CN113880715B - Purification method for electrochemical synthesis of dimethyl sebacate - Google Patents
Purification method for electrochemical synthesis of dimethyl sebacate Download PDFInfo
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- CN113880715B CN113880715B CN202111169306.6A CN202111169306A CN113880715B CN 113880715 B CN113880715 B CN 113880715B CN 202111169306 A CN202111169306 A CN 202111169306A CN 113880715 B CN113880715 B CN 113880715B
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- ALOUNLDAKADEEB-UHFFFAOYSA-N dimethyl sebacate Chemical compound COC(=O)CCCCCCCCC(=O)OC ALOUNLDAKADEEB-UHFFFAOYSA-N 0.000 title claims abstract description 258
- 229940014772 dimethyl sebacate Drugs 0.000 title claims abstract description 129
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000000746 purification Methods 0.000 title claims abstract description 45
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 7
- RDQSIADLBQFVMY-UHFFFAOYSA-N 2,6-Di-tert-butylbenzoquinone Chemical compound CC(C)(C)C1=CC(=O)C=C(C(C)(C)C)C1=O RDQSIADLBQFVMY-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000012043 crude product Substances 0.000 claims abstract description 43
- GMDNUWQNDQDBNQ-UHFFFAOYSA-L magnesium;diformate Chemical compound [Mg+2].[O-]C=O.[O-]C=O GMDNUWQNDQDBNQ-UHFFFAOYSA-L 0.000 claims abstract description 32
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 230000006837 decompression Effects 0.000 claims abstract description 5
- UOBSVARXACCLLH-UHFFFAOYSA-N monomethyl adipate Chemical compound COC(=O)CCCCC(O)=O UOBSVARXACCLLH-UHFFFAOYSA-N 0.000 claims description 36
- ZDJFDFNNEAPGOP-UHFFFAOYSA-N dimethyl tetradecanedioate Chemical compound COC(=O)CCCCCCCCCCCCC(=O)OC ZDJFDFNNEAPGOP-UHFFFAOYSA-N 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000012856 packing Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 12
- HNBDRPTVWVGKBR-UHFFFAOYSA-N n-pentanoic acid methyl ester Natural products CCCCC(=O)OC HNBDRPTVWVGKBR-UHFFFAOYSA-N 0.000 claims description 10
- 239000006260 foam Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- ZSDQQJHSRVEGTJ-UHFFFAOYSA-N 2-(6-amino-1h-indol-3-yl)acetonitrile Chemical compound NC1=CC=C2C(CC#N)=CNC2=C1 ZSDQQJHSRVEGTJ-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 5
- 238000002848 electrochemical method Methods 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 3
- MBAHGFJTIVZLFB-UHFFFAOYSA-N methyl pent-2-enoate Chemical compound CCC=CC(=O)OC MBAHGFJTIVZLFB-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 21
- 239000002253 acid Substances 0.000 abstract description 15
- 239000000047 product Substances 0.000 abstract description 9
- 230000005518 electrochemistry Effects 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- 239000000945 filler Substances 0.000 description 31
- 239000002994 raw material Substances 0.000 description 15
- 239000012295 chemical reaction liquid Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 12
- 230000002194 synthesizing effect Effects 0.000 description 9
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 235000011037 adipic acid Nutrition 0.000 description 7
- 239000001361 adipic acid Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000011343 solid material Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- -1 UV-750 Chemical compound 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical group O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 239000012461 cellulose resin Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000016507 interphase Effects 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- UUWCBFKLGFQDME-UHFFFAOYSA-N platinum titanium Chemical compound [Ti].[Pt] UUWCBFKLGFQDME-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000010850 salt effect Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- XXLJGBGJDROPKW-UHFFFAOYSA-N antimony;oxotin Chemical compound [Sb].[Sn]=O XXLJGBGJDROPKW-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 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
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—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
-
- 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
- C07C67/62—Use of additives, e.g. for stabilisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a purification method for electrochemical synthesis of dimethyl sebacate. The method comprises the steps of adding 2, 6-di-tert-butyl-1, 4-benzoquinone and magnesium formate into a dimethyl sebacate crude product synthesized by electrochemistry, and obtaining the dimethyl sebacate through decompression hypergravity rectification, thereby completing separation and purification. The purification method can solve the problems of low product purity, high acid value, low rectification yield and easy polymerization of heavy components in the tower kettle obtained by the traditional rectification and purification process, has the advantages of simple process and low energy consumption, and is suitable for wide industrial application.
Description
Technical Field
The invention relates to a purification method for electrochemically synthesizing dimethyl sebacate, in particular to a method for purifying dimethyl sebacate by salt effect and hypergravity rectification.
Background
Dimethyl sebacate is a wide range of plastic industrial plasticizers, lubricants and diluents for lubricants, can be used as plasticizers, softeners and solvents for cellulose resins, vinyl resins and synthetic rubbers, is widely used as a main raw material for producing light stabilizers UV-770, UV-750, UV-123 and the like, is used as a solvent and plasticizer for cellulose resins and vinyl resins, and can also be used as an intermediate for organic synthesis.
The adipic acid is used as a raw material for esterification synthesis of an adipic acid ester compound, and then the adipic acid ester compound is synthesized through Brown-Walker electrolytic decarboxylation coupling, and then the adipic acid ester compound is hydrolyzed into sebacic acid, so that the method is an effective approach. For example, the following technical scheme is disclosed in the literature "preparation of sebacic acid from adipic acid, liaoning chemical industry, 1981 (03): 66-67":
esterification of adipic acid to methyl adipate:
HOOC(CH 2 ) 4 COOH+CH 3 OH→CH 3 OOC(CH 2 ) 4 COOH+H 2 O
the dimethyl adipate is decarboxylated and coupled to produce dimethyl sebacate:
2CH 3 OOC(CH 2 ) 4 COOH→CH 3 OOC(CH 2 ) 8 COOCH 3 +H 2 +2CO 2
hydrolysis of dimethyl sebacate to give sebacic acid:
CH 3 OOC(CH 2 ) 8 COOCH 3 +2H 2 O→HOOC(CH 2 )8COOH+2CH 3 OH
the dimethyl sebacate reaction liquid prepared by the existing electrochemical method is subjected to water addition and rectification to remove methanol and methyl valerate to obtain a dimethyl sebacate crude product, but the inventor discovers that 0.5-3% of raw material monomethyl adipate and 2-6% of heavy components remain in the dimethyl sebacate crude product, the methyl adipate and the dimethyl sebacate are azeotroped in the rectification process, so that the purity of the product dimethyl sebacate is not high, the acid value is more than 2mgKOH/g, the requirement of a downstream manufacturer (less than 0.08 mgKOH/g) cannot be met, meanwhile, the traditional reduced pressure rectification is adopted, the heavy component kettle residue is easy to polymerize in the concentration lifting process and is easy to adhere to the pipe wall to cause blockage, so that the residual part of dimethyl sebacate is required to slow down the polymerization in the concentration lifting process, the heavy components stay too long in the high Wen Dafu, the polymerization solidification of the heavy components is accelerated, a large amount of dimethyl sebacate is caused to enter the kettle residue, the reduced pressure rectification yield is low, and the problem is not solved effectively at present.
CN 103319340B provides a continuous rectification method for separating dimethyl sebacate. The method adopts the steps that the crude dimethyl sebacate is pumped into a light component removal tower for heating, and the light component is distilled out by reflux; the crude ester in the light component removing tower enters a heavy component removing tower to carry out reflux collection, the heavy component is discharged from the bottom of a reboiler, and the reflux collection product is cooled to obtain the finished product of dimethyl sebacate. The technology is characterized in that the crude dimethyl sebacate is formed by esterifying sebacic acid and methanol under the action of a catalyst, and does not contain monomethyl adipate azeotroped with the dimethyl sebacate and heavy components with larger viscosity, so that the separation technology is not suitable for an electrochemical method for synthesizing the dimethyl sebacate by adopting the monomethyl adipate as a raw material.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a purification method for electrochemically synthesizing dimethyl sebacate, which can obviously reduce the acid value of the product, simultaneously avoid polymerization of heavy components in the tower bottom and improve the yield and purity of the dimethyl sebacate.
In order to achieve the technical effects, the invention adopts the following technical scheme:
the invention provides a purification method for electrochemical synthesis of dimethyl sebacate, which comprises the steps of adding 2, 6-di-tert-butyl-1, 4-benzoquinone and magnesium formate into a crude product of the electrochemical synthesis of dimethyl sebacate, and obtaining the dimethyl sebacate through decompression hypergravity rectification, thus completing separation and purification.
In the method, the electrochemical synthesized dimethyl sebacate crude product is obtained by adding water into dimethyl sebacate reaction liquid prepared by the existing electrochemical method, rectifying and removing methanol, methyl valerate and methyl pentenoate;
preferably, the electrochemical synthesized dimethyl sebacate crude product comprises the following components in percentage by mass: 88-93wt% of dimethyl sebacate, 0.5-3wt% of monomethyl adipate, 0.5-3wt% of dimethyl tetradecanedioate and the balance of components; wherein the weight fraction is about 4.5 to 7wt%, and comprises mainly C 14 H 24 O 7 1-4wt％、C 18 H 32 O 6 0.5-2wt％、C 40 H 70 O 8 1-3wt％；
More preferably, the electrochemical synthesized dimethyl sebacate crude product comprises the following components in percentage by mass: 90-92wt% of dimethyl sebacate, 1.5-2wt% of monomethyl adipate and 1-1.5wt% of dimethyl tetradecanedioate;
preferably, the electrochemically synthesized dimethyl sebacate reaction solution is prepared by electrolyzing monomethyl adipate by an anode electrode, and the anode is preferably platinum, platinum titanium or Ti-based PbO 2 、PtO 2 、IrO 2 、RuO 2 Or tin antimony oxide.
In the method of the invention, the addition amount of the 2, 6-di-tert-butyl-1, 4-benzoquinone is 0.5-2 per mill, preferably 1-1.5 per mill of the mass of the crude product of dimethyl sebacate.
In the method of the invention, the addition amount of the magnesium formate is 1-5% of the mass of the crude product of the dimethyl sebacate, and preferably 2-4%.
In the method of the invention, the reduced pressure hypergravity rectification has a vacuum degree (absolute pressure) of 0.5-20KPa, preferably 5-10KPa; the rotation speed is 1000-4000rpm, preferably 2000-3000rpm; the heating temperature of the tower kettle is 220-255 ℃, preferably 230-240 ℃; reflux ratio was 5:1-0.5:1, preferably 2:1-1:1.
In the method, the decompression hypergravity rectification is completed by a hypergravity rectification machine, wherein the hypergravity rectification machine is selected from BZ650 type and BZ850 type of Zhejiang chemical equipment limited company, BZ650 type and BZ750 type of Shanghai power king environmental protection engineering limited company, and the like, and is preferably BZ650-3P type of Hangzhou power chemical equipment limited company.
Preferably, the internal rotor filler of the super-gravity rectifying machine is an integral structured filler, and the integral structured filler is selected from any one or a combination of at least two of foam silicon carbide corrugated structured filler, foam nickel structured filler, titanium alloy structured filler, fin guide plate structured filler and modified plastic structured filler; foam silicon carbide corrugated structured packing and/or titanium alloy structured packing are preferred.
Preferably, the integral packing of the hypergravity rectifying machine has an inner diameter of 10-300mm, an outer diameter of 650-850mm and a height of 100-500mm.
In the method, the reduced pressure hypergravity rectification starts timing when a first drop of liquid appears at the top of the hypergravity rectification machine, and the light components at the top of the tower, which are extracted within 3-5 hours, are collected to obtain purified dimethyl sebacate;
preferably, the light component extraction temperature is 155-170 ℃, namely the temperature starts to collect when the first drop of liquid appears on the tower top is about 155 ℃, and the collection is stopped when the temperature rises to 170 ℃, and the collection time is about 3-5 hours, preferably 4.1-4.6 hours;
preferably, the purified dimethyl sebacate is extracted from the top of the hypergravity rectifying machine, and the extraction mass is more than 87%, preferably more than 90%, more preferably more than 92% of the feeding mass of the crude dimethyl sebacate;
in the method, the light component extracted from the top of the hypergravity rectifying machine is purified dimethyl sebacate, the purity of the light component is more than 99.5%, and the recovery rate of the dimethyl sebacate is more than 98%; the acid value of the purified dimethyl sebacate is lower than 0.05mgKOH/g, preferably 0.02-0.04mgKOH/g;
the recombinant group produced at the bottom of the hypergravity rectifying machine comprises: dimethyl sebacate, magnesium formate, monomethyl adipate, 2, 6-di-tert-butyl-1, 4-benzoquinone and heavy components; wherein the dimethyl sebacate is less than 14% by weight, the other components include magnesium formate 8-36%, monomethyl adipate 4-18%, 2, 6-di-tert-butyl-1, 4-benzoquinone 0.4-1.3%, and heavy components about 38-51% (mainly including C) 14 H 24 O 7 、C 18 H 32 O 6 、C 40 H 70 O 8 ) The method comprises the steps of carrying out a first treatment on the surface of the The polymerization conversion of the heavy component is lower than 5%.
In the prior art, adipic acid is used as a starting material, and the crude product of dimethyl sebacate synthesized by an electrochemical method contains monomethyl adipate, heavy components and the like, so that the problem of azeotropy with the dimethyl sebacate exists during rectification, the high-purity and the dimethyl sebacate are difficult to obtain, and meanwhile, the problem of pipeline blockage is caused by polymerization of the heavy components at high temperature. The invention adopts the hypergravity rectification technology to purify the dimethyl sebacate crude product, strengthens interphase mass transfer by utilizing centrifugal force, can increase the content of light components in gas phase products, and achieves more excellent separation effect. The magnesium formate is added to improve the relative volatility between the monomethyl adipate and the dimethyl sebacate through a salt effect, so that the constant boiling points of the monomethyl adipate and the dimethyl sebacate are moved upwards. In addition, the added magnesium formate and 2, 6-di-tert-butyl-1, 4-benzoquinone can inhibit C in the tower kettle 14 H 24 O 7 ，C 18 H 32 O 6 ，C 40 H 70 O 8 The equal weight component is polymerized at high temperature, wherein the magnesium formate can be added to perform esterification reaction with hydroxyl functional groups in the weight component, so that polymerization caused by esterification reaction with carboxyl groups of other weight component molecules is avoided, and the 2, 6-di-tert-butyl-1, 4-benzoquinone can inhibit the weight componentThe unsaturated bond initiated polymerization reaction effectively avoids the problem of pipeline blockage caused by heavy component polymerization under the combined action of magnesium formate and 2, 6-di-tert-butyl-1, 4-benzoquinone.
According to the invention, magnesium formate and 2, 6-di-tert-butyl-1, 4-benzoquinone are simultaneously introduced into a rectification system for electrochemically synthesizing dimethyl sebacate, the separation effect is improved, heavy component polymerization is inhibited through the synergistic effect of the magnesium formate and the 2, 6-di-tert-butyl-1, 4-benzoquinone, reduced pressure hypergravity rectification is adopted, interphase mass transfer is enhanced by utilizing centrifugal force, the residue of dimethyl sebacate in monomethyl adipate is reduced, the purity of a product is improved, the residence time of materials in a tower kettle is reduced, and the possibility of recombining, distributing and polymerizing in the tower kettle and blocking a pipeline is further reduced. The purity of the purified dimethyl sebacate can reach more than 99.5%, and the yield can reach more than 98%.
Detailed Description
The invention is further illustrated by the following examples, which are not to be construed as limiting the scope of the invention as claimed.
The main raw materials and equipment information used in the embodiment of the invention:
dimethyl sebacate crude 1: platinum electrode is used as anode to electrolyze adipic acid monomethyl ester to obtain reaction liquid, then water is added, and methanol and methyl valerate are distilled off to obtain the product, which comprises 93wt% dimethyl sebacate, 0.5wt% monomethyl adipate, 0.5wt% dimethyl tetradecanedioate and 6wt% heavy component (mainly comprising C) 14 H 24 O 7 3wt％、C 18 H 32 O 6 1.5wt％、C 40 H 70 O 8 1.5wt％)；
Dimethyl sebacate crude 2: platinum-titanium electrode is used as anode to electrolyze adipic acid monomethyl ester to obtain reaction liquid, then water is added, and methanol and methyl valerate are distilled off to obtain the product, which comprises 92wt% dimethyl sebacate, 1wt% monomethyl adipate, 1.5wt% dimethyl tetradecanedioate and 5.5wt% heavy component (mainly comprising C) 14 H 24 O 7 2wt％、C 18 H 32 O 6 0.5wt％、C 40 H 70 O 8 3wt％)；
Dimethyl sebacate crude 3: from Ti-based PbO 2 The electrode is used as anode to electrolyze adipic acid monomethyl ester to obtain reaction liquid, and then the reaction liquid is prepared by adding water, rectifying to remove methanol and methyl valerate, and the reaction liquid consists of 88wt% dimethyl sebacate, 3wt% monomethyl adipate, 2wt% dimethyl tetradecanedioate and 7wt% heavy component (mainly comprising C) 14 H 24 O 7 4wt％、C 18 H 32 O 6 2wt％、C 40 H 70 O 8 1wt％)；
Crude dimethyl sebacate 4: from Ti-based PtO 2 The electrode is used as anode to electrolyze adipic acid monomethyl ester to obtain reaction liquid, and then the reaction liquid is prepared by adding water, rectifying to remove methanol and methyl valerate, wherein the reaction liquid comprises 90wt% of dimethyl sebacate, 2wt% of monomethyl adipate, 1wt% of dimethyl tetradecanedioate and 7wt% of heavy component (mainly comprising C) 14 H 24 O 7 4wt％、C 18 H 32 O 6 1.5wt％、C 40 H 70 O 8 1.5wt％)；
Crude dimethyl sebacate 5: from Ti-based IrO 2 The electrode is used as anode to electrolyze adipic acid monomethyl ester to obtain reaction liquid, and then the reaction liquid is prepared by adding water, rectifying to remove methanol and methyl valerate, and the reaction liquid consists of 91wt% dimethyl sebacate, 1.5wt% monomethyl adipate, 3wt% dimethyl tetradecanedioate and 4.5wt% heavy component (mainly comprising C) 14 H 24 O 7 1wt％、C 18 H 32 O 6 1.5wt％、C 40 H 70 O 8 2wt％)；
Unless otherwise specified, the other materials are all common materials purchased in the market.
Hypergravity rectifier: the number of stages is 3, the diameter of the rotor is 650mm, the height of the inner cavity of the rectifying machine is 900mm, and BZ650-3P of Hangzhou Keli chemical equipment is available;
foam silicon carbide corrugated structured packing: inner diameter 150mm, outer diameter 650mm, height 200mm, hangzhou Keli chemical equipment limited SUS316L;
fin baffle structured packing: inner diameter 150mm, outer diameter 650mm, height 200mm, hangzhou Keli chemical equipment limited SUS316L;
foam nickel structured packing: inner diameter 150mm, outer diameter 650mm, height 200mm, hangzhou Keli chemical equipment limited SUS316L;
titanium alloy structured packing, wherein the inner diameter of the packing is 100mm, the outer diameter of the packing is 850mm, the height of the packing is 300mm, and the company of Jiangzhuang chemical equipment is 850 x 300;
modified plastic structured packing with inner diameter of 300mm, outer diameter of 650mm and height of 500mm is 650 x 500 of Shanghai power king environmental protection engineering Co.
The detection method used in the examples is described below:
the conversion rate and the selectivity are determined by using gas chromatography area correction normalization analysis, and chromatographic analysis conditions are as follows:
instrument model: island GC2010; chromatographic column: DB-5 (30X 0.32X 0.25); column temperature: programmed heating (50 ℃ for 4min, then heating to 100 ℃ at a heating rate of 5 ℃/min, then heating to 300 ℃ at a heating rate of 25 ℃/min, and holding for 5 min); sample inlet temperature: 230 ℃; FID temperature: 300 ℃; n (N) 2 Flow rate: 1mL/min; h 2 Flow rate: 40mL/min; spacer purge (N) 2 ) Flow rate: 3mL/min; carrier gas (N) 2 ) Flow rate: 1mL/min; split sample injection, split ratio: 50; sample injection amount: 0.1. Mu.L.
Example 1
The rotor filler in the hypergravity rectifying machine is foam silicon carbide corrugated structured filler, the inner diameter of the filler is 150mm, the outer diameter of the filler is 650mm, and the height of the filler is 200mm.
The dimethyl sebacate crude product 1 to be purified comprises the following components in percentage by mass: 93wt% of dimethyl sebacate, 0.5wt% of monomethyl adipate, 0.5wt% of dimethyl tetradecanedioate, and 6wt% of heavy component (mainly comprising C 14 H 24 O 7 3wt％、C 18 H 32 O 6 1.5wt％、C 40 H 70 O 8 1.5wt％)。
A purification method for electrochemically synthesizing dimethyl sebacate comprises the following steps:
taking 300Kg of dimethyl sebacate crude product, adding 0.15Kg of 2, 6-di-tert-butyl-1, 4-benzoquinone and 15Kg of magnesium formate, uniformly mixing, wherein the mass of the 2, 6-di-tert-butyl-1, 4-benzoquinone accounts for 0.5 per mill of the mass of the crude product raw material, and the mass of the magnesium formate accounts for 5% of the mass of the crude product raw material, and transferring to a hypergravity rectifying machine for reduced pressure rectification operation. Setting the vacuum degree (absolute pressure) of the rectification process to be 0.5KPa, starting the hypergravity rectification machine, gradually adjusting the rotating speed to 1000rpm, and heating the oil temperature of the tower kettle to be 230 ℃.
When the first drop of liquid appears at the top of the hypergravity rectifying machine, the temperature of the top of the tower is 155 ℃ and the reflux ratio is 5:1, after the collection for 5 hours, the temperature of the top of the tower rises to 170 ℃ to stop the collection, 276Kg of light component is extracted from the top of the tower, 92% of the feeding mass of the dimethyl sebacate crude product, and the rest of the material is heavy component extracted from the bottom of the tower.
The light component extracted from the top of the tower is purified dimethyl sebacate, the purity is 99.8 percent, and the purification yield is 98.7 percent; the acid value was 0.05mgKOH/g.
About 39.15kg of heavy components recovered from the bottom of the column comprises: dimethyl sebacate 9.07% and heavy fraction 45.98% (mainly including C) 14 H 24 O 7 23％、C 18 H 32 O 6 11.5％、C 40 H 70 O 8 11.5%) of magnesium formate, monomethyl adipate, 2, 6-di-tert-butyl-1, 4-benzoquinone. The tower bottom has no solidified material, and the polymerization conversion rate of heavy components is 2%.
Example 2
The rotor filler in the hypergravity rectifying machine is foam nickel structured filler, the inner diameter of the filler is 150mm, the outer diameter of the filler is 650mm, and the height of the filler is 200mm.
The dimethyl sebacate crude product 2 to be purified comprises the following components in percentage by mass: 92wt% of dimethyl sebacate, 1wt% of monomethyl adipate, 1.5wt% of dimethyl tetradecanedioate, and 5.5wt% of heavy component (mainly comprising C 14 H 24 O 7 2wt％、C 18 H 32 O 6 0.5wt％、C 40 H 70 O 8 3wt％)。
A purification method for electrochemically synthesizing dimethyl sebacate comprises the following steps:
taking 300kg of dimethyl sebacate crude product, adding 0.3kg of 2, 6-di-tert-butyl-1, 4-benzoquinone and 12kg of magnesium formate, uniformly mixing, wherein the mass of the 2, 6-di-tert-butyl-1, 4-benzoquinone accounts for 1 per mill of the mass of the crude product raw material, and the mass of the magnesium formate accounts for 4% of the mass of the crude product raw material, and transferring to a supergravity rectifying machine for decompression rectifying operation. Setting the vacuum degree (absolute pressure) of the rectification process to be 5KPa, starting the hypergravity rectification machine, gradually adjusting the rotating speed to 2000rpm, and heating the oil temperature of the tower kettle to be 240 ℃.
When the first drop of liquid appears at the top of the hypergravity rectifying machine, the temperature of the top of the tower is 155 ℃ and the reflux ratio is 2:1, after 4.7 hours of collection, the temperature of the top of the tower rises to 170 ℃ at this time, the collection is stopped, 272Kg of light component is extracted from the top of the tower, 91% of the feeding mass of the dimethyl sebacate crude product, and the rest of the materials are heavy components extracted from the bottom of the tower.
The light component extracted from the top of the tower is purified dimethyl sebacate, the purity is 99.5 percent, and the purification yield is 98.1 percent; the acid value was 0.04mgKOH/g.
The heavy component extracted from the bottom of the tower is about 40.3Kg, and the composition comprises: dimethyl sebacate 13.3% and heavy fraction 47.2% (mainly including C) 14 H 24 O 7 14.9wt％、C 18 H 32 O 6 10wt％、C 40 H 70 O 8 22.3% by weight of magnesium formate, monomethyl adipate, 2, 6-di-tert-butyl-1, 4-benzoquinone. The tower bottom has no solidified material, and the polymerization conversion rate of heavy components is 3.1%.
Example 3
The rotor packing used by the hypergravity rectifying machine is titanium alloy structured packing, the inner diameter of the packing is 100mm, the outer diameter is 850mm, and the height is 300mm.
The dimethyl sebacate crude product 3 to be purified comprises the following components in percentage by mass: 88wt% of dimethyl sebacate, 3wt% of monomethyl adipate, 2wt% of dimethyl tetradecanedioate and 7wt% of heavy component (mainly comprising C 14 H 24 O 7 4wt％、C 18 H 32 O 6 2wt％、C 40 H 70 O 8 1wt％)。
A purification method for electrochemically synthesizing dimethyl sebacate comprises the following steps:
taking 300Kg of dimethyl sebacate crude product, adding 0.45Kg of 2, 6-di-tert-butyl-1, 4-benzoquinone and 6Kg of magnesium formate, uniformly mixing, wherein the mass of the 2, 6-di-tert-butyl-1, 4-benzoquinone accounts for 1.5 per mill of the mass of the crude product raw material, and the mass of the magnesium formate accounts for 2% of the mass of the crude product raw material, and transferring to a hypergravity rectifying machine for reduced pressure rectification operation. Setting the vacuum degree (absolute pressure) in the rectification process to be 10KPa, starting the hypergravity rectification machine, gradually adjusting the rotating speed to 3000rpm, and heating the oil temperature of the tower kettle to be 220 ℃.
When the first drop of liquid appears at the top of the hypergravity rectifying machine, the temperature of the top of the tower is 155 ℃ and the reflux ratio is 1:1, after 4.2 hours of collection, the temperature of the top of the tower rises to 170 ℃ at this time, the collection is stopped, 261Kg of light component is extracted from the top of the tower, the light component is 87% of the feeding mass of the dimethyl sebacate crude product, and the rest of the materials are heavy components extracted from the bottom of the tower.
The light component extracted from the top of the tower is purified dimethyl sebacate, the purity is 99.6 percent, and the purification yield is 98.5 percent; the acid value was 0.02mgKOH/g.
The heavy component extracted from the bottom of the tower is about 45.45Kg, and the composition comprises: dimethyl sebacate is 8.9% and heavy component is about 46.2% (mainly including C 14 H 24 O 7 26.4wt％、C 18 H 32 O 6 13.2wt％、C 40 H 70 O 8 6.6 wt.%) other components magnesium formate, monomethyl adipate, 2, 6-di-tert-butyl-1, 4-benzoquinone. The tower bottom has no solidified material, and the polymerization conversion rate of heavy components is 5.0%.
Example 4
The rotor filler in the hypergravity rectifying machine is fin guide plate structured filler, the inner diameter of the filler is 150mm, the outer diameter of the filler is 650mm, and the height of the filler is 200mm.
The dimethyl sebacate crude product 4 to be purified comprises the following components in percentage by mass: 90% by weight of dimethyl sebacate, 2% by weight of monomethyl adipate, 1% by weight of dimethyl tetradecanedioate, 7% by weight of heavy components (mainly comprising C 14 H 24 O 7 4wt％、C 18 H 32 O 6 1.5wt％、C 40 H 70 O 8 1.5wt％)。
A purification method for electrochemically synthesizing dimethyl sebacate comprises the following steps:
taking 300Kg of dimethyl sebacate crude product, adding 0.6Kg of 2, 6-di-tert-butyl-1, 4-benzoquinone and 9Kg of magnesium formate, uniformly mixing, wherein the mass of the 2, 6-di-tert-butyl-1, 4-benzoquinone accounts for 2 per mill of the mass of the crude product raw material, and the mass of the magnesium formate accounts for 3 percent of the mass of the crude product raw material, and transferring to a hypergravity rectifying machine for reduced pressure rectification operation. Setting the vacuum degree (absolute pressure) of the rectification process to be 20KPa, starting the hypergravity rectification machine, gradually adjusting the rotating speed to 4000rpm, and heating the oil temperature of the tower kettle to be 255 ℃.
When the first drop of liquid appears at the top of the hypergravity rectifying machine, the light component starts to be collected, the temperature of the top of the tower is 155 ℃ at the moment, the reflux ratio is 0.5:1, after the collection for 3.3 hours, the temperature of the top of the tower rises to 170 ℃, the collection is stopped, 268Kg of light component is extracted from the top of the tower, 89% of the feeding mass of the dimethyl sebacate crude product, and the rest of the materials are heavy components extracted from the bottom of the tower.
The light component extracted from the top of the tower is purified dimethyl sebacate, the purity is 99.9 percent, and the purification yield is 99.1 percent; the acid value was 0.03mgKOH/g.
The heavy fraction recovered from the bottom of the column was about 41.6Kg, and the composition included: dimethyl sebacate is 5.45% and heavy component is about 50.6% (mainly including C 14 H 24 O 7 28.8wt％、C 18 H 32 O 6 10.8wt％、C 40 H 70 O 8 11.0 wt.%) other components magnesium formate, monomethyl adipate, 2, 6-di-tert-butyl-1, 4-benzoquinone. The tower bottom has no solidified material, and the polymerization conversion rate of heavy components is 3.2%.
Example 5
The rotor filler in the hypergravity rectifying machine is modified plastic structured filler, the inner diameter of the filler is 300mm, the outer diameter of the filler is 650mm, and the height of the filler is 500mm.
The dimethyl sebacate crude product 5 to be purified comprises the following components in percentage by mass: 91wt% of dimethyl sebacate, 1.5wt% of monomethyl adipate, 3wt% of dimethyl tetradecanedioate and 4.5wt% of heavy components (mainly comprising C 14 H 24 O 7 1wt％、C 18 H 32 O 6 1.5wt％、C 40 H 70 O 8 2wt％)。
A purification method for electrochemically synthesizing dimethyl sebacate comprises the following steps:
taking 300Kg of dimethyl sebacate crude product, adding 0.45Kg of 2, 6-di-tert-butyl-1, 4-benzoquinone and 3Kg of magnesium formate, uniformly mixing, wherein the mass of the 2, 6-di-tert-butyl-1, 4-benzoquinone accounts for 1.5 per mill of the mass of the crude product raw material, and the mass of the magnesium formate accounts for 1% of the mass of the crude product raw material, and transferring to a hypergravity rectifying machine for reduced pressure rectification operation. Setting the vacuum degree (absolute pressure) in the rectification process to be 10KPa, starting the hypergravity rectification machine, gradually adjusting the rotating speed to 1000rpm, and heating the oil temperature of the tower kettle to be 240 ℃.
When the first drop of liquid appears at the top of the hypergravity rectifying machine, the temperature of the top of the tower is 155 ℃ and the reflux ratio is 1:1, after the collection is carried out for 250min, the temperature of the top of the tower is raised to 170 ℃ to stop the collection, 270Kg of light components are extracted from the top of the tower, the light components are 90% of the feeding mass of the dimethyl sebacate crude product, and the rest materials are heavy components extracted from the bottom of the tower.
The light component extracted from the top of the tower is purified dimethyl sebacate, the purity is 99.5 percent, and the purification yield is 98.4 percent; the acid value was 0.04mgKOH/g.
The heavy fraction recovered from the bottom of the column was about 33.45Kg, and the composition included: dimethyl sebacate 13% and heavy fraction 40.36% (mainly including C) 14 H 24 O 7 8.97wt％、C 18 H 32 O 6 13.45wt％、C 40 H 70 O 8 17.94% by weight of magnesium formate, monomethyl adipate, 2, 6-di-tert-butyl-1, 4-benzoquinone as other components. The tower bottom has no solidified material, and the polymerization conversion rate of heavy components is 2.4%.
Comparative example 1
The purification method of example 1 was followed except that 2, 6-di-t-butyl-1, 4-benzoquinone was not added, and the crude dimethyl sebacate was purified directly into a hypergravity rectifier for rectification, and other operations and parameters were the same as in example 1.
248Kg of light component is extracted from the top of the tower, which is 83% of the feeding mass of the crude dimethyl sebacate.
The light component extracted from the top of the tower is purified dimethyl sebacate, the purity is 81.5%, and the purification yield is 72%; the acid value was 2.5mgKOH/g.
12.6Kg of solid material is collected at the tower bottom, and the polymerization conversion rate of heavy components is 70.2%.
Comparative example 2
The purification process was followed in example 1 except that 2, 6-di-tert-butyl-1, 4-benzoquinone was replaced with p-benzoquinone of equal mass and then distilled in a hypergravity rectifier with the same other operations and parameters as in example 1.
236Kg of light component is extracted from the top of the tower, which is 78.7 percent of the feeding mass of the dimethyl sebacate crude product.
The light component extracted from the top of the tower is purified dimethyl sebacate, the purity is 91.8 percent, and the purification yield is 78 percent; the acid value was 3.2mgKOH/g.
The solid material is collected at the tower bottom, 15.5Kg, and the polymerization conversion rate of heavy components is 86%.
Comparative example 3
The purification method of example 1 was followed except that magnesium formate was not added and the crude dimethyl sebacate was directly distilled in a hypergravity distillation machine, and the other operations and parameters were the same as in example 1.
231Kg of light component is extracted from the top of the tower, which is 77 percent of the feeding mass of the dimethyl sebacate crude product.
The light component extracted from the top of the tower is purified dimethyl sebacate, the purity is 90.1 percent, and the purification yield is 73 percent; the acid value was 2.8mgKOH/g.
7.65Kg of solid material is collected at the tower bottom, and the polymerization conversion rate of heavy components is 42.5%.
Comparative example 4
The purification process was followed in example 1, except that magnesium formate was replaced with equal mass of sodium formate and then distilled in a hypergravity rectifier, with the other operations and parameters being the same as in example 1.
225Kg of light component is extracted from the top of the tower, which is 75 percent of the feeding mass of the crude dimethyl sebacate.
The light component extracted from the top of the tower is purified dimethyl sebacate, the purity is 89.4%, and the purification yield is 72%; the acid value was 1.66mgKOH/g.
4.82Kg of solid material is collected at the tower bottom, and the polymerization conversion rate of heavy components is 26.8%.
Comparative example 5
The purification method according to example 1 was carried out only with the difference that the hypergravity rectifying machine was used as a common rectifying tower, the centrifuge was not turned on, and other operations and parameters were the same as in example 1.
235Kg of light component is extracted from the top of the tower, which is 78 percent of the feeding mass of the crude dimethyl sebacate.
The light component extracted from the top of the tower is purified dimethyl sebacate, the purity is 92.1 percent, and the purification yield is 78 percent; the acid value was 3.7mgKOH/g.
The solid material is collected in the tower kettle in a quantity of 10.66Kg, and the polymerization conversion rate of the heavy component is 59.2%.
Comparative example 6
The method adopts a conventional rectification mode of dimethyl sebacate (common rectification without adding 2, 6-di-tert-butyl-1, 4-benzoquinone and magnesium formate), and comprises the following steps:
the common rectifying tower filler is titanium alloy regular filler, the diameter of the filler is 100mm, and the height is 2000mm.
The crude dimethyl sebacate to be purified is the same as in example 1.
And (3) taking 300Kg of dimethyl sebacate crude product to a common rectifying tower for vacuum rectification operation. Setting the vacuum degree (absolute pressure) of the rectification process to be 0.5KPa and the heating oil temperature of the tower kettle to be 220 ℃.
When the first drop of liquid appears at the top of the hypergravity rectifying machine to start collecting light components, the temperature of the top of the tower is 160 ℃ and the reflux ratio is 10:1, after 400 minutes of collection, the temperature of the top of the tower is raised to 170 ℃ to stop collection,
195Kg of light component is extracted from the top of the tower, which is 65 percent of the feeding mass of the crude dimethyl sebacate.
The light component extracted from the top of the tower is purified dimethyl sebacate, the purity is 87.6 percent, and the purification yield is 61 percent; the acid value was 2.6mgKOH/g.
16.97Kg of solid material is collected at the tower bottom, and the polymerization conversion rate of heavy components is 94.3%.
Claims (18)
1. The method is characterized in that 2, 6-di-tert-butyl-1, 4-benzoquinone and magnesium formate are added into a crude product of the electrochemical synthesized dimethyl sebacate, and the dimethyl sebacate is obtained through decompression hypergravity rectification, so that separation and purification are completed;
the electrochemical synthesized dimethyl sebacate crude product comprises the following components in percentage by mass: 88-93wt% of dimethyl sebacate, 0.5-3wt% of monomethyl adipate, 0.5-3wt wt% of dimethyl tetradecanedioate and the balance of components; wherein the weight fraction is 4.5-7wt% and comprises C 14 H 24 O 7 1-4wt%、C 18 H 32 O 6 0.5-2wt%、C 40 H 70 O 8 1-3wt%。
2. The purification method according to claim 1, wherein the electrochemical synthesized dimethyl sebacate crude product is obtained by adding water into a dimethyl sebacate reaction solution prepared by an electrochemical method, rectifying and removing methanol, methyl valerate and methyl pentenoate.
3. The purification method according to claim 1, wherein the electrochemical synthesis of the crude dimethyl sebacate comprises the following components in percentage by mass: 90-92wt% of dimethyl sebacate, 1.5-2wt% of monomethyl adipate and 1-1.5wt wt% of dimethyl tetradecanedioate.
4. The purification method according to claim 1, wherein the addition amount of 2, 6-di-tert-butyl-1, 4-benzoquinone is 0.5-2% by weight of the crude product of dimethyl sebacate.
5. The method according to claim 4, wherein the amount of 2, 6-di-tert-butyl-1, 4-benzoquinone is 1-1.5% by weight of the crude dimethyl sebacate.
6. The purification method according to claim 1, wherein the magnesium formate is added in an amount of 1-5% by mass of the crude dimethyl sebacate.
7. The method according to claim 6, wherein the magnesium formate is added in an amount of 2 to 4% by mass of the crude dimethyl sebacate.
8. The purification method according to claim 1, wherein the reduced pressure hypergravity rectification has a vacuum degree of 0.5 to 20KPa; the rotating speed is 1000-4000rpm; the heating temperature of the tower kettle is 220-255 ℃; reflux ratio was 5:1-0.5:1.
9. The method of purifying according to claim 8, wherein the vacuum degree is 5 to 10KPa.
10. The purification method according to claim 8, wherein the rotational speed is 2000-3000rpm.
11. The purification process of claim 8, wherein the column bottoms heating temperature is 230-240 ℃.
12. The purification method according to claim 8, wherein the reflux ratio is 2:1-1:1.
13. The purification method according to claim 1, wherein the reduced pressure hypergravity distillation is performed by a hypergravity distillation machine selected from the group consisting of BZ650 type, BZ850 type, BZ650 type, BZ750 type.
14. The purification method according to claim 13, wherein the internal rotor packing of the hypergravity rectifier is a monolithic structured packing selected from any one or a combination of at least two of a foam silicon carbide corrugated structured packing, a foam nickel structured packing, a titanium alloy structured packing, a fin baffle structured packing, a modified plastic structured packing.
15. The purification method according to claim 13, wherein the integral packing of the hypergravity rectifying machine has an inner diameter of 10-300mm, an outer diameter of 650-850mm and a height of 100-500mm.
16. The purification method according to claim 13, wherein the reduced pressure hypergravity distillation is performed, and the first drop of liquid at the top of the hypergravity distillation machine is counted from the beginning, and the light components at the top of the tower, which are extracted within 3-5 hours, are collected, so as to obtain the purified dimethyl sebacate.
17. The method of claim 16, wherein the light fraction extraction temperature is 155-170 ℃ and the collection time is 3-5 hours.
18. The purification method of claim 17, wherein the collection time is 4.1-4.6 hours.
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