CN109949874A - A kind of risk stratification method of fine chemistry industry production process security evaluation - Google Patents
A kind of risk stratification method of fine chemistry industry production process security evaluation Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000011156 evaluation Methods 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000013517 stratification Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 221
- 238000001816 cooling Methods 0.000 claims abstract description 35
- 230000008569 process Effects 0.000 claims abstract description 12
- 230000001174 ascending effect Effects 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 61
- 238000000354 decomposition reaction Methods 0.000 claims description 45
- 238000002474 experimental method Methods 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- 238000004458 analytical method Methods 0.000 claims description 7
- 238000009825 accumulation Methods 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000007707 calorimetry Methods 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 4
- 238000013178 mathematical model Methods 0.000 claims description 4
- 230000001960 triggered effect Effects 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 235000013399 edible fruits Nutrition 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- 230000010512 thermal transition Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000001311 chemical methods and process Methods 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract description 2
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 description 30
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical group CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- -1 t-butyl peroxy Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
A kind of risk stratification method of fine chemistry industry production process security evaluation of the present invention is related to organic chemical processes safety evaluation areas, is a kind of risk stratification method for fine chemistry industry production process security evaluation.Comprising steps of 1) get parms;2) evaluation index is calculated;3) danger level grade is divided;The operation temperature obtained based on abovementioned steps;After reaction system cooling failure, the attainable maximum temperature of synthetic reaction;The initial temperature that unstable products are decomposed;Because of the limitation of technical conditions, maximum temperature that reaction kettle can bear;And the final temperature under adiabatic condition, the size sort ascending of this 5 key temperatures form different types of situation, are classified according to danger level index.The thermal runaway risk that appropriately can accurately assess synthetic reaction instructs chemical company's optimization process operating parameter, formulates risk reduction measures, instructs chemical company to select and define risk reduction measures, improves process safety, improves Business Economic Benefit.
Description
Technical field
A kind of risk stratification method of fine chemistry industry production process security evaluation of the present invention is related to organic chemical process peace
Full evaluation areas is a kind of risk stratification method for fine chemistry industry production process security evaluation.
Background technique
Fine chemistry industry has been the essential a part of human society.It also brings many while providing convenient
It is dangerous.Make in the inherent peril of chemical company, the complexity of synthetic reaction process, the risk of chemical substance and exothermic reaction
Reaction unit part Frequent Accidents.Once thermal runaway occurs for reaction, the temperature and pressure in reaction kettle steeply rises, easily causes
The accidents such as fire, explosion, poisoning.For the severity for reducing a possibility that thermal runaway occurs and causing consequence, our primary is appointed
Business is accurate evaluation synthetic reaction thermal runaway risk, realizes that parameters of technique process optimizes, improves the essence of synthetic reaction process
Level of security.
At present to the thermal runaway risk of exothermic reaction, Gygax proposes that thermal runaway occurs under conditions of the worst, i.e. cooling system
It unites entirely ineffective, entire reaction system is in adiabatci condition.Stoessel is proposed based on process temperature under cooling failure situation
The thermal hazard appraisal procedure of parameter.This method considers a possibility that synthetic reaction thermal runaway occurs, but exists and exaggerate accident
The deficiency of risk.For example, commercial scale prepares azanol, must during temperature rises if synthetic reaction generation is out of control
Azanol second decomposition can be so triggered, but temperature is not above the maximum that reaction kettle can bear during decomposition reaction is out of control
Temperature, evaporation at this time is cooling or emergency decompression can be used as last one of safety curtain, reduces accident risk.But it is commented with this method
The risk for estimating production process show that enterprise is highly desirable to redesign the conclusion of technique.The assessment result exaggerates hot mistake
The risk occurred is controlled, a degree of economic loss can be brought to chemical company.It therefore, can be into there is an urgent need for a kind of method
The more accurate and reliable assessment of row.
Summary of the invention
Object of the present invention is in view of the above shortcomings, provide a kind of danger level of fine chemistry industry production process security evaluation
Stage division, this method are based on cooling failure situation, comprehensively consider each key temperatures parameter occurred in synthetic reaction process,
With one minor sort of size of accident possibility occurrence, a kind of more accurate and reliable thermal hazard appraisal procedure is provided.
The present invention adopts the following technical solutions to achieve:
A kind of risk stratification method of fine chemistry industry production process security evaluation, includes the following steps:
1) it gets parms
It 1-1) determines assessment object, and acquires the operating condition of the synthesis technology;
1-2) with laboratory scale, the synthetic reaction isothermal calorimetric experiment of assessment object is carried out, rate of heat release, thermal transition are obtained
The data such as rate, charging rate;Determine the total reaction heat of the synthetic reaction, unit is;The specific heat capacity of reaction mixture,
Unit is;The gross mass of reaction kettle reaction mixture, unit is;Accumulation of material in moment reaction kettle
Degree, unit %;
Reaction product is analyzed using product analysis instrument, determines reaction yield, unit %;
1-3) adiabatic calorimetry experiment is carried out with the product of the synthetic reaction of step (1-2);
The initial concentration of product 1-3-1) is determined first, and unit is;
Temperature/pressure-time graph 1-3-2) is drawn using response data, determines the initial temperature that product decomposes, unit is
℃;Attainable maximum temperature, unit is DEG C;Adiabatic temperature rise, unit is DEG C;
Temperature rise rate-temperature curve 1-3-3) is drawn, and carries out nonlinear fitting using mathematical model and obtains thermokinetic parameters,
Including apparent activation energy, unit is;Pre-exponential factor A, order of reaction n;
If 1-4) synthetic reaction system is open system, the boiling point of solvent is determined, accounting is maximum in the reaction system for solvent;If
Closed system, it is determined that temperature corresponding to reaction kettle maximum allowble pressure, the reaction kettle maximum allowble pressure refer to safety
Valve or rupture disk set pressure.
Operating condition described in step (1-1) includes using interval or the production method of semi-batch operation, operation temperature, behaviour
Make pressure, material proportion, solvent, charging sequence and feed rate, agitator speed etc..
2) evaluation index is calculated
2-1) operation temperature is denoted as T1, is determined by the operating condition of synthetic reaction, and the initial temperature of cooling failure situation takes T1;
2-2) after reaction system cooling failure, the attainable maximum temperature of synthetic reaction is denoted as T2;
Total adiabatic temperature rise of synthetic reaction, unit is DEG C;T2 andIt is calculated by following formula,
In formula,It is the accessible temperature of synthetic reaction after reaction system cooling failure, unit is DEG C;T2 takesMaximum
Value;
It is assessed to be conservative, in intermittent reaction,;
In Semi-batch reaction,;
2-3) the initial temperature that unstable products are decomposed, is denoted as T3;
The initial temperature T3 that unstable products are decomposed is desirable, and the maximum reaction rate arrival time that product decomposes is corresponding for 24 hours
Reaction initial temperature.It is determined by following equation (3);
;
2-4) because of the limitation of technical conditions, the maximum temperature that reaction kettle can bear is denoted as T4;
In open system, T4 is the boiling point of solvent;In closed system, T4 is temperature corresponding to reaction kettle maximum allowble pressure
Degree;Reaction kettle maximum allowble pressure refers to safety valve or rupture disk setting pressure;
2-5) final temperature under adiabatic condition is denoted as T5;
After cooling failure, when the attainable maximum temperature T2 of the synthetic reaction is less than the initial temperature T3 that unstable products are decomposed,
Second decomposition reaction is difficult to be initiated, at this point,
;
When the maximum temperature T2 of synthetic reaction is greater than the initial temperature T3 that product decomposes, the decomposition reaction of product is initiated, this
When,
;
3) danger level grade is divided;
The operation temperature T1 obtained based on abovementioned steps;After reaction system cooling failure;The attainable maximum temperature of synthetic reaction
T2;The initial temperature T3 that unstable products are decomposed;Because of the limitation of technical conditions, maximum temperature T4 that reaction kettle can bear;With
And the final temperature T5 under adiabatic condition, the size sort ascending of this 5 key temperatures form different types of situation, according to
Danger level index is classified;
The classification is as follows,
3-1) 1 grade of danger level situation, including 2 kinds of situations;
The first situation, T1 < T2 < T4 < T3 < T5;In this case, after synthetic reaction is out of control, temperature does not reach reaction kettle
The maximum temperature T4 that can bear, and product decomposition will not be caused, it is only stopped reaction mass is in heat history very long
It can be only achieved the maximum temperature T4 that reaction kettle can bear after a period of time;
Second situation, T1 < T2 < T3 < T5 < T4;In this case, after synthetic reaction is out of control, product decomposition will not be caused, such as
Fruit reaction mass rests on heat history state for a long time, is possible to cause second decomposition reaction, but reacted under adiabatic condition
The maximum temperature T4 that reaction kettle can bear is not achieved in final temperature T5, and evaporation is cooling or emergency discharge can play additional safety
The effect of barrier;
3-2) 2 grades of danger level situations, T1 < T2 < T3 < T4 < T5;After synthetic reaction is out of control, reaction kettle, which is not achieved, in temperature be can bear
Maximum temperature T4, and will not cause product decomposition, if reaction mass for a long time rest on heat history state, two will be caused
Secondary decomposition reaction, and temperature reaches the maximum temperature T4 that reaction kettle can bear.If synthetic reaction rate of heat release in T4
It is very high, danger may be triggered;
3-3) 3 grades of danger level situations, including 2 kinds of situations;
The first situation, T1 < T4 < T2 < T3 < T5;After synthetic reaction is out of control, temperature reaches the maximum temperature that reaction kettle can bear
T4, but not cause product and decompose.Reaction process depends on safely the rate of heat release of synthetic reaction when T4;
Second situation, T1 < T3 < T2 < T5 < T4;After synthetic reaction is out of control, system will cause the reaction of product second decomposition, but absolutely
Final temperature T5 under heat condition does not reach the maximum temperature T4 that reaction kettle can bear, and evaporation is cooling or emergency decompression can be with
As last one of safety curtain.
3-4) 4 grades of danger level situations, T1 < T4 < T3 < T2 < T5;After synthetic reaction is out of control, temperature is up to technological limit, and
And theoretically analysis can cause product decomposition;Reaction process depends on safely conjunction when the maximum temperature T4 that reaction kettle can bear
At the sum of the rate of heat release of reaction and second decomposition reaction;
3-5) 5 grades of danger level situations, T1 < T3 < T2 < T4 < T5;After synthetic reaction is out of control, system will cause product and decompose, and temperature
Reach the maximum temperature T4 that reaction kettle can bear in the process kind of second decomposition runaway reaction, at this point, evaporation is cooling or urgent
Pressure release cannot play the role of safety curtain.
The present invention is to identificate and evaluate the thermal runaway risk of synthetic reaction, provides a kind of relatively reliable, accurate method,
The thermal runaway risk that appropriately can accurately assess synthetic reaction helps to instruct chemical company's optimization process operating parameter,
Risk reduction measures are formulated, chemical company is instructed to select and define enough risk reduction measures, improve process safety, improve enterprise
The economic benefit of industry.
Detailed description of the invention
Below with reference to attached drawing, the invention will be further described:
Fig. 1 is the dangerous diagram classification schematic table that the method for the present invention is established;
Fig. 2 is temperature and heat release rate profile in TBPA synthetic reaction of the embodiment of the present invention;
Fig. 3 is temperature and pressure curve in TBPA decomposition reaction of the embodiment of the present invention;
Fig. 4 is temperature rise rate curve and dynamics fitted figure in TBPA decomposition reaction of the embodiment of the present invention;
Fig. 5 is the accessible final temperature of TBPA synthetic reaction after cooling failure of the embodiment of the present inventionCurve.
Specific embodiment
Below with reference to the drawings and specific embodiments, the invention will be further described.
Digital representation danger level grade in Fig. 1, in X-axis;
The longitudinal axis indicates temperature, wherein mark:
T1 indicates operation temperature;
After T2 indicates reaction system cooling failure, the attainable maximum temperature of synthetic reaction;
T3 indicates the initial temperature that unstable products are decomposed;
T4 indicates the limitation because of technical conditions, the maximum temperature that reaction kettle can bear;
T5 indicates the final temperature under adiabatic condition.
Referring to attached drawing 1, the risk stratification method of fine chemistry industry production process security evaluation includes the following steps:
1) it gets parms
It 1-1) determines assessment object, and acquires the operating condition of the synthesis technology;
1-2) with laboratory scale, the synthetic reaction isothermal calorimetric experiment of assessment object is carried out, rate of heat release, thermal transition are obtained
The data such as rate, charging rate;Determine the total reaction heat of the synthetic reaction;The specific heat capacity of reaction mixture;It is anti-in reaction kettle
Answer the gross mass of mixture;Accumulation of material degree in moment reaction kettle;
Reaction product is analyzed using product analysis instrument, determines reaction yield;
1-3) adiabatic calorimetry experiment is carried out with the product of the synthetic reaction of step (1-2);
The initial concentration of product 1-3-1) is determined first;
Temperature/pressure-time graph 1-3-2) is drawn using response data, determines the initial temperature that product decomposes, can reach
Maximum temperature, adiabatic temperature rise;
Temperature rise rate-temperature curve 1-3-3) is drawn, and carries out nonlinear fitting using mathematical model and obtains thermokinetic parameters,
Including apparent activation energy;Pre-exponential factor A, order of reaction n;
If 1-4) reaction system is open system, the boiling point of solvent is determined, accounting is maximum in the reaction system for solvent;If envelope
Close system, it is determined that temperature corresponding to reaction kettle maximum allowble pressure, the reaction kettle maximum allowble pressure refer to safety valve
Or rupture disk sets pressure.
2) evaluation index is calculated
2-1) operation temperature is denoted as T1, is determined by the operating condition of synthetic reaction, and the initial temperature of cooling failure situation takes T1;
2-2) after reaction system cooling failure, the attainable maximum temperature of synthetic reaction is denoted as T2;
Total adiabatic temperature rise of synthetic reaction;T2 andIt is calculated by following formula,
In formula,It is the accessible temperature of synthetic reaction after reaction system cooling failure, unit is DEG C;T2 takesMaximum
Value;
It is assessed to be conservative, in intermittent reaction,;
In Semi-batch reaction,;
2-3) the initial temperature that unstable products are decomposed, is denoted as T3;
The initial temperature T3 that unstable products are decomposed is desirable, the maximum reaction rate arrival time that product decomposes be for 24 hours, it is corresponding
Reaction initial temperature determined by following equation (3);
;
2-4) because of the limitation of technical conditions, the maximum temperature that reaction kettle can bear is denoted as T4;
In open system, T4 is the boiling point of solvent;In closed system, T4 is temperature corresponding to reaction kettle maximum allowble pressure
Degree;Reaction kettle maximum allowble pressure refers to safety valve or rupture disk setting pressure;
2-5) final temperature under adiabatic condition is denoted as T5;
After cooling failure, when the attainable maximum temperature T2 of the synthetic reaction is less than the initial temperature T3 that unstable products are decomposed,
Second decomposition reaction is difficult to be initiated, at this point,
;
When the maximum temperature T2 of synthetic reaction is greater than the initial temperature T3 that product decomposes, the decomposition reaction of product is initiated, this
When,
;
3) danger level grade is divided;
The operation temperature T1 obtained based on abovementioned steps;After reaction system cooling failure;The attainable maximum temperature of synthetic reaction
T2;The initial temperature T3 that unstable products are decomposed;Because of the limitation of technical conditions, maximum temperature T4 that reaction kettle can bear;With
And the final temperature T5 under adiabatic condition, the size sort ascending of this 5 key temperatures form different types of situation, according to
Danger level index is classified;
The classification is as follows,
3-1) 1 grade of danger level situation, including 2 kinds of situations;
The first situation, T1 < T2 < T4 < T3 < T5;In this case, after synthetic reaction is out of control, temperature does not reach reaction kettle
The maximum temperature T4 that can bear, and product decomposition will not be caused, it is only stopped reaction mass is in heat history very long
It can be only achieved T4 after a period of time;
Second situation, T1 < T2 < T3 < T5 < T4;In this case, after synthetic reaction is out of control, product decomposition will not be caused, such as
Fruit reaction mass rests on heat history state for a long time, is possible to cause second decomposition reaction, but reacted under adiabatic condition
The maximum temperature T4 that reaction kettle can bear is not achieved in final temperature T5, and evaporation is cooling or emergency discharge can play additional safety
The effect of barrier;
3-2) 2 grades of danger level situations, T1 < T2 < T3 < T4 < T5;After synthetic reaction is out of control, reaction kettle, which is not achieved, in temperature be can bear
Maximum temperature T4, and will not cause product decomposition, if reaction mass for a long time rest on heat history state, two will be caused
Secondary decomposition reaction, and temperature reaches the maximum temperature T4 that reaction kettle can bear.If synthetic reaction rate of heat release in T4
It is very high, danger may be triggered;
3-3) 3 grades of danger level situations, including 2 kinds of situations;
The first situation, T1 < T4 < T2 < T3 < T5;After synthetic reaction is out of control, temperature reaches the maximum temperature that reaction kettle can bear
T4, but not cause product and decompose.Reaction process depends on safely the rate of heat release of synthetic reaction when T4;
Second situation, T1 < T3 < T2 < T5 < T4;After synthetic reaction is out of control, system will cause the reaction of product second decomposition, but absolutely
Final temperature T5 under heat condition does not reach the maximum temperature T4 that reaction kettle can bear, and evaporation is cooling or emergency decompression can be with
As last one of safety curtain.
3-4) 4 grades of danger level situations, T1 < T4 < T3 < T2 < T5;After synthetic reaction is out of control, temperature is up to technological limit, and
And theoretically analysis can cause product decomposition;What synthetic reaction and second decomposition reacted when reaction process depends on safely T4 puts
The sum of hot rate;
3-5) 5 grades of danger level situations, T1 < T3 < T2 < T4 < T5;After synthetic reaction is out of control, system will cause product and decompose, and temperature
Reach the maximum temperature T4 that reaction kettle can bear in the process kind of second decomposition runaway reaction, at this point, evaporation is cooling or urgent
Pressure release cannot play the role of safety curtain.
Embodiment:
1, it gets parms
1-1) determine that assessment object is, under basic reaction conditions, the process safety of tert-butyl peroxy acetate (TBPA) synthesis technology
Assessment.
In actual process production, first there is tert-butyl hydroperoxide (TBHP) to react with sodium hydroxide and generate t-butyl peroxy
Change the organic slat solution of hydrogen, acetic anhydride (Ac2O) then is added, turn on agitator react with organic salt generating TBPA.Instead
Reaction temperature should be controlled with chilled brine in the process, reaction temperature is 20 DEG C.The technique is semi-batch operation, and reaction equation is such as
Under:
。
1-2) carry out TBPA synthesis isothermal calorimetric experiment;
The laboratory apparatus used is to react calorimeter;
Experimental procedure is as follows:
Reaction calorimeter temp-controled mode 1-2-1) is set as isothermal mode, reaction temperature is set as 20 DEG C, and stirring rate is set as
150rpm/min, feed rate are set as 4.5g/min.
1-2-2) reacted
TBPA synthetic reaction is divided into the progress of two steps under alkaline condition, and 953.4g tert-butyl hydroperoxide is added into reaction kettle for the first step
Hydrogen/sodium hydroxide salting liquid, second step are that 222.7g acetic anhydride is added dropwise with the feed rate of program setting to be reacted.Reaction
The total 1176.1g of the quality of mixture.The exothermic character of second step main reaction is studied.
Under alkaline condition in TBPA synthetic reaction process, jacket temperature (Tj), temperature of reaction kettle (Tr), rate of heat release (qr)
Change curve and corresponding charging curve such as Fig. 2.The total reaction heat of the synthetic reaction can be obtained to qr-t curve integral.Experiment measures the specific heat capacity of reaction mixture,。
Synthesis product component is analyzed using product analysis instrument, under alkaline condition, product oil water phase is layered, in oily phase
Product component mainly has tert-butyl hydroperoxide (TBHP), di-tert-butyl hydrogen peroxide (DTBP) and tert-butyl peroxy acetate
(TBPA).Yield by can be calculated TBPA under alkaline condition is 71%.
1-3) carry out TBPA Adiabatic Decomposition calorimetric experiment;
Laboratory apparatus uses adiabatic calorimetry instrument;
Experimental procedure is that 0.8gTBPA sample is taken to be packed into voltage-withstand test bead, determines initial concentration.Experiment sets initial temperature as 70 DEG C, and final temperature is 250 DEG C, and heating temperature step is 5
DEG C, waiting time 10min.Using heating-waiting-search (H-W-S) mode, if equipment detects self-heating rate automatically and reaches just
When 0.02 DEG C/min of beginning setting value, it is believed that TBPA starts decomposition caused heat release, and system enters adiabatci condition.Automatically record temperature (T),
Pressure (P), temperature rise rate (dT/dt) curve that (t) changes at any time, are shown in Fig. 3 and Fig. 4.
Know TBPA sample initial decomposition temperature, final temperature, decomposition reaction
Adiabatic temperature rise.Utilize mathematical modelIt is right
DT/dt-t curve carries out nonlinear fitting, can obtain order of reaction n=0.61, apparent activation energy;
Pre-exponential factor。
1-4) alkalinity synthesis TBPA technique carries out under atmospheric pressure, and the boiling point of aqueous solvent is 100 DEG C.
2, evaluation index is calculated
1) operation temperature T1, wherein T1=20 DEG C;
2) after reaction system cooling failure, the attainable maximum temperature T2 of synthetic reaction:
By the total reaction heat of synthetic reaction, the specific heat capacity of reaction mixture,
Mass M=1176.1g of reaction mixture, yield Y=71% substitute into equation (1), total adiabatic temperature rise of synthetic reaction are calculated, corrected through yield;
TBPA synthesis is semi-batch process, synthesizes isothermal calorimetric experimental data using TBPA, can draw charging rate and heat conversion
Curve, accumulation degree=charging rate-heat conversion.By operation temperature T1, total adiabatic temperature riseWith accumulation degreeNumber
Value brings equation (2) into, can obtain the accessible final temperature of reaction system after cooling failureThe curve changed over time, is shown in figure
5。
And after determining reaction system cooling failure, attainable maximum temperature T2=62.5 DEG C of synthetic reaction.
3) the initial temperature T3 that unstable products are decomposed;
By the data obtained in TBPA Adiabatic Decomposition calorimetric experiment, including TBPA initial concentration;
Decomposition reaction final temperature, react adiabatic temperature rise;Order of reaction n=0.61, table
See activation energy;Pre-exponential factor;It substitutes into following
Equation (3),
Solve equation unstable products decompose initial temperature T3=60.3 DEG C.
4) because of the limitation of technical conditions, maximum temperature T4 that reaction kettle can bear;
Because alkalinity synthesis TBPA technique carries out under atmospheric pressure, the maximum for taking the boiling point of aqueous solvent that can bear for reaction kettle
Temperature, so T4=100 DEG C.
5) the final temperature T5 under adiabatic condition;
By above-mentioned calculating, it is known that in TBPA synthetic reaction, inherently trigger TBPA second decomposition.The operation of alkalinity synthesis TBPA
Temperature T1=20 DEG C;TBPA synthesizes measured adiabatic temperature rise in isothermal calorimetric experiment, repaired without yield
Just;Adiabatic temperature rise measured by institute in TBPA Adiabatic Decomposition calorimetric experiment.Above-mentioned value is substituted into equation
(5), final temperature T5=96.5 DEG C under adiabatic condition can be obtained.
3, danger level grade is divided
In alkalinity synthesis TBPA technique, above-mentioned 5 key temperatures arrangement is shown in Table 1.
5 key temperatures in 1 alkalinity synthesis TBPA technique of table
Because of T1 < T3 < T2 < T5 < T4, the danger level grade of TBPA synthesis technology is 3.
In view of assessment result, it is proposed that enterprise takes design distilling apparatus, using reserved cooling system, dump reaction mass or
The technical measures such as quenching.
The present invention is based on the 5 key temperatures parameters occurred in reaction process, comprehensively consider the difficulty or ease journey of thermal runaway generation
Degree, is assessed and is classified to the thermal hazard of synthetic reaction, and assessment result is more accurate and appropriate.Enterprise can be instructed to carry out work
Corresponding safety prevention measure is formulated in skill safe design and management, prevents the generation of thermal runaway and thermal explosion.Ensuring to give birth to safely
Under the premise of production, maximization of economic benefit is pursued, this has very big meaning for the development of enterprise.So that it is guaranteed that enterprise is pacified
Full investment optimizes.
Claims (3)
1. a kind of risk stratification method of fine chemistry industry production process security evaluation, which comprises the steps of:
1) it gets parms
It 1-1) determines assessment object, and acquires the operating condition of the synthesis technology;
1-2) with laboratory scale, the synthetic reaction isothermal calorimetric experiment of assessment object is carried out, rate of heat release, thermal transition are obtained
The data such as rate, charging rate;Determine the total reaction heat of the synthetic reaction, unit is;The specific heat capacity of reaction mixture,
Unit is;The gross mass of reaction kettle reaction mixture, unit is;Accumulation of material degree in moment reaction kettle, unit %;
Reaction product is analyzed using product analysis instrument, determines reaction yield, unit %;
1-3) adiabatic calorimetry experiment is carried out with the product of the synthetic reaction of step (1-2);
The initial concentration of product 1-3-1) is determined first, unit is;
Temperature/pressure-time graph 1-3-2) is drawn using response data, determines the initial temperature that product decomposes, unit is
℃;Attainable maximum temperature, unit is DEG C;Adiabatic temperature rise, unit is DEG C;
Temperature rise rate-temperature curve 1-3-3) is drawn, and carries out nonlinear fitting using mathematical model and obtains thermokinetic parameters,
Including apparent activation energy, unit is;Pre-exponential factor A, order of reaction n;
If 1-4) synthetic reaction system is open system, the boiling point of solvent is determined, accounting is maximum in the reaction system for solvent;If
Closed system, it is determined that temperature corresponding to reaction kettle maximum allowble pressure, the reaction kettle maximum allowble pressure refer to safety
Valve or rupture disk set pressure;
2) evaluation index is calculated
2-1) operation temperature is denoted as T1, is determined by the operating condition of synthetic reaction, and the initial temperature of cooling failure situation takes T1;
2-2) after reaction system cooling failure, the attainable maximum temperature of synthetic reaction is denoted as T2;
Total adiabatic temperature rise of synthetic reaction, unit is DEG C;T2 andIt is calculated by following formula,
In formula,It is the accessible temperature of synthetic reaction after reaction system cooling failure, unit is DEG C;T2 takesMaximum
Value;
It is assessed to be conservative, in intermittent reaction,;
In Semi-batch reaction,;
2-3) the initial temperature that unstable products are decomposed, is denoted as T3;
The initial temperature T3 that unstable products are decomposed is desirable, and the maximum reaction rate arrival time that product decomposes is corresponding for 24 hours
Reaction initial temperature;
It is determined by following equation (3);
;
2-4) because of the limitation of technical conditions, the maximum temperature that reaction kettle can bear is denoted as T4;
In open system, T4 is the boiling point of solvent;In closed system, T4 is temperature corresponding to reaction kettle maximum allowble pressure
Degree;Reaction kettle maximum allowble pressure refers to safety valve or rupture disk setting pressure;
2-5) final temperature under adiabatic condition is denoted as T5;
After cooling failure, when the attainable maximum temperature T2 of the synthetic reaction is less than the initial temperature T3 that unstable products are decomposed,
Second decomposition reaction is difficult to be initiated, at this point,
;
When the maximum temperature T2 of synthetic reaction is greater than the initial temperature T3 that product decomposes, the decomposition reaction of product is initiated, this
When,
;
3) danger level grade is divided;
The operation temperature T1 obtained based on abovementioned steps;After reaction system cooling failure, the attainable maximum temperature of synthetic reaction
T2;The initial temperature T3 that unstable products are decomposed;Because of the limitation of technical conditions, maximum temperature T4 that reaction kettle can bear;With
And the final temperature T5 under adiabatic condition, the size sort ascending of this 5 key temperatures form different types of situation, according to
Danger level index is classified.
2. the risk stratification method of fine chemistry industry production process security evaluation according to claim 1, which is characterized in that
Operating condition described in step (1-1) include using interval or the production method of semi-batch operation, operation temperature, operating pressure,
Material proportion, solvent, charging sequence and feed rate and agitator speed.
3. the risk stratification method of fine chemistry industry production process security evaluation according to claim 1, which is characterized in that
Classification described in step (3) is as follows:
3-1) 1 grade of danger level situation, including 2 kinds of situations;
The first situation, T1 < T2 < T4 < T3 < T5;In this case, after synthetic reaction is out of control, temperature does not reach reaction kettle
The maximum temperature T4 that can bear, and product decomposition will not be caused, it is only stopped reaction mass is in heat history very long
It can be only achieved the maximum temperature T4 that reaction kettle can bear after a period of time;
Second situation, T1 < T2 < T3 < T5 < T4;In this case, after synthetic reaction is out of control, product decomposition will not be caused, such as
Fruit reaction mass rests on heat history state for a long time, is possible to cause second decomposition reaction, but reacted under adiabatic condition
The maximum temperature T4 that reaction kettle can bear is not achieved in final temperature T5, and evaporation is cooling or emergency discharge can play additional safety
The effect of barrier;
3-2) 2 grades of danger level situations, T1 < T2 < T3 < T4 < T5;After synthetic reaction is out of control, reaction kettle, which is not achieved, in temperature be can bear
Maximum temperature T4, and will not cause product decomposition, if reaction mass for a long time rest on heat history state, two will be caused
Secondary decomposition reaction, and temperature reaches the maximum temperature T4 that reaction kettle can bear;If synthetic reaction rate of heat release in T4
It is very high, danger may be triggered;
3-3) 3 grades of danger level situations, including 2 kinds of situations;
The first situation, T1 < T4 < T2 < T3 < T5;After synthetic reaction is out of control, temperature reaches the maximum temperature that reaction kettle can bear
T4, but not cause product and decompose;Reaction process depends on safely the rate of heat release of synthetic reaction when T4;
Second situation, T1 < T3 < T2 < T5 < T4;After synthetic reaction is out of control, system will cause the reaction of product second decomposition, but absolutely
Final temperature T5 under heat condition does not reach the maximum temperature T4 that reaction kettle can bear, and evaporation is cooling or emergency decompression can be with
As last one of safety curtain;
3-4) 4 grades of danger level situations, T1 < T4 < T3 < T2 < T5;After synthetic reaction is out of control, temperature is up to technological limit, and from
Theoretically analysis can cause product decomposition;It is anti-that reaction process depends on safely synthesis when the maximum temperature T4 that reaction kettle can bear
The sum of the rate of heat release that should be reacted with second decomposition;
3-5) 5 grades of danger level situations, T1 < T3 < T2 < T4 < T5;After synthetic reaction is out of control, system will cause product and decompose, and temperature
Reach the maximum temperature T4 that reaction kettle can bear in the process kind of second decomposition runaway reaction, at this point, evaporation is cooling or urgent
Pressure release cannot play the role of safety curtain.
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