CN106008772B - The method of controlling security of vinyl acetate-methyl alcohol mixed liquor polymerisation - Google Patents
The method of controlling security of vinyl acetate-methyl alcohol mixed liquor polymerisation Download PDFInfo
- Publication number
- CN106008772B CN106008772B CN201610545740.2A CN201610545740A CN106008772B CN 106008772 B CN106008772 B CN 106008772B CN 201610545740 A CN201610545740 A CN 201610545740A CN 106008772 B CN106008772 B CN 106008772B
- Authority
- CN
- China
- Prior art keywords
- methanol
- mixed liquor
- vinyl acetate
- thiocarbamide
- polymerisation
- 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.)
- Active
Links
Classifications
-
- 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
- C08F118/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F118/02—Esters of monocarboxylic acids
- C08F118/04—Vinyl esters
- C08F118/08—Vinyl acetate
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
-
- 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
- C08F2400/00—Characteristics for processes of polymerization
- C08F2400/02—Control or adjustment of polymerization parameters
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a kind of method of controlling security of vinyl acetate methyl alcohol mixed liquor polymerisation, the concentration of methanol in mixed liquor is divided into three areas by this method first, then according to the concentration of methanol in each area, the alarm temperature of premixed device is set, such as when concentration of the methanol in mixed liquor is 10~20%, premixed device alarm temperature is set as 55 DEG C, more than cutting off inlet valve after alarm temperature, reduce mixed liquor liquid level to 60% hereinafter, and into the premixed device inject the thiocarbamide of acetone semicarbazone containing 3ppm methanol；When concentration of the methanol in mixed liquor is 20~30%, premixed device alarm temperature is set as 60 DEG C, more than inlet valve is cut off after alarm temperature, reduce the liquid level of mixed liquor to 60% hereinafter, and into the premixed device inject the thiocarbamide of acetone semicarbazone containing 5ppm methanol.Control method of the present invention is safe and reliable, available in actual production.
Description
Technical field
The present invention relates to vinyl acetate-methyl alcohol mixed liquor polymerization technique fields, and in particular to a kind of vinyl acetate-first
The method of controlling security of alcohol mixed liquor polymerisation.
Background technology
Vinyl acetate is one of 50 kinds of industrial chemicals of yield maximum in the world.The conjunction that vinyl acetate polymerize or copolymerization obtains
Into high-molecular compound, vinyl acetate by producing a series of derivatives such as polyvinyl acetate, polyvinyl alcohol, acetal resin,
The fields such as coating, synthetic fibers, leather processing, soil improvement are more and more widely used.
Vinyl acetate monomer (VA) is a kind of easy chemical intermediate that polymerisation occurs and many polymer and breast
One of constituent of liquid application.Laboratory data shows that the restricted class vinyl acetate monomer (VA) preserved under normal circumstances is no
Polymer can be formed, but empirical evidence, polymerization initiator are easy to be introduced into system, so as to cause vinyl acetate monomer
(VA) polymerisation.Easily it polymerize just because of the substance, to prevent the generation of polymerization accident out of control, should takes more
Kind safety precaution.Polymerisation out of control refers to that uncontrollable polymerisation occurs for vinyl acetate (VA), controllable
Under situation, vinyl acetate monomer (VA) can polymerize to form vinyl acetate polymer, but when free-radical contents are excessively high, Jiu Huifa
Raw polymerisation out of control, vinyl acetate polymerisation out of control is very violent, and the pressure oscillation of generation can reach 40 bars
(580psig), and most storage tanks can not bear these pressure environments.
Example in related report, occurs as in the previous in the thick vinyl acetate storage tank of in August, the 2008 Guangxi vinylon plant of 26 days
Explosion, causes great production safety liability accident.In addition, the mistake of peracetic acid ethylene storage tank occurs for major vinyl acetate production producer
Control the near accident of polymerization.Most of pure vinyl acetate storage tank is added without under normal circumstances due to the needs of follow-up polymerization process
Polymerization inhibitor, autohemagglutination situation will be far above thick vinyl acetate storage tank, the lighter's polymer plugging equipment, pipeline, and severe one may cause
It is sudden and violent poly-, lead to fire explosion.
In the production of polyvinyl acetate, vinyl acetate monomer first has to be made into the mixed liquor of different proportion with methanol, should
For mixed liquor due to part Methanol Recovery process misoperation and with a small amount of initiator or living radical, that causes is sudden and violent
Poly- accident happens occasionally.Therefore, for vinyl acetate-methyl alcohol mixed liquor, a set of effective polymerization runaway reaction of exploitation is controlled safely
Method processed is of great significance.
Invention content
For Methanol Recovery process misoperation present in current vinyl acetate-methyl alcohol mixed liquor polymerisation, cause
It is with a small amount of initiator or living radical, thus the problem of easily causing sudden and violent poly- accident, the present invention proposes a kind of acetic acid
The method of controlling security of ethylene-methyl alcohol mixed liquor polymerization runaway reaction, this method is safe and reliable, available in actual production.
Its technical solution includes：
A kind of method of controlling security of vinyl acetate-methyl alcohol mixed liquor polymerisation, includes the following steps successively：
The first step, by raw material vinyl acetate and methanol add in in premixed device mixed liquor, methanol in the mixed liquor
Mass percentage concentration is divided into：Ith area, 10~20%, the area of IIth area, 20~30% and III, 30~45%；
Second step formulates corresponding control method according to the division region of above-mentioned methanol concentration, respectively：
A, for mixed liquor of the methanol quality percentage concentration in Ith area, premixed device alarm temperature is set as 55 DEG C, more than alarm
Inlet valve is cut off after temperature, reduces the liquid level of mixed liquor to 60% hereinafter, and injection acetone containing the 3ppm contracting into the premixed device
The methanol of thiosemicarbazides；
B, for mixed liquor of the methanol quality percentage concentration in IIth area, premixed device alarm temperature is set as 60 DEG C, more than report
Inlet valve is cut off after alert temperature, reduces the liquid level of mixed liquor to 60% hereinafter, and the injection acetone containing 5ppm into the premixed device
The methanol of thiosemicarbazones；
C, for mixed liquor of the methanol quality percentage concentration in IIIth area, premixed device alarm temperature is set as 65 DEG C, more than report
Inlet valve is cut off after alert temperature, reduces the liquid level of mixed liquor to 60% hereinafter, and the injection acetone containing 8ppm into the premixed device
The methanol of thiosemicarbazones.
As the preferred embodiment of the present invention, in step a, the addition of the methanol of the thiocarbamide of acetone semicarbazone containing 3ppm is
The 12~18% of mixeding liquid volume.
As another preferred embodiment of the present invention, in step b, the addition of the methanol of the thiocarbamide of acetone semicarbazone containing 5ppm
12~18% for mixeding liquid volume.
Preferably, in step c, the addition of the methanol of the thiocarbamide of acetone semicarbazone containing 8ppm for mixeding liquid volume 12~
18%.
Preferably, in step a, the addition of the methanol of the thiocarbamide of acetone semicarbazone containing 3ppm is the 15% of mixeding liquid volume.
Preferably, the addition of the methanol of the thiocarbamide of acetone semicarbazone containing 5ppm is the 15% of mixeding liquid volume.
Preferably, the addition of the methanol of the thiocarbamide of acetone semicarbazone containing 8ppm is the 15% of mixeding liquid volume.
The present invention is divided by the concentration to methanol in mixed liquor, is carried after distillation system due to recycling methanol
Initiator or living radical concentration are certain, therefore by being divided to the methanol concentration in mixed liquor so that acetic acid second
Methanol concentration is different in alkene-methyl alcohol mixed liquor, and required safety measure is also different under polymerization out-of-control condition, as methanol is dense
The thermal runaway data in Ith areas of Du are with reference to the mixed liquor that methanol concentration is 20%, and methanol concentration is in the thermal runaway data reference in IIth area
Methanol concentration is 30% mixed liquor, the mixed liquor that thermal runaway data reference methanol concentration of the methanol concentration in IIIth area is 45%.
The present invention is orderly divided methanol concentration, and corresponding thermal runaway data can be determined according to various concentration, is prevented
Only in polymerisation sudden and violent poly- accident generation.
Specific embodiment
The present invention proposes a kind of method of controlling security of vinyl acetate-methyl alcohol mixed liquor polymerization runaway reaction, in order to make
Advantages of the present invention, technical solution are clearer, clear and definite, and with reference to specific embodiment, the present invention will be further described.
The present invention, the method for controlling security of vinyl acetate-methyl alcohol mixed liquor polymerization runaway reaction, specifically includes following step
Suddenly：
First, raw material vinyl acetate and methanol are added in into premixed device to obtain mixed liquor, methanol is according to quality in mixed liquor
Percentage concentration is divided into：Ith, 10~20%, II, 20~30%, III, 30~45%；
Secondly, corresponding control method is formulated according to the division region of above-mentioned methanol concentration, respectively：
A, for mixed liquor of the methanol quality percentage concentration in Ith area, premixed device alarm temperature is set as 55 DEG C, more than alarm
Inlet valve is cut off after temperature, reduce the liquid level of mixed liquor to 60% hereinafter, injected into premixed device mixeding liquid volume containing 3ppm
The methanol of acetone semicarbazone thiocarbamide；
B, for mixed liquor of the methanol quality percentage concentration in IIth area, premixed device alarm temperature is set as 60 DEG C, more than report
Inlet valve is cut off after alert temperature, reduces the liquid level of mixed liquor to 60% hereinafter, and the injection acetone containing 5ppm into the premixed device
The methanol of thiosemicarbazones；
C, for mixed liquor of the methanol quality percentage concentration in IIIth area, premixed device alarm temperature is set as 65 DEG C, more than report
Inlet valve is cut off after alert temperature, reduces the liquid level of mixed liquor to 60% hereinafter, and the injection acetone containing 8ppm into the premixed device
The methanol of thiosemicarbazones；
Finally, vinyl acetate-methyl alcohol mixed liquor polymerisation can be realized according to the control method of above-mentioned steps a, b, c
Safety.
Embodiment 1
When vinyl acetate-methyl alcohol mixed liquor methanol quality percentage concentration is 15% in premixed device, methanol concentration is I
Area.With reference to thermal runaway data of the methanol concentration in Ith area, in the thermal runaway data in Ith area, premixed device alarm temperature is set as methanol concentration
55 DEG C, more than following measures should be taken after alarm temperature：Inlet valve is cut off, reduces liquid level to 60% hereinafter, injection is containing 3ppm third
The methanol of ketone thiosemicarbazones, injection rate are 15% of stock volume in premixed device.
Embodiment 2
When vinyl acetate-methyl alcohol mixed liquor methanol quality percentage concentration is 20% in premixed device, methanol concentration is II
Area.With reference to thermal runaway data of the methanol concentration in IIth area, premixed device alarm temperature is set as 60 DEG C, should be taken more than after alarm temperature
Following measures：Inlet valve is cut off, reduces liquid level to 60% hereinafter, the methanol of the injection thiocarbamide of acetone semicarbazone containing 5ppm, injection rate
15% for stock volume in premixed device.
Embodiment 3
When vinyl acetate-methyl alcohol mixed liquor methanol quality percentage concentration is 29% in premixed device, methanol concentration is II
Area.With reference to thermal runaway data of the methanol concentration in IIth area, premixed device alarm temperature is set as 60 DEG C, should be taken more than after alarm temperature
Following measures：Inlet valve is cut off, reduces liquid level to 60% hereinafter, the methanol of the injection thiocarbamide of acetone semicarbazone containing 5ppm, injection rate
15% for stock volume in premixed device.
Embodiment 4
When vinyl acetate-methyl alcohol mixed liquor methanol quality percentage concentration is 40% in premixed device, methanol concentration is III
Area.With reference to thermal runaway data of the methanol concentration in IIIth area, premixed device alarm temperature is set as 65 DEG C, should be taken more than after alarm temperature
Following measures：Inlet valve is cut off, reduces liquid level to 60% hereinafter, the methanol of the injection thiocarbamide of acetone semicarbazone containing 8ppm, injection rate
15% for stock volume in premixed device.
It should be noted that those skilled in the art are made under the introduction of this specification any equivalent way or
Obvious variant should all be within the scope of the present invention.
Claims (7)
1. the method for controlling security of a kind of vinyl acetate-methyl alcohol mixed liquor polymerisation, which is characterized in that successively including following step
Suddenly：
The first step, by raw material vinyl acetate and methanol add in in premixed device mixed liquor, the quality of methanol in the mixed liquor
Percentage concentration is divided into：Ith area, more than 10% and less than 20%, IIth area more than or equal to 20% and less than 30% and IIIth area, is more than
Equal to 30% and less than 45%；
Second step formulates corresponding control method according to the division region of above-mentioned methanol concentration, respectively：
A, for mixed liquor of the methanol quality percentage concentration in Ith area, premixed device alarm temperature is set as 55 DEG C, more than alarm temperature
After cut off inlet valve, reduce the liquid level of mixed liquor to 60% hereinafter, and into the premixed device inject acetone semicarbazone containing 3ppm
The methanol of thiocarbamide；
B, for mixed liquor of the methanol quality percentage concentration in IIth area, premixed device alarm temperature is set as 60 DEG C, more than alarm temperature
Inlet valve is cut off after degree, reduces the liquid level of mixed liquor to 60% hereinafter, and the injection contracting ammonia of acetone containing 5ppm into the premixed device
The methanol of base thiocarbamide；
C, for mixed liquor of the methanol quality percentage concentration in IIIth area, premixed device alarm temperature is set as 65 DEG C, more than alarm temperature
Inlet valve is cut off after degree, reduces the liquid level of mixed liquor to 60% hereinafter, and the injection contracting ammonia of acetone containing 8ppm into the premixed device
The methanol of base thiocarbamide.
2. the method for controlling security of vinyl acetate according to claim 1-methyl alcohol mixed liquor polymerisation, feature exist
In：In step a, the addition of the methanol of the thiocarbamide of acetone semicarbazone containing 3ppm is the 12~18% of mixeding liquid volume.
3. the method for controlling security of vinyl acetate according to claim 1-methyl alcohol mixed liquor polymerisation, feature exist
In：In step b, the addition of the methanol of the thiocarbamide of acetone semicarbazone containing 5ppm is the 12~18% of mixeding liquid volume.
4. the method for controlling security of vinyl acetate according to claim 1-methyl alcohol mixed liquor polymerisation, feature exist
In：In step c, the addition of the methanol of the thiocarbamide of acetone semicarbazone containing 8ppm is the 12~18% of mixeding liquid volume.
5. the method for controlling security of vinyl acetate according to claim 2-methyl alcohol mixed liquor polymerisation, feature exist
In：In step a, the addition of the methanol of the thiocarbamide of acetone semicarbazone containing 3ppm is the 15% of mixeding liquid volume.
6. the method for controlling security of vinyl acetate according to claim 3-methyl alcohol mixed liquor polymerisation, feature exist
In：The addition of the methanol of the thiocarbamide of acetone semicarbazone containing 5ppm is the 15% of mixeding liquid volume.
7. the method for controlling security of vinyl acetate according to claim 4-methyl alcohol mixed liquor polymerisation, feature exist
In：The addition of the methanol of the thiocarbamide of acetone semicarbazone containing 8ppm is the 15% of mixeding liquid volume.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610545740.2A CN106008772B (en) | 2016-07-12 | 2016-07-12 | The method of controlling security of vinyl acetate-methyl alcohol mixed liquor polymerisation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610545740.2A CN106008772B (en) | 2016-07-12 | 2016-07-12 | The method of controlling security of vinyl acetate-methyl alcohol mixed liquor polymerisation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106008772A CN106008772A (en) | 2016-10-12 |
| CN106008772B true CN106008772B (en) | 2018-06-19 |
Family
ID=57109985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610545740.2A Active CN106008772B (en) | 2016-07-12 | 2016-07-12 | The method of controlling security of vinyl acetate-methyl alcohol mixed liquor polymerisation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106008772B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1330090A (en) * | 2001-08-01 | 2002-01-09 | 青岛化工学院 | Process for preparing polyvinyl alcohol with low alcoholysis level |
| CN201864242U (en) * | 2010-11-01 | 2011-06-15 | 台光电子材料(昆山)有限公司 | Chemical storage tank temperature and pressure protection system |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297454C (en) * | 2001-11-07 | 2007-01-31 | 三菱化学株式会社 | Storage tank for easily polymerizable compound and method of storage |
-
2016
- 2016-07-12 CN CN201610545740.2A patent/CN106008772B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1330090A (en) * | 2001-08-01 | 2002-01-09 | 青岛化工学院 | Process for preparing polyvinyl alcohol with low alcoholysis level |
| CN201864242U (en) * | 2010-11-01 | 2011-06-15 | 台光电子材料(昆山)有限公司 | Chemical storage tank temperature and pressure protection system |
Non-Patent Citations (2)
| Title |
|---|
| 聚醋酸乙烯生产爆聚的防备及处置;丘天荣;《化学工程与装备》;20090715(第7期);第51-54页 * |
| 醋酸乙烯爆聚机理初探及防范措施;邱剑峰;《化学工程与装备》;20090915(第9期);第97-100页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106008772A (en) | 2016-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3708465A (en) | Method and apparatus for interrupting the polymerization of olefins | |
| US3048553A (en) | Blending wax with an ethylene- | |
| KR102282049B1 (en) | An improved process for producing pelletized polymer compositions | |
| CN106008772B (en) | The method of controlling security of vinyl acetate-methyl alcohol mixed liquor polymerisation | |
| CN112375171B (en) | Preparation method of polypropylene material | |
| CN106187769B (en) | Vinyl acetate containing acetaldehyde-acetic acid mixed liquor polymerize emergence treating method out of control | |
| CN106243338A (en) | The preparation method of the polyether polyol of low abnormal smells from the patient low volatile | |
| CN112479963B (en) | Method and device for preparing peroxyacetic acid | |
| CN106187764B (en) | The sudden and violent poly- emergence treating method of vinyl acetate and acetic acid mixed liquor | |
| CN106188358B (en) | Vinyl acetate polymerize suppressing method out of control with acetic acid mixed liquor | |
| CN110121512B (en) | Process for preparing polyethylene resin | |
| CN106046220B (en) | Vinyl acetate and the anti-riot poly- method of controlling security of acetic acid mixed liquor | |
| CN106243257B (en) | Vinyl acetate containing acetaldehyde-acetic acid mixed liquor polymerize runaway safe control method | |
| WO2005080440A1 (en) | Polyolefin production using high olefin concentration | |
| US5268440A (en) | Process for the preparation of polyethylenes | |
| US5064917A (en) | Process of polymerizing vinyl chloride with washing of charging passage | |
| US2698319A (en) | Furfuryl alcohol polymer and continuous process for making the same | |
| US6465608B1 (en) | Method for drying and degassing polyolefins | |
| Kumpinsky | A study on resol-type phenol-formaldehyde runaway reactions | |
| CN106187768A (en) | For the collaborative suppressing method that vinyl acetate polymerization is out of control | |
| JP3189333B2 (en) | Method for producing polyolefin | |
| CN109679074A (en) | A kind of polylactic acid poly shares compound stabilizer and application thereof and application method | |
| FI58337B (en) | FOERFARANDE FOER AVBRYTANDE AV VATTENEMULSIONSPOLYMERISATIONEN AV VINYLKLORID I EN VATTENEMULSION | |
| CN104774149A (en) | Vinyl acetate gas-phase inhibition method | |
| US4954595A (en) | Method for preparing vinyl chloride 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |