CN102924275B - Refining method for alcoholysis waste liquid in PVA (polyvinyl alcohol) production and test device for same - Google Patents
Refining method for alcoholysis waste liquid in PVA (polyvinyl alcohol) production and test device for same Download PDFInfo
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- CN102924275B CN102924275B CN201210488315.6A CN201210488315A CN102924275B CN 102924275 B CN102924275 B CN 102924275B CN 201210488315 A CN201210488315 A CN 201210488315A CN 102924275 B CN102924275 B CN 102924275B
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Abstract
The invention relates to a refining method for an alcoholysis waste liquid in PVA (polyvinyl alcohol) production and a test device for the refining method, wherein the process method is that under the action of a catalyst, an extraction reaction rectification method is adopted, and acetic acid is added as an extractant and a reactant for reacting methanol in the azeotrope of methyl acetate and methanol to generate methyl acetate. The method specifically comprises the following steps of: 1) conveying the measured azeotrope of methyl acetate and methanol from the middle-lower part of an extraction reaction rectification tower, conveying the measured and proportioned extractant, namely, the acetic acid solution, from the upper part of the extraction reaction rectification tower, obtaining the methyl acetate in a concentration of 99.5% on the tower top of the extraction reaction rectification tower, and obtaining the acetic acid solution containing a small amount of methyl acetate, methanol and water on the tower bottom; and 2) conveying the residue from the extraction reaction rectification tower in an extractant recovery tower, rectifying out methyl acetate and methanol on the tower top of the extractant recovery tower and returning the methyl acetate and the methanol into the alcoholysis liquid azeotropic rectification tower of a PVA system, obtaining an acetic acid aqueous solution on the tower bottom of the extractant recovery tower and returning the acetic acid aqueous solution into the acetic acid concentration tower of the PVA system.
Description
Technical field
The present invention relates to the purification techniques of a kind of polyvinyl alcohol (PVA) alcohol liquid waste solution, be specifically related to alcohol liquid waste solution process for purification and testing apparatus thereof in a kind of PVA production, especially adopt the ritalin purification techniques that extracting rectifying and reactive distillation combine.
Background technology
In polyvinyl alcohol (PVA) production process, time Vinyl Acetate Copolymer alcoholysis generates polyvinyl alcohol, a large amount of by-product methyl acetates can be produced, under normal circumstances, often synthesize 1 ton of PVA, obtain about 1.68 tons of ritalins simultaneously.In alcohol liquid waste solution, ritalin purity is not high, and containing more methyl alcohol, wherein methanol content is generally 74wt%, and ritalin is 18wt%, and also have other impurity a small amount of, the value directly utilized is little, usually needs to carry out Separation and Recovery.Alcohol liquid waste solution is general first through azeotropic distillation, and obtaining crude carbinol at the bottom of tower, tower top obtains ritalin and methanol azeotrope, is then method separating acetic acid methyl esters and the methyl alcohol of extraction agent extracting rectifying with water.But ritalin and water form azeotrope, and containing 3.0 ~ 8.0% water and a small amount of methyl alcohol in the ritalin that extracting rectifying tower top obtains, ritalin quality is not high, and industrial value is still little.Therefore methyl acetate hydrolysis is that acetic acid and methyl alcohol reclaim respectively by the method for the follow-up employing fixed bed of PVA factory or reactive distillation mostly.Because hydrolysis reaction is reversible reaction, ritalin can not realize complete hydrolysis, and obtaining product after hydrolysis is quaternary product, wherein still there is the separation problem of methyl acetate and methanol, ritalin-water azeotrope.The energy consumption of whole PVA factory has 50% ~ 60% for recycle section, and the energy consumption needed for recovery of acetic acid methyl esters accounts for about 70% of recycle section energy consumption.Seek a kind of technique is simple, energy consumption is low ritalin process for purification to PVA factory important in inhibiting as seen.
Ritalin is a kind of important solvent and Organic Chemicals, industrially be commonly used for the quick-drying solvent of PAA-CN-CA, for paint, be the raw material manufacturing dyestuff and medicine, also can be used for the manufacture of leatheroid and spices and be used as the extraction agent of grease.High-purity methyl acetate can be used for acetic acid synthesized, aceticanhydride, methyl acrylate, vinyl acetate between to for plastic and ethanamide etc.The market value of high-purity methyl acetate is compared low-purity ritalin and is exceeded 2 ~ 4 times.Therefore, produce highly purified ritalin and there is larger economic benefit.
Summary of the invention
Alcohol liquid waste solution process for purification and testing apparatus thereof in the object of the present invention is to provide a kind of PVA to produce, the method is the technology that a kind of extracting rectifying and reactive distillation combine, be mainly used in refining polyvinyl alcohol industry by-product methyl acetate, overcome the difficulty of ritalin and methyl alcohol, ritalin and water Azeotrope separation, after refining, ritalin purity reaches more than 99.5%, realizes by-product resource and utilizes.The present invention makes that ritalin purification techniques technique is simple, less investment, energy consumption are low.
One of technical scheme of the present invention is: alcohol liquid waste solution process for purification during a kind of PVA produces, it is characterized in that this processing method is under the effect of catalyzer, adopt extractive reaction rectificating method, add acetic acid as extraction agent and reactant, methyl alcohol reaction in ritalin and methanol azeotrope is generated ritalin, specifically comprises the steps:
1) ritalin measured and methanol azeotrope enter from the middle and lower part of extractive reaction rectifying tower, the extraction agent acetum of metering proportion enters from the top of extractive reaction rectifying tower, obtain concentration more than 99.5% ritalin at the tower top of extractive reaction rectifying tower, tower reactor is the acetum containing a small amount of ritalin, methyl alcohol, water;
2) the still liquid from extractive reaction rectifying tower enters extraction agent recovery tower, distillate at the tower top of extraction agent recovery tower the alcoholysis liquid azeotropy rectification column that ritalin and methyl alcohol return PVA system, the tower reactor of described extraction agent recovery tower obtains the acetic acid concentration tower that aqueous acetic acid returns PVA system.
Further, above-mentioned extractive reaction rectifying tower comprises rectifying section, extraction section, reactive distillation section and stripping section; It is rectifying section that extractive reaction rectifying tower top to acetic acid adds entrance, and it is extraction section that acetic acid adds entrance to the topmost of catalyst filling, and the part that catalyst filling is housed is reactive distillation section, and it is stripping section that ritalin and methanol azeotrope add below entrance.
Further, acetic acid destroys the binary azeotrope of ritalin, the formation of methanol in the extraction section of extractive reaction rectifying tower, reacts simultaneously generate ritalin with methyl alcohol in the reactive distillation section of extractive reaction rectifying tower; After the rectifying section rectifying separation of extractive reaction rectifying tower, tower top obtains highly purified ritalin; A small amount of ritalin, unreacted methyl alcohol, water and acetic acid are discharged from the tower reactor of extractive reaction rectifying tower.
Further, described catalyzer is storng-acid cation exchange resin.
Further, the solvent ratio of described extraction agent and raw material is 2 ~ 3, and the reflux ratio of extractive reaction rectifying tower is 2 ~ 3, and described raw material is ritalin and methanol azeotrope.
Further, described extraction agent temperature is 5 ~ 40 DEG C.
Further, described extractive reaction rectifying tower theoretical stage is 20 ~ 40; Extraction agent recovery tower theoretical stage 15 ~ 30.
Further, the reflux ratio of described extraction agent recovery tower is 0.2 ~ 1.0.
To sum up sum up: processing condition of the present invention are: enter methanol content 15% ~ 20% in the raw material ritalin carbinol mixture of rectifying tower; Extraction agent temperature 5 ~ 40 DEG C; Catalyzer is storng-acid cation exchange resin; Rectifier column reflux is than 2 ~ 3; Extraction agent recovery tower reflux ratio 0.2 ~ 1.0.In such a situa-tion, rectifying tower methanol conversion is greater than 85%, and product ritalin purity is greater than 99.5%.
Two of technical scheme of the present invention is: during a kind of PVA produces, alcohol liquid waste solution refines testing apparatus, comprise the first feed storage tank for depositing acetum, for depositing the second feed storage tank and the extractive reaction rectifying tower of ritalin and methanol azeotrope, it is characterized in that: described first feed storage tank leads to the ingress, middle and upper part of extractive reaction rectifying tower through the first fresh feed pump, described second feed storage tank leads to the ingress, middle and lower part of extractive reaction rectifying tower through the second fresh feed pump, the middle part of described extractive reaction rectifying tower is provided with catalyst filling, condenser is provided with on the upside of described extractive reaction rectifying tower top, described extractive reaction rectifying tower top subordinate side is disposed with magnetic valve, reflux ratio controller and splitter, one branch road of described splitter is back to the rectifying section of extractive reaction rectifying tower, another branch road of described splitter leads to product storage tank, still liquid in the tower reactor of described extractive reaction rectifying tower pumps to still liquid storage tank through still liquid extraction pump, rectifying section and the stripping section of described extractive reaction rectifying tower are respectively arranged with temperature controller, described tower reactor is arranged in thermostatic bath, is provided with the thermometer for measuring still liquid temp in described tower reactor.
Principal feature of the present invention and beneficial effect as follows:
1, from ritalin and the methanol azeotrope (containing other impurity a small amount of) of PVA alcoholysis workshop section, wherein ritalin content about 82%, methanol content about 18%, enter from extractive reaction rectifying tower middle and lower part, acetum enters from extractive reaction rectifying tower middle and upper part as extraction agent, tower top obtains high-purity methyl acetate product, and tower reactor is the acetum containing a small amount of ritalin, methyl alcohol, water.Still liquid goes out organism ritalin, methyl alcohol through extraction agent recovery tower rectifying separation, and return the alcoholysis of PVA system and to boil liquid azeotropy rectification column, still liquid is extraction agent aqueous acetic acid, returns PVA system acetic acid concentration tower concentrate Posterior circle and uses.
First the present invention make use of acetic acid and first alcohol and water extracting and separating from azeotrope out, is then made acetic acid and methyl alcohol react by esterification and generates ritalin, thus obtained highly purified ritalin.
2, the theoretical stage of extractive reaction rectifying tower is 20 ~ 40, and the number of theoretical plate of extraction agent recovery tower is 15 ~ 30 grades and is advisable.
3, the still liquid of extractive reaction rectifying tower enters extraction agent recovery tower from middle and lower part, and tower top distillates ritalin and methyl alcohol, and tower reactor obtains acetum and returns PVA system acetic acid concentration tower and use through concentrate Posterior circle.
4, maximum feature of the present invention is that technical process is simple, and energy-conservation, product purity is high.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Label declaration: T-101 extractive reaction rectifying tower, T-102 extraction agent recovery tower; A represents acetum, and b represents ritalin methanol azeotrope, and c represents ritalin product, and d flows stock and enters alcohol liquid waste solution azeotropy rectification column, and e flows stock and enters PVA system acetic acid concentration tower.
Fig. 2 is the testing apparatus schematic diagram of extractive reaction rectifying tower.
Label declaration: 1 first feed storage tank, 2 first fresh feed pumps, 3 second fresh feed pumps, 4 second feed storage tank, 5 thermometers, 6 tower reactors, 7 thermostatic baths, 8 still liquid extraction pumps, 9 still liquid storage tanks, 10 product storage tanks, 11,12,13 temperature controllers, 14 stripping sections, 15 reactive distillation sections, 16 rectifying sections, 17 reflux ratio controllers, 18 splitters, 19 magnetic valves, 20 condensers.
Embodiment
By describing technology contents of the present invention, structural attitude in detail, realized object and effect, accompanying drawing is coordinated to be explained in detail below in conjunction with embodiment.
Alcohol liquid waste solution process for purification during a kind of PVA produces, this processing method is under the effect of catalyzer, adopts extractive reaction rectificating method, adds acetic acid as extraction agent and reactant, methyl alcohol reaction in ritalin and methanol azeotrope is generated ritalin, specifically comprises the steps:
1) ritalin measured and methanol azeotrope enter from the middle and lower part of extractive reaction rectifying tower, the extraction agent acetum of metering proportion enters from the top of extractive reaction rectifying tower, obtain concentration more than 99.5% ritalin at the tower top of extractive reaction rectifying tower, tower reactor is the acetum containing a small amount of ritalin, methyl alcohol, water;
2) the still liquid from extractive reaction rectifying tower enters extraction agent recovery tower, distillate at the tower top of extraction agent recovery tower the alcoholysis liquid azeotropy rectification column that ritalin and methyl alcohol return PVA system, the tower reactor of described extraction agent recovery tower obtains the acetic acid concentration tower that aqueous acetic acid returns PVA system.
In the present embodiment, described extractive reaction rectifying tower comprises rectifying section, extraction section, reactive distillation section and stripping section; It is rectifying section that extractive reaction rectifying tower top to acetic acid adds entrance, and it is extraction section that acetic acid adds entrance to the topmost of catalyst filling, and the part that catalyst filling is housed is reactive distillation section, and it is stripping section that ritalin and methanol azeotrope add below entrance.Acetic acid destroys the binary azeotrope of ritalin, the formation of methanol in the extraction section of extractive reaction rectifying tower, reacts simultaneously generate ritalin with methyl alcohol in the reactive distillation section of extractive reaction rectifying tower; After the rectifying section rectifying separation of extractive reaction rectifying tower, tower top obtains highly purified ritalin; A small amount of ritalin, unreacted methyl alcohol, water and acetic acid are discharged from the tower reactor of extractive reaction rectifying tower.
In the present embodiment, described catalyzer is storng-acid cation exchange resin.The solvent ratio of described extraction agent and raw material is 2 ~ 3, and the reflux ratio of extractive reaction rectifying tower is 2 ~ 3, and described raw material is ritalin and methanol azeotrope.Described extraction agent temperature is 5 ~ 40 DEG C.Described extractive reaction rectifying tower theoretical stage is 20 ~ 40; Extraction agent recovery tower theoretical stage 15 ~ 30.The reflux ratio of described extraction agent recovery tower is 0.2 ~ 1.0.
During a kind of PVA produces, alcohol liquid waste solution refines testing apparatus, this testing apparatus comprises the first feed storage tank 1 for depositing acetum, for depositing the second feed storage tank 4 and the extractive reaction rectifying tower of ritalin and methanol azeotrope, described first feed storage tank 1 leads to the ingress, middle and upper part of extractive reaction rectifying tower through the first fresh feed pump 2, described second feed storage tank 4 leads to the ingress, middle and lower part of extractive reaction rectifying tower through the second fresh feed pump 3, the middle part of described extractive reaction rectifying tower is provided with catalyst filling, condenser 20 is provided with on the upside of described extractive reaction rectifying tower top, described extractive reaction rectifying tower top subordinate side is disposed with magnetic valve 19, reflux ratio controller 17 and splitter 18, one branch road of described splitter 18 is back to the rectifying section 16 of extractive reaction rectifying tower, another branch road of described splitter 18 leads to product storage tank 10, still liquid in the tower reactor 6 of described extractive reaction rectifying tower pumps to still liquid storage tank 9 through still liquid extraction pump 8, the rectifying section of described extractive reaction rectifying tower and stripping section are respectively arranged with temperature controller 13,11, described tower reactor 6 is arranged in thermostatic bath 7, is provided with the thermometer 5 for measuring still liquid temp in described tower reactor 6.
[embodiment 1]
As shown in Figure 2, raw material is 81.70wt% ritalin to ritalin purification techniques of the present invention, and 17.8wt% methyl alcohol adds tower T-101 from middle and lower part; Extraction agent is acetum, adds tower T-101 from middle and upper part.Tower pressure is normal pressure, and service temperature is room temperature 25 DEG C, solvent ratio 2:1, and reflux ratio is 2.5, the theoretical stage of tower 31 grades.Tower top obtains product ritalin.The composition of tower top and tower reactor in table 1, the transformation efficiency 96.14% of methyl alcohol.Still liquid enters from solvent recovery tower T-102 tower middle and lower part, and tower top distillates ritalin, first alcohol and water, and still liquid is acetum.
[embodiment 2]
In embodiment 2, difference from Example 1 is solvent ratio is 3:1, and transformation efficiency is 91.77%.Experimental result is in table 2.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every utilize specification sheets of the present invention and accompanying drawing content to do equivalent structure or equivalent flow process conversion; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (7)
1. alcohol liquid waste solution process for purification in a PVA production, it is characterized in that this processing method is under the effect of catalyzer, adopt extractive reaction rectificating method, add acetic acid as extraction agent and reactant, methyl alcohol reaction in ritalin and methanol azeotrope is generated ritalin, specifically comprises the steps:
1) ritalin measured and methanol azeotrope enter from the middle and lower part of extractive reaction rectifying tower, the extraction agent acetum of metering proportion enters from the top of extractive reaction rectifying tower, obtain concentration more than 99.5% ritalin at the tower top of extractive reaction rectifying tower, tower reactor is the acetum containing a small amount of ritalin, methyl alcohol, water;
2) the still liquid from extractive reaction rectifying tower enters extraction agent recovery tower, distillate at the tower top of extraction agent recovery tower the alcoholysis liquid azeotropy rectification column that ritalin and methyl alcohol return PVA system, the tower reactor of described extraction agent recovery tower obtains the acetic acid concentration tower that aqueous acetic acid returns PVA system;
Described extractive reaction rectifying tower comprises rectifying section, extraction section, reactive distillation section and stripping section; It is rectifying section that extractive reaction rectifying tower top to acetic acid adds entrance, and it is extraction section that acetic acid adds entrance to the topmost of catalyst filling, and the part that catalyst filling is housed is reactive distillation section, and it is stripping section that ritalin and methanol azeotrope add below entrance;
Described extraction agent temperature is 5 ~ 40 DEG C.
2. alcohol liquid waste solution process for purification in PVA production according to claim 2, it is characterized in that: acetic acid destroys the binary azeotrope of ritalin, the formation of methanol in the extraction section of extractive reaction rectifying tower, react in the reactive distillation section of extractive reaction rectifying tower with methyl alcohol simultaneously and generate ritalin; After the rectifying section rectifying separation of extractive reaction rectifying tower, tower top obtains highly purified ritalin; A small amount of ritalin, unreacted methyl alcohol, water and acetic acid are discharged from the tower reactor of extractive reaction rectifying tower.
3. alcohol liquid waste solution process for purification in PVA production according to claim 1, is characterized in that: described catalyzer is storng-acid cation exchange resin.
4. alcohol liquid waste solution process for purification in PVA production according to claim 1, it is characterized in that: the solvent ratio of described extraction agent and raw material is 2 ~ 3, the reflux ratio of extractive reaction rectifying tower is 2 ~ 3, and described raw material is ritalin and methanol azeotrope.
5. alcohol liquid waste solution process for purification in PVA production according to claim 1, is characterized in that: described extractive reaction rectifying tower theoretical stage is 20 ~ 40; Extraction agent recovery tower theoretical stage 15 ~ 30.
6. alcohol liquid waste solution process for purification in PVA production according to claim 1, is characterized in that: the reflux ratio of described extraction agent recovery tower is 0.2 ~ 1.0.
7. in a PVA production, alcohol liquid waste solution refines testing apparatus, comprise the first feed storage tank for depositing acetum, for depositing the second feed storage tank and the extractive reaction rectifying tower of ritalin and methanol azeotrope, it is characterized in that: described first feed storage tank leads to the ingress, middle and upper part of extractive reaction rectifying tower through the first fresh feed pump, described second feed storage tank leads to the ingress, middle and lower part of extractive reaction rectifying tower through the second fresh feed pump, the middle part of described extractive reaction rectifying tower is provided with catalyst filling, condenser is provided with on the upside of described extractive reaction rectifying tower top, described extractive reaction rectifying tower top subordinate side is disposed with magnetic valve, reflux ratio controller and splitter, one branch road of described splitter is back to the rectifying section of extractive reaction rectifying tower, another branch road of described splitter leads to product storage tank, still liquid in the tower reactor of described extractive reaction rectifying tower pumps to still liquid storage tank through still liquid extraction pump, rectifying section and the stripping section of described extractive reaction rectifying tower are respectively arranged with temperature controller, described tower reactor is arranged in thermostatic bath, is provided with the thermometer for measuring still liquid temp in described tower reactor.
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| CN201210488315.6A CN102924275B (en) | 2012-11-27 | 2012-11-27 | Refining method for alcoholysis waste liquid in PVA (polyvinyl alcohol) production and test device for same |
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| CN103360247A (en) * | 2013-07-23 | 2013-10-23 | 福州大学 | Purification method of by-product acetic acid methyl ester |
| CN109467497B (en) * | 2018-08-03 | 2023-11-10 | 内蒙古蒙维科技有限公司 | Recovery process and device for polyvinyl alcohol alcoholysis mother liquor |
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| CN101898963A (en) * | 2010-05-10 | 2010-12-01 | 南京师范大学 | Method for separating methyl acetate-methanol-water by adopting extractive distillation separation method with two-solvent lateral feed |
| CN102757342A (en) * | 2012-07-19 | 2012-10-31 | 安徽皖维高新材料股份有限公司 | Method for purifying by-product methyl acetate generated during production of PVA (polyvinyl acetate) |
| CN102766044A (en) * | 2012-08-07 | 2012-11-07 | 天津凯赛特科技有限公司 | Reaction and rectification system and method for recycling acetic acid from diluted acetic acid solution |
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