CN106187769A - Vinyl acetate acetic acid mixed liquor containing acetaldehyde is polymerized emergence treating method out of control - Google Patents
Vinyl acetate acetic acid mixed liquor containing acetaldehyde is polymerized emergence treating method out of control Download PDFInfo
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- CN106187769A CN106187769A CN201610547321.2A CN201610547321A CN106187769A CN 106187769 A CN106187769 A CN 106187769A CN 201610547321 A CN201610547321 A CN 201610547321A CN 106187769 A CN106187769 A CN 106187769A
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- processing temperature
- emergency processing
- acetaldehyde
- vinyl acetate
- mixed liquor
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/62—Use of additives, e.g. for stabilisation
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Abstract
The invention discloses a kind of vinyl acetate acetic acid mixed liquor containing acetaldehyde and be polymerized emergence treating method out of control, first vinyl acetate in production phase mixed liquor is divided into four districts according to mass percentage concentration by it, then according to the district divided and combine the thermodynamic data in thermokinetic analysis determines each district, state according to mixed liquor determines emergency processing temperature, according to vinyl acetate polymerization-stable Journal of Sex Research, according to the content of acetaldehyde in mixed liquor, emergent treatment temperature is adjusted, finally determines emergency processing temperature.The present invention can be according to acetaldehyde, and the vinyl acetate acetic acid mixed liquor being in storage state and dynamic running process for each production phase of vinyl acetate device sets rational safe emergency processing temperature, and proposes practicable safety prevention measure.
Description
Technical field
The present invention relates to vinyl acetate production and technical field of memory, be specifically related to a kind of vinyl acetate containing acetaldehyde
Acid mixed liquor is polymerized emergence treating method out of control.
Background technology
Vinyl acetate is one of 50 kinds of industrial chemicals that yield is maximum in the world.The conjunction that vinyl acetate polymerization or copolymerization obtain
Become macromolecular compound, vinyl acetate by producing a series of derivants such as polyvinyl acetate, polyvinyl alcohol, acetal resin,
The fields such as coating, synthetic fibers, leather processing, soil improvement have obtained increasingly being widely applied.
VAM (VA) is a kind of chemical intermediate being susceptible to polyreaction, is also many polymer and breast
One of constituent of liquid application.Laboratory data shows, the restricted class VAM (VA) preserved under normal circumstances is no
Can form polymer, but empirical evidence, and polymerization initiator is easy to be introduced in system, thus causes VAM
(VA) polyreaction.It is susceptible to polymerization just because of this material, for preventing the generation of polymerization accident out of control, should take many
Plant safety precaution.Polyreaction out of control refers to that vinyl acetate (VA) occurs uncontrollable polyreaction.Controlled
Under situation, VAM (VA) can be polymerized formation vinyl acetate polymer, but when free-radical contents is too high, Jiu Huifa
Raw polyreaction out of control.Vinyl acetate polyreaction out of control is very violent, and the pressure oscillation of generation can reach 40 bars
(580psig).And majority storage tank cannot bear these pressure environments.
In prior art, relevant report, explodes in the thick vinyl acetate storage tank of Guangxi vinylon plant on August 26th, 2008,
Cause great production safety liability accident.It addition, Ge great vinyl acetate production producer all occurs peracetic acid ethylene storage tank out of control poly-
The near accident closed.The pure vinyl acetate storage tank of major part, due to the needs of follow-up polymerization process, is generally added without inhibition
Agent, its autohemagglutination situation to be far above thick vinyl acetate storage tank, the lighter's polymer plugging equipment, pipeline, and severe one may cause sudden and violent poly-,
Fire explosion is caused to occur.
The acetic acid second of different vinyl acetate concentration (25～100%) is there is in each stage of vinyl acetate production
Alkene acetic acid mixed liquor.The vinyl acetate of variable concentrations, it is the most different that it gathers danger cruelly.Vinyl acetate is polymerized by temperature, gold
Belong to the impact of the factors such as ion concentration, acetaldehyde, water content, vinyl acetate concentration.Owing to acetaldehyde is that wherein content is higher
Impurity, for preventing the generation of vinyl acetate autohemagglutination, the emergency disposal of the vinyl acetate acetic acid mixed liquor of different acetaldehydes
Measure also needs to adjust.
Summary of the invention
For technical problem present in above-mentioned prior art, the present invention proposes a kind of vinyl acetate-vinegar containing acetaldehyde
Acid mixed liquor is polymerized emergence treating method out of control, by being defined the content of acetaldehyde in mixed liquor, in conjunction with to variable concentrations
The safety control measures of the vinyl acetate of scope is adjusted, thus realizes safety in production.
Its technical solution includes:
A kind of vinyl acetate-acetic acid mixed liquor containing acetaldehyde is polymerized emergence treating method out of control, comprises the following steps successively:
The first step, the vinyl acetate-acetic acid mixed liquor produced in each stage of vinyl acetate production are according to vinyl acetate
Mass percentage concentration divides, and is respectively as follows: Ith district, 25～40%, IIth district, 40～60%, IIIth district, 60～80% and IVth district, 80
～100%；
Second step, according to the district divided and combine the acetaldehyde span of control in thermokinetic analysis determines each district
And thermodynamic data, vinyl acetate concentration acetaldehyde span of control in Ith district and thermodynamic data are with reference to acetic acid second
Alkene concentration is the mixed liquor of 40%, vinyl acetate concentration acetaldehyde span of control in IIth district and thermodynamic data reference
Vinyl acetate concentration is the mixed liquor of 60%, vinyl acetate concentration acetaldehyde span of control in IIIth district and thermokinetics number
According to being the mixed liquor of 80% with reference to vinyl acetate concentration, vinyl acetate concentration acetaldehyde span of control in IVth district and heat are dynamic
The VAM of Mechanical Data reference 100%；
3rd step, state according to mixed liquor determine emergency processing temperature,
When mixed liquor is in storage state, it is arrived under adiabatic conditions maximum reaction rate required time TMRad=
Temperature corresponding during 24h is defined as emergency processing temperature；When mixed liquor is in running, by it under adiabatic conditions
Arrive maximum reaction rate required time TMRadTemperature corresponding during=6h is defined as emergency processing temperature；
4th step, assume the content X% of acetaldehyde in mixed liquor, according to the content of acetaldehyde on the basis of emergency processing temperature
Determine final emergency processing temperature,
For above-mentioned I district, if acetaldehyde is 0～1%, final emergency processing temperature is on the basis of emergency processing temperature
Upper downward 3.2X DEG C；If acetaldehyde is 1～5%, final emergency processing temperature is lowered on the basis of emergency processing temperature
(2.4+0.8X)℃；If acetaldehyde is higher than 5%, final emergency processing temperature is lowered on the basis of emergency processing temperature
1.28X；
For above-mentioned IIth district, if acetaldehyde is 0～1%, final emergency processing temperature is at the base of emergency processing temperature
4.8X DEG C is lowered on plinth；If acetaldehyde is 1～5%, at final emergency processing temperature is on the basis of emergency processing temperature
Adjust (3.6+1.2X) DEG C；If acetaldehyde is higher than 5%, final emergency processing temperature is lowered on the basis of emergency processing temperature
1.92X℃；
For above-mentioned IIIth district, if acetaldehyde is 0～1%, final emergency processing temperature is at the base of emergency processing temperature
6.4X DEG C is lowered on plinth；If acetaldehyde is 1～5%, at final emergency processing temperature is on the basis of emergency processing temperature
Adjust (4.8+1.6X) DEG C；If acetaldehyde is higher than 5%, final emergency processing temperature is lowered on the basis of emergency processing temperature
2.56X℃；
For above-mentioned IVth district, if acetaldehyde is 0～1%, final emergency processing temperature is at the base of emergency processing temperature
8X DEG C is lowered on plinth；If acetaldehyde is 1～5%, final emergency processing temperature is lowered on the basis of emergency processing temperature
(6+2X)℃；If acetaldehyde is higher than 5%, final emergency processing temperature lowers 3.2X on the basis of emergency processing temperature
℃；
5th step, according to the final emergency processing temperature in the 4th step, take cooling measure to prevent runaway reaction.
As a preferred version of the present invention, in the 5th step, for storing the mixed liquor of state, it should cut off charging,
A large amount of polymerization inhibitor is added in the tank for storing mixed liquor, and by cooled for material in tank device dump to stand-by provision；
For the mixed liquor in running, charging should be cut off, inject methanol or acetic acid cooling, and add a large amount of inhibition at different parts
Agent, prevents from being polymerized out of control.
As another preferred version of the present invention, the TMR in the 3rd stepadCalculated by the thermodynamic data of mixed liquor and obtain
?.
In the production phase of vinyl acetate, its sudden and violent poly-danger of the vinyl acetate of different quality percentage concentration also differs,
The present invention, first against the mass percent concentration of each section vinyl acetate, determines its thermodynamic data and acetaldehyde control
Scope processed, if vinyl acetate concentration thermodynamic data in Ith district and acetaldehyde span of control are with reference to vinyl acetate concentration
Being the mixed liquor of 40%, vinyl acetate concentration thermodynamic data in IIth district and acetaldehyde span of control are with reference to acetic acid second
Alkene concentration is the mixed liquor of 60%, sets its emergency processing temperature in conjunction with the state of mixed liquor, then according in mixed liquor not
With the acetaldehyde of content, on the basis of emergency processing temperature, adjust temperature further, so that it is determined that final emergency processing temperature,
For the emergency processing temperature of different conditions mixed liquor, take corresponding cooling measure to prevent runaway reaction.
The present invention can be in storage state for each production phase of vinyl acetate device according to acetaldehyde and dynamically transport
The vinyl acetate acetic acid mixed liquor of row process sets rational safe emergency processing temperature, and proposes practicable safety
Safeguard procedures.
Detailed description of the invention
The invention discloses a kind of vinyl acetate acetic acid mixed liquor containing acetaldehyde and be polymerized emergence treating method out of control, in order to
Making advantages of the present invention, technical scheme clearer, clear and definite, below in conjunction with specific embodiment, the present invention will be further described.
Embodiment 1:
In storage tank acetaldehyde be 1%, the vinyl acetate acetic acid mixed liquor emergency disposal of vinyl acetate concentration 30%
The determination of measure: this mixed liquor belongs to storing process Zhong I district in classification, and emergency processing temperature should take TMRadCorrespondence during=24h
Temperature, to take initial value be 62 DEG C to the vinyl acetate acetic acid mixed liquor with reference to 40%, lowers 3.2 DEG C, final emergency processing temperature
Angle value takes 58.8 DEG C；After operation temperature reaches emergency processing temperature, should take urgent measure, cut off charging, add in storage tank
A large amount of polymerization inhibitors, and by cooled for material in tank device dump to stand-by provision, prevent the generation of the sudden and violent poly-accident of vinyl acetate.
Embodiment 2:
Rectifier bottoms acetaldehyde is 1.5%, the vinyl acetate acetic acid mixed liquor of vinyl acetate concentration 50% should
The determination of anxious Disposal Measures: this mixed liquor belongs to storing process Zhong II district in classification, and emergency processing temperature should take TMRad=6h
Time corresponding temperature, it is 155 DEG C that the vinyl acetate acetic acid mixed liquor with reference to 60% takes initial value, lowers 5.4 DEG C, finally meets an urgent need
Treatment temperature value takes 149.6 DEG C；After operation temperature reaches emergency processing temperature, should take urgent measure, cut off charging, inject first
Alcohol or acetic acid cooling, and add a large amount of polymerization inhibitors at different parts, prevent the generation of the sudden and violent poly-accident of vinyl acetate.
Embodiment 3:
Rectifying column top acetaldehyde is 6%, the vinyl acetate acetic acid mixed liquor of vinyl acetate concentration 98% is met an urgent need
The determination of Disposal Measures: this mixed liquor belongs to storing process Zhong IV district in classification, and emergency processing temperature should take TMRadDuring=6h
Corresponding temperature, taking initial value with reference to VAM is 104 DEG C, lowers 19.2 DEG C, and final emergency processing temperature value takes 84.8
℃；After operation temperature reaches emergency processing temperature, should take urgent measure, cut off charging, inject methanol or acetic acid is lowered the temperature, and
Different parts adds a large amount of polymerization inhibitors, prevents the generation of the sudden and violent poly-accident of vinyl acetate.
Embodiment 4:
In storage tank acetaldehyde be 0.5%, the vinyl acetate acetic acid of vinyl acetate mass percentage concentration 70% mixing
The determination of liquid emergency disposal measure: this mixed liquor belongs to storing process Zhong III district in classification, and emergency processing temperature should take TMRad
Temperature corresponding during=24h, it is 50 DEG C that the vinyl acetate acetic acid mixed liquor with reference to 80% carries out value, lowers 3.2 DEG C, finally
Emergency processing temperature value takes 46.8 DEG C；After operation temperature reaches emergency processing temperature, should take urgent measure, cut off charging, to
Add a large amount of polymerization inhibitors in storage tank, and by cooled for material in tank device dump to stand-by provision, prevent vinyl acetate the most poly-
The generation of accident.
It should be noted that any equivalent way that those skilled in the art are made under the teaching of this specification, or
Substantially variant all should be within the scope of the present invention.
Claims (3)
1. vinyl acetate-acetic acid the mixed liquor containing acetaldehyde is polymerized emergence treating method out of control, it is characterised in that include successively
Following steps:
The first step, the vinyl acetate-acetic acid mixed liquor produced in each stage of vinyl acetate production are according to vinyl acetate quality
Percentage concentration divides, and is respectively as follows: Ith district, 25～40%, IIth district, 40～60%, IIIth district, 60～80% and IVth district, 80～
100%；
Second step, according to the district divided and combine acetaldehyde span of control and the heat that thermokinetic analysis determines in each district
Dynamics data, vinyl acetate concentration acetaldehyde span of control in Ith district and thermodynamic data are dense with reference to vinyl acetate
Degree is the mixed liquor of 40%, and vinyl acetate concentration acetaldehyde span of control in IIth district and thermodynamic data are with reference to acetic acid
Ethylene concentration is the mixed liquor of 60%, vinyl acetate concentration acetaldehyde span of control in IIIth district and thermodynamic data ginseng
It is the mixed liquor of 80% according to vinyl acetate concentration, vinyl acetate concentration acetaldehyde span of control in IVth district and thermokinetics
The VAM of data reference 100%；
3rd step, state according to mixed liquor determine emergency processing temperature,
When mixed liquor is in storage state, it is arrived under adiabatic conditions maximum reaction rate required time TMRad=24h
Time corresponding temperature be defined as emergency processing temperature；When mixed liquor is in running, it is arrived under adiabatic conditions
Reach maximum reaction rate required time TMRadTemperature corresponding during=6h is defined as emergency processing temperature；
4th step, assume the content X% of acetaldehyde in mixed liquor, come really on the basis of emergency processing temperature according to the content of acetaldehyde
Fixed final emergency processing temperature,
For above-mentioned I district, if acetaldehyde is 0～1%, at final emergency processing temperature is on the basis of emergency processing temperature
Adjust 3.2X DEG C；If acetaldehyde is 1～5%, final emergency processing temperature lowers (2.4+ on the basis of emergency processing temperature
0.8X)℃；If acetaldehyde is higher than 5%, final emergency processing temperature lowers 1.28X on the basis of emergency processing temperature；
For above-mentioned IIth district, if acetaldehyde is 0～1%, final emergency processing temperature is on the basis of emergency processing temperature
Lower 4.8X DEG C；If acetaldehyde is 1～5%, final emergency processing temperature is lowered on the basis of emergency processing temperature
(3.6+1.2X)℃；If acetaldehyde is higher than 5%, final emergency processing temperature is lowered on the basis of emergency processing temperature
1.92X℃；
For above-mentioned IIIth district, if acetaldehyde is 0～1%, final emergency processing temperature is on the basis of emergency processing temperature
Lower 6.4X DEG C；If acetaldehyde is 1～5%, final emergency processing temperature is lowered on the basis of emergency processing temperature
(4.8+1.6X)℃；If acetaldehyde is higher than 5%, final emergency processing temperature is lowered on the basis of emergency processing temperature
2.56X℃；
For above-mentioned IVth district, if acetaldehyde is 0～1%, final emergency processing temperature is on the basis of emergency processing temperature
Lower 8X DEG C；If acetaldehyde is 1～5%, final emergency processing temperature lowers (6+ on the basis of emergency processing temperature
2X)℃；If acetaldehyde is higher than 5%, final emergency processing temperature lowers 3.2X DEG C on the basis of emergency processing temperature；
5th step, according to the final emergency processing temperature in the 4th step, take cooling measure to prevent runaway reaction.
Vinyl acetate-acetic acid mixed liquor containing acetaldehyde the most according to claim 1 is polymerized emergence treating method out of control, and it is special
Levy and be: in the 5th step, for storing the mixed liquor of state, it should cut off charging, add in the tank for storing mixed liquor
A large amount of polymerization inhibitors, and by cooled for material in tank device dump to stand-by provision；For the mixed liquor in running, should cut
Disconnected charging, injects methanol or acetic acid cooling, and adds a large amount of polymerization inhibitors at different parts, prevents from being polymerized out of control.
Vinyl acetate-acetic acid mixed liquor containing acetaldehyde the most according to claim 1 is polymerized emergence treating method out of control, and it is special
Levy and be: the TMR in the 3rd stepadCalculated by the thermodynamic data of mixed liquor and obtain.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610547321.2A CN106187769B (en) | 2016-07-12 | 2016-07-12 | Vinyl acetate containing acetaldehyde-acetic acid mixed liquor polymerize emergence treating method out of control |
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|---|---|---|---|
| CN201610547321.2A CN106187769B (en) | 2016-07-12 | 2016-07-12 | Vinyl acetate containing acetaldehyde-acetic acid mixed liquor polymerize emergence treating method out of control |
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| CN106187769A true CN106187769A (en) | 2016-12-07 |
| CN106187769B CN106187769B (en) | 2018-09-04 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102514844A (en) * | 2011-12-16 | 2012-06-27 | 中国石油化工股份有限公司 | Vinyl acetate storage device and alarm and control method for crude vinyl acetate |
| CN102514845A (en) * | 2011-12-16 | 2012-06-27 | 中国石油化工股份有限公司 | Vinyl acetate storage device and emergency treatment method for crude vinyl acetate |
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2016
- 2016-07-12 CN CN201610547321.2A patent/CN106187769B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102514844A (en) * | 2011-12-16 | 2012-06-27 | 中国石油化工股份有限公司 | Vinyl acetate storage device and alarm and control method for crude vinyl acetate |
| CN102514845A (en) * | 2011-12-16 | 2012-06-27 | 中国石油化工股份有限公司 | Vinyl acetate storage device and emergency treatment method for crude vinyl acetate |
Non-Patent Citations (1)
| Title |
|---|
| 崔克清主编: "《安全工程实验与鉴别技术》", 30 November 2005 * |
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