CN113979861A - Method for preparing propylene glycol monomethyl ether acetate by catalytic distillation - Google Patents
Method for preparing propylene glycol monomethyl ether acetate by catalytic distillation Download PDFInfo
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- CN113979861A CN113979861A CN202111430256.2A CN202111430256A CN113979861A CN 113979861 A CN113979861 A CN 113979861A CN 202111430256 A CN202111430256 A CN 202111430256A CN 113979861 A CN113979861 A CN 113979861A
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- propylene glycol
- methyl ether
- acetate
- glycol methyl
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- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000004821 distillation Methods 0.000 title claims abstract description 13
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims abstract description 110
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 49
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims abstract description 49
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 239000011949 solid catalyst Substances 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000012856 packing Methods 0.000 claims description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000011973 solid acid Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 4
- 229960001545 hydrotalcite Drugs 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003729 cation exchange resin Substances 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 27
- 239000000047 product Substances 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 239000003377 acid catalyst Substances 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- GQKDBQTXMIUPSY-UHFFFAOYSA-N 1-methoxypropan-2-ol;1-methoxypropan-2-yl acetate Chemical compound COCC(C)O.COCC(C)OC(C)=O GQKDBQTXMIUPSY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- QZJVWTNHFOMVHX-UHFFFAOYSA-N methanol;methyl acetate Chemical compound OC.COC(C)=O QZJVWTNHFOMVHX-UHFFFAOYSA-N 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- -1 propylene glycol ethers Chemical class 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LAVARTIQQDZFNT-UHFFFAOYSA-N 1-(1-methoxypropan-2-yloxy)propan-2-yl acetate Chemical compound COCC(C)OCC(C)OC(C)=O LAVARTIQQDZFNT-UHFFFAOYSA-N 0.000 description 1
- VBVHNUMQFSVYGE-UHFFFAOYSA-N 1-[1-(1-methoxypropan-2-yloxy)propan-2-yloxy]propan-2-yl acetate Chemical compound COCC(C)OCC(C)OCC(C)OC(C)=O VBVHNUMQFSVYGE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019714 Nb2O3 Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. 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
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing propylene glycol monomethyl ether acetate by catalytic distillation. The method comprises the following steps: propylene glycol methyl ether is fed from the upper part of the reaction section of the catalytic rectifying tower, methyl acetate is fed from the lower part of the reaction section of the catalytic rectifying tower, and the propylene glycol methyl ether and the methyl acetate carry out heterogeneous catalytic reaction in the reaction section; after the propylene glycol methyl ether and the methyl acetate react, the top of the tower is a mixed solution of methanol and methyl acetate, and the bottom of the tower is a mixed solution of propylene glycol methyl ether and propylene glycol methyl ether acetate; solid catalyst is distributed in the reaction section. The method has the advantages of high conversion rate of the glycol methyl ether, environment-friendly catalyst, easy recovery, simple process, easy operation, small hazard, high safety and the like.
Description
Technical Field
The invention relates to a preparation method of propylene glycol monomethyl ether acetate, in particular to a method for synthesizing propylene glycol monomethyl ether acetate by catalytic distillation.
Background
Propylene glycol monomethyl ether acetate (PMA) is an important industrial solvent, has ether bonds, alkyl and carbonyl in molecules, has good dissolving capacity for polar and non-polar substances, and has the dissolving performance greatly higher than that of common solvents and propylene glycol ethers and ethylene glycol ethers. Because of its high solvent performance, good thermal stability, small viscosity change, high foaming and small corrosivity, it is widely used in paint, detergent, printing and dyeing, pesticide and high-molecular adjuvant, and also can be used as cleaning agent of liquid crystal display.
The synthesis method of propylene glycol monomethyl ether acetate mainly comprises three methods: propylene oxide one-step process, transesterification process and direct esterification process.
The one-step synthesis method of the propylene oxide is to synthesize the target product propylene glycol monomethyl ether acetate in one step by using the propylene oxide, methyl acetate and methanol as raw materials, and the method is a series reaction and is easy to generate PPG-2 methyl ether acetate, tripropylene glycol monomethyl ether acetate and other byproducts. CN102617300A discloses a method for joint production of propylene glycol methyl ether and propylene glycol methyl ether acetate, which comprises the steps of taking propylene oxide, methyl acetate and methanol as raw materials, taking sodium methoxide as a catalyst, reacting in an intermittent reaction kettle at 50 ℃ for 3 hours, and distilling a reaction product at normal pressure after the reaction is finished to obtain propylene glycol methyl ether acetate (the purity is 99.4%) and the selectivity of the propylene glycol methyl ether acetate is 20.2%. The method for synthesizing propylene glycol methyl ether acetate has low conversion per pass and poor selectivity, the boiling point of the reactant propylene oxide is 34 ℃ under normal pressure, the propylene oxide belongs to a low-boiling-point volatile substance, the reaction needs to be carried out under high pressure, equipment is resistant to high pressure, and the operation cost is increased. This method has so far been used less.
The esterification method takes propylene glycol methyl ether and acetic acid as raw materials to synthesize propylene glycol methyl ether acetate under the action of an acid catalyst, and the esterification process is carried outLiquid acid (sulfuric acid, phosphoric acid, benzenesulfonic acid and the like) is commonly used as a catalyst to produce propylene glycol methyl ether acetate by an intermittent process. The liquid acid is used as the catalyst, although the catalyst has higher catalytic capability, the side reaction is more, the liquid acid is difficult to separate from the product, and the liquid acid has higher corrosivity on pipeline equipment. Currently, some solid acid catalysts are mainly researched and developed to replace liquid acid to participate in esterification reaction. CN112691658A discloses a method for synthesizing propylene glycol methyl ether acetate by direct esterification and catalysis of a solid acid catalyst, which comprises the steps of pre-reacting propylene glycol methyl ether and anhydrous acetic acid in a certain proportion in a fixed bed under the action of an acid catalyst, allowing the pre-reaction product to enter a catalytic rectifying tower filled with the acid catalyst for continuous reaction, using an entrainer benzene to carry away water in the reaction product, obtaining propylene glycol methyl ether acetate (with the purity of 99.5%) in a tower kettle, wherein the acid catalyst in the fixed bed and the catalytic rectifying tower is the same, and the components and the weight percentage of the acid catalyst are Al2O322.0％～35.0％、SiO225.0％～45.0％、TiO24.0％～12％、B2O35.0％～15.0％、ZrO21.0％～4.0％、Nb2O30.5 to 1.5 percent and the balance of C. In the method, water is generated, benzene is used as an entrainer, and the benzene has certain toxicity, can bring harm to human bodies and the environment, and has high energy consumption and large equipment investment.
The ester exchange method is to synthesize propylene glycol methyl ether acetate by ester exchange reaction of propylene glycol methyl ether and ethyl acetate (or methyl acetate) as raw materials. The method has the advantages that the obtained by-product is ethanol (methanol), acetic acid is not used as a raw material, the acid value problem of the product is avoided, the requirement of the reaction on the catalyst is not high without side reaction, and the method with low cost, high efficiency, cleanness, environmental protection and high yield is provided for the production of the propylene glycol monomethyl ether acetate. CN109265314A discloses a preparation method and a preparation device of propylene glycol methyl ether acetate, which take propylene glycol methyl ether and methyl acetate as raw materials and sodium methoxide as a catalyst, react in a reactive distillation column, and obtain a mixture of propylene glycol methyl ether acetate, propylene glycol methyl ether and the catalyst through reaction and a column bottom, wherein the conversion rate of the separated propylene glycol methyl ether is 75.2%, and the yield of the propylene glycol methyl ether acetate is 96.5%. In the method, the conversion rate of propylene glycol methyl ether is low, a sodium methoxide catalyst is easy to corrode equipment, and a large amount of corrosive wastewater is generated, so that the production cost is high, and the environmental pollution is serious; and the sodium methoxide is easy to dissolve in methanol and ethanol, the separation difficulty of the catalyst and the product is high, the catalyst cannot be reused, the equipment cost is high, and the energy consumption is high.
Disclosure of Invention
In order to overcome the problems of the process, a preparation method and equipment for synthesizing propylene glycol monomethyl ether acetate by catalytic distillation of a solid catalyst are provided. The method takes propylene glycol methyl ether and methyl acetate as raw materials, and uses a solid catalyst to carry out reaction in a catalytic rectifying tower. The method has the advantages of high conversion rate of the glycol methyl ether, environment-friendly catalyst, easy recovery, simple process, easy operation, small hazard, high safety and the like.
The technical scheme adopted by the invention is as follows:
a method for preparing propylene glycol monomethyl ether acetate by catalytic distillation comprises the following steps:
(1) propylene glycol methyl ether is fed from the upper part of the reaction section of the catalytic rectifying tower, methyl acetate is fed from the lower part of the reaction section of the catalytic rectifying tower, and the propylene glycol methyl ether and the methyl acetate carry out heterogeneous catalytic reaction in the reaction section.
(2) After the propylene glycol methyl ether and the methyl acetate react, the top of the tower is a mixed solution of methanol and methyl acetate, and the bottom of the tower is a mixed solution of propylene glycol methyl ether and propylene glycol methyl ether acetate.
(3) Separating the mixed solution of methanol and methyl acetate, extracting methanol, and returning the unreacted methyl acetate to the feeding position of the methyl acetate; separating the mixed solution of propylene glycol methyl ether and propylene glycol methyl ether acetate, collecting propylene glycol methyl ether acetate, and returning the unreacted propylene glycol methyl ether to the feeding position of the propylene glycol methyl ether.
The propylene glycol methyl ether and the methyl acetate are fed at normal temperature, and the feeding molar ratio is 1: 1-1: 4.
The pressure of the catalytic rectifying tower is 0.3-2 MPa, and the reflux ratio of the catalytic rectifying tower is 1-15.
The reaction temperature of the catalytic rectification tower is 50-150 ℃, the temperature of the tower kettle is 100-150 ℃, and the temperature of the tower top is 50-100 ℃.
The catalytic rectifying tower is a packed tower, the number of theoretical plates is 18-36, and the catalytic rectifying tower sequentially comprises a rectifying section, a reaction section and a stripping section from top to bottom; wherein the number of theoretical plates of the rectifying section is 5-10; the number of theoretical plates of the reaction section is 8-16, and the number of theoretical plates of the stripping section is 5-10; wherein the feeding position of propylene glycol methyl ether is 8-15 plates; the feeding position of the methyl acetate is 9-16 plates; all from top to bottom.
The packing in the reaction section is loaded with a solid catalyst in a mixing way; the volume ratio of the solid catalyst to the metal plate mesh corrugated packing is 1: 2-1: 5.
the solid catalyst comprises a solid base catalyst or a solid acid catalyst.
The solid acid catalyst is one or more of acidic cation exchange resin, beta molecular sieve, H-Y molecular sieve, MCM-41, HZSM-5 and the like; the solid base catalyst is Ca-Al hydrotalcite, Ni-Ce-Al hydrotalcite, KF/MgO-CeO2、KOH/Al2O3、K2CO3/Al2O3、K2CO3One or more kinds of MgO and the like.
The filler is metal plate net corrugated filler, and the type of the metal plate net corrugated filler is one or two of 450X and 650Y.
The invention has the beneficial effects that:
(1) according to the preparation method of propylene glycol methyl ether acetate provided by the invention, propylene glycol methyl ether and methyl acetate are used as raw materials, and a solid catalyst is used for carrying out ester exchange reaction, so that a product can be removed in time, unreacted raw materials continue to participate in the reaction, the reaction conversion rate and yield are improved, and the utilization rate of the raw materials is increased. The conversion rate of the glycol methyl ether is more than 86.3 percent and is far higher than 75.2 percent of the conversion rate of the propylene glycol methyl ether in CN 109265314A.
(2) The solid catalyst adopted by the invention is non-corrosive, environment-friendly, easier to separate from a liquid product, higher in activity and selectivity and longer in catalyst life; meanwhile, the phenomenon of serious corrosion of equipment is relieved, the catalyst adopts a filling technology, the separation difficulty is reduced, the catalyst can be recycled, the cost is reduced, resources are saved, and good economic benefits are created.
(3) The invention has the advantages of simple process, easy operation, small hazard, high safety, reasonable device structure, low equipment investment, safe operation, stability and reliability.
Drawings
FIG. 1 is a schematic diagram of a catalytic distillation reaction apparatus.
The system comprises a 1-propylene glycol methyl ether raw material tank, a 2-methyl acetate raw material tank, a 3-catalytic rectifying tower rectifying section, a 4-catalytic rectifying tower reaction section, a 5-catalytic rectifying tower stripping section, a 6-methyl acetate and methanol separation tower, a 7-propylene glycol methyl ether and propylene glycol methyl ether acetate separation tower, an 8-methanol product tank, a 9-propylene glycol methyl ether acetate product tank, a 10-condenser and an 11-reboiler.
Detailed Description
The following examples will further illustrate the process provided by the present invention but the invention is not limited to the examples listed but also includes any other known variations within the scope of the claims claimed herein.
The catalytic reaction rectifying tower comprises a rectifying section, a reaction section and a stripping section from top to bottom in sequence, the material is stainless steel 316L, the inner diameter is 220mm, the height of the catalytic rectifying tower is 8m, the number of theoretical plates is 24, wherein the height of the rectifying section is 3m, the number of theoretical plates is 9, the height of the reaction section is 2m, the number of theoretical plates is 6, the height of the stripping section is 3m, and the number of theoretical plates is 9. The solid catalyst in the reaction section is acidic cation resin (the particle diameter is 0.4-0.6mm), the filler is 450X metal plate mesh corrugated filler (the diameter is 40mm), and the solid catalyst and the 450X metal plate mesh corrugated filler are mixed in a ratio of 1: 2, and after the catalyst is uniformly distributed in the aperture of the 450X metal plate mesh corrugated packing, filling the catalyst into a reaction section (from top to bottom and 10 th to 15 th theoretical plates) of the rectifying tower.
The gas chromatographic analysis of the product was as follows: KB-1701(30m by 0.32mm by 0.50 μm) capillary chromatography column, FID hydrogen flame detector; initial temperature of 50 deg.C, holding for 1min, final temperature of 250 deg.C, and holdingHolding for 8min, heating rate 11 deg.C/min-1(ii) a The temperature of the detector is 250 ℃, the temperature of the vaporization chamber is 250 ℃, and the flow rate of the carrier gas is 40 mL/min-1The sample size was 0.2. mu.L, and the split ratio was 1/30.
Propylene glycol methyl ether enters the upper part of the reaction section of the catalytic rectifying tower from a propylene glycol methyl ether raw material tank, methyl acetate enters the lower part of the reaction section of the catalytic rectifying tower from a methyl acetate raw material tank, and propylene glycol methyl ether and methyl acetate perform ester exchange reaction in the reaction section of the catalytic rectifying tower. The reacted tower bottom material is sent to a propylene glycol methyl ether and propylene glycol methyl ether acetate separation tower, the high-purity propylene glycol methyl ether acetate is sent to a propylene glycol methyl ether acetate product tank after separation, and the unreacted propylene glycol methyl ether is returned to a propylene glycol methyl ether raw material tank to continue to participate in the reaction; and (3) sending the reacted tower top material to a methyl acetate and methanol separation tower, separating, sending methanol to a methanol product tank, and returning unreacted methyl acetate to a methyl acetate raw material tank to continuously participate in the reaction.
Example 1
Propylene glycol methyl ether and methyl acetate in a ratio of 1:1, the feed is carried out at normal temperature, the flow of propylene glycol methyl ether is 120kg/h, the propylene glycol methyl ether enters a 10 th theoretical plate of a catalytic rectifying tower from a propylene glycol methyl ether raw material tank, the flow of methyl acetate is 100kg/h, the methyl acetate enters a 13 th theoretical plate of the catalytic rectifying tower from the methyl acetate raw material tank, the pressure of the catalytic rectifying tower is 0.6MPa, the reaction temperature is 90 ℃, the temperature of a tower kettle is 150 ℃, the temperature of a tower top is 55 ℃, and the reflux ratio is 10: 1. After the reaction, the gas phase analysis of the top and the bottom of the rectifying tower shows that the yield of the propylene glycol methyl ether acetate is more than 97%, the product purity of the propylene glycol methyl ether acetate is more than 99%, and the results are shown in Table 1.
TABLE 1
| Tower top | Methanol | Acetic acid methyl ester |
| Mass fraction | 6.7％ | 93.2％ |
| Tower kettle | Propylene glycol methyl ether | Propylene glycol methyl ether acetate |
| Mass fraction | 2.5％ | 97.5％ |
Example 2
Propylene glycol methyl ether and methyl acetate in a ratio of 1: 2, feeding at normal temperature, wherein the flow of propylene glycol methyl ether is 90kg/h, the propylene glycol methyl ether enters a 10 th theoretical plate of the catalytic rectifying tower from a propylene glycol methyl ether raw material tank, the flow of methyl acetate is 150kg/h, the methyl acetate enters a 13 th theoretical plate of the catalytic rectifying tower from the methyl acetate raw material tank, the pressure of the catalytic rectifying tower is 0.5MPa, the reaction temperature is 100 ℃, the temperature of a tower kettle is 140 ℃, the temperature of a tower top is 60 ℃, and the reflux ratio is 8: 1. After the reaction, the gas phase analysis of the top and the bottom of the rectifying tower shows that the yield of the propylene glycol methyl ether acetate is more than 98%, the purity of the propylene glycol methyl ether acetate is more than 99%, and the results are shown in Table 2.
TABLE 2
| Tower top | Methanol | Acetic acid methyl ester |
| Mass fraction | 49.2％ | 50.8％ |
| Tower kettle | Propylene glycol methyl ether | Propylene glycol methyl ether acetate |
| Mass fraction | 1.6％ | 98.4％ |
Example 3
Propylene glycol methyl ether and methyl acetate in a ratio of 1: 3, feeding at normal temperature, wherein the flow of propylene glycol methyl ether is 80kg/h, the propylene glycol methyl ether enters a 10 th theoretical plate of the catalytic rectifying tower from a propylene glycol methyl ether raw material tank, the flow of methyl acetate is 200kg/h, the methyl acetate enters a 13 th theoretical plate of the catalytic rectifying tower from the methyl acetate raw material tank, the pressure of the catalytic rectifying tower is 0.4MPa, the reaction temperature is 110 ℃, the temperature of a tower kettle is 130 ℃, the temperature of a tower top is 65 ℃, and the reflux ratio is 6: 1. After the reaction, the gas phase analysis of the top and the bottom of the rectifying tower shows that the yield of the propylene glycol methyl ether acetate is more than 98%, the purity of the propylene glycol methyl ether acetate is more than 99%, and the results are shown in Table 3.
TABLE 3
| Tower kettle | Methanol | Acetic acid methyl ester |
| Mass fraction | 32.8％ | 67.2％ |
| Tower kettle | Propylene glycol methyl ether | Propylene glycol methyl ether acetate |
| Mass fraction | 1.4％ | 98.6％ |
Example 4
Propylene glycol methyl ether and methyl acetate in a ratio of 1:4, the raw material is fed at normal temperature, the flow of propylene glycol methyl ether is 80kg/h, the raw material enters a 10 th theoretical plate of a catalytic rectifying tower from a propylene glycol methyl ether raw material tank, the flow of methyl acetate is 250kg/h, the raw material enters a 13 th theoretical plate of the catalytic rectifying tower from the methyl acetate raw material tank, the pressure of the catalytic rectifying tower is 0.3MPa, the reaction temperature is 120 ℃, the temperature of a tower kettle is 140 ℃, the temperature of a tower top is 70 ℃, and the reflux ratio is 4: 1. After the reaction, the gas phase analysis of the top and the bottom of the rectifying tower shows that the yield of the propylene glycol methyl ether acetate is more than 96%, the purity of the propylene glycol methyl ether acetate is more than 99%, and the results are shown in Table 4.
TABLE 4
| Tower top | Methanol | Acetic acid methyl ester |
| Mass fraction | 23.8％ | 76.2％ |
| Tower kettle | Propylene glycol methyl ether | Propylene glycol methyl ether acetate |
| Mass fraction | 3.6％ | 96.4％ |
The invention is not the best known technology.
Claims (5)
1. A method for preparing propylene glycol monomethyl ether acetate by catalytic rectification is characterized by comprising the following steps:
(1) propylene glycol methyl ether is fed from the upper part of the reaction section of the catalytic rectifying tower, methyl acetate is fed from the lower part of the reaction section of the catalytic rectifying tower, and the propylene glycol methyl ether and the methyl acetate carry out heterogeneous catalytic reaction in the reaction section;
(2) after the propylene glycol methyl ether and the methyl acetate react, the top of the tower is a mixed solution of methanol and methyl acetate, and the bottom of the tower is a mixed solution of propylene glycol methyl ether and propylene glycol methyl ether acetate;
(3) separating the mixed solution of methanol and methyl acetate, extracting methanol, and returning the unreacted methyl acetate to the feeding position of the methyl acetate; separating the mixed solution of propylene glycol methyl ether and propylene glycol methyl ether acetate, collecting propylene glycol methyl ether acetate, and returning unreacted propylene glycol methyl ether to the feeding position of propylene glycol methyl ether;
the propylene glycol methyl ether and the methyl acetate are fed at normal temperature, and the feeding molar ratio is 1: 1-1: 4;
the pressure of the catalytic rectifying tower is 0.3-2 MPa, and the reflux ratio of the catalytic rectifying tower is 1-15;
the reaction temperature of the catalytic rectification tower is 50-150 ℃, the temperature of the tower kettle is 100-150 ℃, and the temperature of the tower top is 50-100 ℃.
2. The method for preparing propylene glycol monomethyl ether acetate by catalytic distillation according to claim 1, wherein the catalytic distillation tower is a packed tower, the number of theoretical plates is 18-36, and the packed tower sequentially comprises a distillation section, a reaction section and a stripping section from top to bottom; wherein the number of theoretical plates of the rectifying section is 5-10; the number of theoretical plates of the reaction section is 8-16, and the number of theoretical plates of the stripping section is 5-10; the feeding position of propylene glycol methyl ether is 8-15 plates; feeding methyl acetate at 9-16 plates from top to bottom;
the packing in the reaction section is loaded with a solid catalyst in a mixing way; the volume ratio of the solid catalyst to the metal plate mesh corrugated packing is 1: 2-1: 5.
3. the method for preparing propylene glycol monomethyl ether acetate by catalytic distillation as claimed in claim 2, wherein the solid catalyst is a solid base catalyst or a solid acid catalyst.
4. The catalytic distillation process for preparing propylene glycol monomethyl ether acetate as claimed in claim 3, wherein the solid acid catalyst is one or more of acidic cation exchange resin, beta molecular sieve, H-Y molecular sieve, MCM-41, HZSM-5, etc.; the solid base catalyst is Ca-Al hydrotalcite, Ni-Ce-Al hydrotalcite, KF/MgO-CeO2、KOH/Al2O3、K2CO3/Al2O3、K2CO3One or more kinds of MgO and the like.
5. The catalytic distillation process for preparing propylene glycol monomethyl ether acetate as claimed in claim 2, wherein the packing is a metal sheet corrugated packing.
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| CN114558341A (en) * | 2022-03-10 | 2022-05-31 | 南京斌柳化工有限公司 | Propylene glycol methyl ether acetate preparation system |
| CN114773198A (en) * | 2022-06-07 | 2022-07-22 | 中建安装集团有限公司 | Method and device for preparing propylene glycol monomethyl ether acetate by suspension catalytic distillation |
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