CN114849694A - 一种基于金属负载氧化钨氢化硝基芳烃的催化剂及其制备方法和应用 - Google Patents
一种基于金属负载氧化钨氢化硝基芳烃的催化剂及其制备方法和应用 Download PDFInfo
- Publication number
- CN114849694A CN114849694A CN202210636583.1A CN202210636583A CN114849694A CN 114849694 A CN114849694 A CN 114849694A CN 202210636583 A CN202210636583 A CN 202210636583A CN 114849694 A CN114849694 A CN 114849694A
- Authority
- CN
- China
- Prior art keywords
- tungsten oxide
- metal
- catalyst
- nitroarene
- hydrogenated
- 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 61
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 38
- 239000002184 metal Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 12
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims abstract description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 23
- 238000011068 loading method Methods 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical group [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 3
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 3
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims 2
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 claims 1
- 239000010937 tungsten Substances 0.000 claims 1
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000005470 impregnation Methods 0.000 abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 18
- 230000009467 reduction Effects 0.000 description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000010948 rhodium Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000002082 metal nanoparticle Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910013633 m-SiO Inorganic materials 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- CPJSUEIXXCENMM-UHFFFAOYSA-N phenacetin Chemical compound CCOC1=CC=C(NC(C)=O)C=C1 CPJSUEIXXCENMM-UHFFFAOYSA-N 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005695 dehalogenation 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
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PPLNRTPNYCWODC-UHFFFAOYSA-N n-(4-chlorophenyl)-2-hydroxy-9h-carbazole-3-carboxamide Chemical compound OC1=CC=2NC3=CC=CC=C3C=2C=C1C(=O)NC1=CC=C(Cl)C=C1 PPLNRTPNYCWODC-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229960003893 phenacetin Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Images
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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明提供了一种基于金属负载氧化钨氢化硝基芳烃的催化剂及其制备方法和应用,其制备方法,包括以下步骤:向仲钨酸铵加入去离子水搅拌,然后滴加稀硝酸溶液,冷凝回流,然后将反应后的沉淀转移到水热釜中,恒温加热,冷却至室温,再依次经离心、过滤、去离子水洗涤和烘干过夜,得氧化钨粉末;在室温下将氧化钨粉末超声搅拌分散在乙醇中,滴加贵金属盐水溶液,搅拌后加热,再在混合气氛中煅烧,得催化剂。本发明还包括上述方法制得的催化剂及其应用。本发明通过浸渍法制备得到的催化剂能够在温和条件下催化对氯硝基苯加氢制备对氯苯胺,有效解决了现有技术中催化剂催化活性低、选择性低和结构不稳定等问题。
Description
技术领域
本发明属于热催化技术领域,具体涉及一种基于金属负载氧化钨氢化硝基芳烃的催化剂及其制备方法和应用。
背景技术
对氯苯胺(p-CAN)是一种重要的化工中间体,在染料、医学医药、农药以及其他精细化学品等领域应用极为广泛,同时是偶氮染料、色酚AS-LB的中间体,也是合成利民宁、非那西丁等药物的中间体。对氯苯胺一般是由对氯硝基苯(p-CNB)还原制得,常用的还原方法有:铁粉还原法、电化学还原法、水合肼还原法、硫化碱还原法、催化加氢还原法等。其中催化加氢还原法相对于其他工艺具有反应温度低、副反应少、污染小、产能大、生产成本低的优势,同时也满足了环境友好以及绿色化工的时代主题,进而成为生产p-CNB应用最为广泛的制备工艺。卤代硝基苯加氢制备卤代苯胺大多使用贵金属催化剂,如Pt、Pd、Ir、Ru、Rh,其原因是贵金属相比于其他过渡金属具有活化氢能力强、产物选择性高等优点。最近,有相关报道Yang等(J Nanosci Nanotechnl,2017,17:3744-3750)合成了一系列不同钯/金比例的AuPd/m-SiO2纳米粒子,AuPd/m-SiO2催化反应中P-CAN的选择性为42%、苯胺(AN)的选择性为55%,而金/钯摩尔比为1时,AN的选择性高达94.7%,表明双金属催化剂的选择性是可调的。Zhang等(J Catal,2021,400:173-183)制备了Pd/C催化剂,在p-CNB加氢反应中,当Pd粒径大于5nm时,催化剂在300min后才有明显反应;当Pd粒径为0.9nm、p-CNB转化率70%时,p-CAN的选择性保持在80%;随着转化率提高至100%,p-CAN的选择性降至75%,而AN的选择性从9%增加至25%。在p-CNB加氢制备p-CAN的反应中,经常会出现脱卤副反应,导致产品收率和纯度的降低,并且在化学反应过程中产生的高强度卤酸还会对实验设备和溶剂等造成污染和腐蚀。综上所述,开发一种活性高、稳定性好、可循环使用且绿色环保的新型催化剂用于对氯硝基苯加氢具有重要意义。
发明内容
针对现有技术中存在的上述问题,本发明提供一种基于金属负载氧化钨氢化硝基芳烃的催化剂及其制备方法和应用,通过浸渍法制备得到具有贵金属负载量低、活性高、选择性高、结构稳定且易于回收利用等优点的催化剂,能够在温和条件下催化对氯硝基苯加氢制备对氯苯胺,有效解决了现有技术中催化剂催化活性低、选择性低和结构不稳定等问题。
为实现上述目的,本发明解决其技术问题所采用的技术方案是:提供一种基于金属负载氧化钨氢化硝基芳烃的催化剂的制备方法,包括以下步骤:
(1)向仲钨酸铵加入去离子水搅拌,然后滴加稀硝酸溶液,冷凝回流,然后将反应后的沉淀转移到聚四氟乙烯内衬的不锈钢水热釜中,恒温加热,冷却至室温,再依次经离心、过滤、去离子水洗涤和烘干过夜,得氧化钨粉末;
(2)在室温下将步骤(1)所得氧化钨粉末超声搅拌分散在乙醇中,滴加贵金属盐水溶液,搅拌1h后加热至乙醇完全蒸干,再在5%H2/Ar混合气氛中煅烧,得基于金属负载氧化钨氢化硝基芳烃的催化剂。
进一步,步骤(1)中,仲钨酸铵和去离子水摩尔体积比为2-3:40mmol/mL,仲钨酸铵和稀硝酸溶液摩尔体积比为2-3:10mmol/mL,稀硝酸溶液浓度为2-3mol/L。
进一步,仲钨酸铵和去离子水摩尔体积比为2.5:40mmol/mL,仲钨酸铵和稀硝酸溶液摩尔体积比为2.5:10mmol/mL,稀硝酸溶液浓度为2.5mol/L。
进一步,步骤(1)中,在80-90℃温度下冷凝回流1h。
进一步,步骤(1)中,在85℃温度下冷凝回流1h。
进一步,步骤(1)中,在150-170℃温度下恒温加热12h。
进一步,步骤(1)中,在60℃温度下恒温加热12h。
进一步,步骤(2)中,氧化钨粉末和乙醇质量体积比为150-250:30mg/mL,氧化钨粉末和贵金属盐水溶液质量体积比为150-250:20mg/μL,贵金属盐水溶液浓度为4-6mg/mL。
进一步,氧化钨粉末和乙醇质量体积比为200:30mg/mL,氧化钨粉末和贵金属盐水溶液质量体积比为200:20mg/μL,贵金属盐水溶液浓度为5mg/mL。
进一步,步骤(2)中,贵金属盐为硝酸钯、硝酸铂、氯化铱或氯化铑。
进一步,步骤(2)中,在5%H2/Ar混合气氛中,以5℃/min速率升温至300-400℃煅烧2h。
进一步,步骤(2)中,在5%H2/Ar混合气氛中,以5℃/min速率升温至350℃煅烧2h。
进一步,所得基于金属负载氧化钨氢化硝基芳烃的催化剂中,贵金属负载量为0.05wt%。
上述基于金属负载氧化钨氢化硝基芳烃的催化剂的制备方法制得的基于金属负载氧化钨氢化硝基芳烃的催化剂。
上述基于金属负载氧化钨氢化硝基芳烃的催化剂在催化对氯硝基苯加氢反应中的应用。
上述基于金属负载氧化钨氢化硝基芳烃的催化剂催化对氯硝基苯加氢反应时,包括以下步骤:
(1)将5mg基于金属负载氧化钨氢化硝基芳烃的催化剂均匀分散在2mL有机溶剂中,然后加入反应物对氯硝基苯,反应体系中溶剂为异丙醇;
(2)将步骤(1)所得混合物转移到500mL高压釜中,用1MPa H2洗气3次后在1MPa H2气氛中进行反应,磁力搅拌,温度控制在60℃进行。
综上所述,本发明具备以下优点:
1、本发明通过浸渍法制备得到具有贵金属负载量低、活性高、选择性高、结构稳定且易于回收利用等优点的催化剂,能够在温和条件下催化对氯硝基苯加氢制备对氯苯胺,有效解决了现有技术中催化剂催化活性低、选择性低和结构不稳定等问题。
2、贵金属与WO3-NR之间存在强电子-金属-载体相互作用(SMSI)以及氧化钨表面存在大量的氧缺陷,利用这些氧缺陷锚定贵金属后,会造成金属与载体间的电子转移,电子从载体转移至贵金属上,并且随着电子的转移,使贵金属纳米粒子的电子密度增强;因此,催化剂对反应物官能团的吸附产生逆转,改变了催化剂的活性。且贵金属电子结构进行了调制,使Pt/WO3-NR能在室温下进行有效的氢活化;同时,贵金属的高电子密度有利于氢化产物的脱附,从而有效地避免了过度氢化。
3、本发明采用浸渍法制备催化剂,简单高效,保证贵金属离子完全负载到氧化钨载体上;同时具有表面氧缺陷的棒状氧化钨材料制备方法简单,原料价格低廉且环保,适合大规模生产。
4、本发明所得催化剂在催化对氯硝基苯加氢方面,选用氢气作为氢离子来源,符合绿色无污染、环境友好的发展理念,在工业上用用广泛。催化反应条件温和,对氯硝基苯转化率高,产物选择性高,催化剂的利用率高,稳定性好,具有重要的工业用用价值。
附图说明
图1为实施例1所得基于金属负载氧化钨氢化硝基芳烃的催化剂(Pd/WO3-NR-0.05)的扫描电镜图(a)和透射电镜图(b);
图2为贵金属Pd不同负载量2wt.%(a)、1wt.%(b)、0.5wt.%(c)、0.2wt.%(d)的Pd/WO3-NR催化剂对4-氯硝基苯加氢催化效果图;
图3为最优金属负载量的0.05wt.%(a)和0.01wt.%(b)Pd/WO3-NR-0.05催化剂对4-氯硝基苯加氢催化效果图;
图4为不同金属Pt、Pd、Rh、Ir相同负载量0.05wt.%所得催化剂对4-氯硝基苯加氢催化效果图(a)和不同金属TOF值图(b)。
具体实施方式
实施例1
一种基于金属负载氧化钨氢化硝基芳烃的催化剂,其制备方法包括以下步骤:
(1)向2.5mmol仲钨酸铵加入40mL去离子水搅拌,然后滴加10mL 2.5mol/L稀硝酸溶液,在85℃温度下冷凝回流1h,然后将反应后的沉淀转移到聚四氟乙烯内衬的不锈钢水热釜中,在160℃温度下恒温加热12h,冷却至室温,再依次经离心、过滤、去离子水洗涤和60℃烘干过夜,得氧化钨粉末;
(2)在室温下将步骤(1)所得200mg氧化钨粉末超声搅拌分散在30mL乙醇中,滴加20μL 5mg/mL硝酸钯水溶液,搅拌1h后加热至乙醇完全蒸干,再在5%H2/Ar混合气氛中,以5℃/min速率升温至50℃煅烧2h,得基于金属负载氧化钨氢化硝基芳烃的催化剂。
实施例2
一种基于金属负载氧化钨氢化硝基芳烃的催化剂,其制备方法包括以下步骤:
(1)向2.5mmol仲钨酸铵加入40mL去离子水搅拌,然后滴加10mL 2.5mol/L稀硝酸溶液,在85℃温度下冷凝回流1h,然后将反应后的沉淀转移到聚四氟乙烯内衬的不锈钢水热釜中,在160℃温度下恒温加热12h,冷却至室温,再依次经离心、过滤、去离子水洗涤和60℃烘干过夜,得氧化钨粉末;
(2)在室温下将步骤(1)所得200mg氧化钨粉末超声搅拌分散在30mL乙醇中,滴加20μL 5mg/mL硝酸铂水溶液,搅拌1h后加热至乙醇完全蒸干,再在5%H2/Ar混合气氛中,以5℃/min速率升温至50℃煅烧2h,得基于金属负载氧化钨氢化硝基芳烃的催化剂。
实施例3
一种基于金属负载氧化钨氢化硝基芳烃的催化剂,其制备方法包括以下步骤:
(1)向2.5mmol仲钨酸铵加入40mL去离子水搅拌,然后滴加10mL 2.5mol/L稀硝酸溶液,在85℃温度下冷凝回流1h,然后将反应后的沉淀转移到聚四氟乙烯内衬的不锈钢水热釜中,在160℃温度下恒温加热12h,冷却至室温,再依次经离心、过滤、去离子水洗涤和60℃烘干过夜,得氧化钨粉末;
(2)在室温下将步骤(1)所得200mg氧化钨粉末超声搅拌分散在30mL乙醇中,滴加20μL 5mg/mL氯化铱水溶液,搅拌1h后加热至乙醇完全蒸干,再在5%H2/Ar混合气氛中,以5℃/min速率升温至50℃煅烧2h,得基于金属负载氧化钨氢化硝基芳烃的催化剂。
实验例1
获取实施例1所得基于金属负载氧化钨氢化硝基芳烃的催化剂(Pd/WO3-NR-0.05)的扫描电镜图和透射电镜图,如图1所示。
由图1a可知,氧化钨载体的棒状结构以及载体表面均匀分布金属纳米粒子;由图1b可知,可以看出明显的氧化钨晶格条纹,说明载体氧化钨结晶性良好。
实验例2
基于金属负载氧化钨氢化硝基芳烃的催化剂催化对氯硝基苯加氢反应时,包括以下步骤:
(1)将5mg实施例1所得基于金属负载氧化钨氢化硝基芳烃的催化剂(Pd/WO3-NR-0.05)均匀分散在2mL有机溶剂中,然后加入反应物4-氯硝基苯,反应体系中溶剂为异丙醇;
(2)将步骤(1)所得混合物转移到500mL高压釜中,用1MPa H2洗气3次后在1MPa H2气氛中进行反应,磁力搅拌,温度控制在60℃进行。
(3)用气相色谱仪定量分析液相组成并记录对氯硝基苯转化率和对氯苯胺选择性,其结果如图2-3所示。
由图2可知,当金属Pd负载量从2wt.%减小到0.5wt.%,主产物4-氯苯胺的选择性从82.24%增长到93.51%,但是4-氯硝基苯转化率逐渐降低。因此当金属负载量偏大时,载体上的金属纳米粒子粒径较大,容易形成较大的团簇影响了活性位点数量与底物的转化率。小的金属负载量使得金属纳米粒子粒径较小且分散均匀,暴露的活性位点较多;且金属粒子粒径变化时,对底物或者产物的吸附能力也会发生变化。所以,随着金属负载量的减小,金属团簇对于主产物的吸附能力变弱,从而抑制了4-氯硝基苯的过度氢化,提高了4-氯硝基苯的选择性。
由图3可知,当金属负载量为0.05wt.%和0.01wt.%时,4-氯苯胺的选择性进一步提高至96.40%和97.82%。然而,Pd/WO3-NR-0.01催化剂金属负载量较低导致大幅度活性降低,影响了4-氯硝基苯的转化率。
再采用不用的贵金属(Pt、Rh、Ir)通过实施例1所示的方法制备出M/WO3-NR-0.05催化剂,并用于4-氯硝基苯加氢制备4-氯苯胺,并获得催化剂对4-氯硝基苯加氢催化效果图和不同金属TOF值图,如图4所示。其中,图4a中,从左到右依次为Pt/WO3-0.05、Pd/WO3-0.05、Rh/WO3-0.05和Ir/WO3-0.05;图4b中,从左到右依次为Pd/WO3-0.05、Pt/WO3-0.05、Rh/WO3-0.05和Ir/WO3-0.05。
由图4可知,当金属负载量相同时,三种催化剂对4-氯苯胺都具有较高的选择性(>99.5%),其中,在相同时间内Pt/WO3-NR-0.05催化剂转化率最高,TOF值更是达到1.22×105(h-1)。Ir/WO3-NR-0.05催化剂转化率最低,推测其原因是金属Ir对氢气活化能力弱,影响了氢溢流的速率,从而导致催化剂活性低。
虽然结合附图对本发明的具体实施方式进行了详细地描述,但不应理解为对本专利的保护范围的限定。在权利要求书所描述的范围内,本领域技术人员不经创造性劳动即可作出的各种修改和变形仍属本专利的保护范围。
Claims (10)
1.一种基于金属负载氧化钨氢化硝基芳烃的催化剂的制备方法,其特征在于,包括以下步骤:
(1)向仲钨酸铵加入去离子水搅拌,然后滴加稀硝酸溶液,冷凝回流,然后将反应后的沉淀转移到聚四氟乙烯内衬的不锈钢水热釜中,恒温加热,冷却至室温,再依次经离心、过滤、去离子水洗涤和烘干过夜,得氧化钨粉末;
(2)在室温下将步骤(1)所得氧化钨粉末超声搅拌分散在乙醇中,滴加贵金属盐水溶液,搅拌1h后加热至乙醇完全蒸干,再在5%H2/Ar混合气氛中煅烧,得基于金属负载氧化钨氢化硝基芳烃的催化剂。
2.如权利要求1所述的基于金属负载氧化钨氢化硝基芳烃的催化剂的制备方法,其特征在于,步骤(1)中,仲钨酸铵和去离子水摩尔体积比为2-3:40mmol/mL,仲钨酸铵和稀硝酸溶液摩尔体积比为2-3:10mmol/mL,稀硝酸溶液浓度为2-3mol/L。
3.如权利要求1所述的基于金属负载氧化钨氢化硝基芳烃的催化剂的制备方法,其特征在于,步骤(1)中,在80-90℃温度下冷凝回流1h。
4.如权利要求1所述的基于金属负载氧化钨氢化硝基芳烃的催化剂的制备方法,其特征在于,步骤(1)中,在150-170℃温度下恒温加热12h。
5.如权利要求1所述的基于金属负载氧化钨氢化硝基芳烃的催化剂的制备方法,其特征在于,步骤(2)中,氧化钨粉末和乙醇质量体积比为150-250:30mg/mL,氧化钨粉末和贵金属盐水溶液质量体积比为150-250:20mg/μL,贵金属盐水溶液浓度为4-6mg/mL。
6.如权利要求1所述的基于金属负载氧化钨氢化硝基芳烃的催化剂的制备方法,其特征在于,步骤(2)中,贵金属盐为硝酸钯、硝酸铂、氯化铱或氯化铑。
7.如权利要求1所述的基于金属负载氧化钨氢化硝基芳烃的催化剂的制备方法,其特征在于,步骤(2)中,在5%H2/Ar混合气氛中,以5℃/min速率升温至300-400℃煅烧2h。
8.如权利要求1所述的基于金属负载氧化钨氢化硝基芳烃的催化剂的制备方法,其特征在于,基于金属负载氧化钨氢化硝基芳烃的催化剂中,贵金属负载量为0.05wt%。
9.权利要求1-8任一项所述的基于金属负载氧化钨氢化硝基芳烃的催化剂的制备方法制得的基于金属负载氧化钨氢化硝基芳烃的催化剂。
10.权利要求9所述的基于金属负载氧化钨氢化硝基芳烃的催化剂在催化对氯硝基苯加氢反应中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210636583.1A CN114849694B (zh) | 2022-06-07 | 2022-06-07 | 一种基于金属负载氧化钨氢化硝基芳烃的催化剂及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210636583.1A CN114849694B (zh) | 2022-06-07 | 2022-06-07 | 一种基于金属负载氧化钨氢化硝基芳烃的催化剂及其制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114849694A true CN114849694A (zh) | 2022-08-05 |
CN114849694B CN114849694B (zh) | 2023-07-21 |
Family
ID=82624526
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210636583.1A Active CN114849694B (zh) | 2022-06-07 | 2022-06-07 | 一种基于金属负载氧化钨氢化硝基芳烃的催化剂及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114849694B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116586077A (zh) * | 2023-06-19 | 2023-08-15 | 福大紫金氢能科技股份有限公司 | 一种整体式催化剂及其制备方法与应用 |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2627708A1 (en) * | 2007-03-30 | 2008-09-30 | National University Corporation Hokkaido University | Tungsten oxide photocatalyst |
CN103030179A (zh) * | 2013-01-08 | 2013-04-10 | 江苏大学 | 水热法制备三氧化钨纳米片及其应用 |
CN103357408A (zh) * | 2012-03-31 | 2013-10-23 | 浙江工业大学 | WC/CNT、WC/CNT/Pt复合材料及其制备方法和应用 |
CN104874389A (zh) * | 2015-05-05 | 2015-09-02 | 上海应用技术学院 | 一种具有氧空位介孔WO3-x可见光催化剂及其制备方法和应用 |
CN106006742A (zh) * | 2016-05-20 | 2016-10-12 | 江钨高技术开发应用有限公司 | 通过仲钨酸铵水热转化制备焦绿石型氧化钨的方法 |
CN106824188A (zh) * | 2017-01-12 | 2017-06-13 | 东南大学 | 一种负载过渡金属的钨基催化剂的制备及应用方法 |
CN106825611A (zh) * | 2016-12-30 | 2017-06-13 | 河南科技大学 | 一种掺杂钨合金粉末及其制备方法 |
CN108031485A (zh) * | 2017-12-14 | 2018-05-15 | 湘潭大学 | 一种对氯硝基苯选择性加氢制备对氯苯胺的方法 |
CN109876801A (zh) * | 2019-03-26 | 2019-06-14 | 中国科学院金属研究所 | 纳米碳负载高分散铂催化剂及其制备方法和在芳香族硝基化合物加氢反应中的应用 |
CN111111658A (zh) * | 2020-01-20 | 2020-05-08 | 山东大学 | 一种超高催化活性的单原子Pt负载氧化钨单层纳米片催化剂及其制备方法与应用 |
-
2022
- 2022-06-07 CN CN202210636583.1A patent/CN114849694B/zh active Active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2627708A1 (en) * | 2007-03-30 | 2008-09-30 | National University Corporation Hokkaido University | Tungsten oxide photocatalyst |
CN103357408A (zh) * | 2012-03-31 | 2013-10-23 | 浙江工业大学 | WC/CNT、WC/CNT/Pt复合材料及其制备方法和应用 |
CN103030179A (zh) * | 2013-01-08 | 2013-04-10 | 江苏大学 | 水热法制备三氧化钨纳米片及其应用 |
CN104874389A (zh) * | 2015-05-05 | 2015-09-02 | 上海应用技术学院 | 一种具有氧空位介孔WO3-x可见光催化剂及其制备方法和应用 |
CN106006742A (zh) * | 2016-05-20 | 2016-10-12 | 江钨高技术开发应用有限公司 | 通过仲钨酸铵水热转化制备焦绿石型氧化钨的方法 |
CN106825611A (zh) * | 2016-12-30 | 2017-06-13 | 河南科技大学 | 一种掺杂钨合金粉末及其制备方法 |
CN106824188A (zh) * | 2017-01-12 | 2017-06-13 | 东南大学 | 一种负载过渡金属的钨基催化剂的制备及应用方法 |
CN108031485A (zh) * | 2017-12-14 | 2018-05-15 | 湘潭大学 | 一种对氯硝基苯选择性加氢制备对氯苯胺的方法 |
CN109876801A (zh) * | 2019-03-26 | 2019-06-14 | 中国科学院金属研究所 | 纳米碳负载高分散铂催化剂及其制备方法和在芳香族硝基化合物加氢反应中的应用 |
CN111111658A (zh) * | 2020-01-20 | 2020-05-08 | 山东大学 | 一种超高催化活性的单原子Pt负载氧化钨单层纳米片催化剂及其制备方法与应用 |
Non-Patent Citations (10)
Title |
---|
HONGBO YU ET AL.: ""Enhanced strong metal–support interactions between Pt and WO3–x nanowires for the selective hydrogenation of p-chloronitrobenzene"", 《NEW JOURNAL OF CHEMISTRY》 * |
HONGBO YU ET AL.: ""Enhanced strong metal–support interactions between Pt and WO3–x nanowires for the selective hydrogenation of p-chloronitrobenzene"", 《NEW JOURNAL OF CHEMISTRY》, vol. 45, no. 38, 25 August 2021 (2021-08-25), pages 2 * |
YU SUN ET AL.: "Hydrogen Spillover-Accelerated Selective Hydrogenation on WO3 with ppm-Level Pd", 《ACS APPL. MATER. INTERFACES》, vol. 15, no. 16, pages 20474 - 20482 * |
刘新梅等: ""负载型铱催化剂催化氯代硝基苯选择性加氢"", 《石油化工》 * |
刘新梅等: ""负载型铱催化剂催化氯代硝基苯选择性加氢"", 《石油化工》, vol. 36, no. 10, 15 October 2007 (2007-10-15) * |
张瀚等: ""Pd/CNTs 金属纳米催化剂的制备及其催化对氯硝基苯加氢性能"", 《化学试剂》 * |
张瀚等: ""Pd/CNTs 金属纳米催化剂的制备及其催化对氯硝基苯加氢性能"", 《化学试剂》, vol. 39, no. 11, 15 November 2017 (2017-11-15) * |
王富等: ""活性炭预处理对Rh/C催化剂活性的影响"", 《贵金属》 * |
王富等: ""活性炭预处理对Rh/C催化剂活性的影响"", 《贵金属》, vol. 32, no. 3, 15 August 2011 (2011-08-15), pages 1 * |
王擎乾: "新型碳材料负载贵金属纳米粒子的制备及其催化性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 5 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116586077A (zh) * | 2023-06-19 | 2023-08-15 | 福大紫金氢能科技股份有限公司 | 一种整体式催化剂及其制备方法与应用 |
CN116586077B (zh) * | 2023-06-19 | 2023-11-17 | 福大紫金氢能科技股份有限公司 | 一种整体式催化剂及其制备方法与应用 |
Also Published As
Publication number | Publication date |
---|---|
CN114849694B (zh) | 2023-07-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN113019414B (zh) | 一种加氢催化剂及其制备方法和应用 | |
EP3092072B1 (en) | A process for vapor-phase methanol carbonylation to methyl formate | |
CN112916033A (zh) | 一种碳氮掺杂二氧化硅负载Co催化剂及其制备方法和应用 | |
EP3187264B1 (en) | Hydrogenation catalyst and manufacturing method therefor | |
EP2418017B1 (en) | Catalyst comprising palladium on crystalline zinc chromite and its use in acetone self-condensation | |
CN113797947B (zh) | C改性铂基催化剂在催化卤代硝基苯加氢反应的应用 | |
CN110639567B (zh) | 一种碳负载磷化二钌纳米团簇双功能催化剂及其制备方法和应用 | |
CN108290139A (zh) | 卤代硝基芳香族化合物的催化氢化方法 | |
CN111266119A (zh) | 一种α,β-不饱和醛酮选择性加氢铂基催化剂及其制备方法和用途 | |
CN114849694B (zh) | 一种基于金属负载氧化钨氢化硝基芳烃的催化剂及其制备方法和应用 | |
Chen et al. | Atomically dispersed metal catalysts on nanodiamond and its derivatives: synthesis and catalytic application | |
US20200070138A1 (en) | Composite Catalyst, Method for Manufacturing Composite Catalyst and Application Thereof | |
CN111389398A (zh) | 分级中空二氧化硅限域氧化亚铜可见光催化剂的制备方法 | |
EP4025340B1 (en) | Materials comprising carbon-embedded nickel nanoparticles, processes for their manufacture, and use as heterogeneous catalysts | |
Xiaonan et al. | Solvent free continuous hydrogenation of chloronitrobenzene over Pt/amide group grafted AC catalysts | |
CN109876821B (zh) | 一种对硝基苯酚加氢用铜锰双金属催化剂的制备方法 | |
CN111686726B (zh) | 碳基贵金属催化剂的制备方法及应用 | |
CN112871159A (zh) | 一种Ru纳米催化剂及其制备方法与应用 | |
CN113842904B (zh) | 一种具有石墨烯基底的钨单原子催化剂、其制备方法和用途 | |
WO2024078481A1 (zh) | 双催化中心的非均相催化剂及其制备方法和应用 | |
CN117899856A (zh) | 一种用于腈加氢制备伯胺的催化剂及其制备方法 | |
CN115414932B (zh) | 一种富电子钯基双金属催化剂及制备方法与应用 | |
CN112108139B (zh) | 一种硝基苯液相加氢合成苯胺用催化剂及其制备方法 | |
CN115532319A (zh) | 一种氢化催化剂及其制备方法和应用 | |
Li et al. | Cu@ SiO2 catalyst with high copper dispersion for chemoselective hydrogenation of p-chloronitrobenzene |
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 |