CN113979861B - Method for preparing propylene glycol methyl ether acetate by catalytic rectification - Google Patents
Method for preparing propylene glycol methyl ether acetate by catalytic rectification Download PDFInfo
- Publication number
- CN113979861B CN113979861B CN202111430256.2A CN202111430256A CN113979861B CN 113979861 B CN113979861 B CN 113979861B CN 202111430256 A CN202111430256 A CN 202111430256A CN 113979861 B CN113979861 B CN 113979861B
- Authority
- CN
- China
- Prior art keywords
- propylene glycol
- methyl ether
- glycol methyl
- acetate
- tower
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 26
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims abstract description 97
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 46
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 46
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000011949 solid catalyst Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 239000000945 filler Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims 2
- 238000012856 packing Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 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 15
- 239000000047 product Substances 0.000 description 12
- 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 5
- 239000002253 acid 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
- 238000005809 transesterification reaction Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- QZJVWTNHFOMVHX-UHFFFAOYSA-N methanol;methyl acetate Chemical compound OC.COC(C)=O QZJVWTNHFOMVHX-UHFFFAOYSA-N 0.000 description 4
- 239000011973 solid acid Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 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 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 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
- 230000009471 action Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 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 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 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
- 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 description 1
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- GWUVEUHFQZHBML-UHFFFAOYSA-N C=CC.COCC(C)O Chemical group C=CC.COCC(C)O GWUVEUHFQZHBML-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000010923 batch production Methods 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
- 239000006227 byproduct Substances 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
- 239000003729 cation exchange resin Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012459 cleaning agent Substances 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
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects 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
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000011049 filling Methods 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
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- -1 printing and dyeing Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
Classifications
-
- 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
Landscapes
- 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 methyl ether acetate by catalytic rectification. The method comprises the following steps: propylene glycol methyl ether is fed from the upper part of a 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 reacts with methyl acetate, the top of the tower is mixed liquid of methanol and methyl acetate, and the bottom of the tower is mixed liquid of propylene glycol methyl ether and propylene glycol methyl ether acetate; the reaction section is distributed with a solid catalyst. The invention has the advantages of high conversion rate of glycol methyl ether, environment-friendly catalyst, easy recovery, simple process, easy operation, low hazard, high safety and the like.
Description
Technical Field
The invention relates to a preparation method of propylene glycol methyl ether acetate, in particular to a method for synthesizing propylene glycol methyl ether acetate by catalytic rectification.
Background
Propylene glycol methyl ether acetate (PMA) is an important industrial solvent, and has ether bond, alkyl and carbonyl in its molecule, and has good dissolving capacity for polar and nonpolar substances, and its dissolving capacity is greatly higher than that of general solvent, propylene glycol ether and glycol ether solvents. The polymer has the characteristics of high solvent performance, good thermal stability, small viscosity change, high foaming, small corrosiveness and the like, and is widely used for paint, detergent, printing and dyeing, pesticide and polymer auxiliary agent, and can also be used as a cleaning agent of a liquid crystal display and the like.
The synthesis method of propylene glycol methyl ether acetate mainly comprises three steps: propylene oxide one-step, transesterification, and direct esterification processes.
The one-step synthesis method of propylene oxide is to synthesize propylene glycol methyl ether acetate serving as a target product by taking propylene oxide, methyl acetate and methanol as raw materials in one step. CN102617300a discloses a method for co-producing propylene glycol methyl ether and propylene glycol methyl ether acetate, using propylene oxide, methyl acetate and methanol as raw materials, using sodium methoxide as a catalyst, reacting for 3 hours at 50 ℃ in an intermittent reaction kettle, and performing atmospheric distillation on the reaction product after the reaction is completed to obtain propylene glycol methyl ether acetate (purity is 99.4%), wherein the selectivity of propylene glycol methyl ether acetate is 20.2%. The method for synthesizing propylene glycol methyl ether acetate has low single pass conversion rate and poor selectivity, and the boiling point of the reactant propylene oxide is 34 ℃ under normal pressure, belongs to low-boiling-point volatile substances, and needs to be carried out under high pressure, equipment is tolerant to high pressure, and the operation cost is increased. So far this method has been applied less often.
The esterification method is to synthesize propylene glycol methyl ether acetate by using propylene glycol methyl ether and acetic acid as raw materials under the action of an acid catalyst, and liquid acid (sulfuric acid, phosphoric acid, benzenesulfonic acid and the like) is often used as a catalyst in the esterification process to produce propylene glycol methyl ether acetate by a batch process. The liquid acid is used as a catalyst, and has higher catalytic capability, but has more side reactions, is difficult to separate from products, and has higher corrosiveness on pipeline equipment. Currently, some solid acid catalysts are mainly researched and developed to replace liquid acid to participate in the esterification reaction. CN112691658A discloses a method for synthesizing propylene glycol methyl ether acetate by direct esterification and catalysis of a solid acid catalyst, wherein propylene glycol methyl ether and anhydrous acetic acid with a certain proportion are pre-reacted in a fixed bed under the action of the acid catalyst, the pre-reacted product enters a catalytic rectifying tower filled with the acid catalyst to continue the reaction, water in the reaction product is carried away by using entrainer benzene, propylene glycol methyl ether acetate (purity is 99.5%) is obtained at the tower bottom, the acid catalysts in the fixed bed and the catalytic rectifying tower are the same, and the components and weight percentage are Al 2 O 3 22.0％～35.0％、SiO 2 25.0％～45.0％、TiO 2 4.0％～12％、B 2 O 3 5.0％～15.0％、ZrO 2 1.0％～4.0％、Nb 2 O 3 0.5% -1.5% 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 transesterification method is to take propylene glycol methyl ether and ethyl acetate (or methyl acetate) as raw materials to carry out transesterification reaction to synthesize propylene glycol methyl ether acetate. The method has the advantages that the obtained by-product is ethanol (methanol), acetic acid is not adopted as a raw material, the acid value problem of the product is avoided, the reaction has no side reaction, the requirement on the catalyst is low, and the method is low in cost, high in efficiency, clean and environment-friendly and high in yield. CN109265314a discloses a preparation method and a preparation device of propylene glycol methyl ether acetate, propylene glycol methyl ether and methyl acetate are used as raw materials, sodium methoxide is used as a catalyst, the raw materials react in a reaction rectifying tower, a mixture of propylene glycol methyl ether acetate, propylene glycol methyl ether and the catalyst is obtained through the reaction in the tower kettle, the conversion rate of propylene glycol methyl ether after separation is 75.2%, and the yield of propylene glycol methyl ether acetate is 96.5%. The method has low conversion rate of propylene glycol methyl ether, the 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 sodium methoxide is easily dissolved in methanol and ethanol, so that the separation difficulty of the catalyst and the product is high, the catalyst can not 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 methyl ether acetate by catalytic rectification 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 react in a catalytic rectifying tower. The invention has the advantages of high conversion rate of glycol methyl ether, environment-friendly catalyst, easy recovery, simple process, easy operation, low hazard, high safety and the like.
The technical scheme adopted by the invention is as follows:
a method for preparing propylene glycol methyl ether acetate by catalytic rectification, which comprises the following steps:
(1) Propylene glycol methyl ether is fed from the upper part of a 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 reacts with methyl acetate, the top of the tower is mixed liquid of methanol and methyl acetate, and the bottom of the tower is mixed liquid 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 unreacted methyl acetate to the feeding position of the methyl acetate; and separating the mixed solution of propylene glycol methyl ether and propylene glycol methyl ether acetate, extracting 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 rectifying tower is 50-150 ℃, the temperature of the tower bottom is 100-150 ℃, and the temperature of the tower top is 50-100 ℃.
The catalytic rectifying tower is a packed tower, the theoretical plate number is 18-36, and a rectifying section, a reaction section and a stripping section are sequentially arranged from top to bottom; wherein the theoretical plate number of the rectifying section is 5-10; the theoretical plate number of the reaction section is 8-16, and the theoretical plate number of the stripping section is 5-10; wherein, the feeding position of propylene glycol methyl ether is 8-15 plates; the feeding position of methyl acetate is 9-16 plates; all counted from top to bottom.
The solid catalyst is mixed and loaded in the filler in the reaction section; the volume ratio of the solid catalyst to the metal expanded metal corrugated filler 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-CeO 2 、KOH/Al 2 O 3 、K 2 CO 3 /Al 2 O 3 、K 2 CO 3 One or more of/MgO, etc.
The filler is metal expanded metal corrugated filler, and the type of the metal expanded metal 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, propylene glycol methyl ether and methyl acetate are used as raw materials, and the solid catalyst is used for carrying out transesterification, so that products can be removed in time, unreacted raw materials continue to participate in the reaction, the reaction conversion rate and the 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 liquid products, higher in activity and selectivity and longer in catalyst life; meanwhile, the phenomenon of serious equipment corrosion is relieved, the catalyst adopts a filling technology, the separation difficulty is reduced, the catalyst can be recycled, the cost is reduced, the resources are saved, and good economic benefits are created.
(3) The invention has simple process, easy operation, little harm, high safety, reasonable structure, low equipment investment, safe operation, stability and reliability.
Drawings
FIG. 1 is a schematic diagram of a catalytic distillation reaction apparatus.
Wherein, 1-propylene glycol methyl ether feed tank, 2-methyl acetate feed tank, 3-catalytic rectifying tower rectifying section, 4-catalytic rectifying tower reaction section, 5-catalytic rectifying tower stripping section, 6-methyl acetate and methanol separation tower, 7-propylene glycol methyl ether and propylene glycol methyl ether acetate separation tower, 8-methanol product tank, 9-propylene glycol methyl ether acetate product tank, 10-condenser, 11-reboiler.
Detailed Description
The following examples will further illustrate the method provided by the present invention, but the invention is not limited to the examples listed and should include any other known modifications within the scope of the claimed invention.
The catalytic reaction rectifying tower sequentially comprises a rectifying section, a reaction section and a stripping section from top to bottom, wherein 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, 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 acid cation resin (particle diameter is 0.4-0.6 mm), the filler is 450X metal plate mesh corrugated filler (diameter is 40 mm), and the solid catalyst and the 450X metal plate mesh corrugated filler are mixed according to the following ratio of 1:2, and after the catalyst is uniformly distributed in the aperture of 450X metal plate net corrugated filler, loading the catalyst into the reaction section of the rectifying tower (10 th to 15 th theoretical plates from top to bottom).
The gas chromatographic analysis of the product is as follows: KB-1701 (30 m.times.0.32 mm.times.0.50 μm) capillary chromatographic column, FID hydrogen flame detector; the initial temperature is 50 ℃, the final temperature is 250 ℃ and 8min, and the heating rate is 11 ℃ and min -1 The method comprises the steps of carrying out a first treatment on the surface of the Detector temperature 250 ℃, vaporization chamber temperature 250 ℃ and carrier gas flow rate 40mL min -1 The sample injection amount is 0.2 mu L, and the split ratio is 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 transesterification reaction in the reaction section of the catalytic rectifying tower. The reacted tower kettle material is sent to a propylene glycol methyl ether and propylene glycol methyl ether acetate separating tower, after separation, the propylene glycol methyl ether acetate with high purity is sent to a propylene glycol methyl ether acetate product tank, and 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 and 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 at 1:1, the flow of propylene glycol methyl ether is 120kg/h, the flow of methyl acetate is 100kg/h, the flow of methyl acetate is 13 th theoretical plate of the catalytic rectifying tower, the pressure of the catalytic rectifying tower is 0.6MPa, the reaction temperature is 90 ℃, the tower bottom temperature is 150 ℃, the tower top temperature is 55 ℃, and the reflux ratio is 10:1. After the reaction, the tower top and the tower bottom of the rectifying tower are subjected to gas phase analysis, the yield of 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 at 1:2, the flow of propylene glycol methyl ether is 90kg/h, the flow of methyl acetate is 150kg/h, the flow of methyl acetate is 13 th theoretical plate of the catalytic rectifying tower, the pressure of the catalytic rectifying tower is 0.5MPa, the reaction temperature is 100 ℃, the tower bottom temperature is 140 ℃, the tower top temperature is 60 ℃, and the reflux ratio is 8:1. After the reaction, the tower top and the tower bottom of the rectifying tower are subjected to gas phase analysis, the yield of 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 at 1:3, the flow of propylene glycol methyl ether is 80kg/h, the flow of methyl acetate is 200kg/h, the flow of methyl acetate is 13 th theoretical plate of the catalytic rectifying tower, the pressure of the catalytic rectifying tower is 0.4MPa, the reaction temperature is 110 ℃, the tower bottom temperature is 130 ℃, the tower top temperature is 65 ℃, and the reflux ratio is 6:1. After the reaction, the tower top and the tower bottom of the rectifying tower are subjected to gas phase analysis, the yield of 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 Table 3
| Tower kettle | Methanol | Acetic acid methyl ester |
| Mass fraction | 32.8％ | 67.2％ |
| Tower kettle | Propylene glycol methyl ether | Propylene glycolMethyl ether acetate |
| Mass fraction | 1.4％ | 98.6％ |
Example 4
Propylene glycol methyl ether and methyl acetate at 1:4, the flow of propylene glycol methyl ether is 80kg/h, the flow of methyl acetate is 250kg/h, the flow of methyl acetate is 13 th theoretical plate of the catalytic rectifying tower, the pressure of the catalytic rectifying tower is 0.3MPa, the reaction temperature is 120 ℃, the tower bottom temperature is 140 ℃, the tower top temperature is 70 ℃, and the reflux ratio is 4:1. After the reaction, the tower top and the tower bottom of the rectifying tower are subjected to gas phase analysis, the yield of 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 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 a matter of the known technology.
Claims (1)
1. A method for preparing propylene glycol methyl ether acetate by catalytic rectification is characterized by comprising the following steps:
(1) Propylene glycol methyl ether is fed from the upper part of a 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 reacts with methyl acetate, the top of the tower is mixed liquid of methanol and methyl acetate, and the bottom of the tower is mixed liquid 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 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, extracting 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 rectifying tower is 50-150 ℃, the temperature of the tower bottom is 100-150 ℃, and the temperature of the tower top is 50-100 ℃;
the catalytic rectifying tower is a packed tower, and solid catalysts are loaded in the packing in the reaction section in a mixing way;
the theoretical plate number of the packed tower is 18-36, and the packed tower sequentially comprises a rectifying section, a reaction section and a stripping section from top to bottom; wherein the theoretical plate number of the rectifying section is 5-10; the theoretical plate number of the reaction section is 8-16, and the theoretical plate number of the stripping section is 5-10; the feeding position of propylene glycol methyl ether is 8-15 plates; the feeding positions of the methyl acetate are 9-16 plates, which are all counted from top to bottom;
the solid catalyst is acidic cationic resin, and the particle size of the acidic cationic resin is 0.4-0.6mm;
the filler is 450X metal plate net corrugated filler with the diameter of 40mm, and the solid catalyst and the 450X metal plate net corrugated filler are mixed according to the following ratio of 1:2, and after the catalyst is uniformly distributed in the aperture of the 450X metal plate net corrugated filler, loading the catalyst into the reaction section of the rectifying tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111430256.2A CN113979861B (en) | 2021-11-29 | 2021-11-29 | Method for preparing propylene glycol methyl ether acetate by catalytic rectification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111430256.2A CN113979861B (en) | 2021-11-29 | 2021-11-29 | Method for preparing propylene glycol methyl ether acetate by catalytic rectification |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113979861A CN113979861A (en) | 2022-01-28 |
| CN113979861B true CN113979861B (en) | 2023-12-22 |
Family
ID=79732378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111430256.2A Active CN113979861B (en) | 2021-11-29 | 2021-11-29 | Method for preparing propylene glycol methyl ether acetate by catalytic rectification |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113979861B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114773198B (en) * | 2022-06-07 | 2023-03-03 | 中建安装集团有限公司 | Method and device for preparing propylene glycol monomethyl ether acetate by suspension catalytic distillation |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4260813A (en) * | 1978-02-02 | 1981-04-07 | Showa Denko K.K. | Process for the continuous production of ethylene glycol monoethyl ether acetate |
| CN101239907A (en) * | 2008-02-26 | 2008-08-13 | 华东师范大学 | Method for preparing glycol methyl ether acetate |
| KR20120024310A (en) * | 2010-09-06 | 2012-03-14 | 이수화학 주식회사 | Preparation method of propylene glycol monomethyl ether acetate |
| CN103896764A (en) * | 2012-12-27 | 2014-07-02 | 胡先念 | Propylene glycol ether acetate preparation method |
| CN109265314A (en) * | 2018-11-28 | 2019-01-25 | 临沂中天环保科技有限公司 | The preparation method and preparation facilities of propylene glycol methyl ether acetate |
| CN109456190A (en) * | 2018-10-18 | 2019-03-12 | 天津大学 | A kind of method of the continuous synthesizing propylene glycol monomethyl ether acetate of the highly selective catalytic distillation of low temperature |
| CN109796335A (en) * | 2019-01-08 | 2019-05-24 | 江门谦信化工发展有限公司 | A kind of method of high efficiency joint production of propylene glycol methyl ether and propylene glycol methyl ether acetate |
| CN209338421U (en) * | 2018-11-28 | 2019-09-03 | 临沂中天环保科技有限公司 | The preparation facilities of propylene glycol methyl ether acetate |
-
2021
- 2021-11-29 CN CN202111430256.2A patent/CN113979861B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4260813A (en) * | 1978-02-02 | 1981-04-07 | Showa Denko K.K. | Process for the continuous production of ethylene glycol monoethyl ether acetate |
| CN101239907A (en) * | 2008-02-26 | 2008-08-13 | 华东师范大学 | Method for preparing glycol methyl ether acetate |
| KR20120024310A (en) * | 2010-09-06 | 2012-03-14 | 이수화학 주식회사 | Preparation method of propylene glycol monomethyl ether acetate |
| CN103896764A (en) * | 2012-12-27 | 2014-07-02 | 胡先念 | Propylene glycol ether acetate preparation method |
| CN109456190A (en) * | 2018-10-18 | 2019-03-12 | 天津大学 | A kind of method of the continuous synthesizing propylene glycol monomethyl ether acetate of the highly selective catalytic distillation of low temperature |
| CN109265314A (en) * | 2018-11-28 | 2019-01-25 | 临沂中天环保科技有限公司 | The preparation method and preparation facilities of propylene glycol methyl ether acetate |
| CN209338421U (en) * | 2018-11-28 | 2019-09-03 | 临沂中天环保科技有限公司 | The preparation facilities of propylene glycol methyl ether acetate |
| CN109796335A (en) * | 2019-01-08 | 2019-05-24 | 江门谦信化工发展有限公司 | A kind of method of high efficiency joint production of propylene glycol methyl ether and propylene glycol methyl ether acetate |
Non-Patent Citations (3)
| Title |
|---|
| 董晓莲.反应精馏合成丙二醇单甲醚醋酸酯过程研究.中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑.2016,(第undefined期),B016-8. * |
| 龚国珍.固体碱催化酯交换法制备乙二醇单***醋酸酯的研究.中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑).2009,(第undefined期),B016-19. * |
| 龚国珍等.固体碱Ｋ2ＣＯ3／Ａｌ2 Ｏ3 催化酯交换法合成乙二醇甲醚乙酸酯.精细化工.2008,第25卷(第25期),982-984、998. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113979861A (en) | 2022-01-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113979861B (en) | Method for preparing propylene glycol methyl ether acetate by catalytic rectification | |
| CN102070448A (en) | Method for preparing dimethyl succinate | |
| CN108276257B (en) | Azeotropic distillation thermal coupling methoxy dimethyl ether synthesis reaction system | |
| CN104761429A (en) | Dimethyl carbonate and ethylene glycol production process | |
| CN105585455A (en) | Method of preparing ethylene glycol monomethyl ether through continuous etherification method | |
| CN101735182B (en) | Process for continuously producing succinic anhydride through hydrogenation of maleic anhydride | |
| CN103102229A (en) | Method for preparing 1,3-dihydric alcohol directly from olefin | |
| CN103965040B (en) | A kind of method of preparing dibasic acid dimethyl ester | |
| WO2016182190A1 (en) | Method for continuously preparing neopentyl glycol | |
| CN1962588A (en) | Method for synthesis of isopropanol | |
| CN102452934A (en) | Preparation method of sec-butyl acetate | |
| CN102190636B (en) | Method for preparing epoxy chloropropane by cyclizing chloropropene | |
| CN113651691A (en) | Method for preparing asymmetric oxalate through catalytic rectification | |
| CN103864587B (en) | A kind of method of synthetic 2-ethyl-2-hexenoic aldehyde | |
| CN110172013B (en) | Process for synthesizing tertiary amyl alcohol based on catalytic distillation solvent method | |
| CN113200853A (en) | Process method for preparing butanediol succinate | |
| CN104829559A (en) | Method of preparing Nu-valerolactone from methyl levulinate | |
| CN115160106A (en) | Production device and method of sec-butyl alcohol | |
| CN110156621B (en) | Method for liquid-liquid homogeneous phase synthesis of N, N-dimethylacetamide in microchannel reactor | |
| CN108863793B (en) | Preparation method of isopropyl acetate | |
| CN216106706U (en) | Device for preparing trioxymethylene | |
| CN115282913A (en) | Reaction system and method for preparing methyl propionate | |
| CN101906020A (en) | Novel process for purifying 1,2-propylene glycol by ester exchange method | |
| CN113582967A (en) | Device and method for preparing trioxymethylene | |
| US9527826B2 (en) | Single step process for conversion of furfural to tetrahydrofuran |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |