CN107096567A - The composite catalyst and preparation method of synthesis of propylene glycol - Google Patents
The composite catalyst and preparation method of synthesis of propylene glycol Download PDFInfo
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- CN107096567A CN107096567A CN201710367120.9A CN201710367120A CN107096567A CN 107096567 A CN107096567 A CN 107096567A CN 201710367120 A CN201710367120 A CN 201710367120A CN 107096567 A CN107096567 A CN 107096567A
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- Prior art keywords
- propylene glycol
- synthesis
- composite catalyst
- silicon
- mesoporous material
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 55
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000001294 propane Substances 0.000 claims abstract description 41
- 239000002608 ionic liquid Substances 0.000 claims abstract description 36
- 239000013335 mesoporous material Substances 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000010703 silicon Substances 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 20
- -1 imidazoles acetate Chemical class 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 11
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 150000005837 radical ions Chemical class 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 84
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 claims description 35
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- HVVRUQBMAZRKPJ-UHFFFAOYSA-N 1,3-dimethylimidazolium Chemical compound CN1C=C[N+](C)=C1 HVVRUQBMAZRKPJ-UHFFFAOYSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 4
- QKXCAKZMAORNSR-UHFFFAOYSA-N azane 1-chlorohexadecane Chemical compound N.CCCCCCCCCCCCCCCCCl QKXCAKZMAORNSR-UHFFFAOYSA-N 0.000 claims description 4
- YVDWMBAZNAOWHG-UHFFFAOYSA-N acetic acid;1h-pyrrole Chemical compound CC(O)=O.C=1C=CNC=1 YVDWMBAZNAOWHG-UHFFFAOYSA-N 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 2
- CLWAXFZCVYJLLM-UHFFFAOYSA-N 1-chlorohexadecane Chemical compound CCCCCCCCCCCCCCCCCl CLWAXFZCVYJLLM-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 39
- 239000000203 mixture Substances 0.000 description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 27
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical class COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 14
- 238000004817 gas chromatography Methods 0.000 description 13
- 239000007791 liquid phase Substances 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000002210 silicon-based material Substances 0.000 description 6
- 238000001802 infusion Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000011017 operating method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000012453 solvate Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- YTTFFPATQICAQN-UHFFFAOYSA-N 2-methoxypropan-1-ol Chemical class COC(C)CO YTTFFPATQICAQN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000010148 water-pollination Effects 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
- 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
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
- B01J31/0295—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by covalent attachment to the substrate, e.g. silica
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to chemical industry catalysis technical field, disclose a kind of composite catalyst of synthesis of propylene glycol, the composite catalyst is that silicon-based mesoporous material loads imidazoles acetate ionic liquid and/or quaternary ammonium methyl carbonic acid radical ion liquid, wherein, the size of silicon-based mesoporous material is 20~500nm.The present invention also provides the preparation method of the composite catalyst of synthesis of propylene glycol, and methods described comprises the following steps：By imidazoles acetate ionic liquid and/or the liquid dispersion of quaternary ammonium methyl carbonic acid radical ion in a solvent, silicon-based mesoporous material is added, is disperseed, solvent is removed, the composite catalyst of the synthesis of propylene glycol is obtained.And, the present invention also provides application of the composite catalyst of above-mentioned synthesis of propylene glycol in alcohol and expoxy propane prepare propylene glycol.The composite catalyst of the synthesis of propylene glycol has the advantages that high activity, high selectivity, easily recovery, energy consumption are low, easily separated.
Description
Technical field
The invention belongs to chemical catalysis field, and in particular to the composite catalyst and preparation method of synthesis of propylene glycol and should
With.
Background technology
Propane diols ether compound is the fine chemicals of function admirable, is also to have in the senior solvent of environment-friendly type, its structure
Two strong solubility functional group-hydroxyls and ehter bond, the former has hydrophily, and the latter has lipophile, thus with very strong
Solvability, have the title of " alembroth ", is widely used in the industries such as coating, ink, paint, printing.Propane diols ethers
Compound is mainly synthesized by expoxy propane and low-carbon alcohols reaction, however, due to the steric effect of expoxy propane, making it in bronsted lowry acids and bases bronsted lowry
Under conditions of the position of open loop can be different, so as to obtain different ether products, alkali generation 1- methoxy-2-propanols, and acid
Generate 2- methoxy-1-propanols.It is more and more of interest by people because the ether product of base catalysis is more environmentally friendly.At present
Industrial propylene glycol synthesis uses traditional strong alkali catalyst sodium alkoxide (potassium) and sodium hydroxide, but these
Catalyst all has corrosivity by force, and three wastes growing amount is big, the shortcomings of catalyst is difficult to reclaim.
The content of the invention
The technical problems to be solved by the invention are defect being combined there is provided synthesis of propylene glycol for overcoming prior art
Catalyst and preparation method and application.
The present invention provides the composite catalyst of synthesis of propylene glycol, and the composite catalyst is that silicon-based mesoporous material loads miaow
Azole acetate ionic liquid and/or quaternary ammonium methyl carbonic acid radical ion liquid, wherein, the size of silicon-based mesoporous material for 20~
500nm。
The present invention also provides the preparation method of the composite catalyst of synthesis of propylene glycol, and methods described comprises the following steps：
By imidazoles acetate ionic liquid and/or the liquid dispersion of quaternary ammonium methyl carbonic acid radical ion in a solvent, add
Silicon-based mesoporous material, disperses, and removes solvent, obtains the composite catalyst of the synthesis of propylene glycol.
And, the composite catalyst that the present invention also provides above-mentioned synthesis of propylene glycol prepares propane diols in alcohol and expoxy propane
Application in ether.
The present invention provides composite catalyst of synthesis of propylene glycol and preparation method thereof, and the composite catalyst is support type
Ionic liquid, its flowing that can maintain ionic liquid or architectural characteristic, increase specific surface area, reduce usage amount, living with height
Property, high selectivity, easily reclaim, energy consumption it is low, it is easily separated the advantages of.Imidazoles acetate ionic liquid and/or quaternary ammonium methyl carbon
Acid ion liquid is easy to load and environment-friendly in silica-base material.Further, such catalyst preparation process is simple, production
Cost is low, is suitable for industrialized production.
Brief description of the drawings
Fig. 1 is the TEM figures of silicon-based mesoporous material material in the embodiment of the present invention 1~3；
Fig. 2 be [N2221] [MC] in MCM-41, [EMIM] [AC]/MCM-41 and embodiment 4 in the embodiment of the present invention 1/
MCM-41 infrared spectrogram.
Fig. 3 is the N2 adsorption/desorption curves of MCM-41, NMS and MS in the embodiment of the present invention 1,2 and 3.
Fig. 4 is [EMIM] [AC]/MCM-41, [EMIM] [AC]/NMS and [EMIM] in the embodiment of the present invention 1,2 and 3
[AC]/MS N2 adsorption/desorption curves.
Fig. 5 is [N2221] [MC]/MCM-41, [N2221] [MC]/NMS and [N2221] in the embodiment of the present invention 4,5 and 6
[MC]/MS N2 adsorption/desorption curves.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
The embodiment of the present invention provides the composite catalyst of synthesis of propylene glycol, and the composite catalyst is silicon-based mesoporous material
Imidazoles acetate ionic liquid and/or quaternary ammonium methyl carbonic acid radical ion liquid are loaded, wherein, the size of silicon-based mesoporous material
For 20~500nm.
Preferably, silicon-based mesoporous material is 30~80nm mesoporous silicon oxide, and mesoporous pore size is 2~5nm.Specifically,
The preparation method of silicon-based mesoporous material is：
Cetyl chloride ammonium is soluble in water, 95 DEG C are stirred and heated to after triethanolamine, positive silicic acid second is then added
Ester, continues to stir 1~2h, with methanol and/or ethanol centrifuge washing, dries, obtains silicon-based mesoporous material, wherein, described 16
The mass ratio of alkyl ammomium chloride, triethanolamine and tetraethyl orthosilicate is 1：0.14~0.2：2~4, cetyl chloride ammonium it is dense
Spend for 10~50g/L.
Preferably, in the imidazoles acetate ionic liquid [EMIM] [AC], [DMIM] [AC] and [BMIM] [AC]
At least one, the quaternary ammonium methyl carbonic acid ester ionic liquid is [N2221][MC]、[N4441] [MC] and [N4444] in [MC] extremely
Few one kind.Its structural formula is as follows：
It is more preferred to, the mass ratio of the ionic liquid and silicon-based mesoporous material is 0.02~0.2：1.It is described
Ionic liquid is at least one of [EMIM] [AC], [DMIM] [AC] and [BMIM] [AC].Glyoxaline ion liquid relative to
Other ionic liquids such as quaternary ammonium ionic liquid, tetramethyl guanidine ionic liquid etc. have higher heat endurance, in catalysis fourth
The alkyl such as alcohol, the tert-butyl alcohol, amylalcohol, hexanol, enanthol, octanol are more than or equal to 4 alcohol and expoxy propane is reacted with bigger
Advantage.Load capacity is high simultaneously, is difficult to reveal in mesoporous hole.Meanwhile, it is silicon-based mesoporous on the significant cyclic number of catalyst
Material load imidazoles acetate ionic liquid has bigger advantage.Therefore, either from the prices of raw materials, or utilize
In efficiency, imidazoles acetate ionic liquid has bigger industrial application value.It is highly preferred that the ionic liquid is
[EMIM][AC]。
The embodiment of the present invention also provides the preparation method of the composite catalyst of synthesis of propylene glycol, and methods described includes as follows
Step：
By imidazoles acetate ionic liquid and/or the liquid dispersion of quaternary ammonium methyl carbonic acid radical ion in a solvent, add
Silicon-based mesoporous material, disperses, and removes solvent, obtains the composite catalyst of the synthesis of propylene glycol.
Specifically, the solvent is that methanol, ethanol etc. can be with the solvents of dissolving ion liquid.Solvent remove can by from
The heart or evaporation under reduced pressure removed.It is described to disperse be a variety of dispersing modes such as dispersed with stirring, ultrasonic disperse.The ionic liquid with
The mass ratio of silicon-based mesoporous material is 0.02~0.2.
Further, the embodiment of the present invention also provides the composite catalyst of above-mentioned synthesis of propylene glycol in alcohol and expoxy propane system
Application in standby propylene glycol.
Specifically, expoxy propane and alcohol are sent into reactor and contacted with the composite catalyst of the synthesis of propylene glycol,
50 DEG C~200 DEG C are heated under closed environment, the propylene glycol is obtained.
More specifically, the mol ratio of the expoxy propane and alcohol is 1：1~1：10, the catalyst and expoxy propane rub
You are than being 1：10~1：1000,30~300min of reaction time.Pressure is usually between 0.1~1MPa.Preferably, the epoxy
The mol ratio of propane and alcohol is 1：5~1：3, the mol ratio of the catalyst and expoxy propane is 1：50~1：200.More preferably
Ground, the alcohol is C1~C8Any one in alcohol.The composite catalyst of the synthesis of propylene glycol is used for alcohol and expoxy propane is anti-
It should prepare propylene glycol, conversion ratio and there is very big advantage selectively relative to prior art, can reach more than 95%.
The preparation method of the composite catalyst of synthesis of propylene glycol is illustrated below by way of specific embodiment and its is answered
With.Meso-porous titanium dioxide silicon carrier and ionic liquid in example below can be directly prepared according to existing method respectively, when
So, directly it can also buy from the market in other embodiments, however it is not limited to this.
Embodiment 1：
Mesoporous silica MCM 41 loads [EMIM] [AC]：
The synthesis of Mesoporous silica MCM 41：
1.0g CTABs are dissolved in 480mL deionized waters, 3.5mL, 2mol/L NaOH is added
Solution adds 5mL tetraethyl orthosilicates after being heated to 80~90 DEG C, stabilization, is stirred continuously, 4~6h of question response obtains white precipitate；
Product Medium speed filter paper suction filtration, water and methanol washing；Gained solid is placed in the mixed solution of methanol and concentrated hydrochloric acid the 12h that flows back
Template is removed above, and centrifugal drying obtains product MCM-41 mesoporous materials, transmission electron microscope phenogram such as Fig. 1 a.
Using mesoporous silicon material MCM-41 as carrier, with infusion process, to [EMIM] [AC], it is loaded, and operating procedure is such as
Under：1g MCM-41 are taken, 10mL methanol solvates are added, 0.5g [EMIM] [AC] is added and is mixed, ultrasonic certain time, until
Mixture is completely into milkiness liquid status.Emulsion is placed in vacuum drying chamber, centrifugation removes solvent and do not entered into hole
Ionic liquid, obtains composite catalyst [EMIM] [AC]/MCM-41 of the synthesis of propylene glycol, and ionic liquid loaded amount is
10%, the infrared spectrogram of composite catalyst is as shown in Figure 2, it can be seen that ionic liquid successfully loads to MCM-41
On.
By [EMIM] in composite catalyst [EMIM] [AC]/MCM-41 of expoxy propane, methanol and synthesis of propylene glycol
[AC] is 1 in molar ratio：3：0.02 it is well mixed after add in microwave reaction pipe, in microwave reactor, be heated to 80 DEG C, instead
Answer 60min.A part is taken to be centrifuged in resulting mixture, the liquid phase mixture obtained using gas chromatography measure
Composition, the conversion ratio for calculating expoxy propane is 76.5%, and the selectivity of propylene glycol monomethyl ether is 87.4%.
Embodiment 2：
Mesoporous material NMS loads [EMIM] [AC]：
Mesoporous material NMS synthesis：
5g cetyl chloride ammoniums are dissolved in 200mL water, add 0.8g triethanolamines after be stirred and heated to 95 DEG C, then by
15mL TEOS are added dropwise to, continues to stir 1h, with the multiple centrifuge washing of methanol, is centrifuged using high speed freezing centrifuge, through dry
It is dry to produce mesoporous nano material NMS, transmission electron microscope phenogram such as Fig. 1 b.
Using mesoporous silicon material NMS as carrier, with infusion process, to [EMIM] [AC], it is loaded, and operating procedure is as follows：
1.2g NMS are taken, 10mL methanol solvates are added, 0.12g [EMIM] [AC] is added and is mixed, ultrasonic certain time, until mixing
Thing is completely into milkiness liquid status.Emulsion is placed in vacuum drying chamber, with P2O5For drier, more than 24h is dried in vacuo, is obtained
Composite catalyst [EMIM] [AC]/NMS of the synthesis of propylene glycol is obtained, ionic liquid loaded amount is 10%.
By [EMIM] [AC] in composite catalyst [EMIM] [AC]/NMS of expoxy propane, methanol and synthesis of propylene glycol
It is 1 in molar ratio：3：0.02 it is well mixed after add in microwave reaction pipe, in microwave reactor, be heated to 90 DEG C, reaction
60min.Take a part to be centrifuged in resulting mixture, the group of obtained liquid phase mixture is determined using gas chromatography
Into the conversion ratio for calculating expoxy propane is 95.3%, and the selectivity of propylene glycol monomethyl ether is 98.0%.
Embodiment 3：
Mesoporous material MS loads [EMIM] [AC]：
Mesoporous material MS synthesis：
2.5g CTABs are added into 350mL water, are separately added into 4mL NH after dissolving successively3H2O
(30%), 75mL ether and 25mL ethanol, are stirring evenly and then adding into 12.5mL tetraethyl orthosilicates and 0.5mL 3- aminopropyls three
Ethoxysilane, 20~25 DEG C of reaction 4h, finally adds the dense HCl terminating reactions of 1mL, centrifuge washing, mesoporous through being drying to obtain at once
Material MS, transmission electron microscope phenogram such as Fig. 1 c.
Using mesoporous silicon material MS as carrier, with infusion process, to [EMIM] [AC], it is loaded, and operating procedure is as follows：Take
1g MS, add 10mL methanol solvates, add 0.5g [EMIM] [AC] and are mixed, ultrasonic certain time, until mixture is complete
Into milkiness liquid status.Emulsion is placed in vacuum drying chamber, centrifugation removes solvent and the ionic liquid not entered into hole, obtains
Composite catalyst [EMIM] [AC]/MS of the synthesis of propylene glycol is obtained, ionic liquid loaded amount is 9%.
By [EMIM] [AC] in composite catalyst [EMIM] [AC]/MS of expoxy propane, methanol and synthesis of propylene glycol
It is 1 in molar ratio：3：0.02 it is well mixed after add in microwave reaction pipe, in microwave reactor, be heated to 80 DEG C, reaction
60min.Take a part to be centrifuged in resulting mixture, the group of obtained liquid phase mixture is determined using gas chromatography
Into the conversion ratio for calculating expoxy propane is 32.3%, and the selectivity of propylene glycol monomethyl ether is 86.3%.
Embodiment 4：
Using mesoporous silicon material MCM-41 as carrier, with infusion process to [N2221] [MC] its loaded, operating procedure is such as
Under：0.57g carrier material MCM-41 are taken, 10mL methanol solvates is added, 0.057g is separately added into by theoretical load capacity 10%
[N2221] [MC] mixed, ultrasonic certain time, until mixture is completely into milkiness liquid status.Emulsion is placed in into vacuum to do
In dry case, with P2O5For drier, more than 24h is dried in vacuo, the composite catalyst [N of the synthesis of propylene glycol is obtained2221]
[MC]/MCM-41, ionic liquid loaded amount is 10%, and the infrared spectrogram of composite catalyst is as shown in Figure 2, it can be seen that ion
Liquid is successfully loaded on MCM-41.
By the composite catalyst [N of expoxy propane, methanol and synthesis of propylene glycol2221] [N in [MC]/MCM-412221]
[MC] is 1 in molar ratio：3：0.02 it is well mixed after add in microwave reaction pipe, in microwave reactor, be heated to 80 DEG C, instead
Answer 60min.A part is taken to be centrifuged in resulting mixture, the liquid phase mixture obtained using gas chromatography measure
Composition, the conversion ratio for calculating expoxy propane is 55.8%, and the selectivity of propylene glycol monomethyl ether is 87.3%.
Embodiment 5：
Using mesoporous silicon material NMS as carrier, with infusion process to [N2221] [MC] its loaded, operating procedure is as follows：
0.2g carrier materials are taken, 10mL methanol solvates are added, 0.062g [N are added2221] [MC] mixed, ultrasonic certain time, directly
To mixture completely into milkiness liquid status.Solvent is removed with Rotary Evaporators, product centrifuge washing is dried in vacuo more than 24h, obtained
Obtain the composite catalyst [N of the synthesis of propylene glycol2221] [MC]/NMS, ionic liquid loaded amount is 20%.
By the composite catalyst [N of expoxy propane, methanol and synthesis of propylene glycol2221] [N in [MC]/NMS2221][MC]
It is 1 in molar ratio：3：0.02 it is well mixed after add in microwave reaction pipe, in microwave reactor, be heated to 80 DEG C, reaction
60min.Take a part to be centrifuged in resulting mixture, the group of obtained liquid phase mixture is determined using gas chromatography
Into the conversion ratio for calculating expoxy propane is 93.0%, and the selectivity of propylene glycol monomethyl ether is 97.8%.
Embodiment 6：
By the composite catalyst [N of expoxy propane, methanol and synthesis of propylene glycol2221] [N in [MC]/MS2221] [MC] press
Mol ratio is 1：3：0.02 it is well mixed after add in microwave reaction pipe, in microwave reactor, be heated to 80 DEG C, reaction
60min.Take a part to be centrifuged in resulting mixture, the group of obtained liquid phase mixture is determined using gas chromatography
Into the conversion ratio for calculating expoxy propane is 20.0%, and the selectivity of propylene glycol monomethyl ether is 84.8%.
Embodiment 7：
By [EMIM] in composite catalyst [EMIM] [AC]/MCM-41 of expoxy propane, methanol and synthesis of propylene glycol
[AC] is 1 in molar ratio：3：0.02 it is well mixed after add in microwave reaction pipe, in microwave reactor, be heated to 90 DEG C, instead
Answer 60min.A part is taken to be centrifuged in resulting mixture, the liquid phase mixture obtained using gas chromatography measure
Composition, the conversion ratio for calculating expoxy propane is 88.3%, and the selectivity of propylene glycol monomethyl ether is 85.2%.
Embodiment 8：
By [EMIM] in composite catalyst [EMIM] [AC]/MCM-41 of expoxy propane, methanol and synthesis of propylene glycol
[AC] is 1 in molar ratio：3：0.02 it is well mixed after add in microwave reaction pipe, in microwave reactor, be heated to 90 DEG C, instead
Answer 60min.A part is taken to be centrifuged in resulting mixture, the liquid phase mixture obtained using gas chromatography measure
Composition, the conversion ratio for calculating expoxy propane is 91.7%, and the selectivity of propylene glycol monomethyl ether is 84.1%.
Embodiment 9：
By [EMIM] [AC] in composite catalyst [EMIM] [AC]/MS of expoxy propane, methanol and synthesis of propylene glycol
It is 1 in molar ratio：3：0.02 it is well mixed after add in microwave reaction pipe, in microwave reactor, be heated to 100 DEG C, reaction
60min.Take a part to be centrifuged in resulting mixture, the group of obtained liquid phase mixture is determined using gas chromatography
Into the conversion ratio for calculating expoxy propane is 63.5%, and the selectivity of propylene glycol monomethyl ether is 84.6%.
Embodiment 10：
By [EMIM] [AC] in composite catalyst [EMIM] [AC]/MS of expoxy propane, methanol and synthesis of propylene glycol
It is 1 in molar ratio：3：0.02 it is well mixed after add in microwave reaction pipe, in microwave reactor, be heated to 120 DEG C, reaction
60min.Take a part to be centrifuged in resulting mixture, the group of obtained liquid phase mixture is determined using gas chromatography
Into the conversion ratio for calculating expoxy propane is 79.7%, and the selectivity of propylene glycol monomethyl ether is 80.5%.
Comparative example 1：
The synthesis of Mesoporous silica MCM 41：
1.0g CTABs are dissolved in 480mL deionized waters, 3.5mL, 2mol/L NaOH is added
Solution adds 5mL tetraethyl orthosilicates after being heated to 80~90 DEG C, stabilization, is stirred continuously, 4~6h of question response obtains white precipitate；
Product Medium speed filter paper suction filtration, water and methanol washing；Gained solid is placed in the mixed solution of methanol and concentrated hydrochloric acid the 12h that flows back
Template is removed above, and centrifugal drying obtains product MCM-41 mesoporous materials.
Added after 0.05mol expoxy propane, 0.15mol methanol and 0.1g MCM-41 are well mixed in microwave reaction pipe,
In microwave reactor, 80 DEG C are heated to, 60min is reacted.Obtained mixture is determined to obtained liquid using gas chromatography
The composition of phase mixture, the conversion ratio for calculating expoxy propane is 9.0%, and the selectivity of propylene glycol monomethyl ether is 88.7%.
Comparative example 2：
Mesoporous material NMS synthesis：
5g cetyl chloride ammoniums are dissolved in 100mL water, add 0.8g triethanolamines after be stirred and heated to 95 DEG C, then by
15mL TEOS are added dropwise to, continues to stir 1h, with the multiple centrifuge washing of methanol, is centrifuged using high speed freezing centrifuge, through dry
It is dry to produce mesoporous nano material NMS.
Added after 0.05mol expoxy propane, 0.15mol methanol and 0.16g NMS are well mixed in microwave reaction pipe,
In microwave reactor, 80 DEG C are heated to, 60min is reacted.Obtained mixture is determined to obtained liquid phase using gas chromatography
The composition of mixture, the conversion ratio for calculating expoxy propane is 49.9%, and the selectivity of propylene glycol monomethyl ether is 82.9%.
Comparative example 3：
Mesoporous material MS synthesis：
2.5g CTABs are added into 350mL water, are separately added into 4mL NH after dissolving successively3H2O
(30%), 75mL ether and 25mL ethanol, are stirring evenly and then adding into 12.5mL tetraethyl orthosilicates and 0.5mL 3- aminopropyls three
Ethoxysilane, 20~25 DEG C of reaction 4h, finally adds the dense HCl terminating reactions of 1mL, centrifuge washing, mesoporous through being drying to obtain at once
Material MS.
Added after 0.05mol expoxy propane, 0.15mol methanol and 0.17g MS are well mixed in microwave reaction pipe,
In microwave reactor, 80 DEG C are heated to, 60min is reacted.Obtained mixture is determined to obtained liquid phase using gas chromatography
The composition of mixture, the conversion ratio for calculating expoxy propane is 3.0%, and the selectivity of propylene glycol monomethyl ether is 75.9%.
As can be seen that the composite catalyst of synthesis of propylene glycol is ionic liquid loaded mesoporous silicon material from Fig. 3~5
Composite catalyst, relative to simple silicon-based mesoporous material, specific surface area has declined, and illustrates that the success of ionic liquid is born
Carry.Meanwhile, from comparative example 1~3 and embodiment 1~10 as can be seen that composite catalyst improves third by ionic liquid loaded
The selectivity and conversion ratio of glycol ethers, have important application potential in commercial Application.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
Any modifications, equivalent substitutions and improvements made within refreshing and principle etc., should be included in the scope of the protection.
Claims (10)
1. the composite catalyst of synthesis of propylene glycol, it is characterised in that the composite catalyst is that silicon-based mesoporous material loads miaow
Azole acetate ionic liquid and/or quaternary ammonium methyl carbonic acid radical ion liquid, wherein, the size of silicon-based mesoporous material for 20~
500nm。
2. the composite catalyst of synthesis of propylene glycol as claimed in claim 1, it is characterised in that the silicon-based mesoporous material
Size is 20~80nm, and mesoporous pore size is 2~5nm.
3. the composite catalyst of synthesis of propylene glycol as claimed in claim 1, it is characterised in that the preparation of silicon-based mesoporous material
Method is：
Cetyl chloride ammonium is soluble in water, 95 DEG C are stirred and heated to after triethanolamine, tetraethyl orthosilicate is then added, after
1~2h of continuous stirring, with methanol and/or ethanol centrifuge washing, dries, obtains silicon-based mesoporous material, wherein, the Cetyl Chloride
The mass ratio for changing ammonium, triethanolamine and tetraethyl orthosilicate is 1：0.14~0.2：2~4, the concentration of cetyl chloride ammonium is 10
~50g/L.
4. the composite catalyst of synthesis of propylene glycol as claimed in claim 1, it is characterised in that the imidazoles acetate from
Sub- liquid is at least one of [EMIM] [AC], [DMIM] [AC] and [BMIM] [AC], the quaternary ammonium methyl carbonic from
Sub- liquid is [N2221][MC]、[N4441] [MC] and [N4444At least one of] [MC], its structural formula is as follows：
5. the composite catalyst of synthesis of propylene glycol as claimed in claim 1, it is characterised in that the ionic liquid is
At least one of [EMIM] [AC], [DMIM] [AC] and [BMIM] [AC].
6. the composite catalyst of synthesis of propylene glycol as claimed in claim 1, it is characterised in that the ionic liquid and silicon substrate
The mass ratio of mesoporous material is 0.02~0.2：1.
7. the preparation method of the composite catalyst of synthesis of propylene glycol, it is characterised in that methods described comprises the following steps：
By imidazoles acetate ionic liquid and/or the liquid dispersion of quaternary ammonium methyl carbonic acid radical ion in a solvent, silicon substrate is added
Mesoporous material, disperses, and removes solvent, obtains the composite catalyst of the synthesis of propylene glycol.
8. the preparation method of the composite catalyst of synthesis of propylene glycol as claimed in claim 7, it is characterised in that the solvent
For methanol/ethanol.
9. application of the composite catalyst of synthesis of propylene glycol in alcohol and expoxy propane prepare propylene glycol.
10. the composite catalyst of synthesis of propylene glycol as claimed in claim 9 is prepared in alcohol and expoxy propane in propylene glycol
Application, it is characterised in that the alcohol be C1~C8Any one in alcohol.
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| CN108262033A (en) * | 2018-01-16 | 2018-07-10 | 中国科学院过程工程研究所 | A kind of preparation method and application of nanometer carbon dots for catalyzing and synthesizing propylene glycol |
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| CN105921172A (en) * | 2016-05-20 | 2016-09-07 | 中国科学院过程工程研究所 | Application of ionic liquid in synthesis of propylene glycol ether and propylene glycol ether synthesis method |
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| CN108212196A (en) * | 2018-01-16 | 2018-06-29 | 中国科学院过程工程研究所 | A kind of preparation method and application of the composite catalyst of synthesis of propylene glycol |
| CN108262033A (en) * | 2018-01-16 | 2018-07-10 | 中国科学院过程工程研究所 | A kind of preparation method and application of nanometer carbon dots for catalyzing and synthesizing propylene glycol |
| CN108212196B (en) * | 2018-01-16 | 2020-05-01 | 中国科学院过程工程研究所 | Preparation method and application of composite catalyst for synthesizing propylene glycol ether |
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