CN106955690A - 一种催化乙醇制备丁醇的固体碱性催化剂及制备方法 - Google Patents
一种催化乙醇制备丁醇的固体碱性催化剂及制备方法 Download PDFInfo
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 title claims abstract description 96
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000007787 solid Substances 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title description 5
- 239000003513 alkali Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 15
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 150000001447 alkali salts Chemical class 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 39
- 229910052799 carbon Inorganic materials 0.000 claims description 33
- 239000002585 base Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 239000003575 carbonaceous material Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 241000737241 Cocos Species 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 229910001963 alkali metal nitrate Inorganic materials 0.000 claims description 2
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims 9
- QDMGKUOANLJICG-UHFFFAOYSA-N [Mg].[N+](=O)(O)[O-] Chemical compound [Mg].[N+](=O)(O)[O-] QDMGKUOANLJICG-UHFFFAOYSA-N 0.000 claims 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 abstract description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 12
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000007790 solid phase Substances 0.000 description 6
- 239000004032 superbase Substances 0.000 description 6
- 150000007525 superbases Chemical class 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 5
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 235000015424 sodium Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 102000007698 Alcohol dehydrogenase Human genes 0.000 description 2
- 108010021809 Alcohol dehydrogenase Proteins 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
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- 238000005984 hydrogenation reaction Methods 0.000 description 2
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- 229910044991 metal oxide Inorganic materials 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PPWHTZKZQNXVAE-UHFFFAOYSA-N Tetracaine hydrochloride Chemical compound Cl.CCCCNC1=CC=C(C(=O)OCCN(C)C)C=C1 PPWHTZKZQNXVAE-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- ZQBZAOZWBKABNC-UHFFFAOYSA-N [P].[Ca] Chemical compound [P].[Ca] ZQBZAOZWBKABNC-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- OCLXJTCGWSSVOE-UHFFFAOYSA-N ethanol etoh Chemical compound CCO.CCO OCLXJTCGWSSVOE-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical class [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- JOPDZQBPOWAEHC-UHFFFAOYSA-H tristrontium;diphosphate Chemical compound [Sr+2].[Sr+2].[Sr+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JOPDZQBPOWAEHC-UHFFFAOYSA-H 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- B01J35/615—
-
- B01J35/617—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
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Abstract
本发明涉及一种催化乙醇制备丁醇的固体碱性催化剂,以对碱高稳定性的材料为载体,通过负载或者在材料合成过程中原位添加碱金属或碱土金属盐,焙烧转变为碱金属或碱土金属氧化物制备而得。乙醇的转化率可达到50%以上,丁醇选择性达到70%以上。
Description
技术领域
本发明为一种催化乙醇制备丁醇的固体碱性催化剂及制备方法,具体涉及一种多孔碳固体碱的制备方法。
背景技术
正丁醇是一种受到国内外广泛关注的化工产品,大量用于萃取剂和生产制造邻苯二甲酸、脂肪族二元酸及磷酸的正丁酯类增塑剂以及丁醛、丁酸、丁胺和乳酸丁酯等的原料。近年来正丁醇代替乙醇作为燃料添加更具有市场前景,因此从生物原料乙醇低成本制备正丁醇成为能源发展的一个方向。
以催化体系分类,有均相液相催化和气固相多相催化。在发表在AngewandteChemie-International Edition,2013,52(34),9005-9008文章中报道,均相催化体系中,采用Ru的有机磷配合物为催化剂正丁醇选择性90%,但是乙醇转化率只能达到20%。而且这种昂贵的金属配合物和高压反应条件并不适于大规模生产。利用固体催化剂在常压气固相流动体系中进行反应,反应设备更加简单有利于工业化生产。而所用固体催化剂主要为碱性催化剂或者过度金属催化。2006年,日本的Takashi等以羟基磷灰石(Ca-HAP)为催化剂通过调节羟基磷灰石的钙磷比(Ca/P=1.50),在320℃接触时间为1.78s时,乙醇的转化率可达到20%,而正丁醇的选择性达到70%,这是至今在气固相催化反应体系中正丁醇选择性最高的报道[Direct synthesis of n-butanol from ethanol overnonstoichiometric hydroxyapatite.Industrial &Engineering Chemistry Research,2006,45(25),8634-8642]。2011年ShuheiOgo发现磷酸锶羟基磷灰石(Sr-HAP)对乙醇转化生成正丁醇也有很好的催化效果,其反应的决速步骤是醇醛缩合。与Ca-HAP相比,Sr-HAP的碱性中心比酸性中心多,所以表现出了更好的正丁醇选择性[1-Butanol synthesis fromethanol over strontium phosphate hydroxyapatite catalysts with various Sr/Pratios.Journal of Catalysis,2012,296,24-30.]。同样的催化机理,2013年,JosephT.Kozlowski等[Sodium modification of zirconia catalysts for ethanol couplingto 1-butanol.Journal of Energy Chemistry,2013,22(1),58-64.]报道了负载了1.0wt%碱金属钠的ZrO2作为催化剂进行乙醇转丁醇的反应。ZrO2同时具有酸性位点和碱性位点,乙醇脱水变成乙烯的速率往往大于脱氢变为乙醛的速率。负载了金属钠以后,表面酸性中心密度减小,乙醇脱水速率下降为原来的5%,产物中乙烯的含量明显下降,丁醇的选择性则增大。
国内外所考察的催化剂主要有两种功能:一是乙醇脱氢制备乙醛;二是乙醛在碱性催化剂作用下缩合的丁醛,然后加氢得到正丁醇。而今报道的各种催化剂在气固相催化反应中,正丁醇最高选择性为70%,但其乙醇转化率只有20%,远远达不到工业化的要求。因此开发具有高选择性和转化率的催化剂成为乙醇缩合生成正丁醇工业化的当务之急,是提高乙醛缩合制备丁醇的关键步骤。
固体碱催化剂在有机合成和化学工业中有着广泛的应用,由于其可以催化很多反应,早已成为催化学科中的一个重要领域。固体碱包括碱土金属氧化物、负载碱金属或者碱金属化合物的金属氧化物、沸石、氮氧化物、氨基功能化的介孔氧化硅、类水滑石化合物和它们的煅烧派生物。但是在应用于乙醇制备丁醇的固体碱催化剂中,乙醇转化率和丁醇选择性较小。
发明内容
本发明的目的就是提供一种多孔碳固体碱,增加碱性和催化剂的比表面积,提高乙醇缩合制备丁醇的催化活性。
本发明的技术方案如下:
一种催化乙醇制备丁醇的固体碱性催化剂,以对碱高稳定性的材料为载体,通过负载或者在材料合成过程中原位添加碱金属或碱土金属盐,焙烧转变为碱金属或碱土金属氧化物制备而得。
优选的是:所述乙醇的转化率可达到50%以上,丁醇选择性达到70%以上。
优选的是:对碱高稳定性的材料为多孔碳材料。
本发明还提供制备上述催化乙醇制备丁醇的固体碱性催化剂的方法,包括以下步骤:
称取碱前驱体溶于水中,加入多孔碳材料,在室温下搅拌0.5-12小时,然后置于60-100℃下搅拌蒸干,得到负载碱前驱体的多孔碳;
然后将所得负载碱前驱体的多孔碳置于惰性气氛下,在300-600℃下焙烧2-8小时得到多孔碳固体碱。
优选的是,碱前驱体为碱金属或碱土金属硝酸盐。
优选的是,碱前驱体为硝酸钾、硝酸钠、硝酸钙或硝酸镁。
优选的是,所负载的碱前驱体与多孔碳的质量比范围为0.05-0.4。
优选的是,所述多孔碳为孔径1-20nm,比表面积300-1500m2/g的椰壳活性碳或介孔碳。
优选的是,惰性气氛为氮气、氩气或氦气。
本发明进一步提供采用上述催化乙醇制备丁醇的固体碱性催化剂进行乙醇缩合的方法,将多孔碳固体碱置于固定床反应器中,氮气下通入乙醇,在260-460℃下常压缩合反应,乙醇流速为6-30mL g-1h-1,冷凝后收集产物。
本发明中催化剂的制备策略为以热稳定性特别是对碱稳定性较高的多孔碳材料为载体,通过负载或者在多孔碳合成过程中原位添加碱金属或碱土金属盐的方法,通过焙烧转变为碱金属或碱土金属氧化物制备固体超强碱,增强催化剂碱性,提高催化活性位的分散,以提高反应活性。
乙醇缩合制备正丁醇过程是通过乙醇脱氢制备乙醛、乙醛缩合脱水形成丁醛然后加氢得到丁醇。催化活性的提高主要从提高乙醇转化率和丁醇选择性两方面来完成。
本发明的多孔碳固体碱的调控也主要围绕这两个方面开展。一是提高催化剂的碱性提高乙醛缩合活性,从而提高乙醇的转化率;二是增大催化剂的比表面积,提高反应质在催化剂中的扩散速率,让生成的产物正丁醇快速脱附从而提高正丁醇的选择性。催化剂制备是通过选择具有高比表面积的多孔碳为载体,利用碳与硝酸盐的反应分解硝酸盐形成碱金属和碱土金属氧化物。特别是,多孔碳的耐碱性和热稳定性使其保持载体的高比表面积,以提高物质的传输速率。
本发明采用不同结构多孔碳材料作为载体,例如椰壳活性碳,介孔碳等,这些碳材料孔隙结构发达,比表面积大,具有良好的化学和物理稳定性,这种多孔碳材料作为载体不但能均匀的分散碱前驱体,使碱性位更好的分布于其表面,提高催化剂的比表面积,增加孔隙率,提高反应物质的传输效率;而且利用碳的还原性降低碱前驱体的分解温度,降低固体碱制备的焙烧温度。
具体实施方式
称取碱前驱体溶于水中,加入多孔碳材料,在室温下搅拌0.5-12小时,然后置于60-100℃下搅拌蒸干,然后将所得负载碱前驱体的多孔碳置于惰性气氛下,在300-600℃下焙烧2-8小时得到多孔碳固体碱。将多孔碳固体碱置于固定床反应器中,氮气下通入乙醇,在260-460℃下常压缩合反应,乙醇流速为6-30mL g-1h-1,冷凝后收集产物。
实施例1
在烧杯中加入1g硝酸钾,然后加入水30mL,搅拌溶解后加入椰壳活性碳10g(比表面积620m2/g,孔径1-2nm),室温搅拌2小时后,然后置于60℃水浴中搅拌蒸干,再置于80℃的烘箱中干燥12小时后得到碱前驱体负载的椰壳活性碳。所得复合物置于管式炉中在600℃氮气气氛下焙烧2小时得到椰壳活性碳固体超强碱。采用固定床反应器,以椰壳活性碳固体超强碱为催化剂,考察了乙醇转丁醇反应,冷却收集产物,用气相色谱仪对产物进行分析产物组成,计算乙醇的转化率和丁醇的选择性。通过进行气固相催化实验,乙醇的转化率可以达到52%,丁醇的选择性达到48%。
实施例2
在烧杯中加入0.5g硝酸镁,然后加入水20mL,搅拌溶解后加入介孔碳3g(比表面积1050m2/g,孔径5-8nm),室温搅拌2小时后,然后置于60℃水浴中搅拌蒸干,再置于80℃的烘箱中干燥12小时后得到碱前驱体负载的介孔碳。所得复合物置于管式炉中在400℃氮气气氛下焙烧5小时得到介孔碳固体超强碱。采用固定床反应器,以介孔碳固体超强碱为催化剂,考察了乙醇转丁醇反应,冷却收集产物,用气相色谱仪对产物进行分析产物组成,计算乙醇的转化率和丁醇的选择性。通过进行气固相催化实验,乙醇的转化率可以达到64%,丁醇的选择性达到46%。
实施例3
在烧杯中加入1g硝酸锂,然后加入水20mL,搅拌溶解后加入木质活性炭6g(比表面积420m2/g,孔径10-30nm),室温搅拌2小时后,然后置于60℃水浴中搅拌蒸干,再置于80℃的烘箱中干燥12小时后得到碱前驱体负载的木质活性炭。所得复合物置于管式炉中在500℃氮气气氛下焙烧3小时得到木质活性炭固体超强碱。采用固定床反应器,以介孔碳固体超强碱为催化剂,考察了乙醇转丁醇反应,冷却收集产物,用气相色谱仪对产物进行分析产物组成,计算乙醇的转化率和丁醇的选择性。通过进行气固相催化实验,乙醇的转化率可以达到44%,丁醇的选择性达到70%。
通过测定样品的氮气等温吸附和二氧化碳程序升温脱附的方法测定了样品的比表面积和碱强度。表1为3个实施例多孔碳固体碱的比表面积和碱强度。
表13个实施例多孔碳固体碱的比表面积和碱强度
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在获知本发明中记载内容后,在不脱离本发明原理的前提下,还可以对其作出若干同等变换和替代,这些同等变换和替代也应视为属于本发明的保护范围。
Claims (10)
1.一种催化乙醇制备丁醇的固体碱性催化剂,其特征在于:以对碱高稳定性的材料为载体,通过负载或者在材料合成过程中原位添加碱金属或碱土金属盐,焙烧转变为碱金属或碱土金属氧化物制备而得。
2.根据权利要求1所述一种催化乙醇制备丁醇的固体碱性催化剂,其特征在于:所述乙醇的转化率可达到50%以上,丁醇选择性达到70%以上。
3.根据权利要求1所述一种催化乙醇制备丁醇的固体碱性催化剂,其特征在于:对碱高稳定性的材料为多孔碳材料。
4.制备根据权利要求1-3任一所述一种催化乙醇制备丁醇的固体碱性催化剂的方法,其特征在于,包括以下步骤:
称取碱前驱体溶于水中,加入多孔碳材料,在室温下搅拌0.5-12小时,然后置于60-100℃下搅拌蒸干,得到负载碱前驱体的多孔碳;
然后将所得负载碱前驱体的多孔碳置于惰性气氛下,在300-600℃下焙烧2-8小时得到多孔碳固体碱。
5.根据权利要求4所述方法,其特征在于,碱前驱体为碱金属或碱土金属硝酸盐。
6.根据权利要求4所述方法,其特征在于,碱前驱体为硝酸钾、硝酸钠、硝酸钙或硝酸镁。
7.根据权利要求4所述方法,其特征在于,所负载的碱前驱体与多孔碳的质量比范围为0.05-0.4。
8.根据权利要求4方法,其特征在于,所述多孔碳为孔径1-20nm,比表面积300-1500m2/g的椰壳活性碳或介孔碳。
9.根据权利要求4所述方法,其特征在于,惰性气氛为氮气、氩气或氦气。
10.采用根据权利要求1-3任一所述一种催化乙醇制备丁醇的固体碱性催化剂进行乙醇缩合的方法,其特征在于:将多孔碳固体碱置于固定床反应器中,氮气下通入乙醇,在260-460℃下常压缩合反应,乙醇流速为6-30mL g-1h-1,冷凝后收集产物。
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