CN111675605A - Preparation method and system of ethylene glycol monoallyl ether - Google Patents
Preparation method and system of ethylene glycol monoallyl ether Download PDFInfo
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- CN111675605A CN111675605A CN202010716921.3A CN202010716921A CN111675605A CN 111675605 A CN111675605 A CN 111675605A CN 202010716921 A CN202010716921 A CN 202010716921A CN 111675605 A CN111675605 A CN 111675605A
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- ethylene glycol
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- monoallyl ether
- glycol monoallyl
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- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 138
- 238000006243 chemical reaction Methods 0.000 claims abstract description 106
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- 239000000463 material Substances 0.000 claims abstract description 43
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000047 product Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000012043 crude product Substances 0.000 claims abstract description 22
- 230000009471 action Effects 0.000 claims abstract description 4
- 238000003860 storage Methods 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 13
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 10
- MKRZFOIRSLOYCE-UHFFFAOYSA-L zinc;methanesulfonate Chemical compound [Zn+2].CS([O-])(=O)=O.CS([O-])(=O)=O MKRZFOIRSLOYCE-UHFFFAOYSA-L 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- YISPIDBWTUCKKH-UHFFFAOYSA-L zinc;4-methylbenzenesulfonate Chemical compound [Zn+2].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 YISPIDBWTUCKKH-UHFFFAOYSA-L 0.000 claims description 7
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000011229 interlayer Substances 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 abstract description 7
- 239000011698 potassium fluoride Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- -1 propenyl glycol ester Chemical class 0.000 description 8
- 239000002699 waste material Substances 0.000 description 8
- 238000005070 sampling Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 238000007259 addition reaction Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- DIOZVWSHACHNRT-UHFFFAOYSA-N 2-(2-prop-2-enoxyethoxy)ethanol Chemical compound OCCOCCOCC=C DIOZVWSHACHNRT-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- PFUXCENAHWMURC-UHFFFAOYSA-N 2-[2-(2-prop-2-enoxyethoxy)ethoxy]ethanol Chemical compound OCCOCCOCCOCC=C PFUXCENAHWMURC-UHFFFAOYSA-N 0.000 description 3
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 235000003270 potassium fluoride Nutrition 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- FSDGGBSMJHFROK-UHFFFAOYSA-N 2-prop-1-enoxyethanol Chemical compound CC=COCCO FSDGGBSMJHFROK-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- JLVUSDMLNQQPCD-UHFFFAOYSA-L zinc;phenylmethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)CC1=CC=CC=C1.[O-]S(=O)(=O)CC1=CC=CC=C1 JLVUSDMLNQQPCD-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- 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
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- 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
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
-
- 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
- Y02P20/584—Recycling of catalysts
Abstract
The invention provides a preparation method and a system of ethylene glycol monoallyl ether, wherein the preparation method adopts the following reaction equation:
the method comprises the following steps: allyl alcohol and ethylene oxide react in the reaction kettle main body under the action of a catalyst to synthesize a crude product of ethylene glycol monoallyl ether; and carrying out reduced pressure rectification on the crude product in a rectifying tower to obtain a finished product of the ethylene glycol monoallyl ether. The preparation system comprises an addition and rectification integrated reaction kettle, the addition and rectification integrated reaction kettle comprises a reaction kettle main body, and a rectification tower is connected above the reaction kettle main body; the reaction kettle main body comprises a reaction feed inlet, a reaction discharge outlet and a material steam outlet, the material steam outlet is connected with a rectification inlet of a rectification tower, and the rectification tower is provided with a rectification inletAnd a rectification outlet, and the rectification tower is also connected with a vacuum device. The ethylene glycol monoallyl ether prepared by the method has high purity (more than or equal to 99.8 percent) and few byproducts.
Description
Technical Field
The invention belongs to the technical field of organic compound preparation, and particularly relates to a preparation method and a system of ethylene glycol monoallyl ether.
Background
Ethylene glycol monoallyl ether, also known as 2-allyloxyethanol, propylene glycol, and the like, is a colorless transparent liquid, and is miscible with water and polar solvents. The double bonds are contained in the molecule, so that the polymer can be used as a monomer of a polymer; a side chain can be introduced because the molecule contains an ether bond and a hydroxyl bond; the alcohol is useful for synthesizing an ester, and is used as an additive monomer for ordinary-temperature curing in the production of a fluororesin soluble in an organic solvent. The acrylic acid/methacrylic acid copolymer has high boiling point and low odor, reacts with acrylic acid and methacrylic acid to prepare propenyl glycol ester, and can be used as a monomer diluent of UV (ultraviolet) coating. With the national advocated energy conservation and environmental protection, the UV coating is an advanced material surface treatment technology which is an industrial technology with the 5E characteristic: 1 efficiency, 2Enabling (wide adaptability), 3Economical (economy), 4Energy Saving and 5Environmental Friendly, is known as a new green industrial technology facing twenty-first century, and has good development prospect.
The current synthesis process routes of ethylene glycol monoallyl ether include two types:
1) an etherification end-capping method, which is disclosed in the article "development of ethylene glycol monoallyl ether" published in 2012, 1.A technical scheme is that allyl chloride and ethylene glycol are subjected to hydroxyl etherification under an alkaline condition, and then rectification purification is adopted.
2) Polymerization method: with alkeneTaking propylene alcohol and ethylene oxide as raw materials, synthesizing a coarse product of ethylene glycol monoallyl ether under the action of an alkaline catalyst, and then neutralizing, rectifying and purifying by acid to obtain a finished product. A scheme is disclosed in the article KF/A1203 preparation, characterization and catalytic synthesis of ethylene glycol propenyl ether published in the university of Changzhou journal, 2013, No. 1, which takes propylene alcohol and ethylene oxide as raw materials, and adopts KF/AI2O3Synthesizing a coarse product of ethylene glycol monoallyl ether by catalyzing with a solid base catalyst; a scheme is disclosed in an article, namely ethylene glycol allyl ether catalyzed and synthesized by attapulgite loaded KF (potassium fluoride) in the 2 nd publication of the chemical engineering journal of colleges and universities 2014, wherein propylene alcohol and ethylene oxide are used as raw materials, a crude product of ethylene glycol allyl ether is synthesized by catalysis of KF/ATP (potassium fluoride)/Al (aluminum phosphate) solid base catalyst, and KF/AI (potassium fluoride)/Al (aluminum chloride) is used as a catalyst2O3And KF/ATP catalyst is used in synthesizing glycol monoallyl ether, and has low catalytic selectivity, low product yield and high production cost. A scheme is disclosed in an article, namely synthesis of ethylene glycol monoallyl ether, published in No. 1 of 2017 of Fine and specialty Chemicals, propylene alcohol and ethylene oxide are used as raw materials, crude ethylene glycol monoallyl ether is synthesized by catalyzing sodium propylene alcohol, and the crude ethylene glycol monoallyl ether is rectified and purified to obtain a finished product, wherein the content of the finished product is more than or equal to 99.5%. Chinese patent CN 103435455B, a preparation method of ethylene glycol monoallyl ether, discloses a preparation method of ethylene glycol monoallyl ether, which takes propylene alcohol and ethylene oxide as raw materials, adopts KOH, NaOH and CH3Synthesizing coarse product of ethylene glycol monoallyl ether by using ONa, Na or sodium allyl alcohol as catalyst, then adding H3PO4、H2SO4Or neutralizing by HAC, and rectifying to obtain the final product with content not less than 99.0%. KOH, sodium allyl alcohol and the like have poor catalytic selectivity, and KF/AI2O3Similar to KF/ATP catalysis, the method also has the disadvantages of high production yield and addition of H along with the generation of a large amount of byproducts such as diethylene glycol monoallyl ether, triethylene glycol monoallyl ether and the like3PO4、H2SO4Or HAC, resulting in a large amount of Na in the crude product2SO4And the impurities of inorganic and organic salts such as NaAC are difficult to removeSo that the residual kettle bottom liquid can not be directly utilized after the crude product is rectified, a large amount of waste liquid is generated, the treatment cost is high, the product is polluted by the environment and the like.
Disclosure of Invention
In order to solve the problems of low purity of synthesized crude products, high production cost, generation of a large amount of waste solids, environmental pollution caused by waste liquid and the like in the two synthesis process routes at present, the invention provides a method and a system for preparing ethylene glycol monoallyl ether, which have the advantages of high catalytic selectivity, low production cost, few byproducts and waste liquid and waste solids, easiness in operation and high efficiency. The technical scheme of the invention is as follows:
the invention provides a preparation system of ethylene glycol monoallyl ether, which comprises an addition and rectification integrated reaction kettle, wherein the addition and rectification integrated reaction kettle comprises a reaction kettle main body, and a rectification tower is connected above the reaction kettle main body; the reaction kettle main body comprises a reaction feed inlet, a reaction discharge outlet and a material steam outlet, and the material steam outlet is connected with a rectification inlet of the rectification tower; the rectifying tower is provided with the rectifying inlet and the rectifying outlet and is also connected with a vacuum device.
Furthermore, the reaction discharge hole is connected with the reaction feed hole through a material return pipeline, and a filter and a material conveying pump are arranged on the material return pipeline.
Further, a stirring device is also arranged in the reaction kettle main body.
Further, the reaction kettle is provided with an interlayer, and the interlayer is used for introducing a temperature control medium.
Further, the preparation system also comprises a raw material storage tank and a product storage tank, wherein the raw material storage tank and the product storage tank are respectively connected with the addition rectification integrated reaction kettle.
In a second aspect, the present invention provides a method for preparing ethylene glycol monoallyl ether, which uses the following reaction equation:
the preparation method adopts the preparation system, and comprises the following steps: allyl alcohol and ethylene oxide react in the reaction kettle main body under the action of a catalyst to synthesize a crude product of ethylene glycol monoallyl ether; and carrying out reduced pressure rectification on the crude product in a rectifying tower to obtain a finished product of the ethylene glycol monoallyl ether.
Further, the preparation method comprises the following steps: mixing allyl alcohol and a catalyst in the reaction vessel body, N2Heating to 90-160 ℃ under protection, adding ethylene oxide, and carrying out heat preservation reaction; separating out the catalyst after the reaction is finished to obtain a crude product of the ethylene glycol monoallyl ether; and carrying out reduced pressure rectification on the ethylene glycol monoallyl ether crude product in the rectifying tower, respectively collecting free allyl alcohol, an ethylene glycol monoallyl ether finished product and kettle bottom liquid, wherein the separated catalyst and free allyl alcohol can be recycled for the reaction process, and the kettle bottom liquid can be directly used for producing an allyl alcohol polyoxyethylene ether surfactant product.
Further, the catalyst is at least one of zinc methanesulfonate or zinc toluenesulfonate.
Further, the mass ratio of the allyl alcohol to the ethylene oxide is: 58: (13.2-52.8), wherein the dosage of the catalyst is 0.3-5 per mill of the total weight of the allyl alcohol and the ethylene oxide.
Preferably, the reaction temperature of the allyl alcohol and the ethylene oxide under the catalysis of the catalyst is 95-150 ℃, and the reaction pressure is-0.05-0.60 MPa.
Further, the vacuum rectification specific process comprises the following steps: vacuumizing the addition rectification integrated reaction kettle to-0.05 MPa, controlling the vacuum degree to be constant, heating the crude ethylene glycol monoallyl ether in the reaction kettle main body, opening rectification and condensation, controlling the temperature of materials at the bottom of the kettle to be 65-80 ℃, controlling the temperature at the top of the kettle to be 50-65 ℃, carrying out total reflux for 30min, then starting to receive allyl alcohol, vacuumizing to improve the vacuum degree in the kettle to be more than or equal to-0.098 MPa after the allyl alcohol is collected and the temperature at the top of the kettle is reduced to normal temperature; heating the materials in the kettle again, controlling the temperature of the materials at the bottom of the kettle to be 80-100 ℃, controlling the temperature at the top of the kettle to be 50-65 ℃, carrying out total reflux for 30min, and then starting to receive the mixture of the ethylene glycol monoallyl ether and the allyl alcohol, wherein the reflux ratio is controlled to be 5: 1, during which the liquid is taken out and detected in the mixtureWhen the content of the ethylene glycol monoallyl ether in the receiving liquid is more than or equal to 99.7 percent, the finished product of the ethylene glycol monoallyl ether is independently received, and when the purity of the ethylene glycol monoallyl ether in the fraction is less than or equal to 99.7 percent, the receiving is stopped, and the rectification is finished. Cooling the bottom liquid to 40 + -2 deg.C, charging N2And (3) putting the kettle bottom liquid into a packaging barrel for producing other allyl alcohol polyoxyethylene ether until the pressure of the reaction kettle is 0.00-0.04 MPa.
Compared with the prior art, the method has the following outstanding advantages and positive effects:
1. the ethylene glycol monoallyl ether prepared by the technical scheme of the invention has high purity (more than or equal to 99.8%) and few byproducts.
2. The preparation method has the advantages of simple process, mild reaction conditions, good selectivity, short production period, low energy consumption, repeated utilization of the catalyst and less three wastes.
3. The preparation system integrates the addition reaction and the rectification process, and the rectification step is directly carried out in the same reaction kettle after the addition reaction is finished, so that the equipment requirement is reduced, the cost is reduced, material transfer is not needed, the material pollution probability is avoided, and the product quality can be ensured.
Drawings
FIG. 1 is a schematic view of the structure of a production system of the present invention.
Fig. 2 is a schematic structural view of a rectifying column of the present invention.
In fig. 1 and 2, 1: ethylene oxide storage tank, 2: material transfer pump, 3: catalyst filter, 4: reaction kettle main body, 5: rectifying tower, 6: n-propanol storage tank, 7: ethylene glycol monopropyl ether reservoir, 8: vacuum pipeline, 9, branch pipeline, 10, reaction feed inlet, 11, reaction discharge outlet, 12, temperature-control steam outlet/cooling water inlet, 13, protective gas port, 14, rectification inlet, 15, rectification outlet, 16, stirring device, 17, interlayer, 18, control valve, 19, vacuumizing port on the storage tank, 20, protective gas port on the storage tank, 21, sampling port, 22, storage tank material outlet, 23, material return pipeline, 24, storage tank material inlet, 25 condenser, 26, temperature-control steam inlet/cooling water outlet, 27, check valve, 28 and vacuum device.
Detailed Description
In the description of the present invention, it is to be noted that those whose specific conditions are not specified in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturers. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The present invention will now be described in further detail with reference to the following figures and specific examples, which are intended to be illustrative, but not limiting, of the invention.
Preparation of the reaction kettle before implementation: washing the main body of the reaction kettle, the rectifying tower, the raw material storage tank and the product storage tank with distilled water for several times until the main body, the rectifying tower, the raw material storage tank and the product storage tank are clean, and heating N2And blowing and drying the reaction kettle main body, the rectifying tower and the storage tank, and cooling to normal temperature for later use.
Example 1
As shown in fig. 1 and 2, this embodiment provides a system for preparing ethylene glycol monoallyl ether, including an addition rectification integrated reaction kettle, where the addition rectification integrated reaction kettle includes a reaction kettle main body 4, and a rectification tower 5 is connected above the reaction kettle main body 4. The reaction kettle main body 4 is provided with an interlayer 17 for introducing a temperature control medium, such as: steam, cooling water (the inlet and outlet of the steam and the cooling water are just opposite), oil and the like. The reaction kettle main body 4 comprises a reaction feed inlet 10, a reaction discharge outlet 11, a protective gas port 13 and a material steam outlet, the reaction feed inlet 10 and the reaction discharge outlet 11 are respectively arranged at the top and the bottom of the reaction kettle main body 4, and the reaction feed inlet 10 and the reaction discharge outlet 11 are provided with control valves 18; the reaction discharge hole 11 is also connected with the reaction feed hole 10 through a return pipe 23, and the return pipe 23 is provided with a catalyst filter 3, a material conveying pump 2 and a control valve 18. A stirring device 16 is arranged in the reaction kettle main body 4; still be equipped with pressure sensor and temperature sensor in the reation kettle main part 4, be used for monitoring reation kettle main part 4 pressure and temperature respectively. The rectifying tower 5 is a plate-type rectifying tower, the bottom of the rectifying tower is provided with a rectifying inlet 14, the top of the rectifying tower is provided with a rectifying outlet 15, the rectifying inlet 14 is connected with a material steam outlet of the reaction kettle main body 4, and a control valve 18 is arranged between the rectifying tower and the material steam outlet. The top of the rectifying tower 5 is communicated with a condenser 25, the condenser 25 is connected with a vacuum device 28 through a vacuum pipeline 8, the rectifying tower 5 is directly connected with two branch pipelines 9, one branch pipeline 9 is connected with an allyl alcohol storage tank 6, the other branch pipeline 9 is connected with an ethylene glycol monoallyl ether storage tank 7 and is respectively used for collecting rectified allyl alcohol and ethylene glycol monoallyl ether, and a control valve 18 and a check valve 27 are arranged on each of the two branch pipelines 9; the vacuum line 8 is also connected to the two branch lines 9. The allyl alcohol storage tank 6 and the ethylene glycol monoallyl ether storage tank 7 are both provided with a vacuumizing port 19 and a protective gas port 20, and are also provided with a material outlet 22. The vacuum line 8 is also provided with a plurality of control valves 18. The vacuum pipe 8 is also provided with a sampling port 21 for sampling and detecting the components of the distillate so as to control the purities of different distillates. The preparation system also comprises an ethylene oxide storage tank 1, wherein the ethylene oxide storage tank 1 is connected with a reaction feeding hole 10 of the reaction kettle main body 4, a vacuumizing hole 19 and a protective gas hole 20 are also arranged on the ethylene oxide storage tank 1, and a material inlet 24 and a material outlet 22 are also arranged on the ethylene oxide storage tank 1.
Example 2
Adding 58kg of allyl alcohol and 0.4 per mill (the proportion of the total material of allyl alcohol and ethylene oxide, the same below) of zinc methanesulfonate catalyst into an addition reaction and rectification integrated kettle, vacuumizing by using a vacuum pump, and adopting N2Displacing air in the reaction kettle, after three times of displacement, the degree of evacuation is more than or equal to-0.096 MPa, heating to 100 ℃, and adding ethylene oxide while heating. The reaction temperature was controlled at 140 ℃ and 150 ℃ and the total ethylene oxide addition was controlled at 14 kg. After the addition of ethylene oxide, the reaction is continued while maintaining the temperature until the pressure does not decrease any more. After the reaction is finished, the temperature is reduced to 50 ℃, and N is filled2Sampling to 0.02MPa, detecting crude product components, opening an external circulation pipeline and a valve, and filtering to recover the catalyst. After the catalyst is completely recovered, closing a kettle bottom valve and an external circulation top valve, opening a valve between the reaction kettle and the rectifying tower and a valve between the rectifying tower and a vacuum pump, vacuumizing to-0.05 MPa, heating kettle materials while maintaining the vacuum degree, and opening a rectifying tower condenser; controlling the temperature of the bottom materials in the kettle at 65-80 ℃ and the temperature at the top of the kettle at 50-65 ℃, carrying out total reflux for 30min, and opening a receiving valve of a first receiving tank to receive allyl alcohol when the total reflux time is up; controlling the vacuum degree to be-0.05 MPa and the bottom material of the kettle to be 65-80 ℃, closing a valve of an allyl alcohol storage tank when the temperature of the top of the tower is reduced to the normal temperature,vacuumizing to more than-0.098 MPa, heating the bottom material of the kettle to 80-100 ℃, carrying out total reflux for 30min at the temperature of 50-65 ℃ at the tower top, wherein the total reflux time is up to the time of opening an allyl alcohol storage tank to receive a mixture of allyl alcohol and ethylene glycol monoallyl ether and sampling and detecting fraction components at random, when the fraction ethylene glycol monoallyl ether is more than or equal to 99.7%, a control valve of the storage tank is closed, a control valve of the ethylene glycol monoallyl ether storage tank is opened to receive the ethylene glycol monoallyl ether, the fraction components are sampled and detected at random, and when the fraction ethylene glycol monoallyl ether is less than 99.7%, the storage tank is closed to stop receiving. Cooling the kettle bottom material to 40 ℃, and charging N2Discharging the kettle bottom liquid to normal pressure, and packaging to produce other allyl alcohol polyoxyethylene ether. The method for detecting purity adopts gas chromatography calibrated by standard substance, the same as below.
Comparative example 1
Adding 58kg of allyl alcohol and 10 per thousand of KOH catalyst into an integrated kettle for addition reaction and rectification, vacuumizing by using a vacuum pump, and adopting N2Displacing air in the reaction kettle, after three times of displacement, the degree of evacuation is more than or equal to-0.096 MPa, heating to 100 ℃, and adding ethylene oxide while heating. The reaction temperature was controlled at 140 ℃ and 150 ℃ and the total ethylene oxide addition was controlled at 14 kg. After the addition of ethylene oxide, the reaction is continued while maintaining the temperature until the pressure does not decrease any more. After the reaction is finished, the temperature is reduced to 50 ℃ and N is filled2Sampling to 0.02MPa, and detecting the crude product components.
Comparative example 2
Adding allyl alcohol 58kg and 15 ‰ KF/ATP catalyst into the addition reaction and rectification kettle, vacuumizing with vacuum pump, and adopting N2Displacing air in the reaction kettle, after three times of displacement, the degree of evacuation is more than or equal to-0.096 MPa, and after the temperature is raised to 100 ℃, adding ethylene oxide for reaction. The reaction temperature is controlled between 98 ℃ and 102 ℃, and the total addition of the ethylene oxide is controlled to be 14 kg. After the addition of ethylene oxide, the reaction is continued while maintaining the temperature until the pressure does not decrease any more. After the reaction is finished, the temperature is reduced to 50 ℃ and N is filled2Sampling to 0.02MPa, and detecting the crude product components.
Effect testing experiment
Comparing the merits of different processes
Examples 3 to 7 the raw materials of allyl alcohol, ethylene oxide, the kind and amount of the catalyst, and the reaction temperature were adjusted, and other process conditions were the same as those in example 1; comparative examples 3 to 7 the raw materials of allyl alcohol, ethylene oxide, the kind and amount of the catalyst, and the reaction temperature were adjusted, and other process conditions were the same as in example 1; the specific crude index (gas chromatography using standard substance, the same applies below) is shown in Table 1
TABLE 1 crude conditions and indices for examples and comparative examples
Note: the catalyst amount is the proportion of the total weight of the allyl alcohol and the ethylene oxide; the 'zinc methanesulfonate: zinc p-toluenesulfonate ═ 1:1 mixture' in the catalyst category is a mixture catalyst in which the weight ratio of zinc methanesulfonate to zinc p-toluenesulfonate in the mixture catalyst is 1:1, example 6 and example 7 are also in the same weight ratio.
As can be seen from the data in Table 1, under the conditions of constant allyl alcohol and ethylene oxide dosage, consistent or similar catalyst dosage and consistent reaction temperature, the crude product synthesized by using the catalyst (zinc methanesulfonate and zinc p-toluenesulfonate) of the invention is more than the crude product synthesized by using KOH, NaOH and CH of the prior art3The content of crude ethylene glycol monoallyl ether synthesized by strong alkaline catalysts such as ONa and sodium allyl alcohol is 22-150%, the difference is more obvious when the weight ratio of ethylene oxide to allyl alcohol is higher, the maximum ethylene glycol monoallyl ether content can be close to 150% (example 7 is compared with comparative example 7), and the residual unreacted allyl alcohol is less; the ratio of byproducts such as diethylene glycol monoallyl ether and triethylene glycol monoallyl ether is determined by using KOH, NaOH and CH in the prior art3The crude products synthesized by strong alkaline catalysts such as ONa and sodium allyl alcohol are remarkably low and are below 1/3. The invention compares KF/ATP, KF/AI2O3The best process available for catalysis (best process summarized in literature), the by-products of diethylene glycol monoallyl ether and triethylene glycol monoallyl ether, etc., 16% and the target product glycol monoallyl ether is higher than the target product glycol monoallyl ether by more than 15%.
Second, the product rectification index
The indexes of the finished products after rectification in examples 2 to 7 are shown in Table 2
TABLE 2 EXAMPLES 2 TO 7 indexes of finished products
The data in table 2 show that the content of ethylene glycol monoallyl ether in the product prepared by the rectification method is more than 99.85%, allyl alcohol is less than 0.002%, and diethylene glycol monoallyl ether is less than 0.003%.
Third, the catalyst uses mechanically
The synthesis reaction process conditions of the catalyst recovery and application experiment are the same as those in example 2, only the type of the catalyst and the application frequency of the catalyst are changed (the amount of the catalyst recovery and application is not enough, and a new catalyst is slightly supplemented), and zinc methanesulfonate and zinc p-toluenesulfonate are taken as examples and applied, and the method is not limited to the above actually. The specific indexes of the crude product are shown in tables 3 and 4
TABLE 3 application parameters and crude index of zinc methanesulfonate catalyst
TABLE 4 application parameters and crude index of zinc p-toluenesulfonate catalyst
The data in tables 3 and 4 show that the catalyst of the invention can be repeatedly used for more than 8 times without obvious reduction of the catalytic effect, which indicates that the catalyst of the invention can be recycled.
Fourthly, recycling allyl alcohol for reuse
Experimental process conditions for recycling and applying allyl alcohol are the same as those in example 2, and only the number of times of applying allyl alcohol is changed (the recycling and applying amount of allyl alcohol is not enough, and the same amount of allyl alcohol is supplemented with new allyl alcohol), but the method is not limited to the above actually. The specific index of the crude product is shown in Table 5.
TABLE 5 allyl alcohol use parameters and crude index
The data in Table 5 show that the recycled allyl alcohol of the present invention is reused 8 times without significant change in catalytic effect, indicating that the recycled allyl alcohol of the present invention can be reused. In the embodiment, only the effect of using n-propanol for 8 times is considered, but according to the result, the n-propanol can be used for at least 8 times without affecting the experimental effect.
Fifth, application example of bottom liquid of autoclave
And (3) using the kettle bottom liquid for synthesizing and producing the allyl alcohol polyoxyethylene ether surfactant: putting the collected kettle bottom liquid into a clean and dry condensation kettle, adding a catalyst KOH with the weight of 0.5 percent of the kettle bottom liquid, and adopting N2Replacing air in the kettle, heating to 100 ℃, adding different amounts of ethylene oxide for reaction (3 batches of reaction are carried out, see application example 1, application example 2 and application example 3), controlling the reaction temperature at 100-fold-120 ℃, obtaining crude allyl alcohol polyoxyethylene ether after the reaction is finished, cooling to 60-70 ℃, transferring to a post-treatment kettle, adding deionized water and 85% phosphoric acid which is 2.1 times of KOH in weight for hydrolysis and neutralization, adding 0.5% of polyether adsorbent in the amount of crude allyl alcohol polyoxyethylene ether, and finally heating to 100-fold-120 ℃ for dehydration. After dehydration, cooling to 60-80 ℃ and filtering to obtain the finished product of the allyl alcohol polyoxyethylene ether surfactant. The product indices obtained are shown in Table 6.
TABLE 6 index of finished product of allyl alcohol polyoxyethylene ether produced from bottom liquid of kettle
The production data in Table 6 show that the product of the allyl alcohol polyoxyethylene ether produced by adopting the kettle bottom liquid completely meets the related requirement indexes of the surfactant (the color is less than or equal to 50Pt-Co, and the double bond retention rate is more than or equal to 90 percent), and can be used for producing the surface active allyl alcohol polyoxyethylene ether.
In summary, the method for preparing ethylene glycol monoallyl ether of the present invention uses weakly acidic solid catalyst such as zinc methanesulfonate or zinc p-toluenesulfonate as catalyst, and uses strong basic catalyst such as KOH, NaOH, sodium methoxide, sodium allyl alcohol, etc. and KF/AI2O3And the KF/ATP catalyst has good reaction selectivity, high purity of the ethylene glycol monoallyl ether, less by-products, mild and safe reaction, reutilization of the catalyst, low cost and less three wastes. Compared with the prior synthesis reaction kettle and the rectification kettle which are required by the prior equipment for preparing the ethylene glycol monoallyl ether, the integrated reaction kettle for synthesis reaction and rectification operation reduces one reaction kettle, equipment investment, equipment cost and production area; meanwhile, materials are not required to be transferred to other kettles from a synthesis reaction to a rectification section, so that the pollution of the materials in the transfer process is reduced, and the product quality is ensured. The invention adopts a rectification method with reduced pressure and accurate control, which comprises the following steps: the whole process adopts reduced pressure rectification, the separation temperature of the materials is reduced, the temperature is only 65-80 ℃ in the stage of allyl alcohol separation, and the material heat energy requirement required by rectification is reduced; the purity of the required ethylene glycol monoallyl ether finished product is accurately controlled to be more than or equal to 99.8 percent by monitoring process fraction components. However, in the conventional atmospheric re-vacuum distillation (for example, chinese patent CN 103435455B) of the current state of the art, the atmospheric distillation is used in the process of separating allyl alcohol, the material temperature needs to be as high as 96-110 ℃, the temperature needs to be reduced to 40 ℃ after the allyl alcohol is separated, and the temperature needs to be heated to 70-110 ℃ after the allyl alcohol is vacuumized, so that the energy waste is increased, and the production cost is increased.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation system of ethylene glycol monoallyl ether is characterized in that: the device comprises an addition and rectification integrated reaction kettle, wherein the addition and rectification integrated reaction kettle comprises a reaction kettle main body, and a rectification tower is connected above the reaction kettle main body; the reaction kettle main body comprises a reaction feed inlet, a reaction discharge outlet and a material steam outlet, and the material steam outlet is connected with a rectification inlet of the rectification tower; the rectifying tower is provided with the rectifying inlet and the rectifying outlet and is also connected with a vacuum device.
2. The system for preparing ethylene glycol monoallyl ether according to claim 1, wherein: the reaction discharge hole is also connected with the reaction feed hole through a material return pipeline, and a filter and a material conveying pump are arranged on the material return pipeline.
3. The system for preparing ethylene glycol monoallyl ether according to claim 1, wherein: the reaction kettle is provided with an interlayer, and the interlayer is used for introducing a temperature control medium.
4. The system for producing ethylene glycol monoallyl ether according to any one of claims 1 to 3, wherein: the preparation system also comprises a raw material storage tank and a product storage tank, wherein the raw material storage tank and the product storage tank are respectively connected with the addition rectification integrated reaction kettle.
5. A preparation method of ethylene glycol monoallyl ether is characterized by comprising the following steps: the following reaction equation is adopted:
the preparation method adopts the preparation system of any one of claims 1 to 4, and comprises the following steps: allyl alcohol and ethylene oxide react in the reaction kettle main body under the action of a catalyst to synthesize a crude product of ethylene glycol monoallyl ether; and carrying out reduced pressure rectification on the crude product in a rectifying tower to obtain a finished product of the ethylene glycol monoallyl ether.
6. The method for preparing ethylene glycol monopropyl ether according to claim 5, wherein: the preparation method comprises the following steps: mixing allyl alcohol and a catalyst in the reaction vessel body, N2Heating to 90-160 ℃ under protection, adding ethylene oxide, and carrying out heat preservation reaction; separating out the catalyst after the reaction is finished to obtain a crude product of the ethylene glycol monoallyl ether; and carrying out reduced pressure rectification on the ethylene glycol monoallyl ether crude product in the rectifying tower, respectively collecting free allyl alcohol, an ethylene glycol monoallyl ether finished product and kettle bottom liquid, wherein the separated catalyst and free allyl alcohol can be recycled for the reaction process, and the kettle bottom liquid can be directly used for producing an allyl alcohol polyoxyethylene ether surfactant product.
7. The method for preparing ethylene glycol monopropyl ether according to claim 5 or 6, characterized in that: the catalyst is at least one of zinc methanesulfonate and zinc p-toluenesulfonate.
8. The method for preparing ethylene glycol monopropyl ether according to claim 5 or 6, characterized in that: the mass ratio of the allyl alcohol to the ethylene oxide is as follows: 58: (13.2-52.8), wherein the dosage of the catalyst is 0.3-5 per mill of the total weight of the allyl alcohol and the ethylene oxide.
9. The method for preparing ethylene glycol monopropyl ether according to claim 5 or 6, characterized in that: the reaction temperature of the allyl alcohol and the ethylene oxide under the catalysis of the catalyst is 95-150 ℃, and the reaction pressure is-0.05-0.60 MPa.
10. The method for preparing ethylene glycol monopropyl ether according to claim 5 or 6, characterized in that: the vacuum rectification specific process comprises the following steps: vacuumizing the addition rectification integrated reaction kettle to-0.05 MPa, and controlling the vacuum degree to be not higher thanHeating the crude ethylene glycol monoallyl ether in the reaction kettle main body, opening rectification and condensing, controlling the temperature of materials at the bottom of the kettle to be 65-80 ℃, controlling the temperature at the top of the kettle to be 50-65 ℃, carrying out total reflux for 30min, then starting to receive allyl alcohol, vacuumizing to improve the vacuum degree in the kettle to be more than or equal to-0.098 MPa when the temperature at the top of the kettle is reduced to normal temperature after the allyl alcohol is collected; heating the materials in the kettle again, controlling the temperature of the materials at the bottom of the kettle to be 80-100 ℃, controlling the temperature at the top of the kettle to be 50-65 ℃, carrying out total reflux for 30min, and then starting to receive the mixture of the ethylene glycol monoallyl ether and the allyl alcohol, wherein the reflux ratio is controlled to be 5: 1, taking liquid during the period to detect the content of the ethylene glycol monoallyl ether in the mixture, starting to receive the finished product of the ethylene glycol monoallyl ether independently when the content of the ethylene glycol monoallyl ether in the receiving liquid is more than or equal to 99.7 percent, stopping receiving when the purity of the ethylene glycol monoallyl ether in the fraction is less than or equal to 99.7 percent, and finishing rectification. Cooling the bottom liquid to 40 + -2 deg.C, charging N2And (3) putting the kettle bottom liquid into a packaging barrel for producing other allyl alcohol polyoxyethylene ether until the pressure of the reaction kettle is 0.00-0.04 MPa.
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