WO2023280276A1 - 一种3-甲基哌啶脱氢催化剂及其制备方法与应用 - Google Patents

一种3-甲基哌啶脱氢催化剂及其制备方法与应用 Download PDF

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WO2023280276A1
WO2023280276A1 PCT/CN2022/104415 CN2022104415W WO2023280276A1 WO 2023280276 A1 WO2023280276 A1 WO 2023280276A1 CN 2022104415 W CN2022104415 W CN 2022104415W WO 2023280276 A1 WO2023280276 A1 WO 2023280276A1
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methylpiperidine
dehydrogenation catalyst
active component
methylpyridine
catalyst
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PCT/CN2022/104415
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English (en)
French (fr)
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陈洪龙
杜翔
王福军
岳瑞宽
罗超然
王文魁
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南京红太阳生物化学有限责任公司
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Priority to GB2401643.8A priority Critical patent/GB2624128A/en
Publication of WO2023280276A1 publication Critical patent/WO2023280276A1/zh

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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
    • B01J23/38—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
    • 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

Definitions

  • the invention belongs to the field of fine chemical industry, and relates to a 3-methylpiperidine dehydrogenation catalyst and a preparation method thereof, and an application of the catalyst for preparing 2-methylpyridine through dehydrogenation.
  • 3-picoline is an important fine chemical raw material, mainly used for the preparation of nicotinic acid and nicotinamide, and also used as an intermediate for the synthesis of spices, dyes, solvents, alcohol denaturants and rubber vulcanization accelerators, etc., with a wide range of uses .
  • the reported preparation methods of 3-picoline include coal tar extraction method, acrolein ammonia method, 2-methyl-1,5-pentanediamine cyclization method and aldehyde ammonia method to produce pyridine base co-production of 3-picoline .
  • the co-production of 3-picoline by aldehyde ammonia method to pyridine base is the main production method.
  • the coal tar extraction method is an early production method, which is inefficient and has long been abandoned.
  • the main problem of the acrolein ammonia method and the cyclization method of 2-methyl-1,5-pentanediamine is that the reaction conditions are harsh and the yield of 3-picoline is low.
  • 3-picoline is only a by-product of this method.
  • the low selectivity of the catalyst is a prominent shortcoming, and there is a problem of separation from pyridine.
  • the dehydrogenation of 3-methylpiperidine to prepare 3-methylpyridine has high selectivity and can avoid separation problems, thus becoming an efficient method for preparing 3-methylpyridine.
  • the 3-methylpiperidine dehydrogenation catalyst has been publicly reported as follows: U.S. Patent No. 8,530,664 discloses a 3-methylpiperidine dehydrogenation catalyst, with silicon-aluminum oxide as a carrier, and noble metal Pd as an active component. 7.5%, using a mixed gas of nitrogen and hydrogen as the carrier gas, the mass space velocity of 3-methylpiperidine is 3h -1 , reacted at 300°C for 509h, and the yield of 3-methylpyridine was stable at 98%.
  • patent US8324388 disclose a kind of 3 -methyl piperidine dehydrogenation catalyst, with ZrO2 as carrier, with precious metal Pd as active component, loading capacity 0.9%, with nitrogen, hydrogen mixed gas as carrier gas,
  • the volume space velocity of 3-methylpiperidine is 0.3h -1 , the conversion rate is 99.5%, and the volume space velocity is 1.2h -1 , the conversion rate is 78%.
  • U.S. Patent No. 4,762,929 discloses a catalyst for preparing 3-picoline by dehydrogenation of 3-methylpiperidine.
  • the noble metal Pd is used as an active component, and the loading capacity is 1%.
  • the conversion rate of 3-methylpiperidine is 95%.
  • the methylpiperidine selectivity is 93%, and the catalyst life is 100 days.
  • the above-mentioned 3-methylpiperidine dehydrogenation catalysts all use a single noble metal palladium as an active component, and have a high loading capacity. During the reaction process, a mixed gas of nitrogen and hydrogen needs to be continuously fed as a carrier gas, which is not conducive to industrial production.
  • the object of the present invention is to provide a 3-methylpiperidine dehydrogenation catalyst, which solves the disadvantages of high loading capacity of noble metals in the prior art and the need to continuously feed nitrogen and hydrogen as carrier gas during the reaction.
  • a kind of 3-methylpiperidine dehydrogenation catalyst is carrier with metal oxide, is active component with precious metal, is auxiliary agent with alkali metal and alkaline earth metal, and the load capacity of active component (with precious metal element quality and The carrier mass ratio) is 0.05-0.5%, and the loading amount of the auxiliary agent (calculated by the ratio of the alkali metal and alkaline earth metal element mass to the carrier mass ratio) is 0.1-1.0%.
  • the loading amount of the active component is 0.05-0.1%; the loading amount of the auxiliary agent is 0.1-0.5%.
  • the mass ratio of the alkali metal to the alkaline earth metal is 1:1-5.
  • the carrier is one of Al 2 O 3 , ZrO 2 , TiO 2 , preferably Al 2 O 3 .
  • the carrier is a small spherical carrier with a diameter of 1-5 mm.
  • the noble metal is one of Ru, Pt, Pd, Rh, preferably Pd.
  • the alkali metal is a combination of at least one of Na or K and at least one of alkaline earth metals Mg and Ca; more preferably, the additive is a combination of K and Mg.
  • the 3-methylpiperidine dehydrogenation catalyst described in the present invention is prepared by an equal-volume impregnation method.
  • Another object of the present invention is to provide the preparation method of the described 3-methylpiperidine dehydrogenation catalyst, comprising: taking a solvent equal to the volume of the saturated absorption of the carrier to be impregnated, the active component precursor, the auxiliary agent precursor 3-Methylpiperidine dehydrogenation catalyst is prepared by dissolving the body in a solvent to form a homogeneous solution, dispersing the carrier in the solution, fully turning and stirring the carrier, so that the solution is fully impregnated on the carrier, and then naturally air-dried, dried, and roasted .
  • the active component precursor is one of noble metals such as chloride salts, nitrates or acetates corresponding to Ru, Pt, Pd and Rh, preferably a chloride salt.
  • noble metals such as chloride salts, nitrates or acetates corresponding to Ru, Pt, Pd and Rh, preferably a chloride salt.
  • the auxiliary agent precursor is one of chloride salts, nitrates or acetates of alkali metals and alkaline earth metals, preferably chloride salts.
  • the solvent is one or a mixture of water, hydrochloric acid, ethanol, and ammonia, preferably water or hydrochloric acid.
  • hydrochloric acid is 5% hydrochloric acid.
  • the drying temperature is 120-140° C., and the drying time is 6-12 hours.
  • the calcination temperature is 500-600° C., and the calcination time is 4-6 hours.
  • Another object of the present invention is to provide the application of the 3-methylpiperidine dehydrogenation catalyst in the preparation of 3-methylpyridine by dehydrogenating 3-methylpyridine.
  • a method for preparing 3-methylpyridine, using 3-methylpiperidine as a raw material, heating and vaporizing, and preparing 3-methylpyridine through a fixed-bed reactor filled with a 3-methylpiperidine dehydrogenation catalyst wherein, the mass space velocity of 3 - methylpiperidine is 1-5h -1 , preferably 2-4h -1 , the process conditions are: normal pressure, and the reaction temperature is 180-300°C, preferably 200-260°C.
  • the present invention has the following beneficial effects:
  • the 3-methylpiperidine dehydrogenation catalyst of the present invention can greatly reduce the noble metal loading by adding cheap and easily available alkali metals and alkaline earth metals as additives, so that the noble metal loading is ⁇ 0.1%.
  • the reaction process does not require a carrier gas.
  • 3-methylpiperidine is produced by fixed-bed reaction.
  • the catalyst's long-term transport activity does not decay, and its lifespan is more than 3000h.
  • the yield of picoline >98%.
  • the 3-methylpiperidine dehydrogenation catalyst of the invention has significant cost advantages and industrial application prospects.
  • Example 1 The support of Example 1 was replaced by dry ZrO pellets with a diameter of 3 mm. Take 100g of dry ZrO pellets with a diameter of 3mm, use water as a solvent, and measure its saturated water absorption to be 87g.
  • Example 1 The support of Example 1 was replaced by dry TiO pellets with a diameter of 3 mm. Take 100g of dry TiO pellets with a diameter of 3mm, use water as a solvent, and measure its saturated water absorption to be 82g.
  • Example 1 The active component precursor palladium chloride in Example 1 was replaced by chloroplatinic acid hexahydrate to prepare a platinum-supported catalyst.
  • Example 2 The active component precursor palladium chloride in Example 1 was replaced by anhydrous ruthenium trichloride to prepare a ruthenium-loaded catalyst.
  • Example 1 The solvent of Example 1 was replaced with 5% hydrochloric acid. Take 100g of dry Al 2 O 3 pellets with a diameter of 3mm, and measure its saturated water absorption to be 102g.
  • the noble metal Pd is not loaded, and only alkali metal and alkaline earth metal additives are impregnated on the carrier.
  • Examples 1 to 3 show that with the same active components, additives and impregnation conditions, the initial activity of the catalyst prepared with Al 2 O 3 as the carrier is higher than that of the catalyst prepared with ZrO 2 and TiO 2 as the carrier. .
  • the catalyst of the present invention greatly reduces the noble metal loading of the catalyst by adding alkali metals and alkaline earth metals, and the performance of the catalyst is significantly improved, and no carrier gas needs to be introduced during the reaction.
  • reaction temperature 250°C and mass space velocity of 2h -1 for a long time
  • the conversion rate of 3-methylpiperidine can be maintained at >99%, and the yield of 3-methylpyridine can be maintained at >98%.
  • the catalyst of the invention has been operated for more than 3000 hours and still maintains stable catalytic activity.
  • the present invention illustrates the detailed methods of the present invention through the above-mentioned examples, but the present invention is not limited to the above-mentioned detailed methods, that is, it does not mean that the present invention must rely on the above-mentioned detailed methods to be implemented.
  • Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present invention.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Hydrogenated Pyridines (AREA)

Abstract

本发明公开了一种3-甲基哌啶脱氢催化剂，以金属氧化物为载体，以贵金属为活性组分，以碱金属和碱土金属为助剂，采用浸渍法负载活性组分和助剂，活性组分的负载量为0.05～0.5％，助剂的负载量为0.1～1.0％。本发明还公开了一种制备3-甲基吡啶的方法，以3-甲基哌啶为原料，经加热汽化，经装填有3-甲基哌啶脱氢催化剂的固定床反应器，制得3-甲基吡啶，催化剂寿命3000h以上，可维持3-甲基哌啶转化率＞99％，3-甲基吡啶收率＞98％。本发明3-甲基哌啶脱氢催化剂用于3-甲基哌啶脱氢制备3-甲基吡啶，贵金属负载量少、3-甲基吡啶收率高、催化剂寿命长，具有显著的成本优势和工业化应用前景。

Description

一种3-甲基哌啶脱氢催化剂及其制备方法与应用 技术领域
本发明属于精细化工领域，涉及一种3-甲基哌啶脱氢催化剂及其制备方法，以及该催化剂用于脱氢制备2-甲基吡啶的应用。
背景技术
3-甲基吡啶是一种重要的精细化工原料，主要用作烟酸、烟酰胺的制备，也用作合成香料、染料、溶剂、酒精变性剂和橡胶硫化促进剂等的中间体，用途广泛。
已报道过的3-甲基吡啶制备方法有煤焦油提取法、丙烯醛氨法、2-甲基-1,5-戊二胺环化法及醛氨法制吡啶碱联产3-甲基吡啶。其中，醛氨法制吡啶碱联产3-甲基吡啶是主要生产方法。煤焦油提取法是早年的生产方法，效率低下，早已被弃用。丙烯醛氨法、2-甲基-1,5-戊二胺环化法的主要问题是反应条件苛刻，3-甲基吡啶收率低。醛氨法制吡啶碱联产3-甲基吡啶中，3-甲基吡啶仅是该法的副产物，催化剂的低选择性是一个突出缺点，且存在与吡啶的分离问题。3-甲基哌啶脱氢制备3-甲基吡啶选择性高，且能避免分离问题，成为一种高效的3-甲基吡啶制备方法。
目前已公开报道3-甲基哌啶脱氢催化剂如下：美国专利US8530664公开了一种3-甲基哌啶脱氢催化剂，以硅铝氧化物为载体，以贵金属Pd为活性组分，负载量7.5％，以氮气、氢气混合气体为载气，3-甲基哌啶质量空速为3h -1，300℃反应509h，3-甲基吡啶收率稳定在98％。中国专利CN101384525与美国专利US8324388公开了一种3-甲基哌啶脱氢催化剂，以ZrO 2为载体，以贵金属Pd为活性组分，负载量0.9％，以氮气、氢气混合气体为载气，3-甲基哌啶体积空速为0.3h -1，转化率99.5％，体积空速1.2h -1，转化率为78％，未见关于催化剂寿命的报道。美国专利US4762929公开了一种3-甲基哌啶脱氢制3-甲基吡啶催化剂，以贵金属Pd为活性组分，负载量为1％，3-甲基哌啶转化率95％，3-甲基哌啶选择性93％，催化剂寿命100天。上述3-甲基哌啶脱氢催化剂均以单一的贵金属钯作为活性组分，负载量高，反应过程中需持续通入氮气、氢气混合气体作载气，不利于工业化生产。
发明内容
本发明的目的在于提供一种3-甲基哌啶脱氢催化剂，解决现有技术中贵金属负载量高、反应中需持续通入氮气、氢气作载气的缺点。
本发明的目的是通过以下技术方案实现的：
一种3-甲基哌啶脱氢催化剂，该催化剂以金属氧化物为载体，以贵金属为活性组分，以 碱金属和碱土金属为助剂，活性组分的负载量(以贵金属元素质量与载体质量之比计算)为0.05～0.5％，助剂的负载量(以碱金属和碱土金属元素质量与载体质量之比计算)为0.1～1.0％。
优选的，所述的活性组分的负载量为0.05～0.1％；所述的助剂的负载量为0.1～0.5％。
优选的，所述的碱金属和碱土金属的质量比为1:1～5。
优选的，所述的载体为Al 2O 3、ZrO 2、TiO 2中的一种，优选为Al 2O 3。
优选的，所述的载体为直径1～5mm的小球状载体。
优选的，所述的贵金属为Ru、Pt、Pd、Rh中的一种，优选为Pd。
优选的，所述的碱金属为Na或K中的至少一种与碱土金属Mg、Ca中的至少一种的组合；进一步优选为所述的助剂为K和Mg的组合。
本发明所述的3-甲基哌啶脱氢催化剂是采用等体积浸渍法制成的。
本发明的另一个目的是提供所述的3-甲基哌啶脱氢催化剂的制备方法，包括：取与待浸渍载体的饱和吸收量等体积的溶剂，将活性组分前驱体、助剂前驱体溶于溶剂中配成均相溶液，将载体分散于溶液中，充分翻动、搅拌载体，使溶液充分浸渍到载体上，经自然风干、干燥、焙烧制得3-甲基哌啶脱氢催化剂。
所述的活性组分前驱体为贵金属如Ru、Pt、Pd、Rh对应的氯盐、硝酸盐或醋酸盐中的一种，优选为氯盐。
所述的助剂前驱体为碱金属和碱土金属的氯盐、硝酸盐或醋酸盐中的一种，优选为氯盐。
所述的溶剂为水、盐酸、乙醇、氨水中的一种或两种混合，优选为水或盐酸。
所述的盐酸为5％盐酸。
所述的干燥温度为120～140℃，干燥时间为6～12h。
所述的焙烧温度为500～600℃，焙烧时间为4～6h。
本发明的另一个目的是提供所述的3-甲基哌啶脱氢催化剂在3-甲基吡啶脱氢制备3-甲基吡啶的应用。
一种制备3-甲基吡啶的方法，以3-甲基哌啶为原料，经加热汽化，经装填有3-甲基哌啶脱氢催化剂的固定床反应器，制得3-甲基吡啶；其中，3-甲基哌啶的质量空速为1～5h - 1，优选为2～4h -1，工艺条件为：常压，反应温度为180～300℃，优选为200～260℃。
与现有技术相比，本发明具有以下有益效果：
本发明3-甲基哌啶脱氢催化剂通过添加廉价易得的碱金属和碱土金属为助剂，可以大幅 减低贵金属负载量，使贵金属负载量≤0.1％。反应过程无需载气，3-甲基哌啶气化后经固定床反应制3-甲基哌啶，催化剂长时间转运活性不衰减，寿命在3000h以上，可维持转化率＞99％，3-甲基吡啶收率＞98％。
本发明3-甲基哌啶脱氢催化剂具有显著的成本优势和工业化应用前景。
具体实施方式
下面结合实施例对本发明的技术方案进行具体描述，但本发明的保护范围不限于此。
实施例1
取100g直径为3mm的干燥Al 2O 3小球，用水做溶剂，测得其饱和吸水量为98g。
称量0.168g无水氯化钯、0.382g氯化钾、0.794g氯化镁加入到98g水中，搅拌溶解得到均匀透明溶液，将溶液逐滴滴加到100g干燥的Al 2O 3小球上，在滴加过程中不停翻动、搅拌载体小球，使溶液均匀浸渍在载体上。滴加完成后置于通风橱自然风干12h，再放置在烘箱中120℃烘干12h，放置在马弗炉中550℃焙烧4h，所得催化剂组成为0.1％Pd+0.2％K+0.2％Mg/Al 2O 3，标记为催化剂1。
实施例2
将实施例1的载体替换为直径为3mm的干燥ZrO 2小球。取100g直径为3mm的干燥ZrO 2小球，用水做溶剂，测得其饱和吸水量为87g。
称量0.168g无水氯化钯、0.382g氯化钾、0.794g氯化镁加入到87g水中，搅拌溶解得到均匀透明溶液，其他操作方法同实施例1，所得催化剂组成为0.1％Pd+0.2％K+0.2％Mg/ZrO 2，标记为催化剂2。
实施例3
将实施例1的载体替换为直径为3mm的干燥TiO 2小球。取100g直径为3mm的干燥TiO 2小球，用水做溶剂，测得其饱和吸水量为82g。
称量0.168g无水氯化钯、0.382g氯化钾、0.794g氯化镁加入到82g水中，搅拌溶解得到均匀透明溶液，其他操作方法同实施例1，所得催化剂组成为0.1％Pd+0.2％K+0.2％Mg/TiO 2，标记为催化剂3。
实施例4
将实施例1的的活性组分前驱体氯化钯替换成六水合氯铂酸，制备负载铂的催化剂。
称量0.266g六水合氯铂酸、0.382g氯化钾、0.794g氯化镁加入到98g水中，搅拌溶解得到均匀透明溶液，其他操作方法同实施例1，所得催化剂组成为0.1％Pt+0.2％K+0.2％Mg/Al 2O 3，标记为催化剂4。
实施例5
将实施例1的活性组分前驱体氯化钯替换成无水三氯化钌，制备负载钌的催化剂。称量0.205g无水氯化钌、0.382g氯化钾、0.794g氯化镁加入到98g水中，搅拌溶解得到均匀透明溶液，其他操作方法同实施例1，所得催化剂组成为0.1％Ru+0.2％K+0.2％Mg/Al 2O 3，标记为催化剂5。
实施例6
将实施例1的溶剂替换成5％盐酸。取100g直径为3mm的干燥Al 2O 3小球，测得其饱和吸水量为102g。
称量0.168g无水氯化钯、0.382g氯化钾、0.794g氯化镁加入到102g 5％盐酸中，搅拌溶解得到均匀透明溶液，其他操作方法同实施例1，所得催化剂组成为0.1％Pd+0.2％K+0.2％Mg/Al 2O 3，标记为催化剂6。
对比例1
本实施例仅负载贵金属Pd，不添加碱金属和碱土金属助剂，单纯的氯化钯在水中溶解度很小，在稀盐酸溶液中有良好的溶解性，以5％盐酸为溶剂。
称量0.168g无水氯化钯，加入到102g 5％盐酸中，使其均匀浸渍在100g直径为3mm的干燥Al 2O 3小球上，其他操作方法同实施例1，所得催化剂组成为0.1％Pd/Al 2O 3，标记为催化剂7。
对比例2
本实施例不负载贵金属Pd，仅在载体上浸渍碱金属和碱土金属助剂。
取100g直径为3mm的干燥Al 2O 3小球，用水做溶剂，测得其饱和吸水量为98g。
称量0.382g氯化钾、0.794g氯化镁加入到98g水中，搅拌溶解得到均匀透明溶液，将溶液逐滴滴加到100g干燥的Al 2O 3小球上，在滴加过程中不停翻动、搅拌载体小球，使溶液均匀浸渍在载体上。滴加完成后置于通风橱自然风干12h，再放置在烘箱中120℃烘干12h，放置在马弗炉中550℃焙烧4h，所得催化剂组成为0.2％K+0.2％Mg/Al 2O 3，标记为催化剂8。
催化剂初活性的评价：
分别取实施例1-实施例6、对比例1和对比例2制得的催化剂10g，装填到内径为2cm的固定床管式反应器中，3-甲基哌啶用计量泵进料，3-甲基哌啶进料量为20g/h，经过预热汽化，进入固定床反应器，催化剂床层温度控制在250℃，反应10h，反应器出口处收集反应产物，取累积产物分析，结果如表1所示。
表1.催化剂初活性评价结果
Figure PCTCN2022104415-appb-000001
由表1可知，实施例1-实施例3表明，同样的活性组分、助剂及浸渍条件，以Al 2O 3为载体制备的催化剂初活性高于ZrO 2、TiO 2为载体制备的催化剂。由实施例1、实施例4、实施例5表明，以Al 2O 3为载体，相同的助催化剂及浸渍条件，以无水氯化钯为活性组分前驱体制备的催化剂，催化初活性高于以六水合氯铂酸、氯化钌为活性组分前驱体制备的催化剂，表明贵金属钯在3-甲基哌啶脱氢反应中催化活性高于贵金属铂、贵金属钌。由实施例1和实施例6相比表明，浸渍溶剂选择水或盐酸对催化剂的活性影响不大。由实施例1和对比实施例1和2比较，可以看出，负载贵金属Pd，同时添加一定量的K、Mg混合物，以Al 2O 3为载体制备的催化剂1有较高的初活性。
催化剂反应寿命评价：
取催化剂6、催化剂7各10g，分别装填到内径为2cm的固定床管式反应器中，3-甲基哌啶用计量泵进料，3-甲基哌啶进料量为20g/h，经过预热汽化，进入固定床管式反应器，控制催化剂床层温度在250℃，装置长时间运转，反应器出口处收集反应产物，间歇取样分析，结果如表2所示。
表2.催化剂反应寿命评价结果
Figure PCTCN2022104415-appb-000002
反应650h后，催化剂7活性迅速降低，停止反应评价。由表2可知，与现有技术相比，本发明催化剂通过添加碱金属和碱土金属，大幅度降低了催化剂的贵金属负载量，且催 化剂性能明显提高，反应过程中无需通入载气。在反应温度250℃、质量空速2h -1条件下长时间运转，可以维持3-甲基哌啶转化率＞99％，3-甲基吡啶收率＞98％。本发明催化剂运行3000h以上，仍保持稳定的催化活性。
发明人采用上述方法考察催化剂4和催化剂5，反应650h后，两种催化剂的催化活性分别与其初始活性持平。反应650h后，催化剂4的活性：3-甲基哌啶转化率维持在99.0％，3-甲基吡啶收率维持在89.5％；催化剂5的活性：3-甲基哌啶转化率维持在89.1％，3-甲基吡啶收率维持在88.4％。运行3000h以上，催化剂4和催化剂5仍保持稳定的催化活性，未见明显下降。
说明本发明催化剂具有显著的成本优势和工业化应用前景。
申请人声明，本发明通过上述实施例来说明本发明的详细方法，但本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (10)

  1. 一种3-甲基哌啶脱氢催化剂，其特征在于所述的催化剂以金属氧化物为载体，以贵金属为活性组分，以碱金属和碱土金属为助剂，活性组分的负载量为0.05～0.5％，助剂的负载量为0.1～1.0％。
  2. 根据权利要求1所述的3-甲基哌啶脱氢催化剂，其特征在于所述的活性组分的负载量为0.05～0.1％；所述的助剂的负载量为0.1～0.5％。
  3. 根据权利要求1所述的3-甲基哌啶脱氢催化剂，其特征在于所述的碱金属和碱土金属的质量比为1:1～5。
  4. 根据权利要求1所述的3-甲基哌啶脱氢催化剂，其特征在于所述的载体为Al 2O 3、ZrO 2、TiO 2中的一种。
  5. 根据权利要求1所述的3-甲基哌啶脱氢催化剂，其特征在于所述的活性组分为Ru、Pt、Pd、Rh中的一种，优选为Pd。
  6. 根据权利要求1所述的3-甲基哌啶脱氢催化剂，其特征在于所述的助剂为碱金属Na、K中的至少一种与碱土金属Mg、Ca中的至少一种的组合，优选为K和Mg的组合。
  7. 权利要求1所述的3-甲基哌啶脱氢催化剂的制备方法，其特征在于包括：取与待浸渍载体的饱和吸收量等体积的溶剂，将活性组分前驱体、助剂前驱体溶于溶剂中配成均相溶液，将载体分散于溶液中使溶液充分浸渍到载体上，经自然风干、干燥、焙烧制得3-甲基哌啶脱氢催化剂。
  8. 根据权利要求7所述的3-甲基哌啶脱氢催化剂的制备方法，其特征在于所述的活性组分前驱体为贵金属对应的氯盐、硝酸盐或醋酸盐中的一种，优选为氯盐；
    所述的助剂前驱体为碱金属和碱土金属对应的氯盐、硝酸盐或醋酸盐中的一种，优选为氯盐；
    所述的溶剂为水、盐酸、乙醇、氨水中的一种或两种混合，优选为水或盐酸。
  9. 权利要求1-6任一项所述的3-甲基哌啶脱氢催化剂在3-甲基吡啶脱氢制备3-甲基吡啶的应用。
  10. 一种制备3-甲基吡啶的方法，其特征在于以3-甲基哌啶为原料，经加热汽化，经装填有权利要求1所述的3-甲基哌啶脱氢催化剂的固定床反应器，制得3-甲基吡啶；其中，3-甲基哌啶的质量空速为1～5h -1，优选为2～4h -1，工艺条件为：常压，反应温度为180～300℃，优选为200～260℃。
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