CN110028602A - A method of reducing impurity content in commercial polyethylene alcohol - Google Patents
A method of reducing impurity content in commercial polyethylene alcohol Download PDFInfo
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- CN110028602A CN110028602A CN201910347763.6A CN201910347763A CN110028602A CN 110028602 A CN110028602 A CN 110028602A CN 201910347763 A CN201910347763 A CN 201910347763A CN 110028602 A CN110028602 A CN 110028602A
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- alcohol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The invention discloses a kind of methods of impurity content in reduction commercial polyethylene alcohol, are that polyvinyl alcohol clinker is first placed in heating stirring in solvent, are then separated by solid-liquid separation, obtained solid through drying, obtains polyvinyl alcohol finished product again.Method of the invention, it is possible to which the content of the impurity such as methanol, methyl acetate, sodium acetate in PVA product is effectively reduced, product quality is improved, method is simple, raw material is cheap, reduces production cost, and can be realized industrialization.
Description
Technical field
The invention belongs to commercial polyethylene alcohol production fields, and in particular to a kind of reduction commercial polyethylene alcohol lmpurities
The method of content.
Background technique
Polyvinyl alcohol (PVA) is a kind of widely used high-molecular compound, and production process mainly includes vinyl acetate
Synthesis, purification and the polymerization of rouge (VAC) and the alcoholysis etc. of polyvinyl acetate (PVAC).Wherein PVAC passes through alkali catalyzed alcoholysis
Solid product is obtained, after pulverizer crushes, is squeezed using extruder and removes most mother liquor, after the completion of the stage
PVA product is referred to as clinker, and clinker conveyor is obtained PVA finished product into drying machine after drying.It is generated in entire production process
A large amount of impurity enters in finished product, such as methyl acetate, methanol, sodium acetate, the conventional PVA product produced such as domestic corporation
In, methanol content, which is generally 1% or so, sodium acetate content and is generally 2.8% or so, methyl acetate content, is generally 1% or so.
These impurity contents are excessively high to affect using and developing for the downstream PVA high value added product.
HAMILTON WILLIAM J was once disclosed a kind of polyvinyl alcohol purification process (patent in 1996
CN1074424C), be PVA finished product is placed in vapour content be 20%~80% unsaturated water solution in be stirred and heat
Processing, obtain methanol and methyl acetate content be below 1% PVA product.Although this method reduces methanol and vinegar in product
Sour methyl ester content, but methanol and methyl acetate content are still difficult to meet the use of downstream high value added product, and cause
The consumption of a large amount of steam and diluent gas, is unfavorable for actual production.
The method of purification of impurity commonly uses water-soluble alcohol deposition method in PVA, points out in patent US20160215076A1, PVA with
95% ethanol water is after 70 DEG C are heated to reflux 2h, after dry at 110 DEG C of centrifuge separation, methanol and methyl acetate content all≤
0.1, and sodium acetate content≤0.3.The method preferably reduces impurity content, but there are many drawbacks for this method, such as: PVA
Product weight loss is big, ethyl alcohol consumption is big, Gao Chengben, and is introduced into ethyl alcohol as new impurity in PVA product.
Summary of the invention
The purpose of the present invention is to provide a kind of methods of impurity content in reduction commercial polyethylene alcohol, to can be effective
Improve the product quality of PVA.
In order to achieve the above object, the technical solution adopted in the present invention is as follows:
A method of impurity content in commercial polyethylene alcohol is reduced, it is characterized in that: it is first to set polyvinyl alcohol clinker
The heating stirring in solvent, is then separated by solid-liquid separation, and obtained solid through drying, obtains polyvinyl alcohol finished product again.
Further, the solvent is made of the mixing of first alcohol and water.Further, in the solvent, first alcohol and water
Mass ratio is 0~1:0~1.
Further, the whipping temp of the heating stirring is 25~35 DEG C, mixing time is 1~3 hour.
Further, in two steps, the first step is dried 0.5~1.5 hour at 55~75 DEG C, and second step is for the drying
It is 0.5~1.5 hour dry at 90~110 DEG C.
Further, the liquid after separation of solid and liquid continues to use as solvent after separating treatment.
Beneficial effects of the present invention:
1, method of the invention, it is possible to which the contents of the impurity such as methanol, methyl acetate, sodium acetate in PVA product is effectively reduced,
Product quality is improved, method is simple, raw material is cheap, reduces production cost, and can be realized industrialization, has important answer
With value.
2, methanol content can be reduced to 0.08%, sodium acetate content energy in the PVA product handled by method of the invention
Can be down to by being reduced to 0.1%, methyl acetate content by ppm grades.
3, method of the invention, raw materials used and equipment are all conventional raw material and equipment, and safety and environmental protection is pollution-free, meets
The policy of national green safety and environmental protection.
Specific embodiment
It elaborates below to the embodiment of the present invention, the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
The present embodiment reduces impurity content in commercial polyethylene alcohol as follows:
1) PVA clinker 50g is added in the mixed solvent 400mL for the first alcohol and water that quality proportioning is 1:0, is 25 in temperature
Mechanical stirring 1 hour at DEG C.
2) sample of step 1) is separated by solid-liquid separation after the completion of stirring, liquid phase can recycle, and solid phase is stand-by；
3) sample of step 2) is dried, it is 0.5 hour dry first at 55 DEG C, it is dry at 90 DEG C again later
It is 0.5 hour, dry to complete to obtain PVA product.
Embodiment 2
1) PVA clinker 50g is added in the mixed solvent 400mL that quality proportioning is 4:1 first alcohol and water, is 30 DEG C in temperature
Lower mechanical stirring 1 hour；
2) sample of step 1) is separated by solid-liquid separation after the completion of stirring, liquid phase can recycle, and solid phase is stand-by；
3) sample of step 2) is dried, 1 hour dry first at 65 DEG C, drying 1 is small at 100 DEG C again later
When, it is dry to complete to obtain PVA product.
Embodiment 3
1) PVA clinker 50g is added in the mixed solvent 400mL that quality proportioning is 3:2 first alcohol and water, is 33 DEG C in temperature
Lower mechanical stirring 2 hours；
2) sample of step 1) is separated by solid-liquid separation after the completion of stirring, liquid phase can recycle, and solid phase is stand-by；
3) sample of step 2) is dried, it is 1.5 hours dry first at 60 DEG C, it is dry at 90 DEG C again later
It is 0.5 hour, dry to complete to obtain PVA product.
Embodiment 4
1) PVA clinker 50g is added in the mixed solvent 400mL that quality proportioning is 2:3 first alcohol and water, is 35 DEG C in temperature
Lower mechanical stirring 3 hours；
2) sample of step 1) is separated by solid-liquid separation after the completion of stirring, liquid phase can recycle, and solid phase is stand-by；
3) sample of step 2) is dried, it is 0.5 hour dry first at 55 DEG C, it is dry at 90 DEG C again later
It is 1.5 hours, dry to complete to obtain PVA product.
Embodiment 5
1) PVA clinker 50g is added in the mixed solvent 400mL that quality proportioning is 1:4 first alcohol and water, is 35 DEG C in temperature
Lower mechanical stirring 2 hours；
2) sample of step 1) is separated by solid-liquid separation after the completion of stirring, liquid phase can recycle, and solid phase is stand-by；
3) sample of step 2) is dried, it is 0.5 hour dry first at 75 DEG C, it is dry at 90 DEG C again later
It is 0.5 hour, dry to complete to obtain PVA product.
Embodiment 6
1) PVA clinker 50g is added in the mixed solvent 400mL that quality proportioning is 0:1 first alcohol and water, is 35 DEG C in temperature
Lower mechanical stirring 3 hours；
2) sample of step 1) is separated by solid-liquid separation after the completion of stirring, liquid phase can recycle, and solid phase is stand-by；
3) sample of step 2) is dried, it is 1.5 hours dry first at 75 DEG C, it is dry at 110 DEG C again later
It is 1.5 hours, dry to complete to obtain PVA product.
To impurity (methanol, the methyl acetate, sodium acetate) content in gained PVA product after the various embodiments described above processing by such as
Lower method is detected:
Chromatographic quantitative analysis: weighing about 0.2030gPVA sample, and 3mL N is added, and N- dimethylformamide is put into 20mL head space
In bottle, it is put into 120 DEG C of baking oven dissolutions (about 50~60 minutes) after covering, is cooled to room temperature after dissolution, sample gelled, it
After be put into head-space sampler, by head space conditional equilibrium, sample introduction is analyzed.
Sodium acetate measuring method (chemical titration): PVA sample is dissolved in water, with methine orchid-dimethyl yellow (1+
1) mixed indicator is titrated with sulfuric acid standard solution, the content of sodium acetate in test sample.
Testing result is as shown in table 1:
Each embodiment testing result of table 1
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (6)
1. a kind of method for reducing impurity content in commercial polyethylene alcohol, it is characterised in that: be first to be placed in polyvinyl alcohol clinker
Heating stirring in solvent, is then separated by solid-liquid separation, and obtained solid through drying, obtains polyvinyl alcohol finished product again.
2. the method according to claim 1 for reducing impurity content in commercial polyethylene alcohol, it is characterised in that: the solvent
It is made of the mixing of first alcohol and water.
3. the method according to claim 2 for reducing impurity content in commercial polyethylene alcohol, it is characterised in that: the solvent
In, the mass ratio of first alcohol and water is 0~1:0~1.
4. the method according to claim 1 or 2 for reducing impurity content in commercial polyethylene alcohol, it is characterised in that: described
The whipping temp of heating stirring is 25~35 DEG C, mixing time is 1~3 hour.
5. the method according to claim 1 or 2 for reducing impurity content in commercial polyethylene alcohol, it is characterised in that: described
It is dry in two steps, the first step be it is 0.5~1.5 hour dry at 55~75 DEG C, second step be 90~110 DEG C dry 0.5~
1.5 hour.
6. the method according to claim 1 or 2 for reducing impurity content in commercial polyethylene alcohol, it is characterised in that: solid-liquid
Liquids recovery after separation utilizes.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910347763.6A CN110028602B (en) | 2019-04-28 | 2019-04-28 | Method for reducing impurity content in industrial polyvinyl alcohol |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910347763.6A CN110028602B (en) | 2019-04-28 | 2019-04-28 | Method for reducing impurity content in industrial polyvinyl alcohol |
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| CN110028602B CN110028602B (en) | 2021-09-10 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110903415A (en) * | 2019-10-30 | 2020-03-24 | 中国石油化工股份有限公司 | Purification method of PVA (polyvinyl alcohol) raw material for optical film |
| CN112592418A (en) * | 2020-12-14 | 2021-04-02 | 安徽皖维高新材料股份有限公司 | Preparation method of polyvinyl alcohol special for optical film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020735A (en) * | 2009-09-17 | 2011-04-20 | 中国石油化工集团公司 | Purification method of polyvinyl alcohol |
| CN102617865A (en) * | 2012-03-22 | 2012-08-01 | 盛世泰科生物医药技术(苏州)有限公司 | Method for refining polyvinyl alcohol as pharmaceutic adjuvant for slow release control agent |
| CN102731696A (en) * | 2012-06-13 | 2012-10-17 | 安徽皖维集团有限责任公司 | Preparation method of low-ash polyvinyl alcohol |
| CN102863567A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工集团公司 | Preparation method of polyvinyl alcohol through low-alkali method |
-
2019
- 2019-04-28 CN CN201910347763.6A patent/CN110028602B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020735A (en) * | 2009-09-17 | 2011-04-20 | 中国石油化工集团公司 | Purification method of polyvinyl alcohol |
| CN102863567A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工集团公司 | Preparation method of polyvinyl alcohol through low-alkali method |
| CN102617865A (en) * | 2012-03-22 | 2012-08-01 | 盛世泰科生物医药技术(苏州)有限公司 | Method for refining polyvinyl alcohol as pharmaceutic adjuvant for slow release control agent |
| CN102731696A (en) * | 2012-06-13 | 2012-10-17 | 安徽皖维集团有限责任公司 | Preparation method of low-ash polyvinyl alcohol |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110903415A (en) * | 2019-10-30 | 2020-03-24 | 中国石油化工股份有限公司 | Purification method of PVA (polyvinyl alcohol) raw material for optical film |
| CN110903415B (en) * | 2019-10-30 | 2023-02-24 | 中国石油化工股份有限公司 | Purification method of PVA (polyvinyl alcohol) raw material for optical film |
| CN112592418A (en) * | 2020-12-14 | 2021-04-02 | 安徽皖维高新材料股份有限公司 | Preparation method of polyvinyl alcohol special for optical film |
| CN112592418B (en) * | 2020-12-14 | 2023-10-27 | 安徽皖维高新材料股份有限公司 | Preparation method of polyvinyl alcohol special for optical film |
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Denomination of invention: Method for reducing impurity content in industrial polyvinyl alcohol Effective date of registration: 20220119 Granted publication date: 20210910 Pledgee: Industrial and Commercial Bank of China Limited Chaohu sub branch Pledgor: ANHUI WANWEI UPDATED HIGH-TECH MATERIAL INDUSTRY Co.,Ltd. Registration number: Y2022980000668 |