CN106188358B - Vinyl acetate polymerize suppressing method out of control with acetic acid mixed liquor - Google Patents
Vinyl acetate polymerize suppressing method out of control with acetic acid mixed liquor Download PDFInfo
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- CN106188358B CN106188358B CN201610546677.4A CN201610546677A CN106188358B CN 106188358 B CN106188358 B CN 106188358B CN 201610546677 A CN201610546677 A CN 201610546677A CN 106188358 B CN106188358 B CN 106188358B
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- vinyl acetate
- mixed liquor
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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
- 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
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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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
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- 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 vinyl acetates to polymerize suppressing method out of control with acetic acid mixed liquor, vinyl acetate in mixed liquor is divided into four areas by it according to mass percentage concentration first, then the water content index in each area is defined, water content index and the thermodynamic data in each area are determined according to the area divided and in conjunction with thermokinetic analysis, and alarm temperature is determined according to the state of mixed liquor；Finally according to alarm temperature, cooling measure is taken to prevent runaway reaction.The present invention sets rational security alarm temperature, realizes safety in production by being adjusted to the water content control in vinyl acetate in various concentration region-acetic acid mixed liquor.
Description
Technical field
The present invention relates to the production of vinyl acetate and technical field of memory, and in particular to a kind of vinyl acetate is mixed with acetic acid
Liquid polymerize suppressing method out of control.
Background technology
Vinyl acetate is one of maximum 50 kinds of industrial chemicals of yield in the world.The conjunction that vinyl acetate polymerize or copolymerization obtains
At high-molecular compound, vinyl acetate by producing polyvinyl acetate, polyvinyl alcohol, a series of derivatives such as 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 chemical intermediate being easy to happen polymerisation and many polymer and breast
One of the 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, to cause vinyl acetate monomer
(VA) polymerisation.It is easy to happen polymerization just because of the substance, to prevent the generation of polymerization accident out of control, should be taken 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.
Report in relation to the prior art explodes in the thick vinyl acetate storage tank of Guangxi vinylon plant on the 26th of August in 2008,
Cause great production safety liability accident.In addition, major vinyl acetate production producer occurs, peracetic acid ethylene storage tank is out of control to be gathered
The near accident of conjunction.Most of pure vinyl acetate storage tank is added without inhibition under normal circumstances due to the needs of follow-up polymerization process
Agent, autohemagglutination situation will be far above thick vinyl acetate storage tank, less serious case's polymer plugging equipment, pipeline, and severe one may cause to gather cruelly,
Lead to fire explosion.Its polymerization inhibitor of the vinyl acetate of addition polymerization inhibitor, if hydroquinone is also only in specified conditions
Under work, in some cases, if the time is more than that polymerization inhibitor caused by the effective life of polymerization inhibitor, unknown cause consumed
Soon, storage temperature is excessively high, and polymerization inhibitor may lose inhibition or inhibition dies down.
Vinyl acetate polymerize by factors such as temperature, metal ion content, acetaldehyde, water content, vinyl acetate concentration
It influences, depends merely on polymerization inhibitor and be unable to get effective control.
Invention content
In order to prevent in vinyl acetate-acetic acid mixed liquor vinyl acetate autohemagglutination generation, the present invention exists for vinyl acetate
Concentration in mixed liquor is divided, also, vinyl acetate in various concentration region --- the water content in acetic acid mixed liquor
Control has also carried out corresponding adjustment, to realize safety in production.
Its technical solution includes：
A kind of vinyl acetate polymerize suppressing method out of control with acetic acid mixed liquor, includes the following steps：
In the first step, the vinyl acetate generated in the vinyl acetate production stage-acetic acid mixed liquor, by vinyl acetate according to
Mass percentage concentration is divided, respectively Ith area, 25~40%, IIth area, 40~60%, the area of IIIth area, 60~80% and IV, 80
~100%；
Second step, for different concentration ranges, determine the water content Con trolling index in each region, wherein I area's water contains
Amount Con trolling index is 0~200ppm；II area's water content Con trolling index is 0~120ppm；III area's water content Con trolling index be 0~
60ppm；IV area's water content Con trolling index is 0~180ppm；
Third step determines alarm temperature according to the state of vinyl acetate-acetic acid mixed liquor；
When mixed liquor is in storage state, it is reached to TMR the time required to maximum reaction rate under adiabatic conditionsad=
Corresponding temperature is determined as alarm temperature when 64h；When mixed liquor is in operational process, it is reached under adiabatic conditions
TMR the time required to maximum reaction rateadCorresponding temperature is determined as alarm temperature when=8h；
4th step, walked according to third in alarm temperature, take cooling measure to prevent runaway reaction.
As a preferred solution of the present invention, water content Con trolling index and thermokinetics of the vinyl acetate concentration in Ith area
Mixed liquor of the data with reference to vinyl acetate a concentration of 40%；Water content Con trolling index and heat power of the vinyl acetate concentration in IIth area
Learn mixed liquor of the data with reference to vinyl acetate a concentration of 60%；Water content Con trolling index and heat of the vinyl acetate concentration in IIIth area are dynamic
Mixed liquor of the Mechanical Data with reference to vinyl acetate a concentration of 80%；Water content Con trolling index and heat of the vinyl acetate concentration in IVth area
Dynamics data is with reference to 100% vinyl acetate monomer.
Further, in above-mentioned 4th step, for the mixed liquor of storage state, by contain the container outer wall of mixed liquor into
The mode of row water spray cools down, and injects a certain amount of polymerization inhibitor；For the mixed liquor in operational process, cooling load should be increased,
And polymerization inhibitor is added in different parts, to prevent runaway reaction.
Further, the TMR in above-mentioned third stepadIt is calculated and is obtained by the thermodynamic data of mixed liquor.
Vinyl acetate is divided into four areas by the present invention according to the concentration in mixed liquor first, then will be in each area
Water content index is defined, and reason is：Its sudden and violent poly- danger of the vinyl acetate of different quality percentage concentration also differs,
Vinyl acetate polymerization is influenced by factors such as temperature, metal ion content, acetaldehyde, water content, vinyl acetate concentration, different
Water content can be in various degree promotion or inhibit vinyl acetate polymerization, to prevent the generation of vinyl acetate autohemagglutination, different vinegar
The vinyl acetate of sour ethylene concentration --- the water content control in acetic acid mixed liquor has also carried out corresponding adjustment,；Then it is directed to every
The mass percent concentration of a section vinyl acetate, determines its thermodynamic data and water content Con trolling index, such as vinyl acetate
Thermodynamic data and water content Con trolling index of the concentration in Ith area are with reference to the mixed liquor of vinyl acetate a concentration of 40%, acetic acid
The mixed liquor of thermodynamic data and water content Con trolling index reference vinyl acetate a concentration of 60% of the ethylene concentration in IIth area,
Its alarm temperature is set in conjunction with the state of mixed liquor, for the alarm temperature of different conditions mixed liquor, takes corresponding cooling
Measure prevents runaway reaction.
The method of the present invention can be vinyl acetate device each production phase to be in storage state and dynamic running process
Vinyl acetate --- acetic acid mixed liquor determines rational water content Con trolling index, sets rational security alarm temperature, and propose
Practicable safety prevention measure.
Specific implementation mode
The present invention proposes a kind of vinyl acetate and polymerize suppressing method out of control with acetic acid mixed liquor, and in order to make, the present invention's is excellent
Point, technical solution are clearer, clear, and with reference to specific embodiment, the present invention will be further described.
Vinyl acetate mentioned in the present invention generates in each stage of vinyl acetate production, usually with acetic acid mixed liquor
A concentration of the 25~100% of vinyl acetate in vinyl acetate-acetic acid mixed liquor.
The present invention, vinyl acetate polymerize suppressing method out of control with acetic acid mixed liquor, include the following steps：
In the first step, the vinyl acetate generated in the vinyl acetate production stage-acetic acid mixed liquor, by vinyl acetate according to
Mass percentage concentration is divided, respectively Ith area, 25~40%, IIth area, 40~60%, the area of IIIth area, 60~80% and IV, 80
~100%；
Second step, for different concentration ranges, determine the water content Con trolling index in each region, wherein I area's water contains
Amount Con trolling index is 0~200ppm；II area's water content Con trolling index is 0~120ppm；III area's water content Con trolling index be 0~
60ppm；IV area's water content Con trolling index is 0~180ppm；Water content Con trolling index and heat power of the vinyl acetate concentration in Ith area
Learn mixed liquor of the data with reference to vinyl acetate a concentration of 40%；Water content Con trolling index and heat of the vinyl acetate concentration in IIth area are dynamic
Mixed liquor of the Mechanical Data with reference to vinyl acetate a concentration of 60%；Water content Con trolling index and heat of the vinyl acetate concentration in IIIth area
Mixed liquor of the dynamics data with reference to vinyl acetate a concentration of 80%；Vinyl acetate concentration IVth area water content Con trolling index and
Thermodynamic data is with reference to 100% vinyl acetate monomer；
Third step determines alarm temperature according to the state of vinyl acetate-acetic acid mixed liquor
When mixed liquor is in storage state, it is reached to TMR the time required to maximum reaction rate under adiabatic conditionsad=
Corresponding temperature is determined as alarm temperature when 64h；When mixed liquor is in operational process, it is reached under adiabatic conditions
TMR the time required to maximum reaction rateadCorresponding temperature is determined as alarm temperature, TMR when=8hadIt is also by mixed liquor
Thermodynamic data, which calculates, to be obtained；
4th step, walked according to third in alarm temperature the appearance for containing mixed liquor is passed through for the mixed liquor of storage state
The mode that device outer wall is sprayed water cools down, and injects a certain amount of polymerization inhibitor；For the mixed liquor in operational process, should increase cold
But load, and polymerization inhibitor is added in different parts, to prevent runaway reaction.
It elaborates with reference to specific embodiment.
Embodiment 1：
The vinyl acetate of vinyl acetate concentration 30% in storage tank --- acetic acid mixing liquid water content controls and corresponding peace
The determination of full control program：The mixed liquor belong to classification in Ith areas storing process Zhong, water content controlling value index be 0~
200ppm；Alarm temperature should take TMRadCorresponding temperature when=64h is taken with reference to 40% vinyl acetate-acetic acid mixed liquor
Value is 50 DEG C；After operation temperature reaches alarm temperature, cooling measure is taken, water spray is carried out to storage tank outer wall, and inject certain
The polymerization inhibitor of amount prevents vinyl acetate self-polymeric reaction from further occurring out of control.
Embodiment 2：
The vinyl acetate of rectifier bottoms vinyl acetate concentration 50% --- acetic acid mixing liquid water content controls and corresponding
Security control scheme determination：The mixed liquor belong to classification in IIth areas storing process Zhong, water content controlling value index be 0~
200ppm, alarm temperature should take TMRadCorresponding temperature when=8h, with reference to 60% vinyl acetate --- acetic acid mixed liquor carries out
Value is 140 DEG C；After operation temperature reaches alarm temperature, cooling load is increased, and in tower top, tower, the increasing of bottom of tower different parts
Big polymerization inhibitor addition, prevents vinyl acetate self-polymeric reaction from further occurring out of control.
Embodiment 3：
The vinyl acetate of vinyl acetate concentration 98% at the top of rectifying column --- acetic acid mixing liquid water content controls and accordingly
Security control scheme determination：The mixed liquor belong to classification in IVth areas storing process Zhong, water content controlling value index be 0~
180ppm；Alarm temperature should take TMRadCorresponding temperature when=8h, it is 95 DEG C to carry out value with reference to vinyl acetate monomer；Operation temperature
After degree reaches alarm temperature, cooling load is increased, and polymerization inhibitor is added in tower top, prevent vinyl acetate self-polymeric reaction from further sending out
Life is out of control.
Embodiment 4：
The vinyl acetate of rectifier bottoms vinyl acetate mass percentage concentration 70% --- acetic acid mixing liquid water content controls
And the determination of corresponding security control scheme：The mixed liquor belongs to IIIth areas storing process Zhong in classification, water content controlling value
Index is 0~60ppm, and alarm temperature should take TMRadCorresponding temperature when=8h, with reference to 80% vinyl acetate --- acetic acid is mixed
It is 115 DEG C to close liquid and carry out value；After operation temperature reaches alarm temperature, increase cooling load, and in tower top, tower, bottom of tower not
Increase polymerization inhibitor addition with position, prevents vinyl acetate self-polymeric reaction from further occurring out of control.
It should be noted that any equivalent way that those skilled in the art are made under the introduction of this specification, or
Obvious variant should all be within the scope of the present invention.
Claims (2)
1. a kind of vinyl acetate polymerize suppressing method out of control with acetic acid mixed liquor, which is characterized in that include the following steps：
In the first step, the vinyl acetate generated in the vinyl acetate production stage-acetic acid mixed liquor, by vinyl acetate according to quality
Percentage concentration is divided, and respectively Ith area is more than 25% and is less than or equal to 40%, and IIth area more than 40% and is less than or equal to
60%, IIIth area is more than 60% and less than or equal to 80% and IVth area, is more than 80% and is less than or equal to 100%；
Second step, for different concentration ranges, determine the water content Con trolling index in each region, wherein the water content control of Ith area
Index processed is 0~200ppm；II area's water content Con trolling index is 0~120ppm；III area's water content Con trolling index is 0~60ppm；
IV area's water content Con trolling index is 0~180ppm；
Third step determines alarm temperature according to the state of vinyl acetate-acetic acid mixed liquor；
When mixed liquor is in storage state, it is reached to TMR the time required to maximum reaction rate under adiabatic conditionsad=64h
When corresponding temperature be determined as alarm temperature；When mixed liquor is in operational process, it is reached most under adiabatic conditions
TMR the time required to big reaction rateadCorresponding temperature is determined as alarm temperature when=8h；
4th step, walked according to third in alarm temperature, take cooling measure to prevent runaway reaction；
Water content Con trolling index and thermodynamic data mixing with reference to vinyl acetate a concentration of 40% of the vinyl acetate concentration in Ith area
Close liquid；Vinyl acetate concentration IIth area water content Con trolling index and thermodynamic data with reference to vinyl acetate a concentration of 60%
Mixed liquor；Water content Con trolling index and thermodynamic data reference vinyl acetate a concentration of 80% of the vinyl acetate concentration in IIIth area
Mixed liquor；Water content Con trolling index and thermodynamic data reference 100% vinyl acetate list of the vinyl acetate concentration in IVth area
Body.
2. vinyl acetate according to claim 1 polymerize suppressing method out of control with acetic acid mixed liquor, it is characterised in that：4th
In step, for the mixed liquor of storage state, the container outer wall containing mixed liquor cools down by way of being sprayed water, and injects one
Quantitative polymerization inhibitor；For the mixed liquor in operational process, cooling load should be increased, and polymerization inhibitor is added in different parts, come
Prevent runaway reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610546677.4A CN106188358B (en) | 2016-07-12 | 2016-07-12 | Vinyl acetate polymerize suppressing method out of control with acetic acid mixed liquor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610546677.4A CN106188358B (en) | 2016-07-12 | 2016-07-12 | Vinyl acetate polymerize suppressing method out of control with acetic acid mixed liquor |
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| Publication Number | Publication Date |
|---|---|
| CN106188358A CN106188358A (en) | 2016-12-07 |
| CN106188358B true CN106188358B (en) | 2018-09-04 |
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|---|---|---|---|
| CN201610546677.4A Active CN106188358B (en) | 2016-07-12 | 2016-07-12 | Vinyl acetate polymerize suppressing method out of control with acetic acid mixed liquor |
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