CN108947934B - Preparation method of piperidine - Google Patents
Preparation method of piperidine Download PDFInfo
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- CN108947934B CN108947934B CN201810716050.8A CN201810716050A CN108947934B CN 108947934 B CN108947934 B CN 108947934B CN 201810716050 A CN201810716050 A CN 201810716050A CN 108947934 B CN108947934 B CN 108947934B
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- Prior art keywords
- oxide
- piperidine
- copper
- piperidone
- hydrogen
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- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VRJHQPZVIGNGMX-UHFFFAOYSA-N 4-piperidinone Chemical compound O=C1CCNCC1 VRJHQPZVIGNGMX-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 36
- 239000001257 hydrogen Substances 0.000 claims abstract description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 229910052802 copper Inorganic materials 0.000 claims abstract description 32
- 239000010949 copper Substances 0.000 claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000011049 filling Methods 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 10
- 239000005751 Copper oxide Substances 0.000 claims description 10
- 229910000431 copper oxide Inorganic materials 0.000 claims description 10
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 10
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 10
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 claims description 10
- 229910003446 platinum oxide Inorganic materials 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 8
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 8
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 30
- 238000000926 separation method Methods 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000010533 azeotropic distillation Methods 0.000 description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000005086 pumping Methods 0.000 description 8
- 239000002808 molecular sieve Substances 0.000 description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910000564 Raney nickel Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003204 osmotic effect Effects 0.000 description 2
- 238000005371 permeation separation Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910002787 Ru-Ni Inorganic materials 0.000 description 1
- 229910002793 Ru–Ni Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- RYGMFSIKBFXOCR-OIOBTWANSA-N copper-61 Chemical compound [61Cu] RYGMFSIKBFXOCR-OIOBTWANSA-N 0.000 description 1
- RYGMFSIKBFXOCR-BJUDXGSMSA-N copper-63 Chemical compound [63Cu] RYGMFSIKBFXOCR-BJUDXGSMSA-N 0.000 description 1
- RYGMFSIKBFXOCR-OUBTZVSYSA-N copper-65 Chemical compound [65Cu] RYGMFSIKBFXOCR-OUBTZVSYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000945 filler Substances 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
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000003589 local anesthetic agent Substances 0.000 description 1
- 229960005015 local anesthetics Drugs 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- 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
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- 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
- B01J23/8946—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
-
- 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
- B01J23/8953—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 zinc, cadmium or mercury
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention belongs to the technical field of compound preparation, and particularly relates to a preparation method of piperidine. The method takes 4-piperidone and hydrogen as raw materials and prepares piperidine by hydrogenation under the action of a copper-based catalyst. The method comprises the following steps: filling a copper-based catalyst into a hydrogenation reactor; gasifying 4-piperidone, mixing with hydrogen, adding the obtained mixture into a hydrogenation reactor through a metering pump, and reacting at the temperature of 180-280 ℃, the reaction pressure of 1.0-5.0 MPa and the liquid hourly space velocity of 0.1-1.0 h‑1Under the condition of (1), 4-piperidone and hydrogen react on a copper-based catalyst to generate piperidine. The method has the advantages of simple process, less three wastes, low investment, simple product separation, less byproducts, easy treatment, enrichment of the method for preparing the piperidine and certain industrial popularization value.
Description
Technical Field
The invention relates to the technical field of compound preparation, in particular to a preparation method of piperidine.
Background
Piperidine, also known as piperidine or azacyclo-cyclohexane, is widely used in the manufacture of local anesthetics, analgesics, bactericides, wetting agents, curing agents for epoxy resins, rubber vulcanization accelerators and the like, and derivatives thereof are widely present in natural products and pharmaceutical intermediates.
The traditional piperidine production method is mainly obtained by pyridine hydrogenation, and Chinese patent CN101723877A discloses a piperidine production method, which uses a supported nickel catalyst, wherein a carrier is silica-alumina, the pyridine conversion rate is 100%, the piperidine yield is above 95%, the reaction pressure is 4.0-10.0 MPa, and the reaction temperature is 140-220 ℃. Chinese patent CN105985300A discloses a continuous production method of piperidine, which comprises the steps of mixing pyridine raw materials with hydrogen on a hydrogenation catalyst to convert the mixture into piperidine products, wherein the active components of the hydrogenation catalyst are one, two or more of cobalt, nickel, palladium, platinum and ruthenium, the reaction temperature is 80-220 ℃, and the reaction pressure (absolute pressure) is 0.1-2.0 MPa. Li Ru et al introduced a method of electrochemical reduction to reduce pyridine to piperidine for production in "a piperidine clean production process conditions" (environmental pollution and prevention, 10/2004, vol. 26, vol. 5), which is tedious in process and relatively harsh in conditions. It has been reported that in the presence of noble metal catalysts such as Ru/C, Pd/C and Ru-Ni/C, pyridine can be catalytically added at 160 deg.C and 8.0MPa to prepare piperidine, the reaction conversion rate is close to 100%, and the noble metal catalyst involved in the method is expensive, and the catalyst life is not reported, so that it is not suitable to use (Chenshengzong, et al, piperidine catalytic synthesis process research, chemical reaction engineering and process, Vol.16, Vol.4, 12.12.2000, Chuanqiao Xiaomo, piperidine synthesis method, JP 63-275573,1988, 585-. The Raney nickel catalyst adopted in domestic factories has high activity, the yield of piperidine is about 88 percent, the price is lower than that of noble metals, but the Raney nickel has poor stability, is easy to self-ignite and inactivate, and is inconvenient to store and use.
In addition, the conventional process technology is characterized by using a high-pressure reaction kettle reactor and using a large amount of solvent, and the technology has obvious disadvantages: firstly, the reaction pressure is high, which undoubtedly increases the investment budget of the plant and degrades the safety performance of the plant; secondly, the used catalyst and liquid need to be separated by a matched project, the loss is large, especially the cost loss is large when a noble metal catalyst is used, and the used Raney nickel catalyst has a large safety risk.
Disclosure of Invention
In order to overcome the technical problems in the production of the conventional piperidine products, the invention provides a preparation method of piperidine, which provides a selection way for obtaining high-quality piperidine products and enriches the preparation method of piperidine. The process has the advantages of simple reaction steps, less three wastes, low investment, simple product separation, less byproducts, easy treatment and certain industrial popularization value.
The invention adopts the following technical scheme:
the invention provides a preparation method of piperidine, which takes 4-piperidone and hydrogen as raw materials, and prepares the piperidine by hydrogenation under the action of a hydrogenation catalyst, wherein the hydrogenation catalyst is a copper-based catalyst.
The main reaction formula for preparing piperidine by hydrogenation of 4-piperidone in the invention is as follows:
further, the preparation method comprises the following steps: placing a copper-based catalyst in a hydrogenation reactor; gasifying 4-piperidone, mixing with hydrogen, adding the obtained mixture into a hydrogenation reactor through a metering pump, and reacting at the temperature of 180-280 ℃, the reaction pressure of 1.0-5.0 MPa and the liquid hourly space velocity of 0.1-1.0 h-1Under the condition of (1), 4-piperidone and hydrogen react on a copper-based catalyst to generate piperidine.
The invention adopts an azeotropic distillation method to purify the obtained crude product. The piperidine obtained by azeotropic distillation can be subjected to molecular sieve separation, membrane separation or the combination of the two to obtain a piperidine product with higher quality.
Further, the molar ratio of the hydrogen to the 4-piperidone is (6-36): 1.
Furthermore, the copper-based catalyst comprises 25-50 wt% of copper oxide and 50-75 wt% of carrier. The copper-based catalyst is prepared by adopting a coprecipitation method.
Further, the carrier is composed of three parts, wherein one part of the carrier is composed of more than two of manganese oxide, zinc oxide, cerium oxide, nickel oxide, cobalt oxide or platinum oxide; the second part of the catalyst consists of one or two of alkali metal oxide or alkaline earth metal oxide; the three parts of the catalyst consist of two or three of silicon oxide, titanium oxide, aluminum oxide, zirconium oxide or activated carbon; wherein the alkali metal oxide or alkaline earth metal oxide is magnesium oxide, potassium oxide, calcium oxide, sodium oxide or barium oxide.
Compared with the prior art, the invention has the following beneficial effects:
1. the copper-based catalyst used in the invention has relatively more mesopores, and the loading capacity of the active component is relatively larger, so that the copper-based catalyst has relatively higher activity, high stability and high selectivity, the reaction steps are simple, and the reaction conditions are mild, thereby reducing the requirements on reaction equipment, reducing the potential safety hazard of production and having higher industrial popularization value.
2. In the process of preparing piperidine by hydrogenation under the action of a catalyst by taking 4-piperidone and hydrogen as raw materials, side reactions often occur due to the existence of intermediate products, and the selection of a proper catalyst is a main mode for inhibiting the occurrence of the side reactions.
3. The copper-based catalyst adopted by the invention does not adopt precious metals, has high catalytic activity, good stability and long service life, has little corrosion to equipment and little pollution to environment in industrial production, and reduces the production cost and environmental protection pressure of enterprises.
4. The preparation method of the invention needs less equipment, has simple industrial amplification, relatively low cost and less technical investment.
Detailed Description
The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
The hydrogenation reactor used in the examples is a tubular fixed bed reactor, the reactor is a pilot plant, the total length of the reactor is 860mm, the diameter of the reactor is 50mm, both ends of the tubular fixed bed reactor are sealed by inert filler ceramic balls, the height of the seal at each end is 10cm, and the filling height of the copper-based catalyst in the tubular fixed bed reactor accounts for 2/3 of the total height of the tubular fixed bed reactor.
The water content of the raw materials used in the examples was below 0.1 wt%.
The present invention will be further described with reference to the following specific examples.
Example 1
Gasifying 4-piperidone, mixing with hydrogen, pumping the mixture into a fixed bed reactor through a metering pump, wherein the molar ratio of the hydrogen to the 4-piperidone is 20:1, and the liquid hourly space velocity of the 4-piperidone is 0.5h-1Controlling the reaction temperature to be 200 ℃, controlling the reaction pressure to be 3MPa, converting 4-piperidone and hydrogen into a piperidine product on a copper-based catalyst, purifying the collected piperidine product by an azeotropic distillation method, and purifying the piperidine obtained by the azeotropic distillation through an HY type molecular sieve to obtain a high-quality piperidine product with the purity of 99.69 wt%. The overall yield of piperidine was 75.6%. The copper-based catalyst consists of 35 wt% of copper oxide and 65 wt% of carrier; wherein the vector consists of three parts: one part of which is composed of nickel oxide, platinum oxide, zinc oxide and cerium oxide, two parts of which are composed of calcium oxide, and three parts of which are composed of silicon oxide, titanium oxide and aluminum oxide.
Example 2
Gasifying 4-piperidone, mixing with hydrogen, pumping the mixture into a fixed bed reactor through a metering pump, wherein the molar ratio of the hydrogen to the 4-piperidone is 26:1, and the liquid hourly space velocity of the 4-piperidone is 1.0h-1Controlling the reaction temperature to be 280 ℃ and the reaction pressure to be 3.0MPa, converting 4-piperidone and hydrogen into a piperidine product on a copper-based catalyst, purifying the collected piperidine product by an azeotropic distillation method, and then carrying out osmotic separation on the piperidine obtained by azeotropic distillation through an HY type molecular sieve and a membrane to obtain a high-quality piperidine product with the weight of 99.73 percent. The overall yield of piperidine was 53.8%. The copper-based catalyst consists of 45 wt% of copper oxide and 55 wt% of carrier; wherein the vector consists of three parts: it is composed ofOne part of the composite consists of nickel oxide, platinum oxide, cobalt oxide and cerium oxide, the other two parts of the composite consist of magnesium oxide, and the other three parts of the composite consist of silicon oxide, activated carbon and aluminum oxide.
Example 3
Gasifying 4-piperidone, mixing with hydrogen, pumping the mixture into a fixed bed reactor through a metering pump, wherein the molar ratio of the hydrogen to the 4-piperidone is 18:1, and the liquid hourly space velocity of the 4-piperidone is 0.8h-1Controlling the reaction temperature to be 220 ℃, controlling the reaction pressure to be 5.0MPa, converting 4-piperidone and hydrogen into a piperidine product on a copper-based catalyst, purifying the collected piperidine product by an azeotropic distillation method, and then performing membrane permeation separation on the piperidine obtained by azeotropic distillation to obtain a high-quality piperidine product with the weight of 99.89 percent. The overall yield of piperidine was 66.9%. The copper-based catalyst consists of 30 wt% of copper oxide and 70 wt% of carrier; wherein the vector consists of three parts: one part of the composite material comprises nickel oxide, platinum oxide and cobalt oxide, the other two parts of the composite material comprise calcium oxide, and the other three parts of the composite material comprise silicon oxide and activated carbon.
Example 4
Gasifying 4-piperidone, mixing with hydrogen, pumping the mixture into a fixed bed reactor through a metering pump, wherein the molar ratio of the hydrogen to the 4-piperidone is 22:1, and the liquid hourly space velocity of the 4-piperidone is 0.6h-1Controlling the reaction temperature to be 230 ℃, controlling the reaction pressure to be 2.0MPa, converting 4-piperidone and hydrogen into a piperidine product on a copper-based catalyst, purifying the collected piperidine product by an azeotropic distillation method, and then performing membrane permeation separation on the piperidine obtained by azeotropic distillation to obtain a high-quality piperidine product with the weight of 99.86 percent. The overall yield of piperidine was 70.2%. The copper-based catalyst consisted of 43 wt% copper oxide and 57 wt% support; wherein the vector consists of three parts: one part of which is composed of nickel oxide, platinum oxide and cobalt oxide, two parts of which are composed of potassium oxide, and three parts of which are composed of alumina, activated carbon and zirconia.
Example 5
Gasifying 4-piperidone, mixing with hydrogen, pumping the mixture into a fixed bed reactor by a metering pump, wherein the molar ratio of the hydrogen to the 4-piperidoneThe liquid hourly space velocity of the mixture is 30:1, 4-piperidone-1Controlling the reaction temperature to be 250 ℃, controlling the reaction pressure to be 3.0MPa, converting 4-piperidone and hydrogen into a piperidine product on a copper-based catalyst, purifying the collected piperidine product by an azeotropic distillation method, and purifying the piperidine subjected to azeotropic distillation by an HY type molecular sieve to obtain a 99.59 wt% high-quality piperidine product. The overall yield of piperidine was 69.1%. The copper-based catalyst consists of 37 weight percent of copper oxide and 63 weight percent of carrier; wherein the vector consists of three parts: one part of which is composed of nickel oxide, platinum oxide, cerium oxide and cobalt oxide, two parts of which are composed of barium oxide, and three parts of which are composed of silicon oxide, activated carbon and aluminum oxide.
Example 6
Gasifying 4-piperidone, mixing with hydrogen, pumping the mixture into a fixed bed reactor through a metering pump, wherein the molar ratio of the hydrogen to the 4-piperidone is 27:1, and the liquid hourly space velocity of the 4-piperidone is 0.7h-1Controlling the reaction temperature to be 240 ℃ and the reaction pressure to be 4.0MPa, converting 4-piperidone and hydrogen into a piperidine product on a copper-based catalyst, purifying the collected piperidine product by an azeotropic distillation method, and purifying the piperidine subjected to azeotropic distillation by an HY type molecular sieve to obtain a 99.78 wt% high-quality piperidine product. The overall yield of piperidine was 72.1%. The copper-based catalyst consists of 39 wt% of copper oxide and 61 wt% of a carrier; wherein the vector consists of three parts: one part of which is composed of nickel oxide, platinum oxide and cobalt oxide, two parts of which are composed of calcium oxide, and three parts of which are composed of silicon oxide, titanium oxide and activated carbon.
Example 7
Gasifying 4-piperidone, mixing with hydrogen, pumping the mixture into a fixed bed reactor through a metering pump, wherein the molar ratio of the hydrogen to the 4-piperidone is 6:1, and the liquid hourly space velocity of the 4-piperidone is 0.1h-1Controlling the reaction temperature to be 280 ℃ and the reaction pressure to be 1.0MPa, converting 4-piperidone and hydrogen into a piperidine product on a copper-based catalyst, purifying the collected piperidine product by adopting an azeotropic distillation method, and then carrying out osmotic separation on the piperidine obtained by azeotropic distillation through an HY type molecular sieve and a membrane to obtain high-quality piperidine with the purity of 99.57 wt% And (5) producing the product. The overall yield of piperidine was 56.12%. The copper-based catalyst consists of 25 wt% of copper oxide and 75 wt% of carrier; wherein the vector consists of three parts: one part of which is composed of nickel oxide, platinum oxide and cobalt oxide, two parts of which are composed of potassium oxide, and three parts of which are composed of alumina, activated carbon and zirconia.
Example 8
Gasifying 4-piperidone, mixing with hydrogen, pumping the mixture into a fixed bed reactor through a metering pump, wherein the molar ratio of the hydrogen to the 4-piperidone is 36:1, and the liquid hourly space velocity of the 4-piperidone is 0.3h-1Controlling the reaction temperature to be 180 ℃, controlling the reaction pressure to be 4.0MPa, converting 4-piperidone and hydrogen into a piperidine product on a copper-based catalyst, purifying the collected piperidine product by an azeotropic distillation method, and purifying the piperidine subjected to azeotropic distillation by an HY type molecular sieve to obtain a high-quality piperidine product with the purity of 96.33 wt%. The overall yield of piperidine was 56.97%. The copper-based catalyst consists of 50 wt% of copper oxide and 50 wt% of carrier; one part of which is composed of nickel oxide, platinum oxide, zinc oxide and cerium oxide, two parts of which are composed of calcium oxide, and three parts of which are composed of silicon oxide, titanium oxide and aluminum oxide.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (3)
1. The preparation method of piperidine is characterized in that 4-piperidone and hydrogen are used as raw materials, piperidine is prepared under the action of a hydrogenation catalyst, and the hydrogenation catalyst is a copper-based catalyst; the copper-based catalyst comprises 25-50 wt% of copper oxide and 50-75 wt% of carrier; the carrier consists of three parts, wherein one part of the carrier consists of more than two of manganese oxide, zinc oxide, cerium oxide, nickel oxide, cobalt oxide or platinum oxide; the second part of the material consists of one or two of magnesium oxide, potassium oxide, calcium oxide, sodium oxide or barium oxide; the three parts of the catalyst consist of two or three of silicon oxide, titanium oxide, aluminum oxide, zirconium oxide or activated carbon.
2. The method of claim 1, comprising the steps of: filling a copper-based catalyst into a hydrogenation reactor; gasifying 4-piperidone, mixing with hydrogen, adding the obtained mixture into a hydrogenation reactor through a metering pump, and reacting at the temperature of 180-280 ℃, the reaction pressure of 1.0-5.0 MPa and the liquid hourly space velocity of 0.1-1.0 h -1Under the condition of (1), 4-piperidone and hydrogen react on a copper-based catalyst to generate piperidine.
3. The preparation method according to claim 1, wherein the molar ratio of the hydrogen gas to the 4-piperidone is (6-36): 1.
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| DE3600609A1 (en) * | 1986-01-11 | 1987-07-16 | Basf Ag | HYDRATION AND REDUCTION WITH THE HYDROCARBON / CARBON SYSTEM |
| CN102093283A (en) * | 2009-12-10 | 2011-06-15 | 中国科学院大连化学物理研究所 | Method for preparing piperidine and piperidine derivative |
| CN106542972A (en) * | 2016-10-30 | 2017-03-29 | 中南民族大学 | A kind of method of normal temperature and pressure reducing carbonyl for methylene |
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| DE3600609A1 (en) * | 1986-01-11 | 1987-07-16 | Basf Ag | HYDRATION AND REDUCTION WITH THE HYDROCARBON / CARBON SYSTEM |
| CN102093283A (en) * | 2009-12-10 | 2011-06-15 | 中国科学院大连化学物理研究所 | Method for preparing piperidine and piperidine derivative |
| CN106542972A (en) * | 2016-10-30 | 2017-03-29 | 中南民族大学 | A kind of method of normal temperature and pressure reducing carbonyl for methylene |
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