CN103446968A - Production method for continuous bubble tower absorption of polysorbate - Google Patents
Production method for continuous bubble tower absorption of polysorbate Download PDFInfo
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- CN103446968A CN103446968A CN2012105641402A CN201210564140A CN103446968A CN 103446968 A CN103446968 A CN 103446968A CN 2012105641402 A CN2012105641402 A CN 2012105641402A CN 201210564140 A CN201210564140 A CN 201210564140A CN 103446968 A CN103446968 A CN 103446968A
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Abstract
The invention provides a production method for continuous bubble tower absorption of polysorbate. The production method is characterized in that butenal and a polymerization catalyst are sprayed and are continuously fed from the top of a secondary spray absorption tower (5), and the butenal and the polymerization catalyst, together with unreacted ketene tail gas released from the top of a bubble packed tower (2), are absorbed to the secondary spray absorption tower (5) through negative pressure formed by a Venturi jet pump (7) for a circulating absorption reaction, are fed to the bottom of the bubble packed tower (2) through a first circulating pump (3), and participate in a ketene and butenal polymerization reaction focusing on downstream negative pressure absorption together with ketene from the bottom of the bubble packed tower (2) under normal pressure; a qualified polyester solution is continuously extracted from the top of the bubble tower. The method can realize continuous reaction between high-concentration butenal and high-concentration ketene within relatively short time, so as to avoid generation of more tar, guarantee safe and stable production, improve the polymerization efficiency and the polyester quality, and reduce the production cost; the method has good reaction 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 (sorbic acid), chemical name is 2, the 4-hexadienoic acid, it is a kind of unrighted acid of gripping altogether diene that has, it is the activity of mould fungus inhibition, saccharomycete and aerobic bacteria effectively, its effect that suppresses the harmful microorganism development and fecundity is 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, vegetables, fruit, 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 the sorbic acid crude product, finally by the refining sorbic acid product that obtains.
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; control the undesirable self-polymerization that can cause ketenes or crotonaldehyde in the polymerization process with crotonaldehyde; the particularly polymerization of ketenes; produce a large amount of side reactions, while causing being hydrolyzed, the sorbic acid yield is on the low side.Avoiding and control autohemagglutination and other side reaction of ketenes, is the key factor that improves the sorbic acid yield.
The desirable reaction pattern of the polymerisation of ketenes (a) and crotonaldehyde (b) is poly-reaction between being, generated ideal polyester molecule composition is approximately ... abababab ... polymer, yet real reaction can not be perfect condition fully, tend to occur the poly-reaction of embedding, the polyester molecule 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, a during polyester molecule forms
nor b
npolymer all is hydrolyzed and generates tar or other by-product impurity when polyester is hydrolyzed, and the key that therefore improves the hydrolysis yield of sorbic acid polyester is how to avoid and during polyester molecule forms while reducing polymerisation ... ab
nab ... or ... aba
nb ... the generation of polymer, particularly ... aba
nb ... the generation of polymer.Be conducive to most theoretically generate ... aba
nb ... the condition of polymer be under relatively low concentration b environment with relative high concentration a reaction, relatively under the low concentration crotonaldehyde, with relative high concentration ethylene reactive ketone, just be conducive to tar and other by-product impurity, so the polymerisation of ketenes and crotonaldehyde should be avoided in relative low concentration crotonaldehyde and reaction under relative high concentration ethylene ketone as far as possible.
In current actual production, the polymerisation of ketenes and crotonaldehyde normally in common enamel reaction still or circulated sprinkling packed tower, under catalyst action intermittently or successive reaction complete, in order to realize the complete reaction of ketenes, normally adopt a plurality of enamel stills or the series connection of circulated sprinkling packed tower to carry out, the first reactor is main reactor.It when intermittent reaction starts, is the reaction of high concentration ethylene ketone and high concentration crotonaldehyde, carrying out along with reaction, crotonaldehyde concentration descends gradually, be conducive to autohemagglutination and other side reaction of ketenes, in actual production, reaction depth is higher, after the polyester hydrolysis, tar is more, and the hydrolysis yield is also lower, so intermittent reaction is not best reaction formation.The successive reaction form of introducing in the disclosed application number 200810098512 of Chinese patent is to adopt a tower reactor material part by extraction continuously, most of as recycle stock enforcement pressurized circulation absorption ketenes, namely the concentration for the material crotonaldehyde that absorbs ketenes declines to a great extent, more be conducive to autohemagglutination and other side reaction of ketenes, produce polyester if adopt the method for adding solvent, therefore effect will be poorer, adopts the method for circulated sprinkling packed tower series connection continuous production of polyesters neither optimal reaction formation.
Summary of the invention
In order to address the above problem, the production method the method that the object of the present invention is to provide a kind of sorbic acid polyester continuous bubbling tower to absorb has been applied and has been comprised and make crotonaldehyde and ketene gas absorb the bubbling packed tower and can keep the combination unit of the secondary spray-absorption packed tower of the micro-negative pressure of bubble tower through the following current of polymerisation, realized making continuously within a short period of time the reaction of high concentration crotonaldehyde and high concentration ethylene ketone, this polymerisation in the following current bubble tower under micro-negative pressure successive reaction complete, avoided the generation of more multifocal oil, improve polymerisation efficiency and polyester hydrolysis yield, reduce production costs.The present invention has realized the serialization of sorbic acid polyester in the sorbic acid manufacture, improve polymerisation efficiency, polyester quality and polyester hydrolysis yield, reduce production costs, guarantee the safety and stability production of Liao Qian road technique ketenes, before thering is good application simultaneously.
Technical solution of the present invention is as follows:
The production method that the continuous bubbling tower of a kind of sorbic acid polyester provided by the invention absorbs, it is characterized in that, crotonaldehyde and polymerization catalyst are after secondary spray absorber 5 tower top sprays enter continuously, discharge and contain unreacted ketenes tail gas with bubbling packed tower 2 tower tops, the negative pressure formed by venturi jet pump 7 is drawn into secondary spray absorber 5 absorption reaction that circulated, again at the bottom of the first circulating pump 3 is sent into bubbling packed tower 2 towers, the negative pressure absorbing that the ketenes entered with normal pressure at the bottom of tower from bubbling packed tower 2 carries out take following current is main ketenes and the polymerisation of crotonaldehyde, qualified sorbic acid polyester liquid is by the continuous extraction of bubble tower tower top.
The production method absorbed according to the continuous bubbling tower of sorbic acid polyester provided by the invention, preferably, described crotonaldehyde and polymerization catalyst are after secondary spray absorber 5 tower top sprays enter continuously, at the bottom of the first circulating pump 3 is sent crotonaldehyde and polymerization catalyst mixed material into bubbling packed tower 2 towers, the ketenes entered with normal pressure at the bottom of tower from 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.
The production method absorbed according to the continuous bubbling tower of sorbic acid polyester provided by the invention, preferably, described crotonaldehyde and polymerization catalyst, after secondary spray absorber 5 tower top sprays enter continuously, are squeezed into secondary spray absorber 5 tower top circulated sprinklings through the second circulating pump 6 by the mixed material of described crotonaldehyde and polymerization catalyst again and are absorbed.
The production method absorbed according to the continuous bubbling tower of sorbic acid polyester provided by the invention, is characterized in that, the negative pressure that described venturi jet pump (7) forms keeps in bubbling packed tower (2) negative pressure and keeps ketenes to add the normal pressure of system.
The production method absorbed according to the continuous bubbling tower of sorbic acid polyester provided by the invention, preferably, the mass percentage content of described crotonaldehyde is 50～100%.
The production method absorbed according to the continuous bubbling tower of sorbic acid polyester provided by the invention, further preferably, the mass percentage content of described crotonaldehyde is 60～80%.
The production method absorbed according to the continuous bubbling tower of sorbic acid polyester provided by the invention, preferably, the reaction conversion ratio of described crotonaldehyde is controlled at 30～80%.
The production method absorbed according to the continuous bubbling tower of sorbic acid polyester provided by the invention, further preferably, the reaction conversion ratio of described crotonaldehyde is controlled at 60～70%.
The production method absorbed according to the continuous bubbling tower of sorbic acid polyester provided by the invention, preferably, described negative pressure is according to the pressure of the ketenes import department of bubbling packed tower, and pressure limit is-100～0mmHg.
The production method absorbed according to the continuous bubbling tower of sorbic acid polyester provided by the invention, preferably, in described bubbling packed tower 2, temperature of charge is 20～100 ℃.
The production method absorbed according to the continuous bubbling tower of sorbic acid polyester provided by the invention, preferably, in described bubbling packed tower 2, temperature of charge is 60～80 ℃.
The production method absorbed according to the continuous bubbling tower of sorbic acid polyester provided by the invention, after the continuous extraction of described sorbic acid polyester, through acidolysis, alkali is molten and decolouring obtains sorbic acid.
The production method absorbed according to the continuous bubbling tower of a kind of sorbic acid polyester provided by the invention, preferably, described bubbling packed tower 2 tower tops discharge and contain negative pressure that unreacted ketenes tail gas forms by venturi jet pump 7 and be drawn into secondary spray absorber 5 and circulated after absorption reaction, carry out toxic emission.
The reaction unit absorbed according to sorbic acid polyester continuous bubbling tower provided by the invention, 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.
The reaction unit absorbed according to sorbic acid polyester continuous bubbling tower provided by the invention, further preferably, the lift 35～40m of described venturi jet pump 7.
The reaction unit absorbed according to sorbic acid polyester continuous bubbling tower provided by the invention, further preferably, the flow 150～250m of described venturi jet pump 7
3/ h.
The reaction unit absorbed according to sorbic acid polyester continuous bubbling tower provided by the invention, further preferably, the rate of air sucked in required 180～260m of described venturi jet pump 7
3/ h.
The reaction unit absorbed according to sorbic acid polyester continuous bubbling tower provided by the invention, preferably, the tower height degree 6～11m of described secondary spray absorber 5, tower diameter 450～750mm.
The reaction unit absorbed according to sorbic acid polyester continuous bubbling tower provided by the invention, further preferably, the tower height degree 7～10m of described secondary spray absorber 5, tower diameter 550～650mm.
The reaction unit absorbed according to sorbic acid polyester continuous bubbling tower provided by the invention, preferably, the tower height degree 3～8m of described bubbling packed tower 2, tower diameter 400～700mm.
The reaction unit absorbed according to sorbic acid polyester continuous bubbling tower provided by the invention, preferably, the tower height degree 4～7m of described bubbling packed tower 2, tower diameter 500～600mm.
The reaction unit absorbed according to sorbic acid polyester continuous bubbling tower provided by the invention, preferably, the lift 30～80m of described the first circulating pump 2.
The reaction unit absorbed according to sorbic acid polyester continuous bubbling tower provided by the invention, preferably, the lift 30～80m of described the 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, the optional 304L of volume or 316L.
The preparation method of a kind of sorbic acid polyester provided by the invention, this technique has comprised makes crotonaldehyde and ketene gas absorb bubbling packed tower and the combination unit (4) that can keep the secondary spray-absorption packed tower of the micro-negative pressure of bubble tower through the following current of polymerisation.Wherein, the polymerisation of crotonaldehyde and ketene gas is mainly to absorb in the bubbling packed tower and carry out continuously in following current, do not absorb ketenes completely enter by outer setting circulating pump is arranged and the secondary spray absorber that can ketenes absorbs through the venturi jet pump in absorb fully after discharge.Fresh crotonaldehyde and polymerization catalyst are entered in tower by secondary spray-absorption column overhead spray, and a spray column tower reactor material part is squeezed into the tower top circulated sprinkling by the outer loop pump and absorbed; A part is squeezed into the venturi jet pump by pump makes following current absorb that the bubbling packed tower is capable becomes micro-negative pressure, extracts the complete ketenes of unreacted simultaneously and enters in spray column, and the vacuum size is controlled by the mass flow of pump; Another part absorbs by being pumped into following current that bubbling packed tower bottom and fresh ethylene ketone are capable becomes the reaction of following current bubble absorption, generates qualified a kind of sorbic acid polyester by tower top overflow extraction, and reaction depth is by the material-handling pump control that enters tower reactor.Realize thus making continuously within a short period of time the reaction of high concentration crotonaldehyde and high concentration ethylene ketone, avoided the generation of more multifocal oil, guaranteed the safety and stability production of Liao Qian road technique ketenes simultaneously.Be exactly by fresh crotonaldehyde, polymerization catalyst with from part recycle stock spray-absorption in the secondary spray absorber of secondary spray absorber tower reactor concretely, in tower, temperature is controlled at 20～100 ℃ 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 is squeezed into the venturi jet pump by pump makes following current absorb micro-negative pressure of import house one-tenth-100～0mmHg of bubbling packed tower ketenes; Entering following current from the material of secondary spray absorber tower reactor and ketenes by tower reactor absorbs in the bubbling packed tower and controls temperature and carry out the reaction of following current bubble absorption at 20～100 ℃, qualified sorbic acid polyester, by bubble tower tower top overflow extraction, has been realized the serialization production of technique.
The production method of sorbic acid polyester provided by the invention is that ketene gas is reacted with crotonaldehyde micro-negative pressure continuous polymerization in bubble tower and generated PET Process, and then polyester is through acid, alkali or add thermal decomposition and obtain sorbic acid.The polymerisation of crotonaldehyde and ketene gas is at least to comprise the bubbling packed tower that following current absorbs and the combination unit that can keep the secondary spray-absorption packed tower of the micro-negative pressure of bubble tower.The packed tower that the secondary spray absorber can be absorbed through the venturi jet pump by circulating pump and ketenes by outer setting forms.This device polymerisation is carried out continuously, will send into the bubble tower bottom from the recycle stock of secondary spray absorber tower reactor and form the following current absorption reaction with ketenes, and qualified polyester liquid is by the bubble tower overhead extraction; Tower top tail gas enters the secondary spray absorber, and the negative pressure formed by venturi jet pump device keeps micro-negative pressure in bubble tower to realize keeping the normal pressure of ketenes system, and unreacted ketene gas suction secondary spray absorber is reacted; Spraying of material enters the filler tower reactor, and the crotonaldehyde in unreacted ketenes and material and the fresh crotonaldehyde entered by secondary spray-absorption column overhead spray circulate and absorb polymerization reaction take place; Be used for the interior circulation of reactor assembly from the material part of secondary spray-absorption packed tower tower reactor, after a part enters bubble tower and fresh ethylene ketone and continues to react by the continuous extraction of bubbling tower top, depth of cure, by the control of the charging rate of fresh crotonaldehyde, is realized serialization production with this.
The production method of sorbic acid polyester provided by the invention:
1., adopted the bubbling packed tower, the micro-negative pressure absorbing that has carried out take following current is main ketenes and the polymerisation of crotonaldehyde;
2., adopted the secondary spray-absorption packed tower that can keep the micro-negative pressure of bubble tower, ketenes is absorbed fully, the packed tower that the secondary spray absorber can be absorbed through the 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 entered continuously by secondary spray-absorption column overhead spray, the unreacted ketenes of absorption reaction bubble tower is circulated, then enter bubbling packed tower and fresh ethylene ketone and carry out again one way following current polymerisation, 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, is realized serialization production with this;
2., fresh ethylene ketone is by entering under bubbling packed tower tower reactor normal pressure state, the micro-negative pressure absorbing that carries out take following current with material from secondary spray-absorption packed tower tower reactor is main ketenes and the polymerisation of crotonaldehyde, the negative pressure that tower top tail gas forms by venturi jet pump device sucks the 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 refers to that crotonaldehyde content, at 50～100% crotonaldehyde, can be pure crotonaldehyde, can be also the crotonaldehyde containing solvent (as toluene, benzene etc.), comprise and reclaim crotonaldehyde and solvent;
2., depth of cure refers to the reaction conversion ratio of crotonaldehyde, control range is 30～80%;
3., micro-negative pressure of bubble tower is as the criterion with tower reactor ketenes inlet pressure, control the emitted dose of the spraying of material stream of secondary spray absorber Wen Qiuli jet pump, make the ketenes inlet pressure form the vacuum of-100～0mmHg, form micro-negative pressure absorbing reaction of bubble tower;
4., by the cooling device arranged in bubbling packed tower tower reactor and tower, in control tower, temperature of charge is 20～100 ℃
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 micro-negative pressure in bubble tower generates polyester, the negative pressure that tail gas forms by venturi jet pump device sucks the secondary spray absorber, carries out the production method of toxic emission after the complete absorption reaction of circulated sprinkling.
Crotonaldehyde is one of main polymer raw of the present invention, and " the fresh crotonaldehyde " mentioned in the present invention refers to that the purity that enters reaction system is greater than 99% crotonaldehyde or the recovery crotonaldehyde in technical process; Can be also contain organic solvent crotonaldehyde content at the mixture more than 40% 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 also is equal to fresh crotonaldehyde defined above.
Following current of the present invention can be understood as liquid in raw material or gas etc. and all moves by equidirectional; The molecular weight of the sorbic acid polyester of gained of the present invention is 30004000.
Useful technique effect of the present invention:
Production method the method that a kind of sorbic acid polyester continuous bubbling tower provided by the invention absorbs has been applied and has been comprised and make crotonaldehyde and ketene gas absorb the bubbling packed tower and can keep the combination unit of the secondary spray-absorption packed tower of the micro-negative pressure of bubble tower through the following current of polymerisation, realized making continuously within a short period of time the reaction of high concentration crotonaldehyde and high concentration ethylene ketone, this polymerisation in the following current bubble tower under micro-negative pressure successive reaction complete, avoided the generation of more multifocal oil, improve polymerisation efficiency and polyester hydrolysis yield, reduce production costs.The present invention has realized the serialization of sorbic acid polyester in the sorbic acid manufacture, improve polymerisation efficiency, polyester quality and polyester hydrolysis yield, reduce production costs, guarantee the safety and stability production of Liao Qian road technique ketenes, before thering is good application simultaneously.
The accompanying drawing explanation
Fig. 1 is reaction unit and the production method schematic diagram that a kind of sorbic acid polyester continuous bubbling tower absorbs;
1-polyester groove in figure, 2-bubbling packed tower, the 3-the first circulating pump, 4-secondary spray-absorption packed tower combination unit, 5-secondary spray absorber, the 6-the second circulating pump, 7-venturi jet pump, 8-crotonaldehyde and catalyst enter continuously, and 9-air is emptying, 10-ketenes enters, 11-qualified polyester.
The specific embodiment
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 the present invention is not formed to any restriction.
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.
By content, being the mixed material of 99% crotonaldehyde and polymerization catalyst is entered in tower by the top spray of spray absorber 5, in tower reactor during the enough systemic circulation of amount of liquid, starting 6 pairs of these crotonaldehyde materials of outside the second circulating pump of tower reactor is circulated, a recycle stock part enters from the tower top spray of spray absorber 5, after the absorption ketenes, returns to tower reactor; Another part enters venturi jet pump 7, make following current absorb bubbling packed tower 2 and form micro-negative pressure, extract the complete ketenes of unreacted simultaneously and enter in the spray column tower reactor, the mass flow of control pump, control the import vacuum of bubbling packed tower ketenes between 50～0mmHg; Some absorbs by being pumped into following current that fresh ethylene ketone that bubbling packed tower bottom produces with the ketenes device is capable becomes the following current bubble absorption to react by spray absorber 5 tower reactor materials, control the bubble absorption reaction temperature at 40～45 ℃, 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 in 50% left and right.
Sorbic acid polyester liquid vacuum distillation obtains the sorbic acid polyester after reclaiming unreacted crotonaldehyde.Get sorbic acid polyester 1000g and add 30% hydrochloric acid 5000g, be warmed up to 80 ℃ of insulation depolymerization reactions 3 hours, cold filtration obtains the crude product sorbic acid.The crude product sorbic acid adds water 5000ml, and to carry out alkali with 30% sodium hydrate aqueous solution molten, after adjusting pH value to 7.5, add the 100g activated carbon decolorizing except tar removing, filter, filtrate is used in hydrochloric acid and acid out, adjusts pH value to 2.5, filter, washing, dry, and obtains white finished product sorbic acid 832g, content is greater than 99.5%, to the depolymerization yield of sorbic acid polyester, is 83.2%.
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.
Operation with reference to embodiment 1, crotonaldehyde by 99% changes into take the 60% crotonaldehyde solution that toluene is solvent, and the reaction conversion ratio of controlling crotonaldehyde is 80%, the sorbic acid polyester liquid obtained operates by the depolymerization post-processing approach of embodiment 1 equally, obtain white finished product sorbic acid 815g, content is greater than 99.5%, to the depolymerization yield of sorbic acid polyester, is 81.5%.
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.
Operation with reference to embodiment 1, crotonaldehyde by 99% changes into take the 80% crotonaldehyde solution that toluene is solvent, and the reaction conversion ratio of controlling crotonaldehyde is 60%, the sorbic acid polyester liquid obtained operates by the depolymerization post-processing approach of embodiment 1 equally, obtain white finished product sorbic acid 823g, content is greater than 99.5%, to the depolymerization yield of sorbic acid polyester, is 82.3%.
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.
Operation with reference to embodiment 1, crotonaldehyde by 99% changes into take the 50% crotonaldehyde solution that toluene is solvent, and the reaction conversion ratio of controlling crotonaldehyde is 70%, the sorbic acid polyester liquid obtained operates by the depolymerization post-processing approach of embodiment 1 equally, obtain white finished product sorbic acid 835g, content is greater than 99.5%, to the depolymerization yield of sorbic acid polyester, is 83.5%.
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.
Operation with reference to embodiment 1, crotonaldehyde by 99% changes into take the 60% crotonaldehyde solution that benzene is solvent, and the reaction conversion ratio of controlling crotonaldehyde is 80%, the sorbic acid polyester liquid obtained operates by the depolymerization post-processing approach of embodiment 1 equally, obtain white finished product sorbic acid 809g, content is greater than 99.5%, to the depolymerization yield of sorbic acid polyester, is 80.9%.
Effect comparison example 1
Be that 99% crotonaldehyde and the mixed material of catalyst add in autoclave intermittent reaction device the reaction that fed intake to obtain the sorbic acid polyester liquid by content, control reaction temperature at 40～50 ℃, the reaction conversion ratio of crotonaldehyde is controlled at 50% left and right.The depolymerization post-processing approach that embodiment 1 press in other operation operates, and obtains white finished product sorbic acid 807g, and content is greater than 99.5%, to the depolymerization yield of sorbic acid polyester, is 80.7%.
Effect comparison example 2
Operation with reference to effect comparison example 1, crotonaldehyde by 99% changes the 60% crotonaldehyde solution that toluene is solvent into, and the reaction conversion ratio of controlling crotonaldehyde is 80%, the sorbic acid polyester liquid obtained operates by the depolymerization post-processing approach of embodiment 1 equally, obtain white finished product sorbic acid 789g, content is greater than 99.5%, to the depolymerization yield of sorbic acid polyester, is 78.9%.
Effect comparison example 3
With reference to the successive reaction form of introducing in the disclosed application number 200810098512 of Chinese patent, with content, it is the reaction that fed intake of 99% crotonaldehyde and the mixed material of catalyst, the sorbic acid polyester liquid obtained operates by the depolymerization post-processing approach of embodiment 1 equally, obtain white finished product sorbic acid 803g, content is greater than 99.5%, to the depolymerization yield of sorbic acid polyester, is 80.3%.
Effect comparison example 4
With reference to the successive reaction form of introducing in the disclosed application number 200810098512 of Chinese patent, the 60% crotonaldehyde solution material that is solvent with the toluene reaction that fed intake, the sorbic acid polyester liquid obtained operates by the depolymerization post-processing approach of embodiment 1 equally, obtain white finished product sorbic acid 624g, content is greater than 99.5%, to the depolymerization yield of sorbic acid polyester, is 62.4%.
Production method the method that this kind of sorbic acid polyester continuous bubbling tower provided by the invention absorbs has been applied and has been comprised and make crotonaldehyde and ketene gas absorb the bubbling packed tower and can keep the combination unit of the secondary spray-absorption packed tower of the micro-negative pressure of bubble tower through the following current of polymerisation, realized making continuously within a short period of time the reaction of high concentration crotonaldehyde and high concentration ethylene ketone, this polymerisation in the following current bubble tower under micro-negative pressure successive reaction complete, avoided the generation of more multifocal oil, improve polymerisation efficiency and polyester hydrolysis yield, reduce production costs.The present invention has realized the serialization of sorbic acid polyester in the sorbic acid manufacture, improve polymerisation efficiency, polyester quality and polyester hydrolysis yield, reduce production costs, guarantee the safety and stability production of Liao Qian road technique ketenes, before thering is good application simultaneously.
Claims (10)
1. the production method that the continuous bubbling tower of a 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 and contain 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) absorption reaction that circulated, again at the bottom of the first circulating pump (3) is sent into bubbling packed tower (2) tower, the negative pressure absorbing that the ketenes entered with normal pressure at the bottom of tower from bubbling packed tower (2) carries out take following current is main ketenes and crotonaldehyde polymerisation, qualified sorbic acid polyester liquid is by the continuous extraction of bubble tower tower top.
2. the production method that the continuous bubbling tower of sorbic acid polyester according to claim 1 absorbs, it is characterized in that, described crotonaldehyde and polymerization catalyst are after secondary spray absorber (5) tower top spray enters continuously, at the bottom of the first circulating pump (3) is sent crotonaldehyde and polymerization catalyst mixed material into bubbling packed tower (2) tower, the ketenes entered with normal pressure at the bottom of tower from 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.
3. the production method that the continuous bubbling tower of sorbic acid polyester according to claim 1 and 2 absorbs, it is characterized in that, described crotonaldehyde and polymerization catalyst, after secondary spray absorber (5) tower top spray enters continuously, are squeezed into secondary spray absorber (5) tower top circulated sprinkling through the second circulating pump (6) by the mixed material of described crotonaldehyde and polymerization catalyst again and are absorbed.
4. the production method that the continuous bubbling tower of sorbic acid polyester according to claim 1 absorbs, is characterized in that, the negative pressure that described venturi jet pump (7) forms keeps the middle negative pressure of bubbling packed tower (2) and keeps ketenes to add the normal pressure of system.
5. the production method absorbed according to the continuous bubbling tower of the described sorbic acid polyester of claim 1 or 4 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.
6. the production method that the continuous bubbling tower of sorbic acid polyester according to claim 1 absorbs is characterized in that the mass percentage content of described crotonaldehyde is 50～100%.
7. the production method that the continuous bubbling tower of sorbic acid polyester according to claim 1 absorbs is characterized in that the reaction conversion ratio of described crotonaldehyde is controlled at 30～80%.
8. the production method that the continuous bubbling tower of sorbic acid polyester according to claim 1 absorbs, is characterized in that, in described bubbling packed tower (2), temperature of charge is 20～100 ℃.
9. the production method that the continuous bubbling tower of sorbic acid polyester according to claim 1 absorbs, is characterized in that, in described bubbling packed tower (2), temperature of charge is 60～80 ℃.
10. the production method that the continuous bubbling tower of sorbic acid polyester according to claim 1 absorbs, it is characterized in that, described bubbling packed tower (2) tower top discharges and contains unreacted ketenes tail gas, the negative pressure formed by venturi jet pump (7) is drawn into secondary spray absorber (5) and is circulated after absorption reaction, then carries out toxic emission.
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| 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 |
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