CN112569965B - 一种双过渡金属多级孔催化剂及其制备方法和应用 - Google Patents
一种双过渡金属多级孔催化剂及其制备方法和应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 33
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 100
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 26
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 17
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 11
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 9
- 239000007791 liquid phase Substances 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052737 gold Inorganic materials 0.000 claims abstract description 3
- 229910052738 indium Inorganic materials 0.000 claims abstract description 3
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
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- 229910052697 platinum Inorganic materials 0.000 claims abstract description 3
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 3
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- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 6
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 6
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- -1 organic acid salt Chemical class 0.000 claims description 6
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- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005859 coupling reaction Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- KTHXBEHDVMTNOH-UHFFFAOYSA-N cyclobutanol Chemical compound OC1CCC1 KTHXBEHDVMTNOH-UHFFFAOYSA-N 0.000 claims description 4
- FHADSMKORVFYOS-UHFFFAOYSA-N cyclooctanol Chemical compound OC1CCCCCCC1 FHADSMKORVFYOS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 3
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 claims description 3
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- QGLBZNZGBLRJGS-UHFFFAOYSA-N Dihydro-3-methyl-2(3H)-furanone Chemical compound CC1CCOC1=O QGLBZNZGBLRJGS-UHFFFAOYSA-N 0.000 claims description 3
- DSLZVSRJTYRBFB-UHFFFAOYSA-N Galactaric acid Natural products OC(=O)C(O)C(O)C(O)C(O)C(O)=O DSLZVSRJTYRBFB-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 claims description 3
- 238000010168 coupling process Methods 0.000 claims description 3
- RLMGYIOTPQVQJR-UHFFFAOYSA-N cyclohexane-1,3-diol Chemical compound OC1CCCC(O)C1 RLMGYIOTPQVQJR-UHFFFAOYSA-N 0.000 claims description 3
- NUUPJBRGQCEZSI-UHFFFAOYSA-N cyclopentane-1,3-diol Chemical compound OC1CCC(O)C1 NUUPJBRGQCEZSI-UHFFFAOYSA-N 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- DSLZVSRJTYRBFB-DUHBMQHGSA-N galactaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)C(O)=O DSLZVSRJTYRBFB-DUHBMQHGSA-N 0.000 claims description 3
- 239000000174 gluconic acid Substances 0.000 claims description 3
- 235000012208 gluconic acid Nutrition 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 3
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- QCRFMSUKWRQZEM-UHFFFAOYSA-N cycloheptanol Chemical compound OC1CCCCCC1 QCRFMSUKWRQZEM-UHFFFAOYSA-N 0.000 claims description 2
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 abstract description 112
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
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- B01J35/647—2-50 nm
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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
- C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
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- C07C2601/14—The ring being saturated
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Abstract
本发明公开了一种双过渡金属多级孔催化剂及其制备方法和应用,该高比表面多级孔催化剂以多级孔SiO2为载体,包括:0.1‑2wt%的贵金属组分和10‑20wt%的过渡金属组分;其中,贵金属组分为Rh、Ru、Pt、Pd、Au、Ir、Os中的一种或两种的混合物,过渡金属组为Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Mo、In、W、Re中的一种或两种的混合物。本发明的双过渡金属多级孔催化剂在液相条件下无需外部氢源即可实现糠醛催化加氢、环醇催化脱氢耦合反应,制备较有价值的糠醇和环酮产物,其中糠醛的转化率最高达98%,加氢产物糠醇选择性最高达92%,环醇脱氢的产物环酮选择性接近100%。
Description
技术领域
本发明涉及化学药剂领域,具体涉及一种双过渡金属多级孔催化剂及其制备方法和应用。
背景技术
目前工业上制取糠醇都是采用糠醛催化加氢法生产。我国是糠醛生产大国,在糠醛深加工后续产品中,糠醇是价值很高的产品之一,其化学名2-羟甲基呋喃,是一种重要的香料、香味剂、医药、农药、溶剂中间体。糠醇又可用于生产乙酰丙酸、糠醛树脂、呋喃树脂、改性脲醛和酚醛树脂等,其中80%~90%的糠醇消耗于呋喃树脂的生产。
目前,工业上糠醛催化加氢制糠醇主要分为高压液相加氢和低压气相加氢两种工艺,这两种工艺各有优缺点(如中国专利CN 1876233 A,CN 106807423A,CN 106749120A,CN109776628A等),尤其是高压液相加氢法对设备要求很高,直接加大了设备投入成本;而低压气相加氢法对催化剂的催化活性要求又比较高。同时,无论在气相还是液相条件下,加氢的共同缺点是需要大量工业H2作为氢源。于此同时,环己醇、环戊醇等环醇的脱氢反应由于其较高的活化能和可逆性,工业上需要高温汽化后在固定床中进行(如中国专利CN103285848B,CN 103861626A,CN 105218342A等),容易产生副反应且脱出的H2无法利用。上述两类过程均导致了较高的能耗和设备成本。
发明内容
为解决上述问题,本发明提供了一种双过渡金属多级孔催化剂及其制备方法和应用。
为实现上述目的,本发明采取的技术方案为:
一种双过渡金属多级孔催化剂,该高比表面多级孔催化剂以多级孔SiO2为载体,包括:0.1-2wt% 的贵金属组分和10-20wt% 的过渡金属组分;其中,贵金属组分为 Rh、Ru、Pt、Pd、Au、Ir、Os中的一种或两种的混合物,过渡金属组为 Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Mo、In、W、Re 中的一种或两种的混合物。
本发明还提供了上述一种双过渡金属多级孔催化剂的制备方法,包括如下步骤:
将过渡金属可溶盐、有机硅烷、水和有机酸造孔剂按质量比为1:(15-20):(25-35):(5-15)的比例混合后,在60-90℃反应并生成硅凝胶,450-550℃焙烧并还原后,即得。
进一步地,所述的过渡金属可溶盐为硝酸盐、氯化盐或有机酸盐,有机硅烷为四甲氧基硅烷、四乙氧基硅烷、四丙氧基硅烷、正硅酸四甲酯、正硅酸四乙酯、正硅酸四丁酯中的一种,有机酸造孔剂为草酸、乙醇酸、柠檬酸、丙二酸、丁二酸、1,2,3,4-丁烷四羧酸、酒石酸、苹果酸、葡萄糖酸、粘酸、对苯二甲酸、1,3,5-苯三甲酸、1,2,4,5-苯四甲酸、2,2-双(羟基甲基)丙酸中的一种或几种的混合物。
进一步地,所述高比表面多级孔催化剂的比表面积为范围为300-800 m2/g,其微孔孔径范围为0.7-1.6 nm,介孔孔径范围为3-14 nm,且催化剂同时含有大量微孔和介孔。
本发明的双过渡金属多级孔催化剂可用于加氢-脱氢耦合反应,不需要氢气作为外部氢源对糠醛催化加氢,也不需将环醇高温气化进行脱氢,不仅降低了成本,提高了安全性,且反应启动温度大大降低,因此本工艺可视为一种新颖且经济可行的工艺,有一定的工业化前景;具体的,包括如下步骤:将生物质糠醛、溶剂和环醇混合,加入双过渡金属多级孔催化剂,双过渡金属多级孔催化剂与醛、环醇的重量比为 1:(1.5-6):(3-12),在液相加热的条件下发生生物质醛-环醇的加氢-脱氢耦合过程,反应温度为165-210℃,反应时间为4-24小时;然后将反应所得的混合物在高速离心机中进行离心,将催化剂与滤液分开。
进一步地,所述生物质糠醛为糠醛(α-呋喃甲醛)、5-羟甲基糠醛的一种或两种的混合物;发生脱氢反应的环醇作为氢源,为环辛醇、环己醇、环戊醇、环丁醇、1,4-环己二醇、1,3-环己二醇、1,3-环戊二醇中的一种。
进一步地,所述的溶剂为甲醇、乙醇、正丁醇、四氢呋喃、异丙醇、苯、烷基苯、环己烷、二氧六环、N-N二甲基甲酰胺(简称DMF),乙酸乙酯、gama-戊内酯等中的一种。
本发明具有以下有益效果:
以糠醛和环醇为原料,使用原位合成的高比表面双金属多级孔催化剂,一釜进行糠醛催化加氢、环醇催化脱氢耦合反应,制备较有价值的糠醇和环酮产物。反应过程中糠醛的转化率最高可达98%,加氢产物糠醇选择性最高可达92%,环醇脱氢的产物环酮最高选择性接近100%。由于本发明是一釜同时制备两种产物,没有中间步骤,也无其他副产物,在较低温度下无需进行复杂的固定床气化传输和后续冷凝处理,而仅仅是对离心分离后的反应液进行蒸馏或精馏即可得到目标产物,故可以增加经济效益。本发明使用的溶剂经蒸馏后可重复使用,甚至本发明的环酮产物自身也可作为溶剂使用,未反应的环醇可重新投料脱氢,故不污染环境;整个过程产物选择性相对较高,操作简便,流程短,成本低,安全性高,过程绿色。具有很好的工业化应用前景,对我国的经济发展具有重要的战略意义。
附图说明
图1为双金属多级孔催化剂催化下的糠醛加氢-环醇脱氢耦合反应流程图。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明,但不以任何形式限制本发明。应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进。这些都属于本发明的保护范围。
实施例1
一种双过渡金属多级孔催化剂的制备方法,包括如下步骤:
将过渡金属可溶盐、有机硅烷、水和有机酸造孔剂按质量比为1:(15-20):(25-35):(5-15)的比例混合后,在60-90℃反应并生成硅凝胶,450-550℃焙烧并还原后,即得。
本实施例中,所述的过渡金属可溶盐为硝酸盐、氯化盐或有机酸盐,有机硅烷为四甲氧基硅烷、四乙氧基硅烷、四丙氧基硅烷、正硅酸四甲酯、正硅酸四乙酯、正硅酸四丁酯中的一种,有机酸造孔剂为草酸、乙醇酸、柠檬酸、丙二酸、丁二酸、1,2,3,4-丁烷四羧酸、酒石酸、苹果酸、葡萄糖酸、粘酸、对苯二甲酸、1,3,5-苯三甲酸、1,2,4,5-苯四甲酸、2,2-双(羟基甲基)丙酸中的一种或几种的混合物。
本实施例中,所述高比表面多级孔催化剂的比表面积为范围为300-800 m2/g,其微孔孔径范围为0.7-1.6 nm,介孔孔径范围为3-14 nm,且催化剂同时含有大量微孔和介孔。
实施例2
实施例1所得的双过渡金属多级孔催化剂可用于加氢-脱氢耦合反应,
如图1所示,糠醛加氢和环醇脱氢的过程耦合同步进行,同时生成目标产物糠醇和环酮,整个过程在同一个反应釜里通过一种多级孔双金属催化剂实现。
操作时,将生物质糠醛、溶剂和环醇混合,加入双过渡金属多级孔催化剂,双过渡金属多级孔催化剂与醛、环醇的重量比为 1:(1.5-6):(3-12),在液相加热的条件下发生生物质醛-环醇的加氢-脱氢耦合过程,反应温度为165-210℃,反应时间为4-24小时;然后将反应所得的混合物在高速离心机中进行离心,将催化剂与滤液分开。
本实施例中,所述生物质糠醛为糠醛(α-呋喃甲醛)、5-羟甲基糠醛的一种或两种的混合物;发生脱氢反应的环醇作为氢源,为环辛醇、环己醇、环戊醇、环丁醇、1,4-环己二醇、1,3-环己二醇、1,3-环戊二醇中的一种。
本实施例中,所述的溶剂为甲醇、乙醇、正丁醇、四氢呋喃、异丙醇、苯、烷基苯、环己烷、二氧六环、N-N二甲基甲酰胺(简称DMF),乙酸乙酯、gama-戊内酯等中的一种。
反应得到的糠醇和环酮产物可与溶剂进行蒸馏提纯。
实施例3
将实施例2中的反应过程细化之后,可以得到具有不同特征的关键反应参数。本实施例有助于技术人员理解溶剂体系对于本发明的影响。将1.5g糠醛、4.5g环己醇和0.5g催化剂(15%Cu-0.5%Pd/SiO2)加入高压反应釜中,每单次加入10.5g不同溶剂,重复多个不同溶剂实验。使其在195℃下磁力高速搅拌反应10h,待反应结束后,利用高速离心机将催化剂与反应液分离。反应液经气相色谱分析,糠醛、氢源的转化率和加氢产物糠醇、脱氢产物环己酮的选择性如表一所示。
表1 不同物质做溶剂时糠醛、环己醇制备糠醇、环己酮的性能
溶剂 | 糠醛转化率(%) | 糠醇选择性(%) | 环己醇转化率(%) | 环己酮选择性(%) |
苯 | 11.8 | 91.2 | 4.5 | 74.7 |
甲苯 | 9.5 | 74.2 | 4.0 | 73.4 |
环己烷 | 20.6 | 59.0 | 6.1 | 65.8 |
四氢呋喃 | 23.3 | 88.8 | 8.1 | 81.7 |
乙酸乙酯 | 58.9 | 85.3 | 20.1 | 83.1 |
乙醇 | 72.9 | 63.4 | 25.6 | 74.6 |
甲醇 | 86.7 | 68.4 | 28.3 | 92.0 |
实施例4
反应原料及步骤同实施例3,使用的溶剂为甲醇,不同在于所加环醇的种类。本实施例有助于技术人员理解氢源体系对本发明的影响。反应液经气相色谱分析,糠醛、环己醇的转化率和糠醇、环酮的选择性如表2所示。
表2不同环醇做氢源时糠醛制备糠醇的性能
环醇氢源 | 糠醛转化率(%) | 糠醇选择性(%) | 环醇转化率(%) | 对应环酮选择性(%) |
环辛醇 | 69.3 | 36.5 | 31.2 | 60.9 |
环庚醇 | 71.3 | 42.8 | 30.4 | 75.6 |
环己醇 | 86.7 | 68.4 | 28.3 | 92.0 |
1,4-环己二醇 | 96.8 | 92.4 | 16.4 | 89.5 |
环戊醇 | 79.3 | 60.1 | 27.1 | 90.9 |
环丁醇 | 70.9 | 65.2 | 38.4 | 57.7 |
实施例5
反应步骤同实施例3,使用的溶剂为甲醇,不同在于改变反应的温度。本实施例有助于技术人员理解温度体系对本发明的影响。反应液经气相色谱分析,糠醛、环己醇的转化率和糠醇、环己酮的选择性如表3所示。
表3 不同温度下糠醛、环己醇制备糠醇、环己酮的性能
反应温度(<sup>o</sup>C) | 糠醛转化率(%) | 糠醇选择性(%) | 环己醇转化率(%) | 环己酮选择性(%) |
185 | 62.6 | 57.4 | 21.2 | 95.4 |
190 | 71.4 | 59.8 | 23.0 | 96.2 |
195 | 86.7 | 68.4 | 28.3 | 92.0 |
200 | 95.0 | 58.6 | 31.7 | 95.5 |
205 | 95.3 | 32.2 | 32.7 | 95.7 |
实施例6
反应原料及步骤同实施例3,使用的溶剂为甲醇,反应温度为195oC,不同在于改变反应的时间。本实施例有助于技术人员理解反应时间对本发明的影响。反应液经气相色谱分析,糠醛、环己醇的转化率和糠醇、环己酮的选择性如表4所示。
表4 不同反应时间下糠醛、环己醇制备糠醇、环己酮的性能
反应时间(h) | 糠醛转化率(%) | 糠醇选择性(%) | 环己醇转化率(%) | 环己酮选择性(%) |
2 | 28.1 | 56.3 | 10.1 | 79.2 |
4 | 52.9 | 66.4 | 17.2 | 87.1 |
6 | 65.9 | 62.6 | 21.0 | 90.5 |
8 | 83.7 | 66.1 | 27.3 | 91.5 |
10 | 86.7 | 68.4 | 28.3 | 92.0 |
12 | 95.2 | 59.8 | 31.5 | 98.0 |
实施例7
反应原料及步骤同实施例3,使用的溶剂为甲醇,不同在于改变催化剂上负载的金属种类(其中贵金属质量分数为为0.5%,非贵金属为15%,以SiO2为100%质量计)。本实施例有助于技术人员理解催化剂中金属组分对加氢-脱氢性能的影响。反应液经气相色谱分析,糠醛、环己醇的转化率和糠醇、环己酮的选择性如表5所示。
表5催化剂上负载不同贵金属糠醛、环己醇制备糠醇、环己酮的性能
贵金属组分 | 糠醛转化率(%) | 糠醇选择性(%) | 环己醇转化率(%) | 环己酮选择性(%) |
(Cu-)Pd | 86.7 | 68.4 | 28.3 | 92.0 |
(Cu-)Ru | 84.9 | 67.2 | 27.0 | 92.7 |
(Cu-)Pt | 89.9 | 69.7 | 31.5 | 94.0 |
(Cu-)Rh | 76.0 | 58.8 | 24.7 | 90.7 |
非贵金属组分 | 糠醛转化率(%) | 糠醇选择性(%) | 环己醇转化率(%) | 环己酮选择性(%) |
Co(-Pd) | 90.8 | 76.4 | 31.0 | 94.8 |
Ni(-Pd) | 91.9 | 87.3 | 33.7 | 98.5 |
Zn(-Pd) | 74.5 | 52.1 | 26.2 | 92.0 |
实施例8
反应原料及步骤同实施例3,使用的溶剂为甲醇,不同在于改变催化剂中两种金属的比例(以SiO2为100%质量计)。本实施例有助于技术人员理解双金属相对含量在本发明中对加氢-脱氢性能的影响。反应液经气相色谱分析,糠醛、环己醇的转化率和糠醇、环己酮的选择性如表6所示。
表6催化剂中金属不同比例下糠醛、环己醇制备糠醇、环己酮的性能
催化剂中金属比例 | 糠醛转化率(%) | 糠醇选择性(%) | 环己醇转化率(%) | 环己酮选择性(%) |
15%Cu-0.25%Pd | 65.7 | 51.3 | 21.2 | 92.0 |
15%Cu-1%Pd | 93.9 | 30.9 | 32.1 | 94.2 |
15%Cu-0.5%Pd | 86.7 | 68.4 | 28.3 | 92.0 |
10%Cu-0.5%Pd | 79.7 | 58.6 | 22.1 | 96.3 |
20%Cu-0.5%Pd | 97.0 | 55.9 | 33.7 | 92.5 |
实施例9
反应原料及步骤同实施例3,使用的溶剂为甲醇,不同在于改变加入催化剂的质量。本实施例有助于技术人员理解催化剂/反应物比例对本发明的影响。反应液经气相色谱分析,糠醛、环己醇的转化率和糠醇、环己酮的选择性如表7所示。
表7不同催化剂质量下糠醛、环己醇制备糠醇、环己酮的性能
催化剂质量(g) | 糠醛转化率(%) | 糠醇选择性(%) | 环己醇转化率(%) | 环己酮选择性(%) |
0.25 | 47.3 | 53.9 | 16.1 | 88.4 |
0.5 | 86.7 | 68.4 | 28.3 | 92.0 |
1 | 91.4 | 29.0 | 24.1 | 96.8 |
实施例10
反应原料及步骤同实施例3,使用的溶剂为甲醇,不同在于加入原料糠醛和环醇的质量比。本实施例有助于技术人员理解待加氢原料和脱氢原料的比例对本发明的影响。反应液经气相色谱分析,糠醛、环醇的转化率和糠醇、环酮的选择性如表8所示。
表8糠醛与环醇的不同质量比下糠醛、环醇制备糠醇、环酮的性能
糠醛:环醇 | 糠醛转化率(%) | 糠醇选择性(%) | 环己醇转化率(%) | 环己酮选择性(%) |
1:6(环己醇) | 98.5 | 54.1 | 17.1 | 88.3 |
1:4(环己醇) | 95.4 | 76.9 | 30.2 | 92.6 |
1:3(环己醇) | 86.7 | 68.4 | 28.3 | 92.0 |
1:2(环己醇) | 59.4 | 42.2 | 25.5 | 91.3 |
1:1.5(环己醇) | 40.3 | 50.5 | 23.9 | 92.0 |
1:6(环戊醇) | 83.1 | 54.2 | 25.4 | 96.1 |
1:3(环戊醇) | 79.3 | 60.1 | 27.1 | 90.9 |
1:2 (环戊醇) | 49.3 | 58.5 | 19.2 | 98.2 |
以上对本发明的具体实施例进行了描述。需要理解的是,本发明并不局限于上述特定实施方式,本领域技术人员可以在权利要求的范围内做出各种变化或修改,这并不影响本发明的实质内容。在不冲突的情况下,本申请的实施例和实施例中的特征可以任意相互组合。
Claims (7)
1.一种双过渡金属多级孔催化剂,其特征在于:高比表面多级孔催化剂以多级孔SiO2为载体,包括:0.1-2wt% 的贵金属组分和10-20wt% 的过渡金属组分;其中,贵金属组分为Rh、Ru、Pt、Pd、Au、Ir、Os中的一种或两种的混合物,过渡金属组分为 Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Mo、In、W、Re 中的一种或两种的混合物;制备时,包括如下步骤:
将过渡金属可溶盐、有机硅烷、水和有机酸造孔剂按质量比为1:(15-20):(25-35):(5-15)的比例混合后,在60-90℃反应并生成硅凝胶,450-550℃焙烧并还原后,即得;
有机酸造孔剂为草酸、乙醇酸、柠檬酸、丙二酸、丁二酸、1,2,3,4-丁烷四羧酸、酒石酸、苹果酸、葡萄糖酸、粘酸、对苯二甲酸、1,3,5-苯三甲酸、1,2,4,5-苯四甲酸、2,2-双(羟基甲基)丙酸中的一种或几种的混合物。
2.如权利要求1所述的一种双过渡金属多级孔催化剂,其特征在于:所述的过渡金属可溶盐为硝酸盐、氯化盐或有机酸盐,有机硅烷为四甲氧基硅烷、四乙氧基硅烷、四丙氧基硅烷、正硅酸四甲酯、正硅酸四乙酯、正硅酸四丁酯中的一种。
3.如权利要求1所述的一种双过渡金属多级孔催化剂,其特征在于:所述高比表面多级孔催化剂的比表面积为范围为300-800 m2/g,其微孔孔径范围为0.7-1.6 nm,介孔孔径范围为3-14 nm,且催化剂同时含有大量微孔和介孔。
4.如权利要求1所述的一种双过渡金属多级孔催化剂的应用,其特征在于:可用于生物质糠醛与环醇之间的加氢-脱氢耦合反应。
5.如权利要求4所述的应用,其特征在于:包括如下步骤:将生物质糠醛、溶剂和环醇混合,加入双过渡金属多级孔催化剂,双过渡金属多级孔催化剂与醛、环醇的重量比为 1:(1.5-6):(3-12),在液相加热的条件下发生生物质醛-环醇的加氢-脱氢耦合过程,反应温度为165-210℃,反应时间为4-24小时;然后将反应所得的混合物在高速离心机中进行离心,将催化剂与滤液分开。
6.如权利要求5所述的应用,其特征在于:所述生物质糠醛为糠醛(α-呋喃甲醛)、5-羟甲基糠醛的一种或两种的混合物;发生脱氢反应的环醇作为氢源,为环辛醇、环庚醇、环己醇、环戊醇、环丁醇、1,4-环己二醇、1,3-环己二醇、1,3-环戊二醇中的一种。
7.如权利要求5所述的应用,其特征在于:所述的溶剂为甲醇、乙醇、正丁醇、四氢呋喃、异丙醇、苯、烷基苯、环己烷、二氧六环、N-N二甲基甲酰胺(简称DMF),乙酸乙酯、gama-戊内酯中的一种。
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