CN113617354B - 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 PDFInfo
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- methylpiperidine
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- JEGMWWXJUXDNJN-UHFFFAOYSA-N 3-methylpiperidine Chemical compound CC1CCCNC1 JEGMWWXJUXDNJN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title description 5
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 22
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 14
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 13
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 13
- 238000011068 loading method Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 230000008016 vaporization Effects 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 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 15
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000012456 homogeneous solution Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 150000003841 chloride salts Chemical group 0.000 claims 2
- 239000010970 precious metal Substances 0.000 claims 1
- 238000005470 impregnation Methods 0.000 abstract description 4
- 238000011049 filling Methods 0.000 abstract description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 16
- 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
- 239000000203 mixture Substances 0.000 description 13
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 10
- 239000011777 magnesium Substances 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
- 239000008188 pellet Substances 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
- 229910052763 palladium Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 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
- 239000002253 acid Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- 238000003756 stirring Methods 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-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
- 239000004480 active ingredient 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
- 239000003517 fume Substances 0.000 description 2
- 239000000047 product 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
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003398 denaturant Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification 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
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- B01J37/02—Impregnation, coating or precipitation
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- 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
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- 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
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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
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ZrO2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Al2O3、ZrO2、TiO2中的一种，优选为Al2O3。
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Al2O3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Al2O3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/Al2O3，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ZrO2小球。取100g直径为3mm的干燥ZrO2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/ZrO2，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TiO2小球。取100g直径为3mm的干燥TiO2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/TiO2，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/Al2O3，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/Al2O3，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Al2O3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/Al2O3，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Al2O3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/Al2O3，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Al2O3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Al2O3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/Al2O3，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
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Al2O3为载体制备的催化剂初活性高于ZrO2、TiO2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Al2O3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Al2O3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
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 (11)
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％；所述的活性组分为Ru、Pt、Pd、Rh中的一种；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，所述的碱金属和碱土金属的质量比为1:1～5。
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，其特征在于所述的载体为Al2O3、ZrO2、TiO2中的一种。
4.根据权利要求1所述的3-甲基哌啶脱氢催化剂，其特征在于所述的活性组分为Pd。
5.根据权利要求1所述的3-甲基哌啶脱氢催化剂，其特征在于所述的助剂为K和Mg的组合。
6.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。
7.根据权利要求6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；
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；
所述的溶剂为水、盐酸、乙醇、氨水中的一种或两种混合。
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；
所述的助剂前驱体为碱金属和碱土金属对应的氯盐；
所述的溶剂为水或盐酸。
9.权利要求1-5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，工艺条件为：常压，反应温度为180～300℃。
11.根据权利要求10所述的制备3-甲基吡啶的方法，其特征在3-甲基哌啶的质量空速为2～4h-1，反应温度为200～260℃。
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