CN108212172B - 一种吡啶类化合物加氢的催化剂及其应用 - Google Patents
一种吡啶类化合物加氢的催化剂及其应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 150000003222 pyridines Chemical class 0.000 title claims abstract description 28
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 106
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000013162 Cocos nucifera Nutrition 0.000 claims abstract description 16
- 244000060011 Cocos nucifera Species 0.000 claims abstract description 16
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 pyridine compound Chemical class 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 238000001802 infusion Methods 0.000 claims description 8
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 6
- HWWYDZCSSYKIAD-UHFFFAOYSA-N 3,5-dimethylpyridine Chemical compound CC1=CN=CC(C)=C1 HWWYDZCSSYKIAD-UHFFFAOYSA-N 0.000 claims description 6
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 6
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 150000003304 ruthenium compounds Chemical class 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- IWTFOFMTUOBLHG-UHFFFAOYSA-N 2-methoxypyridine Chemical compound COC1=CC=CC=N1 IWTFOFMTUOBLHG-UHFFFAOYSA-N 0.000 claims description 3
- NSNVGCNCRLAWOJ-UHFFFAOYSA-N [N+](=O)([O-])[O-].N(=O)[Ru+2].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].N(=O)[Ru+2].[N+](=O)([O-])[O-] NSNVGCNCRLAWOJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 1
- 239000001569 carbon dioxide Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 8
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 150000003053 piperidines Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- YLPJWCDYYXQCIP-UHFFFAOYSA-N nitroso nitrate;ruthenium Chemical compound [Ru].[O-][N+](=O)ON=O YLPJWCDYYXQCIP-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- SDGKUVSVPIIUCF-UHFFFAOYSA-N 2,6-dimethylpiperidine Chemical compound CC1CCCC(C)N1 SDGKUVSVPIIUCF-UHFFFAOYSA-N 0.000 description 1
- NNWUEBIEOFQMSS-UHFFFAOYSA-N 2-Methylpiperidine Chemical compound CC1CCCCN1 NNWUEBIEOFQMSS-UHFFFAOYSA-N 0.000 description 1
- DNYWGUIJLFDIPD-UHFFFAOYSA-N 2-methoxypiperidine Chemical compound COC1CCCCN1 DNYWGUIJLFDIPD-UHFFFAOYSA-N 0.000 description 1
- IDWRJRPUIXRFRX-UHFFFAOYSA-N 3,5-dimethylpiperidine Chemical compound CC1CNCC(C)C1 IDWRJRPUIXRFRX-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229940035676 analgesics Drugs 0.000 description 1
- 239000000730 antalgic agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003589 local anesthetic agent Substances 0.000 description 1
- 229960005015 local anesthetics Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 238000000926 separation method Methods 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
- 239000000080 wetting agent Substances 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/02—Preparation by ring-closure or hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
- C07D211/10—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms
- C07D211/12—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms with only hydrogen atoms attached to the ring nitrogen atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members 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
- C07D211/40—Oxygen atoms
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- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种吡啶类化合物加氢的催化剂及其应用,该催化剂中Ru含量为1wt%~3wt%,Li、Sm、Fe中至少一种的总含量为0.5wt%~1wt%,TiO2的含量为1wt%~5wt%,其余为椰壳活性炭;本发明是在微型固定床反应器的反应管中原位完成催化剂的制备和吡啶类化合物的加氢,该催化剂能够有效的催化吡啶类化合物加氢制备相应的哌啶类化合物,催化剂活性好,加氢效率高,在最佳体积空速下原料的转化率和产物的选择性均可达到100%。
Description
技术领域
本发明属于催化剂技术领域,具体涉及一种吡啶类化合物加氢的催化剂。
背景技术
哌啶类化合物是一种非常有用的有机化合物中间体,主要用于合成医药、农药、制造杀菌剂、局部麻醉药、润湿剂、止痛药以及橡胶硫化促进剂、环氧树脂的固化剂等方面,其衍生物也广泛存在于天然产物和药物中间体中。哌啶类化合物主要是通过相应的吡啶类化合物在催化剂作用下经过催化加氢得到的。目前工业上仍然采用传统的釜式反应工艺催化吡啶类化合物加氢生产相应的哌啶类化合物,催化剂种类较多,但仍然存在生产工艺复杂、成本高、原料转化率和产品纯度不高的缺陷。
中国专利201710141448.9公开了一种镍基非晶态催化剂及其制备方法和催化吡啶类化合物加氢反应的应用,催化剂是负载型的镍催化剂,包含过渡金属助剂,活性组分是镍,采用固定床反应装置,连续化程度高,操作方便,能够有效地催化吡啶类化合物加氢,但在转化率和选择性方面还是有不足之处,增加了后续分离纯化的成本。催化剂上吡啶类化合物的转化率接近100%,对于哌啶类化合物的选择性为96%以上。
中国专利201310320791.1描述了一种吡啶类化合物加氢用催化剂的制备方法及应用,催化剂载体为活性炭或氧化铝,活性组分为金属钌,载体经过一系列的改性和处理,使得金属钌颗粒高度分散在载体表面,从而获得了较高的吡啶类活化加氢的催化活性。采用的是传统的釜式反应工艺,部分实验中还添加了溶剂,不利于生产效率的提高和成本的控制,对一些吡啶类化合物的加氢的转化率和选择性也不能达到100%。钌基催化剂由于活性较高,在空气中容易部分氧化,可能会对催化反应中钌催化剂的活性造成影响。此外,制备钌基催化剂使用的前驱体通常是三氯化钌,金属钌负载到催化剂上的同时也引入了氯元素,氯元素较难去除,在某些反应中会对钌催化剂的活性造成影响。
发明内容
本发明所要解决的技术问题在于针对上述现有技术的不足,提供一种催化剂活性好、吡啶类化合物加氢效率高的催化剂,并为该催化剂提供一种新用途。
解决上述技术问题所采用催化剂中Ru含量为1wt%~3wt%,Li、Sm、Fe中至少一种的总含量为0.5wt%~1wt%,TiO2的含量为1wt%~5wt%,其余为椰壳活性炭;该催化剂由下述方法制备得到:
1、将椰壳活性炭与纳米钛溶胶混合均匀,室温浸泡8~24小时后,120~180℃干燥至恒重,记为TiO2-C。
2、将上述TiO2-C装填到微型固定床反应器的反应管中,室温下连续通入氮气,以1~5℃/分钟的速率将反应管温度升至200~500℃,保持2小时后降至室温。
3、保持氮气的通入,将活性组分的水溶液通过输液泵输送到反应管中,与TiO2-C接触进行吸附,多余的溶液从反应管下端流出,再经过输液泵输送重新进入到反应管中,经过不断的循环,活性组分水溶液中的金属离子逐渐吸附到TiO2-C上,直到反应管下端流出的溶液中Ru含量低于0.05wt%为止或流出的溶液为无色透明为止,在吸附的过程中将反应管的温度升至45~85℃,吸附结束后,将反应管温度升至100~150℃,保持3~9小时后,降至室温。
4、将氮气切换为氢气,继续通入反应管中,以1~5℃/分钟的速率将反应管的温度升高到200~300℃,还原2~4小时后降至室温,得到催化剂。
上述的活性组分的水溶液是含钌化合物和助剂的去离子水溶液,其中钌化合物为亚硝酰基硝酸合钌或三氯化钌,助剂为硝酸锂、硝酸钐、九水合硝酸铁中至少一种。
上述催化剂中优选Ru含量为2.5wt%~3wt%,Li、Sm、Fe中至少一种的总含量为0.5wt%,TiO2的含量为1wt%,其余为椰壳活性炭。
上述椰壳活性炭的颗粒尺寸为1~1.5mm,比表面积为1000~1500m2/g。
上述的钌化合物为三氯化钌时,为了避免氯离子对催化剂性能的影响,需要进一步向得到的催化剂上滴加去离子水洗涤,直到洗出的水用硝酸银溶液测不出氯离子为止。
本发明催化剂在吡啶类化合物加氢中的用途,具体使用方法为:在催化剂制备结束后,向反应管中持续通入氢气,然后将反应压力调节到0.5~2MPa,温度设定到140~160℃,用高压液相泵将吡啶类化合物连续输送到反应管中,氢气与吡啶类化合物的摩尔比5~9:1,吡啶类化合物的体积空速为0.2~1.1h-1。
上述的吡啶类化合物为吡啶、2-甲基吡啶、3-甲基吡啶、4-甲基吡啶、3,5-二甲基吡啶、2,6-二甲基吡啶、2-甲氧基吡啶中的任意一种。
本发明在微型固定床反应器的反应管中原位完成催化剂的制备和吡啶类化合物的加氢,该催化剂能够有效的催化吡啶类化合物加氢制备相应的哌啶类化合物,催化剂活性好,加氢效率高,较优条件下原料的转化率和产物的选择性均可达到100%,原料的体积空速最大为1.1h-1。与现有技术相比,本发明具有以下优点:
1、本发明催化剂制备操作简单,原料易得,整个制备过程中催化剂没有接触空气,避免还原后的贵金属Ru部分氧化,造成活性组分的损失。采用原位循环浸渍液的方式将贵金属Ru和助剂均匀分散到催化剂载体上,使催化剂能够更好的发挥催化活性。
2、本发明催化剂载体为椰壳活性炭,结构稳定,孔道丰富,比表面积大于1000m2/g,吸附能力强,颗粒强度高。添加纳米钛溶胶后能够增加TiO2的表面性质,加强了TiO2与C的相互作用,为制备高性能Ru基吡啶类化合物加氢催化剂提供了条件。
3、本发明催化剂活性较高,能够在相对温和的条件下催化吡啶、2-甲基吡啶、3-甲基吡啶、4-甲基吡啶、3,5-二甲基吡啶、2,6-二甲基吡啶和2-甲氧基吡啶加氢生成哌啶、2-甲基哌啶、3-甲基哌啶、3-甲基哌啶、3,5-二甲基哌啶、2,6-二甲基哌啶和2-甲氧基哌啶。
4、本发明催化反应中不添加任何溶剂,在最佳体积空速下原料的转化率和产物的选择性均可达到100%。
具体实施方式
下面结合实施例对本发明进一步详细说明,但本发明的保护范围不仅限于这些实施例。
实施例1
1、将4g粒径为5~20nm纳米二氧化钛粉体均匀分散于150mL去离子水中,形成纳米钛溶胶,向该纳米钛溶胶中加入93.0g椰壳活性炭(颗粒尺寸为1mm,比表面积为1500m2/g),搅拌均匀,室温浸泡20h后,置于150℃的烘箱中干燥至恒重,取出,记为TiO2-C。
2、将上述TiO2-C装填到微型固定床反应器的反应管中,室温下连续通入氮气,以2℃/min的速率将反应管温度升至300℃,保持2h后降至室温。
3、将6.27g亚硝酰基硝酸合钌、4.97g硝酸锂和3.62g九水合硝酸铁溶解于350mL去离子水中,得到活性组分水溶液;保持氮气的通入,将活性组分水溶液通过输液泵输送到反应管中并逐滴滴加到TiO2-C上,进行吸附,多余的溶液从反应管下端流出,再经过输液泵输送重新进入到反应管中,经过不断的循环,直到反应管下端流出的溶液中Ru含量低于0.05wt%时停止滴加(滴加过程至少持续3h以上),在滴加的过程中将反应管的温度升至60℃,滴加结束后,继续将反应管温度升至120℃,保持5h后,降至室温。
4、将氮气切换为氢气,继续通入反应管中,以1℃/min的速率将反应管的温度升高到200℃,保持2.5h后降至室温,得到催化剂,该催化剂中Ru含量为2wt%,Li和Fe的总含量为1wt%,TiO2的含量为4wt%,其余为活性炭。
实施例2
1、将3g粒径为5~20nm纳米二氧化钛粉体均匀分散于150mL去离子水中,形成纳米钛溶胶,向该纳米钛溶胶中加入93.2g椰壳活性炭(颗粒尺寸为1mm,比表面积为1400m2/g),搅拌均匀,室温浸泡20h后,置于160℃的烘箱中干燥至恒重,取出,记为TiO2-C。
2、将上述TiO2-C装填到微型固定床反应器的反应管中,室温下连续通入氮气,以2℃/min的速率将反应管温度升至400℃,保持2h后降至室温。
3、将9.41g亚硝酰基硝酸合钌、2.98g硝酸锂和3.62g九水合硝酸铁溶解于400mL去离子水中,得到活性组分水溶液;保持氮气的通入,将活性组分水溶液通过输液泵输送到反应管中并逐滴滴加到TiO2-C上,进行吸附,多余的溶液从反应管下端流出,再经过输液泵输送重新进入到反应管中,经过不断的循环,直到反应管下端流出的溶液中Ru含量低于0.05wt%时停止滴加(滴加过程至少持续3h以上),在滴加的过程中将反应管的温度升至55℃,滴加结束后,继续将反应管温度升至130℃,保持9h后,降至室温。
4、将氮气切换为氢气,继续通入反应管中,以1℃/min的速率将反应管的温度升高到220℃,保持3.5h后降至室温,得到催化剂,该催化剂中Ru含量为3wt%,Li和Fe的总含量为0.8wt%,TiO2的含量为3wt%,其余为活性炭。
实施例3
1、将5g粒径为5~20nm纳米二氧化钛粉体均匀分散于150mL去离子水中,形成纳米钛溶胶,向该纳米钛溶胶中加入92.6g椰壳活性炭(颗粒尺寸为1mm,比表面积为1100m2/g),搅拌均匀,室温浸泡20h后,置于180℃的烘箱中干燥至恒重,取出,记为TiO2-C。
2、将上述TiO2-C装填到微型固定床反应器的反应管中,室温下连续通入氮气,以2℃/min的速率将反应管温度升至200℃,保持2h后降至室温。
3、将4.71g亚硝酰基硝酸合钌、2.98g硝酸锂、0.67g硝酸钐和2.17g九水合硝酸铁溶解于300mL去离子水中,得到活性组分水溶液;保持氮气的通入,将活性组分水溶液通过输液泵输送到反应管中并逐滴滴加到TiO2-C上,进行吸附,多余的溶液从反应管下端流出,再经过输液泵输送重新进入到反应管中,经过不断的循环,直到反应管下端流出的溶液中Ru含量低于0.05wt%时停止滴加(滴加过程至少持续3h以上),在滴加的过程中将反应管的温度升至45℃,滴加结束后,继续将反应管温度升至150℃,保持6h后,降至室温。
4、将氮气切换为氢气,继续通入反应管中,以1℃/min的速率将反应管的温度升高到260℃,保持3h后降至室温,得到催化剂,该催化剂中Ru含量为1.5wt%,Li、Sm和Fe的总含量为0.9wt%,TiO2的含量为5wt%,其余为活性炭。
实施例4
1、将2g粒径为5~20nm纳米二氧化钛粉体均匀分散于150mL去离子水中,形成纳米钛溶胶,向该纳米钛溶胶中加入96.3g椰壳活性炭(颗粒尺寸为1.5mm,比表面积为1000m2/g),搅拌均匀,室温浸泡20h后,置于170℃的烘箱中干燥至恒重,取出,记为TiO2-C。
2、将上述TiO2-C装填到微型固定床反应器的反应管中,室温下连续通入氮气,以2℃/min的速率将反应管温度升至300℃,保持2h后降至室温。
3、将2.7g三氯化钌和1.57g硝酸钐溶解于300mL去离子水中,得到活性组分水溶液;保持氮气的通入,将活性组分水溶液通过输液泵输送到反应管中并逐滴滴加到TiO2-C上,进行吸附,多余的溶液从反应管下端流出,再经过输液泵输送重新进入到反应管中,经过不断的循环,直到反应管下端流出的溶液中Ru含量低于0.05wt%时停止滴加(滴加过程至少持续3h以上),在滴加的过程中将反应管的温度升至45℃,滴加结束后,继续将反应管温度升至150℃,保持6h后,降至室温。
4、将氮气切换为氢气,继续通入反应管中,以1℃/min的速率将反应管的温度升高到260℃,保持3h后降至室温,滴加去离子水洗涤,直到洗出的水用硝酸银溶液测不出氯离子为止,得到催化剂,该催化剂中Ru含量为1wt%,Sm的含量为0.7wt%,TiO2的含量为2wt%,其余为活性炭。
实施例5
1、将1g粒径为5~20nm纳米二氧化钛粉体均匀分散于150mL去离子水中,形成纳米钛溶胶,向该纳米钛溶胶中加入96.0g椰壳活性炭(颗粒尺寸为1.5mm,比表面积为1000m2/g),搅拌均匀,室温浸泡20h后,置于130℃的烘箱中干燥至恒重,取出,记为TiO2-C。
2、将上述TiO2-C装填到微型固定床反应器的反应管中,室温下连续通入氮气,以3℃/min的速率将反应管温度升至500℃,保持2h后降至室温。
3、将6.76g三氯化钌和4.97g硝酸锂溶解于400mL去离子水中,得到活性组分水溶液;保持氮气的通入,将活性组分水溶液通过输液泵输送到反应管中并逐滴滴加到TiO2-C上,进行吸附,多余的溶液从反应管下端流出,再经过输液泵输送重新进入到反应管中,经过不断的循环,直到反应管下端流出的溶液中Ru含量低于0.05wt%时停止滴加(滴加过程至少持续3h以上),在滴加的过程中将反应管的温度升至85℃,滴加结束后,继续将反应管温度升至100℃,保持3h后,降至室温。
4、将氮气切换为氢气,继续通入反应管中,以1℃/min的速率将反应管的温度升高到300℃,保持3h后降至室温,滴加去离子水洗涤,直到洗出的水用硝酸银溶液测不出氯离子为止,得到催化剂,该催化剂中Ru含量为2.5wt%,Li的含量为0.5wt%,TiO2的含量为1wt%,其余为活性炭。
实施例6
1、将2.4g粒径为5~20nm纳米二氧化钛粉体均匀分散于150mL去离子水中,形成纳米钛溶胶,向该纳米钛溶胶中加入95.0g椰壳活性炭(颗粒尺寸为1.5mm,比表面积为1000m2/g),搅拌均匀,室温浸泡20h后,置于120℃的烘箱中干燥至恒重,取出,记为TiO2-C。
2、将上述TiO2-C装填到微型固定床反应器的反应管中,室温下连续通入氮气,以2℃/min的速率将反应管温度升至350℃,保持2h后降至室温。
3、将5.41g三氯化钌和4.34g硝酸铁溶解于350mL去离子水中,得到活性组分水溶液;保持氮气的通入,将活性组分水溶液通过输液泵输送到反应管中并逐滴滴加到TiO2-C上,进行吸附,多余的溶液从反应管下端流出,再经过输液泵输送重新进入到反应管中,经过不断的循环,直到反应管下端流出的溶液中Ru含量低于0.05wt%时停止滴加(滴加过程至少持续3h以上),在滴加的过程中将反应管的温度升至75℃,滴加结束后,继续将反应管温度升至130℃,保持4h后,降至室温。
4、将氮气切换为氢气,继续通入反应管中,以1℃/min的速率将反应管的温度升高到280℃,保持2h后降至室温,滴加去离子水洗涤,直到洗出的水用硝酸银溶液测不出氯离子为止,得到催化剂,该催化剂中Ru含量为2wt%,Fe的含量为0.6wt%,TiO2的含量为2.4wt%,其余为活性炭。
实施例7
实施例1~6制备的催化剂在吡啶类化合物加氢中的用途,具体使用方法为:在催化剂制备结束后,向反应管中持续通入氢气,然后将反应压力调节到1.8Pa,温度设定到140℃,用高压液相泵将表1所示的吡啶类化合物连续输送到反应管中,开始反应,氢气与吡啶类化合物的摩尔比3:1。各种催化剂对应的吡啶类化合物催化加氢的结果如表1所示。
表1
注:表中数据都是连续运行72小时的结果。
由表1可以看出,本发明催化剂能够有效地催化不同吡啶类化合物加氢生成相应的哌啶类化合物,催化剂活性较好,在最佳体积空速下能够将吡啶类化合物完全加氢到对应的哌啶类化合物,比如实施例1~6的催化剂,在体积空速为1.1h-1下,连续运行72小时,吡啶的转化率和哌啶的选择性都是100%。
Claims (6)
1.一种吡啶类化合物加氢的催化剂,其特征在于:所述催化剂中Ru含量为1wt%~3wt%,Li、Sm、Fe中至少一种的总含量为0.5wt%~1wt%,TiO2的含量为1wt%~5wt%,其余为椰壳活性炭;该催化剂由下述方法制备得到:
(1)将椰壳活性炭与纳米钛溶胶混合均匀,室温浸泡8~24小时后,120~180℃干燥至恒重,记为TiO2-C;
(2)将上述TiO2-C装填到微型固定床反应器的反应管中,室温下连续通入氮气,以1~5℃/分钟的速率将反应管温度升至200~500℃,保持2小时后降至室温;
(3)保持氮气的通入,将活性组分的水溶液通过输液泵输送到反应管中,与TiO2-C接触进行吸附,多余的溶液从反应管下端流出,再经过输液泵输送重新进入到反应管中,经过不断的循环,活性组分水溶液中的金属离子逐渐吸附到TiO2-C上,直到反应管下端流出的溶液中Ru含量低于0.05wt%为止或流出的溶液为无色透明为止,在吸附的过程中将反应管的温度升至45~85℃,吸附结束后,将反应管温度升至100~150℃,保持3~9小时后,降至室温;
(4)将氮气切换为氢气,继续通入反应管中,以1~5℃/分钟的速率将反应管的温度升高到200~300℃,还原2~4小时后降至室温,得到催化剂;
上述的活性组分的水溶液是含钌化合物和助剂的去离子水溶液,其中钌化合物为亚硝酰基硝酸合钌或三氯化钌,助剂为硝酸锂、硝酸钐、九水合硝酸铁中至少一种。
2.根据权利要求1所述的吡啶类化合物加氢的催化剂,其特征在于:所述催化剂中Ru含量为2.5wt%~3wt%,Li、Sm、Fe中至少一种的总含量为0.5wt%,TiO2的含量为1wt%,其余为椰壳活性炭。
3.根据权利要求1或2所述的吡啶类化合物加氢的催化剂,其特征在于:所述椰壳活性炭的颗粒尺寸为1~1.5mm,比表面积为1000~1500m2/g。
4.根据权利要求3所述的吡啶类化合物加氢的催化剂,其特征在于:所述的钌化合物为三氯化钌时,向得到的催化剂上滴加去离子水洗涤,直到洗出的水用硝酸银溶液测不出氯离子为止。
5.权利要求1所述的催化剂在吡啶类化合物加氢中的用途,具体使用方法为:在催化剂制备结束后,向反应管中持续通入氢气,然后将反应压力调节到0.5~2MPa,温度设定到140~160℃,用高压液相泵将吡啶类化合物连续输送到反应管中,氢气与吡啶类化合物的摩尔比5~9:1,吡啶类化合物的体积空速为0.2~1.1h-1。
6.根据权利要求5所述的催化剂在吡啶类化合物加氢中的用途,其特征在于:所述的吡啶类化合物为吡啶、2-甲基吡啶、3-甲基吡啶、4-甲基吡啶、3,5-二甲基吡啶、2,6-二甲基吡啶、2-甲氧基吡啶中的任意一种。
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