CN108579808B - 一种用于合成四氢呋喃-3-甲醛的复合催化剂及使用其合成四氢呋喃-3-甲醛的方法 - Google Patents
一种用于合成四氢呋喃-3-甲醛的复合催化剂及使用其合成四氢呋喃-3-甲醛的方法 Download PDFInfo
- Publication number
- CN108579808B CN108579808B CN201810344166.3A CN201810344166A CN108579808B CN 108579808 B CN108579808 B CN 108579808B CN 201810344166 A CN201810344166 A CN 201810344166A CN 108579808 B CN108579808 B CN 108579808B
- Authority
- CN
- China
- Prior art keywords
- formaldehyde
- tetrahydrofuran
- dihydrofuran
- composite catalyst
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- GSUBXIVOZXWGKF-UHFFFAOYSA-N oxolane-3-carbaldehyde Chemical compound O=CC1CCOC1 GSUBXIVOZXWGKF-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 15
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- -1 Iron compound Chemical class 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 12
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000004714 phosphonium salts Chemical group 0.000 claims abstract description 7
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- ARGCQEVBJHPOGB-UHFFFAOYSA-N 2,5-dihydrofuran Chemical compound C1OCC=C1 ARGCQEVBJHPOGB-UHFFFAOYSA-N 0.000 claims description 54
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 31
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 29
- 239000001257 hydrogen Substances 0.000 claims description 27
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 18
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 11
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- 150000002506 iron compounds Chemical class 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 abstract description 13
- 229910052703 rhodium Inorganic materials 0.000 abstract description 11
- 230000007547 defect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 12
- 238000007037 hydroformylation reaction Methods 0.000 description 10
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 8
- 229910017147 Fe(CO)5 Inorganic materials 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- WPWHSFAFEBZWBB-UHFFFAOYSA-N 1-butyl radical Chemical compound [CH2]CCC WPWHSFAFEBZWBB-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- OVUFERFKGZMJHQ-UHFFFAOYSA-N cobalt;phosphanylidenemethanone Chemical compound [Co].O=C=P OVUFERFKGZMJHQ-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/20—Carbonyls
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- C07D307/10—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/12—Radicals substituted by oxygen atoms
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明公开了一种用于合成四氢呋喃‑3‑甲醛的复合催化剂，包括钴簇化合物RCCo3(CO)9、铁化合物以及季铵盐R1 3R2NCl或季膦盐R1 3R2PCl。本发明还公开了使用该复合催化剂合成四氢呋喃‑3‑甲醛的方法。本发明既克服了传统钴基催化剂必须在高温高压下才能进行的缺点，反应条件温和，又解决了羰基铑催化剂价格昂贵的问题。
Description
技术领域
本发明涉及化学合成技术领域，具体涉及一种用于合成四氢呋喃-3-甲醛的复合催化剂，以及利用该催化剂合成四氢呋喃-3-甲醛的方法。
背景技术
烯烃氢甲酰化反应是合成有机中间体醛的重要途径，随着四氢呋喃-3-甲醛用途的不断扩大，2,5-二氢呋喃氢甲酰化合成四氢呋喃-3-甲醛的意义也愈加重大。催化剂是氢甲酰化技术路线的关键，主要有钴基催化剂和铑基催化剂两类，钴基催化剂活性不高、反应条件苛刻；铑基催化剂虽然价格昂贵，但活性高、反应条件温和，是研究的热点。
1938年Otto Roelen在研究F-T合成时，发现在Co催化剂和加热加压的条件下，乙烯和一氧化碳、氢气可以反应生成丙醛，这引起了研究者的极大兴趣。研究者对Co催化剂进行了全面研究，开发了第一代氢甲酰化催化剂，即羰基钴催化剂[HCo(CO)4]，并于40年代后期应用与工业生产，目前仍占很大比重。由于钴基催化剂的有效成分HCo(CO)4容易分解，需要维持较高的合成气压力(20-30MPa)，因此这种催化反应方法又称“高压钴法”。在这种情况下，必须在较高温度下才能保证适当的反应速率，致使工业生产条件异常苛刻，随着配位化学的迅速发展，有机配体开始应用于氢甲酰化催化剂中，有机膦配体被引入以显著降低反应压力。如羰基钴-膦配合物催化剂中的膦配体主要是三烷基膦，其中最著名的是以三正丁基膦为配体[HCo(CO)3P(n-C4H9)3]。但这种改性后的钴体系也会带来一些新问题，如活性下降、加氢副反应活性增大。
20世纪50年代中期，研究者发现在氢甲酰化反应中Rh的催化活性远远高于Co，未修饰的羰基铑催化剂的氢甲酰化活性是钴的102-104倍，Rh也是目前发现的活性最高的金属，且其配合物稳定性好，操作条件温和，加氢活性低，但是得到的产物的正异构比非常低，且铑为贵金属，世界范围储量仅为778t，加上其它领域(如高附加值的手性合成)对铑的需求量也在日益增加。由此带来的成本上的劣势远远超过了铑催化剂在催化活性上的优势，使得其很长一段时间没有工业化应用。因此，积极开发非贵金属催化剂在烯烃氢甲酰化反应中具有重要意义。
发明内容
本发明的目的在于克服现有技术的缺陷，提供一种用于合成四氢呋喃-3-甲醛的复合催化剂，既克服了传统贵金属催化剂存在的成本高、反应条件苛刻的问题，又提高了反应收率和选择性。
为了实现上述目的，本发明采取的技术方案如下：
一种用于合成四氢呋喃-3-甲醛的复合催化剂，包括钴簇化合物RCCo3(CO)9、铁化合物以及季铵盐R1 3R2NCl或季膦盐R1 3R2PCl，其中铁化合物选自Fe(OAc)2、Fe(OAc)3、FeCl2、FeCl3、Fe(NO3)3、FeSO4、R1 4NFeCo3(CO)12或Fe(CO)5中的任意一种，R选自H、F、Cl、Br、甲基、乙基、甲苯基以及苯基，R1选自C1-C4的烷基，R2选自C1-C18的链状烷基。
优选地，所述复合催化剂中，以质量比计，RCCo3(CO)9：铁化合物：R1 3R2NCl或R1 3R2PCl＝1-8:1-6:1-8。
本发明还提供利用上述复合催化剂合成四氢呋喃-3-甲醛的方法：在所述复合催化剂存在下，向2,5-二氢呋喃中通入氢气及一氧化碳，加热反应，反应结束后，通过蒸馏的方式得到四氢呋喃-3-甲醛。
优选地，所述复合催化剂中RCCo3(CO)9的用量为2,5-二氢呋喃质量的1-10％；铁化合物的用量为2,5-二氢呋喃质量的1-8％；季铵盐R1 3R2NCl或季膦盐R1 3R2PCl的用量为2,5-二氢呋喃质量的1-10％。
优选地，所述氢气与一氧化碳的摩尔比为1:1-1:2。
优选地，所述2,5-二氢呋喃溶解在溶剂中，所述溶剂选自甲苯、二氯甲烷、四氢呋喃、甲基叔丁基醚及丁醚；所述溶剂的用量为2,5-二氢呋喃摩尔量的0-10倍，且溶剂中含水质量分数为0.1-0.3％。
优选地，所述反应温度控制在50-120℃。
优选地，所述反应压力控制在1.0-6.0MPa。
优选地，所述反应时间为3-50h。
氢甲酰化反应的工业生产过程中，催化体系的选择决定了整体工艺的性能和技术先进性。传统的钴基催化剂的有效成分HCo(CO)4容易分解，需要维持较高的合成气压力(20-30MPa)，致使工业生产条件异常苛刻，随着配位化学的迅速发展，有机膦配体被引入以显著降低反应压力。但这种改性后的钴体系也会带来一些新问题，如活性下降、加氢副反应活性增大。羰基铑催化剂的氢甲酰化活性虽然高，但铑为贵金属，世界范围储量仅为778t，加上其它领域(如高附加值的手性合成)对铑的需求量也在日益增加。由此带来的成本上的劣势远远超过了铑催化剂在催化活性上的优势，使得其很长一段时间没有工业化应用。
本发明采用钴簇化合物RCCo3(CO)9、铁化合物以及季铵盐R1 3R2NCl或季膦盐R1 3R2PCl组成的复合催化剂，既克服了传统钴基催化剂必须在高温高压下才能进行的缺点，反应条件温和，又解决了羰基铑催化剂价格昂贵的问题。
本发明利用RCCo3(CO)9、铁化合物以及季铵盐R1 3R2NCl或季膦盐R1 3R2PCl三种催化剂的的协同效应，对催化剂的活性和选择性产生显著影响，所得产品收率和选择性明显高于单一催化剂的使用效果。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
实施例1
1L高压釜内加入2,5-二氢呋喃150g，加入四氢呋喃308g(含水质量分数为0.1％)，加入催化剂HCCo3(CO)9 1.5g、Fe(CO)51.5g及四丁基氯化铵12g，通入氢气置换反应釜内空气后，再通入氢气0.5MPa，一氧化碳0.5MPa，加热至60℃，反应50h。反应结束后常压蒸出溶剂四氢呋喃回收套用，再减压蒸馏蒸出产品四氢呋喃-3-甲醛，纯度98％，收率90.6％。剩余催化剂回收套用。
实施例2
1L高压釜内加入2,5-二氢呋喃150g，加入四氢呋喃308g(含水质量分数为0.3％)，加入催化剂HCCo3(CO)9 12g、Fe(CO)5 9g及四丁基氯化铵1.5g，通入氢气置换反应釜内空气后，再通入氢气2.0MPa，一氧化碳4.0MPa，加热至120℃，反应3h。反应结束后常压蒸出溶剂四氢呋喃回收套用，再减压蒸馏蒸出产品四氢呋喃-3-甲醛，纯度98％，收率89.2％。剩余催化剂回收套用。
实施例3
2L高压釜内加入2,5-二氢呋喃150g、甲基叔丁基醚1508g(含水质量分数为0.1％)，加入催化剂ClCCo3(CO)9 6g、Fe(OAc)2 6g及十二烷基三甲基氯化铵4.5g，通入氢气置换釜内空气后，再通入氢气1.5MPa，一氧化碳1.5MPa，加热至80℃，反应40h。反应结束后常压蒸出溶剂甲基叔丁基醚回收套用，再减压蒸馏蒸出产品四氢呋喃-3-甲醛，纯度97％，收率93.3％。剩余催化剂回收套用。
实施例4
1L高压釜内加入2,5-二氢呋喃150g、二氯甲烷364g(含水质量分数为0.2％)，加入催化剂CH3CCo3(CO)9 4.5g、FeCl3 3g及三甲基丁基氯化膦3g，通入氢气置换釜内空气后，再通入氢气1.5MPa，一氧化碳1.5MPa，加热至100℃，反应30h。反应结束后常压蒸出溶剂二氯甲烷回收套用，再减压蒸馏蒸出产品四氢呋喃-3-甲醛，纯度98％，收率90.4％。剩余催化剂回收套用。
实施例5
1L高压釜内加入2,5-二氢呋喃150g、二氯甲烷364g(含水质量分数为0.2％)，加入催化剂CH3CCo3(CO)9 4.5g、FeCl3 3g及三甲基丁基氯化膦3g，通入氢气置换釜内空气后，再通入氢气3.0MPa，一氧化碳3.0MPa，加热至100℃，反应30h。反应结束后常压蒸出溶剂二氯甲烷回收套用，再减压蒸馏蒸出产品四氢呋喃-3-甲醛，纯度98％，收率92.3％。剩余催化剂回收套用。
实施例6
1L高压釜内加入2,5-二氢呋喃150g、甲苯394g(含水质量分数为0.1％)，加入催化剂PhCCo3(CO)9 3g、Fe(CO)5 4.5g及四丙基氯化膦3g，通入氢气置换釜内空气后，再通入氢气1.0MPa，一氧化碳1.0MPa，加热至90℃，反应45h。反应结束后常压蒸出产品四氢呋喃-3-甲醛，纯度97％，收率93.6％，再减压蒸馏蒸出溶剂甲苯回收套用。剩余催化剂回收套用。
实施例7
1L高压釜内加入2,5-二氢呋喃150g、甲苯394g(含水质量分数为0.1％)，加入催化剂PhCCo3(CO)9 3g、Fe(CO)5 4.5g及四丙基氯化膦3g，通入氢气置换釜内空气后，再通入氢气1.0MPa，一氧化碳1.0MPa，加热至90℃，反应10h。反应结束后常压蒸出产品四氢呋喃-3-甲醛，纯度97％，收率87.8％，再减压蒸馏蒸出溶剂甲苯回收套用。剩余催化剂回收套用。
实施例8
1L高压釜内加入2,5-二氢呋喃150g、二氯甲烷364g(含水质量分数为0.2％)，加入催化剂CH3CCo3(CO)9 4.5g、FeCl3 3g及三甲基丁基氯化膦3g，通入氢气置换釜内空气后，再通入氢气1.5MPa，一氧化碳1.5MPa，加热至120℃，反应30h。反应结束后常压蒸出溶剂二氯甲烷回收套用，再减压蒸馏蒸出产品四氢呋喃-3-甲醛，纯度98％，收率92.4％。剩余催化剂回收套用。
实施例9
1L高压釜内加入2,5-二氢呋喃150g、二氯甲烷364g(含水质量分数为0.2％)，加入催化剂CH3CCo3(CO)9 7.5g、FeCl3 4.5g及三甲基丁基氯化膦4.5g，通入氢气置换釜内空气后，再通入氢气1.5MPa，一氧化碳1.5MPa，加热至100℃，反应30h。反应结束后常压蒸出溶剂二氯甲烷回收套用，再减压蒸馏蒸出产品四氢呋喃-3-甲醛，纯度98％，收率93.6％。剩余催化剂回收套用。
实施例10
250mL高压釜内加入2,5-二氢呋喃150g，加入催化剂CH3CCo3(CO)94.5g、FeCl3 3g及三甲基丁基氯化膦3g，通入氢气置换釜内空气后，再通入氢气1.5MPa，一氧化碳1.5MPa，加热至120℃，反应30h。反应结束后常压蒸出产品四氢呋喃-3-甲醛，纯度96％，收率89.7％。剩余催化剂回收套用。
对比例1
1L高压釜内加入2,5-二氢呋喃150g、甲苯394g(含水质量分数为0.1％)，加入催化剂PhCCo3(CO)9 11g，通入氢气置换釜内空气后，再通入氢气1.0MPa，一氧化碳1.0MPa，加热至90℃，反应10h。反应结束后常压蒸出产品四氢呋喃-3-甲醛，纯度94％，收率72％，再减压蒸馏蒸出溶剂甲苯回收套用。剩余催化剂回收套用。
对比例2
1L高压釜内加入2,5-二氢呋喃150g、甲苯394g(含水质量分数为0.1％)，加入催化剂PhCCo3(CO)9 3g、Fe(CO)5 4.5g，通入氢气置换釜内空气后，再通入氢气1.0MPa，一氧化碳1.0MPa，加热至90℃，反应10h。反应结束后常压蒸出产品四氢呋喃-3-甲醛，纯度93％，收率78.9％，再减压蒸馏蒸出溶剂甲苯回收套用。剩余催化剂回收套用。
对比例3
1L高压釜内加入2,5-二氢呋喃150g、甲苯394g(含水质量分数为0.1％)，加入催化剂PhCCo3(CO)9 3g、四丙基氯化膦3g，通入氢气置换釜内空气后，再通入氢气1.0MPa，一氧化碳1.0MPa，加热至90℃，反应10h。反应结束后常压蒸出产品四氢呋喃-3-甲醛，纯度95％，收率81.2％，再减压蒸馏蒸出溶剂甲苯回收套用。剩余催化剂回收套用。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换或改进等，均应包含在本发明的保护范围之内。
Claims (9)
1.一种用于合成四氢呋喃-3-甲醛的复合催化剂，其特征在于：所述复合催化剂用于催化2,5-二氢呋喃合成四氢呋喃-3-甲醛，所述复合催化剂包括钴簇化合物RCCo3(CO)9、铁化合物以及季铵盐R1 3R2NCl或季膦盐R1 3R2PCl，其中铁化合物选自Fe(OAc)2、Fe(OAc)3、FeCl2、FeCl3、Fe(NO3)3、FeSO4、R1 4NFeCo3(CO)12或Fe(CO)5中的任意一种，R选自H、F、Cl、Br、甲基、乙基、甲苯基以及苯基，R1选自C1-C4的烷基，R2选自C1-C18的链状烷基。
2.如权利要求1所述的复合催化剂，其特征在于：所述复合催化剂中，以质量比计，RCCo3(CO)9：铁化合物：R1 3R2NCl或R1 3R2PCl＝1-8:1-6:1-8。
3.利用权利要求1或2所述的复合催化剂合成四氢呋喃-3-甲醛的方法，其特征在于：在所述复合催化剂存在下，向2,5-二氢呋喃中通入氢气及一氧化碳，加热反应，反应结束后，通过蒸馏的方式得到四氢呋喃-3-甲醛。
4.如权利要求3所述的方法，其特征在于：所述复合催化剂中RCCo3(CO)9的用量为2,5-二氢呋喃质量的1-10％；铁化合物的用量为2,5-二氢呋喃质量的1-8％；季铵盐R1 3R2NCl或季膦盐R1 3R2PCl的用量为2,5-二氢呋喃质量的1-10％。
5.如权利要求3所述的方法，其特征在于：所述氢气与一氧化碳的摩尔比为1:1-1:2。
6.如权利要求3所述的方法，其特征在于：所述2,5-二氢呋喃溶解在溶剂中，所述溶剂选自甲苯、二氯甲烷、四氢呋喃、甲基叔丁基醚及丁醚；所述溶剂的用量为2,5-二氢呋喃摩尔量的0-10倍，且溶剂中含水质量分数为0.1-0.3％。
7.如权利要求3所述的方法，其特征在于：所述反应温度控制在50-120℃。
8.如权利要求3所述的方法，其特征在于：所述反应压力控制在1.0-6.0MPa。
9.如权利要求3所述的方法，其特征在于：所述反应时间为3-50h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810344166.3A CN108579808B (zh) | 2018-04-17 | 2018-04-17 | 一种用于合成四氢呋喃-3-甲醛的复合催化剂及使用其合成四氢呋喃-3-甲醛的方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810344166.3A CN108579808B (zh) | 2018-04-17 | 2018-04-17 | 一种用于合成四氢呋喃-3-甲醛的复合催化剂及使用其合成四氢呋喃-3-甲醛的方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108579808A CN108579808A (zh) | 2018-09-28 |
| CN108579808B true CN108579808B (zh) | 2020-11-24 |
Family
ID=63622981
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810344166.3A Active CN108579808B (zh) | 2018-04-17 | 2018-04-17 | 一种用于合成四氢呋喃-3-甲醛的复合催化剂及使用其合成四氢呋喃-3-甲醛的方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108579808B (zh) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109553594B (zh) * | 2018-12-25 | 2020-12-18 | 山东新和成药业有限公司 | 一种四氢呋喃-3-甲醛的制备方法 |
| CN110407776B (zh) * | 2019-07-30 | 2021-04-02 | 石家庄手性化学有限公司 | 一种3-氨甲基四氢呋喃的制备方法 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB505600A (en) * | 1936-11-14 | 1939-05-15 | Deutsche Hydrierwerke Ag | Improvements in or relating to the manufacture of hydrogenation products of furfurol |
| US4376208A (en) * | 1981-08-17 | 1983-03-08 | The Quaker Oats Company | Hydroformylation of dihydrofuran |
| CN1088905A (zh) * | 1992-12-29 | 1994-07-06 | 中国石化兰州炼油化工总厂 | 烯烃氢甲酰化合成醛的方法 |
| JPH08295683A (ja) * | 1995-04-28 | 1996-11-12 | Mitsui Toatsu Chem Inc | ３−ホルミルテトラヒドロフランの製造法 |
| CN106103399A (zh) * | 2013-12-19 | 2016-11-09 | 陶氏技术投资有限责任公司 | 氢甲酰化方法 |
-
2018
- 2018-04-17 CN CN201810344166.3A patent/CN108579808B/zh active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB505600A (en) * | 1936-11-14 | 1939-05-15 | Deutsche Hydrierwerke Ag | Improvements in or relating to the manufacture of hydrogenation products of furfurol |
| US4376208A (en) * | 1981-08-17 | 1983-03-08 | The Quaker Oats Company | Hydroformylation of dihydrofuran |
| CN1088905A (zh) * | 1992-12-29 | 1994-07-06 | 中国石化兰州炼油化工总厂 | 烯烃氢甲酰化合成醛的方法 |
| JPH08295683A (ja) * | 1995-04-28 | 1996-11-12 | Mitsui Toatsu Chem Inc | ３−ホルミルテトラヒドロフランの製造法 |
| CN106103399A (zh) * | 2013-12-19 | 2016-11-09 | 陶氏技术投资有限责任公司 | 氢甲酰化方法 |
Non-Patent Citations (2)
| Title |
|---|
| 金属原子簇的催化作用-乙烯氢甲酰化反应;傅宏祥等;《分子催化》;19871231;第1卷(第4期);第215-220页 * |
| 铁钴异核簇HFeCo3(CO)12在丙烯氢甲酰化反应中催化作用的研究;戴伟等;《石油化工》;19881231;第17卷(第11期);第707-713页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108579808A (zh) | 2018-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Klankermayer et al. | Selective catalytic synthesis using the combination of carbon dioxide and hydrogen: catalytic chess at the interface of energy and chemistry | |
| CA1157453A (en) | Process for the selective production of ethanol and methanol directly from synthesis gas | |
| SG185947A1 (en) | Process for the production of alcohol from a carbonaceous feedstock | |
| WO2009077719A1 (en) | Process for the conversion of hydrocarbons to ethanol | |
| WO2009077729A1 (en) | Process for the production of ethanol from a carbonaceous feedstock | |
| JPH027295B2 (zh) | ||
| CN108579808B (zh) | 一种用于合成四氢呋喃-3-甲醛的复合催化剂及使用其合成四氢呋喃-3-甲醛的方法 | |
| CN113416211A (zh) | 一种乙烯基官能团化膦配体合成方法及膦配体和应用 | |
| Wang et al. | Ruthenium-catalyzed hydrogenation of CO 2 as a route to methyl esters for use as biofuels or fine chemicals | |
| Xu et al. | Ethylene as a synthon in carbonylative synthesis | |
| JP2018537461A (ja) | 均一触媒反応において水性媒質中で二酸化炭素および水素ガスからメタノールを生産するための方法 | |
| EP0027000B1 (en) | Methanol conversion with co or co+h2 using iron-cobalt catalyst | |
| Manar et al. | Promising Catalytic Application by Pincer Metal Complexes: Recent Advances in Hydrogenation of Carbon‐Based Molecules | |
| Zhang et al. | The preparation and catalytic performance of novel amine-modified silica supported ruthenium complexes for supercritical carbon dioxide hydrogenation to formic acid | |
| JP3712093B2 (ja) | トリシクロデカンジカルバルデヒドの製造法 | |
| JP7149424B2 (ja) | 選択的均一系水素化触媒の回収方法および再使用方法 | |
| Qadir et al. | Transition metal-catalyzed hydrogenation of carbon dioxide in ionic liquids | |
| JPH0530502B2 (zh) | ||
| CN110372513B (zh) | 一种醋酸乙烯酯氢甲酰化的方法 | |
| Volkman et al. | Cobalt‐Catalyzed Carbonylations | |
| JP6835403B2 (ja) | ジアルデヒド化合物の製造方法 | |
| CA3096309C (en) | Catalytic conversion of carbon dioxide to methanol | |
| CA3059585A1 (en) | Process for the preparation of deuterated ethanol from d2o | |
| CN115594716B (zh) | 一种用于催化烯烃氢甲酰化反应制备支链醛的配体及其制备方法和用途 | |
| EP2747885A1 (en) | Promoted ruthenium catalyzed conversion of syngas to alcohols |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |