CN104262086A - Device for synthesizing carbonic ester by removing methanol by adopting packed bed ester exchange-adsorption - Google Patents
Device for synthesizing carbonic ester by removing methanol by adopting packed bed ester exchange-adsorption Download PDFInfo
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- CN104262086A CN104262086A CN201410443824.6A CN201410443824A CN104262086A CN 104262086 A CN104262086 A CN 104262086A CN 201410443824 A CN201410443824 A CN 201410443824A CN 104262086 A CN104262086 A CN 104262086A
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- packed bed
- methanol
- ester
- absorption
- transesterify
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/128—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis
- C07C29/1285—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis of esters of organic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
In order to increase the yield of carbonic ester, the invention discloses a technical device for producing carbonic ester by using a solid catalyst to catalyze the reaction of dimethyl carbonate (DMC) and alcohol and adopting a solid adsorbent to adsorb a product methanol. According to a method, a packed bed is in series connection outside an ester exchange reactor to adsorb methanol, so that the yield of carbonic ester is increased. According to the device for synthesizing carbonic ester by a packed bed ester exchange-adsorption and methanol removal combination process, the method comprises the following steps: (1) selecting a packed bed absorbing tower (a methanol adsorbing device); and (2) installing an ester exchange reactor-packed bed. According to the method disclosed by the invention, a technology of enabling DMC to externally circulate and using an adsorbing and methanol removing device is adopted in a process of catalyzing the reaction of DMC and methanol by virtue of the solid catalyst, so that reference is provided for development and research in preparing carbonic ester by adopting a packed bed ester exchange-adsorption combination process as well as ester exchange esterification process production in the industry, and practical and economic significances are also achieved.
Description
Technical field
What the present invention proposed is the coupling solid adsorbent adsorbed product methanol production carbonic ether technique device when catalysis of solid catalyst methylcarbonate and alcohol react.
Background technology
Along with people are to the attention of environment protection, industrial chemicals environmentally friendly in Chemical Manufacture is subject to increasing favor.In recent years, green chemical industry oxide spinel dimethyl ester (DMC) becomes the organic synthesis intermediate of domestic and international chemical field extensive concern, is described as " the new foundation stone " of organic synthesis.When carbonic ether is discharged in environment, carbonic acid gas and the harmless product of unit molecule alcohol two kinds can be hydrolyzed to lentamente.Containing reactive groups such as alkyl, alkoxyl group, carbonyl and carbonyl alkoxyl groups in the molecular structure of carbonic ether; chemical property is very active; can react with compounds such as alcohol, phenol, amine, ester and amino alcohols, be important organic synthesis intermediate, there is very high industrial application value.
As Methyl ethyl carbonate, dipropyl carbonate can be used as lithium-ion battery electrolytes,, safety and stability strong to the solvability of lithium salts, energy density and the loading capacity of battery can be improved, good low temperature use properties, be widely used in the high-grade electric appliance such as mobile phone, notebook computer; Diethyl carbonate can be used as paint, Mierocrystalline cellulose and resin equal solvent, fixes in paint for vacuum tube cathode, as tensio-active agent and lithium cell solution additive, substitute the oxygenated additive etc. that methyl tertiary butyl ether (MTBE) makes gasoline and diesel-fuel; Dibutyl carbonate can be used to diphenyl carbonate synthesis, and then polycarbonate synthesis, also can be used as the substrate material of lubricating oil, for industries such as metal degreasing, leather process; Di-2-ethyhexyl carbonate0 can be used as the dispersion agent of photographic camera photosensitive system material, and has good lubricity, is a kind of excellent lubrication base material; Carbonic acid high-carbon alcohol ester (C12-C18) carbonic acid two lauryl alcohol ester is a kind of transparent liquid or oily matter, there is lower pour point and good oilness, self-cleaning property, wear resistance, erosion resistance, higher thermo-oxidative stability, with hydrocarbon-type oil, there is good solubility, biodegradable, be a kind of well lubricating oil base.Although and in the ester-interchange method synthesis technique of carbonic ether, have higher selectivity, there is ester yield low, after underpressure distillation, be difficult to obtain the problems such as purer carbonic ether; If methylcarbonate and carbon alcohol carry out can be real-time in transesterify synthesizing carbonate ester reaction process technique effectively remove secondary resultant methyl alcohol, the direction that just balance can be made to generate to reactant is moved, promote that reaction positive dirction is carried out, to increase esterification yield and yield, obtain more product; Simplify follow-up process for refining simultaneously, reduce in purified product process and produce load, save the energy.
Therefore invented in the ester-interchange method synthetic reaction process of carbonic ether, utilize DMC and methyl alcohol outer circulation also by the technology of adsorbing separating methanol device methanol removal, this transesterify absorption dealcoholysis process integration is that the development and research adopting packed bed transesterify absorption process integration to prepare carbonic ether provides reference, also has practical and economic double meaning simultaneously.
Summary of the invention
In order to improve the yield of carbonic ether, when the present invention proposes in catalysis of solid catalyst methylcarbonate and carbon alcohol reaction process, utilization is under boiling or micro-state of boiling, and the methyl alcohol that the methylcarbonate of components vaporize and reaction generate enters outer circulation also by the new technology of absorption separating methanol device continuously through gas phase condenser condensation.The method to be connected outward packed bed absorption tower in transesterification reactor, technical grade 4A molecular sieve adsorption methyl alcohol is filled in packed bed absorption tower, thus can be real-time in ester-exchange reaction effectively remove by-product carbinol, destruction transesterification reaction balances, improve molecular balance transformation efficiency, and then improve the yield of carbonic ether.
the scheme that packed bed transesterify of the present invention-absorption separating methanol integrated process carbonate synthesis ester apparatus is taked is:
1, the selecting of packed bed absorption tower (absorption methanol device)
Choose the packed bed absorption tower of suitable shape, the then full methanol adsorption agent of filling in tower body, then install with transesterification reactor.
2, transesterification reactor-packed bed is installed
By being sequentially connected in series interchanger outside transesterification reactor, water distributing can, packed bed absorption tower form a closed circulating reaction system.
Packed bed transesterify can be adopted in catalysis of solid catalyst methylcarbonate and alcohol reaction process to adsorb separating methanol process integration by arranging the molecular sieve filled bed of outer circulation by method of the present invention, adopt the by-product carbinol that the reaction of molecular sieve liquid phase adsorption separating methanol technology separation generates, the energy consumption of whole production process is lower, DMC simultaneously after separating methanol returns transesterification reactor continuously, ensure that transesterification reaction is carried out under the condition of higher ester/alcohol mol ratio, the chemical equilibrium of transesterification reaction is constantly moved, whole esterification system is made to react more abundant, the features such as whole reaction process has that process energy consumption is low, product yield is high, the throughput of reactor is large and sepn process load is little.Therefore, adopt the technology of packed bed transesterify-absorption separating methanol integrated process carbonate synthesis ester apparatus will produce for transesterify esterification technique in chemical industry production and provide reference, also there is practical and economic double meaning simultaneously.
Accompanying drawing explanation
Fig. 1 is packed bed of the present invention transesterify-absorption separating methanol integrated process carbonate synthesis ester apparatus.
Embodiment
Packed bed transesterify according to Fig. 1-absorption separating methanol integrated process carbonate synthesis ester apparatus carries out the yield improving carbonic ether in the ester-interchange method reaction process of carbonic ether.
1, the selecting of packed bed absorption tower (absorption methanol device)
Choose the absorption tower T04 of packed bed as shown in Figure 1 of suitable shape, then the full methanol adsorption agent 4A molecular sieve of filling in tower body, utilize 4A adsorbent of molecular sieve in the T04 of packed bed absorption tower to carry out Methanol product in absorption reaction system, then install with transesterification reactor R01.
2, transesterification reactor-packed bed is installed
Install by Fig. 1 shown device figure, interchanger E02 is sequentially connected in series outside transesterification reactor R01, relay tank V03, packed bed absorption tower T04, again packed bed absorption tower T04 is connected and be back to transesterification reactor R01, full methanol adsorption agent (4A molecular sieve) is filled in the T04 of packed bed absorption tower, 4A molecular sieve in the T04 of packed bed absorption tower is utilized to carry out by-product carbinol in absorption reaction system, constitute closed circulating reaction system, the Methanol product generated in Exchange Ester Process can constantly to be adsorbed effectively in real time, shift out reaction system, thus accelerate the carrying out of transesterification reaction, strengthen esterification yield, reach the object improving carbonic ether yield.
Claims (3)
1. utilize and react simultaneously at catalysis of solid catalyst methylcarbonate and alcohol, solid adsorbent adsorbed product methanol production carbonic ether technique device is adopted to inhale the method improving the yield of carbonic ether, this installs with transesterification reactor-packed bed comprising selecting of packed bed (absorption methanol device), adopts packed bed transesterify-absorption separating methanol integrated process carbonate synthesis ester apparatus detailed process as follows:
Selecting of packed bed absorption tower (absorption methanol device)
Choose the packed bed absorption tower of suitable shape, the then full methanol adsorption agent of filling in tower body, then install with transesterification reactor.
2. transesterification reactor-packed bed is installed
By being sequentially connected in series interchanger outside transesterification reactor, water distributing can, packed bed absorption tower form a closed circulating reaction system.
3. by method of the present invention can in catalysis of solid catalyst methylcarbonate and carbon alcohol reaction process time, utilize under boiling or micro-state of boiling, the by-product carbinol that the methylcarbonate of components vaporize and reaction generate enters outer circulation continuously through gas phase condenser condensation and uses the technology of absorption separating methanol device, this transesterify and absorption separating methanol process integration are adopts packed bed transesterify adsorb process integration to prepare transesterify lactate synthesis explained hereafter in the development and research of ester and industry and provide reference, while also there is practicality and economic double meaning.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410443824.6A CN104262086A (en) | 2014-09-03 | 2014-09-03 | Device for synthesizing carbonic ester by removing methanol by adopting packed bed ester exchange-adsorption |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410443824.6A CN104262086A (en) | 2014-09-03 | 2014-09-03 | Device for synthesizing carbonic ester by removing methanol by adopting packed bed ester exchange-adsorption |
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| CN104262086A true CN104262086A (en) | 2015-01-07 |
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| CN201410443824.6A Pending CN104262086A (en) | 2014-09-03 | 2014-09-03 | Device for synthesizing carbonic ester by removing methanol by adopting packed bed ester exchange-adsorption |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610059A (en) * | 2015-01-15 | 2015-05-13 | 吉林化工学院 | Method for synthesizing methyl-acrylate through ester exchange and adsorption removal of methanol |
| CN104710306A (en) * | 2015-01-12 | 2015-06-17 | 吉林化工学院 | Method for preparing acetate through ester interchange-adsorption ethanol removal combined technology |
| CN107459461A (en) * | 2017-09-22 | 2017-12-12 | 吉林化工学院 | It is a kind of（Alkyl）The preparation method and system of acrylate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320594A (en) * | 2001-04-03 | 2001-11-07 | 华东理工大学 | Process for continuously preparing diethyl carbonate |
| CN1569811A (en) * | 2004-04-22 | 2005-01-26 | 宁夏大学 | Process for synthesizing dibutyl carbonate |
-
2014
- 2014-09-03 CN CN201410443824.6A patent/CN104262086A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320594A (en) * | 2001-04-03 | 2001-11-07 | 华东理工大学 | Process for continuously preparing diethyl carbonate |
| CN1569811A (en) * | 2004-04-22 | 2005-01-26 | 宁夏大学 | Process for synthesizing dibutyl carbonate |
Non-Patent Citations (6)
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| 丁斌等: "丁二酸催化酯化−吸附脱水联合工艺", 《过程工程学报》 * |
| 丁斌等: "丁二酸催化酯化−吸附脱水联合工艺", 《过程工程学报》, vol. 7, no. 1, 28 February 2007 (2007-02-28), pages 100 - 104 * |
| 丁斌等: "催化酯化-吸附脱水联合工艺合成特戊酸乙酯及动力学", 《日用化学工业》 * |
| 俞能志: "酯交换法合成碳酸二乙酯工艺过程控制", 《安徽化工》 * |
| 关昶等: "酯交换－吸附脱甲醇工艺制备碳酸异辛酯的研究", 《化学世界》 * |
| 李祥等: "丁二酸二异丙酯的合成及其动力学研究", 《日用化学工业》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710306A (en) * | 2015-01-12 | 2015-06-17 | 吉林化工学院 | Method for preparing acetate through ester interchange-adsorption ethanol removal combined technology |
| CN104610059A (en) * | 2015-01-15 | 2015-05-13 | 吉林化工学院 | Method for synthesizing methyl-acrylate through ester exchange and adsorption removal of methanol |
| CN107459461A (en) * | 2017-09-22 | 2017-12-12 | 吉林化工学院 | It is a kind of（Alkyl）The preparation method and system of acrylate |
| CN107459461B (en) * | 2017-09-22 | 2020-05-08 | 吉林化工学院 | Preparation method and system of (alkyl) acrylate |
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Application publication date: 20150107 |