like
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
- C07D215/54—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 3
- C07D215/56—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 3 with oxygen atoms in position 4
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/40—Constitutive chemical elements of heterogeneous catalysts of Group IV (IVA or IVB) of the Periodic Table
- B01J2523/41—Silicon
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/60—Constitutive chemical elements of heterogeneous catalysts of Group VI (VIA or VIB) of the Periodic Table
- B01J2523/69—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
- B01J2523/84—Metals of the iron group
- B01J2523/842—Iron
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种核‑壳结构负载型钨复合催化剂及其制备方法和应用。现有喹诺酮类药物主环的合成大多存在着合成步骤长、操作繁琐、三废量大和成本较高等缺陷。本发明通过制备Fe3O4胶体、SiO2/Fe3O4复合纳米粒子制备磁分离核‑壳负载型钨复合催化剂WO3/SiO2/Fe3O4，此磁分离核‑壳负载型钨复合催化剂WO3/SiO2/Fe3O4用于催化合喹诺酮类化合物，提供了一种高效、催化剂可磁分离回收并循环利用的喹诺酮类化合物制备方法，本发明制备之催化剂能在喹诺酮类化合物的制备中重复利用，催化剂仍保有原来活性没有失活现象，不仅大大提高了生产效率，而且减少了环境的污染。
Description
技术领域
本发明是有关于催化剂、制备方法及其应用，特别是有关磁分离核-壳结构负载型钨复合催化剂、制备方法及其应用于喹诺酮类化合物合成的制备方法。
背景技术
喹诺酮类抗菌药是临床使用最广的抗感染药之一，由于喹诺酮类药物具有抗菌谱广、抗菌活性强、给药方便、不良反应小、与其他抗生素无交叉耐药性等优点而成为临床联合用药的首选，市场需求量大。
近年来研究发现，喹诺酮类药物在抗疟、抗艾滋病、抗肿瘤等多种疾病上有新的疗效，喹诺酮类化合物对原核II型拓扑异构酶、促旋酶和DNA拓扑异构酶IV也具有较好的活性，其活性谱和应用范围正在不断拓展。
然而，喹诺酮类药物主环的合成基本上都要经过三步反应才能得到其关键中间体，进而去进行水解和取代反应得到喹诺酮类药物，存在着合成步骤长、操作繁琐、三废量大和成本较高等缺陷。因此，寻找新的合成技术、探索新的催化剂制备方法，是目前研究工作的重点。式(Ⅰ)为喹诺酮分子结构。
发明内容
本发明的目的之一是提供一种磁分离核-壳结构负载型钨复合催化剂的制备方法，其制得的磁分离核-壳结构负载型钨复合催化剂用于合成喹诺酮类化合物时，降低生产成本，减少三废，提高产品质量。
为此，本发明采用的技术方案为：一种核-壳结构负载型钨复合催化剂的制备方法，其包含如下步骤：
步骤1)，在铁化合物水溶液中加入还原剂和碱，加温至50-80℃并搅拌，得到Fe3O4胶体；
步骤2)，在适量的分散溶剂中加入步骤1)得到的Fe3O4胶体、正硅酸乙酯和水解催化剂，反应4-8小时，得到SiO2/Fe3O4复合纳米粒子；
步骤3)，在偏钨酸铵水溶液中加入步骤2)得到的SiO2/Fe3O4复合纳米粒子，搅拌8-14小时，于90-150℃下干燥得第一固体，该第一固体经450-650℃焙烧1-6小时，得到磁分离核-壳结构负载型钨复合催化剂WO3/SiO2/Fe3O4；
上述铁化合物：正硅酸乙酯：偏钨酸铵的摩尔数比＝1:1-10:0.1-1；
其中，所述的铁化合物为FeCl3、FeCl3·6H2O或三乙酰丙酮铁；所述的还原剂为Na2SO3、抗坏血酸或水合肼；所述的碱为氨水、氢氧化钠或醋酸钠。
作为上述技术方案的优选，所述的铁化合物为FeCl3。
作为上述技术方案的优选，所述的还原剂为Na2SO3。
作为上述技术方案的优选，所述的碱为氨水。
作为上述技术方案的优选，步骤1)加温后，加入作为表面活性剂的聚乙烯吡咯烷酮，持续搅拌，之后离心并用水洗涤，最后分散再去除水得到Fe3O4胶体。
作为上述技术方案的优选，步骤2)中，所述的分散溶剂为乙醇，所述的水解催化剂为氨水。
作为上述技术方案的优选，步骤3)中，所述的第一固体先经研磨过120目标准筛后再经450-650℃焙烧1-6小时。
本发明的另一目的是提供上述制备方法得到的磁分离核-壳结构负载型钨复合催化剂WO3/SiO2/Fe3O4。
本发明的又一个目的是提供上述磁分离核-壳结构负载型钨复合催化剂WO3/SiO2/Fe3O4在合成喹诺酮类化合物中的应用，反应步骤如下：
步骤1)，搅拌混合甲酰基乙酸乙酯钠盐、非极性有机溶剂和WO3/SiO2/Fe3O4催化剂，通入胺类化合物，加入2，4-二氯-5-氟苯甲酰氯，反应0.5-3小时；
步骤2)，接着步骤1)，滴加伯胺同时通入CO2，控制反应压力为1-5个大气压，反应0.5-3小时；
步骤3)，接着步骤2)，加入碱金属氢氧化物和非极性有机溶剂，搅拌升温至100℃，保温半小时，过滤回收催化剂，加压回收非极性有机溶剂；
步骤4)，接着步骤3)，加适量水，升温至100℃，滴加盐酸调节酸碱度控制pH值范围在4.8-6.5，待晶体析出后，离心、烘干得喹诺酮类化合物；
其中，所述的非极性有机溶剂为甲苯、二甲苯或前两者的混合物，所述的胺类化合物为二甲胺、二乙胺或二环己胺，所述的伯胺为环丙胺或S-丙二醇胺，所述的碱金属氢氧化物为氢氧化钠、氢氧化锂或氢氧化钾。
本发明喹诺酮类药物关键中间体的合成方法，以甲酰基乙酸乙酯盐和环丙胺等为主要起始原料，在新型磁分离核-壳负载型钨复合催化剂WO3/SiO2/Fe3O4催化下，与多卤代芳酰氯“一锅法”制备得喹诺酮主环化合物。
作为上述技术方案的优选，所述的非极性有机溶剂为甲苯，所述的胺类化合物为二甲胺，所述的伯胺为环丙胺，所述的碱金属氢氧化物为氢氧化钠。
喹诺酮类化合物的制备流程如下：
本发明具有的优点是：本发明制备了磁分离核-壳负载型钨复合催化剂WO3/SiO2/Fe3O4，利用其催化合喹诺酮类化合物，并通过磁分离方式回收催化剂。与传统使用强碱催化剂相比，C-N偶联硫效率明显提高，反应时间缩短，工艺成本明显降低。同时，提供了一种高效、催化剂可磁分离回收并循环利用的喹诺酮类化合物制备方法，本发明制备之催化剂能在喹诺酮类化合物的制备中重复利用，催化剂仍保有原来活性没有失活现象，不仅大大提高了生产效率，而且减少了环境的污染。与传统工艺相比，本发明喹诺酮类化合物的制备方法具有操作简单，生产效率高，强碱用量少，生产成本低等优点，是一种高效、经济、环保的生产工艺。
附图说明
图1为本发明磁分离核-壳负载型钨复合催化剂WO3/SiO2/Fe3O4的结构示意图；
图2为本发明实施例5的核-壳催化剂的投射电镜(TEM)图；
从图2中可以看出制备的催化剂具有包裹均匀、粒径小、团聚少等特点，有助于高效催化环合反应。
具体实施方式
下面结合实施例对本发明作进一步说明，但本发明的保护范围并不限于此。
本发明磁分离核-壳负载型钨复合催化剂WO3/SiO2/Fe3O4的制备流程如下：
首先运用部分还原-共沉淀法制备Fe3O4纳米粒子，然后通过溶胶凝胶法制备得到SiO2/Fe3O4复合纳米粒子，最后通过浸渍焙烧法制备得到磁分离核-壳负载型钨复合催化剂WO3/SiO2/Fe3O4。
实施例1-12
制备磁分离核-壳负载型钨复合催化剂WO3/SiO2/Fe3O4的制备方法，依次按以下步骤进行：
1)、制备Fe3O4纳米粒子
运用部分还原-共沉淀法制备Fe3O4纳米粒子。在室温下将16.3g FeCl3加入到250mL烧瓶中，并用水溶解。在氮气保护下，缓缓加入还原剂Na2SO3溶液(含2.7g Na2SO3)并搅拌，10分钟后迅速加入40.8mL质量分数为28％的氨水，即可观察到黑色粒子生成。将恒温水浴温度升到70℃，并加入2mL油胺作为表面活性剂，持续搅拌6小时，之后将产物离心并用去离子水洗涤数次，最后分散再去除离子水，得到稳定的Fe3O4胶体。
2)、制备SiO2/Fe3O4复合纳米粒子
在常温下，往100mL烧杯中依次加入10mL EtOH，1.16g Fe3O4胶体，8mL去离子水和12.5g TEOS(正硅酸乙酯)，持续搅拌30分钟，然后加入42mL质量分数为28％的氨水催化TEOS(正硅酸乙酯)水解、缩合，密封反应6小时后将产物离心分离，分别经EtOH，去离子水清洗数次，得到SiO2/Fe3O4复合纳米粒子。
3)、制备磁分离Core-Shell负载型钨复合催化剂WO3/SiO2/Fe3O4
在常温下，往50mL烧杯中依次加入17.7g偏钨酸铵，10mL去离子水，并持续搅拌至完全溶解后，加入步骤2)制备所得的SiO2/Fe3O4复合纳米粒子，并持续强烈搅拌12小时。之后置于在烘箱中于110℃下干燥12小时。接着用研钵研磨，并过120目标准筛。将得到的固体粉末置于马弗炉中，于550℃下焙烧3小时，得到磁分离Core-Shell负载型钨复合催化剂WO3/SiO2/Fe3O4，备用。
实施例1-12除了使用的偏钨酸铵：TEOS：FeCl3摩尔数比列于表1，其他实施步骤和实施条件均相同。
表1：实施例1-12使用的偏钨酸铵：TEOS：FeCl3摩尔数比
实施例a1-a12：喹诺酮类化合物的制备方法
向反应釜内投入24.6g甲酰基乙酸乙酯钠盐，100mL甲苯和4g WO3/SiO2/Fe3O4催化剂，在搅拌下通入8.7g二甲胺，加入10g 2，4-二氯-5-氟苯甲酰氯，保温反应1小时，在50℃下滴加环丙胺，同时通入CO2，控制反应压力为1.5-2个大气压。反应1小时后，在反应液中加入12g片碱和200mL甲苯，搅拌升温至100℃，保温半小时，过滤回收催化剂，加压回收甲苯至干。加适量水，升温至100℃，体系澄清后滴加盐酸调节酸碱度，待晶体析出后，离心、烘干得式(Ⅴ)的有机胺化物。
实施例a1-a12使用催化剂WO3/SiO2/Fe3O4来源的列于表2，其他实施步骤和实施条件均相同。
表2.实施例a1-a12各实施例条件及收率
以实施例a12为例，催化剂实施例12在这个条件下可以产率79.5％，另外在此催化条件下，催化剂实施例12磁分离核-壳负载型钨复合催化剂WO3/SiO2/Fe3O回收、循环使用第5次，仍保有优异的式(Ⅴ)的有机胺化物收率，催化效果没有明显下降，具体见下表3：
表3.磁分离核-壳负载型钨复合催化剂WO3/SiO2/Fe3O4的循环套用实验
以上列举的仅是本发明的若干个具体实施例。显然，本发明不限于以上实施例，还可以有许多变形。本领域的普通技术人员能从本发明公开的内容直接导出或联想到的所有变形，均应认为是本发明的保护范围。
Claims (10)
1.一种核-壳结构负载型钨复合催化剂的制备方法，其包含如下步骤：
步骤1)，在铁化合物水溶液中加入还原剂和碱，加温至50-80℃并搅拌，得到Fe3O4胶体；
步骤2)，在适量的分散溶剂中加入步骤1)得到的Fe3O4胶体、正硅酸乙酯和水解催化剂，反应4-8小时，得到SiO2/Fe3O4复合纳米粒子；
步骤3)，在偏钨酸铵水溶液中加入步骤2)得到的SiO2/Fe3O4复合纳米粒子，搅拌8-14小时，于90-150℃下干燥得第一固体，该第一固体经450-650℃焙烧1-6小时，得到磁分离核-壳结构负载型钨复合催化剂WO3/SiO2/Fe3O4；
上述铁化合物：正硅酸乙酯：偏钨酸铵的摩尔数比＝1:1-10:0.1-1；
其中，所述的铁化合物为FeCl3、FeCl3·6H2O或三乙酰丙酮铁；所述的还原剂为Na2SO3、抗坏血酸或水合肼；所述的碱为氨水、氢氧化钠或醋酸钠。
2.根据权利要求1的制备方法，其特征在于，所述的铁化合物为FeCl3。
3.根据权利要求1的制备方法，其特征在于，所述的还原剂为Na2SO3。
4.根据权利要求1的制备方法，其特征在于，所述的碱为氨水。
5.根据权利要求1的制备方法，其特征在于，步骤1)加温后，加入作为表面活性剂的聚乙烯吡咯烷酮，持续搅拌，之后离心并用水洗涤，最后分散再去除水得到Fe3O4胶体。
6.根据权利要求1的制备方法，其特征在于，步骤2)中，所述的分散溶剂为乙醇，所述的水解催化剂为氨水。
7.根据权利要求1的制备方法，其特征在于，步骤3)中，所述的第一固体先经研磨过120目标准筛后再经450-650℃焙烧1-6小时。
8.由权利要求1-7任一项制备方法制备的磁分离核-壳结构负载型钨复合催化剂WO3/SiO2/Fe3O4。
9.权利要求8所述磁分离核-壳结构负载型钨复合催化剂WO3/SiO2/Fe3O4在合成喹诺酮类化合物中的应用，反应步骤如下：
步骤1)，搅拌混合甲酰基乙酸乙酯钠盐、非极性有机溶剂和WO3/SiO2/Fe3O4催化剂，通入胺类化合物，加入2，4-二氯-5-氟苯甲酰氯，反应0.5-3小时；
步骤2)，接着步骤1)，滴加伯胺同时通入CO2，控制反应压力为1-5个大气压，反应0.5-3小时；
步骤3)，接着步骤2)，加入碱金属氢氧化物和非极性有机溶剂，搅拌升温至100℃，保温半小时，过滤回收催化剂，加压回收非极性有机溶剂；
步骤4)，接着步骤3)，加适量水，升温至100℃，滴加盐酸调节酸碱度控制pH值范围在4.8-6.5，待晶体析出后，离心、烘干得喹诺酮类化合物；
其中，所述的非极性有机溶剂为甲苯、二甲苯或前两者的混合物，所述的胺类化合物为二甲胺、二乙胺或二环己胺，所述的伯胺为环丙胺或S-丙二醇胺，所述的碱金属氢氧化物为氢氧化钠、氢氧化锂或氢氧化钾。
10.根据权利要求9所述的应用，其特征在于，所述的非极性有机溶剂为甲苯，所述的胺类化合物为二甲胺，所述的伯胺为环丙胺，所述的碱金属氢氧化物为氢氧化钠。
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710540001.9A CN107469828B (zh) | 2017-07-05 | 2017-07-05 | 一种核-壳结构负载型钨复合催化剂及其制备方法和应用 |
| US15/848,821 US10500568B2 (en) | 2017-07-05 | 2017-12-20 | Core-shell structure supported tungsten composite catalyst and preparation method and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710540001.9A CN107469828B (zh) | 2017-07-05 | 2017-07-05 | 一种核-壳结构负载型钨复合催化剂及其制备方法和应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107469828A true CN107469828A (zh) | 2017-12-15 |
| CN107469828B CN107469828B (zh) | 2018-12-11 |
Family
ID=60595388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710540001.9A Active CN107469828B (zh) | 2017-07-05 | 2017-07-05 | 一种核-壳结构负载型钨复合催化剂及其制备方法和应用 |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US10500568B2 (zh) |
| CN (1) | CN107469828B (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108325553A (zh) * | 2018-02-02 | 2018-07-27 | 河南科技大学 | 一种具有包覆磁芯结构的氮化钛微球催化剂的制备方法 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111956810A (zh) * | 2020-08-03 | 2020-11-20 | 南京大学 | 一种双模血管造影剂的制备方法和应用 |
| CN113755884A (zh) * | 2021-08-19 | 2021-12-07 | 武汉工程大学 | 一种可复用纳米核-壳结构模拟酶材料及其制备方法 |
| CN115178275B (zh) * | 2022-06-09 | 2024-02-27 | 中国科学院青岛生物能源与过程研究所 | 一种核壳结构MXOy@mSiO2-SO3H型催化剂及其制备和催化玉米芯制备糠醛的方法 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008221113A (ja) * | 2007-03-12 | 2008-09-25 | Osaka Univ | 浮遊性光触媒及びそれを用いた汚染水処理方法 |
| CN105056926A (zh) * | 2015-07-24 | 2015-11-18 | 武汉纺织大学 | 一种新型TiO2/WO3包覆的磁性纳米复合粒子及其制备方法和用途 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020658B (zh) * | 2007-02-14 | 2010-12-15 | 杭州师范学院 | 喹诺酮主环化合物的合成方法 |
| CN101838238B (zh) * | 2010-04-30 | 2012-05-23 | 杭州广林生物医药有限公司 | 一种喹诺酮主环化合物的合成方法 |
| CN107175131A (zh) * | 2017-06-02 | 2017-09-19 | 扬州大学 | 阳离子修饰法制备磁性杂多酸盐催化剂的方法 |
-
2017
- 2017-07-05 CN CN201710540001.9A patent/CN107469828B/zh active Active
- 2017-12-20 US US15/848,821 patent/US10500568B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008221113A (ja) * | 2007-03-12 | 2008-09-25 | Osaka Univ | 浮遊性光触媒及びそれを用いた汚染水処理方法 |
| CN105056926A (zh) * | 2015-07-24 | 2015-11-18 | 武汉纺织大学 | 一种新型TiO2/WO3包覆的磁性纳米复合粒子及其制备方法和用途 |
Non-Patent Citations (3)
| Title |
|---|
| ANAL K. JHA等: "Synthesis of nanomaterials using expired medicines: an eco-friendly option", 《NANOTECHNOLOGY DEVELOPMENT》 * |
| XIANJUN TAN等: "Facile Synthesis of Bimodal Mesoporous Fe3O4@SiO2 Composite for Efficient Removal of Methylene Blue", 《EUR. J. INORG. CHEM.》 * |
| 包淑娟等: "磁载WO3-TiO2/SiO2/Fe3O4复合光催化剂的制备及其光催化活性", 《催化学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108325553A (zh) * | 2018-02-02 | 2018-07-27 | 河南科技大学 | 一种具有包覆磁芯结构的氮化钛微球催化剂的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107469828B (zh) | 2018-12-11 |
| US10500568B2 (en) | 2019-12-10 |
| US20190009255A1 (en) | 2019-01-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107469828A (zh) | 一种核‑壳结构负载型钨复合催化剂及其制备方法和应用 | |
| Safari et al. | Magnetic Fe3O4 nanoparticles as efficient and reusable catalyst for the green synthesis of 2-amino-4 H-chromene in aqueous media | |
| Bhuyan et al. | ZnO nanoparticles embedded in SBA-15 as an efficient heterogeneous catalyst for the synthesis of dihydropyrimidinones via Biginelli condensation reaction | |
| CN103193223A (zh) | 具有空心结构石墨化碳球的可控合成方法 | |
| CN102239003A (zh) | 用于在存在氯化氢和/或氯情况下进行的氧化反应的催化剂、其生产方法及其用途 | |
| WO2016065950A1 (zh) | 一种碱式氯化锌的制备方法 | |
| Elhampour et al. | Nano‐Fe3O4@ TiO2/Cu2O Core‐shell Composite: A Convenient Magnetic Separable Catalyst for A3 and KA2 Coupling | |
| CN104926798B (zh) | 阿法替尼中间体的高纯度制备方法 | |
| CN104826623B (zh) | 一种氧化铋光催化剂及其制备方法和应用 | |
| CN107235506A (zh) | 一种纳米氧化锌异质结构的制备方法 | |
| CN103241763A (zh) | 金/金属氧化物核壳结构纳米材料的制备方法 | |
| CN113318768A (zh) | 一种复合光催化剂及其制备方法 | |
| CN109535083B (zh) | 2，4，5-三氨基-6-羟基嘧啶硫酸盐及叶酸的制备方法 | |
| CN108889342B (zh) | 用于丁腈橡胶非均相加氢催化剂的再生及回收再利用方法 | |
| CN114011454B (zh) | 用于氯化氢氧化制氯的催化剂及其制备方法 | |
| CN104910901A (zh) | 一种制备ZnO/SiO2纳米复合材料的方法 | |
| CN106348336B (zh) | 一种纳米氧化锌及其制备方法 | |
| CN112645900B (zh) | 促进剂dcbs的合成方法 | |
| CN109225294A (zh) | 一种绿色催化合成安息香的方法 | |
| CN108273525A (zh) | 一种磁性纳米固体酸催化制备化工中间体的方法 | |
| CN109589998B (zh) | 一种新型ZnO/Se/SiO2复合材料的制备方法及其在制备苯酞中应用 | |
| CN107138147B (zh) | 以介孔二氧化硅为硬模板制备高比表面二氧化锡催化剂的方法 | |
| CN113800528A (zh) | 一种以石英砂尾矿为原料制备功能化介孔纳米SiO2材料的方法及其应用 | |
| CN109261174A (zh) | 一种BiOCl微米环及制备方法 | |
| CN104860344A (zh) | 球形碳酸锶的制备方法 |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |