Summary of the invention
The purpose of this invention is to provide a kind of polymer polymerization reaction temperature control method, solved macromolecular compound, particularly machine fluorine monomer very exothermic reaction needed in course of reaction is removed heat fast, improve the selectivity and the yield of reactive material, control temperature of reaction well, prolong the serviceable life of reactor simultaneously.
In addition, the present invention also provides a kind of macromolecular polymerization reaction temperature control equipment.
Macromolecular polymerization reaction is to add monomer continuously, and in course of reaction, add relevant auxiliary agent, and its reaction velocity is very responsive to temperature of reaction, and temperature is high more, react fast more, heat release Shaoxing opera is strong, and temperature is more just reacted speed more, heat release is few more, therefore controlling temperature of reaction well, is controls reaction speed, improves the selectivity of reactive material and a key of yield.
A kind of polymer polymerization reaction temperature control method of the present invention, it comprises the steps:
(1) sets temperature of reaction t;
(2) heating reactor: when decomposition induction time need heat, recirculated water variable valve in the standard-sized sheet, close the outer circulation water regulating valve, open steam control valve, steam is by steam heater and the abundant Hybrid Heating recirculated water of recirculated water, recirculated water is by reacting kettle jacketing time heating reactor, after reactor temperature reaches temperature of reaction t ± 1 ℃, stops heating;
(3) in course of reaction,, determine the temperature t that reacting kettle jacketing recirculated water is required by the linear model internalarithmetic according to reaction velocity
The water inlet temperature,, calculate the temperature difference between interior temperature of reactor and the chuck chilled water, just in time to take away the reaction liberated heat promptly according to the feed rate size.With t
The water inlet temperatureBe setting value, by interior circulating water temperature PID controller, control outer circulation water valve aperture, emit the hot water in the circulation in the part from outer circulation, produce negative pressure this moment in interior circulation, and interior recirculated water and circulating water chennel form pressure reduction, from circulating water chennel, replenish equivalent cold water automatically and enter reacting kettle jacketing (siphon principle), the cold water that enters in the reacting kettle jacketing mixes rapidly with recirculated water in the original reactor chuck, and circulating water temperature in reducing fast makes the temperature of chuck recirculated water satisfy t
The water inlet temperatureWhen the temperature of interior recirculated water is higher than t
The water inlet temperatureThe time, the aperture of regulating the outer circulation water valve by interior circulating water temperature PID controller.Temperature deviation is big more, and valve opening speed is fast more, and aperture is big more, and according to siphon principle, the chilled water that is entered reacting kettle jacketing by circulating water chennel is fast more, many more, and the reacting kettle jacketing water temperature descends fast more; Otherwise valve opening speed is slow more, and aperture is more little, and the chilled water that is entered reacting kettle jacketing by circulating water chennel is slow more, few more, and the reacting kettle jacketing water temperature descends slow more.By said process, temperature remains on t ± 1 ℃ in the control reactor.
For eliminating of the influence of some uncertain factors to temperature of reaction, accurately control temperature in the reactor, by the aperture of recirculated water variable valve in changing, adjust temperature of reaction among a small circle, make it to remain in t ± 1 ℃.In the reactor and the reacting kettle jacketing chilled water has the temperature difference, the aperture by recirculated water variable valve in changing changes recirculated water flow velocity in the reacting kettle jacketing, increase or reduce the recirculated water heat transfer rate, with this as a kind of auxiliary control method, to improve control accuracy.When reactor temperature is t ± 0.2 ℃, the recirculated water control valve opening is at 60-70% in the control, and when reactor temperature is higher than t+0.2 ℃, and temperature is when rising formula, recirculated water variable valve in the standard-sized sheet, the aperture that interior circulating water temperature PID controller is regulated the outer circulation water regulating valve automatically; When reactor temperature is lower than t-0.2 ℃, and during the temperature downtrending, in the control recirculated water control valve opening 20%, outer circulation water regulating valve complete shut-down.
When the temperature of circulating water chennel outer circulation water is higher than certain value, outer circulation tank PID controller Control Circulation tank refrigerant operation valve, refrigerant is lowered the temperature through the external recirculated water of coil pipe, with the temperature that keeps outer circulation water within the specific limits, according to different products, temperature required difference, the ordinary rubber base polymer, temperature is at 35~40 ℃, the resene polymkeric substance, and temperature is at 30~35 ℃.
Polymer polymerization reaction temperature control method of the present invention, wherein in circulation be that recirculated water is successively through reacting kettle jacketing, interior recirculated water variable valve, water circulating pump, steam heater, enter reacting kettle jacketing again; Outer circulation is that recirculated water flows out from internal recycle pipeline, enters the outer circulation pipeline, and flow through outer circulation water regulating valve and circulating water chennel enter internal recycle pipeline again.
A kind of macromolecular polymerization reaction temperature control equipment, circulation and outer circulation in comprising, it is characterized in that, described in circulation comprise internal recycle pipeline that two ends are connected with reacting kettle jacketing, be installed in interior recirculated water variable valve, water circulating pump, steam heater on the internal recycle pipeline successively; Described outer circulation comprises the outer circulation pipeline that two ends are connected with internal recycle pipeline, and is installed in outer circulation water regulating valve, circulating water chennel on the outer circulation pipeline successively.
Macromolecular polymerization reaction temperature control equipment of the present invention, the linear model arithmetical unit that also comprise the material feed rate measuring instrument that is installed on the reactor feed pipe, is connected with material feed rate measuring instrument successively with interior circulating water temperature PID controller, be installed in the circulating water temperature measuring instrument on the internal recycle pipeline, the steam control valve that is connected temperature measurement instrument in the reactor on the reactor, is connected with steam heater.
Macromolecular polymerization reaction temperature control equipment of the present invention is connected with circulating water chennel temperature measuring set and circulating water chennel refrigerant operation valve on the wherein said circulating water chennel, inside is equipped with coil pipe.
The bright described macromolecular polymerization reaction temperature control equipment of this law, wherein said circulating water chennel temperature measuring set are connected with circulating water chennel refrigerant operation valve respectively with outer circulation tank temperature PID controller and are connected.
Circulating water temperature PID controller is connected with the outer circulation water regulating valve with reacting kettle jacketing import circulating water temperature measuring instrument respectively in of the present invention.
Refrigerant of the present invention can be the medium that routine is used to cool off.
In course of reaction, heat release is more violent, but the transmission of temperature is slower, and in time taking away the reaction liberated heat, the variation of reacting kettle jacketing circulating water temperature need have a lead.Feed rate is a sensitive parameter that characterizes the poly-strong degree of reaction in polyreaction, therefore set up the mathematical model relation between feed rate and the chuck circulating water temperature, in time adjust the temperature of reacting kettle jacketing chilled water, can fine control polymeric reaction temperature.Under general condition, the relation between reaction feed flow and the interior circulating water temperature is followed the linear model relation:
t
The water inlet temperature=t-f
Charging* k+t
Drift correction
Wherein:
t
The water inlet temperature: reacting kettle jacketing circulating water intake temperature, ℃.
T: temperature in the given reactor, ℃.
f
Charging: reactor material feed rate, kg/h.
t
Drift correction: the temperature difference correction of different trade mark products, ℃.
K: flux temperature coefficient, be that the reactor feed rate is to the Temperature Influence coefficient, obtain by experiment, ℃/(kg/h), the centigrade degree that circulating water temperature need descend in 1 kilogram of/hour mix monomer feed rate of promptly every increase chuck is because the Organic fluoride polymerization theory is complicated, the factor that influence is conducted heat is more, these data are generally with the control feed rate, and the method experiment of manual adjustment circulating water temperature draws, and does more and can obtain more accurate K value several times.
With t
The water inlet temperatureAs reacting kettle jacketing import circulating water temperature set-point, by the linear model internalarithmetic, automatically control the aperture of outer circulation water regulating valve by interior circulating water temperature PID controller, change and enter the round-robin cooling water inflow, reach the purpose that reduces the reacting kettle jacketing circulating water temperature.
The PID controller is ratio, integration, three kinds of combinations of regulating rule of differential, is a kind of autocontrol method of classics, and its transport function is:
G
e(s)=K
e(1+1/T
is)+T
ds
Described PID controller relates to complicated controls such as the chain control of aperture that PID regulates computing, inside and outside circulation valve position, the judgement of temperature of reaction lifting trend and calculates, and general the recommendation waited and realized with programmable intelligent PID controller or with PLC (Programmable logic controllor), DCS (Distributed computer system).
The beneficial effect of polymer polymerization reaction temperature control method of the present invention:
Solved macromolecular compound, particularly the very exothermic reaction needed is removed heat fast in the machine fluorine monomer polymerization process, improve the selectivity and the yield of reactive material, temperature in the stable control reactor, prolong the selectivity that has improved reactive material serviceable life and the yield of reactor simultaneously, yield can improve more than 20%, has saved steam and cold and has consumed more than 15%.
Embodiment
The present invention is described further below in conjunction with accompanying drawing, but be not used for limiting the scope of the invention.
The application of embodiment 1 linear model
If interior warm t=80 ℃ of given reactor is current feed rate f
Charging=80kg/h, flux temperature coefficient k=0.4 ℃/(kg/h), current production synthetic rubber temperature deviation correction t
Drift correction=3 ℃, the temperature of chilled water in the then current reacting kettle jacketing 2:
T is intake warm=80-80*0.4+3=51 ℃
Embodiment 2 Organic fluoride macromolecular polymerization reaction temperature control equipments
Be a kind of Organic fluoride macromolecular polymerization reaction temperature control equipment that is used for as shown in Figure 1, comprise outer circulation and interior circulation, interior circulation comprises the internal recycle pipeline 13 that two ends are connected with reacting kettle jacketing 2, and is installed in interior recirculated water variable valve 4, water circulating pump 1, steam heater 10 on the internal recycle pipeline 13 successively.Described outer circulation comprises the outer circulation pipeline 16 that two ends are connected with internal recycle pipeline 13, and is installed in outer circulation water regulating valve 5, circulating water chennel 14 on the outer circulation pipeline 16 successively.Be connected with steam control valve 12 on the steam heater 10.Circulating water chennel 14 is connected with circulating water chennel temperature measuring set 6 and circulating water chennel refrigerant operation valve 7, and circulating water chennel 14 inside are equipped with coil pipe 18.In this control device, material feed rate measuring instrument 8 is installed on the feed pipe that is connected with reactor 17, linear model arithmetical unit 15 is connected with interior circulating water temperature PID controller 11 with material feed rate measuring instrument 8 respectively, interior circulating water temperature PID controller 11 respectively with outer circulation water regulating valve 5, reactor in temperature measurement instrument 3, interior recirculated water variable valve 4 be connected with reactor import circulating water temperature measuring instrument 9, outer circulation tank temperature PID controller 19 is connected with circulating water chennel temperature measuring set 6 with refrigerant operation valve 7 respectively.Reactor import circulating water temperature measuring instrument 9 is installed in internal recycle pipeline 13 near the reacting kettle jacketing entrance point, and temperature measurement instrument 3 is installed on the reactor 17 in the reactor.
The control of embodiment 3 Organic fluoride macromolecular polymerization reaction temperature
The vinylidene fluoride monomers induced reaction that must heat up before homopolymerization and the polymerization process in reactor, the reaction of present embodiment is temperature required to be set at 80 ℃.Reaction induced intensification begins, recirculated water variable valve 4 in the standard-sized sheet, close outer circulation water regulating valve 5, open steam control valve 12, the control steam flow, steam mixes with recirculated water by steam heater 10, heat cycles water, the recirculated water of heating gives reactor 17 heating by reaction chuck 2, the water that comes out from reacting kettle jacketing 2 enters steam heater 10 once more and heats through internal recycle pipeline 13, interior recirculated water variable valve 4, water circulating pump 1 successively again, so circulation, this cyclic process belongs to interior circulation.The control of steam flow with the designed capacity of steam heater 10 and do not produce the vibration be principle, The faster the better for programming rate.When temperature of reaction kettle reaches 80 ± 1 ℃, steam off operation valve 12 stops heating, interior recirculated water variable valve 4 apertures 70%, and the intensification induction period is finished.
Temperature controlling stages, open the material inlet valve, enter the macromolecular polymerization reaction stage, measure the mass flow that enters reactor by material feed rate measuring instrument 8, and add up, the signal of measuring mass flow outputs to linear model arithmetical unit 15, and circulating water temperature PID controller 11 was as the set-point of controller in the operation result of linear operator 15 outputed to, and this set-point is as current required chuck cooling water temperature t
The water inlet temperatureThe circulating water temperature of measuring when reacting kettle jacketing import circulating water temperature measuring instrument 9 is than current t
The water inlet temperatureHigh, PID controller 11 can receive signal, automatically control the aperture of outer circulation water regulating valve 5, emit the recirculated water of heat, the recirculated water of heat flow to circulating water chennel 14 through outer circulation pipeline 16, and according to siphon principle, the cold water that has equivalent in the circulating water chennel 14 enters internal recycle pipeline 13, mix rapidly with recirculated water in the original reactor chuck 2, circulating water temperature is to t in reducing fast
The water inlet temperature, when so the interior recirculated water of temperature is through reacting kettle jacketing 2, just in time take away the reaction liberated heat, reach the purpose of temperature in the control reaction.Interior circulating water temperature is different and different according to the severe degree of reaction with the temperature difference of the interior temperature of reactor, the t that its value calculates with linear model arithmetical unit 15
The water inlet temperatureAnd change.
For eliminating of the influence of some uncertain factors to temperature of reaction, accurately control temperature in the reactor, control reactor temperature at 80 ± 1 ℃ by the aperture scope of recirculated water variable valve 4 in changing.With the 3 assaying reaction temperature in the kettle of temperature measurement instrument in the reactor, when reactor temperature is 80 ± 0.2 ℃, recirculated water variable valve 4 apertures are 60-70% in regulating, when reactor temperature is higher than 80+0.2 ℃, and temperature rises when becoming formula, and recirculated water variable valve 4 in the standard-sized sheet strengthens the flow velocity by the recirculated water of reaction chuck 2, take away the reaction liberated heat fast, by interior circulating water temperature PID controller 11 automatic apertures of regulating outer circulation water regulating valve 5; When reactor temperature is lower than 80-0.2 ℃, and temperature descends when becoming formula, and interior recirculated water variable valve 4 apertures are 20%, outer circulation water regulating valve 5 complete shut-downs, slow down flow velocity, slow down and take away the speed of reaction liberated heat, keep temperature of reaction at 80 ± 1 ℃ by the recirculated water of reaction chuck 2.
In the course of reaction, the temperature that circulating water chennel temperature measuring set 6 is measured circulating water chennel recirculated water is higher than 35~40 ℃, the output measuring-signal is to outer circulation tank temperature PID controller 19, the aperture of the automatic Control Circulation tank of outer circulation tank temperature PID controller refrigerant operation valve 7, refrigerant is lowered the temperature, to keep circulating water temperature at 35~40 ℃ through 18 pairs of recirculated waters of coil pipe.
Reaction is closed the material inlet valve after finishing, and stops charging, closes circulating water chennel refrigerant operation valve 7, and discharging is prepared in circulation in recirculated water continues.
The used refrigerant of present embodiment is 5 ℃ a water.
The Organic fluoride polyreaction is the process of a homopolymerization and copolymerization, the key of product quality is the pressure and temperature of control reaction, general pressure ratio is more easy to control, temperature control is difficult, accurately control temperature by the method, the product performance index of different batches is more approaching, good reproducibility, the yield of reaction product improves more than 20%, saves cold and steam more than 15%.