CN101386610B - 由1,4-丁二醇制备四氢呋喃的方法 - Google Patents
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 title claims abstract description 82
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 25
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 title abstract description 7
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 27
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 8
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000002203 pretreatment Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 15
- 239000005955 Ferric phosphate Substances 0.000 abstract description 4
- 229940032958 ferric phosphate Drugs 0.000 abstract description 4
- 229910000399 iron(III) phosphate Inorganic materials 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
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- 238000002360 preparation method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 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
- 238000001035 drying Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- 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
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
- C07D307/08—Preparation of tetrahydrofuran
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
- B01J37/08—Heat treatment
Abstract
本发明涉及一种在存在磷酸铁(FePO4)作为催化剂的条件下通过1,4-丁二醇的脱水反应来制备四氢呋喃的方法。通过使用磷酸铁作为催化剂,本发明可以以安全、简单的方式高收率地制备四氢呋喃。
Description
技术领域
本发明涉及一种在使用磷酸铁催化剂的条件下由1,4-丁二醇制备四氢呋喃的方法。
背景技术
一般来说,四氢呋喃(下文中称作“THF”)被广泛地用作有机化合物的溶剂和高分子合成的主要原料。近年来随着THF被用作各种合成聚合物的原料和作为添加剂,其用途越来越广。
现有技术中已知有多种制备THF的方法。最常用的制备THF的方法为使1,4-丁二醇脱水或者对呋喃进行氢化。
通过使1,4-丁二醇脱水来制备THF的方法包括下列步骤:在酸性催化剂存在下使1,4-丁二醇发生反应,并将水分从其中含有在前一步骤中产生的一定量的水分的THF中分离出来。所述反应的效率取决于反应中所使用的酸性催化剂的性能,因此最重要的是开发一种有效地用于1,4-丁二醇脱水的催化剂。
一种使用无机酸(例如硫酸)作为脱水催化剂的方法在美国专利No.4,665,205中有所描述。然而,该发明中使用的无机酸使用起来很危险并且会使反应装置受到不利的腐蚀。
多个其它发明提出了脱水过程中的不同的催化剂,例如氧化铝(美国专利No.6,204,399)、硅铝催化剂(日本专利No.p9-059191)、浸渍于氧化铝中的氧化钨(美国专利No.4,136,099)以及杂多酸(日本专利No.s61-126080)。使用这些不同的酸性催化剂来制备THF的方法已被公开。此外,每个专利分别描述了在每种不同的酸性催化剂存在下制备THF的方法。然而,现有技术中的方法存在着催化剂活性低和使用寿命短的缺点。
为了解决上述方法中的收率低和具有危险性的问题,本发明提出了一种制备THF的、安全简便并且收率高的方法。
发明内容
根据本发明的优选实施方案,提供一种在催化剂存在下通过1,4-丁二醇的脱水反应来制备THF的方法,其中使用磷酸铁作为催化剂。
根据本发明的另一优选实施方案,在存在磷酸铁作为催化剂的条件下,在150℃至300℃下进行1,4-丁二醇的反应。
根据本发明的再一优选实施方案,磷酸铁以其本身使用,或者负载于载体中使用。
根据本发明的又一优选实施方案,在脱水前,在200℃至400℃下用稀有气体对磷酸铁进行预处理。
本发明涉及一种在存在磷酸铁作为具有高活性和高效率的催化剂的条件下制备THF的方法。
所述磷酸铁催化剂的特征在于其具有优异的活性、优异的选择性和长的使用寿命。一般来说,所述磷酸铁催化剂以其本身使用,或者负载于诸如氧化铝、二氧化硅、二氧化钛、沸石和活性炭之类的载体中使用。
根据本发明,所述磷酸铁(FePO4)催化剂可以通过包含下述步骤的方法来制备:按照Fe与P的比例为1至1.5,将1M的磷酸(H3PO4)或者磷酸二氢铵(NH4H2PO4)加入到1M的硝酸铁(Fe(NO3)3)溶液中,将该混合物在90℃下搅拌2小时并用干燥设备干燥24小时。所制得的磷酸铁催化剂可以以其本身使用或者负载于载体中使用。
所述磷酸铁催化剂可以在不进行预处理操作的条件下使用,但是通过使用惰性气体(例如氢气、氮气、氦气、氩气等)在200℃至400℃下进行处理,催化剂的活性可得到提高。在低于200℃的温度下,无法有效地除去催化剂表面上的水分和杂质。然而,在超过400℃的温度下,由于磷酸铁催化剂发生分解,所以催化剂的活性降低。
根据本发明,THF可以通过气相反应器或液相反应器来制备。该方法如下所述。
为了使用气相固定床反应器制备THF,将磷酸铁催化剂装入管形反应器中,然后通过使惰性气体流入反应器将所述催化剂在200℃至300℃下活化。通过使1,4-丁二醇和惰性气体一起以3h-1至10h-1的液体时空速流入该反应器,反应在150℃至300℃、优选200℃至250℃下进行。
为了使用液相浆料反应器制备THF,将磷酸铁催化剂在200℃至300℃下活化,并将磷酸铁催化剂和1,4-丁二醇装入所述反应器中,其中所述催化剂与1,4-丁二醇的重量比为0.1重量%至20重量%。然后将所述反应器在150℃至300℃、优选在200℃至250℃下加热。
在所述方法中,理想的反应温度为150℃至300℃,并且特别是在200℃至250℃的温度下反应的效率会提高。在低于150℃的温度下,反应可能不会很好地进行。然而,在超过300℃的温度下,THF在高温下会分解,这可能会使选择性降低。
附图简要说明
图1示出了通过1,4-丁二醇的脱水反应制备THF的示意性方法。
具体实施方式
下面参照图1描述制备THF的方法。
图1示出了一种制备THF的方法。将1,4-丁二醇通过管线1 L1加入到其中填充有磷酸铁催化剂的液相或气相反应器11中。将1,4-丁二醇置于反应器11中一段时间,然后其转化成THF。通过管线2L2将从反应器11所得到的产物加入到第一分离器12中。从反应器11所得到的产物包含THF、水和1,4-丁二醇。其中未反应的1,4-丁二醇通过第一分离器12而被分离出来并通过管线3 L3循环回到反应器11中。从第一分离器12得到的产物由THF和水组成,使这种共沸混合物通过管线4 L4而加入到第二分离器13中,并通过第二分离器13,从而得到高纯度的THF。
例子
下面将参照例子对本发明进行详细地描述。提供这些例子仅仅是用于示例性的目的,而不应当被理解成其对本发明的范围进行了限制。
实施例1
使用固定床管形反应器(直径为2mm,长度为520mm)来进行气相催化反应。将3g的磷酸铁催化剂装入反应器中,然后利用氦气在300℃下活化2小时。将1,4-丁二醇与氦气混合并利用注射泵以5.0升/小时的速度注入反应器中。在200℃和大气压力下进行反应。通过装备有Poropak QS柱和火焰离子化检测器(FID)的在线气相色谱仪来分析产物。在到达稳定态之后,THF的收率为99.5%。
实施例2
使用装备有磁力搅拌器和回流冷凝管的500ml的三颈反应器来进行液相催化反应。在反应之前,将该催化剂用氦气在250℃下活化2小时。将1g的经过预处理的磷酸铁催化剂和100g的1,4-丁二醇加入到反应器中。在200℃下反应1小时。产物通过冷凝管冷凝,然后进行蒸馏以分离出未反应的1,4-丁二醇。按照与实施例1相同的方式通过气相色谱法分析产物。THF的产物收率为99.5%。
对比例1至3
按照与实施例2相同的方式进行制备THF,不同之处在于使用100g的1,4-丁二醇以及1g的酸性氧化铝、钨磷酸(一种杂多酸)或者硅铝催化剂,并且反应进行40分钟。反应后的收率如表1所示。
[表1]
实施例1 | 实施例2 | 对比例1 | 对比例2 | 对比例3 | |
催化剂 | 磷酸铁 | 磷酸铁 | 酸性氧化铝 | 钨磷酸 | 硅铝催化剂 |
产物收率(%) | 99.5 | 99.5 | 76.1 | 83.4 | 73.2 |
发明的效果
根据本发明,通过使用磷酸铁作为催化剂可以以安全且简单的方式高收率地制备THF。
Claims (3)
1.一种在催化剂存在下通过1,4-丁二醇的脱水反应来制备四氢呋喃的方法,其特征在于,使用磷酸铁作为所述催化剂,并且在所述反应之前在200℃至400℃下用惰性气体对所述磷酸铁催化剂进行预处理。
2.根据权利要求1所述的制备四氢呋喃的方法,其中所述反应温度为150℃至300℃。
3.根据权利要求1所述的制备四氢呋喃的方法,其中所述磷酸铁催化剂以其本身使用或者负载于载体中使用。
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CN103182316B (zh) * | 2011-12-30 | 2015-02-04 | 北京北大先锋科技有限公司 | 一种用于黄磷尾气脱磷的催化剂及其制备方法 |
EP2882755B1 (en) * | 2012-08-08 | 2019-02-06 | Roquette Freres | Method of synthesis of a composition containing at least one internal dehydration product of a hydrogenated sugar by heterogeneous catalysis |
CN104072448A (zh) * | 2014-06-13 | 2014-10-01 | 中国科学院山西煤炭化学研究所 | 一种l酸催化1,4-丁二醇脱水生产四氢呋喃的方法 |
CN110698438A (zh) * | 2019-10-16 | 2020-01-17 | 中国石化长城能源化工(宁夏)有限公司 | 一种固体催化剂催化1,4-丁二醇脱水制备四氢呋喃的方法 |
CN115960058A (zh) * | 2023-02-02 | 2023-04-14 | 华东师范大学 | 一种无机铁盐催化1,4-丁二醇环化脱水制备四氢呋喃的方法 |
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derwent publications ltd..AN:1979-70446B/39.《Derwent Innovation Index》.1979, * |
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