GB2624128A - 3-Methylpiperidine dehydrogenation catalyst, and preparation method therefor and application thereof - Google Patents
3-Methylpiperidine dehydrogenation catalyst, and preparation method therefor and application thereof Download PDFInfo
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- GB2624128A GB2624128A GB2401643.8A GB202401643A GB2624128A GB 2624128 A GB2624128 A GB 2624128A GB 202401643 A GB202401643 A GB 202401643A GB 2624128 A GB2624128 A GB 2624128A
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- Prior art keywords
- methylpiperidine
- dehydrogenation catalyst
- active component
- carrier
- methylpyridine
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- JEGMWWXJUXDNJN-UHFFFAOYSA-N 3-methylpiperidine Chemical compound CC1CCCNC1 JEGMWWXJUXDNJN-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims description 7
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 19
- 238000011068 loading method Methods 0.000 claims abstract description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 15
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 15
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 14
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 3
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 150000003841 chloride salts Chemical class 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000012456 homogeneous solution Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- NRGGMCIBEHEAIL-UHFFFAOYSA-N 2-ethylpyridine Chemical compound CCC1=CC=CC=N1 NRGGMCIBEHEAIL-UHFFFAOYSA-N 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 238000009834 vaporization Methods 0.000 abstract 1
- 230000008016 vaporization Effects 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 18
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 14
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 14
- 239000011777 magnesium Substances 0.000 description 9
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 229910001629 magnesium chloride Inorganic materials 0.000 description 7
- 239000001103 potassium chloride Substances 0.000 description 7
- 235000011164 potassium chloride Nutrition 0.000 description 7
- 239000012159 carrier gas Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- UJPKMTDFFUTLGM-UHFFFAOYSA-N 1-aminoethanol Chemical compound CC(N)O UJPKMTDFFUTLGM-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000004687 hexahydrates Chemical class 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- ZTWQTBDEQSLEAF-UHFFFAOYSA-N C(=O)C=C.N Chemical compound C(=O)C=C.N ZTWQTBDEQSLEAF-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- DFPAKSUCGFBDDF-ZQBYOMGUSA-N [14c]-nicotinamide Chemical compound N[14C](=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-ZQBYOMGUSA-N 0.000 description 1
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003398 denaturant Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 235000005152 nicotinamide Nutrition 0.000 description 1
- 239000011570 nicotinamide Substances 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- DFPAKSUCGFBDDF-UHFFFAOYSA-N nicotinic acid amide Natural products NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 1
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—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
- B01J23/58—Platinum group metals 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
-
- 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
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/133—Preparation by dehydrogenation of hydrogenated pyridine compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Hydrogenated Pyridines (AREA)
Abstract
Disclosed is a 3-methylpiperidine dehydrogenation catalyst, which uses a metal oxide as a carrier, a noble metal as an active component, and an alkali metal and alkaline earth metal as auxiliary agents. The active component and the auxiliary agents are loaded by means of impregnation; the loading amount of the active component is 0.05-0.5%; and the loading amount of the auxiliary agents is 0.1-1.0%. Also disclosed is a method for preparing 3-methylpyridine: using 3-methylpiperidine as a raw material, carrying out vaporization by heating, and using a fixed bed reactor filled with the 3-methylpiperidine dehydrogenation catalyst to obtain 3-methylpyridine. The catalyst has a service life of more than 3000 hours and can maintain a conversion rate of 3-methylpiperidine of higher than 99% and a yield of 3-methylpyridine of high than 98%. The 3-methylpiperidine dehydrogenation catalyst of the present invention is used for 3-methylpiperidine dehydrogenation to prepare 3-methylpyridine, can achieve less noble metal loading and a high 3-methylpyridine yield, and has a long service life as well as significant cost advantages and good industrial application prospects.
Description
3-METHYLPIPERIDINE DEHYDROGENATION CATALYST AND
PREPARATION METHOD THEREFOR AND USE THEREOF
TECHNICAL FIELD
The present invention belongs to the field of fine chemical industry and relates to a 3-methylpiperidine dehydrogenation catalyst and a preparation method therefor, and use of the catalyst in the preparation of 2-methylpyridine by dehydrogenation.
BACKGROUND
3-methylpyridine is an important fine chemical raw material and has wide application. It is mainly used for preparing nicotinic acid and nicotinamide, and also used as an intermediate for synthesizing spices, dyes, solvents, alcohol denaturants, rubber vulcanization accelerators and the like.
Reported methods for preparing 3-methylpyridine include a coal tar extraction, an acrolein ammonia method, a 2-methyl-1,5-pentanediamine cyclization, and an aldehyde ammonia method to prepare a pyridine base with the coproduction of 3-methylpyridine. The aldehyde ammonia method to prepare a pyridine base with the coproduction of 3-methylpyridine is a main production method. The coal tar extraction is an early production method, has low efficiency and thus is abandoned for a long time. The main problems of the acrolein ammonia method and the 2-methyl-1,5-pentanediamine cyclization are that the reaction conditions are harsh and the yield of 3-methylpyridine is low. In the aldehyde ammonia method to prepare a pyridine base with the coproduction of 3-methylpyridine, 3-methylpyridine is only a by-product. The method has a significant disadvantage of low selectivity of catalysts and a problem of separation from pyridine. A preparation of 3-methylpyridine by dehydrogenating 3-methylpiperidine has high selectivity, can avoid the separation problem, and becomes an efficient method for preparing 3-methylpyridine.
It has been reported that 3-methylpiperidine dehydrogenation catalysts are as follows: U.S. Patent No. 8530664 discloses a 3-methylpiperidine dehydrogenation catalyst, which takes a silicon-aluminum oxide as a carrier, a noble metal Pd as an active component with the loading capacity of 7.5%, and mixed gas of nitrogen and hydrogen as a carrier gas, the mass space velocity of 3-methylpiperidine is 3 WI, the reaction is carried out at 300°C for 509 h, and the yield of 3-methylpyridine is stabilized at 98%. Chinese patent CN101384525 and U.S. Patent No. 8324388 disclose a 3-methylpiperidine dehydrogenation catalyst, which takes ZrO2 as a carrier, a noble metal Pd as an active component with the loading capacity of 0.9%, and mixed gas of nitrogen and hydrogen as a carrier gas, the volume space velocity of 3-methylpiperidine is 0.3 the conversion rate is 99.5%, the volume space velocity is k2 11-1, and the conversion rate is 78%. There is no report about a service life of the catalyst. U.S. Patent No. 4762929 discloses a catalyst for preparing 3-methylpyridine by dehydrogenating 3-methylpiperidine, which takes a noble metal Pd as an active component with the loading capacity of 1%, the conversion rate of 3-methylpiperidine is 95%, the selectivity of 3-methylpiperidine is 93%, and a service life of the catalyst is 100 days. The 3-methylpiperidine dehydrogenation catalysts all take a single noble metal palladium as an active component, have high loading capacity, require continuous introduction of mixed gas of nitrogen and hydrogen as a carrier gas in the reaction process, and are not beneficial to industrial production.
SUMMARY
The present invention aims to provide a 3-methylpiperidine dehydrogenation catalyst, which solves the problems that the prior art has high loading capacity of a noble metal, and nitrogen and hydrogen as a carrier gas are required to be continuously introduced in a reaction.
The objectives of the present invention are achieved by the following technical solutions: a 3-methylpiperidine dehydrogenation catalyst, which takes a metal oxide as a carrier, a noble metal as an active component, and an alkali metal and an alkaline earth metal as an auxiliary agent, the loading capacity of the active component (calculated by a mass ratio of the noble metal element to the carrier) is 0.05%-0.5%, and the loading capacity of the auxiliary agent (calculated by a mass ratio of the alkali metal element and the alkaline earth metal element to the carrier) is 0.1%-1.0%.
Preferably, the loading capacity of the active component is 0.05%-0.1% and the loading capacity of the auxiliary agent is 0.1%-0.5%.
Preferably, a mass ratio of the alkali metal to the alkaline earth metal is 1:0-5).
Preferably, the carrier is one of A1203, Zr02, and Ti02, preferably A1203.
Preferably, the carrier is a globular carrier with the diameter of 1-5 mm.
Preferably, the noble metal is one of Ru, Pt, Pd, and Rh, preferably Pd.
Preferably, the alkali metal is at least one of alkali metals Na or K and combined with at least one of alkaline earth metals Mg and Ca; and further preferably, the auxiliary agent is a combination of K and Mg.
The 3-methylpiperidine dehydrogenation catalyst of the present invention is prepared by using an isovolumetric soaking method.
Another objective of the present invention is to provide a method for preparing the 3-methylpiperidine dehydrogenation catalyst, comprising: taking a solvent with the same volume as the saturated absorption capacity of the carrier to be soaked, dissolving an active component precursor and an auxiliary agent precursor in the solvent to prepare a homogeneous solution, dispersing the carrier in the solution, fully turning over and stirring the carrier to fully soak the carrier with the solution, and naturally drying, drying and roasting same to prepare the 3-methylpiperidine dehydrogenation catalyst.
The active component precursor is one of a chloride salt, a nitrate or an acetate corresponding to the noble metal such as Ru, Pt, Pd, and Rh, preferably a chloride salt.
The auxiliary agent precursor is one of a chloride salt, a nitrate or an acetate of the alkali metal to the alkaline earth metal, preferably a chloride salt.
The solvent is one or a mixture of two of water, hydrochloric acid, ethanol, and ammonium hydroxide, preferably water or hydrochloric acid The hydrochloric acid is 5% hydrochloric acid.
The drying temperature is 120-140°C and the drying time is 6-12 h. The roasting temperature is 500-600°C and the roasting time is 4-6 h. Another objective of the present invention is to provide use of the 3-methylpiperidine dehydrogenation catalyst in the preparation of 3-methylpyridine by dehydrogenating 3 -methylpyri dine A method for preparing 3-methylpyridine, wherein 3-methylpiperidine is used as a raw material, and heated and vaporized, and passes through a fixed bed reactor packed with the 3 -m ethyl pi peri dine dehydrogenation catalyst, the mass space velocity of the 3-methylpiperidine is 1-5 11-1, preferably 2-4 II', and the process conditions are as follows: normal pressure and reaction temperature of 180-300°C, preferably 200-260°C.
Compared with the prior art, the present invention has the following beneficial effects: the 3-methylpiperidine dehydrogenation catalyst of the present invention can greatly reduce the loading capacity of a noble metal to be < 0.1% by adding cheap and easily obtained alkali metals and alkaline earth metals as auxiliary agents. No carrier gas is required during the reaction process, 3-methylpiperidine is vaporized and reacted by a fixed bed to prepare 3-methylpiperidine, the activity of the catalyst is not attenuated after a long-time running, a service life is 3,000 h or more, the conversion rate can be maintained to be > 99%, and the yield of the 3-methylpyridine is > 98% The 3-methylpiperidine dehydrogenation catalyst has an obvious cost advantage and industrial application prospect
DETAILED DESCRIPTION
The technical solutions of the present invention are described in detail below in conjunction with the examples, but the protection scope of the present invention is not limited thereto.
Example 1
g of dried A1203 globules having the diameter of 3 mm were taken, water was used as a solvent, and the saturated water absorption capacity was determined to be 98 g.
0.168 g of anhydrous palladium chloride, 0.382 g of potassium chloride, and 0.794 g of magnesium chloride were weighed and added into 98 g of water, and stirred and dissolved to obtain a uniform transparent solution, the solution was dropwise added onto 100 g of the dried A1203 globules, and the carrier globules were turned over and stirred continuously during the dropwise addition process to ensure that the carrier was uniformly soaked in the solution. After the dropwise addition, the carrier was placed in a fuming cupboard for natural air-drying for 12 h, then placed in an oven for drying at 120°C for 12 h, and placed in a muffle furnace for roasting at 550°C for 4 h, and the obtained catalyst comprised 0.1%Pd+0.2%K+0.2%Mg/A1203 and was marked as catalyst 1.
Example 2
The carrier of example 1 was replaced by dried Zr02 globules having the diameter of 3 mm. 100 g of dried Zr02 globules having the diameter of 3 mm were taken, water was used as a solvent, and the saturated water absorption capacity was determined to be 87 g.
0.168 g of anhydrous palladium chloride, 0.382 g of potassium chloride, and 0.794 g of magnesium chloride were weighed and added into 87 g of water, and stirred and dissolved to obtain a uniform transparent solution, other operation methods were the same as those in example 1, and the obtained catalyst comprised 0.1%Pd+0.2%1C+0.2%Mg/Zr02 and was marked as catalyst 2.
Example 3
The carrier of example 1 was replaced by dried TiO2 globules having the diameter of 3 mm. 100 g of dried TiO2 globules having the diameter of 3 mm were taken, water was used as a solvent, and the saturated water absorption capacity was determined to be 82 g.
0.168 g of anhydrous palladium chloride, 0.382 g of potassium chloride, and 0.794 g of magnesium chloride were weighed and added into 82 g of water, and stirred and dissolved to obtain a uniform transparent solution, other operation methods were the same as those in example 1, and the obtained catalyst comprised 0.1%Pd+0.2%K+0.2%Mg/Ti02 and was marked as catalyst 3.
Example 4
The active component precursor palladium chloride of example 1 was replaced by chloroplatinic acid hexahydrate to prepare a platinum-loaded catalyst.
0.266 g of chloroplatinic acid hexahydrate, 0.382 g of potassium chloride, and 0.794 g of magnesium chloride were weighed and added into 98 g of water, and stirred and dissolved to obtain a uniform transparent solution, other operation methods were the same as those in example 1, and the obtained catalyst comprised 0.1%Pt+0.2%K+0.2%Mg1A1203 and was marked as catalyst 4.
Example 5
The active component precursor palladium chloride of example 1 was replaced by anhydrous ruthenium trichloride to prepare a ruthenium-loaded catalyst.
0.205 g of anhydrous ruthenium chloride, 0.382 g of potassium chloride, and 0.794 g of magnesium chloride were weighed and added into 98 g of water, and stirred and dissolved to obtain a uniform transparent solution, other operation methods were the same as those in example 1, and the obtained catalyst comprised 0.1%Ru+0.2%K+0.2%Mg/A1203 and was marked as catalyst 5.
Example 6
The solvent of example 1 was replaced by 5% hydrochloric acid. 100 g of dried A1203 globules having the diameter of 3 mm were taken, and the saturated water absorption capacity was determined to be 102 g 0.168 g of anhydrous palladium chloride, 0.382 g of potassium chloride, and 0.794 g of magnesium chloride were weighed and added into 102 g of 5% hydrochloric acid, and stirred and dissolved to obtain a uniform transparent solution, other operation methods were the same as those in example 1, and the obtained catalyst comprised 0.1%Pd+0.2%K+0.2%Mg/A1203 and was marked as catalyst 6.
Comparative example 1 In the present example, only a noble metal Pd was loaded, alkali metal and alkaline earth metal auxiliary agents were not added, pure palladium chloride had very low solubility in water, but good solubility in a dilute hydrochloric acid solution, and thus 5% hydrochloric acid was used as a solvent.
0.168 g of anhydrous palladium chloride was weighed and added into 102 g of 5% hydrochloric acid to ensure that 100 g of dried A1203 globules having the diameter of 3 mm were uniformly soaked in the solution, other operation methods were the same as those in example 1, and the obtained catalyst comprised 0.1%Pd/A1203 and was marked as catalyst 7.
Comparative example 2 In the present example, a noble metal Pd was not loaded, and a carrier was only soaked with alkali metal and alkaline earth metal auxiliary agents.
g of dried A1203 globules having the diameter of 3 mm were taken, water is used as a solvent, and the saturated water absorption capacity was determined to be 98 g.
0.382 g of potassium chloride and 0.794 g of magnesium chloride were weighed and added into 98 g of water, and stirred and dissolved to obtain a uniform transparent solution, the solution was dropwise added onto 100 g of the dried A1203 globules, and the carrier globules were turned over and stirred continuously during the dropwise addition process to ensure that the carrier was uniformly soaked in the solution. After the dropwise addition, the carrier was placed in a fuming cupboard for natural air-drying for 12 h, then placed in an oven for drying at 120°C for 12 h, and placed in a muffle furnace for roasting at 550°C for 4 h, and the obtained catalyst comprised 0.2%K+0.2%Mg/A1203 and was marked as catalyst 8.
Initial activity evaluation of catalysts g of the catalysts prepared in examples 1-6 and comparative examples 1-2 were respectively taken and packed into a fixed bed tubular reactor having the inner diameter of 2 cm, 3-methylpiperidine was fed by a metering pump with the feeding amount of 20 g/h, and preheated and vaporized, and entered the fixed bed reactor, the temperature of a catalyst bed was controlled at 250°C, the reaction was carried out for 10 h, a reaction product was collected at an outlet of the reactor, and the cumulative product was taken and analyzed. The results were shown in Table 1.
Table 1 Results of initial activity evaluation of catalysts Catalyst Conversion rate of 3-methylpiperidine/% Yield of 3-methylpyridine/% 1 99.9 99.5 2 93.6 92.1 3 94.7 93.8 4 90.3 89.9 89.4 88.7 6 99.5 99.1 7 89.7 88.3 8 0.5 Not produced It can be seen from Table 1, examples 1-3 showed that the catalyst prepared by using A1203 as the carrier had higher initial activity than the catalyst prepared by using Zr02 and TiO2 as the carriers with the same active component, auxiliary agent and soaking condition Examples 1, 4, and 5 showed that the catalyst prepared by taking A1203 as a carrier and anhydrous palladium chloride as an active component precursor under the same cocatalyst and soaking condition had higher catalytic initial activity than the catalyst prepared by using chloroplatinic acid hexahydrate and ruthenium chloride as active component precursors, indicating that the noble metal palladium had higher catalytic activity in the dehydrogenation reaction of 3-methylpiperidine than the noble metals platinum ruthenium. The comparison of example 1 with example 6 showed that the selection of water or hydrochloric acid as a soaking solvent had little effect on the activity of the catalyst. From the comparison between example 1 and comparative examples 1-2, it can be seen that catalyst 1 prepared by loading the noble metal Pd and simultaneously adding a certain amount of a mixture of K and Mg, and using A1203 as a carrier had higher initial activity.
Reaction service life evaluation of catalysts Each 10 g of catalysts 6 and 7 was taken and packed into a fixed bed tubular reactor having the inner diameter of 2 cm, 3-methylpiperidine was fed by a metering pump with the feeding amount of 20 g/h, and preheated and vaporized, and entered the fixed bed tubular reactor, the temperature of a catalyst bed was controlled at 250°C, the device ran for a long time, a reaction product was collected at an outlet of the reactor, and a sample was taken intermittently and analyzed. The results were shown in Table 2.
Table 2 Results of reaction service life evaluation of catalysts Catalyst 6 Catalyst 7 Reaction Conversion rate of Yield of Conversion rate of Yield of time/h 3 -methylpiperidine/ 3 -methylpyridine/ 3 -methylpiperidine/ 3 -methylpyri dine/ 99.8 99.4 87.1 86.2 99.6 99.1 85.2 84.5 202 99.5 99.0 83.7 82.1 509 99.3 98.7 70.4 68.9 650 99.3 98.8 32.5 29.3 1013 99.4 98.7 2007 99.1 98.5 - 3006 99.2 98.3 After 650 h of the reaction, the activity of catalyst 7 rapidly decreased and the reaction evaluation was stopped. It can be seen from Table 2, compared with the prior art, the noble metal loading capacity of the catalyst of the present invention was greatly reduced by adding the alkali metal and the alkaline earth metal, the performances of the catalyst were obviously improved, and no carrier gas was required to be introduced during the reaction process. The long-time operation was carried out at the reaction temperature of 250°C and the mass space velocity of 2 h.', and can maintain the conversion rate of 3-methylpiperidine > 99% and the yield of 3-methylpyridine > 98%. The catalyst of the present invention can still maintain stable catalytic activity after running for 3,000 h. The inventors examined catalyst 4 and catalysts by the above method. After 650 h of the reaction, the catalytic activities of the two catalysts were respectively equal to their initial activities. After 650 h of the reaction, the activity of catalyst 4 was as follows: the conversion rate of 3-methylpiperidine was maintained at 99.0% and the yield of 3-methylpyridine was maintained at 89.5% percent; and the activity of catalyst 5 was as follows: the conversion rate of 3-methylpiperidine was maintained at 89.1% and the yield of 3-methylpyridine was maintained at 88.4%. When ran for 3,000 h or more, catalyst 4 and catalyst 5 still kept stable catalytic activity which was not obviously reduced.
It is indicated that the catalyst of the present invention has an obvious cost advantage and industrial application prospect.
The applicant claims that the present invention describes detailed methods of the present invention through the above examples, but the present invention is not limited to the above detailed methods, that is, the above description does not mean that the present invention must rely on the above detailed methods to be implemented. Those skilled in the art should understand that any improvement to the present invention, equivalent replacement of each raw material of the product of the present invention, addition of auxiliary components, selection of specific methods and the like fall within the scope of protection and disclosure of the present invention.
Claims (10)
- CLAIMSWhat is claimed is: 1. A 3-methylpiperidine dehydrogenation catalyst, wherein the catalyst takes a metal oxide as a carrier, a noble metal as an active component, and an alkali metal and an alkaline earth metal as an auxiliary agent, the loading capacity of the active component is 0.05%-0.5%, and the loading capacity of the auxiliary agent is 0.1%-1.0%.
- 2. The 3-methylpiperidine dehydrogenation catalyst according to claim 1, wherein the loading capacity of the active component is 0.05%4/1% and the loading capacity of the auxiliary agent is 0.1%-0.5%.
- 3. The 3-methylpiperidine dehydrogenation catalyst according to claim 1, wherein a mass ratio of the alkali metal to the alkaline earth metal is 1:(1-5)
- 4. The 3-methylpiperidine dehydrogenation catalyst according to claim 1, wherein the carrier is one of A1203, Zr02, and Ti02.
- 5. The 3-methylpiperidine dehydrogenation catalyst according to claim 1, wherein the active component is one of Ru, Pt, Pd, and Rh, preferably Pd.
- 6. The 3-methylpiperidine dehydrogenation catalyst according to claim 1, wherein the auxiliary agent is a combination of at least one of alkali metals Na and K and at least one of alkaline earth metals Mg and Ca, preferably a combination of K and Mg.
- 7. A method for preparing the 3-methylpiperidine dehydrogenation catalyst according to claim 1, comprising: taking a solvent with the same volume as the saturated absorption capacity of the carrier to be soaked, dissolving an active component precursor and an auxiliary agent precursor in the solvent to prepare a homogeneous solution, dispersing the carrier in the solution to fully soak the carrier with the solution, and naturally drying, drying and roasting same to prepare the 3-methyl piperidine dehydrogenation catalyst.
- 8. The method for preparing the 3-methylpiperidine dehydrogenation catalyst according to claim 7, wherein the active component precursor is one of a chloride salt, a nitrate or an acetate corresponding to the noble metal, preferably a chloride salt; the auxiliary agent precursor is one of a chloride salt, a nitrate or an acetate corresponding to the alkali metal to the alkaline earth metal, preferably a chloride salt; and the solvent is one or a mixture of two of water, hydrochloric acid, ethanol, and ammonium hydroxide, preferably water or hydrochloric acid.
- 9. Use of the 3-methylpiperidine dehydrogenation catalyst according to any one of claims 1-6 in the preparation of 3 -m ethyl pyri dine by dehydrogenating 3 -m ethyl pyri dine.
- 10. A method for preparing 3-methylpyridine, wherein 3-methylpiperidine is used as a raw material, and heated and vaporized, and passes through a fixed bed reactor packed with the 3-methylpiperidine dehydrogenation catalyst according to claim 1 to prepare 3-methylpyridine, the mass space velocity of the 3-methylpiperidine is 1-5 h-1, preferably 2-4 h-1, and the process conditions are as follows: normal pressure and reaction temperature of 180-300°C, preferably 200-260°C.
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| PCT/CN2022/104415 WO2023280276A1 (en) | 2021-07-08 | 2022-07-07 | 3-methylpiperidine dehydrogenation catalyst, and preparation method therefor and application thereof |
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| CN114105869B (en) * | 2022-01-24 | 2022-11-08 | 苏州开元民生科技股份有限公司 | Preparation method of 2-propyl-4-cyanopyridine |
| CN114797947A (en) * | 2022-05-19 | 2022-07-29 | 兄弟科技股份有限公司 | Efficient dehydrogenation catalyst and application thereof in preparation of pyridine by dehydrogenation of piperidine raw materials |
| CN115709088A (en) * | 2022-06-21 | 2023-02-24 | 南京红太阳生物化学有限责任公司 | Preparation method of piperidine deoxidation catalyst |
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| US5149816A (en) * | 1988-07-11 | 1992-09-22 | Reilly Industries | High temperature process for selective production of 3-methylpyridine |
| CN1903842A (en) * | 2005-07-29 | 2007-01-31 | 浙江爱迪亚营养科技开发有限公司 | Preparation method of 3-methyl pyridine |
| CN101433842A (en) * | 2008-09-27 | 2009-05-20 | 中国石油天然气股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN113617354A (en) * | 2021-07-08 | 2021-11-09 | 南京红太阳生物化学有限责任公司 | 3-methylpiperidine dehydrogenation catalyst, and preparation method and application thereof |
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| CN102649055A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Catalyst for oxidative dehydrogenation of raw materials containing CO (carbon monoxide) gas |
| CN103044317B (en) * | 2013-01-07 | 2015-07-29 | 清华大学 | The method and system of preparation 3-picoline |
| CN105566218A (en) * | 2014-10-11 | 2016-05-11 | 中国科学院大连化学物理研究所 | Palladium carbon catalyzed selective partial dehydrogenation method of tetrahydroisoquinoline |
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| US5149816A (en) * | 1988-07-11 | 1992-09-22 | Reilly Industries | High temperature process for selective production of 3-methylpyridine |
| CN1903842A (en) * | 2005-07-29 | 2007-01-31 | 浙江爱迪亚营养科技开发有限公司 | Preparation method of 3-methyl pyridine |
| CN101433842A (en) * | 2008-09-27 | 2009-05-20 | 中国石油天然气股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN113617354A (en) * | 2021-07-08 | 2021-11-09 | 南京红太阳生物化学有限责任公司 | 3-methylpiperidine dehydrogenation catalyst, and preparation method and application thereof |
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