CN103446968B - The production method that sorbic acid polyester continuous bubbling tower absorbs - Google Patents
The production method that sorbic acid polyester continuous bubbling tower absorbs Download PDFInfo
- Publication number
- CN103446968B CN103446968B CN201210564140.2A CN201210564140A CN103446968B CN 103446968 B CN103446968 B CN 103446968B CN 201210564140 A CN201210564140 A CN 201210564140A CN 103446968 B CN103446968 B CN 103446968B
- Authority
- CN
- China
- Prior art keywords
- tower
- bubbling
- sorbic acid
- crotonaldehyde
- acid polyester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The production method that the continuous bubbling tower that the invention provides a kind of sorbic acid polyester absorbs, it is characterized in that, crotonaldehyde and polymerization catalyst are after secondary spray absorber (5) tower top spray enters continuously, discharge containing unreacted ketenes tail gas with bubbling packed tower (2) tower top, the negative pressure formed by venturi jet pump (7) is drawn into secondary spray absorber (5) and carries out cyclic absorption reaction, send at the bottom of bubbling packed tower (2) tower through the first circulating pump (3) again, the ketenes entered with normal pressure at the bottom of the tower of bubbling packed tower (2) carries out based on the ketenes of the negative pressure absorbing of following current and crotonaldehyde polymerisation, qualified sorbic acid polyester liquid is by the continuous extraction of bubble tower tower top.The method realizes the reaction that within a short period of time makes high concentration crotonaldehyde and high concentration ethylene ketone continuously, avoid the generation of more multifocal oil, ensure that safety and stability is produced, improve polymerisation efficiency and polyester quality, reduce production cost, have a good application prospect.
Description
Technical field
The invention belongs to chemical field, be specifically related to the production method that sorbic acid polyester continuous bubbling tower absorbs.
Background technology
Sorbic acid (sorbicacid), chemical name is 2,4-hexadienoic acid, a kind of there is the unrighted acid gripping diene altogether, it can the activity of mould fungus inhibition, saccharomycete and aerobic bacteria effectively, it suppresses the effect of harmful microorganism development and fecundity stronger than bactericidal action, is the anticorrisive agent that the United Nations's grain tissue is recommended to countries in the world.Sorbic acid has been widely used in the anticorrosion and fresh-keeping of the industries such as various food, veterinary antibiotics, medicine, rubber, papermaking, animal feed, cosmetics, paint, tobacco, beverage.
At present, the main syntheti c route that sorbic acid adopts is that the polymerization of crotonaldehyde and ketenes generates polyester, then utilizes hydrochloric acid to divide and solves sorbic acid crude product, obtain sorbic acid product finally by refining.
The reaction equation of this process route is as follows:
The chemical property of ketenes and crotonaldehyde is active; particularly the character of ketenes is very active; with the polymerization process of crotonaldehyde in control the undesirable self-polymerization that can cause ketenes or crotonaldehyde; the particularly polymerization of ketenes; produce a large amount of side reaction, when causing being hydrolyzed, sorbic acid yield is on the low side.Avoiding and control autohemagglutination and other side reaction of ketenes, is the key factor improving sorbic acid yield.
The desirable reaction pattern of the polymerisation of ketenes (a) and crotonaldehyde (b) be between poly-reaction, generated ideal polyester molecule composition is approximately ... abababab ... polymer, but real reaction can not be perfect condition completely, embedding poly-reaction often occurs, and the polyester molecule namely generated composition is approximately ... ab
nab ... or ... aba
nb ... polymer, the character of ketenes is much more active than crotonaldehyde ... aba
nb ... polymer should compare ... ab
nab ... polymer much more, polyester molecule composition in a
nor b
npolymer is all hydrolyzed when polyester is hydrolyzed and generates tar or other by-product impurity, and therefore raising sorbic acid gathers the key of ester hydrolysis yield is during when how to avoid and reduce polymerisation, polyester molecule forms ... ab
nab ... or ... aba
nb ... the generation of polymer, particularly ... aba
nb ... the generation of polymer.Be conducive to most theoretically generating ... aba
nb ... the condition of polymer be react with rather high concentration a under relatively low concentration b environment, namely react with rather high concentration ketenes under relative lower concentration crotonaldehyde and be just conducive to tar and other by-product impurity, therefore the polymerisation of ketenes and crotonaldehyde should avoid the reaction under relative lower concentration crotonaldehyde and rather high concentration ketenes as far as possible.
In current actual production, polymerisation interval or successive reaction normally in common enamel reactor or circulated sprinkling packed tower, under catalyst action of ketenes and crotonaldehyde complete, in order to realize the complete reaction of ketenes, normally adopt multiple enamel still or the series connection of circulated sprinkling packed tower to carry out, the first reactor is main reactor.It is the reaction of high concentration ethylene ketone and high concentration crotonaldehyde when intermittent reaction starts, along with the carrying out of reaction, crotonaldehyde concentration declines gradually, be conducive to autohemagglutination and other side reaction of ketenes, in actual production, reaction depth is higher, after polyester hydrolysis, tar is more, and hydrolysis yield is also lower, and therefore intermittent reaction is not best reaction formation.The successive reaction form introduced in application number 200810098512 disclosed in Chinese patent adopts a kettle material part by continuous extraction, major part is implemented pressurized circulation as recycle stock and is absorbed ketenes, namely for absorb ketenes material in the concentration of crotonaldehyde decline to a great extent, advantageously in autohemagglutination and other side reaction of ketenes, if adopt the method for adding solvent to produce polyester, effect will be poorer, and therefore the method for employing circulated sprinkling packed tower series connection continuous production of polyesters neither optimal reaction formation.
Summary of the invention
In order to solve the problem, the production method the method that the object of the present invention is to provide sorbic acid polyester continuous bubbling tower to absorb applies the combination unit comprising the secondary spray-absorption packed tower making crotonaldehyde and ketene gas absorb bubbling packed tower through the following current of polymerisation and can keep bubble tower tiny structure, achieve the reaction that within a short period of time makes high concentration crotonaldehyde and high concentration ethylene ketone continuously, this polymerisation in following current bubble tower under tiny structure successive reaction complete, avoid the generation of more multifocal oil, improve polymerisation efficiency and polyester hydrolysis yield, reduce production cost.The present invention achieves the serialization of sorbic acid polyester in sorbic acid manufacture, improve polymerisation efficiency, polyester quality and polyester hydrolysis yield, reduce production cost, ensure that the safety and stability of front road technique ketenes is produced, before having good application simultaneously.
Technical solution of the present invention is as follows:
The production method of the continuous bubbling tower absorption of sorbic acid polyester provided by the invention, it is characterized in that, crotonaldehyde and polymerization catalyst are after secondary spray absorber 5 tower top spray enters continuously, discharge containing unreacted ketenes tail gas with bubbling packed tower 2 tower top, the negative pressure formed by venturi jet pump 7 is drawn into secondary spray absorber 5 and carries out cyclic absorption reaction, send at the bottom of bubbling packed tower 2 tower through the first circulating pump 3 again, the ketenes entered with normal pressure at the bottom of the tower of bubbling packed tower 2 carries out the polymerisation based on the ketenes of the negative pressure absorbing of following current and crotonaldehyde, qualified sorbic acid polyester liquid is by the continuous extraction of bubble tower tower top.
According to the production method that the continuous bubbling tower of sorbic acid polyester provided by the invention absorbs, preferably, described crotonaldehyde and polymerization catalyst are after secondary spray absorber 5 tower top spray enters continuously, through the first circulating pump 3, crotonaldehyde and polymerization catalyst mixture material are sent at the bottom of bubbling packed tower 2 tower, the ketenes entered with normal pressure at the bottom of the tower of bubbling packed tower 2 carries out one way following current polymerisation, and qualified sorbic acid polyester liquid is by the continuous extraction of bubble tower tower top.
According to the production method that the continuous bubbling tower of sorbic acid polyester provided by the invention absorbs, preferably, the mixed material of described crotonaldehyde and polymerization catalyst, after secondary spray absorber 5 tower top spray enters continuously, is squeezed into the absorption of secondary spray absorber 5 tower top circulated sprinkling through the second circulating pump 6 by described crotonaldehyde and polymerization catalyst again.
According to the production method that the continuous bubbling tower of sorbic acid polyester provided by the invention absorbs, it is characterized in that, the negative pressure that described venturi jet pump (7) is formed keeps negative pressure and maintenance ketenes in bubbling packed tower (2) to add the normal pressure of system.
According to the production method that the continuous bubbling tower of sorbic acid polyester provided by the invention absorbs, preferably, the mass percentage content of described crotonaldehyde is 50 ~ 100%.
According to the production method that the continuous bubbling tower of sorbic acid polyester provided by the invention absorbs, further preferably, the mass percentage content of described crotonaldehyde is 60 ~ 80%.
According to the production method that the continuous bubbling tower of sorbic acid polyester provided by the invention absorbs, preferably, the reaction conversion ratio of described crotonaldehyde controls 30 ~ 80%.
According to the production method that the continuous bubbling tower of sorbic acid polyester provided by the invention absorbs, further preferably, the reaction conversion ratio of described crotonaldehyde controls 60 ~ 70%.
According to the production method that the continuous bubbling tower of sorbic acid polyester provided by the invention absorbs, preferably, described negative pressure is according to the pressure of the ketenes import department of bubbling packed tower, and pressure limit is-100 ~ 0mmHg.
According to the production method that the continuous bubbling tower of sorbic acid polyester provided by the invention absorbs, preferably, in described bubbling packed tower 2, temperature of charge is 20 ~ 100 DEG C.
According to the production method that the continuous bubbling tower of sorbic acid polyester provided by the invention absorbs, preferably, in described bubbling packed tower 2, temperature of charge is 60 ~ 80 DEG C.
According to the production method that the continuous bubbling tower of sorbic acid polyester provided by the invention absorbs, after the described continuous extraction of sorbic acid polyester, through acidolysis, alkali, molten and decolouring obtains sorbic acid.
According to the production method that the continuous bubbling tower of a kind of sorbic acid polyester provided by the invention absorbs, preferably, described bubbling packed tower 2 tower top release is drawn into after secondary spray absorber 5 carries out cyclic absorption reaction containing unreacted ketenes tail gas by the negative pressure that venturi jet pump 7 is formed, and carries out toxic emission.
According to the reaction unit that sorbic acid polyester continuous bubbling tower provided by the invention absorbs, preferably, the lift 30 ~ 50m of described venturi jet pump 7, flow 100 ~ 300m
3/ h, rate of air sucked in required 150 ~ 300m
3/ h.
According to the reaction unit that sorbic acid polyester continuous bubbling tower provided by the invention absorbs, further preferably, the lift 35 ~ 40m of described venturi jet pump 7.
According to the reaction unit that sorbic acid polyester continuous bubbling tower provided by the invention absorbs, further preferably, the flow 150 ~ 250m of described venturi jet pump 7
3/ h.
According to the reaction unit that sorbic acid polyester continuous bubbling tower provided by the invention absorbs, further preferably, the rate of air sucked in required 180 ~ 260m of described venturi jet pump 7
3/ h.
According to the reaction unit that sorbic acid polyester continuous bubbling tower provided by the invention absorbs, preferably, the tower height degree 6 ~ 11m of described secondary spray absorber 5, tower diameter 450 ~ 750mm.
According to the reaction unit that sorbic acid polyester continuous bubbling tower provided by the invention absorbs, further preferably, the tower height degree 7 ~ 10m of described secondary spray absorber 5, tower diameter 550 ~ 650mm.
According to the reaction unit that sorbic acid polyester continuous bubbling tower provided by the invention absorbs, preferably, the tower height degree 3 ~ 8m of described bubbling packed tower 2, tower diameter 400 ~ 700mm.
According to the reaction unit that sorbic acid polyester continuous bubbling tower provided by the invention absorbs, preferably, the tower height degree 4 ~ 7m of described bubbling packed tower 2, tower diameter 500 ~ 600mm.
According to the reaction unit that sorbic acid polyester continuous bubbling tower provided by the invention absorbs, preferably, the lift 30 ~ 80m of described first circulating pump 2.
According to the reaction unit that sorbic acid polyester continuous bubbling tower provided by the invention absorbs, preferably, the lift 30 ~ 80m of described second circulating pump 2.
The material of bubbling packed tower 2 of the present invention and secondary spray absorber 5 is stainless steel Pall ring material, optional 304L or 316L of volume.
The preparation method of sorbic acid polyester provided by the invention, this technique includes the combination unit (4) of the secondary spray-absorption packed tower making crotonaldehyde and ketene gas absorb bubbling packed tower through the following current of polymerisation and can keep bubble tower tiny structure.Wherein, the polymerisation of crotonaldehyde and ketene gas mainly absorbs in bubbling packed tower in following current carries out continuously, do not absorb ketenes completely enter by outer setting have circulating pump and can ketenes in the secondary spray absorber that venturi jet pump absorbs completely absorb after discharge.Fresh crotonaldehyde and polymerization catalyst are sprayed by secondary spray-absorption column overhead and enter in tower, and a spray column kettle material part is squeezed into tower top circulated sprinkling by outer loop pump and absorbed; A part by pump squeeze into venturi jet pump make following current absorb bubbling packed tower capable become tiny structure, extract the complete ketenes of unreacted simultaneously and enter in spray column, vacuum size is controlled by the mass flow of pump; Another part by be pumped into following current absorb bottom bubbling packed tower capable with fresh ethylene ketone become following current bubble absorption react, generate qualified a kind of sorbic acid polyester by tower top overflow extraction, reaction depth is controlled by the material-handling pump entering tower reactor.Thus achieve the reaction that within a short period of time makes high concentration crotonaldehyde and high concentration ethylene ketone continuously, avoid the generation of more multifocal oil, ensure that the safety and stability of front road technique ketenes is produced simultaneously.Be exactly by fresh crotonaldehyde, polymerization catalyst and the component loops material spray-absorption in secondary spray absorber from secondary spray absorber tower reactor concretely, in tower, temperature controls 20 ~ 100 DEG C of reactions, and charging rate is controlled by the rate of withdrawal of qualified polyester; A part of material in secondary spray absorber tower reactor squeezes into venturi jet pump by pump makes following current absorb the tiny structure of import house one-tenth-100 ~ 0mmHg of bubbling packed tower ketenes; Enter following current from the material of secondary spray absorber tower reactor and ketenes by tower reactor to absorb control temperature in bubbling packed tower and carry out the reaction of following current bubble absorption at 20 ~ 100 DEG C, qualified sorbic acid polyester, by bubble tower tower top overflow extraction, achieves the continuous prodution of technique.
The production method of sorbic acid polyester provided by the invention is that ketene gas and crotonaldehyde tiny structure continuous polymerization in bubble tower are reacted and generated PET Process, and then polyester obtains sorbic acid through acid, alkali or heat resolve.The polymerisation of crotonaldehyde and ketene gas is at the combination unit at least including the bubbling packed tower that following current absorbs and the secondary spray-absorption packed tower that can keep bubble tower tiny structure.The packed tower that secondary spray absorber can be absorbed through venturi jet pump by circulating pump and ketenes by outer setting forms.This device polymerisation is carried out continuously, and sent into bottom bubble tower by the recycle stock from secondary spray absorber tower reactor and form following current absorption reaction with ketenes, qualified polyester liquid is by bubble tower overhead extraction; Tower top tail gas enters secondary spray absorber, and the negative pressure formed by venturi jet pump device keeps tiny structure in bubble tower to realize keeping the normal pressure of ketenes system, and is reacted by unreacted ketene gas suction secondary spray absorber; Spraying of material enters filler tower reactor, the crotonaldehyde in unreacted ketenes and material and spray by secondary spray-absorption column overhead the fresh crotonaldehyde entered and carry out cyclic absorption polymerization reaction take place; A material part from secondary spray-absorption packed tower tower reactor is used for the Inner eycle of reactor assembly, a part enter bubble tower and fresh ethylene ketone continue to react after by the continuous extraction of bubbling tower top, depth of cure, by the control of the charging rate of fresh crotonaldehyde, realizes continuous prodution with this.
The production method of sorbic acid polyester provided by the invention:
1., have employed bubbling packed tower device, carried out being absorbed as main ketenes and the polymerisation of crotonaldehyde with the tiny structure of following current;
2., have employed the secondary spray-absorption packed tower that can keep bubble tower tiny structure, absorbed completely by ketenes, the packed tower that secondary spray absorber can be absorbed through venturi jet pump by circulating pump and ketenes by outer setting forms.
The production method of sorbic acid polyester provided by the invention:
1., fresh crotonaldehyde and catalyst are sprayed by secondary spray-absorption column overhead and enter continuously, carry out the unreacted ketenes of cyclic absorption reaction bubble tower, then bubbling packed tower device is entered and fresh ethylene ketone carries out one way following current polymerisation again, qualified polyester liquid is by the continuous extraction of bubble tower tower top, depth of cure, by the control of the charging rate of fresh crotonaldehyde, realizes continuous prodution with this;
2., fresh ethylene ketone enters by under bubbling packed tower tower reactor normal-pressure situations, carry out being absorbed as main ketenes and the polymerisation of crotonaldehyde with the tiny structure of following current with the material from secondary spray-absorption packed tower tower reactor, the negative pressure that tower top tail gas is formed by venturi jet pump device sucks secondary spray absorber, carries out toxic emission after the complete absorption reaction of circulated sprinkling.
The production method of sorbic acid polyester provided by the invention:
1., fresh crotonaldehyde refer to crotonaldehyde content 50 ~ 100% crotonaldehyde, can be pure crotonaldehyde, also can be the crotonaldehyde containing solvent (as toluene, benzene etc.), comprises and reclaim crotonaldehyde and solvent;
2., depth of cure refers to the reaction conversion ratio of crotonaldehyde, and control range is 30 ~ 80%;
3., the tiny structure of bubble tower is as the criterion with tower reactor ketenes inlet pressure, control the emitted dose of the ejecta stream of secondary spray absorber Wen Qiuli jet pump, make ketenes inlet pressure form the vacuum of-100 ~ 0mmHg, form the tiny structure absorption reaction of bubble tower;
4. the cooling device, by arranging in bubbling packed tower tower reactor and tower, in control tower, temperature of charge is 20 ~ 100 DEG C
The production method of sorbic acid polyester provided by the invention is continuous producing method, the method is that the continuous one way polymerisation of ketene gas and crotonaldehyde tiny structure in bubble tower generates polyester, the negative pressure that tail gas is formed by venturi jet pump device sucks secondary spray absorber, carries out the production method of toxic emission after the complete absorption reaction of circulated sprinkling.
Crotonaldehyde is one of main polymerisation raw material of the present invention, " the fresh crotonaldehyde " mentioned in the present invention refer to the purity entering reaction system be greater than 99% crotonaldehyde or technical process in recovery crotonaldehyde; Also can be the mixture of crotonaldehyde content more than 40% containing organic solvent or the recovery mixture in technical process.Organic solvent refers to as atent solvents such as toluene, dimethylbenzene, benzene.Except specified otherwise, " crotonaldehyde " mentioned in the present invention is also equal to fresh crotonaldehyde defined above.
Liquid or gas etc. that following current of the present invention can be understood as in raw material all move by equidirectional; The molecular weight of the sorbic acid polyester of gained of the present invention is at 3000-4000.
Advantageous Effects of the present invention:
Production method the method that sorbic acid polyester continuous bubbling tower provided by the invention absorbs applies to comprise and makes crotonaldehyde and ketene gas absorb bubbling packed tower and the combination unit of secondary spray-absorption packed tower that can keep bubble tower tiny structure through the following current of polymerisation, achieve the reaction that within a short period of time makes high concentration crotonaldehyde and high concentration ethylene ketone continuously, this polymerisation in following current bubble tower under tiny structure successive reaction complete, avoid the generation of more multifocal oil, improve polymerisation efficiency and polyester hydrolysis yield, reduce production cost.The present invention achieves the serialization of sorbic acid polyester in sorbic acid manufacture, improve polymerisation efficiency, polyester quality and polyester hydrolysis yield, reduce production cost, ensure that the safety and stability of front road technique ketenes is produced, before having good application simultaneously.
Accompanying drawing explanation
Fig. 1 is reaction unit and the production method schematic diagram of the absorption of a kind of sorbic acid polyester continuous bubbling tower;
1-polyester groove in figure, 2-bubbling packed tower, 3-the first circulating pump, 4-secondary spray-absorption packed tower combination unit, 5-secondary spray absorber, 6-second circulating pump, 7-venturi jet pump, 8-crotonaldehyde and catalyst enter continuously, and 9-air is emptying, 10-ketenes enters, 11-qualified polyester.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further elaborated, it will be appreciated by those skilled in the art that described embodiment is only for example, and do not form any restriction to the present invention.
Embodiment 1
The reaction unit schematic diagram that sorbic acid polyester continuous bubbling tower absorbs as shown in Figure 1.
The lift 30m of venturi jet pump 7, flow 100m
3/ h, rate of air sucked in required 150m
3/ h; The tower height degree 6m of secondary spray absorber 5, tower diameter 450mm; The tower height degree 3m of bubbling packed tower 2, tower diameter 400mm; The lift 30m of the first circulating pump 3; The lift 30m of the second circulating pump 6.
Be that the material that 99% crotonaldehyde and polymerization catalyst mix enters in tower by the top spray of spray absorber 5 by content, when the enough systemic circulation of amount of liquid in tower reactor, start outside second circulating pump 6 of tower reactor to circulate to this crotonaldehyde material, a recycle stock part enters from the tower top spray of spray absorber 5, returns tower reactor after absorbing ketenes; Another part enters venturi jet pump 7, make following current absorb bubbling packed tower 2 and form tiny structure, the ketenes simultaneously extracting unreacted complete enters in spray column tower reactor, the mass flow of control pump, controls the import vacuum of bubbling packed tower ketenes between 50 ~ 0mmHg; Some by spray absorber 5 kettle material by be pumped into following current absorb the fresh ethylene ketone produced with ketenes device bottom bubbling packed tower capable become following current bubble absorption react, control bubble absorption reaction temperature at 40 ~ 45 DEG C, generate qualified sorbic acid polyester liquid by tower top overflow extraction, control the flow of tower reactor material-handling pump, control the reaction conversion ratio of crotonaldehyde about 50%.
Sorbic acid polyester is obtained after sorbic acid polyester liquid vacuum distillation reclaims unreacted crotonaldehyde.Get the hydrochloric acid 5000g that sorbic acid polyester 1000g adds 30%, be warmed up to 80 DEG C of insulation depolymerization reactions 3 hours, cold filtration obtains crude product sorbic acid.Crude product sorbic acid add water 5000ml with 30% sodium hydrate aqueous solution to carry out alkali molten, 100g activated carbon decolorizing is added except tar removing after adjusting pH value to 7.5, filter, in filtrate hydrochloric acid and acid out, adjust pH value to 2.5, filter, washing, dries, and obtains the finished product sorbic acid 832g of white, content is greater than 99.5%, is 83.2% to the depolymerization yield of sorbic acid polyester.
Embodiment 2
The reaction unit schematic diagram that sorbic acid polyester continuous bubbling tower absorbs as shown in Figure 1.
The lift 35m of venturi jet pump 7, flow 150m
3/ h, rate of air sucked in required 180m
3/ h; The tower height degree 7m of secondary spray absorber 5, tower diameter 550mm; The tower height degree 4m of bubbling packed tower 2, tower diameter 500mm; The lift 50m of the first circulating pump 3; The lift 50m of the second circulating pump 6.
With reference to the operation of embodiment 1, being changed into by the crotonaldehyde of 99% with toluene is 60% crotonaldehyde solution of solvent, and the reaction conversion ratio controlling crotonaldehyde is 80%, the sorbic acid polyester liquid obtained operates by the depolymerization post-processing approach of embodiment 1 equally, obtain the finished product sorbic acid 815g of white, content is greater than 99.5%, is 81.5% to the depolymerization yield of sorbic acid polyester.
Embodiment 3
The reaction unit schematic diagram that sorbic acid polyester continuous bubbling tower absorbs as shown in Figure 1.
The lift 40m of venturi jet pump 7, flow 250m
3/ h, rate of air sucked in required 260m
3/ h; The tower height degree 10m of secondary spray absorber 5, tower diameter 650mm; The tower height degree 7m of bubbling packed tower 2, tower diameter 600mm; The lift 60m of the first circulating pump 3; The lift 50m of the second circulating pump 6.
With reference to the operation of embodiment 1, being changed into by the crotonaldehyde of 99% with toluene is 80% crotonaldehyde solution of solvent, and the reaction conversion ratio controlling crotonaldehyde is 60%, the sorbic acid polyester liquid obtained operates by the depolymerization post-processing approach of embodiment 1 equally, obtain the finished product sorbic acid 823g of white, content is greater than 99.5%, is 82.3% to the depolymerization yield of sorbic acid polyester.
Embodiment 4
The reaction unit schematic diagram that sorbic acid polyester continuous bubbling tower absorbs as shown in Figure 1.
The lift 35m of venturi jet pump 7, flow 250m
3/ h, rate of air sucked in required 180m
3/ h; The tower height degree 10m of secondary spray absorber 5, tower diameter 550mm; The tower height degree 7m of bubbling packed tower 2, tower diameter 600mm; The lift 60m of the first circulating pump 3; The lift 60m of the second circulating pump 6.
With reference to the operation of embodiment 1, being changed into by the crotonaldehyde of 99% with toluene is 50% crotonaldehyde solution of solvent, and the reaction conversion ratio controlling crotonaldehyde is 70%, the sorbic acid polyester liquid obtained operates by the depolymerization post-processing approach of embodiment 1 equally, obtain the finished product sorbic acid 835g of white, content is greater than 99.5%, is 83.5% to the depolymerization yield of sorbic acid polyester.
Embodiment 5
The reaction unit schematic diagram that sorbic acid polyester continuous bubbling tower absorbs as shown in Figure 1.
The lift 50m of venturi jet pump 7, flow 300m
3/ h, rate of air sucked in required 300m
3/ h; The tower height degree 11m of secondary spray absorber 5, tower diameter 750mm; The tower height degree 8m of bubbling packed tower 2, tower diameter 700mm; The lift 80m of the first circulating pump 3; The lift 80m of the second circulating pump 6.
With reference to the operation of embodiment 1, being changed into by the crotonaldehyde of 99% with benzene is 60% crotonaldehyde solution of solvent, and the reaction conversion ratio controlling crotonaldehyde is 80%, the sorbic acid polyester liquid obtained operates by the depolymerization post-processing approach of embodiment 1 equally, obtain the finished product sorbic acid 809g of white, content is greater than 99.5%, is 80.9% to the depolymerization yield of sorbic acid polyester.
Effect comparison example 1
Be that the mixed material of 99% crotonaldehyde and catalyst adds in autoclave intermittent reaction device to carry out feeding intake and is obtained by reacting sorbic acid polyester liquid by content, control reaction temperature at 40 ~ 50 DEG C, the reaction conversion ratio of crotonaldehyde controls about 50%.Other operation operates by the depolymerization post-processing approach of embodiment 1, and obtain the finished product sorbic acid 807g of white, content is greater than 99.5%, is 80.7% to the depolymerization yield of sorbic acid polyester.
Effect comparison example 2
With reference to the operation of effect comparison example 1, the crotonaldehyde of 99% is changed into the 60% crotonaldehyde solution that toluene is solvent, and the reaction conversion ratio controlling crotonaldehyde is 80%, the sorbic acid polyester liquid obtained operates by the depolymerization post-processing approach of embodiment 1 equally, obtain the finished product sorbic acid 789g of white, content is greater than 99.5%, is 78.9% to the depolymerization yield of sorbic acid polyester.
Effect comparison example 3
The successive reaction form introduced in application number 200810098512 disclosed in reference Chinese patent, be that the mixed material of 99% crotonaldehyde and catalyst carries out the reaction that feeds intake with content, the sorbic acid polyester liquid obtained operates by the depolymerization post-processing approach of embodiment 1 equally, obtain the finished product sorbic acid 803g of white, content is greater than 99.5%, is 80.3% to the depolymerization yield of sorbic acid polyester.
Effect comparison example 4
The successive reaction form introduced in application number 200810098512 disclosed in reference Chinese patent, the reaction that feeds intake is carried out with the 60% crotonaldehyde solution material that toluene is solvent, the sorbic acid polyester liquid obtained operates by the depolymerization post-processing approach of embodiment 1 equally, obtain the finished product sorbic acid 624g of white, content is greater than 99.5%, is 62.4% to the depolymerization yield of sorbic acid polyester.
Production method the method that this sorbic acid polyester continuous bubbling tower provided by the invention absorbs applies to comprise and makes crotonaldehyde and ketene gas absorb bubbling packed tower and the combination unit of secondary spray-absorption packed tower that can keep bubble tower tiny structure through the following current of polymerisation, achieve the reaction that within a short period of time makes high concentration crotonaldehyde and high concentration ethylene ketone continuously, this polymerisation in following current bubble tower under tiny structure successive reaction complete, avoid the generation of more multifocal oil, improve polymerisation efficiency and polyester hydrolysis yield, reduce production cost.The present invention achieves the serialization of sorbic acid polyester in sorbic acid manufacture, improve polymerisation efficiency, polyester quality and polyester hydrolysis yield, reduce production cost, ensure that the safety and stability of front road technique ketenes is produced, before having good application simultaneously.
Claims (8)
1. the production method of the continuous bubbling tower absorption of a sorbic acid polyester, it is characterized in that, crotonaldehyde and polymerization catalyst are after secondary spray absorber (5) tower top spray enters continuously, discharge containing unreacted ketenes tail gas with bubbling packed tower (2) tower top, the negative pressure formed by venturi jet pump (7) is drawn into secondary spray absorber (5) and carries out cyclic absorption reaction, send at the bottom of bubbling packed tower (2) tower through the first circulating pump (3) again, the ketenes entered with normal pressure at the bottom of the tower of bubbling packed tower (2) carries out based on the ketenes of the negative pressure absorbing of following current and crotonaldehyde polymerisation, qualified sorbic acid polyester liquid is by the continuous extraction of bubble tower tower top, the negative pressure that described venturi jet pump (7) is formed keeps negative pressure and maintenance ketenes in bubbling packed tower (2) to add the normal pressure of system,
Or crotonaldehyde and polymerization catalyst are after secondary spray absorber (5) tower top spray enters continuously, through the first circulating pump (3), crotonaldehyde and polymerization catalyst mixture material are sent at the bottom of bubbling packed tower (2) tower, the ketenes entered with normal pressure at the bottom of the tower of bubbling packed tower (2) carries out one way following current polymerisation, and qualified sorbic acid polyester liquid is by the continuous extraction of bubble tower tower top.
2. the production method of the continuous bubbling tower absorption of sorbic acid polyester according to claim 1, it is characterized in that, the mixed material of described crotonaldehyde and polymerization catalyst, after secondary spray absorber (5) tower top spray enters continuously, is squeezed into the absorption of secondary spray absorber (5) tower top circulated sprinkling through the second circulating pump (6) by described crotonaldehyde and polymerization catalyst again.
3. the production method of the continuous bubbling tower absorption of sorbic acid polyester according to claim 1, it is characterized in that, described negative pressure is according to the pressure of the ketenes import department of bubbling packed tower, and pressure limit is-100 ~ 0mmHg.
4. the production method of the continuous bubbling tower absorption of sorbic acid polyester according to claim 1, it is characterized in that, the mass percentage content of described crotonaldehyde is 50 ~ 100%.
5. the production method of the continuous bubbling tower absorption of sorbic acid polyester according to claim 1, it is characterized in that, the reaction conversion ratio of described crotonaldehyde controls 30 ~ 80%.
6. the production method of the continuous bubbling tower absorption of sorbic acid polyester according to claim 1, it is characterized in that, in described bubbling packed tower (2), temperature of charge is 20 ~ 100 DEG C.
7. the production method of the continuous bubbling tower absorption of sorbic acid polyester according to claim 1, it is characterized in that, in described bubbling packed tower (2), temperature of charge is 60 ~ 80 DEG C.
8. the production method of the continuous bubbling tower absorption of sorbic acid polyester according to claim 1, it is characterized in that, described bubbling packed tower (2) tower top release is containing unreacted ketenes tail gas, the negative pressure formed by venturi jet pump (7) is drawn into after secondary spray absorber (5) carries out cyclic absorption reaction, then carries out toxic emission.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210564140.2A CN103446968B (en) | 2012-12-21 | 2012-12-21 | The production method that sorbic acid polyester continuous bubbling tower absorbs |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210564140.2A CN103446968B (en) | 2012-12-21 | 2012-12-21 | The production method that sorbic acid polyester continuous bubbling tower absorbs |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103446968A CN103446968A (en) | 2013-12-18 |
| CN103446968B true CN103446968B (en) | 2015-11-25 |
Family
ID=49730047
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210564140.2A Active CN103446968B (en) | 2012-12-21 | 2012-12-21 | The production method that sorbic acid polyester continuous bubbling tower absorbs |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103446968B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115057765A (en) * | 2022-07-27 | 2022-09-16 | 江苏道尔顿石化科技有限公司 | Production method for sorbic acid continuous condensation reaction |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1471997A (en) * | 2003-06-17 | 2004-02-04 | 东华工程科技股份有限公司 | Washing method and apparatus for phosphoric acid reacting trough extracting tail gas |
| CN101318891A (en) * | 2008-05-08 | 2008-12-10 | 山东金能煤炭气化有限公司 | Process for preparing sorbic acid |
| CN101654450A (en) * | 2009-09-11 | 2010-02-24 | 连云港宏业化工有限公司 | Method and device for producing thiophene and derivative thereof in direct-cooled mode |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080119552A1 (en) * | 2006-11-17 | 2008-05-22 | Novus International Inc. | Matrix-embedded compositions having organic acids and fatty acids |
-
2012
- 2012-12-21 CN CN201210564140.2A patent/CN103446968B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1471997A (en) * | 2003-06-17 | 2004-02-04 | 东华工程科技股份有限公司 | Washing method and apparatus for phosphoric acid reacting trough extracting tail gas |
| CN101318891A (en) * | 2008-05-08 | 2008-12-10 | 山东金能煤炭气化有限公司 | Process for preparing sorbic acid |
| CN101654450A (en) * | 2009-09-11 | 2010-02-24 | 连云港宏业化工有限公司 | Method and device for producing thiophene and derivative thereof in direct-cooled mode |
Non-Patent Citations (1)
| Title |
|---|
| 小川明等.文丘里喷射器.《气体中颗粒的分离》.化学工业出版社,1991,第354-360页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103446968A (en) | 2013-12-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101318891B (en) | Process for preparing sorbic acid | |
| CN103965045B (en) | Preparation process and device for glycerol triacetate | |
| CN104262299B (en) | A kind of ketene dimer production technique of high-efficiency environment friendly | |
| CN103755543B (en) | The air oxidation of cyclohexane that utilizes being separated synchronous reaction device based on gas-liquid-solid heterogeneous reaction produces the method for hexanodioic acid | |
| US20230338936A1 (en) | Stannous salt complex catalyst and method for producing l-lactide by using the same | |
| CN108586423A (en) | A kind of production technology of novel chlorocarbonic acid vinyl acetate | |
| CN106883121A (en) | The method that methyl formate hydrolysis prepares anhydrous formic acid | |
| CN202983658U (en) | Sorbic acid polyester continuous bubble tower absorption reaction device | |
| CN103446968B (en) | The production method that sorbic acid polyester continuous bubbling tower absorbs | |
| CN103446967B (en) | Reaction device for continuous bubble tower absorption of polysorbate | |
| CN102020628B (en) | Improved method of preparation process of polylactic acid midbody lactide | |
| CN1309112A (en) | Method for preparing alkylene diol | |
| CN1709847A (en) | Continuous synthesizing method of vinyl isobutyl ether | |
| CN105084657B (en) | Methionine produces the Biochemical pretreatment method of waste water | |
| CN110407780A (en) | A kind of refining methd of furfural | |
| CN204874355U (en) | Device of preparation lactide | |
| CN104592165A (en) | Method for producing epoxy chloropropane by gas-phase saponification of dichloropropanol | |
| CN107365245B (en) | A kind of methallyl alcohol production system and method | |
| CN111808005A (en) | Continuous synthesis method of 2-chloro-3-isothiocyanic acid-1-propylene | |
| KR20140014504A (en) | Methods for manufacturing lactic acid and lactide from ammonium lactate | |
| CN210915873U (en) | 1,1, 2-trichloroethane reactor | |
| CN216512941U (en) | Treatment system for leading-out water phase of hydration reactor in sec-butyl alcohol preparation through direct hydration method | |
| CN218945044U (en) | Glycolide or lactide oligomer cracking, dewatering and deacidifying device | |
| CN112279783B (en) | Method for preparing 3-hydroxypropionitrile under supercritical condition | |
| CN218458684U (en) | System for recovering benzyl alcohol as byproduct in production of phenylacetic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |