CN216826190U - Production device of poly (butylene succinate) - Google Patents
Production device of poly (butylene succinate) Download PDFInfo
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- CN216826190U CN216826190U CN202220232932.9U CN202220232932U CN216826190U CN 216826190 U CN216826190 U CN 216826190U CN 202220232932 U CN202220232932 U CN 202220232932U CN 216826190 U CN216826190 U CN 216826190U
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Abstract
A production device of poly (butylene succinate) relates to the technical field of PBS production, and is used for preparing high-yield PBS resin. It includes succinic acid dimethyl ester jar, 1, 4-butanediol jar, catalyst jar and ester exchange cauldron, succinic acid dimethyl ester jar, 1, 4-butanediol jar, catalyst jar all are connected through pipeline and ester exchange cauldron, its characterized in that, the ester exchange cauldron lower part is passed through the pipeline and is connected with polycondensation reaction cauldron upper portion, polycondensation reaction cauldron passes through the pipeline and is connected with oligomer depolymerization cauldron upper portion, oligomer depolymerization cauldron lower part is passed through the pipeline and is connected with the filter, the filter is connected with first methanol removing tower. The utility model discloses can obtain high yield's PBS resin, and no hydrogen chloride produces, realized the maximize utilization of raw materials.
Description
Technical Field
The utility model belongs to the technical field of the polybutylene succinate production technique and specifically relates to a polybutylene succinate's apparatus for producing.
Background
Biodegradable plastics are considered to be one of the effective ways to solve the problem of "white pollution" because they can be degraded into substances harmless to the environment under natural environmental conditions after use. From the aspects of industrialization degree, degradability and the like, the PBS is a completely degradable plastic variety with the best comprehensive performance recognized in the world at present, and the market prospect of the PBS is wide in the future.
PBS is called poly (butylene succinate) and poly (butylene succinate) in English, and is a biodegradable high polymer material. The PBS polyester has good comprehensive performance, not only can the mechanical property meet the use requirement of general plastics, but also can be degraded only under the condition that compost and the like contact microorganisms, and the performance is very stable in the normal storage and use processes. Secondly, the PBS can be subjected to various molding processing on general processing equipment, has very good processing performance, and is the best processing performance in the current general degradable plastics. In addition, the PBS series polyester has excellent heat resistance, the heat distortion temperature is close to 100 ℃, the modified polyester can exceed 100 ℃ (the heat resistance is the best in completely biodegradable polyester), the heat resistance requirement of daily necessities is met, and the PBS series polyester can be used for preparing cold and hot drink packages and lunch boxes. Meanwhile, the PBS polyester has price advantage, and the price can reach the level of PET polyester after large-scale production.
At present, the preparation method of PBS is mainly a melt polycondensation method, which can be divided into a direct esterification method and an ester exchange method, and the production method of commercially available PBS is basically a direct esterification method. The direct esterification method is to take succinic acid and 1, 4-butanediol as polymerization monomers, firstly carry out esterification reaction to produce PBS oligomer, and then the PBS oligomer is generated by the oligomer under the action of high temperature, high vacuum and high-efficiency catalyst, but the method has the following defects: (1) the raw material corrosivity is strong, and the equipment manufacturing cost is high; (2) the esterification reaction is a reversible reaction, and the equilibrium constant is small; (3)1, 4-butanediol is easy to cyclize to generate tetrahydrofuran and the like which are byproducts, and the esterification reaction rate and the reaction degree are seriously influenced. In addition, as the succinic acid reaction is incomplete, side reactions such as decarboxylation, cyclization and thermal degradation are easy to occur in the polycondensation stage, particularly under the conditions of high temperature and high vacuum, and further improvement of the molecular weight of PBS and improvement of the color of the product are seriously influenced.
SUMMERY OF THE UTILITY MODEL
An object of the utility model is to provide a production device of poly succinic acid butanediol ester that synthetic route is simple, equipment maintenance is with low costs for the preparation obtains the PBS resin of high yield.
The utility model provides a technical scheme that its technical problem adopted is: the utility model provides a production device of olybuthylenesuccinate, it includes succinic acid dimethyl ester jar, 1, 4-butanediol jar, catalyst jar and ester exchange cauldron, succinic acid dimethyl ester jar, 1, 4-butanediol jar, catalyst jar all are connected through pipeline and ester exchange cauldron, a serial communication port, the ester exchange cauldron lower part is passed through the pipeline and is connected with polycondensation reaction cauldron upper portion, polycondensation reaction cauldron passes through the pipeline and is connected with oligomer depolymerization cauldron upper portion, oligomer depolymerization cauldron lower part is passed through the pipeline and is connected with the filter, the filter is connected with first dealcoholization tower.
Further, the bottom of the first methanol removal tower is connected with the first rectification tower through a pipeline.
Further, the lower part of the first rectifying tower is connected with the second rectifying tower through a pipeline.
Further, the upper part of the first rectifying tower is connected with a dimethyl succinate tank through a pipeline.
Furthermore, the upper part of the second rectifying tower is connected with a 1, 4-butanediol tank through a pipeline, and heavy components extracted from the bottom of the second rectifying tower are subjected to post-treatment.
Further, the upper part of the ester exchange kettle is connected with a second methanol removing tower through a pipeline.
Further, the lower part of the second methanol removing tower is connected with a pipeline between the second methanol removing tower and the upper part of the ester exchange kettle through a pipeline.
Further, the filter is a centrifugal filter, a filter pressing device or a fiber filter cloth filter.
The utility model has the advantages that: the utility model provides a pair of production device of olybuthylenesuccinate has following advantage:
(1) the preparation process of the utility model is easy to control, no hydrogen chloride is generated in the synthesis process, no subsequent treatment process is needed, the pollution is little, and the preparation process is safer and more environment-friendly;
(2) based on the process and the control process of the utility model, the by-product is further recycled, and the PBS yield is more than 90%;
(3) the utility model discloses carry out processing to the low polymer distillate, adopt alkaline catalyst to carry out ester exchange reaction, the low polymer that will distill off is handled into dimethyl succinate and 1, 4-butanediol, through the rectification under reduced pressure be used for PBS again to synthesize, has realized the maximize utilization of raw materials.
Drawings
Fig. 1 is a schematic structural view of the present invention;
in the figure: 1: dimethyl succinate tank, 2: 1, 4-butanediol tank, 3: catalyst pot, 4: ester exchange kettle, 5: first demethanizer, 6: polycondensation reaction kettle, 7: oligomer depolymerization kettle, 8: a filter, 9: second demethanizer, 10: first rectifying column, 11: a second rectifying tower.
Detailed Description
As shown in fig. 1, the present invention mainly includes a dimethyl succinate tank 1, a 1, 4-butanediol tank 2, a catalyst tank 3, an ester exchange kettle 4, a first demethanizer 5, a polycondensation reaction kettle 6, a low polymer depolymerization kettle 7, a filter 8, a second demethanizer 9, a first rectification tower 10 and a second rectification tower 11, and the present invention will be described in detail with reference to the accompanying drawings.
As shown in fig. 1, a dimethyl succinate tank 1 is used for storing dimethyl succinate, a 1, 4-butanediol tank 2 is used for storing 1, 4-butanediol, and a catalyst tank 3 is used for storing a catalyst (such as an organic titanium catalyst). The dimethyl succinate tank 1 is connected with the ester exchange kettle 4 through a pipeline, the 1, 4-butanediol tank 2 is connected with the ester exchange kettle 4 through a pipeline, and the catalyst tank 3 is also connected with the ester exchange kettle 4 through a pipeline. Thus, the dimethyl succinate in the dimethyl succinate tank 1, the 1, 4-butanediol in the 1, 4-butanediol tank 2 and the catalyst in the catalyst tank 3 can be added into the ester exchange kettle 4 through pipelines to carry out ester exchange reaction in the ester exchange kettle 4, and distillate is obtained, wherein the content of methanol in the distillate is more than 99 percent.
As shown in fig. 1, the ester exchange kettle 4 is connected with the upper part of the polycondensation reaction kettle 6 through a pipeline, the materials after the ester exchange reaction enter the polycondensation reaction kettle 6 through the pipeline, the high-temperature polycondensation reaction is carried out in the polycondensation reaction kettle 6 to obtain PBS, and the PBS is discharged from a discharge port at the lower part of the polycondensation reaction kettle 6; the polycondensation distillate is discharged from the gas phase outlet at the upper part of the polycondensation reaction kettle 6. The upper part of the polycondensation reaction kettle 6 is connected with an oligomer depolymerization kettle 7 through a pipeline, the polycondensation distillate enters the oligomer depolymerization kettle 7 after being condensed, an alkaline catalyst is added into the oligomer depolymerization kettle 7 to carry out depolymerization reaction on the condensed polycondensation distillate, and the oligomer content in the product after the depolymerization reaction can be less than 2%.
As shown in fig. 1, the lower part of the oligomer depolymerization kettle 7 is connected to a filter 8 through a pipe, the product after the depolymerization reaction enters the filter 8, the depolymerization product is filtered in the filter 8, and impurities such as unreacted polymer particles and trace oxides are filtered out. The filter 8 may be a centrifugal filter, a filter press device or a fibre cloth filter. The filter 8 is connected to the first methanol removal tower 5 through a pipe, and the product after the depolymerization reaction is introduced into the first methanol removal tower 5 to be subjected to methanol removal treatment. As shown in fig. 1, the lower portion of the first methanol removing column 5 is connected to a first rectifying column 10 through a pipeline, the lower portion of the first rectifying column 10 is connected to a second rectifying column 11 through a pipeline, the upper portion of the first rectifying column 10 is connected to a dimethyl succinate tank 1 through a pipeline, and the upper portion of the second rectifying column 11 is connected to a 1, 4-butanediol tank 2 through a pipeline. Separating the product of depolymerization reaction for removing part of methanol in a first rectifying tower 10 to obtain 1, 4-butanediol and dimethyl succinate, wherein the dimethyl succinate is conveyed into a dimethyl succinate tank 1 through a pipeline for recycling; discharging from the lower part of the first rectifying tower 10 to enter a second rectifying tower 11, separating 1, 4-butanediol in the second rectifying tower 11, enabling the 1, 4-butanediol to enter a 1, 4-butanediol tank 2 through a pipeline for cyclic utilization, and extracting heavy components from the lower part of the second rectifying tower 11 for post-treatment.
As shown in fig. 1, the transesterification tank 4 is connected to a second methanol removal column 9 through a pipe, and the distillate in the transesterification tank 4 is introduced into the second methanol removal column 9 to remove methanol in the second methanol removal column 9. In order to ensure the methanol removal effect of the second methanol removal tower 9, the bottom of the second methanol removal tower 9 is also connected with the pipeline between the second methanol removal tower 9 and the transesterification tank 4, and the distillate without complete methanol removal enters the second methanol removal tower 9 again to remove methanol after being removed from the second methanol removal tower 9. The methanol removed in the first and second demethanizers 5 and 9 is removed through the upper portions of the first and second demethanizers 5 and 9.
The following describes the production process of polybutylene succinate of the present invention:
(1) esterification reaction
1200g of dimethyl succinate is taken from a dimethyl succinate tank 1, 800g of 1, 4-butanediol 700-one-shot material is taken from a 1, 4-butanediol tank 2, 2-3g of organic titanium catalyst is taken from a catalyst tank 3, the addition amount of the organic titanium catalyst is 50ppm-1000ppm (calculated by titanium content), and the ratio of the 1, 4-butanediol to the dimethyl succinate is (1-1.3): 1. 1200g of dimethyl succinate and 800g of 1, 4-butanediol are added into an ester exchange kettle 4, and the ester exchange kettle is heated to 40-80 ℃. Then adding 2-3g of catalyst into the ester exchange kettle 4, heating the ester exchange kettle 4 to 140 ℃ at the temperature of 120-; then the reaction temperature in the ester exchange kettle is continuously increased at the speed of 2-5 ℃/min, the step heating operation is adopted, the temperature rise gradient of each stage is 5-20 ℃, the constant temperature of each stage is 0.5-1h, the reaction end temperature is 160-200 ℃, the ester exchange time is 2-4h, the methanol distillate is 85-95% of the theoretical distillate at the end of the reaction, the methanol content in the distillate is more than or equal to 99%, the rest components are dimethyl succinate and trace tetrahydrofuran (less than 0.5%), and the materials enter the polycondensation reaction kettle 6 after the reaction in the ester exchange kettle 4 is finished.
(2) High-temperature polycondensation:
in the polycondensation reaction kettle 6, the temperature is adjusted to 170-200 ℃, and a certain amount of phosphate ester cocatalyst is added, wherein the cocatalyst is one or two of 60-90% phosphoric acid, trimethyl phosphate, triethyl phosphate and triphenyl phosphate, and the addition amount is 0.2-1.0 g. Adding nitrogen for protection, stirring, and reacting at constant temperature for 0.5-1 h. The pressure in the high-temperature polycondensation process is negative pressure, a rotary-vane vacuum pump is adopted to control the pressure in the polycondensation reaction, the pressure is gradually reduced from normal pressure to 50-200Pa, the reaction temperature is increased to 250 ℃ at the speed of 2-5 ℃/min, the stirring speed is 50-250rpm, the reaction is finished when the stirring torque value reaches 2.0-5.0N/m, the polycondensation time is 3-5h, the vacuumizing is stopped, the nitrogen is used for pressurizing to normal pressure, the reaction kettle is cooled to 240 ℃ with 180 ℃ with the addition of impurities, the nitrogen is pressurized to 2-5bar, the product is extruded from a discharge port at the lower part of the polycondensation reaction kettle 6, the residual product is taken out after the kettle is opened, the PBS yield is 90-95%, the weight average molecular weight is more than 15 ten thousand, and the molecular weight distribution coefficient is 1.4-2.0. The polycondensation distillate is discharged from the gas phase outlet at the upper part of the polycondensation reaction kettle 6, and enters the oligomer depolymerization kettle 7 after being condensed.
(3) Distillate recovery and utilization
Depolymerizing the polycondensation distillate in an oligomer depolymerization kettle 7 under the action of an alkaline catalyst, wherein the catalyst can be one or more of nano magnesium oxide, calcium oxide, sodium hydroxide and potassium hydroxide, the dosage of the catalyst is 0.5-2% of the high-temperature polycondensation distillate, the reaction temperature is 150-200 ℃, the reaction time is 2-4h, and the content of the oligomer in the product after the reaction is reduced to below 2%. After the depolymerization reaction is finished, the product enters a first methanol removing tower 5 through a filter 8 to remove part of methanol, and then is separated by a first rectifying tower 10 and a second rectifying tower 11 to obtain 1, 4-butanediol and dimethyl succinate, the dimethyl succinate extracted from the top of the first rectifying tower 10 is circulated to a dimethyl succinate tank 1 for recycling, the discharged material at the bottom of the tower enters the second rectifying tower 11, the 1, 4-butanediol extracted from the top of the second rectifying tower 11 is conveyed to a 1, 4-butanediol tank 2 for recycling, and the heavy component extracted from the bottom of the second rectifying tower 11 is subjected to post-treatment.
The following describes the production process of polybutylene succinate according to the present invention with reference to specific embodiments:
the ester exchange process is as follows: 1200g of succinic acid dimethyl ester with the water content of 400PPm and 788g of 1, 4-butanediol with the water content of 1000PPm are weighed and added into a reaction kettle, and the temperature is heated to 50 ℃. Weighing 2.8g of tetraisopropyl titanate catalyst with the titanium content of 0.35%, adding the tetraisopropyl titanate catalyst into an ester exchange kettle, heating the ester exchange kettle to 130 ℃ at the speed of 3 ℃/min, rotating at the speed of 250rpm, carrying out constant-temperature reaction for 1h, continuously heating at the speed of 3 ℃/min, wherein the temperature rise gradient of each stage is 10 ℃, the constant temperature is 0.5h, the reaction end temperature is 170 ℃, the ester exchange time is 2.5h, the distilled amount of methanol is 478g when the reaction is finished, the methanol content in the distillate is 99.1%, and the dimethyl succinate content is 0.9%.
Adjusting the temperature to 180 ℃, adding 0.22g of 85% phosphoric acid, adding nitrogen for protection, stirring, and reacting at constant temperature for 0.5 h. Adjusting the pressure in the polycondensation reaction kettle to 50000Pa, starting heating, heating to 220 ℃ at the heating rate of 2 ℃/min, gradually reducing the pressure in the polycondensation reaction kettle to 100Pa, continuing heating to 240 ℃, wherein the stirring speed is 250rpm, reducing the stirring speed when the stirring torque value reaches 3.0N/m, finishing the reaction when the rotating speed is reduced to 50rpm and the torque is 4.0N/m, the polycondensation time is 3.5h, stopping vacuumizing, pressurizing to normal pressure by using nitrogen, cooling the polycondensation reaction kettle to 220 ℃, extruding a product from a discharge port at the lower part of the polycondensation reaction kettle, opening the residual product, and then taking out, wherein the yield of PBS is 91%, the weight average molecular weight is more than 16 ten thousand, and the molecular weight distribution coefficient is 1.7.
The polycondensation distillate was condensed and collected in a receiver bottle to detect the amount of the distillate as 250g and the oligomer content as 35%. Adding 250g of polycondensation distillate into an oligomer depolymerization kettle, adding 2g of calcium oxide, reacting at 180 ℃ for 3h, and sampling and analyzing the products, wherein the oligomer content is 1.5%, the 1, 4-butanediol content is 56.5%, the dimethyl succinate content is 25.2%, and the methanol content is 18.3%.
The utility model has the advantages that:
(1) the preparation process of the utility model is easy to control, no hydrogen chloride is generated in the synthesis process, no subsequent treatment process is needed, the pollution is little, and the preparation process is safer and more environment-friendly;
(2) based on the process and the control process of the utility model, the by-product is further recycled, and the PBS yield is more than 90%;
(3) the utility model discloses carry out processing to the low polymer distillate, adopt alkaline catalyst to carry out ester exchange reaction, the low polymer that will distill off is handled into dimethyl succinate and 1, 4-butanediol, through the rectification under reduced pressure be used for PBS again to synthesize, has realized the maximize utilization of raw materials.
Claims (7)
1. The utility model provides a production device of olybuthylenesuccinate, it includes succinic acid dimethyl ester jar, 1, 4-butanediol jar, catalyst jar and ester exchange cauldron, succinic acid dimethyl ester jar, 1, 4-butanediol jar, catalyst jar all are connected through pipeline and ester exchange cauldron, a serial communication port, the ester exchange cauldron lower part is passed through the pipeline and is connected with polycondensation reaction cauldron upper portion, polycondensation reaction cauldron passes through the pipeline and is connected with oligomer depolymerization cauldron upper portion, oligomer depolymerization cauldron lower part is passed through the pipeline and is connected with the filter, the filter is connected with first dealcoholization tower.
2. The apparatus for producing polybutylene succinate according to claim 1, wherein the bottom of the first demethanizer is connected to the first fractionator via a pipe.
3. The apparatus for producing polybutylene succinate according to claim 2, wherein the lower part of the first rectifying tower is connected with the second rectifying tower through a pipeline.
4. The apparatus for producing polybutylene succinate according to claim 3, wherein the upper part of the first rectifying tower is connected with a dimethyl succinate tank through a pipeline.
5. The apparatus for producing poly (butylene succinate) according to claim 3, wherein the upper part of the second rectifying tower is connected with the 1, 4-butanediol tank through a pipeline, and heavy components are extracted from the bottom of the second rectifying tower for post-treatment.
6. The apparatus for producing poly (butylene succinate) according to claim 1, wherein the upper part of the ester exchange kettle is connected with the second methanol removing tower through a pipeline.
7. The apparatus for producing polybutylene succinate according to claim 6, wherein the lower portion of the second demethanizer is connected to the upper portion of the second demethanizer and the transesterification tank via a pipe.
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| CN202220232932.9U CN216826190U (en) | 2022-01-27 | 2022-01-27 | Production device of poly (butylene succinate) |
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| CN202220232932.9U CN216826190U (en) | 2022-01-27 | 2022-01-27 | Production device of poly (butylene succinate) |
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