CN103467283B - 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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- CN103467283B CN103467283B CN201310466318.4A CN201310466318A CN103467283B CN 103467283 B CN103467283 B CN 103467283B CN 201310466318 A CN201310466318 A CN 201310466318A CN 103467283 B CN103467283 B CN 103467283B
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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 and methylcarbonate ester exchange synthesizing diphenyl carbonate react, disproportionation reaction Formed diphenyl phthalate and methylcarbonate can be there is in self, so the yield important to ester-interchange method diphenyl carbonate synthesis, and it is also an important indicator of methylcarbonate transformation efficiency.
The method preparing methyl benzol carbonate at present mainly contains two kinds: one generates methyl benzol carbonate with phenyl chloroformate and methyl alcohol reaction, the shortcoming of the method is: the phenyl chloroformate employing severe toxicity is raw material, also containing toxic substance methylene dichloride in resultant, and reacted product needs could obtain the higher methyl benzol carbonate of purity after the washing of multiple working procedure, drying and purification.Another kind method uses 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 needs the methyl benzol carbonate that just can obtain higher degree after multi step strategy.The research group at contriver place discloses one and prepares high-purity methyl benzol carbonate method, publication number is CN102531908A, the method is for raw material with methylcarbonate and diphenyl carbonate, at Lewis acid, metal oxide, under titanate or organic tin catalyst, reacted by intermittent warming treatment, be prepared into methyl benzol carbonate, the method advantage to obtain highly purified methyl benzol carbonate, pollute little, but belong to rhythmic reaction, need through synthesis under normal pressure process, and rectification under vacuum is progressively separated, final acquisition target product, be unfavorable for that industrial mass is synthesized.
Summary of the invention
Technical problem to be solved by this invention is to overcome in existing methyl benzol carbonate preparation method and uses the shortcoming that hypertoxic raw material, resultant of reaction are poisonous, product yield is not high and purification process is difficult, 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 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, gained mixed solution pumps in reactive distillation column with the flow velocity of 10 ~ 120mL/ minute and reacts, the tower top temperature of reactive distillation column is 80 ~ 95 DEG C, reflux ratio is 10:1 ~ 10, bottom temperature is 150 ~ 250 DEG C, light constituent is overflowed by reactive distillation top of tower, condensation rear portion returns reactive distillation column trim the top of column, another part enters light constituent tank, the thick product of methyl benzol carbonate that reaction generates is flowed out by 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 DEG C, reflux ratio is 5:1 ~ 10, bottom temperature is 180 ~ 240 DEG C, methyl benzol carbonate is overflowed by rectifying purification column top, condensation rear portion returns rectifying purification column trim the top of column, a part enters products pot.
Above-mentioned methylcarbonate and preferred 1:0.5 ~ 2 of the mol ratio of diphenyl carbonate, the mol ratio preferably 0.01 ~ 0.03:1 of catalyzer and diphenyl carbonate.
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 reactive distillation column with the flow velocity of 30 ~ 50mL/ minute and reacts, the tower top temperature of reactive distillation column is 88 ~ 90 DEG C, reflux ratio is 10:3 ~ 5, bottom temperature is 200 ~ 220 DEG C, and the tower top pressure of rectifying purification column is-0.094 ~-0.097MPa, temperature is 110 ~ 120 DEG C, reflux ratio is 5:3 ~ 5, bottom temperature is 210 ~ 220 DEG C.
The present invention compared with prior art has following outstanding effect:
1, preparation technology's flow process is simple, process continuous, and be coupled by double tower, having the features such as energy consumption is low, pollution-free, is a kind of efficiently feasible methyl benzol carbonate continuous synthesis technique.
2, use advantages of nontoxic raw materials, the present invention uses methylcarbonate and diphenyl carbonate to be raw material, avoids and uses 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.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the embodiment of the present invention.
In figure, 1 be mixing of materials tank, 2 are reactive distillation columns, 3 are light constituent condensers, 4 are light constituent backflashes, 5 are light constituent water coolers, 6 are light constituent tanks, 7 are overhead condensers, 8 are return tanks, 9 are traps, 10 are reactor product coolers, 11 are products pots, 12 are vacuum coolers, 13 are vacuum buffer tanks, 14 are rectifying purification column reboilers, 15 are rectifying purification column, 16 is reactive distillation column reboilers.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in more detail, but the invention is not restricted to these embodiments.
Embodiment 1
Methylcarbonate, diphenyl carbonate and lead phenolate is added 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, material is fully dissolved, mixes, obtain stock liquid.Gained stock liquid fresh feed pump is transported in reactive distillation column 2 with the flow velocity of 30mL/min and reacts, and reactive distillation column 2, by the compound material convection current of the reactive distillation column reboiler Final 16, reaction, promotes the Energy harvesting of reactive distillation column 2.
Light constituent (methylcarbonate) is overflowed by reactive distillation column 2 top, after light constituent condenser 3 condensation, flow into light constituent backflash 4, in light constituent backflash 4, light constituent returns reactive distillation column 2 trim the top of column by a reflux pump part, another part enters light constituent tank 6 recycling after light constituent water cooler 5 further cooling, the thick product of methyl benzol carbonate that reaction generates flows out by bottom reactive distillation column 2, pumps into separating-purifying in rectifying purification column 15 with fresh feed pump.The working pressure of reactive distillation column 2 is normal pressure, and the tower top temperature of reactive distillation column 2 is 90 DEG C, reflux ratio is 5:2, bottom temperature is 220 DEG C.
Methyl benzol carbonate in rectifying purification column 15 is overflowed by rectifying purification column 15 top, after overhead condenser 7 and vacuum trap 9 condensation, flow into return tank 8, a methyl benzol carbonate part in return tank 8 returns rectifying purification column 15 trim the top of column, another part enters products pot 11 after reactor product cooler 10 cools, diphenyl carbonate and lead phenolate go out from rectifying purification column 15 tower bottom flow, can be recycled.The tower top pressure of rectifying purification column 15 is-0.095MPa, and temperature is 116 DEG C, reflux ratio is 2, bottom temperature is 200 DEG C.Rectifying purification column 15 strengthens material convection current by rectifying purification column reboiler 14, promotes the Energy harvesting of rectifying purification column 15.The present embodiment is vacuumized from trap 9 and return tank 8 top by vacuum system, and keep rectification and purification tower 15 to be action required pressure, vacuum system is made up 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%.
The rectifying purification column reboiler 14 of the present embodiment and reactive distillation column reboiler 16 are thermosyphon reboiler, and reactive distillation column 2 and rectifying purification column 15 are packing tower, and its filler is Dixon filler, and tower height is 8m, and filler specification is
Embodiment 2
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 in reactive distillation column 2 with the flow velocity of 50mL/min and reacts, the working pressure of reactive distillation column 2 is normal pressure, the tower top temperature of reactive distillation column 2 is 90 DEG C, reflux ratio is 3, bottom temperature is 225 DEG C, the tower top pressure of rectifying purification column 15 is-0.09MPa, temperature is 121 DEG C, reflux ratio is 5:2, bottom temperature is 210 DEG C, and other operation stepss are identical with embodiment 1.The purity of products obtained therefrom methyl benzol carbonate is more than 99.96%.
Embodiment 3
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 in reactive distillation column 2 with the flow velocity of 120mL/min and reacts, the working pressure of reactive distillation column 2 is normal pressure, the tower top temperature of reactive distillation column 2 is 85,95 DEG C, reflux ratio is 10:1, bottom temperature is 150 DEG C, the tower top pressure of rectifying purification column 15 is-0.07MPa, temperature is 90 DEG C, reflux ratio is 5:1, bottom temperature 240 DEG C, and other operation stepss are identical with embodiment 1.The purity more than 99.91% of products obtained therefrom methyl benzol carbonate.
Embodiment 4
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 in reactive distillation column 2 with the flow velocity of 10mL/min and reacts, the working pressure of reactive distillation column 2 is normal pressure, the tower top temperature of reactive distillation column 2 is 92,80 DEG C, reflux ratio is 1, bottom temperature 250 DEG C, the tower top pressure of rectifying purification column 15 is-0.099MPa, temperature, 90,160 DEG C, reflux ratio is 1:2, bottom temperature is 180 DEG C, other operation stepss are identical with embodiment 1.The purity more than 99.9% of products obtained therefrom methyl benzol carbonate.
Embodiment 5
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 in reactive distillation column 2 with the flow velocity of 80mL/min and reacts, the working pressure of reactive distillation column 2 is normal pressure, the tower top temperature 93 DEG C of reactive distillation column 2, reflux ratio are 10:3, bottom temperature 230 DEG C, the tower top pressure of rectifying purification column 15 is-0.094MPa, temperature 120 DEG C, reflux ratio are 5:3, bottom temperature is 220 DEG C, and other operation stepss are identical with embodiment 1.The purity more than 99.95% of products obtained therefrom methyl benzol carbonate.
Embodiment 6
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 in reactive distillation column 2 with the flow velocity of 60mL/min and reacts, the working pressure of reactive distillation column 2 is normal pressure, the tower top temperature of reactive distillation column 2 is 90 DEG C, reflux ratio is 2:1, bottom temperature is 210 DEG C, the tower top pressure of rectifying purification column 15 is-0.097MPa, temperature is 90 DEG C, reflux ratio is 1, bottom temperature 200 DEG C, and other operation stepss are identical with embodiment 1.The purity more than 99.91% of products obtained therefrom methyl benzol carbonate.
Embodiment 7
In embodiment 1 ~ 6, the equimolar Dibutyltin oxide of lead phenolate used is replaced, and other steps are identical with corresponding embodiment.
The Dibutyltin oxide of the present embodiment also can be replaced with equimolar tetrabutyl titanate, tetraethyl titanate, metatitanic acid orthocarbonate, tetraphenyl titanate, AlCl3, tributyltin oxide, diethyl stannic oxide or dioctyl tin oxide.
Claims (4)
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, gained mixed solution pumps into reaction in reactive distillation column (2) with the flow velocity of 10 ~ 120mL/ minute, light constituent is overflowed by reactive distillation column (2) top, condensation rear portion returns reactive distillation column (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 reactive distillation column (2) bottom, enter rectifying purification column (15) separating-purifying, methyl benzol carbonate is overflowed by rectifying purification column (15) top, condensation rear portion returns rectifying purification column (15) trim the top of column, a part enters products pot (11),
The tower top temperature of described reactive distillation column (2) is 80 ~ 95 DEG C, reflux ratio is 10:1 ~ 10, bottom temperature is 150 ~ 250 DEG C, and the tower top pressure of rectifying purification column (15) is-0.07 ~-0.099MPa, temperature is 90 ~ 160 DEG C, reflux ratio is 5:1 ~ 10, bottom temperature is 180 ~ 240 DEG C;
Above-mentioned catalyzer is lead phenolate, titanate ester compound, organo-tin compound; Described titanate ester compound is tetrabutyl titanate, tetraethyl titanate, metatitanic acid orthocarbonate or tetraphenyl titanate; Described organo-tin compound is Dibutyltin oxide, tributyltin oxide, diethyl stannic oxide or dioctyl tin oxide.
2. the method for serialization synthesis of high purity methyl benzol carbonate according to claim 1, it is characterized in that: described methylcarbonate and the mol ratio of diphenyl carbonate are 1:0.5 ~ 2, described catalyzer and the mol ratio of diphenyl carbonate are 0.01 ~ 0.03:1.
3. the method for serialization synthesis of high purity methyl benzol carbonate according to claim 2, is characterized in that: described mixed solution pumps into reaction in reactive distillation column (2) with the flow velocity of 30 ~ 50mL/ minute.
4. according to the method for the serialization synthesis of high purity methyl benzol carbonate in claims 1 to 3 described in any one, it is characterized in that: the tower top temperature of described reactive distillation column (2) is 88 ~ 90 DEG C, reflux ratio is 10:3 ~ 5, bottom temperature is 200 ~ 220 DEG C; The tower top pressure of described rectifying purification column (15) is-0.094 ~-0.097MPa, temperature is 110 ~ 120 DEG C, reflux ratio is 5:3 ~ 5, bottom temperature is 210 ~ 220 DEG C.
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| CN103467283B true CN103467283B (en) | 2015-06-10 |
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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 |