CN103467283A - Method for using double towers to ceaselessly compound high-purity methyl phenyl carbonic ester - Google Patents
Method for using double towers to ceaselessly compound high-purity methyl phenyl carbonic ester Download PDFInfo
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Abstract
The invention provides a method for ceaselessly compounding high-purity methyl phenyl carbonic ester. The method includes the steps of using diphenyl carbonate and dimethyl carbonate as raw materials under the action of catalysts, carrying out synthesis and preliminary separation on the methyl phenyl carbonic ester through a reactive distillation tower, enabling crude products in the bottom of the tower to be subjected to separation and purification of a distillation and purification tower to obtain the methyl phenyl carbonic ester products with the purity of more than 99.9%. Through the method, the whole process flow is reasonable, and procedures are successive. The method has the advantages of low energy consumption, high product quality, no pollution and the like. The process is the high-efficiency and feasible continuous synthesis process of the methyl phenyl carbonic ester.
Description
Technical field
The invention belongs to the preparing technical field of methyl benzol carbonate, be specifically related to a kind of method of serialization synthesis of methyl phenyl carbonic ether.
Background technology
Methyl benzol carbonate is the intermediate product that phenol reacts with the methylcarbonate ester exchange synthesizing diphenyl carbonate, disproportionation reaction Formed diphenyl phthalate and methylcarbonate can occur in self, so to the yield important of ester-interchange method diphenyl carbonate synthesis, and be also an important indicator of methylcarbonate transformation efficiency.
The method for preparing at present methyl benzol carbonate mainly contains two kinds: a kind of is to generate methyl benzol carbonate with phenyl chloroformate and methyl alcohol reaction, the shortcoming of the method is: used hypertoxic phenyl chloroformate for raw material, also contain the toxic substance methylene dichloride in resultant, and reacted product need to could obtain the methyl benzol carbonate that purity is higher after washing, drying and the purification of multiple working procedure.Another kind method is to use phenol and methylcarbonate to carry out transesterification reaction to generate methyl benzol carbonate, the shortcoming of the method is: react wayward, methyl benzol carbonate is easy to disproportionation Formed diphenyl phthalate, and the yield of methyl benzol carbonate is very low, reacted product need to just can obtain the methyl benzol carbonate of higher degree after multistep is processed.The research group at contriver place discloses a kind of high-purity methyl benzol carbonate method for preparing, publication number is CN102531908A, the method is that to take methylcarbonate and diphenyl carbonate be raw material, at Lewis acid, metal oxide, under titanate or organic tin catalyst, by intermittent warming treatment, react, be prepared into methyl benzol carbonate, the method advantage is to obtain highly purified methyl benzol carbonate, pollute little, but belong to rhythmic reaction, need through the synthesis under normal pressure process, and rectification under vacuum progressively separates, the final target product that obtains, be unfavorable for that industrial mass is synthetic.
Summary of the invention
Technical problem to be solved by this invention is to overcome in existing methyl benzol carbonate preparation method uses hypertoxic raw material, resultant of reaction is poisonous, product yield is not high and purification process is difficult shortcoming, provides that a kind of energy consumption is low, quality product is high, the method for free of contamination serialization synthesis of high purity methyl benzol carbonate.
Solving the problems of the technologies described above adopted technical scheme is: by methylcarbonate and diphenyl carbonate, catalyzer adds in the material mixing tank, the mol ratio of methylcarbonate and diphenyl carbonate is 1:0.2～5, the mol ratio of catalyzer and diphenyl carbonate is 0.002～0.10:1, open heating and the whipping appts of mixing of materials tank, fully mix, the gained mixed solution pumps in reaction fractionating tower and reacts with the flow velocity of 10～120mL/ minute, the tower top temperature of reaction fractionating tower is 80～95 ℃, reflux ratio is 10:1～10, the tower reactor temperature is 150～250 ℃, light constituent is overflowed by the reactive distillation top of tower, the condensation rear portion is returned to the reaction fractionating tower trim the top of column, another part enters the light constituent tank, the thick product of methyl benzol carbonate that reaction generates is flowed out by the reactive distillation tower bottom, enter rectifying purification column separating-purifying, the tower top pressure of rectifying purification column is-0.07～-0.099MPa, temperature is 90～160 ℃, reflux ratio is 5:1～10, the tower reactor temperature is 180～240 ℃, methyl benzol carbonate is overflowed by rectifying purification column top, the condensation rear portion is returned to rectifying purification column trim the top of column, a part enters products pot.
Above-mentioned methylcarbonate and the preferred 1:0.5 of the mol ratio of diphenyl carbonate～2, the mol ratio of catalyzer and diphenyl carbonate is 0.01～0.03:1 preferably.
Above-mentioned catalyzer is Lewis acid, lead phenolate, titanate ester compound, Organotin oxide compound or organotin oxides, described titanate ester compound can be specifically tetrabutyl titanate, tetraethyl titanate, metatitanic acid orthocarbonate, tetraphenyl titanate etc., and described organo-tin compound can be specifically Dibutyltin oxide, tributyltin oxide, diethyl stannic oxide, dioctyl tin oxide etc.
The preferred lead phenolate of catalyzer of the present invention or Dibutyltin oxide.
The preferred mixed solution of the present invention pumps in reaction fractionating tower and reacts with the flow velocity of 30～50mL/ minute, the tower top temperature of reaction fractionating tower is that 88～90 ℃, reflux ratio are that 10:3～5, tower reactor temperature are 200～220 ℃, the tower top pressure of rectifying purification column is-0.094～-0.097MPa, temperature are that 110～120 ℃, reflux ratio are that 5:3～5, tower reactor temperature are 210～220 ℃.
The present invention compared with prior art has following outstanding effect:
1, preparation technology's flow process is simple, process is continuous, by double tower, is coupled, and has the characteristics such as energy consumption is low, pollution-free, is a kind of efficient feasible continuous synthesis technique of methyl benzol carbonate.
2, use advantages of nontoxic raw materials, it is raw material that the present invention uses methylcarbonate and diphenyl carbonate, has avoided using hypertoxic raw material phenyl chloroformate.
3, preparing product purity is high, and methyl benzol carbonate purity prepared by the present invention reaches more than 99.9%.
4, preparation method's process is continuous, and suitability for industrialized is produced in enormous quantities.
The accompanying drawing explanation
Fig. 1 is the process flow diagram of the embodiment of the present invention.
In figure, 1 is mixing of materials tank, the 2nd, reaction fractionating tower, the 3rd, light constituent condenser, the 4th, light constituent backflash, the 5th, light constituent water cooler, the 6th, light constituent tank, the 7th, overhead condenser, the 8th, return tank, the 9th, trap, the 10th, reactor product cooler, the 11st, products pot, the 12nd, vacuum cooler, the 13rd, vacuum buffer tank, the 14th, rectifying purification column reboiler, the 15th, rectifying purification column, the 16th, reaction fractionating tower reboiler.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in more detail, but the invention is not restricted to these embodiment.
Add methylcarbonate, diphenyl carbonate and lead phenolate in mixing of materials tank 1, the mol ratio of methylcarbonate and diphenyl carbonate is 1.5:1, the mol ratio of lead phenolate and diphenyl carbonate is 0.015:1, open heating and the whipping appts of mixing of materials tank 1, make material fully dissolve, mix, obtain stock liquid.The gained stock liquid is transported to reaction in reaction fractionating tower 2 with fresh feed pump with the flow velocity of 30mL/min, and reaction fractionating tower 2, by the compound material convection current of the reaction fractionating tower reboiler Final 16, reaction, promotes the energy utilization of reaction fractionating tower 2.
Light constituent (methylcarbonate) is overflowed by reaction fractionating tower 2 tops, after 3 condensations of light constituent condenser, flow into light constituent backflash 4, in light constituent backflash 4, light constituent returns to reaction fractionating tower 2 trim the top of column by a reflux pump part, another part enters 6 recyclings of light constituent tank after light constituent water cooler 5 is further cooling, the thick product of methyl benzol carbonate that reaction generates is flowed out by reaction fractionating tower 2 bottoms, with fresh feed pump, pumps into separating-purifying in rectifying purification column 15.The working pressure of reaction fractionating tower 2 is normal pressure, and the tower top temperature of reaction fractionating tower 2 is that 90 ℃, reflux ratio are that 5:2, tower reactor temperature are 220 ℃.
Methyl benzol carbonate in rectifying purification column 15 is overflowed by rectifying purification column 15 tops, after overhead condenser 7 and vacuum trap 9 condensations, flow into return tank 8, a methyl benzol carbonate part in return tank 8 is returned to rectifying purification column 15 trim the top of column, another part enters products pot 11 after product water cooler 10 is cooling, diphenyl carbonate and lead phenolate go out from rectifying purification column 15 tower bottom flows, can be recycled.The tower top pressure of rectifying purification column 15 is-0.095MPa, and temperature is that 116 ℃, reflux ratio are 2, the tower reactor temperature is 200 ℃.Rectifying purification column 15, by the 14 strengthening material convection current of rectifying purification column reboiler, promotes the energy utilization of rectifying purification column 15.The present embodiment vacuumizes from trap 9 and return tank 8 tops by vacuum system, and keeping rectification and purification tower 15 is action required pressure, and vacuum system is comprised of vacuum pump, vacuum buffer tank 13, vacuum cooler 12.The purity of the methyl benzol carbonate in the present embodiment products pot 11 is more than 99.92%.
Rectifying purification column reboiler 14 and the reaction fractionating tower reboiler 16 of the present embodiment are thermosyphon reboiler, and reaction fractionating tower 2 and rectifying purification column 15 are packing tower, and its filler is the Dixon filler, and tower height is 8m, and the filler specification is
In the mixing of materials tank 1 of the present embodiment, the mol ratio of methylcarbonate and diphenyl carbonate is 1:0.5, the mol ratio of lead phenolate and diphenyl carbonate is 0.015:1, stock liquid is transported to reaction in reaction fractionating tower 2 with the flow velocity of 50mL/min, the working pressure of reaction fractionating tower 2 is normal pressure, the tower top temperature of reaction fractionating tower 2 is that 90 ℃, reflux ratio are 3, the tower reactor temperature is 225 ℃, the tower top pressure of rectifying purification column 15 is-0.09MPa, temperature is that 121 ℃, reflux ratio are that 5:2, tower reactor temperature are 210 ℃, and other operation stepss are identical with embodiment 1.The purity of products obtained therefrom methyl benzol carbonate is more than 99.96%.
In the mixing of materials tank 1 of the present embodiment, the mol ratio of methylcarbonate and diphenyl carbonate is 1:0.2, the mol ratio of lead phenolate and diphenyl carbonate is 0.002:1, stock liquid is transported to reaction in reaction fractionating tower 2 with the flow velocity of 120mL/min, the working pressure of reaction fractionating tower 2 is normal pressure, the tower top temperature of reaction fractionating tower 2 is 85,95 ℃, reflux ratio are that 10:1, tower reactor temperature are 150 ℃, the tower top pressure of rectifying purification column 15 is-0.07MPa, temperature is that 90 ℃, reflux ratio are 240 ℃ of 5:1, tower reactor temperature, and other operation stepss are identical with embodiment 1.The purity of products obtained therefrom methyl benzol carbonate is more than 99.91%.
In the mixing of materials tank 1 of the present embodiment, the mol ratio of methylcarbonate and diphenyl carbonate is 1:5, the mol ratio of lead phenolate and diphenyl carbonate is 0.10:1, stock liquid is transported to reaction in reaction fractionating tower 2 with the flow velocity of 10mL/min, the working pressure of reaction fractionating tower 2 is normal pressure, the tower top temperature of reaction fractionating tower 2 is 92,80 ℃, reflux ratio are 1,250 ℃ of tower reactor temperature, the tower top pressure of rectifying purification column 15 is-0.099MPa, temperature, 90,160 ℃, reflux ratio are that 1:2, tower reactor temperature are 180 ℃, and other operation stepss are identical with embodiment 1.The purity of products obtained therefrom methyl benzol carbonate is more than 99.9%.
In the mixing of materials tank 1 of the present embodiment, the mol ratio of methylcarbonate and diphenyl carbonate is 1:2, the mol ratio of lead phenolate and diphenyl carbonate is 0.01:1, stock liquid is transported to reaction in reaction fractionating tower 2 with the flow velocity of 80mL/min, the working pressure of reaction fractionating tower 2 is normal pressure, 93 ℃ of the tower top temperatures of reaction fractionating tower 2, reflux ratio are 230 ℃ of 10:3, tower reactor temperature, the tower top pressure of rectifying purification column 15 is-0.094MPa, 120 ℃ of temperature, reflux ratio are that 5:3, tower reactor temperature are 220 ℃, and other operation stepss are identical with embodiment 1.The purity of products obtained therefrom methyl benzol carbonate is more than 99.95%.
In the mixing of materials tank 1 of the present embodiment, the mol ratio of methylcarbonate and diphenyl carbonate is 1:3, the mol ratio of lead phenolate and diphenyl carbonate is 0.03:1, stock liquid is transported to reaction in reaction fractionating tower 2 with the flow velocity of 60mL/min, the working pressure of reaction fractionating tower 2 is normal pressure, the tower top temperature of reaction fractionating tower 2 is that 90 ℃, reflux ratio are that 2:1, tower reactor temperature are 210 ℃, the tower top pressure of rectifying purification column 15 is-0.097MPa, temperature is that 90 ℃, reflux ratio are 1,200 ℃ of tower reactor temperature, and other operation stepss are identical with embodiment 1.The purity of products obtained therefrom methyl benzol carbonate is more than 99.91%.
In embodiment 1～6, lead phenolate used is replaced with equimolar Dibutyltin oxide, and other steps are identical with corresponding embodiment.
The Dibutyltin oxide of the present embodiment also available equimolar tetrabutyl titanate, tetraethyl titanate, metatitanic acid orthocarbonate, tetraphenyl titanate, AlCl3, tributyltin oxide, diethyl stannic oxide or dioctyl tin oxide is replaced.
Claims (9)
1. the method for a serialization synthesis of high purity methyl benzol carbonate, it is characterized in that: by methylcarbonate and diphenyl carbonate, catalyzer adds in material mixing tank (1), the mol ratio of methylcarbonate and diphenyl carbonate is 1:0.2～5, the mol ratio of catalyzer and diphenyl carbonate is 0.002～0.10:1, open heating and the whipping appts of mixing of materials tank (1), fully mix, the gained mixed solution pumps into reaction in reaction fractionating tower (2) with the flow velocity of 10～120mL/ minute, light constituent is overflowed by reaction fractionating tower (2) top, the condensation rear portion is returned to reaction fractionating tower (2) trim the top of column, another part enters light constituent tank (6), the thick product of methyl benzol carbonate that reaction generates is flowed out by reaction fractionating tower (2) bottom, enter rectifying purification column (15) separating-purifying, methyl benzol carbonate is overflowed by rectifying purification column (15) top, the condensation rear portion is returned to rectifying purification column (15) trim the top of column, a part enters products pot (11),
The tower top temperature of described reaction fractionating tower (2) is that 80～95 ℃, reflux ratio are that 10:1～10, tower reactor temperature are 150～250 ℃, the tower top pressure of rectifying purification column (15) is-0.07～-0.099MPa, temperature are that 90～160 ℃, reflux ratio are that 5:1～10, tower reactor temperature are 180～240 ℃.
2. the method for serialization synthesis of high purity methyl benzol carbonate according to claim 1, it is characterized in that: described catalyzer is Lewis acid, lead phenolate, titanate ester compound, organo-tin compound.
3. the method for serialization synthesis of high purity methyl benzol carbonate according to claim 2, it is characterized in that: described titanate ester compound is tetrabutyl titanate, tetraethyl titanate, metatitanic acid orthocarbonate or tetraphenyl titanate.
4. the method for serialization synthesis of high purity methyl benzol carbonate according to claim 2, it is characterized in that: described organo-tin compound is Dibutyltin oxide, tributyltin oxide, diethyl stannic oxide or dioctyl tin oxide.
5. the method for serialization synthesis of high purity methyl benzol carbonate according to claim 1, it is characterized in that: described catalyzer is lead phenolate or Dibutyltin oxide.
6. according to the method for the described serialization synthesis of high purity of any one in claim 1～5 methyl benzol carbonate, it is characterized in that: the mol ratio of described methylcarbonate and diphenyl carbonate is 1:0.5～2, and the mol ratio of described catalyzer and diphenyl carbonate is 0.01～0.03:1.
7. the method for serialization synthesis of high purity methyl benzol carbonate according to claim 6 is characterized in that: described mixed solution pumps into reaction in reaction fractionating tower (2) with the flow velocity of 30～50mL/ minute.
8. according to the method for the described serialization synthesis of high purity of any one methyl benzol carbonate in claim 1～5 or 7, it is characterized in that: the tower top temperature of described reaction fractionating tower (2) is that 88～90 ℃, reflux ratio are that 10:3～5, tower reactor temperature are 200～220 ℃; The tower top pressure of described rectifying purification column (15) is-0.094～-0.097MPa, temperature are that 110～120 ℃, reflux ratio are that 5:3～5, tower reactor temperature are 210～220 ℃.
9. the method for serialization synthesis of high purity methyl benzol carbonate according to claim 6 is characterized in that: the tower top temperature of described reaction fractionating tower (2) is that 88～90 ℃, reflux ratio are that 10:3～5, tower reactor temperature are 200～220 ℃; The tower top pressure of described rectifying purification column (15) is-0.094～-0.097MPa, temperature are that 110～120 ℃, reflux ratio are that 5:3～5, tower reactor temperature are 210～220 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111961205A (en) * | 2020-08-13 | 2020-11-20 | 江西蓝星星火有机硅有限公司 | Process for continuously producing various low-viscosity methyl silicone oils by comprehensively utilizing methyl silicone oil polymerization material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0959224A (en) * | 1995-08-17 | 1997-03-04 | Mitsubishi Chem Corp | Production of alkylarylcarbonate |
| CN102531908A (en) * | 2011-12-21 | 2012-07-04 | 陕西省石油化工研究设计院 | Preparation method of methyl phenyl carbonic ester |
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- 2013-09-29 CN CN201310466318.4A patent/CN103467283B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0959224A (en) * | 1995-08-17 | 1997-03-04 | Mitsubishi Chem Corp | Production of alkylarylcarbonate |
| CN102531908A (en) * | 2011-12-21 | 2012-07-04 | 陕西省石油化工研究设计院 | Preparation method of methyl phenyl carbonic ester |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111961205A (en) * | 2020-08-13 | 2020-11-20 | 江西蓝星星火有机硅有限公司 | Process for continuously producing various low-viscosity methyl silicone oils by comprehensively utilizing methyl silicone oil polymerization material |
| CN111961205B (en) * | 2020-08-13 | 2021-12-14 | 江西蓝星星火有机硅有限公司 | Process for continuously producing various low-viscosity methyl silicone oils by comprehensively utilizing methyl silicone oil polymerization material |
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Address after: No.61 Xiyan Road, Xi'an City, Shaanxi Province 710054 Patentee after: Shaanxi Chemical Research Institute Co.,Ltd. Address before: No.61 Xiyan Road, Xi'an City, Shaanxi Province 710054 Patentee before: SHAANXI RESEARCH DESIGN INSTITUTE OF PETROLEUM CHEMICAL INDUSTRY |
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