CN1523005A - Reaction rectification process for interesterification synthesis of carbonic acid diaryl ester - Google Patents
Reaction rectification process for interesterification synthesis of carbonic acid diaryl ester Download PDFInfo
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- CN1523005A CN1523005A CNA031357458A CN03135745A CN1523005A CN 1523005 A CN1523005 A CN 1523005A CN A031357458 A CNA031357458 A CN A031357458A CN 03135745 A CN03135745 A CN 03135745A CN 1523005 A CN1523005 A CN 1523005A
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Abstract
The present invention relates to a reaction rectification integrated process for synthesizing diaryl carbonate (for example diphenyl carbonate) by using dialkyl carbonate (for example dimethyl carbonate) and monoarylhydroxyl compound (for example phenol) as raw material and adopting ester exchange reaction. It is characterized by that said process includes the following steps: preheating and mixing the ester exchange catalyst and arylhydroxyl compound, continuously feeding the obtained mixture into the tower top of reaction rectification equipment, controlling proportion of reaction materials, reaction temp. and pressure to make whole reaction be favorable for formation of diaryl carbonate, and can effectively destroy the azeotropic phenomenon produced by dialkyl carbonate and low-carbon alcohol so as to can high-effectively obtain low-carbon alcohol from tower top. Said invention also provides the reaction condition for implementing ester exchange.
Description
The present invention relates to a kind of is raw material with dialkyl carbonate (as methylcarbonate) and single aromatic hydroxy compound (as phenol), the reactive distillation integral process of transesterify carbonate synthesis diaryl ester (as diphenyl carbonate).
Diaryl carbonate (particularly diphenyl carbonate) is a kind of important organic intermediate, can be used for synthetic medicine, agricultural chemicals and other products.And diaryl carbonate is the important intermediate that melt transesterification prepares polycarbonate, has very high industrial value.The method that melting state transesterification reaction prepares polycarbonate is a kind of eco-friendly method, and it has avoided employed objectionable impurities in the traditional method, as phosgene, METHYLENE CHLORIDE etc.
Melting state transesterification reaction prepares employed diaryl carbonate in the polycarbonate (for example diphenyl carbonate), and available a kind of single aromatic hydroxy compound (for example phenol, methylphenol, xylenol etc.) carries out transesterification reaction with a kind of dialkyl carbonate (as methylcarbonate, diethyl carbonate) and makes.Typical catalyzer is organo-tin compound (as a Dibutyltin oxide), organic titanic compound (as tetrabutyl titanate).
The technology of carbonate synthesis diaryl ester has multiple, and the synthesis route that wherein belongs to the transesterify class mainly contains following several:
Chinese patent CN 1394848 introduced a kind of with hydrotalcite or houghite as catalyzer, catalysis of phenol or fortified phenol and methylcarbonate carry out the processing method of transesterify carbonate synthesis diaryl ester.The mol ratio of phenol or fortified phenol/methylcarbonate is 2～4/1, and catalyzer accounts for 1.0～5.0% of system gross weight, reacts 150～250 ℃ of temperature of reaction, reaction times 8～24hr under nitrogen protection.Product can obtain purity greater than 99.5% diaryl carbonate product through separating.Productive rate is 24.7～33.4%, product selectivity 87.0～90.3%.Catalyzer is recyclable.This technology is raw material and the disposable adding of catalyzer, is actually with transesterify three and is reflected in the reactor and finishes, and temperature constantly raising, belongs to a kind of astable reaction process in the reaction process, is unfavorable for industrial implementation.And in reaction process timely separating by-products---low-carbon alcohol (methyl alcohol), make that the overall yield of this technology is not high.
Japanese Patent JP7330687 has introduced a kind of ester exchange process of reaction, extraction rectifying.Catalyzer, methylcarbonate and small amount of phenol are added at the bottom of the still of reaction and rectification device, most of phenol is added from cat head.Methyl alcohol that transesterification reaction produces and dimethyl carbonate azeotrope are destroyed by the phenol that adds from top, and methylcarbonate is extracted, but cat head extraction high purity methanol.The continuous extraction reaction solution of tower still.
European patent EP 0780361, EP0781760 have introduced a kind of pressurization successive reactive distillation process, and methylcarbonate adds from reactor bottom, phenol and catalyzer or add from the reactor bottom, and perhaps the middle part from rectifying tower adds.Cat head tower still is continuous extraction material respectively, makes system reach balance.The temperature of reaction of system is 220～250 ℃, and pressure is 8～14atm, reflux ratio 1: 1.DMC in this technology is excessive with respect to phenol, and ester exchange offspring mainly is a methyl benzol carbonate.Because it is not obvious that phenol amount relative deficiency, phenol are destroyed the extraction effect of azeotrope.
The present invention relates to a kind of is raw material with dialkyl carbonate (as methylcarbonate) and single aromatic hydroxy compound (as phenol), the reactive distillation integral process and the equipment of transesterify carbonate synthesis diaryl ester (as diphenyl carbonate) are applicable to homogeneous phase or heterogeneous catalyst system.The net reaction of transesterify is as follows:
R in the formula
1Represent any one in the following group: H, CH
3, CH
3CH
2, F, Cl, Br, NO
2, CN, RO.R
2Represent CH
3Or CH
2CH
3
(1) reaction process of formula can be divided into following three the step carry out:
The major equipment that ester exchange process described in the invention comprises comprises: equipment such as premix still, transesterification reactor, multi-functional extractive distillation column, disproportionation tower, interchanger, gas-liquid separator, transferpump, relay tank.The schema of this trans-esterification processes is seen accompanying drawing 1.
Description of drawings: accompanying drawing 1 is a technical process schematic diagram of the present invention.Wherein, R101---premix still; R102---transesterification reactor; T101---multi-functional extractive distillation column; T102---disproportionation tower; V101---middle tank body; V102,103---gas-liquid separator; E---interchanger; P---transferpump
Ester exchange technique described in the invention mainly contains following characteristics:
(A) adopt the two-part reaction process, in ester exchange reaction device R102, the reaction of (2)～(4) formula is all being carried out, and purpose is that the conversion ratio with reaction raw materials remains on a higher level; In disproportionation tower T102, mainly take reaction (3) as main, purpose is to improve the concentration of diaryl carbonate with selective, is beneficial to separate.
(B) the molar flow ratio of single aromatic hydroxy compound and dialkyl carbonate is 6～10/1, the excessive purpose of single aromatic hydroxy compound has two: first, the dialkyl carbonate that a large amount of single aromatic hydroxy compounds can produce R102 and the azeotropic mixture of low-carbon alcohols destroy, so that the T101 extractive distillation column the highly purified low-carbon alcohols of the direct extraction of cat head, reduced post processing. The second, the excessive course of reaction highly selective that can guarantee of single aromatic hydroxy compound generates diaryl carbonate, has simplified separating technology.
(C) catalyst and single aromatic hydroxy compound add from cat head, can not only effectively destroy the azeotropic mixture that enters at the bottom of the tower, make the highly purified low-carbon alcohols of extractive distillation column cat head energy extraction, and prolonged the time of staying of catalyst in reaction system, improved conversion ratio and the target product productive rate of raw material.
(D) the extraction rectification process adopts pressure process, pressurization can destroy the azeotropic mixture that enters at the bottom of the extractive distillation column tower, efficiently separates low-carbon alcohols, and reduces the consumption as single aromatic hydroxy compound of extractant.
Operating process:
Aromatic hydroxy compound enters premix still R101, under heating condition catalyzer is fully dissolved.This solution adds from the top of multi-functional extractive distillation column T101.The dialkyl carbonate ester cpds enters transesterification reactor R102 and reacts, and the low-carbon alcohol of generation and part dialkyl carbonate azeotropic come out, and enter the bottom of multi-functional extractive distillation column T101.
Above-mentioned two strands of materials interact at T101: the aromatic hydroxy compound that adds from cat head can destroy the azeotrope that enters at the bottom of the tower effectively, makes the T101 cat head can the higher low-carbon alcohol of extraction purity; In addition, the aromatic hydroxy compound that has dissolved catalyzer can react in tower body with dialkyl carbonate, and the Single-aryl ester carbonate of generation and diaryl ester compound also can play the effect that destroys azeotrope.
Material in the T101 reboiler pumps into the further transesterify of transesterification reactor R102, and keeps the material balance of R102.Enter disproportionation tower T102 from the reaction solution of R102 extraction.In the disproportionation tower, the Single-aryl ester carbonate disproportionation generates diaryl carbonate.T102 cat head extraction disproportionation by product dialkyl carbonate returns R102 and recycles; The thick product of extraction diaryl carbonate at the bottom of the tower.
Specific implementation method:
[example one] adopts technical process shown in the accompanying drawing 1, reaction process as previously mentioned, dialkyl carbonate is a methylcarbonate, aromatic hydroxy compound is a phenol, the Single-aryl ester carbonate that generates is a methyl benzol carbonate, and the diaryl carbonate of generation is a diphenyl carbonate.Wherein, the R101 preheating temperature is 80 ℃, and the R102 temperature of reaction is 245 ℃, reaction pressure 0.33MPa.The T101 tower top temperature is 97 ℃, and tower still temperature is 228 ℃, and pressure is 0.33MPa.The T102 tower top temperature is 120 ℃, and tower still temperature is 221 ℃, and working pressure is 0.25MPa.Whole process is full steady-state process continuously, methylcarbonate per pass conversion 93.2%, diphenyl carbonate selectivity 86.6% after the disproportionation.The mass flow Measurement and analysis value of each operating point is as shown in table 1.
The mass flow of each operating point (g/hr) in table 1. example one
| Material variety | The material point | |||||||
| ????A | ????B | ???C | ????D | ????E | ????F | ????G | ???H | |
| Methylcarbonate | ??125.8 | ???0 | ??488.8 | ??478.2 | ??8.5 | ???0.8 | ????18.9 | ???0 |
| Phenol | ??0 | ???1223.6 | ??0 | ??1198.1 | ??1026.2 | ???0 | ????0 | ???1018.3 |
| Methyl alcohol | ??0 | ???0 | ??65.1 | ??0 | ??0 | ???64.2 | ????0 | ???0 |
| Methyl benzol carbonate | ??0 | ???0 | ??0 | ??9.1 | ??71.6 | ???0 | ????0 | ???6.3 |
| Diphenyl carbonate | ??0 | ???0 | ??0 | ??1.2 | ??167.3 | ???0 | ????0 | ???259.2 |
| Catalyzer | ??0 | ???267.5 | ??0 | ??264.5 | ??265.8 | ???0 | ????0 | ???262.1 |
Claims (4)
1. one kind is raw material with dialkyl carbonate (as methylcarbonate) and single aromatic hydroxy compound (as phenol), the reactive distillation integral process of transesterify carbonate synthesis diaryl ester (as diphenyl carbonate).It is characterized in that the main equipment of technical process is premix still, transesterification reactor, multi-functional extractive distillation column, disproportionation tower, interchanger, gas-liquid separator, transferpump, relay tank etc.Whole technology is divided into following step:
(1) dialkyl carbonate directly adds transesterification reactor.
(2) aromatic hydroxy compound mixes stirring with catalyzer at the premix still, after preheating, adds from multi-functional extracting rectifying top of tower, destroys the azeotrope that dialkyl carbonate and by product low-carbon alcohol form.
(3) multi-functional extractive distillation column has certain working pressure, is used to destroy the azeotrope of dialkyl carbonate and low-carbon alcohol formation.
(4) partial material in the cat head extraction low-carbon alcohol of multi-functional extractive distillation column, reboiler is returned transesterification reactor, to keep material balance, extraction reaction solution at the bottom of the transesterification reactor still.
(5) reaction solution enters the disproportionation tower, and the dialkyl carbonate of disproportionation column overhead extraction returns transesterification reactor and recycles, the thick product of tower still extraction diaryl carbonate.
(6) entire reaction is full successive processes, and system is in stable state.
2. during stable state, the mol ratio of the single aromatic hydroxy compound that replenishes and the flow of dialkyl carbonate is 6～10/1,180～250 ℃ of transesterification reaction temperature, transesterification reaction pressure 0.1～1.5MPa, 90～130 ℃ of multi-functional extractive distillation column tower top temperatures, 190～250 ℃ of tower still temperature, 120～250 ℃ of disproportionation reaction temperature, disproportionation reaction pressure 0.1～1.5MPa.
3. as technology as described in claim 1 and 2, it is characterized in that controlling 180～220 ℃ of transesterification reaction temperature, 180～220 ℃ of disproportionation temperature.
4. as technology as described in claim 1 and 2, it is characterized in that controlling reaction pressure at 0.1～0.5MPa, disproportionation pressure is at 0.1～0.5MPa.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA031357458A CN1523005A (en) | 2003-09-04 | 2003-09-04 | Reaction rectification process for interesterification synthesis of carbonic acid diaryl ester |
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| CNA031357458A CN1523005A (en) | 2003-09-04 | 2003-09-04 | Reaction rectification process for interesterification synthesis of carbonic acid diaryl ester |
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| CNA031357458A Pending CN1523005A (en) | 2003-09-04 | 2003-09-04 | Reaction rectification process for interesterification synthesis of carbonic acid diaryl ester |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100343223C (en) * | 2005-03-07 | 2007-10-17 | 常州市智能动物药业有限公司 | Ester compound of thymol and/or carvacrol, preparing method and its medicinal active composition |
| CN101768082A (en) * | 2010-01-26 | 2010-07-07 | 华东理工大学 | Method for continuously diphenyl carbonate |
| CN107739311A (en) * | 2017-11-28 | 2018-02-27 | 屈强好 | The method that azeotropic mixture is handled in dimethyl carbonate technique and diphenyl carbonate technique |
| CN111943872A (en) * | 2019-05-17 | 2020-11-17 | 北京芯友工程技术有限公司 | Continuous process and device for synthesizing high-ester exchange rate sodium bis (hydroxyethyl) isophthalate-5-sulfonate through catalytic reaction rectification |
| CN111943873A (en) * | 2019-05-17 | 2020-11-17 | 北京芯友工程技术有限公司 | Semi-continuous process and device for synthesizing m-phthalic acid dihydroxy ethyl ester-5-sodium sulfonate with high ester exchange rate through catalytic reaction rectification |
| CN113577814A (en) * | 2021-08-16 | 2021-11-02 | 四川中蓝国塑新材料科技有限公司 | Diphenyl carbonate recovery device and method for industrial production of polycarbonate |
-
2003
- 2003-09-04 CN CNA031357458A patent/CN1523005A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100343223C (en) * | 2005-03-07 | 2007-10-17 | 常州市智能动物药业有限公司 | Ester compound of thymol and/or carvacrol, preparing method and its medicinal active composition |
| CN101768082A (en) * | 2010-01-26 | 2010-07-07 | 华东理工大学 | Method for continuously diphenyl carbonate |
| CN101768082B (en) * | 2010-01-26 | 2013-06-19 | 华东理工大学 | Method for continuously diphenyl carbonate |
| CN107739311A (en) * | 2017-11-28 | 2018-02-27 | 屈强好 | The method that azeotropic mixture is handled in dimethyl carbonate technique and diphenyl carbonate technique |
| CN111943872A (en) * | 2019-05-17 | 2020-11-17 | 北京芯友工程技术有限公司 | Continuous process and device for synthesizing high-ester exchange rate sodium bis (hydroxyethyl) isophthalate-5-sulfonate through catalytic reaction rectification |
| CN111943873A (en) * | 2019-05-17 | 2020-11-17 | 北京芯友工程技术有限公司 | Semi-continuous process and device for synthesizing m-phthalic acid dihydroxy ethyl ester-5-sodium sulfonate with high ester exchange rate through catalytic reaction rectification |
| CN113577814A (en) * | 2021-08-16 | 2021-11-02 | 四川中蓝国塑新材料科技有限公司 | Diphenyl carbonate recovery device and method for industrial production of polycarbonate |
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