CN1562955A - Technique and equipment for synthesizing diaryl carbonate through catalyzing rectification - Google Patents
Technique and equipment for synthesizing diaryl carbonate through catalyzing rectification Download PDFInfo
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- CN1562955A CN1562955A CN 200410012900 CN200410012900A CN1562955A CN 1562955 A CN1562955 A CN 1562955A CN 200410012900 CN200410012900 CN 200410012900 CN 200410012900 A CN200410012900 A CN 200410012900A CN 1562955 A CN1562955 A CN 1562955A
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Abstract
This invention relates to ester-exchange reaction to produce diaryl carbonate; by using phenol, substituted phenol, aromatic alcohols reacting with dimethyl carbonate in an integral reaction/separation system. In said system, synthetic reactor and rectifying still are combined, reactor and pressure rectifying still are connected to form a set of processing system. Advantages are: fully utilizing dimethyl carbonate, high yield of diaryl carbonate, simplifying prodn. process, lowering prodn. cost.
Description
Technical field
The present invention relates to a kind of phenol, fortified phenol or aromatic alcohol and methylcarbonate production technique and reaction unit under the compression rectification catalytic reaction condition through the transesterification reaction synthesizing diaryl carbonic acid ester.
Background technology
Diaryl carbonate particularly diphenyl carbonate (DPC) is subjected to the extensive concern of each side because of its wide application prospect, and its industrial production method mainly contains phosgenation, oxidation of phenol carbonyl process and ester-interchange method.Because phosgenation can cause environmental pollution and equipment corrosion, should not promote.Research to DPC both at home and abroad focuses mostly at oxidative carbonylation and ester-interchange method, but the catalyst efficiency that the oxidative carbonylation method is used is not high, realizes that the industrialization difficulty is very big.Ester-interchange method reaction conditions gentleness, the product yield height is so ester-interchange method is considered to the synthetic at present optimum method of DPC.But ester-interchange method is owing to be subjected to the restriction of thermodynamic(al)equilibrium, exists that per pass conversion is low, methylcarbonate (DMC) and by-product carbinol (CH
3OH) problem such as difficult separations, a whole set of technical process is comparatively complicated, syntheticly needs proceed step by step or adopts subregion to react and separating technology with separating.
In the reaction of phenol, fortified phenol or aromatic alcohol and DMC synthesizing diaryl carbonic acid ester, mainly there are following three reactions.
Wherein phenol, fortified phenol or aromatic alcohol and DMC synthesizing diaryl carbonic acid ester are balanced reaction.If the by-product carbinol of reaction is removed from reaction system, can break molecular balance, balance is moved to the direction that generates diaryl carbonate, can improve the transformation efficiency of DMC like this and shorten the reaction times.
Traditional ester-interchange method synthesizing diaryl carbonic acid ester technology as the synthetic DPC of catalytic transesterification method, is to react under non-pressurized condition, DMC and the by product CH that is produced
3OH mixes and steams, and transfers to then and separates CH in another distillation system
3OH and DMC.
Propose with two separation columns as document JP-07101908-A, one is used for carbonate synthesis aminomethyl phenyl ester (MPC) and DPC, and another is extraction agent extracting and separating DMC and CH with dimethyl oxalate (DMO)
3OH, DMC then circulates.Also take similar technology to synthesize MPC among the EP-785184-A.
Used two bank of reactor and two separation columns to synthesize MPC and DPC, separation of C H respectively in the JP-04235951-A document
3OH and DMC.DMC and phenol add continuously from the top of first separation column, are fed in then in the outer bank of reactor (4 reactors, catalyzer therein) of tower, and the MPC mixture of generation is recycled in the separation column again, CH
3OH discharges from cat head, and MPC discharges at the bottom of tower, delivers to the top of second separation column, flows into downwards in second bank of reactor, and the MPC reaction generates the mixture of DPC and DMC, is recycled in second separation column and separates, and the DMC circulation obtains DPC at the bottom of the tower.
Document JP-0959225-A has designed three separation columns, synthetic MPC in first tower, and cat head is discharged DMC, CH
3The azeotrope of OH generates DPC and DMC by the MPC disproportionation reaction in second tower, and DMC recycles, the DMC that generates in the 3rd tower, CH
3OH etc. send in first tower and circulate.
Designed one in the WO-18458-A document and overlapped the device that contains 3 continuous reaction zones, DPC is synthetic in the 3rd district.The gas phase DMC and the CH that generate in preceding two districts
3OH sends in the separation column and separates, the DMC circulation.
Compression rectification is separated two kinds of materials the characteristics that Raoult's law produces deviation according to the M1-M2 azeotrope, and pressurize can change the azeotropic point of azeotrope that M1-M2 forms, and changes the composition of azeotrope.Adopt the compression rectification method can make DMC and CH
3The OH azeotrope is effectively separated, and (different pressures is to DMC and CH
3The relation that the OH azeotrope is formed is seen attached list).Under elevated pressures, cat head can obtain with CH
3OH is main azeotrope (CH
3OH content 〉=93wt%), obtain pure DMC at the bottom of the tower.
CH under the subordinate list different pressures
3The composition of OH-DMC azeotrope and the relation of azeotropic temperature
Pressure/MPa 0.1 0.2 0.4 0.8 1.0 1.5
Azeotropic composition/%CH
3OH 70.0 73.4 79.3 85.2 87.7 93.0
(massfraction) DMC 30.0 26.6 17.5 14.8 12.4 7.0
Azeotropic temperature/℃ 64.0 82.0 104.0 118.0 138.0 155.0
If the reacting phase of compression rectification with the ester-interchange method synthesizing diaryl carbonic acid ester combined, can reach and remove the by product CH that reaction generates
3The purpose of OH also can reduce with CH simultaneously significantly
3The amount of the DMC that OH removed, thus make reaction raw materials DMC obtain fully effectively utilizing, improve the productive rate of purpose product diaryl carbonate, simultaneously, reactor and rectifying tower are carried out integrated combination, both improved productive rate, simplify technical process again greatly, reduced facility investment.
As previously mentioned, traditional ester-interchange method synthesizing diaryl carbonic acid ester technology synthetic is carried out with separating separately, and per pass conversion is low, long flow path, complex process, production cost height.In addition, because CH
3OH and DMC form azeotrope, steam CH
3Also taken away a large amount of DMC in the time of OH, the result causes the concentration of DMC in the reactor to reduce, and the equilibrium conversion of synthesizing diaryl carbonic acid ester is reduced.
Summary of the invention
At the deficiency of traditional ester-interchange method synthesizing diaryl carbonic acid ester technology, the invention provides a kind of realization phenol, fortified phenol or aromatic alcohol and DMC transesterification reaction synthesizing diaryl carbonic acid ester and and CH
3The technology of the isolation integral of OH/DMC azeotrope.The reaction unit that adopts building-up reactions and rectifying to combine in this technology can make by product CH
3OH shifts out from reaction system, and does not take away reaction raw materials DMC.Reactor and compression rectification tower link together in this device, form a cover catalytic distillation coupled reaction system.
The flow process of synthetic method of the present invention is as follows:
(1) phenol or fortified phenol or aromatic alcohol and catalyzer were pressed mass ratio 70: 1～100: 1, were fed into reactor; Methylcarbonate is preheated to 150～170 ℃ and is fed into reactor through fresh feed pump pressurization, interchanger;
(2) phenol or fortified phenol or aromatic alcohol and methylcarbonate reacting by heating in reactor, 170～190 ℃ of temperature of reaction, pressure 1.0～1.5MPa;
(3) steam of reaction generation is after the compression rectification tower on still top separates, and the methanol steam that cat head produces is part backflow after the overhead condenser cooling, and a part is in the extraction of methyl alcohol discharge port; Catalyzer and crude product are from the bottom extraction of tower still, and the catalyst recirculation after the separation is used, and product is delivered to purification workshop section through discharge port and separated purification.
Be used to realize that the device of the inventive method mainly comprises:
A storage tank (2) that is used to adorn methylcarbonate;
A fresh feed pump (3) that is used for the methylcarbonate charging;
Two interchanger (4) and (8) that are respectively applied for to methylcarbonate and methyl alcohol heating and condensation;
Be used for the reactor (6) that phenol or fortified phenol or aromatic alcohol and methylcarbonate carry out transesterification reaction;
The compression rectification tower (7) that is used for separating dimethyl carbonate and methyl alcohol;
Be used for temporarily stocking the backflash (9) of methyl alcohol;
Reactor (6) is also linking to each other with miscellaneous part with pipeline of directly connecting together with compression rectification tower (7).
The major advantage of technology of the present invention and device is: the synthetic and CH of diaryl carbonate
3Being separated in the reactor of OH and DMC azeotrope finished.Utilize material self to add the pressure of thermogenesis, can make phenol, fortified phenol or aromatic alcohol and DMC carry out DMC and the CH that forms in the transesterification reaction synthesizing diaryl carbonic acid ester reaction process
3The azeotrope of OH is effectively separated by rectifier unit.This reaction unit can make by product CH
3OH shifts out from reaction system, and does not take away reaction raw materials DMC.And make reactant DMC obtain fully effectively utilizing, improve the productive rate of diaryl carbonate.A large amount of CH that can obtain fractionating out at cat head
3OH (〉=93wt%) and a small amount of DMC (≤7wt%) mixture, tower bottoms phase crude product Returning reacting system continues to participate in transesterification reaction, the reactor bottom obtains purpose product D PC.
This technical process is simple, and the transformation efficiency height is easy to operate, has reduced investment and production cost.
Description of drawings
Accompanying drawing is technological process device figure of the present invention.
1. opening for feed, the 2.DMC storage tank, 3. fresh feed pump, 4. and 8. interchanger, 5. heating jacket, 6. reactor, 7. compression rectification tower, 9. backflash, 10. methyl alcohol discharge port, 11. crude product DPC discharge ports.
Reactor is also linking to each other with miscellaneous part with pipeline of connecting together with the compression rectification tower among the figure, forms a cover catalytic distillation coupling system, realizes the synthetic and CH of catalysis of diaryl carbonate
3OH, DMC azeotrope isolation integral.
Embodiment
Embodiment 1: drop into 47.0kg phenol at reactor 6 places, 0.7kg catalyzer, be warmed up to 190 ℃ gradually, DMC by pump 4 metering and be preheating to 170 ℃ from the rectifying tower middle part with the 3.5kg/h charging, after reaction pressure reaches 1.5MPa, from cat head extraction methyl alcohol and DMC mixture (mass ratio 93: 7), reach balance behind the reaction 7h.The reaction back obtains MPC 5.7kg by reaction product being separated with purifying, its productive rate 7.2%, DPC 19.4kg, its productive rate 37.0%, selectivity 92.5%.
The comparative example 1: add 47.0kg phenol in autoclave, 22.5kg DMC and 0.7kg catalyzer are warmed up to 190 ℃ gradually, reaction 12h.The reaction back obtains MPC 9.1kg by reaction product being separated with purifying, its productive rate 11.5%, DPC 9.4kg.Its productive rate 18.0%, selectivity 75.1%.
Embodiment 2: add 70kg p-NP and 0.9kg catalyzer at reactor 6 places, be warmed up to 210 ℃ gradually, DMC by pump 4 metering and be preheating to 210 ℃ from the rectifying tower middle part with the 3.5kg/h charging, after reaction pressure reaches 1.5MPa, from cat head extraction methyl alcohol and DMC mixture (mass ratio 93: 7), reach balance behind the reaction 8h.The reaction back obtains methyl p-nitrophenyl carbonic ether 9.2kg by reaction product being separated with purifying, and its productive rate is 8.1%, two p-nitrophenyl carbonic ether 33.5kg, and its productive rate is 44.0%, selectivity 95.5%.
The comparative example 2: add the 70kg p-NP in autoclave, 22.5kg DMC and 0.9kg catalyzer are warmed up to 210 ℃ gradually, reaction 15h.The reaction back obtains methyl p-nitrophenyl carbonic ether 12.3kg by reaction product being separated with purifying, and its productive rate is 10.8%, obtains two p-nitrophenyl carbonic ether 22.3kg, and its productive rate is 29.3%, selectivity 78.2%.
Embodiment 3: add 47.0kg phenol and 0.7kg catalyzer at reactor 6 places, be warmed up to 190 ℃ gradually, DMC by pump 4 metering and be preheating to 190 ℃ from the rectifying tower middle part with the 3.5kg/h charging, after reaction pressure reaches 1.5MPa, from cat head extraction methyl alcohol and DMC mixture (mass ratio 93: 7), reach balance behind the reaction 8h.The reaction back obtains MPC 4.8kg by reaction product being separated with purifying, its productive rate 7.9%, DPC 16.7g.Its productive rate 32.0%, selectivity 90.5%.
The comparative example 3: add 47.0kg phenol in autoclave, 22.5kg DMC and 0.7kg catalyzer are warmed up to 190 ℃ gradually, reaction 15h.The reaction back obtains MPC 6.6kg by reaction product being separated with purifying, its productive rate 10.8%, DPC 9.3kg.Its productive rate 17.7%, selectivity 78.5%.
Claims (2)
1. processing method that adopts phenol, fortified phenol or aromatic alcohol and methylcarbonate transesterify synthesizing diaryl carbonic acid ester, it is characterized in that, the reaction of transesterification reaction synthesizing diaryl carbonic acid ester and with the technology of the isolation integral of methylcarbonate, methanol azeotrope, this method may further comprise the steps:
(1) phenol or fortified phenol or aromatic alcohol and catalyzer were fed into reactor in 70: 1～100: 1 by mass ratio; Methylcarbonate is preheated to 150～170 ℃ and is fed into reactor through fresh feed pump pressurization, interchanger;
(2) phenol or fortified phenol or aromatic alcohol and methylcarbonate reacting by heating in reactor, 170～190 ℃ of temperature of reaction, pressure 1.0～1.5MPa;
(3) steam of reaction generation is after the compression rectification tower on still top separates, and the methanol steam that cat head produces is part backflow after the overhead condenser cooling, and a part is in the extraction of methyl alcohol discharge port; Catalyzer and crude product are from the bottom extraction of tower still, and the catalyst recirculation after the separation is used, and product is delivered to purification workshop section through discharge port and separated purification.
2. device that is used to realize claim 1 processing method, this main device comprises: a fresh feed pump (3) that is used for the methylcarbonate charging;
Two interchanger (4) and (8) that are respectively applied for to methylcarbonate and methyl alcohol heating and condensation;
Be used for the reactor (6) that phenol or fortified phenol or aromatic alcohol and methylcarbonate carry out transesterification reaction;
The compression rectification tower (7) that is used for separating dimethyl carbonate and methyl alcohol;
Reactor (6) is also linking to each other with miscellaneous part with pipeline of directly connecting together with compression rectification tower (7).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410012900 CN1247520C (en) | 2004-03-25 | 2004-03-25 | Technique and equipment for synthesizing diaryl carbonate through catalyzing rectification |
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|---|---|---|---|
| CN 200410012900 CN1247520C (en) | 2004-03-25 | 2004-03-25 | Technique and equipment for synthesizing diaryl carbonate through catalyzing rectification |
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| CN1562955A true CN1562955A (en) | 2005-01-12 |
| CN1247520C CN1247520C (en) | 2006-03-29 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357890B (en) * | 2008-09-17 | 2011-06-01 | 西安交通大学 | Methyl carbonate synthesis and refining technique using heat pump technique and apparatus thereof |
| TWI412516B (en) * | 2007-05-25 | 2013-10-21 | Bayer Materialscience Ag | Process for the preparation of diaryl carbonates or arylalkyl carbonates from dialkyl carbonates |
| CN105198746A (en) * | 2015-10-14 | 2015-12-30 | 中建安装工程有限公司 | Method and device for preparing diphenyl carbonate by using phenol and dimethyl carbonate through one-step method |
| 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 |
| 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 |
-
2004
- 2004-03-25 CN CN 200410012900 patent/CN1247520C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI412516B (en) * | 2007-05-25 | 2013-10-21 | Bayer Materialscience Ag | Process for the preparation of diaryl carbonates or arylalkyl carbonates from dialkyl carbonates |
| CN101357890B (en) * | 2008-09-17 | 2011-06-01 | 西安交通大学 | Methyl carbonate synthesis and refining technique using heat pump technique and apparatus thereof |
| CN105198746A (en) * | 2015-10-14 | 2015-12-30 | 中建安装工程有限公司 | Method and device for preparing diphenyl carbonate by using phenol and dimethyl carbonate through one-step method |
| CN105198746B (en) * | 2015-10-14 | 2017-08-04 | 中建安装工程有限公司 | A kind of phenol and dimethyl carbonate one-step method prepares the method and device of diphenyl carbonate |
| 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 |
| 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 |
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|---|---|
| CN1247520C (en) | 2006-03-29 |
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