CN103373919A - Method and equipment for separating and recycling alcoholysis waste liquid in polyvinyl alcohol production - Google Patents
Method and equipment for separating and recycling alcoholysis waste liquid in polyvinyl alcohol production Download PDFInfo
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Abstract
The invention relates to a method and equipment for separating and recycling an alcoholysis waste liquid in polyvinyl alcohol production. A PVA alcoholysis waste liquid separation device consists of a heavy substance eliminating and stabilizing tower T1, a methanol tower T2, a dehydrating tower T3 and a methyl acetate tower T4; the raw material, that is, the PVA alcoholysis waste liquid, is fed into the heavy substance eliminating and stabilizing tower T1 through a pipeline; stable azeotrope collected from the tower top is fed into the middle part of the methanol tower T2 through another pipeline; methanol-water enrichment collected from the tower bottom is fed into the dehydrating tower T3 through another pipeline; low-pressure azeotrope collected from the top of the methanol tower T2 is fed into the middle part of the methyl acetate tower T4 through another pipeline; a tower kettle methanol liquid is collected from a tower kettle; high-pressure azeotrope is collected from the top of the methyl acetate tower T4 and is fed into the heavy substance eliminating and stabilizing tower T1 for circulation operation through another pipeline; methyl acetate 8 is collected from the tower kettle; a tower top methanol liquid is collected from the top of the dehydrating tower T3; water is collected from the tower kettle. By using the method and the equipment, the purposes that methyl acetate and methanol are separated and recycled and the water is enabled to meet the emission standard, are achieved, the investment cost is low, and good economic and environmental benefits are achieved.
Description
Technical field
The present invention relates to separation and recovery method and the equipment of pure liquid waste solution in a kind of polyvinyl alcohol (PVA) production, be specifically related to a kind of azeotropic composition difference of from ritalin-Methanol-water system, utilizing pressure change to make system and reach Separation and Recovery ritalin, methyl alcohol and make water reach the method for emission standard.
Background technology
Ritalin is a kind of important organic solvent and industrial chemicals, the industrial raw material that is widely used as oil extraction agent, coating washing composition, leatheroid and spices, the quick dry agent of nitrocellulose and cellulose acetate.Obtain at present ritalin and mainly contain two approach: 1, methodology of organic synthesis is directly synthetic by acetic acid and methyl alcohol; 2, obtain by the existing method of purifying.But the ritalin that obtains higher degree all relates to the purification of ritalin.
Can produce a large amount of alkyd methyl esters in the middle of polyvinyl alcohol (PVA) production process, the PVA that every production is 1 ton just produces the pure liquid waste solution of 1.5-1.7 ton, and chief component is the impurity such as acetaldehyde of ritalin, methyl alcohol, water, sodium-acetate and trace.The separating difficulty of this system is larger, has multiple two yuan, ternary azeotrope.
Separate for ritalin at present and mainly contain following methods:
(1) patent 200510110282.1 discloses a kind of method of separating acetic acid methyl esters-methyl alcohol, but this patent is limited to ritalin-methyl alcohol binary system, restricted application.
(2) patent 200810053554.2 discloses a kind of processing method and device of producing high-purity methyl acetate, and this method has just been introduced purity and the output that how to improve in process of production ritalin, does not have the detailed situation of introducing product separation.
(3) patent 201010167288.3 discloses two kinds of methods that the solvent side entry feed is slightly got rectifying separation ritalin-Methanol-water, employing be extraction rectification technique, need extra increase extraction agent, technique is complicated.
(4) favourablely in addition directly the PVA by product is hydrolyzed with method for hydrolysis, and then separates, per pass conversion is low, and energy consumption is huge; Relate to the separation of acetic acid, water, methyl alcohol, ritalin quaternary system after the hydrolysis, all very strict to the requirement of equipment and control, segregational load is large; Saline extraction technique, the screening operation of acceptable acid addition salts is complicated, loaded down with trivial details, and the salt recovery processing technique is complicated, and is high to equipment requirements.
For the deficiencies in the prior art and limitation, complicated azeotropic system to first ritalin-Methanol-water composition, the present invention passes through the deep research of PVA alcoholysis waste liquid system, invented the method and apparatus that a cover adopts 4 tower variable-pressure rectification techniques that PVA alcohol liquid waste solution is separated, cost of investment is low, has preferably economic benefit and environmental benefit.
Summary of the invention
The method and apparatus of rectifying separation PVA of the present invention alcohol liquid waste solution ritalin-Methanol-water system recovery of acetic acid methyl esters, methyl alcohol is as shown in drawings:
Concrete technical scheme is:
The separating and reclaiming device of pure liquid waste solution forms by taking off heavy stabilizer tower T1, methanol column T2, dehydration tower T3 and ritalin tower T4 in the polyvinyl alcohol production, raw material PVA alcohol liquid waste solution enters by pipeline and takes off heavy stabilizer tower T1, the stable azeotrope 1 of stablizing overhead extraction enters methanol column T2 middle part by pipeline, stablizes tower reactor extraction Methanol-water pregnant solution 2 and enters dehydration tower T3 by pipeline; Methanol column T2 top extraction low pressure azeotrope 3 enters into ritalin tower T4 middle part by pipeline, and the methyl alcohol tower reactor arranges extraction tower reactor methanol solution 4 pipelines; Ritalin tower T4 overhead extraction high pressure azeotrope 7 enters into by pipeline and takes off heavy stabilizer tower T1, and the ritalin tower reactor arranges extraction ritalin 8 pipelines; Dehydration tower T3 cat head arranges extraction cat head methanol solution 5 pipelines, and the ritalin tower reactor arranges recovered water 6 pipelines; Four cats head all arrange condenser, utilize water quench, and reboiler all is set at the bottom of four towers, and tower reactor is all taked steam heating.
Operational path mainly may further comprise the steps:
Raw material PVA alcohol liquid waste solution enters and takes off heavy stabilizer tower T1 and carry out atmospheric operation, takes off extraction Methanol-water pregnant solution 2 at the bottom of the heavy stabilizer tower T1 tower, and cat head gets extraction and stablizes azeotrope 1;
The T1 overhead extraction is stablized azeotrope 1 and is entered methanol column T2 and carry out decompression operation, the reduction of pressure so that in the azeotropic system of ritalin-methyl alcohol the content of ritalin increase tower reactor extraction tower reactor methanol solution 4 mass content 〉=99.5%.Low pressure azeotrope 3 under this pressure of overhead extraction;
T2 overhead extraction low pressure azeotrope 3 enters ritalin tower T4 and carries out pressurized operation, pressure increases so that the content in the azeotrope system of ritalin, ritalin more than needed is by tower reactor extraction ritalin 8, the mass content of ritalin 〉=99.5%, the recycle stream high pressure azeotrope 7 of overhead extraction enters the T1 cyclical operation;
T1 tower reactor extraction Methanol-water pregnant solution 2 enters T3 and carries out atmospheric operation separation of methanol-water, overhead extraction cat head methanol solution 3, the mass content of methyl alcohol 〉=99.5%, the water 6 of tower reactor extraction qualified discharge, organic content≤0.1%.
Described heavy stabilizer tower T1, methanol column T2, dehydration tower T3, ritalin tower T4 employing packing tower or the tray column of taking off, cat head adopts liquid distributor that withdrawing fluid is distributed, as adopt packing tower, adopt gas-liquid redistributor to carry out gas between each section filler and liquid distributes again; As adopting tray column, column plate adopts float valve or sieve tray, and downtake and overflow weir are set.
The described number of theoretical plate that takes off heavy stabilizer tower T1 is that 30～60, working pressure are in 100～120kpa(absolute pressure), tower top temperature is that 69～73 ℃, quality reflux ratio are 2～4 at 53～58 ℃, tower reactor temperature;
The number of theoretical plate of described methanol column T2 is that 30～50, working pressure are in 65～80kpa(absolute pressure), tower top temperature is that 42～47 ℃, tower reactor temperature are that 60～64 ℃, quality reflux ratio are 0.5～2;
The number of theoretical plate of described dehydration tower T3 is 10～20, working pressure 100～120kpa(absolute pressure), tower top temperature is that 64～69 ℃, tower reactor temperature are that 100～106 ℃, quality reflux ratio are 0.5～2.
The number of theoretical plate of described ritalin tower T4 is 25～50, working pressure 500～1000kpa(absolute pressure), tower top temperature is that 103～131 ℃, tower reactor temperature are that 113～143 ℃, quality reflux ratio are 2～5.
The present invention compares with existing technique and has the following advantages: by to the deep research of PVA alcoholysis waste liquid system, invented a cover and adopted 4 tower variable-pressure rectification techniques PVA alcohol liquid waste solution to be carried out the method and apparatus of Separation and Recovery.Solve the Separation and Recovery difficult problem of ritalin-Methanol-water by simple distillation operation, separated a kind of economically viable method that provides for the many azeotropic systems of alcohol-ester
Description of drawings
Accompanying drawing: be variable-pressure rectification Separation and Recovery ritalin, methanol technics schema
Wherein: T1, take off heavy stabilizer tower; T2, methanol column; T3, dehydration tower; T4, ritalin tower; Raw material, PVA alcohol liquid waste solution; 1, stablizes azeotrope; 2, Methanol-water pregnant solution; 3, low pressure azeotrope; 4, tower reactor methanol solution; 5, cat head methanol solution; 6, water; 7, high pressure azeotrope; 8, ritalin.
Embodiment
Specifically describe the present invention below in conjunction with drawings and Examples, but the present invention is not limited to drawings and Examples.
Stabilizer tower T1, methanol column T2, dehydration tower T3, ritalin tower T4 form description of equipment: PVA alcohol liquid waste solution tripping device by taking off heavily, raw material PVA alcohol liquid waste solution enters by pipeline and takes off heavy stabilizer tower T1, the stable azeotrope 1 of overhead extraction enters methanol column T2 middle part by pipeline, and tower reactor extraction Methanol-water pregnant solution 2 enters dehydration tower T3 by pipeline.Methanol column T2 top extraction low pressure azeotrope 3 enters into ritalin tower T4 middle part, tower reactor extraction tower reactor methanol solution 4 by pipeline.Ritalin tower T4 overhead extraction high pressure azeotrope 7 enters into by pipeline and takes off heavy stabilizer tower T1 cyclical operation, tower reactor extraction ritalin 8.Dehydration tower T3 overhead extraction cat head methanol solution 5, tower reactor recovered water 6.Four cats head all arrange condenser, utilize water quench, and reboiler all is set at the bottom of four towers, and tower reactor is all taked steam heating.Four cats head all arrange condenser, utilize water quench, and reboiler all is set at the bottom of four towers, and tower reactor is all taked steam heating.
Embodiment 1:
Table 1 raw material forms
| Component | Content wt% |
| Ritalin | 30.7 |
| Methyl alcohol | 66.6 |
| Water | 2.56 |
Raw material 1(raw material formed as shown in table 1) send into 25kg/h and take off heavy stabilizer tower T1 and carry out the atmospheric distillation operation, 30 ℃ of feeding temperatures, tower top pressure is controlled at the 100kpa(absolute pressure), tower top temperature is 53 ℃, the tower reactor temperature is 69 ℃, the quality control of reflux ratio is 2, the extraction of T1 top is stablized azeotrope 2 and is entered methanol column T2, methanol column T2 pressure on top surface control 65kpa (absolute pressure), tower top temperature is 42 ℃, the tower reactor temperature is 47 ℃, and the quality control of reflux ratio is 0.5, methanol column tower reactor extraction methyl alcohol, purity 〉=99.5%, low pressure azeotrope 3 under this pressure of overhead extraction enters into ritalin tower T4 and carries out the compression rectification operation, and ritalin tower T4 tower top pressure is controlled at the 500kpa(absolute pressure), tower top temperature is 103 ℃, the tower reactor temperature is 113 ℃, the quality control of reflux ratio is 2, by tower reactor extraction ritalin 8 products, purity 〉=99.5%.Take off heavy stabilizer tower T1 tower reactor extraction Methanol-water pregnant solution 2 and enter into dehydration tower T3, dehydration tower T3 tower top pressure is controlled at the 100kpa(absolute pressure), tower top temperature is 64 ℃, the tower reactor temperature is 100 ℃, the quality control of reflux ratio is 0.5, overhead extraction methanol product, purity 〉=99.5%, the tower reactor extraction contains a small amount of organic water 6, wherein organic content≤0.1%.Take off heavy stabilizer tower T1, methanol column T2, dehydration tower T3, ritalin tower T4 and adopts packing tower, cat head adopts liquid distributor that withdrawing fluid is distributed, and the employing gas-liquid redistributor carries out gas and liquid distributes again between each section filler.The purity of each product and quality see Table 2 among the embodiment 1.
Table 2 data sheet
The yield of ritalin 〉=99.9% as can be seen from Table 2, methyl alcohol yield 〉=99% has satisfied the technique of Separation and Recovery ritalin-methyl alcohol.
Embodiment 2:
Raw material 1(raw material formed as shown in table 1) send into 20kg/h and take off heavy stabilizer tower T1 and carry out the atmospheric distillation operation, 30 ℃ of feeding temperatures, tower top pressure is controlled at the 120kpa(absolute pressure), tower top temperature is 58 ℃, the tower reactor temperature is 73 ℃, the quality control of reflux ratio is stablized azeotrope 2 in the extraction of 4, T1 top and is entered methanol column T2, methanol column T2 pressure on top surface control 80kpa (absolute pressure), tower top temperature is 47 ℃, the tower reactor temperature is 64 ℃, and the quality control of reflux ratio is 2, methanol column T2 tower reactor extraction methyl alcohol, purity 〉=99.5%, low pressure azeotrope 3 under this pressure of overhead extraction enters into ritalin tower T4 pressurized operation, and ritalin tower T4 tower top pressure is controlled at the 1000kpa(absolute pressure), tower top temperature is 131 ℃, the tower reactor temperature is 143 ℃, the quality control of reflux ratio is 3, by tower reactor extraction ritalin 8 products, purity 〉=99.5%.Take off heavy stabilizer tower T1 tower reactor extraction Methanol-water pregnant solution 2 and enter into dehydration tower T3, dehydration tower T3 tower top pressure is controlled at the 120kpa(absolute pressure), tower top temperature is 69 ℃, the tower reactor temperature is 106 ℃, the quality control of reflux ratio is 2, overhead extraction methanol product, purity 〉=99.5%, the tower reactor extraction contains a small amount of organic water 6, wherein organic content≤0.1%.Take off heavy stabilizer tower T1, methanol column T2, dehydration tower T3, ritalin tower T4 and adopts tray column, column plate employing float valve or sieve tray, and downtake and overflow weir are set.The purity of each product and quality see Table 3 among the embodiment 2.
Table 3 data sheet
The yield of ritalin 〉=99.9% as can be seen from Table 3, methyl alcohol yield 〉=99% has satisfied the technique of Separation and Recovery ritalin-methyl alcohol.
Embodiment 3:
Table 4 raw material 2 forms
| Component | Content wt% |
| Ritalin | 10.1 |
| Methyl alcohol | 85.7 |
| Water | 4.2 |
Raw material 2(raw material formed as shown in table 4) send into 20kg/h and take off heavy stabilizer tower T1 and carry out the atmospheric distillation operation, 30 ℃ of feeding temperatures, tower top pressure is controlled at the 110kpa(absolute pressure), tower top temperature is 56 ℃, the tower reactor temperature is 71 ℃, the quality control of reflux ratio is stablized azeotrope 2 in the extraction of 3, T1 top and is entered methanol column T2, methanol column T2 pressure on top surface control 70kpa (absolute pressure), tower top temperature is 44 ℃, the tower reactor temperature is 61 ℃, and the quality control of reflux ratio is 1, methanol column T2 tower reactor extraction methyl alcohol, purity 〉=99.5%, low pressure azeotrope 3 under this pressure of overhead extraction enters into ritalin tower T4 pressurized operation, and ritalin tower T4 tower top pressure is controlled at the 700kpa(absolute pressure), tower top temperature is 116 ℃, the tower reactor temperature is 127 ℃, the quality control of reflux ratio is 4, by tower reactor extraction ritalin 8 products, purity 〉=99.5%.Take off heavy stabilizer tower T1 tower reactor extraction Methanol-water pregnant solution 2 and enter into dehydration tower T3, dehydration tower T3 tower top pressure is controlled at the 110kpa(absolute pressure), tower top temperature is 67 ℃, the tower reactor temperature is 104 ℃, the quality control of reflux ratio is 1, overhead extraction methanol product, purity 〉=99.5%, the tower reactor extraction contains a small amount of organic water 6, wherein organic content≤0.1%.Take off heavy stabilizer tower T1, methanol column T2, dehydration tower T3, ritalin tower T4 and adopts packing tower, cat head adopts liquid distributor that withdrawing fluid is distributed, and the employing gas-liquid redistributor carries out gas and liquid distributes again between each section filler.The purity of each product and quality see Table 5 among the embodiment 3.
Table 5 data sheet
Embodiment 4:
Table 6 raw material 3 forms
| Component | Content wt% |
| Ritalin | 65.5 |
| Methyl alcohol | 33.0 |
| Water | 1.5 |
Raw material 3(raw material formed as shown in table 5) send into 30kg/h and take off heavy stabilizer tower T1 and carry out the atmospheric distillation operation, 30 ℃ of feeding temperatures, tower top pressure is controlled at the 120kpa(absolute pressure), tower top temperature is 58 ℃, the tower reactor temperature is 73 ℃, the quality control of reflux ratio is stablized azeotrope 2 in the extraction of 2, T1 top and is entered methanol column T2, methanol column T2 pressure on top surface control 80kpa (absolute pressure), tower top temperature is 47 ℃, the tower reactor temperature is 64 ℃, and the quality control of reflux ratio is 0.5, methanol column T2 tower reactor extraction methyl alcohol, purity 〉=99.5%, low pressure azeotrope 3 under this pressure of overhead extraction enters into ritalin tower T4 pressurized operation, and ritalin tower T4 tower top pressure is controlled at the 1000kpa(absolute pressure), tower top temperature is 131 ℃, the tower reactor temperature is 143 ℃, the quality control of reflux ratio is 5, by tower reactor extraction ritalin 8 products, purity 〉=99.5%.Take off heavy stabilizer tower T1 tower reactor extraction Methanol-water pregnant solution 2 and enter into dehydration tower T3, dehydration tower T3 tower top pressure is controlled at the 120kpa(absolute pressure), tower top temperature is 69 ℃, the tower reactor temperature is 106 ℃, the quality control of reflux ratio is 0.5, overhead extraction methanol product, purity 〉=99.5%, the tower reactor extraction contains a small amount of organic water 6, wherein organic content≤0.1%.Take off heavy stabilizer tower T1, methanol column T2, dehydration tower T3, ritalin tower T4 and adopts tray column, column plate employing float valve or sieve tray, and downtake and overflow weir are set.The purity of each product and quality see Table 7 among the embodiment 4.
Table 7 data sheet
The present invention proposes separation and recovery method and the equipment of pure liquid waste solution in kind of a polyvinyl alcohol (PVA) production, be described by preferred embodiment, person skilled obviously can be within not breaking away from content of the present invention, spirit and scope to structure as herein described with technological method is changed or suitably change and combination, realize the technology of the present invention.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are deemed to be included in spirit of the present invention, scope and the content.
Claims (9)
1. the separating and reclaiming device of pure liquid waste solution during a polyvinyl alcohol is produced; It is characterized in that forming by taking off heavy stabilizer tower T1, methanol column T2, dehydration tower T3 and ritalin tower T4, raw material PVA alcohol liquid waste solution enters by pipeline and takes off heavy stabilizer tower T1, the stable azeotrope (1) of stablizing overhead extraction enters methanol column T2 middle part by pipeline, stablizes tower reactor extraction Methanol-water pregnant solution (2) and enters dehydration tower T3 by pipeline; Methanol column T2 top extraction low pressure azeotrope (3) enters into ritalin tower T4 middle part by pipeline, and the methyl alcohol tower reactor arranges extraction tower reactor methanol solution (4) pipeline; Ritalin tower T4 overhead extraction high pressure azeotrope (7) enters into by pipeline and takes off heavy stabilizer tower T1, and the ritalin tower reactor arranges extraction ritalin (8) pipeline; Dehydration tower T3 cat head arranges extraction cat head methanol solution (5) pipeline, and the ritalin tower reactor arranges recovered water (6) pipeline; Four cats head all arrange condenser, utilize water quench, and reboiler all is set at the bottom of four towers, and tower reactor is all taked steam heating.
2. device as claimed in claim 1 is characterized in that described heavy stabilizer tower T1, methanol column T2, dehydration tower T3 and the ritalin tower T4 of taking off adopts packing tower or tray column, and cat head adopts liquid distributor that withdrawing fluid is distributed.
3. device as claimed in claim 2 is characterized in that adopting packing tower, adopts gas-liquid redistributor to carry out gas between each section filler and liquid distributes again.
4. device as claimed in claim 2 is characterized in that adopting tray column, and column plate adopts float valve or sieve tray, and downtake and overflow weir are set.
5. the equipment of employing claim 1 carries out the separation and recovery method of pure liquid waste solution in the polyvinyl alcohol production, it is characterized in that:
Raw material PVA alcohol liquid waste solution enters and takes off heavy stabilizer tower T1 and carry out atmospheric operation;
The T1 overhead extraction is stablized azeotrope 1 and is entered methanol column T2 and carry out decompression operation;
T1 tower reactor extraction Methanol-water pregnant solution 2 enters T3 and carries out atmospheric operation separation of methanol-water;
T2 overhead extraction low pressure azeotrope 3 enters ritalin tower T4 and carries out pressurized operation;
The recycle stream high pressure azeotrope 7 of overhead extraction enters the T1 cyclical operation.
6. method as claimed in claim 3, the number of theoretical plate that it is characterized in that taking off heavy stabilizer tower T1 are 30～60, working pressure at 100～120kpa, tower top temperature is that 69～73 ℃, quality reflux ratio are 2～4 at 53～58 ℃, tower reactor temperature.
7. method as claimed in claim 3, the number of theoretical plate that it is characterized in that methanol column T2 are 30～50, working pressure in 65～80kpa, tower top temperature is that 42～47 ℃, tower reactor temperature are that 60～64 ℃, quality reflux ratio are 0.5～2.
8. method as claimed in claim 3, the number of theoretical plate that it is characterized in that dehydration tower T3 are that 10～20, working pressure 100～120kpa, tower top temperature are that 64～69 ℃, tower reactor temperature are that 100～106 ℃, quality reflux ratio are 0.5～2.
9. method as claimed in claim 3, the number of theoretical plate that it is characterized in that ritalin tower T4 are that 25～50, working pressure 500～1000kpa, tower top temperature are that 103～131 ℃, tower reactor temperature are that 113～143 ℃, quality reflux ratio are 2～5.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106621437A (en) * | 2016-10-21 | 2017-05-10 | 中国石化长城能源化工（宁夏）有限公司 | Method for effectively improving separation effect of fourth polymerization tower |
| CN109467497A (en) * | 2018-08-03 | 2019-03-15 | 内蒙古蒙维科技有限公司 | A kind of recovery process and device of polyvinyl alcohol alcohol hydrolysis mother liquor |
| CN109721484A (en) * | 2019-01-21 | 2019-05-07 | 中国石化长城能源化工（宁夏）有限公司 | A kind of system and device and preparation method thereof using polyvinyl alcohol by-product methyl acetate production acetic acid |
| CN112679350A (en) * | 2020-12-29 | 2021-04-20 | 内蒙古双欣环保材料股份有限公司 | Recovery system of alcoholysis waste liquid |
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| CN1962587A (en) * | 2005-11-11 | 2007-05-16 | 中国石油化工股份有限公司 | Method of separating methyl acetate and methanol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1962587A (en) * | 2005-11-11 | 2007-05-16 | 中国石油化工股份有限公司 | Method of separating methyl acetate and methanol |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106621437A (en) * | 2016-10-21 | 2017-05-10 | 中国石化长城能源化工（宁夏）有限公司 | Method for effectively improving separation effect of fourth polymerization tower |
| CN109467497A (en) * | 2018-08-03 | 2019-03-15 | 内蒙古蒙维科技有限公司 | A kind of recovery process and device of polyvinyl alcohol alcohol hydrolysis mother liquor |
| 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 |
| CN109721484A (en) * | 2019-01-21 | 2019-05-07 | 中国石化长城能源化工（宁夏）有限公司 | A kind of system and device and preparation method thereof using polyvinyl alcohol by-product methyl acetate production acetic acid |
| CN112679350A (en) * | 2020-12-29 | 2021-04-20 | 内蒙古双欣环保材料股份有限公司 | Recovery system of alcoholysis waste liquid |
| CN112679350B (en) * | 2020-12-29 | 2023-07-11 | 内蒙古双欣环保材料股份有限公司 | Recovery system of alcoholysis waste liquid |
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Application publication date: 20131030 |