CN1448386A - Recovery method and polymerization system of non-reaction monomer in polymerization of acrylic monomer - Google Patents
Recovery method and polymerization system of non-reaction monomer in polymerization of acrylic monomer Download PDFInfo
- Publication number
- CN1448386A CN1448386A CN 03121561 CN03121561A CN1448386A CN 1448386 A CN1448386 A CN 1448386A CN 03121561 CN03121561 CN 03121561 CN 03121561 A CN03121561 A CN 03121561A CN 1448386 A CN1448386 A CN 1448386A
- Authority
- CN
- China
- Prior art keywords
- monomer
- mentioned
- resistance
- polymerizing agent
- monomer component
- 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.)
- Granted
Links
Images
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
To provide a method for recovering a monomer by which only a pure monomer component of an acrylonitrile-based polymer can be recovered while preventing the polymer formed by the polymerization after condensation from being mixed in the unreacted monomer component recovered in a monomer-recovering step. The monomer component and water are evaporated and separated from the polymer by distilling a mixture of the monomer, the polymer and the water obtained at a polymerization step, and the evaporated monomer component and water are condensed to recover the monomer component. A small amount of a polymerization inhibitor is added to the mixture when transferring the mixture from an evaporation step to a condensation step to extremely reduce the formation of the polymer formed at the condensing and liquefying step, and to eliminate the coexistence of the polymer in the monomer component to be recovered.
Description
Technical field
The recovery method of the present invention's residual monomer component during and the paradigmatic system of acrylic copolymer relevant for a kind of polymerization of the acrylic copolymer by water system suspension polymerization, and particularly relevant for a kind of starting monomer during as polymerization and reclaimed with unreacted aforementioned monomer composition, the efficient recovery method of recycle unreacted monomer, and the paradigmatic system of this acrylic copolymer.
Background technology
Acrylic fibers has as character such as the good bulkiness of woolen, sense of touch and vision, dyeing distinctiveness, and is applied to the purposes of wide scope.And the also many raw materials as carbon fiber of this acrylic fibre use.In its spin processes,, make it form fiber or filament by wet type spin processes, dry spinning method or half dry type spin processes via being dissolved in the dissolution process of organic solvent and inorganic solvent as the acrylic copolymer of raw material.As the acrylic copolymer of raw material, by acrylonitrile monemer with can with the comonomer of the nonionic of the acrylate of its copolymerization, methacrylic ester, vinyl acetate, vinylformic acid vinegar amine etc. and radical polymerization with manufacturing.
The manufacturing of acrylic copolymer is adopted with the continuous suspension polymerization of water as reaction solvent more.This continuous suspension polymerization measures the monomer and the comonomer of vinyl cyanide individually by raw material tank and MONOMER RECOVERY operation, to be supplied to the monomer preparation vessel.Monomer in the preparation vessel is inner to be formed, and forms than the copolymerization of manufacturing polymkeric substance, is considering vinyl cyanide and copolymerization reactwity of monomer ratio, then must be tight be set in certain value.
In polymeric kettle (still), modulated vinyl cyanide places with comonomer, water, catalyst etc., adds polymerization starter to carry out polymerization.This moment, polymerization starter generally was to use inorganic series initiators.The most use of inorganic series initiators for example is the combination of the oxidation-reduction system of ammonium persulfate-sodium bisulfite-ferrous sulfate, with the vinyl cyanide that comprises above-mentioned comonomer monomer component as principal constituent, with words as the sulfuric acid water generates polyreaction of reaction solvent, then can form tens of microns particle shaped polymer, and obtain being the acrylic polymkeric substance of aqueous liquid dispersion state.
In the polymkeric substance that takes out by polymeric kettle, add the resistance polymerizing agent with stopped reaction.Resistance polymerizing agent make acrylic polymkeric substance occasion with water system suspension polymerization must keep the function of the acidic aqueous solution of neutralization reaction, and uses the aqueous electrolyte liquid of SODIUMNITRATE, Sodium Hydrogen Carbonate, ethene diamino 4 acetate 2 sodium salts etc.And, in storage or acrylonitrile monemer in transit must suppress its polymerization, normally adding in advance in starting monomer for example is the resistance polymerizing agent of right-methoxyl group phenol etc.
The short-stopper of polyreaction does not have problem usually making the words of using when the acrylic polymkeric substance in water system suspension polymerization mode.After in aqueous solutions of polymers, adding short-stopper, carry out the recovery of unreacted monomer.The recovery method of unreacted monomer, for example be with behind the aqueous solutions of polymers straight run distillation, to vaporize and isolating unreacted monomer composition and water are sent into distiller and condensed, forming monomers/water solution, this solution by decanting vessel (decanter) with monomer component and water sepn.Isolating monomer component is sent polymeric kettle back to.On the other hand, in the polymkeric substance remaining moisture be to remove by common drying mode.
And, in sulfuric acid water during polypropylene nitrile based polymer, as the combination of the ammonium persulfate-sodium bisulfite-ferrous sulfate of polymerization starter, can be as described below be decomposed into radical.
Polymerization initiation reaction by the redox reaction catalyst is as follows
Carrying out, this moment, sulfurous acid was as follows with sulfurous gas system maintenance
Relation and maintain equilibrium state.
The bisulfite sodium oxide (NaHSO that in polymeric kettle, is added as polymerization starter
3) among, untapped radical forms a part of SO in sour environment gas
2, the monomers/water in distillation tower is sent into distiller.At SO
2And when monomers/water condenses, soluble in water and form HSO
3 -, this is in order to as polymerization starter, and makes the monomer component polymerization of acrylic.
According to this, in the isolating recovery monomer of decanting vessel, also contain polymeric material more, and when returning polymeric kettle, can produce all problems.That is be, foregoing, drop into inner composition of monomer in the preparation vessel before the polymeric kettle, considering vinyl cyanide and copolymerization with monomeric reaction ratio, must be tight be set in certain value.
Therefore, in this polymerization process, according to reclaiming monomeric quality, can produce delicate influence to copolymerization composition, the polymerization degree, the distribution of polymerization degree of the polymkeric substance of the feed rate polymerization temperature of the inside composition of starting monomer, water, catalyst etc.On the other hand, in the monomer component (vinyl cyanide/comonomer) that the MONOMER RECOVERY operation is reclaimed, sneak into polymeric polymkeric substance, then this mixed volume can't become a certain amount of and change constantly.And, in the successive polymerization operation, to calculate very difficulty of the monomeric mixed volume of aforementioned recovery.Even supposition can be calculated,, as previously mentioned, be on reality is carried out, still to be infeasible therefore via tight modulation in response to the input amount of the starting monomer that drops in the preparation vessel of this calculated amount.Moreover, sneak into solid-state polymkeric substance in the monomeric recovery process, the situation that solution then can block.
Summary of the invention
For head it off, purpose of the present invention provides the paradigmatic system of a kind of MONOMER RECOVERY method and acrylic polymkeric substance, particularly in the monomer component that the MONOMER RECOVERY operation is reclaimed, the polymkeric substance that post polymerization generated that can prevent to condense is sneaked into, and the pure monomer component of recover acrylonitrile based polymer only.
Present inventors are considering: suppress the acrylic monomer through distillation tower with in the condensing of distiller or condense post polymerization, the HSO of free existence in the mixed solution of the monomers/water after importantly must will condensing
3 -Become stabile material.The words of adding the resistance polymerizing agent herein then can not generate polymkeric substance.The occasion that adds this kind resistance polymerizing agent is considered the stage interpolation of fully condensing and liquefying at monomer component.And the resistance polymerizing agent of this interpolation can be other modulation add.Do not adding the occasion of inhibitor, can also cool off fully so that polyreaction can not produce.
Yet even add the resistance polymerizing agent in the stage that the monomer component of vaporizing fully condenses, liquefies, same meeting generates polymkeric substance.And, suppress the polymerization of the monomer component condense, liquefy by cooling, must install cooling tubing equipment.Present inventors further examine, and have the beginning polymerization at the monomer component that imports distiller in mind, may be that the monomer of vaporization also begins this fact of polyreaction in the moment that will begin of condensing, liquefy.The result has then reached the present invention according to this.
The 1st basic comprising of the present invention, recovery method for a kind of acrylic monomer component, in the recovery method of the monomer component that the water system suspension polymerization operation of acrylic polymkeric substance is taken place, possess: with the mixture of the monomer/polymer/water of polymerization process gained, make monomer, water separate by distillation by vaporization in the polymkeric substance, and the condense monomer component of gained of will vaporize monomer and water reclaims, and it is characterized in that comprising by vaporization process being transferred to the resistance polymerizing agent that adds trace when condensing operation.
That is be, the present invention is the mixture distillation with the monomer/polymer/water of polymerization process gained, so that monomer, water are separated by vaporization in the polymkeric substance, and the monomer component recovery that monomer and the water of vaporization is condensed gained, and when monomer and water are transferred to the operation of condensing by vaporization process, for example add the resistance polymerizing agent of trace in the ingress of the operation of condensing, being added to independent resistance polymerizing agent or mixing other material of this moment carried out with vaporific spraying or in the mode of drippage.This resistance polymerizing agent mixes with water with monomer component and is transferred to the downstream side, and in the condensation stage of monomer component and water and as the HSO of polymerization starter
3 -In conjunction with to change stable material into, to stop the polymerization of monomer component.
The polymerisate of aforementioned polymerization process gained, the ratio of monomer/polymer/water is 2～7%/10～35%/58～88% scope usually, and contains 0.02～0.20% SO
2The source.To the monomer component of the aforementioned operation gained that condenses, being preferably the interpolation weight ratio is the resistance polymerizing agent of 4～150ppm.Then addition is very few to be less than the words of 4ppm.Can't be fully and residual SO
2Source reactant and produce polymerization.Surpass 150ppm, can be residual in the monomer that reclaims, sneak into unnecessary resistance polymerizing agent.And when polyreaction, must add extra polymerization starter, and may the control of polyreaction be impacted.
To stating monomer component before the aforementioned operation gained that condenses, adding weight ratio is the resistance polymerizing agent of 20～100ppm, the unreacted above-mentioned monomer component residual to polyreaction is preferably that to add weight ratio be the aforementioned monomer composition that this kind of 20%～150% has been added with the resistance polymerizing agent.In this occasion, the amount of the last resistance polymerizing agent that adds in the operation of condensing equates slightly with aforementioned, and the modulation that does not need the resistance polymerizing agent is set is in addition equipped, aforementioned monomer composition in the operation gained that condenses adds directly resistance polymerizing agent, these are a little owing to import the operations and by gradually dilution of condensing, in the monomer component that liquefies fully condensing, the amount of the polymkeric substance that is contained becomes the denier that can ignore, this returns preparation vessel a bit again, modulation for forming with the inside of the starting monomer composition in the groove does not need other operation.
The product of polymerization of aforementioned polymerization process gained, the ratio of monomer/polymer/water is 2～7%/10～35%/58～88% scope usually, and contains 0.02～0.20% SO
2Originating, contain the acrylic starting monomer of the resistance polymerizing agent of weight ratio 20～100ppm, is the weight ratio that can add the above-mentioned monomer component 20～150% of the operation gained that condenses.
In this occasion, the final resistance polymerizing agent addition that adds in the operation of condensing slightly equates with the aforementioned field contract, at the resistance polymerizing agent of the starting monomer interpolation of original vinyl cyanide with importing the operation of condensing with starting monomer.Therefore pipeline sets to wait and carries out easily, does not need to be provided with in addition the preparation facilities that hinders polymerizing agent.And the addition of resistance polymerizing agent also can be set easily.
And, the of the present invention the 2nd constitutes, paradigmatic system for a kind of acrylic polymkeric substance, in the paradigmatic system of the acrylic polymkeric substance that passes through water system suspension polymerization mode, possess converging portion arranged, with the distiller that is connected with converging portion and with the distiller that is connected with distiller, it is characterized in that near the gas introduction port of the distiller that connects aforementioned distiller, more being provided with the introducing port of resistance polymerizing agent.System according to this, the recovery method of the unreacted monomer composition the during polymerization of aforesaid propylene nitrile based polymer can really and be easy to carry out by the interpolation of resistance polymerizing agent.
In this invention, the introducing port of aforementioned resistance polymerizing agent, with set after the above-mentioned operation of condensing monomer is connected with the monomer derivation pipeline of the separation circuit of water sepn, the introducing port of aforementioned resistance polymerizing agent and the monomer of aforementioned separation circuit are derived between the pipeline, and the introduction part of resistance polymerizing agent can also be set.In this occasion, by the separation circuit of monomer component and water some systems of isolated monomer component return in the operation of condensing.In the way that this returns, import the resistance polymerizing agent of necessary addition by the introduction part of resistance polymerizing agent.Sneak in unreacted monomer composition and water, as the HSO of polymerization starter via the operation of condensing
3 -The operation of condensing is returned in the source once again, and the some by the resistance polymerizing agent in the way that this returns makes it stabilization, and simultaneously by the new importing same resistance polymerizing agent of operation that condenses, with vaporization, monomers/water/SO of importing
2In SO
2React and stabilization.Among this repeatable operation, by the monomer and the highly purified stabilization of water system of operation liquefaction of condensing.
Moreover in the present invention, the introducing port of aforementioned resistance polymerizing agent can also be connected with the supply source of the vinyl cyanide starting monomer that contains aforementioned resistance polymerizing agent.In starting monomer, be added with the predetermined amount resistance polymerizing agent that produces polymerization when avoiding storing or transporting and add in advance.This invention, starting monomer is connected in the resistance polymerizing agent introducing port of the operation of condensing according to this.Constitute by this, make the adjustment control of addition of the resistance polymerizing agent that imports the operation of condensing become easily, and the supply unit of starting monomer also can simply set with pipeline between the introducing port that hinders polymerizing agent.
Description of drawings
Fig. 1 is the polymeric paradigmatic system of acrylic that possesses MONOMER RECOVERY device of the present invention.
Fig. 2 is the process picture sheet of the MONOMER RECOVERY operation of representative embodiment of the present invention.
Fig. 3 is the process picture sheet of the MONOMER RECOVERY operation of other embodiment of the present invention.
1: the storage tanks of vinyl cyanide
2a, 2b: volume pump
3: the monomer preparation vessel
4: polymerization reaction kettle
5: distillation tower
6: distiller
6a: mixed gas introducing port
6b, 6c: resistance polymerizing agent introducing port
7: decanting vessel
8: reclaim monomer
9,10a: pipe arrangement
10b: branch pipe
Embodiment
Below be embodiment based on the representative of the present invention of graphic more detailed description.
The present invention is relevant to the unreacted monomer composition that produces when making the acrylic polymkeric substance by water system suspension polymerization mode, sends the preparation vessel of starting monomer back to and the efficient technology that is reclaimed.
The all mode of Fig. 1 polymerization for this reason, recovery process.At first, the storage tanks 1 from as the vinyl cyanide of main raw material carries out the metering of vinyl cyanide via volume pump 2a, and the vinyl cyanide of predetermined amount is dropped in the preparation vessel 3.In present embodiment, in storage, do not produce polyreaction in order to make the vinyl cyanide of being stored in the aforementioned bin 1, adding weight ratio is right-methoxyl group phenol of 20～100ppm.The resistance polymerizing agent except aforesaid right-methoxyl group phenol, can also use Resorcinol (hydroguinone), to the bitter vinegar hydrazine (diphenyl picrylhydrazyl) of t-butyl catechol (p-t-butylcatechol), hexichol, benzoquinones (benzpquinone), galvinoxyl, 1,3,5-triphenylfeldazyl etc.
In aforementioned monomer preparation vessel 3, more will with the comonomer of the 2nd composition of copolymerization of acrylonitrile, when dropping into via metering and with predetermined proportion equally, unreacted during with polymerization and the monomer component of sending polymerization reaction kettle 4 is sent back to.In 3 synthetic sticky stock liquids of monomer preparation vessel, the volume pump 2b by thereafter sends into polymerization reaction kettle 4.Supply with the pure water of necessary amount in this polymerization reaction kettle 4 in addition, the while is also added polymerization starter and various auxiliary agents.
Polymerization starter of the present invention, using inorganic is the redox reaction initiator.Inorganic is that the redox reaction initiator can be by selecting in general oxygenant, the reductive agent.The occasion of forming the redox reaction agent by oxygenant and reductive agent, words as representational material, oxygenant is ammonium persulphate (ammonium persulfate), Potassium Persulphate (potassiumpersulfate), Sodium Persulfate normally used materials such as (sodium persufate), reductive agent uses ammonium persulphate (ammonium persulfate) usually, Potassium Persulphate (potassiumpersulfate), Sodium Persulfate (sodium persufate) etc., deoxidizer is normally used S-WAT (sodium sulfite), ammonium sulphite (ammonium sulfite), sodium bisulfite (sodiumhydrogen sulfite), ammonium bisulfite (ammonium hydrogen sulfite), Sulfothiorine (sodium thiosulfate), ammonium thiosulfate (ammonium thiosulfate), V-Brite B (sodium dithionite), sodium sulfoxylate formaldehyde (sodium formaldehydesulfoxylate), left-handed vitamin C (L-ascorbic acid), glucose (dextrose) or the like normally used material.The compound that ferrous sulfate also capable of being combined or copper sulfate etc. use is to use.Wherein, the combination of ammonium persulfate-sodium bisulfite (ammonium)-ferrous sulfate is preferable.Reductive agent and oxygenant may be any ratio, consider down at the more efficient polymeric that carries out, the equivalence ratio of reductive agent and oxygenant is 1～4 to be preferable.
The employed acrylic polymkeric substance of present embodiment can also be other repeating unit that can be constituted with the monoolefine monomer of its copolymerization of acrylonitrile monemer, and acrylic polymkeric substance herein needs to be made of the acrylonitrile monemer of 60 weight % at least.This be because the amount of acrylic synthon less than 60 weight %, then the acrylic synthon can not be possessed original fiber function.Monoolefine monomer that herein can copolymerization for example is to use vinylformic acid, methacrylic acid (methacrylic acid) and this a little ester (ester), acrylamide (acrylamide), vinyl acetate (vinyl acetate), vinylbenzene (styrene), vinylchlorid (vinyl chrorite), ethylene chloride fork (vinylidene chloride), MALEIC ANHYDRIDE (maleicanhydride), N-to replace maleic two vinegar imines (maleinimide), divinyl (butadien), isoprene (isoprene) etc.Again, to sulphur vinegar methallyl ethers (p-sulfonylmethallylether), methallyl sulfonic acid (methallyl sulfonic acid), propenyl sulfonic acid (allylsulfonic acid), styrene sulfonic acid (styrene sulfonic acid), 2-acrylamide-2-methyl propane sulfonic acid (2-acrylamide-2-methylpropan sulfonic acid), 2-thio-ethyl acrylate (2-sulfo ethyl methacrylate) and a little therewith salt also can copolymerization monomer.
The monomeric polymerization of acrylic is carried out according to following condition.That is be that polymeric reaction temperature is preferably 30～80 degree Celsius.Polymerization temperature surpasses the then vinyl cyanide evaporation of words of 80 degree Celsius, and loss makes polymerisation conversion low to reactive system.And low less than the words polymerization velocity of 30 degree Celsius, not only productivity is low, also undermines the polymerization stability.Water as polymer solvent is preferably the use ion exchanged water.Moreover to the ratio of monomeric ion exchanged water (hereinafter referred to as water/monomer than) can be any ratio, yet preferable water/monomer ratio is about 1.0～5.0.Monomer average retention time in the polymerization reaction kettle can adopt the common time of being adopted when making the acrylic polymkeric substance in water system suspension polymerization mode.Hydrogen ion concentration in the polymerization reaction kettle as long as can make employed catalyst produce redox reaction fast, is preferably the acidic region in pH2.0～3.5.
In by the polymer that polymerization reaction kettle took out, add short-stopper with stopped reaction.The agent that stops of polyreaction is not limited to usually to use when the water system suspension polymerization manufacturing acrylic polymkeric substance.After aqueous solutions of polymers adds short-stopper, carry out the recovery of unreacted monomer.The recovery method system of unreacted monomer adopts the method with the aqueous solutions of polymers straight run distillation.In present embodiment,, as shown in Figure 2, after the taking-up of polymerization reaction kettle 4 places, import distillation tower 5 in polymerization reaction kettle 4 polymeric aqueous solutions of polymers.With polymkeric substance and isolating while of monomers/water, the mixed solution of monomers/water is distilled vaporization in distillation tower 5 in distillation tower 5, import distiller 6 and also condense to become the mixed solution of unreacted monomer component and water.Monomer component in distiller 6 liquefaction separates via decanting vessel with the mixed solution of water, and monomer component returns polymerization reaction kettle 4 via reclaiming monomer groove 8.
Yet,, except monomer component and water, only sneak into the SO2 of some in vaporizing and sending in the mixed gas of distiller 6.This SO2 condenses to liquefy and dissolves in the water, as described above, and as the polymerization starter of sneaking into the monomer component in the identical water.Therefore, preferable after sending into distiller 6 before the mixed gas of sending into distiller 6 condenses, hardens in order to avoid this reaction, importantly add the resistance polymerizing agent at once.Interpolation hinders polymerizing agent before importing distiller 6, and the some of resistance polymerizing agent may flow into the upstream side of distillation tower 5, because the fixing event of this addition makes the adjustment of addition become difficult.
Fig. 2 is for to add an example of the method for aforementioned resistance polymerizing agent according to the present invention.In the present invention, can be with the resistance polymerizing agent of necessary amount, by directly importing near the mixed gas introducing port of distiller 6, and present embodiment is connected near the introducing port 6b of the resistance polymerizing agent that forms in addition the mixed gas introducing port 6a of distiller 6 and the storage tanks 1 of vinyl cyanide with pipe arrangement 10a, and the pure raw material of the acrylic of necessary amount is sent into distiller 6.
In the pure raw material of vinyl cyanide, as previously mentioned, (20～100ppm) are added with the resistance polymerizing agent with predetermined weight ratio.Therefore, as previously mentioned,, the necessary amount of the pure raw material of vinyl cyanide stored in the storage tanks 1 is sent into distiller 6, consequently imported the resistance polymerizing agent of necessary amount by introducing port 6b from the resistance polymerizing agent of distiller 6.
Usually, the polymerisate of aforementioned polymerization process gained, the ratio of monomer/polymer/water, its discrete part by weight are 2～7%/10～35%/58～88% scope, and, contain SO this moment in the polymerisate as the polymerization starter function
2Source 0.02～0.20%.According to the vinyl cyanide starting monomer of present embodiment, for the above-mentioned monomer component amount in response to the operation gained that condenses adds 20～150% weight ratios.
Fig. 3 is for to add another example of the method for aforementioned resistance polymerizing agent according to the present invention.Present embodiment is by being equipped on pipe arrangement 9 between distiller 6 and the decanting vessel 7 with branch pipe 10b difference, and near the introducing port 6b of the resistance polymerizing agent that forms in addition the mixed gas introducing port 6a of distiller 6 connects with branch pipe 10b.Form the introducing port 6c that hinders polymerizing agent in this branch pipe 10b, supply with the resistance polymerizing agent via resistance polymerizing agent introducing port 6c in branch pipe 10b.Hinder the supply of polymerizing agent this moment, supply resistance polymerizing agent that can be independent, or can also be as the starting monomer of aforesaid supply vinyl cyanide.The resistance polymerizing agent addition of this moment, the weight ratio interpolation 20～150% of the monomer component that distiller 6 is condensed, liquefy.
Secondly, use the recovery of the monomer component of above-mentioned monomer component recovery system with specific description based on embodiment.
(the 1st embodiment)
By water system suspension polymerization, the ratio of the monomer/polymer/water of vinyl cyanide and vinyl acetate copolymerization gained becomes 3%/22%/75% (weight ratio), and the mixture that contains the sodium bisulfite 0.075～0.0125% (weight ratio) of originating as SO2 is supplied to distillation tower, to monomer 1.2t/hr, add containing of 120% (weight ratio) and hinder the starting monomer (vinyl cyanide) of polymerizing agent methoxyl group phenol 40ppm (weight ratio) by the cat head gained.Starting monomer is that the importing side spray in the multitube distiller adds.Even after continuing above-mentioned condition between 6 months, in the scope, do not find to block, and almost be not mixed with polymkeric substance in the monomer component that reclaims in the pipe that the starting monomer spraying fluid of multitube distiller passes through.
(the 1st comparative example)
Except the spraying of not carrying out the starting monomer in distiller, with the occasion of carrying out with the 1st embodiment same procedure, between 6 months, continue after the above-mentioned condition, find that in the multitube distiller volume blocks.And sneak into the polymkeric substance of volume in the monomer layer of the later decanting vessel of multitube distiller.
As mentioned above, according to the present invention, after the monomer component that will be by distillation vaporization and the mixture of water condense, liquefy with distiller, with water sepn with when reclaiming monomer component, owing near the introducing port of the aforementioned mixed gas of distiller, import the resistance polymerizing agent, pass through the resistance polymerizing agent that added, suppress the polymerization of monomer component, reclaim the polymkeric substance of sneaking in the monomer component to reduce at the liquefaction stage that mixes composition.
Claims (7)
1. the recovery method of an acrylic monomer component in the monomer component recovery method that the water system suspension polymerization operation of acrylic polymkeric substance is taken place, is characterized in that this method comprises:
With the mixture distillation of the monomer/polymer/water of polymerization process gained, so that monomer component is separated by the polymkeric substance vaporization with water; And
The monomer component and the water of vaporization are condensed to reclaim monomer component;
Wherein be transferred to the resistance polymerizing agent that adds trace when condensing operation by vaporization process.
2. recovery method as claimed in claim 1 is characterized in that, comprising: the ratio of the monomer/polymer/water of the product of polymerization of above-mentioned polymerization process gained is 2～7%/10～35%/58～88%, and comprises SO
2Source 0.02～0.20%; And
To the above-mentioned operation gained monomer component that condenses, adding weight ratio is the resistance polymerizing agent of 4～150ppm.
3. recovery method as claimed in claim 2 is characterized in that, comprising: the resistance polymerizing agent that interpolation is 20～100ppm to the above-mentioned monomer component weight ratio of the above-mentioned operation gained that condenses; And
To the importing monomer component of operation that condenses, add weight ratio and be 20%～150% the above-mentioned monomer component that is added with the resistance polymerizing agent.
4. recovery method as claimed in claim 1 is characterized in that, comprising: the ratio of the monomer/polymer/water of the product of polymerization of above-mentioned polymerization process gained is 2～7%/10～35%/58～88%, and comprises SO
2Source 0.02～0.20%; And
To the above-mentioned monomer component of the operation gained that condenses, add weight ratio and be 20%～150% the starting monomer of vinyl cyanide that weight ratio is the resistance polymerizing agent of 20～100ppm that contains.
5. the paradigmatic system of an acrylonitrile polymer by in the paradigmatic system of water system suspension polymerization acrylic polymkeric substance, possesses:
Converging portion;
The distiller that is connected with above-mentioned converging portion; And
The distiller that is connected with above-mentioned distiller;
It is characterized in that, near the gas introduction port of the above-mentioned portion of condensing that is connected in above-mentioned distiller, more be provided with the introducing port of resistance polymerizing agent.
6. paradigmatic system as claimed in claim 5, it is characterized in that, the introducing port of above-mentioned resistance polymerizing agent, connect the monomer export mouth be disposed at the monomers/water separation circuit after the above-mentioned operation of condensing, and between the monomer export mouth of the introducing port of above-mentioned resistance polymerizing agent and above-mentioned separation circuit, have more the introduction part that hinders polymerizing agent.
7. paradigmatic system as claimed in claim 5 is characterized in that, the introducing port of above-mentioned resistance polymerizing agent, and the starting monomer that connects the vinyl cyanide that contains above-mentioned resistance polymerizing agent is supplied with the source.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002-102813 | 2002-04-04 | ||
| JP2002102813A JP3768167B2 (en) | 2002-04-04 | 2002-04-04 | Recovery method and polymerization system of unreacted monomer components during polymerization of acrylonitrile monomers |
| JP2002102813 | 2002-04-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1448386A true CN1448386A (en) | 2003-10-15 |
| CN100432048C CN100432048C (en) | 2008-11-12 |
Family
ID=28786274
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031215610A Expired - Fee Related CN100432048C (en) | 2002-04-04 | 2003-03-31 | Recovery method and polymerization system of non-reaction monomer in polymerization of acrylic monomer |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3768167B2 (en) |
| CN (1) | CN100432048C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317296A (en) * | 2015-06-18 | 2017-01-11 | 中国石油化工股份有限公司 | Monomer recovery process for dry-process acrylic fibers |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4886990B2 (en) * | 2005-02-15 | 2012-02-29 | 三菱レイヨン株式会社 | Method and system for recovering unreacted monomer components during polymerization of acrylonitrile monomers |
| KR102142550B1 (en) * | 2016-12-16 | 2020-08-07 | 주식회사 엘지화학 | Method for separating non-reacted monomer from mixture comprising non-reacted monomer |
| KR102435545B1 (en) | 2018-12-18 | 2022-08-24 | 주식회사 엘지화학 | Method and apparatus for preparing aromatic vinyl compound-vinylcyan compound copolymer |
| KR20220034443A (en) * | 2020-09-11 | 2022-03-18 | 주식회사 엘지화학 | Nitrile-based monomer recovery method and solvent recovery apparatus |
| CN115894760B (en) * | 2022-11-11 | 2024-04-30 | 广东石油化工学院 | De-monomer tower and application thereof in preparation of polyolefin elastomer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3650975B2 (en) * | 1995-07-28 | 2005-05-25 | 日本エクスラン工業株式会社 | Process for producing improved acrylonitrile polymer melt |
-
2002
- 2002-04-04 JP JP2002102813A patent/JP3768167B2/en not_active Expired - Fee Related
-
2003
- 2003-03-31 CN CNB031215610A patent/CN100432048C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317296A (en) * | 2015-06-18 | 2017-01-11 | 中国石油化工股份有限公司 | Monomer recovery process for dry-process acrylic fibers |
| CN106317296B (en) * | 2015-06-18 | 2018-07-06 | 中国石油化工股份有限公司 | For the MONOMER RECOVERY technique of dry acrylic fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003292528A (en) | 2003-10-15 |
| JP3768167B2 (en) | 2006-04-19 |
| CN100432048C (en) | 2008-11-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10759880B2 (en) | Process for recovering hydrocarbons in a solution polymerisation process | |
| Muroi et al. | Morphology of core‐shell latex particles | |
| US3060157A (en) | Acrylonitrile polymerization | |
| US5980790A (en) | Process for producing a copolymer | |
| US10829610B2 (en) | Process and apparatus for in-line blending of polymers | |
| CN101260167B (en) | Finishing design to increase the polymer content in an olefin solution polymerization process | |
| CN1448386A (en) | Recovery method and polymerization system of non-reaction monomer in polymerization of acrylic monomer | |
| CN1784260B (en) | Method of treating a gas mixture comprising propane and propylene | |
| CN1243028C (en) | Method and apparatus for continuous polymerization of polymer | |
| CN101977894A (en) | Vinyl sulfonic acid, polymer thereof, and production method thereof | |
| CN104672741A (en) | High-solid-content anionic self-emulsified water-borne epoxy resin emulsion and preparation method thereof | |
| CN1919880A (en) | Degassing process | |
| CN104151487A (en) | Water-phase suspension production system and method for acrylonitrile polymer for PNA carbon fiber precursor | |
| CN104558397A (en) | Preparation method of ammoniation-degree-controllable high-hydrophily acrylonitrile copolymer spinning solution | |
| CN114011107A (en) | Novel device and method for continuously producing high-purity vinylene carbonate | |
| US3635917A (en) | Method of producing highly concentrated acrylonitrile polymer and copolymer solutions | |
| CN1215736A (en) | Suspension polymerization for preparing polyolefins | |
| CN102199794B (en) | Method for removing acrylonitrile monomer in spinning solution | |
| US3686112A (en) | Process for polymerizing acrylonitrile | |
| WO2020178010A1 (en) | Polymerization process | |
| CN1063289A (en) | The preparation method of the vinyl cyanide/methacrylonitrile copolymers of melt-processable | |
| JP2005529205A (en) | Process for producing perfluorosulfonate polymers containing sulfonyl functional groups | |
| CN104710550A (en) | High molecular weight polyvinylidene fluoride resin and preparation method thereof | |
| CN1230454C (en) | Process for preparing perfluorosulfonyl resin | |
| US3463616A (en) | Apparatus for the industrial production of spinnable acrylonitrile-based polymers |
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 | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Tokyo port area, Japan Patentee after: MITSUBISHI CHEMICAL Corp. Address before: Tokyo port area, Japan Patentee before: MITSUBISHI RAYON Co.,Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081112 |