CN111100004A - Method and integrated device for refining dimethyl carbonate - Google Patents
Method and integrated device for refining dimethyl carbonate Download PDFInfo
- Publication number
- CN111100004A CN111100004A CN201911391630.5A CN201911391630A CN111100004A CN 111100004 A CN111100004 A CN 111100004A CN 201911391630 A CN201911391630 A CN 201911391630A CN 111100004 A CN111100004 A CN 111100004A
- Authority
- CN
- China
- Prior art keywords
- tower
- adsorption
- adsorption tower
- dimethyl carbonate
- rectifying 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.)
- Granted
Links
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000007670 refining Methods 0.000 title claims abstract description 8
- 238000001179 sorption measurement Methods 0.000 claims abstract description 154
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 108
- 239000000463 material Substances 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000010992 reflux Methods 0.000 claims abstract description 10
- 239000003463 adsorbent Substances 0.000 claims description 38
- 239000002808 molecular sieve Substances 0.000 claims description 36
- 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 36
- 229920005989 resin Polymers 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 24
- 125000002091 cationic group Chemical group 0.000 claims description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 239000011152 fibreglass Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 16
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 description 26
- 239000000047 product Substances 0.000 description 22
- 238000000926 separation method Methods 0.000 description 10
- 239000012528 membrane Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- 238000000605 extraction Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 3
- 238000000895 extractive distillation Methods 0.000 description 3
- 239000012510 hollow fiber Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 238000000066 reactive distillation Methods 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000001944 continuous distillation Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- GUNDKLAGHABJDI-UHFFFAOYSA-N dimethyl carbonate;methanol Chemical compound OC.COC(=O)OC GUNDKLAGHABJDI-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/08—Purification; Separation; Stabilisation
-
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a method and an integrated device for refining dimethyl carbonate, wherein the method comprises the following steps: adsorbing the materials by a first adsorption tower, and then sequentially introducing the materials into a first rectifying tower, a second rectifying tower and a third rectifying tower to obtain a primary product from the top of the third rectifying tower; and adsorbing the primary product by using a second adsorption tower, then shunting, introducing a part of the primary product into a third rectifying tower for reflux treatment, and introducing the other part of the primary product into a third adsorption tower for adsorption to obtain refined dimethyl carbonate. The method and the integrated device of the invention can effectively reduce the contents of methanol and water in the dimethyl carbonate by arranging the multi-stage adsorption tower in the continuous rectification process unit, ensure that the index requirements of battery-grade products are met, greatly reduce the energy consumption of the continuous rectification unit in the production process and save the production cost.
Description
Technical Field
The invention relates to the technical field of industrial production processes of dimethyl carbonate, in particular to a method for refining dimethyl carbonate.
Background
Dimethyl carbonate (DMC) has low toxicity, excellent environmental protection performance and wide application, the melting point is 0.5 ℃, the boiling point is 90.2 ℃, the relative density is 1.073(20 ℃), and the lightning is 18 ℃, and is an important organic synthesis intermediate. Because dimethyl carbonate contains methoxyl, methyl, carbonyl and carbonylmethoxyl in molecules, the dimethyl carbonate has good reaction activity, can replace virulent phosgene as a carbonylation reagent and dimethyl sulfate as a methylation reagent, and can directly synthesize food additives, antioxidants, plant protection agents, high-grade resins, fuels, drug intermediates, surfactants and the like; meanwhile, the oxygen content of the dimethyl carbonate is as high as 53.3 percent, and the dimethyl carbonate can be used as an environment-friendly vehicle gasoline additive and is superior to the currently used methyl tert-butyl ether in the aspects of increasing the octane number and reducing the emissions.
The industrial production method of the dimethyl carbonate comprises the following steps: phosgene method, carbonyl oxide method and ester exchange method. The traditional phosgene method has high toxicity and serious environmental pollution and is basically eliminated; the carbonyl oxide method has high technical difficulty, strict requirements on process design and equipment material selection and high investment; the ester exchange method has the advantages of cheap raw materials, low toxicity, no generation of three wastes, high yield and low corrosivity, and the byproduct ethylene glycol can also be used as an important chemical raw material, so the method is a relatively advanced preparation method.
The production of dimethyl carbonate by the transesterification of ethylene carbonate adopts the processes of reactive distillation and continuous distillation purification, and the main byproducts of the reactive distillation unit are ethylene carbonate, ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether and the like; the continuous rectification adopts multistage series rectification operation to obtain industrial grade dimethyl carbonate and battery grade dimethyl carbonate, and the rectification operation mainly aims at removing methanol and water. Typical refining processes are low-temperature crystallization, pressurized distillation, hydrocarbon-adding azeotropic distillation and extractive distillation.
Spence first reported in 1986 that adsorption separation of dimethyl carbonate in methanol increased the DMC content of the solution from 2% to 20%. The silicalite Si-1 and the HZSM-5 with high silica-alumina ratio are used as adsorbents to study the gas phase adsorption process and the adsorption mechanism of the dimethyl carbonate and methanol azeotrope (the inner diameter of an adsorption rectifying tower is 25mm, the filling height of the adsorbent is 50cm, the dimethyl carbonate and methanol azeotrope is gasified and then passes through the adsorption rectifying tower from bottom to top, and the treated product is obtained by condensing the top of the tower).
CN203281056U discloses a separation device of an azeotrope of dimethyl carbonate and methanol in a process of producing dimethyl carbonate by an ester exchange method, which consists of a reaction rectifying tower and a pressurized rectifying tower and changes the original three-tower reaction and separation system; and the condenser of the pressurized rectifying tower is removed; directly feeding the material at the top of the pressurized rectifying tower into a reactive rectifying tower; the investment of the device is reduced, part of waste heat is recovered, and the process operation is improved. Can be applied to all ester exchange methods for producing dimethyl carbonate pressure swing separation devices.
CN107739311A discloses a method for treating azeotrope in dimethyl carbonate process and diphenyl carbonate process, which adopts phenol to destroy azeotropic composition of dimethyl carbonate and methanol to obtain mixture of phenol and dimethyl carbonate, wherein phenol and dimethyl carbonate are raw materials for synthesizing diphenyl carbonate, and can be directly used for production of diphenyl carbonate without separation, thereby shortening process flow and reducing energy consumption.
CN204298289U discloses a device for separating methanol-dimethyl carbonate azeotrope: and during pressure separation, a plate tower is selected, a mixed material with the ratio of methanol to dimethyl carbonate of 70:30 enters a preheater from a feeding tank, enters the plate tower after preheating, is subjected to pressure rectification to obtain the dimethyl carbonate with higher purity at the tower bottom, is condensed, refluxed and discharged at the tower top, enters the feeding tank, enters an atmospheric pressure rectification tower from the feeding tank, is cooled, refluxed and discharged at the tower top, returns to the feeding tank, and obtains relatively pure methanol at the tower bottom.
CN203999448U discloses a single-tower heat recovery device for continuous rectification of a dimethyl carbonate product, and relates to a device for producing the dimethyl carbonate product by continuous rectification of a dimethyl carbonate crude product and recovering the heat energy of a rectifying tower per se. The device is technically characterized by comprising a dimethyl carbonate rectifying tower, a heat exchanger I, a heat exchanger II and a heat exchanger III, wherein the connection mode is that feeding materials are heated by the heat exchanger I and the heat exchanger III and then enter the rectifying tower, gas phase at the top of the tower enters the heat exchanger I and the heat exchanger II to be cooled, part of discharging materials flows back, the heat exchanger II is cooled by water, and a dimethyl carbonate product is extracted from a lateral line and enters the heat exchanger III to be cooled. The waste heat of the rectifying tower is recovered, and the energy is saved.
CN101143803A discloses a method for separating dimethyl carbonate and methanol, which mainly solves the problem of unstable device operation in the continuous production process when ionic liquid is used as an extracting agent. The separation method is extractive distillation, mixed extracting agents are adopted in the extractive distillation, one of the mixed extracting agents is ionic liquid with anion being bis (trifluoromethanesulfonimide) imide, and the other of the mixed extracting agents is one of diethylene glycol dimethyl ether, triethylene glycol dimethyl ether or tetraethylene glycol dimethyl ether. The separation method can realize continuous separation of dimethyl carbonate and methanol, has stable product quality and stable device operation, and can be used in industrial production process.
CN101362694A discloses a new method for separating azeotropic mixture of methanol and dimethyl carbonate: the mixed solution of methanol and dimethyl carbonate is circulated and supplied at the upstream side of the molecular sieve membrane, and the downstream side of the molecular sieve membrane is connected with a vacuum system. Because the molecular sieve membrane has very high permselectivity to methanol, methanol in the mixed solution preferentially permeates through the molecular sieve membrane, is evaporated and desorbed at the downstream side of the membrane, and is condensed and recovered by a vacuum system. The mixed solution can be completely separated from the methyl carbonate after being circulated for many times. Compared with the traditional rectification method, the method has the advantages of low energy consumption, no pollution, compact device, high separation efficiency and the like, and has very important significance for industrial production of dimethyl carbonate and preparation of other organic chemical raw materials from dimethyl carbonate.
CN102921313A discloses a preparation method of a hollow fiber composite membrane for separating methanol/dimethyl carbonate mixture, comprising the following steps: (1) respectively preparing 1-10 wt.% aqueous solution from polyvinyl alcohol (PVA) and perfluorosulfonic acid (PFSA), mixing and stirring at any ratio to prepare PFSA-PVA coating solution, and standing for defoaming; coating the PFSA-PVA coating liquid on a Polyacrylonitrile (PAN) hollow fiber ultrafiltration membrane, airing in a dust-free environment, standing for 10-20h, coating again, standing and airing; each coating time was 30 s; (2) vacuum drying the composite film prepared in the step (1), wherein the heat treatment temperature is as follows: and (3) at 80-170 ℃, and the heat treatment time is as follows: 1-3 h. The hollow fiber composite membrane prepared by the invention can permeate methanol preferentially, can be used for separating a methanol/dimethyl carbonate mixture, and has the advantages of low energy consumption, no pollution, simple operation and the like.
The adsorption rectification disclosed in the previous patent and literature documents uses an adsorbent as a rectification tower packing, can achieve the purpose of certain dehydration and methanol adsorption, but has the defects of high energy consumption and large operation difficulty.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method and an integrated device for removing water and methanol by multistage adsorption of dimethyl carbonate in a continuous rectification process unit.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of refining dimethyl carbonate comprising:
adsorbing the materials by a first adsorption tower, and then sequentially introducing the materials into a first rectifying tower, a second rectifying tower and a third rectifying tower to obtain a primary product from the top of the third rectifying tower; and
and adsorbing the primary product by using a second adsorption tower, then shunting, introducing a part of the primary product into a third rectifying tower for reflux treatment, and introducing the other part of the primary product into a third adsorption tower for adsorption to obtain refined dimethyl carbonate.
In some embodiments, the material is a mixture of dimethyl carbonate and water, methanol, ethylene carbonate, ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether.
In some embodiments, the adsorbents in the first adsorption column, the second adsorption column, and the third adsorption column are each independently a mixture of two or more of a porous molecular sieve, a cationic resin, and alumina.
In some embodiments, the porous molecular sieve is used in an amount of 20 wt% to 40 wt% and the cationic resin is used in an amount of 60 wt% to 80 wt% in the first adsorption column.
In some embodiments, the porous molecular sieve is used in an amount of 80 wt% to 90 wt% and the cationic resin is used in an amount of 10 wt% to 20 wt% in the second adsorption column.
In some embodiments, in the third adsorption tower, the porous molecular sieve is used in an amount of 40 wt% to 60 wt%, and the alumina is used in an amount of 40 wt% to 60 wt%.
In some embodiments, the total content of methanol and water in the refined dimethyl carbonate is less than 30 PPm.
In another aspect, the present invention also provides an integrated apparatus for refining dimethyl carbonate, comprising:
a material supply device;
a first adsorption tower, wherein the feeding end of the first adsorption tower is connected with the discharging end of the material supply device;
the feed end of the first rectifying tower is connected with the discharge end of the first adsorption tower;
the feed end of the second rectifying tower is connected with the discharge end of the first rectifying tower;
the feed end of the third rectifying tower is connected with the discharge end of the second rectifying tower;
a feed end of the second adsorption tower is connected with the top of the third rectifying tower, and a discharge end of the second adsorption tower is connected with the bottom of the third rectifying tower; and
and the feed end of the third adsorption tower is connected with the discharge end of the second adsorption tower.
In some embodiments, the first adsorption tower, the second adsorption tower and the third adsorption tower are made of glass fiber reinforced plastic or polytetrafluoroethylene.
In some embodiments, the adsorbents in the first adsorption column, the second adsorption column, and the third adsorption column are each independently a mixture of two or more of a porous molecular sieve, a cationic resin, and alumina.
The method and the integrated device of the invention can effectively reduce the contents of methanol and water in the dimethyl carbonate by arranging the multi-stage adsorption tower in the continuous rectification process unit, ensure that the index requirement (99.99%) of a battery-grade product is met, greatly reduce the energy consumption of the continuous rectification unit in the production process and save the production cost.
Drawings
FIG. 1 is a schematic structural diagram of a process apparatus according to an embodiment of the present invention.
Detailed Description
The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way.
Fig. 1 is a schematic structural view of a process apparatus according to an embodiment of the present invention, and referring to fig. 1, the method for purifying dimethyl carbonate according to the present invention includes the following steps:
adsorbing the material by a first adsorption tower (adsorption tower I), then sequentially introducing the material into a first rectifying tower (rectifying tower I), a second rectifying tower (rectifying tower II) and a third rectifying tower (rectifying tower III), and obtaining a primary product from an outlet of a condenser at the top of the third rectifying tower;
and then, adsorbing the primary product by using a second adsorption tower (an adsorption tower II), then shunting, introducing a part of the primary product into a third rectifying tower (a rectifying tower III) for reflux treatment, and introducing the other part of the primary product into a third adsorption tower (an adsorption tower III) for adsorption to obtain the refined dimethyl carbonate.
The main component of the material treated by the invention is dimethyl carbonate, the purity of which is about 99.7 percent, and the material also comprises byproducts brought by the prior reaction rectification process, such as ethylene carbonate, ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether, water, methanol and the like.
In the method of the present invention, the first adsorption column, the second adsorption column, and the third adsorption column are filled with a composite adsorbent in which a plurality of adsorbents are mixed, and the composite adsorbent may be, for example, a mixture of two or more of a porous molecular sieve, a cationic resin, and alumina.
Aiming at different components of the processed materials, different compound adsorbent compatibility schemes can be adopted at the first adsorption tower, the second adsorption tower and the third adsorption tower respectively, so that a better adsorption effect is obtained.
The material treated by the first adsorption tower contains larger molecular substances such as ethylene glycol, diethylene glycol and the like, so that the dosage of the mesoporous molecular sieve in the composite adsorbent is 20-40 wt%, and the dosage of the cationic resin is 60-80 wt%.
The material treated by the second adsorption tower does not contain larger molecular substances such as ethylene glycol, diethylene glycol and the like basically, so that the dosage of the porous molecular sieve in the composite adsorbent is 80-90 wt%, and the dosage of the cationic resin is 10-20 wt%.
The impurities in the material treated by the third adsorption tower are trace methanol and water, so that the dosage of the porous molecular sieve in the composite adsorbent is 40-60 wt%, and the dosage of the aluminum oxide is 40-60 wt%.
After the treatment, the total content of methanol and water in the refined dimethyl carbonate is less than 30PPm, so that the content of methanol and water in the dimethyl carbonate can be effectively reduced, and the requirement of battery-grade product index can be met.
On the other hand, as shown in fig. 1, the integrated apparatus for purifying dimethyl carbonate of the present invention comprises:
a material supply (the device on which "material" is located in fig. 1);
the feeding end of the first adsorption tower (adsorption tower I) is connected with the discharging end of the material supply device;
the feed end of the first rectifying tower (rectifying tower I) is connected with the discharge end of the first adsorption tower;
the feed end of the second rectifying tower (rectifying tower II) is connected with the discharge end of the first rectifying tower;
a third rectifying tower (rectifying tower III), wherein the feed end of the third rectifying tower is connected with the discharge end of the second rectifying tower;
the feed end of the second adsorption tower (adsorption tower II) is connected with the top discharge end (outlet of the condenser) of the third rectifying tower, and the discharge end of the second adsorption tower is connected with the bottom feed end of the third rectifying tower; and
and the feed end of the third adsorption tower (adsorption tower III) is connected with the discharge end of the second adsorption tower.
In the method and the integrated device, a first rectifying tower (rectifying tower I), a second rectifying tower (rectifying tower II) and a third rectifying tower (rectifying tower III) are all conventional rectifying towers.
In the method and the integrated device, the first adsorption tower (adsorption tower I), the second adsorption tower (adsorption tower II) and the third adsorption tower (adsorption tower III) are also conventional adsorption towers, adopt a multistage structure, are convenient to install, inspect and maintain, are made of glass fiber reinforced plastics or polytetrafluoroethylene, and are made of polytetrafluoroethylene and glass fiber as internal components.
Unless otherwise defined, all terms used herein have the meanings that are commonly understood by those skilled in the art.
The present invention will be described in further detail with reference to examples.
Examples
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Example 1
Introducing dimethyl carbonate material with the concentration of 99.7% into the integrated device shown in figure 1 in sequence, wherein the mixture ratio of the compound adsorbent in each adsorption tower is shown as follows;
(1) an adsorption tower (No. 1 adsorption tower) at a feeding position of continuous rectification, wherein the dosage of the cationic resin in the composite adsorbent is 60 percent, and the dosage of the porous molecular sieve is 40 percent;
(2) an adsorption tower (2# adsorption tower) at the top reflux position of the low-pressure rectification tower, wherein the dosage of the cationic resin in the composite adsorbent is 10 percent, and the dosage of the porous molecular sieve is 90 percent;
(3) the adsorption tower (3# adsorption tower) at the product extraction position has the usage amount of the composite adsorbent porous molecular sieve of 50 percent and the aluminum oxide of 50 percent.
The DMC purity and the methanol and water content data of the material after being processed by the No. 1 adsorption tower, the No. 2 adsorption tower and the No. 3 adsorption tower are shown in Table 1.
TABLE 1
Example 2
Introducing dimethyl carbonate material with the concentration of 99.7% into the integrated device shown in figure 1 in sequence, wherein the mixture ratio of the compound adsorbent in each adsorption tower is shown as follows;
(1) an adsorption tower (No. 1 adsorption tower) at a feeding position of continuous rectification, wherein the dosage of the cationic resin in the composite adsorbent is 80 percent, and the dosage of the porous molecular sieve is 20 percent;
(2) an adsorption tower (2# adsorption tower) at the top reflux position of the low-pressure rectification tower, wherein the dosage of the cationic resin in the composite adsorbent is 10 percent, and the dosage of the porous molecular sieve is 90 percent;
(3) the adsorption tower (3# adsorption tower) at the product extraction position has the usage amount of the composite adsorbent porous molecular sieve of 50 percent and the aluminum oxide of 50 percent.
The DMC purity and the methanol and water content data of the material after being processed by the No. 1 adsorption tower, the No. 2 adsorption tower and the No. 3 adsorption tower are shown in Table 2.
TABLE 2
Example 3
Introducing dimethyl carbonate material with the concentration of 99.7% into the integrated device shown in figure 1 in sequence, wherein the mixture ratio of the compound adsorbent in each adsorption tower is shown as follows;
(1) an adsorption tower (No. 1 adsorption tower) at a feeding position of continuous rectification, wherein the dosage of the cationic resin in the composite adsorbent is 50 percent, and the dosage of the porous molecular sieve is 50 percent;
(2) an adsorption tower (2# adsorption tower) at the top reflux position of the low-pressure rectification tower, wherein the dosage of the cationic resin in the composite adsorbent is 10 percent, and the dosage of the porous molecular sieve is 90 percent;
(3) the adsorption tower (3# adsorption tower) at the product extraction position has the usage amount of the composite adsorbent porous molecular sieve of 50 percent and the aluminum oxide of 50 percent.
The DMC purity and the methanol and water content data of the material after being processed by the No. 1 adsorption tower, the No. 2 adsorption tower and the No. 3 adsorption tower are shown in Table 3.
TABLE 3
Example 4
Introducing dimethyl carbonate material with the concentration of 99.7% into the integrated device shown in figure 1 in sequence, wherein the mixture ratio of the compound adsorbent in each adsorption tower is shown as follows;
(1) an adsorption tower (No. 1 adsorption tower) at a feeding position of continuous rectification, wherein the dosage of the cationic resin in the composite adsorbent is 60 percent, and the dosage of the porous molecular sieve is 40 percent;
(2) an adsorption tower (2# adsorption tower) at the top reflux position of the low-pressure rectification tower, wherein the dosage of the cationic resin in the composite adsorbent is 20 percent, and the dosage of the porous molecular sieve is 80 percent;
(3) the adsorption tower (3# adsorption tower) at the product extraction position has the usage amount of the composite adsorbent porous molecular sieve of 50 percent and the aluminum oxide of 50 percent.
The DMC purity and the methanol and water content data of the material after being processed by the No. 1 adsorption tower, the No. 2 adsorption tower and the No. 3 adsorption tower are shown in Table 4.
TABLE 4
Example 5
Introducing dimethyl carbonate material with the concentration of 99.7% into the integrated device shown in figure 1 in sequence, wherein the mixture ratio of the compound adsorbent in each adsorption tower is shown as follows;
(1) an adsorption tower (No. 1 adsorption tower) at a feeding position of continuous rectification, wherein the dosage of the cationic resin in the composite adsorbent is 60 percent, and the dosage of the porous molecular sieve is 40 percent;
(2) an adsorption tower (2# adsorption tower) at the top reflux position of the low-pressure rectification tower, wherein the dosage of the cationic resin in the composite adsorbent is 50 percent, and the dosage of the porous molecular sieve is 50 percent;
(3) the adsorption tower (3# adsorption tower) at the product extraction position has the usage amount of the composite adsorbent porous molecular sieve of 50 percent and the aluminum oxide of 50 percent.
The DMC purity and the methanol and water content data of the material after being treated by the No. 1 adsorption tower, the No. 2 adsorption tower and the No. 3 adsorption tower are shown in Table 5.
TABLE 5
Example 6
Introducing dimethyl carbonate material with the concentration of 99.7% into the integrated device shown in figure 1 in sequence, wherein the mixture ratio of the compound adsorbent in each adsorption tower is shown as follows;
(1) an adsorption tower (No. 1 adsorption tower) at a feeding position of continuous rectification, wherein the dosage of the cationic resin in the composite adsorbent is 60 percent, and the dosage of the porous molecular sieve is 40 percent;
(2) an adsorption tower (2# adsorption tower) at the top reflux position of the low-pressure rectification tower, wherein the dosage of the cationic resin in the composite adsorbent is 10 percent, and the dosage of the porous molecular sieve is 90 percent;
(3) the adsorption tower (3# adsorption tower) at the product extraction position has the usage of 80% of the porous molecular sieve of the composite adsorbent and 20% of the aluminum oxide.
The DMC purity and the methanol and water content data of the material after being treated by the No. 1 adsorption tower, the No. 2 adsorption tower and the No. 3 adsorption tower are shown in Table 6.
TABLE 6
From the results in tables 1 to 6, it can be seen that the content of methanol and water in the dimethyl carbonate can be effectively reduced by installing a multi-stage adsorption column in the continuous rectification process unit, so that the purity of the finally obtained refined dimethyl carbonate can reach the battery grade product index requirement (99.99%).
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (10)
1. A method for purifying dimethyl carbonate, comprising:
adsorbing the materials by a first adsorption tower, and then sequentially introducing the materials into a first rectifying tower, a second rectifying tower and a third rectifying tower to obtain a primary product from the top of the third rectifying tower; and
and adsorbing the primary product by using a second adsorption tower, then shunting, introducing a part of the primary product into a third rectifying tower for reflux treatment, and introducing the other part of the primary product into a third adsorption tower for adsorption to obtain refined dimethyl carbonate.
2. The method of claim 1, wherein the material is a mixture of dimethyl carbonate and water, methanol, ethylene carbonate, ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether.
3. The method according to claim 1, wherein the adsorbents in the first adsorption column, the second adsorption column and the third adsorption column are each independently a mixture of two or more of a porous molecular sieve, a cationic resin and alumina.
4. The method according to claim 3, wherein the porous molecular sieve is used in an amount of 20 wt% to 40 wt% and the cationic resin is used in an amount of 60 wt% to 80 wt% in the first adsorption column.
5. The method according to claim 3, wherein the porous molecular sieve is used in an amount of 80 to 90 wt% and the cationic resin is used in an amount of 10 to 20 wt% in the second adsorption column.
6. The method of claim 3, wherein the porous molecular sieve is used in an amount of 40 wt% to 60 wt% and the alumina is used in an amount of 40 wt% to 60 wt% in the third adsorption column.
7. The method of claim 1, wherein the total content of methanol and water in the refined dimethyl carbonate is less than 30 PPm.
8. An integrated apparatus for refining dimethyl carbonate, comprising:
a material supply device;
a first adsorption tower, wherein the feeding end of the first adsorption tower is connected with the discharging end of the material supply device;
the feed end of the first rectifying tower is connected with the discharge end of the first adsorption tower;
the feed end of the second rectifying tower is connected with the discharge end of the first rectifying tower;
the feed end of the third rectifying tower is connected with the discharge end of the second rectifying tower;
a feed end of the second adsorption tower is connected with the top of the third rectifying tower, and a discharge end of the second adsorption tower is connected with the bottom of the third rectifying tower; and
and the feed end of the third adsorption tower is connected with the discharge end of the second adsorption tower.
9. The integrated device of claim 8, wherein the first adsorption tower, the second adsorption tower and the third adsorption tower are made of glass fiber reinforced plastic or polytetrafluoroethylene.
10. The integrated device according to claim 8, wherein the adsorbents in the first adsorption column, the second adsorption column, and the third adsorption column are each independently a mixture of two or more of a porous molecular sieve, a cationic resin, and alumina.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911391630.5A CN111100004B (en) | 2019-12-30 | 2019-12-30 | Method and integrated device for refining dimethyl carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911391630.5A CN111100004B (en) | 2019-12-30 | 2019-12-30 | Method and integrated device for refining dimethyl carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111100004A true CN111100004A (en) | 2020-05-05 |
| CN111100004B CN111100004B (en) | 2022-07-08 |
Family
ID=70424535
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911391630.5A Active CN111100004B (en) | 2019-12-30 | 2019-12-30 | Method and integrated device for refining dimethyl carbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111100004B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114349637A (en) * | 2022-01-06 | 2022-04-15 | 中建石化工程有限公司 | Method and device for preparing electronic grade dimethyl carbonate by melt crystallization coupling adsorption dehydration |
| CN115228119A (en) * | 2022-08-10 | 2022-10-25 | 宁波中科远东催化工程技术有限公司 | Dimethyl carbonate purification system and method |
| CN115417768A (en) * | 2022-09-23 | 2022-12-02 | 中国五环工程有限公司 | Energy coupling process for preparing dimethyl carbonate by liquid-phase oxidative carbonylation of methanol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105949061A (en) * | 2016-06-06 | 2016-09-21 | 南京工业大学 | Process and device for recovering dimethyl carbonate by steam permeation method |
| CN110105217A (en) * | 2019-06-12 | 2019-08-09 | 江苏凯美普瑞工程技术有限公司 | A kind of LITHIUM BATTERY dimethyl carbonate refining plant and method |
-
2019
- 2019-12-30 CN CN201911391630.5A patent/CN111100004B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105949061A (en) * | 2016-06-06 | 2016-09-21 | 南京工业大学 | Process and device for recovering dimethyl carbonate by steam permeation method |
| CN110105217A (en) * | 2019-06-12 | 2019-08-09 | 江苏凯美普瑞工程技术有限公司 | A kind of LITHIUM BATTERY dimethyl carbonate refining plant and method |
Non-Patent Citations (1)
| Title |
|---|
| 张丽红等: "《碳酸二甲酯提纯方法的研究进展》", 《河北化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114349637A (en) * | 2022-01-06 | 2022-04-15 | 中建石化工程有限公司 | Method and device for preparing electronic grade dimethyl carbonate by melt crystallization coupling adsorption dehydration |
| CN115228119A (en) * | 2022-08-10 | 2022-10-25 | 宁波中科远东催化工程技术有限公司 | Dimethyl carbonate purification system and method |
| CN115228119B (en) * | 2022-08-10 | 2024-04-02 | 宁波中科远东催化工程技术有限公司 | Dimethyl carbonate purification system and method |
| CN115417768A (en) * | 2022-09-23 | 2022-12-02 | 中国五环工程有限公司 | Energy coupling process for preparing dimethyl carbonate by liquid-phase oxidative carbonylation of methanol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111100004B (en) | 2022-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111100004B (en) | Method and integrated device for refining dimethyl carbonate | |
| CN102898405B (en) | Process for preparing epoxypropane by directly using epoxidation propylene through hydrogen peroxide | |
| CN105111079A (en) | Method and device for separating acetic acid sec-butyl ester and sec-butyl alcohol | |
| CN112225650B (en) | Refining method for obtaining high-purity methylal by purifying industrial-grade methylal | |
| CN117599690B (en) | Device and method for producing methyl ethyl carbonate and diethyl carbonate | |
| CN111087288B (en) | Purification method of dimeric methoxy dimethyl ether | |
| CN111072481A (en) | Device and method for producing high-concentration dimethyl carbonate | |
| CN112010755B (en) | System for purifying crude dimethyl carbonate by pressure-variable double-effect rectification | |
| CN102471194A (en) | Method and system for producing methanol and dimethyl ether | |
| CN111377801B (en) | Method and system for refining low carbon alcohol | |
| CN218636644U (en) | Device for separating dimethyl carbonate and methanol azeotrope with low energy consumption | |
| CN111087286A (en) | Method for refining polymethoxy dimethyl ether dimer | |
| CN115057761A (en) | Method for producing purified ethyl tert-butyl ether by reactive distillation coupled extraction distillation dividing wall tower technology | |
| CN211946867U (en) | Device for preparing high-purity methylal by synchronously operating extraction and rectification | |
| CN114949907A (en) | Device and method for separating dimethyl carbonate and methanol azeotrope with low energy consumption | |
| CN114249676A (en) | Method and device for purifying and separating methyl mercaptan | |
| CN208279528U (en) | A kind of integrated acetylene recycle device | |
| CN110698340A (en) | Process method for producing ethyl lactate by reactive distillation dividing wall tower technology | |
| CN110668920A (en) | Method for preparing ethanol and co-producing cyclohexanol by using reactive distillation method | |
| CN201823480U (en) | Concentration-separation device for di methyl carbonate and methanol | |
| CN111646900A (en) | Separation system and separation method for dimethyl carbonate and methanol | |
| CN220513452U (en) | Piperidine separation and purification system | |
| CN115228119B (en) | Dimethyl carbonate purification system and method | |
| CN216725835U (en) | Partition plate type methyl propionate reaction rectifying tower with coupling hydrogenation | |
| CN115724717B (en) | Method for co-production of methanol by separating low-carbon mixed alcohol |
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 | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A method and integrated device for refining dimethyl carbonate Effective date of registration: 20221226 Granted publication date: 20220708 Pledgee: Bank of China Limited by Share Ltd. Yizheng branch Pledgor: JIANGSU OXIRANCHEM Co.,Ltd. Registration number: Y2022980028595 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Granted publication date: 20220708 Pledgee: Bank of China Limited by Share Ltd. Yizheng branch Pledgor: JIANGSU OXIRANCHEM Co.,Ltd. Registration number: Y2022980028595 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |