CN109689606A - 制备1,3-环己烷二甲醇的方法 - Google Patents
制备1,3-环己烷二甲醇的方法 Download PDFInfo
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- CN109689606A CN109689606A CN201780054605.0A CN201780054605A CN109689606A CN 109689606 A CN109689606 A CN 109689606A CN 201780054605 A CN201780054605 A CN 201780054605A CN 109689606 A CN109689606 A CN 109689606A
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- metallic catalyst
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- 238000000034 method Methods 0.000 title claims abstract description 62
- LUSFFPXRDZKBMF-UHFFFAOYSA-N [3-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCC(CO)C1 LUSFFPXRDZKBMF-UHFFFAOYSA-N 0.000 title abstract description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 87
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 150000001875 compounds Chemical class 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000003863 metallic catalyst Substances 0.000 claims abstract description 45
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 31
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 31
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 27
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 27
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 claims description 31
- 230000009467 reduction Effects 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000004364 calculation method Methods 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 23
- 239000000376 reactant Substances 0.000 abstract description 19
- 239000006227 byproduct Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 description 29
- 229910052751 metal Inorganic materials 0.000 description 22
- 239000002184 metal Substances 0.000 description 22
- 229910052718 tin Inorganic materials 0.000 description 22
- 238000006722 reduction reaction Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000003247 decreasing effect Effects 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- LAWHHRXCBUNWFI-UHFFFAOYSA-N 2-pentylpropanedioic acid Chemical compound CCCCCC(C(O)=O)C(O)=O LAWHHRXCBUNWFI-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- -1 alkane dicarboxylic acids Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- CUGZEDSDRBMZMY-UHFFFAOYSA-N trihydrate;hydrochloride Chemical compound O.O.O.Cl CUGZEDSDRBMZMY-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
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- C07C29/147—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 carboxylic acids or derivatives thereof
- C07C29/149—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 carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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Abstract
本发明涉及一种制备高纯度1,3‑环己烷二甲醇的方法,该方法能够通过使大部分反应物参与反应来实现高转化率,并且通过进一步简化反应过程来提高反应效率和经济效益,同时在较短时间段内使副产物最少化。具体而言,制备1,3‑环己烷二甲醇的方法包括在金属催化剂存在下还原1,3‑环己烷二羧酸,该金属催化剂固定在二氧化硅载体上,并且包括重量比为1:0.8~1.2:1.2~2.4的钌(Ru)化合物、锡(Sn)化合物和铂(Pt)化合物。
Description
技术领域
本发明涉及一种制备1,3-环己烷二甲醇的方法。更具体地,本发明涉及一种制备高纯度1,3-环己烷二甲醇的方法,该方法能够通过使大部分反应物参与反应来实现高转化率,并且通过进一步简化反应过程来提高反应效率和经济效益,同时在较短时间段内使副产物最少化。
背景技术
传统的制备1,3-环己烷二甲醇的方法是这样的方法:通过异酞酸的酯化反应形成成间苯二甲酸二甲酯,然后在相当高的温度和高压下使用间苯二甲酸二甲酯进行加氢反应通过1,3-环己烷二羧酸二甲酯来合成1,3-环己烷二甲醇。然而,这些技术的缺点在于,它们涉及复杂的工艺步骤且需要高压,因此不经济。
日本公开特许公报第1991-184928号公开了一种制备1,3-环己烷二甲醇的方法,其使用铜铬催化剂,在碱金属共催化剂(如钡)的存在下,使1,3-环己烷二羧酸二乙基己酯进行加氢反应。然而,该制备方法在工业上是不利的,因为1,3-环己烷二羧酸二乙基己酯被用作原料,因此,由于其独特的特性,很难获得原料,且采用下流法作为反应方法。
美国专利第8877984号公开了一种通过异酞酸的酯化且随后加氢来制备1,3-环己烷二甲醇的工艺。但是,缺点是,从酯化材料开始,加氢反应应该按两步顺序进行,因此工艺复杂,且需要相当高的压力和时间。
因此,需要开发一种新的制备工艺技术,以取代本领域已知常规的制备1,3-环己烷二甲醇的工艺。
【现有技术文件】
【专利文件】
(专利文件1)日本公开特许公报1991-184928号
(专利文件2)美国专利号8877984
发明内容
【技术问题】
本发明的目的是意图提供一种制备1,3-环己烷二甲醇的方法,包括在金属催化剂存在下还原1,3-环己烷二羧酸的步骤,该金属催化剂固定在二氧化硅载体上,并且包括重量比为1:0.8~1.2:1.2~2.4的钌(Ru)化合物、锡(Sn)化合物和铂(Pt)化合物。
下文将更详细地描述根据本发明的具体实施方式的制备1,3-环己烷二甲醇的方法。
【技术方案】
根据本发明的一个实施方式,可提供制备1,3-环己烷二甲醇的方法,包括在金属催化剂存在下还原1,3-环己烷二羧酸的步骤,该金属催化剂固定在二氧化硅载体上,并且包括重量比为1:0.8~1.2:1.2~2.4的钌(Ru)化合物、锡(Sn)化合物和铂(Pt)化合物。
本发明的发明人研究了通过脂环二羧酸直接加氢来合成环烷二醇的方法,并通过实验发现,当使用固定到特定载体上且满足特定活性组分之间重量比的金属催化剂时,与传统工艺相比,通过简化的工艺,可在相对温和的温度和压力条件下以高转化率制备高纯度1,3-环己烷二甲醇,从而完成本发明。
具体而言,当使用固定到二氧化硅载体上并且包括特定重量比的钌(Ru)化合物、锡(Sn)化合物和铂(Pt)化合物的金属催化剂还原1,3-环己烷二羧酸时,几乎所有作为反应物的1,3-环己烷二羧酸都可以参与到反应中以获得高转化率,因此,可以提供高纯度的1,3-环己烷二甲醇,同时在较短的时间段内最少化副产物。
此外,在一个实施方式的制备方法中,使用其中金属催化剂的活性组分固定到特定的二氧化硅载体上的状态下的金属催化剂。由于活性组分固定到二氧化硅载体上,因此可以确保90%或更高的高反应转化率,从而实现这样的结果:确保最终制备的产品中1,3-环己烷二甲醇的选择性达到89%或更高。这种效果似乎归因于根据二氧化硅载体的孔隙特性的光滑反应效应。
进一步,基于根据一个实施方式的制备1,3-环己烷二甲醇的方法,在从1,3-环己烷二羧酸合成1,3-环己烷二甲醇的过程中,产生最少的副产物,使得可以省略分离和回收副产物的额外过程或步骤,并且可以最少化用于提高纯度的纯化过程。此外,根据一个实施方式的制备1,3-环己烷二甲醇的方法允许相对简化的反应设计,并且可以在较短的时间段内以高的产率提供高纯度的1,3-环己烷二甲醇,因此,可提高整个制备过程的效率和经济效益。
具体而言,根据一个实施方式的制备1,3-环己烷二甲醇的方法可以包括在金属催化剂存在下还原1,3-环己烷二羧酸,该金属催化剂固定到二氧化硅载体上,并且包括重量比为1:0.8~1.2:1.2~2.4的钌(Ru)化合物、锡(Sn)化合物和铂(Pt)化合物。
作为金属催化剂,可以使用钌(Ru)化合物、锡(Sn)化合物和铂(Pt)化合物作为活性组分,并且活性组分可以固定到二氧化硅载体上。制备上述金属催化剂的方法不受特别限制,并且可以通过在本发明所属技术领域中通常用于在多孔载体上负载催化活性金属的负载方法来实施。
具体而言,金属催化剂中包括的二氧化硅载体的比表面积可为100m2/g至500m2/g、200m2/g至300m2/g或250m2/g至260m2/g。当二氧化硅载体的比表面积过小时,反应物和催化剂的活性位点可减少,从而使反应不能顺利进行,或在催化剂中起着重要作用的金属可能无法在载体中得到适当的负载,因此,可能会出现孔隙堵塞或破裂的现象。而且,当二氧化硅载体的比表面积过大时,催化剂金属的分散度可能会过度增大,因此反应可能无法顺利进行。
金属催化剂中包括的二氧化硅载体的总孔隙体积可以是2cm3/g或更小、0.5cm3/g至2cm3/g、1cm3/g至2cm3/g、1cm3/g至1.5cm3/g或1cm3/g至1.1cm3/g。测量孔隙体积的方法的示例不受特别限制,并且,例如,可以使用BET测量方法。当金属催化剂中包括的二氧化硅载体的总孔隙体积过大时,反应物与催化剂之间的反应速度可能加速,因此可产生过量的副产物。而且,金属(活性组分)可能没有充分分散,使得反应物和催化剂之间的接触效率可能显著降低,因此反应可能无法顺利进行。
金属催化剂中包括的二氧化硅载体的平均孔径可以是至或至 如本文所用,平均孔径是指关于二氧化硅载体中含有的不同直径的孔的直径平均值。
二氧化硅载体可包括选自由二氧化硅、二氧化硅-氧化铝和二氧化硅-氧化镁组成的组中的至少一种化合物。
此外,金属催化剂中包括的二氧化硅载体的水含量可为0.1wt%至10wt%。如本文所用,载体的“水含量”定义为载体中所含的水的重量相对于载体总重量的百分比。
在负载催化剂之前二氧化硅载体可通过从平均气候条件的湿气中自然吸收水分而含有10wt%或更少的量的水分。当二氧化硅载体的水含量过高时,可能减少用于溶解金属组分的负载溶液的体积,并且当催化剂以过高的浓度制备时,分散度可能降低,而且,可使用根据需要通过单独的干燥过程降低水含量的二氧化硅载体。但是,从催化剂制备成本的经济角度考虑,可以省略或增加单独的干燥过程的应用。
金属催化剂中包括的二氧化硅载体可以通过各种方法制备,并且可以具有各种结构和形状。例如,它可以是几毫米大小的加工小球的形式(其可以通过从具有纳米或微米大小的外径的颗粒挤出来加工,并且其形状和尺寸没有限制)。
如上文所述,通过将二氧化硅载体用作负载金属催化剂中的活性组分的载体,可以具有以下技术优势:可以制备比传统使用的沸石或活性炭具有改善的选择性和耐久性的催化剂。在沸石载体的情况下,存在的缺点是,其中结构上包含的铝组分可能被洗脱以引起微孔结构的崩解,并且洗脱的铝组分可能在反应体系中引起副反应,或者可能在分离和纯化步骤中充当不必要的物质。在活性炭载体的情况下,存在的缺点是,由于其特性,不能采用高温热处理工艺,并且载体与金属活性组分之间的结合相对较弱,从而增加了活性组分分离和失活的可能性。
同时,金属催化剂中包括的钌似乎在将二羧酸转化为一元醇方面起作用,锡似乎在增加作为合成产物的醇的选择性方面起作用,而铂似乎在通过增加催化剂的活性来抑制副反应方面起作用。
当1,3-环己烷二羧酸在金属催化剂存在下被还原时,可形成包括1,3-环己烷二甲醇的反应产物。
金属催化剂可包括重量比为1:0.8~1.2:1.2~2.4、1:1:0.9~1.1:1.6~2.0或1:0.95~1.05:1.7~1.9的钌(Ru)化合物、锡(Sn)化合物和铂(Pt)化合物。更具体地,金属催化剂可以包括重量比为1:0.8~1.2:1.2~2.4、1:0.9~1.1:1.6~2.0或1:0.95~1.05:1.7~1.9的包含在钌(Ru)化合物中的钌(Ru)、包含在锡(Sn)化合物中的锡(Sn)和包含在铂化合物中的铂(Pt)。
如后文将要描述的实施例中所证实的,通过使用以特定重量比包括钌(Ru)化合物、锡(Sn)化合物和铂(Pt)化合物的金属催化剂,可通过允许几乎所有用作反应物的1,3-环己烷二羧酸参与反应来实现高转化率,且可以高度维持最终制备的反应产物中1,3-环己烷二甲醇的选择性。
如本文所用,钌(Ru)化合物是指金属钌本身、钌的有机盐或钌的无机盐(例如卤化物或卤化物水合物)。这同样适用于锡(sn)化合物和铂(pt)化合物。
金属催化剂可包括0.5wt%至10wt%或0.5wt%至1.5wt%的量的钌(Ru)化合物。金属催化剂中锡(Sn)化合物和铂(Pt)化合物的量可由钌化合物的量和金属化合物之间的重量比确定。
当金属催化剂中的钌(Ru)化合物、锡(Sn)化合物和铂(Pt)化合物的量过小时,可能降低还原反应的效率,或可能降低最终制备的反应产物中1,3-环己烷二甲醇的选择性。而且,由于未反应的羧酸或羧酸酐的形成,反应产率可能降低,并且当分离或回收最终反应产物时,效率可能降低或能耗可能增加。
进一步,当金属催化剂中的钌(Ru)化合物、锡(Sn)化合物和铂(Pt)化合物的量过大时,可能会发生过量的额外反应,因此,可能会形成一元醇类、其水解或其烷烃等同物,降低了反应产率或降低了最终反应产物的纯度。此外,必须进一步进行多步骤过程以去除产生的副产物,从而可能还降低工艺的经济效益。
尤其,金属催化剂可包括与传统金属催化剂相比更多量的铂(Pt)化合物作为活性组分,以便在用作反应物的1,3-环己烷二羧酸的还原过程中实现高转化率和选择性。因此,与使用含有相对于钌(Ru)或锡(Sn)的量的更少量的铂(Pt)的传统金属催化剂相比,可实现进一步提高的转化率和选择性。
具体而言,金属催化剂可包括锡(Sn)化合物,其量为30至80重量份或40至70重量份(相对于100重量份的铂(Pt)化合物)。当锡(Sn)化合物的含量过少时(相对于100重量份的铂(Pt)化合物,少于30重量份),由于锡化合物而提高的醇的选择性的效果可能无法充分实现。当锡(Sn)化合物含量过多时(相对于100重量份的铂(Pt)化合物,大于80重量份),由于铂而提高的催化活性的效果可能不能充分实现,使得1,3-环己烷二羧酸作为反应物的转化率可能显著降低至约20%至30%,因此,产物中1,3-环己烷二甲醇的选择性也可能降低至约20%至30%。
此外,相对于100重量份铂(Pt)化合物,金属催化剂可包括30至80重量份的量的钌(Ru)化合物,或40至70重量份的钌(Ru)化合物。
同时,在还原1,3-环己烷二羧酸的步骤中可以使用各种还原方法,例如,还原步骤可以包括使1,3-环己烷二羧酸与氢气接触。
而且,在还原1,3-环己烷二羧酸的步骤中,可以不受特别限制地使用已知用于脂环羧酸的还原反应的方法、反应条件和设备,例如,还原1,3-环己烷二羧酸的步骤可以在30巴至150巴或40巴至120巴的压力下在50℃至350℃或100℃至300℃的温度下进行。
具体而言,还原1,3-环己烷二羧酸的步骤可通过包括如下进行:在将其中存在金属催化剂和1,3-环己烷二羧酸的反应器内部转变为惰性气体气氛后,引入氢气并提高内部温度。
也就是说,还原1,3-环己烷二羧酸的步骤可以包括在反应器内部的惰性气体气氛下混合金属催化剂和1,3-环己烷二羧酸;向反应器中引入氢气;以及提高反应器的温度以进行还原反应。
如本文所用,惰性气体不仅包括周期表上第18族的气体组分,还包括其他不直接影响氢化反应的气体,如氮气。
在还原1,3-环己烷二羧酸的步骤中,可以在其中作为反应物的1,3-环己烷二羧酸、金属催化剂和反应溶剂混合的反应体系中,以10重量份至300重量份、50重量份至300重量份或50重量份至200重量份(相对于100重量份的1,3-环己烷二羧酸)的量使用金属催化剂。
当金属催化剂相对于1,3-环己烷二羧酸的量或用量过小时,还原反应的效率可能降低,或最终制备的反应产物中1,3-环己烷二甲醇的选择性可能降低。当催化剂的量小于上述范围时,可能降低反应设备的生产效率,并且在得到最终产品后进行分离/回收时,可能降低设备的效率或可能增加能耗。
而且,当金属催化剂相对于1,3-环己烷二羧酸的量或用量过大时,在反应过程中会产生过量的副产物,使得必须另外进行多步骤过程以去除副产物。因此,这是不经济的,并且最终制备的产品的纯度可能会降低。
同时,在制备1,3-环己烷二甲醇的方法中,通过使用3-环己烷二羧酸为反应物进行直接还原反应,因此可在单一步骤中快速完成该过程,且由于不进行由两个或更多个步骤组成的多步骤过程,可以改善工艺效率如生产率和经济效益。
在还原1,3-环己烷二羧酸的步骤中,反应物本身可经受直接还原反应,并且在其中反应物存在于溶剂中的状态下可发生还原反应。
可用的溶剂的实例不受特别限制,例如可使用水或有机溶剂。作为有机溶剂的实例,可使用诸如甲醇、乙醇、丙醇及环己醇的脂肪族醇、诸如己烷及环己烷的脂肪族烃、诸如二乙醚及四氢呋喃的醚类,或其两种或更多种的混合物。
所用的有机溶剂的量不受特别限制,例如,相对于作为反应物的1,3-环己烷二羧酸的重量,可以以10%至1000%的量使用有机溶剂。
一个实施方式的制备1,3-环己烷二甲醇的方法还可以包括在还原反应过程完成时分离所用催化剂后对反应产物进行纯化。可用于纯化的方法不受特别限制,但分离和纯化可根据蒸馏法、萃取法和色谱法进行。
同时,根据一个实施方式的制备1,3-环己烷二甲醇的方法可具有由以下计算公式定义的90%或更高、95%或更高、99%或更高、90%至100%、95%至100%或99%至100%的转化率:
[计算公式]
转化率(%)=[(引入的1,3-环己烷二羧酸的量(mol%))-(反应后剩余1,3-环己烷二羧酸的量(mol%))]/[引入的1,3-环己烷二羧酸的量(mol%)]*100。
随着根据上述计算公式的转化率的增加,可以暗示反应通过作为反应物引入的1,3-环己烷二羧酸继续进行,并且也可以证实,由于根据一个实施方式的制备1,3-环己烷二甲醇的方法满足高转化率,因此该方法由于金属催化剂而显示出高的反应性。
【有益效果】
根据本发明,可以提供一种制备高纯度1,3-环己烷二甲醇的方法,该方法能够通过使大部分反应物参与反应来实现高转化率,并且通过进一步简化反应过程来提高反应效率和经济效益,同时在较短的时间段内最少化副产物。
具体实施方式
将通过下面所示的实施例更详细地描述本发明。然而,这些实施例仅为说明目的而给出,并且本发明的范围并不意图局限于这些实施例或由这些实施例限定。
<制备例:金属催化剂的制备>
制备例1
称取氯化锡二水合物、氯化钌三水合物和氯铂酸六水合物,溶解于0.1标准浓度的氯化氢水溶液中,制备金属前体溶液。以等于二氧化硅载体[比表面积:约255m2/g,总孔体积:1.03cm3/g,平均孔径:]的内孔体积的量滴入金属前体溶液以负载催化剂,然后在120℃下干燥催化剂12小时。此后,在600℃的空气条件下烧结催化剂,以获得其中以复合金属形式负载钌、锡和铂的催化剂(钌(Ru)、锡(Sn)和铂(Pt)的重量比如以下表1中所示)。
制备例2
以与制备例1相同的方式制备金属催化剂,除了使用不同重量比的钌(Ru)、锡(Sn)和铂(Pt),如以下表1中所示。
制备例3
以与制备例1相同的方式制备金属催化剂,除了使用不同重量比的钌(Ru)、锡(Sn)和铂(Pt),如以下表1中所示。
制备例4
以与制备例1相同的方式制备金属催化剂,除了使用Y型沸石代替二氧化硅载体。
<实施例1和2:1,3-环己烷二甲醇的制备>
实施例1
将在制备例1中获得的金属负载催化剂、1,3-环己烷二羧酸和离子交换水装入配备搅拌器的500ml高压反应器中,以满足以下表1所示的重量比。在室温下用氮气置换高压反应器中的气氛后,将高压反应器中的温度提高到210℃,以在100巴的压力下进行加氢反应,同时将氢气引入高压反应器。此时,高压反应器中的搅拌速度固定为350rpm,且反应进行3小时。当达到反应时间时,将反应器内部冷却至室温,并拆卸反应器以收集反应产物。通过使用旋转蒸发器蒸馏,从收集的反应产物中除去水,得到1,3-环己烷二甲醇作为最终产物。
实施例2
以与实施例1相同的方式制备1,3-环己烷二甲醇,除了装入20wt%的1,3-CHDA并进行反应3.5小时,如以下表1中所示。
<比较例1至3:1,3-环己烷二甲醇的制备>
比较例1
以与实施例1相同的方式制备1,3-环己烷二甲醇,除了装入在制备例2中获得的金属负载催化剂。
比较例2
以与实施例1相同的方式制备1,3-环己烷二甲醇,除了使用在制备例3中获得的金属负载催化剂。
比较例3
以与实施例1相同的方式制备1,3-环己烷二甲醇,除了使用在制备例4中获得的金属负载催化剂。
<实验例:在实施例和比较例中获得的1,3-环己烷二甲醇的物理性质的测量>
通过以下方法测量上述实施例和比较例中获得的1,3-环己烷二甲醇的物理性质,结果如表1中所示。
实验例1:转化率和选择性
对于实施例和比较例中得到的最终产物,用气相色谱法(GC)测量反应物(1,3-环己烷二羧酸)的转化率以及1,3-环己烷二甲醇的选择性。
具体而言,用甲醇稀释由反应物(1,3-环己烷二羧酸)的还原反应(加氢)得到的反应产物。用气相色谱法(GC)分析稀释液,来根据以下计算公式确定选择性和转化率。在计算公式中,将每个数值转换为摩尔比(%)的单位并应用。
选择性(%)=[(1,3-环己烷二甲醇的量(mol%)/反应产物的量(mol%))*100]
转化率(%)=[(引入的1,3-环己烷二羧酸的量(mol%))-(反应后剩余的1,3-环己烷二羧酸的量(mol%))]/[引入的1,3-环己烷二羧酸的量(mol%)]*100。
<气相色谱(GC)条件>
1)柱:Agilent 19091J-413(柱长:30米,内径:0.32mm,膜厚:0.25μm)
2)GC系统:气相色谱型Agilent 7890
3)载气:氦
4)检测器:火焰离子化检测器(FID)
表1
实施例和比较例的实验例1的结果
如表1所示,证实了在实施例1中,作为反应物的1,3-环己烷二羧酸100%转化,并且生成产物中1,3-环己烷二甲醇的选择性为90%或更高。在实施例2的情况下,即使当要反应的1,3-环己烷二羧酸的量增加时,也可以发现转化率为100%,且生成的1,3-环己烷二甲醇的选择性也很好,发现其为89%或更高。
相比之下,当使用其中负载铂金属的量减少的催化剂同时保持反应物和引入的催化剂的量时,如比较例1中所示,转化率降低,且最终制备的产物的选择性也显著降低。在使用不负载铂金属的催化剂的比较例2的情况下,可以发现转化率降低到14%,并且没有生成1,3-环己烷二甲醇。
此外,在使用基于沸石的化合物作为载体的比较例3的情况下,1,3-环己烷二甲醇的选择性非常低,发现其为60.3%,证实了在其中使用特定二氧化硅载体的实施例中可实现高选择性。
Claims (13)
1.一种制备1,3-环己烷二甲醇的方法,包括:
在金属催化剂的存在下还原1,3-环己烷二羧酸,所述金属催化剂固定到二氧化硅载体上,并且包括重量比为1:0.8~1.2:1.2~2.4的钌(Ru)化合物、锡(Sn)化合物和铂(Pt)化合物。
2.根据权利要求1所述的制备1,3-环己烷二甲醇的方法,其中所述金属催化剂中包括的所述二氧化硅载体的比表面积为100m2/g至500m2/g。
3.根据权利要求1所述的制备1,3-环己烷二甲醇的方法,其中所述金属催化剂中包括的所述二氧化硅载体的总孔隙体积为2cm3/g或更小。
4.根据权利要求1所述的制备1,3-环己烷二甲醇的方法,其中所述金属催化剂中包括的所述二氧化硅载体的平均孔径为至
5.根据权利要求1所述的制备1,3-环己烷二甲醇的方法,其中所述金属催化剂中包括的所述二氧化硅载体的水含量为0.1wt%至10wt%。
6.根据权利要求1所述的制备1,3-环己烷二甲醇的方法,其中所述金属催化剂包括0.5wt%至10wt%的所述钌(Ru)化合物。
7.根据权利要求1所述的制备1,3-环己烷二甲醇的方法,其中相对于100重量份的所述铂(Pt)化合物,所述金属催化剂包括30重量份至80重量份的所述锡(Sn)化合物。
8.根据权利要求1所述的制备1,3-环己烷二甲醇的方法,其中所述还原1,3-环己烷二羧酸的步骤包括使所述1,3-环己烷二羧酸与氢气接触。
9.根据权利要求1所述的制备1,3-环己烷二甲醇的方法,其中所述还原1,3-环己烷二羧酸的步骤在50℃至350℃下进行。
10.根据权利要求1所述的制备1,3-环己烷二甲醇的方法,其中所述还原1,3-环己烷二羧酸的步骤在30巴至150巴的压力下进行。
11.根据权利要求1所述的制备1,3-环己烷二甲醇的方法,其中相对于100重量份的所述1,3-环己烷二羧酸,以10重量份至300重量份的量使用所述金属催化剂。
12.根据权利要求1所述的制备1,3-环己烷二甲醇的方法,其中所述金属催化剂包括重量比为1:0.9~1.1:1.6~2.0的钌(Ru)化合物、锡(Sn)化合物和铂(Pt)化合物。
13.根据权利要求1所述的制备1,3-环己烷二甲醇的方法,其中由下面的计算公式定义的转化率为90%或更高:
[计算公式]
转化率(%)=[(引入的1,3-环己烷二羧酸的量(mol%))-(反应后剩余1,3-环己烷二羧酸的量(mol%))]/[引入的1,3-环己烷二羧酸的量(mol%)]*100。
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- 2017-09-05 US US16/331,506 patent/US10597344B2/en active Active
- 2017-09-05 CN CN201780054605.0A patent/CN109689606A/zh not_active Withdrawn
- 2017-09-05 EP EP17849059.5A patent/EP3511313A4/en not_active Withdrawn
- 2017-09-05 JP JP2019512624A patent/JP6718017B2/ja active Active
- 2017-09-05 WO PCT/KR2017/009715 patent/WO2018048175A1/ko unknown
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CN114901618A (zh) * | 2019-12-27 | 2022-08-12 | 韩华思路信(株) | 生产1,4-环己烷二甲醇的方法 |
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JP6718017B2 (ja) | 2020-07-08 |
KR101828002B1 (ko) | 2018-02-13 |
EP3511313A1 (en) | 2019-07-17 |
US20190202761A1 (en) | 2019-07-04 |
WO2018048175A1 (ko) | 2018-03-15 |
US10597344B2 (en) | 2020-03-24 |
JP2019526588A (ja) | 2019-09-19 |
EP3511313A4 (en) | 2020-01-22 |
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