CN108329433B - Production system of medium-impact polystyrene resin - Google Patents
Production system of medium-impact polystyrene resin Download PDFInfo
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- CN108329433B CN108329433B CN201810225424.6A CN201810225424A CN108329433B CN 108329433 B CN108329433 B CN 108329433B CN 201810225424 A CN201810225424 A CN 201810225424A CN 108329433 B CN108329433 B CN 108329433B
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
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Abstract
The invention discloses a production system of medium-impact polystyrene resin. The system comprises a system sol tank, a mixed feeding tank, a two-stage prepolymerization reactor, a multi-stage polymerization reactor, a two-stage devolatilization device and a granulator which are sequentially connected in series, wherein an ultrafine powder mixing tank is connected with an ultrafine powder feeding tank in series and then connected with an inlet of a first-stage polymerization reactor of the multi-stage polymerization reactor; the pre-polymerization preheater is arranged on a pipeline between the mixed feed tank and the first-stage pre-polymerization reactor; the devolatilization preheater is arranged on a pipeline between the last stage polymerization reactor and the first stage devolatilization reactor of the multi-stage polymerization reactors; the upper parts of the end parts of the first-stage devolatilizer and the second-stage devolatilizer are connected in series and then are connected with a circulating condenser through a conveying pipeline, a collecting tank is connected to the bottom of the circulating condenser, and an outlet at the bottom of the collecting tank is connected with an inlet of a prepolymerization preheater. The invention adopts a multi-stage prepolymerization-multi-stage polymerization-multi-stage devolatilization combined system, can meet the requirements of users on impact-resistant products, and is easy for large-scale production.
Description
Technical Field
The invention belongs to the technical field of resin synthesis. And more particularly, to a medium impact polystyrene resin production system.
Background
Polystyrene (PS) has the advantages of excellent moldability, good transparency, high rigidity, good electrical insulation performance, easy dyeing, low moisture absorption, low price and the like, has been widely used in the industries of packaging, electronics, construction, automobiles, home appliances, instruments, daily necessities, toys and the like, and becomes one of the fastest-developing varieties of the current general synthetic resins. Polystyrene can be mainly classified into transparent grade polystyrene (GPPS, commonly known as permethyl benzene) and high impact grade polystyrene (HIPS, commonly known as styrene). Wherein GPPS is polymerized by styrene monomer, has colorless or light blue transparent particles, and is used in daily necessities, disposable plastic tableware, transparent packages, toys, plastic plates and the like; the HIPS is added with rubber in the polymerization process of styrene monomer to modify and toughen so as to endow the product with certain impact resistance, so that the HIPS has higher impact resistance strength and elongation compared with GPPS, is white in appearance, and is mainly used for household appliances, electronic office equipment shells, toy stationery, electronic equipment, food packaging and the like.
Because different plastic products and the like have different requirements on the strength of products, for example, under the condition that general toys and stationery products do not need too high impact strength, but no middle impact-resistant products exist in the current market, the method of blending transparent polystyrene in high impact-resistant polystyrene resin is usually adopted to reduce the strength of the products and reduce certain cost, but the method has the defects of labor increase, poor secondary blending effect, incapability of maximally playing the toughening effect of rubber and the like. Generally, in terms of the production process of HIPS, the smaller the rubber particles dispersed in polystyrene, the better the transparency but the worse the impact strength, whereas the larger the rubber particles dispersed in polystyrene, the better the impact strength but the worse the transparency. In addition, the rigidity and toughness are two key indexes of HIPS products, how to control the molecular weight and distribution of the PS body and the particle size and distribution of rubber in the molecular structure of the products, so that the rubber forms an effective sea-island structure in the PS and is grafted with the PS body to achieve better combination of the rubber and the PS, and how to maintain the rigidity of the polystyrene and simultaneously have high impact resistance, so that the optimal balance of the impact resistance and the rigidity of the products is controlled, and the problem to be solved at present is urgently solved.
Accordingly, there is a strong need in the art to develop an intermediate impact polystyrene resin and related manufacturing equipment that maintains an optimum balance of both impact resistance and stiffness while maintaining good processing flowability and improving processing efficiency.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a production system of medium-impact polystyrene resin. The invention organically combines the operation of each mechanism together by adopting a multi-stage prepolymerization-multi-stage polymerization-multi-stage devolatilization combined system and using a continuous bulk polymerization process of a segmented polymerization system, thereby realizing continuous and stable operation, fully playing the toughening role of rubber while greatly saving the use amount of the rubber, effectively controlling the strength and rigidity of the medium impact polystyrene resin, and simultaneously controlling the performance indexes of the products to be stable and consistent.
The invention aims to provide a production system of medium-impact polystyrene resin.
The above purpose of the invention is realized by the following technical scheme:
a production system of medium impact polystyrene resin comprises a sol tank, a mixed feeding tank, an ultrafine powder batching tank, an ultrafine powder feeding tank, a prepolymerization preheater, a first-stage prepolymerization reactor, a second-stage prepolymerization reactor, a multi-stage polymerization reactor, a devolatilization preheater, a first-stage devolatilization device, a second-stage devolatilization device, a third-stage vacuum pump, a circulating condenser, a collecting tank and a granulator; the sol tank, the mixed feeding tank, the superfine powder batching tank, the superfine powder feeding tank, the first-stage prepolymerization reactor, the second-stage prepolymerization reactor, the multistage polymerization reactor, the first-stage devolatilization device, the second-stage devolatilization device and the collecting tank are respectively and independently provided with a metering conveying pump; the sol tank, the mixed feeding tank, the first-stage prepolymerization reactor, the second-stage prepolymerization reactor, the multistage polymerization reactor, the first-stage devolatilization device, the second-stage devolatilization device and the granulator are sequentially connected in series, and the superfine powder batching tank is connected with the superfine powder feeding tank in series and then connected with an inlet of the first-stage polymerization reactor of the multistage polymerization reactor; the pre-polymerization preheater is arranged on a pipeline between the mixed feed tank and the first-stage pre-polymerization reactor; the devolatilization preheater is arranged on a pipeline between the last stage polymerization reactor and the first stage devolatilization reactor of the multi-stage polymerization reactors; in addition, the upper parts of the end parts of the first-stage devolatilizer and the second-stage devolatilizer are connected in series through a conveying pipeline and are connected with a circulating condenser, a collecting tank is connected to the bottom of the circulating condenser, an outlet at the bottom of the collecting tank is connected with an inlet of a pre-polymerization preheater, and a third-stage vacuum pump is arranged on the conveying pipelines of the devolatilizer and the circulating condenser.
Preferably, the medium impact polystyrene resin production system is further provided with an initiator feeding device, and the initiator feeding device is arranged at the top of the upper end of the first-stage prepolymerization reactor, so that the initiator can be conveniently and accurately added and the reaction process can be accurately controlled.
Preferably, the production system of the medium impact polystyrene resin is also provided with a dust removal and granule stabilization device matched with the granulator. The dedusting and granulating device can separate and collect the fine dust after the original material is granulated, fully utilize the existing equipment, improve the utilization rate of the raw materials and reduce the consumption.
Preferably, the multistage polymerization reactor consists of four stages of plug flow reactors connected in series one after the other.
More preferably, a piston flow stirrer is further arranged in the polymerization reactor, and the piston flow stirrer comprises a motor, a stirring paddle, a stirring shaft and a shaft end baffle plate, and is used for removing reaction heat generated by the polymerization reaction in time, accurately controlling the temperature of the polymerization reactor, and controlling the polymerization reaction to be stably carried out, so that the required conversion rate is better achieved.
Preferably, the inner coil pipes which can be controlled in a sectional way are arranged in each stage of prepolymerization reactor and polymerization reactor, and each inner coil pipe is composed of a multi-stage single-layer coil pipe or a multi-stage double-layer coil pipe; the outer part of each prepolymerization reactor and each polymerization reactor is provided with an outer jacket for leading heat conduction oil, and the outer jacket is provided with a heat conduction oil inlet and a heat conduction oil outlet. The outer jacket is positioned outside the reactor cylinder, and the inner coil is positioned inside the reactor cylinder; the materials and the heat conducting oil carry away the reaction heat of the materials through the heat exchange between the wall of the inner coil and the wall of the jacket.
More preferably, the polishing degree Ra of the accessories such as the inner wall of the cylinder body of the plug flow reactor, the outer wall of the inner coil pipe, the stirring shaft, the end cover and the like which are in direct contact with the polymerization material is less than 0.5 μm, so that the material is prevented from accumulating at the accessories, and the heat transfer effect is influenced.
More preferably, the length-diameter ratio of the plug flow reactor is 6-4: 1. too small a length-diameter ratio is not favorable for forming plug flow, and too large an effective volume of the reactor is small, so that the reaction efficiency is influenced.
Preferably, the production system further comprises a total heat conduction oil system, the total heat conduction oil system comprises a heat conduction oil circulation system and a heat conduction oil intelligent temperature control system, and the heat conduction oil intelligent temperature control system is formed by mutually connecting a heat conduction oil pipeline with an inner coil pipe and an outer jacket of the reactor.
Under normal conditions, the temperature of the polymerization reactor is controlled by the circulation of heat conducting oil of the inner coil pipe and the outer jacket, reaction heat generated by polymerization reaction is removed in time, and when necessary, the temperature of materials in the polymerization reactor can be rapidly cooled by cold heat conducting oil.
Preferably, the heat conduction oil intelligent temperature control system is formed by sequentially connecting a heat conduction oil storage tank, a cold heat conduction oil storage tank, a hot oil furnace heater and a heat conduction oil cooler to form a cycle. The total heat conduction oil system provides heat conduction hot oil with the temperature not more than 280 ℃ and cold heat conduction oil with the temperature not more than 90 ℃, the heat conduction hot oil and the cold heat conduction oil are supplied to the polymerization system and the devolatilization system through the conveying pipeline for use, and the heat exchange with the materials is carried out and then the heat exchange returns to the total heat conduction oil system.
Preferably, a heat conduction oil delivery pump and a control valve are arranged on a circulating pipeline of the heat conduction oil intelligent temperature control system; and temperature controllers are arranged on the hot oil furnace heater and the heat conduction oil cooler.
The heat-conducting oil which takes away the heat of polymerization reaction from the polymerization reactor can be used as the oil supply of the pre-polymerization preheater, the medium-temperature oil from the polymerization reactor returns to the heat-conducting oil which can enter the heat-conducting oil circulation system of the pre-polymerization preheater with the heat-conducting oil of the heat-conducting oil supply pipeline through the control valve, and the required temperature for preheating the styrene is provided. Under the normal operation condition, the energy consumption of production can be saved by preheating the styrene feed liquid by utilizing the polymerization heat of the polymerization reactor. The temperature of the polymer in the polymerization reactor is controlled by temperature controllers which control the supply control valves of heat conducting oil and cold conducting oil from the total heat conducting oil system, the control valves put the required amount of heat conducting oil or cold conducting oil into the heat conducting oil circulating system, and the polymerization reactor circularly adds cold conducting oil through an inner coil and an outer jacket in the polymerization reactor to remove reaction heat so as to keep the temperature set by the polymerization reactor.
The devolatilization preheater, the first-stage devolatilizer and the second-stage devolatilizer directly use hot oil from a total heat conduction oil system to heat materials of the devolatilizer, and simultaneously keep the temperature of the first-stage devolatilizer and the second-stage devolatilizer, so that the devolatilization temperature is ensured to completely remove unreacted styrene monomers and other volatile matters, and the quality of products is ensured.
Preferably, the first-stage prepolymerization reactor is operated in a full kettle mode, the second-stage prepolymerization reactor is operated in a half kettle mode, and a first reflux condenser is arranged on the second-stage prepolymerization reactor.
Preferably, the production system further comprises a tertiary vacuum system comprising a primary vacuum pump, a secondary vacuum pump and a tertiary vacuum pump; the top outlet pipeline of the second-stage prepolymerization reactor is connected in parallel with the top outlet pipeline of the first-stage devolatilization device through a first reflux condenser, and then is connected with a second-stage vacuum pump through a circulating condenser and then is connected with a first-stage vacuum pump; and an outlet pipeline of the second-stage devolatilization device is connected with the circulating condenser after passing through the second reflux condenser and the third-stage vacuum pump in sequence.
More preferably, a vacuum regulating valve is arranged on a conveying pipeline between the first reflux condenser and the first-stage devolatilizer, a vacuum pressure gauge is arranged on the second-stage prepolymerization reactor, and the vacuum regulating valve is in signal linkage with the vacuum pressure gauge for detecting the second-stage prepolymerization reactor.
More preferably, the second and third stage vacuum pumps adopt roots vacuum fans, the first stage vacuum pump can adopt a venturi ejector or a liquid ring vacuum pump, and the circulating liquid containing styrene is used as power fluid of the venturi ejector or sealing circulating liquid of the liquid ring vacuum pump.
The first stage vacuum degree of the production system is controlled below 80mmHg, and the second stage vacuum degree is controlled below 16 mmHg. The outlet pipeline of the second-stage devolatilizer is connected with the inlet of the third-stage vacuum pump through the reflux condenser, so that the gas flow and the temperature entering the third-stage vacuum pump can be reduced, the load of the third-stage vacuum pump is lightened, the service life of equipment is prolonged, and the production stability is ensured.
The vacuum degree of the first-stage devolatilization device and the vacuum degree of the second-stage devolatilization device are respectively controlled below 16mmHg and below 4 mmHg. The polymerized polymer solution is pumped to a devolatilization preheater for preheating and then enters a devolatilization device, polymer materials are flashed through two devolatilization devices with different vacuum degrees, unpolymerized styrene monomers and volatile solvents are removed, residual monomers in the polymer are controlled to be below 800ppm, and evaporated volatile matters are condensed, recovered and proportionally sent to a prepolymerization reactor for reuse.
Preferably, the first-stage prepolymerization reactor and the second-stage prepolymerization reactor are both continuous stirred tank type full mixed flow reactors; the continuous stirring kettle type full mixing flow reactor is provided with a stirrer, the stirrer comprises a stirring power assembly and a stirring shaft which are fixedly connected in a detachable mode, and the stirring shaft is provided with a plurality of combined stirring blades.
More preferably, the continuous stirred tank type full mixed flow reactor is also provided with a side baffle.
More preferably, the upper part of the stirring blade of the first-stage prepolymerization reactor is a turbine, the middle part of the stirring blade is an inclined paddle, and the lower part of the stirring blade is a turbine; and the stirring blades of the second-stage prepolymerization reactor are inclined paddles.
Preferably, each level of prepolymerization reactor and each level of polymerization reactor are provided with real-time detection devices, and each real-time detection device comprises a viscosity detector, a pressure detector, a temperature detector, a liquid level detector, an alarm for sending out an alarm signal and a control system electrically connected with the alarm; the lower sections of the temperature detector and the viscosity detector extend into the reaction liquid; the viscosity detector, the pressure detector, the temperature detector and the liquid level detector are respectively electrically connected with the control system.
The present invention provides a production system, which is obtained by a great deal of research and study by the inventor, wherein the production system is respectively provided with a sol tank and an ultrafine powder mixing tank, the sol tank and the ultrafine powder mixing tank are connected with a prepolymerization reactor through a metering delivery pump, the two stages of prepolymerization reactors are arranged in series, so that a prepared new feed liquid and a circulating liquid from a circulating and vacuum system are preheated in proportion and then are sent into the prepolymerization reactor for polymerization, before the first stage of prepolymerization reactor is accurately controlled at a phase transition point, the grafting rate of rubber molecules reaches a limit as high as possible, the particle size distribution of rubber particles is controlled in the second stage of prepolymerization reactor, along with the reaction, the rubber is separated from a continuous phase under the continuous shearing of a stirrer to form colloidal particles, and a part of styrene is grafted on the rubber to form a polystyrene chain connected on the rubber chain. Then the reaction product passes through a first-stage prepolymerization reactor and a second-stage prepolymerization reactor to reach a preset conversion rate, reinforced modified superfine powder solution is added into the reactors to further carry out in-situ polymerization modification, and finally the material in the first-stage reactor is sent to a subsequent devolatilization section.
The impact strength of the cantilever beam of the medium-impact polystyrene resin prepared by the invention is not lower than 60J/m. The invention can fully play the role of toughening rubber while greatly saving the use amount of the rubber, properly improve the strength and rigidity of the product, obviously improve the processing fluidity of the product and improve the processing efficiency.
Compared with the prior art, the invention has the following beneficial effects:
1. the production system of the medium impact polystyrene resin fills up the domestic blank, keeps or improves the strength, rigidity and fluidity of the product to the maximum extent, has good glossiness, can meet the requirements of users on medium impact products, is easy to carry out large-scale continuous production, and has obvious economic benefit and environmental benefit.
2. According to the characteristics of the medium impact resistant product, the continuous bulk polymerization process is strictly controlled by adopting a four-stage segmented polymerization system, the polymerization speed and the grafting rate can be effectively controlled, the optimal crosslinking density is easily achieved, the rubber can form a stable sea-island structure in PS, and the comprehensive mechanical properties of the product such as impact strength, tensile strength, bending strength and the like can be obviously improved.
3. The volatile components evaporated by the invention are condensed, recovered and sent into the prepolymerization reactor in proportion for reuse, thereby meeting the use requirements and reducing the cost, and being beneficial to safety, environmental protection and cost reduction.
4. The invention adopts the sol tank and the superfine powder batching tank to feed in two stages, which not only can obviously improve the processing fluidity of products, but also can keep the rigidity through the reinforcing effect of the superfine powder material on the basis of improving the fluidity, and can keep or improve the strength of the material to the maximum extent while obtaining the optimal glossiness and fluidity, thereby expanding the application of the polystyrene resin in the fields of household appliances, electronic office equipment shells, toy stationery, electronic equipment, food packaging and the like.
Drawings
FIG. 1 is a schematic structural diagram of the present invention.
FIG. 2 is a schematic connection diagram of the intelligent temperature control system for heat transfer oil.
Wherein, 7 is a third-stage vacuum pump; 8 is a secondary vacuum pump; 9, a granulator; 10 is a dust removing and granule finishing device; 11 is an ultrafine powder batching tank; 12 is a superfine powder feeding tank; 21 is a sol tank; 22 is a mixed feeding tank; 23 is an initiator feeding device; 31 is a first-stage prepolymerization reactor; 32 is a second-stage prepolymerization reactor; 41 is a first-stage polymerization reactor; 42 is a second stage polymerization reactor; 43 is a third stage polymerization reactor; 44 is a fourth stage polymerization reactor; 51 is a prepolymerization preheater; 52 is a first reflux condenser; 53 is a devolatilization preheater; 54 is a second reflux condenser; 55 is a circulating condenser; 61 is a first-stage devolatilizer; 62 is a second-stage devolatilizer; 63 is a collecting tank; 801 is a heat conductive hot oil storage tank; 802 is a cold heat conducting oil storage tank; 803 is a hot oil furnace heater; 804 is a heat-conducting oil cooler; 805 is a reactor cylinder; 806 is a plug flow agitator; 807 is a heat transfer oil transfer pump; 808 is a control valve; 101 is a metering conveying pump of an ultrafine powder batching tank; 102 is a metering delivery pump of a superfine powder feeding tank; 201 is a metering delivery pump of a sol tank; 202 is a mixed feed tank metering delivery pump; 301 is a metering transfer pump of a first-stage prepolymerization reactor; 302 is a second-stage prepolymerization reactor metering delivery pump; 401 is a first-stage polymerization reactor metering delivery pump; 402 is a second stage polymerization reactor metering transfer pump; 403 is a metering delivery pump of the third stage polymerization reactor; 404 is a fourth stage polymerization reactor metering transfer pump; 601 is a first-stage devolatilizer metering delivery pump; 602 is a second stage devolatilizer metering delivery pump; 603 is a collection tank metering delivery pump.
Detailed Description
The invention is further described below with reference to the figures and the specific examples. The following examples are preferred embodiments of the present invention, but are not intended to limit the scope of the present invention in any manner. The present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are intended to be included in the scope of the present invention.
Example 1 production System of Medium impact polystyrene resin
As shown in fig. 1, a medium impact polystyrene resin production system comprises a sol tank 21, a mixed feed tank 22, an ultrafine powder batching tank 11, an ultrafine powder feed tank 12, a prepolymerization preheater 51, a first-stage prepolymerization reactor 31, a second-stage prepolymerization reactor 32, a first-stage polymerization reactor 41, a second-stage polymerization reactor 42, a third-stage polymerization reactor 43, a fourth-stage polymerization reactor 44, a devolatilization preheater 53, a first-stage devolatilization device 61, a second-stage devolatilization device 62, a circulating condenser 55, a collection tank 63 and a pelletizer 9; the sol tank 21, the mixed feed tank 22, the ultrafine powder blending tank 11, the ultrafine powder feed tank 12, the first-stage prepolymerization reactor 31, the second-stage prepolymerization reactor 32, the multistage polymerization reactor, the first-stage devolatilization device 61, the second-stage devolatilization device 62 and the collection tank 63 are respectively and independently provided with a metering delivery pump, the device comprises a sol tank metering and conveying pump 201, a mixed feeding tank metering and conveying pump 202, an ultrafine powder batching tank metering and conveying pump 101, an ultrafine powder feeding tank metering and conveying pump 102, a first-stage prepolymerization reactor metering and conveying pump 301, a second-stage prepolymerization reactor metering and conveying pump 302, a first-stage polymerization reactor metering and conveying pump 401, a second-stage polymerization reactor metering and conveying pump 402, a third-stage polymerization reactor metering and conveying pump 403, a fourth-stage polymerization reactor metering and conveying pump 404, a first-stage devolatilization device metering and conveying pump 601, a second-stage devolatilization device metering and conveying pump 602 and a collecting tank metering and conveying pump 603.
The sol tank 21, the mixed feeding tank 22, the first-stage prepolymerization reactor 31, the second-stage prepolymerization reactor 32, the first-stage polymerization reactor 41, the second-stage polymerization reactor 42, the third-stage polymerization reactor 43, the fourth-stage polymerization reactor 44, the first-stage devolatilization device 61, the second-stage devolatilization device 62 and the granulator 9 are sequentially connected in series, and the ultrafine powder batching tank 11 is connected with the ultrafine powder feeding tank 12 in series and then connected with the inlet of the first-stage polymerization reactor 41; the pre-polymerization preheater 51 is disposed on the piping between the mixed feed tank 22 and the first-stage pre-polymerization reactor 31; the devolatilization preheater 53 is disposed on the piping between the fourth-stage polymerization reactor 44 and the first-stage devolatilizer 61; the upper parts of the ends of the first-stage devolatilizer 61 and the second-stage devolatilizer 62 are connected in series and then connected to the circulating condenser 55 through a transfer line, the collection tank 63 is connected to the bottom of the circulating condenser 55, and the outlet at the bottom of the collection tank 63 is connected to the inlet of the prepolymerization preheater 51.
The transfer piping of the devolatilizer and the recycle condenser 55 is provided with a tertiary vacuum pump 7, and the vacuum degrees of the primary devolatilizer 61 and the secondary devolatilizer 62 are controlled to be 16mmHg or less and 4mmHg or less, respectively, by a vacuum system. The polymerized polymer solution is pumped to a devolatilization preheater 53 to be preheated and then enters a devolatilizer, polymer materials are flashed through two devolatilizers with different vacuum degrees, unpolymerized styrene monomers and volatile solvents are removed, residual monomers in the polymer are controlled below 800ppm, and evaporated volatile matters are condensed, recovered and proportionally sent to a prepolymerization reactor for reuse.
This well anti polystyrene resin production system still is equipped with initiator feed arrangement 23, and this initiator feed arrangement 23 sets up at first order prepolymerization reactor 31 upper end top, and convenient accurate initiator of adding and accurate control reaction process.
The production system of the medium impact polystyrene resin is also provided with a dust removal and granule stabilization device 10 matched with the granulator 9. The dedusting and granulating device 10 can separate and collect the fine dust after the original material granulation, fully utilize the existing equipment, improve the utilization rate of the raw materials and reduce the consumption.
The piston flow stirrer 806 is arranged in each stage of polymerization reactor and comprises a motor, a stirring paddle, a stirring shaft and a shaft end baffle plate, and has the functions of removing reaction heat generated by polymerization reaction in time, accurately controlling the temperature of the polymerization reactor and controlling the polymerization reaction to be stably carried out, so that the required conversion rate is better achieved. The polishing degree Ra of the accessories such as the inner wall of the cylinder body of the plug flow reactor 806, the outer wall of the inner coil pipe, the stirring shaft, the end cover and the like which are in direct contact with the polymerization materials is less than 0.5 mu m, so that the materials are prevented from accumulating at the accessories, and the heat transfer effect is influenced. The length-diameter ratio of the plug flow reactor is 5: 1. too small a length-diameter ratio is not favorable for forming plug flow, and too large an effective volume of the reactor is small, so that the reaction efficiency is influenced.
The first-stage prepolymerization reactor 31 and the second-stage prepolymerization reactor 32 are both continuous stirred tank type full mixing flow reactors; the continuous stirring kettle type full mixing flow reactor is provided with a stirrer, the stirrer comprises a stirring power assembly and a stirring shaft which are fixedly connected in a detachable mode, and the stirring shaft is provided with a plurality of combined stirring blades. The continuous stirred tank type full-mixing flow reactor is also provided with a side baffle.
Each level of prepolymerization reactor and polymerization reactor is provided with an outer jacket for introducing heat-conducting oil, and the outer jacket is provided with a heat-conducting oil inlet and a heat-conducting oil outlet; the inner coil pipes which can be controlled in a sectional way are arranged in each stage of prepolymerization reactor and polymerization reactor, and each inner coil pipe is composed of a multi-stage single-layer coil pipe or a multi-stage double-layer coil pipe. The outer jacket is located outside the reactor cylinder 805, the inner coil is located inside the reactor cylinder 805, and heat exchange is carried out through contact between the wall of the inner coil and the polymer to carry away the reaction heat of the materials.
The inner walls of each prepolymerization reactor and each polymerization reactor are provided with real-time detection devices, and each real-time detection device comprises a viscosity detector, a pressure detector, a temperature detector, a liquid level detector, an alarm for sending an alarm signal and a control system electrically connected with the alarm; the lower sections of the temperature detector and the viscosity detector extend into the reaction liquid; the viscosity detector, the pressure detector, the temperature detector and the liquid level detector are respectively electrically connected with the control system.
Embodiment 2 moderate-impact polystyrene resin production system
As a further modification to embodiment 1, the production system of this embodiment further includes a three-stage vacuum system.
The three-stage vacuum system comprises a primary vacuum pump, a secondary vacuum pump 8 and a tertiary vacuum pump 7; the third-stage vacuum pump 7 is arranged on a conveying pipeline of the devolatilizer and the circulating condenser 55; the top outlet pipeline of the second-stage prepolymerization reactor 32 is connected in parallel with the top outlet pipeline of the first-stage devolatilizer 61 through a first reflux condenser 52, and then is connected with a second-stage vacuum pump 8 through a circulating condenser 55 and then is connected with a first-stage vacuum pump; an outlet pipeline of the second-stage devolatilizer 62 is connected with the circulating condenser 55 after passing through the second reflux condenser 54 and the third-stage vacuum pump 7 in sequence; a vacuum regulating valve is arranged on a conveying pipeline between the first reflux condenser 52 and the first-stage devolatilizer 61, a vacuum pressure gauge is arranged on the second-stage prepolymerization reactor 32, and the vacuum regulating valve is linked with the vacuum pressure gauge for detecting the second-stage prepolymerization reactor 32 through signals.
The second and third vacuum systems adopt Roots vacuum blower, the first vacuum system can adopt Venturi ejector or liquid ring vacuum pump, and the circulating liquid containing styrene is used as Venturi ejector power fluid or liquid ring vacuum pump sealing circulating liquid.
The first stage vacuum degree of the production system is controlled below 80mmHg, and the second stage vacuum degree is controlled below 16 mmHg. The outlet pipeline of the second-stage devolatilizer 62 is connected to the inlet of the third-stage vacuum pump 7 through the second reflux condenser 54, so that the gas flow and temperature entering the third-stage vacuum pump 7 can be reduced, the load of the third-stage vacuum pump 7 can be reduced, the service life of the equipment can be prolonged, and the stable production can be ensured.
Embodiment 3 production system of medium impact polystyrene resin
As shown in fig. 2, as a further modification to embodiment 1, the production system of this embodiment further includes a total heat transfer oil system.
The total heat conduction oil system comprises a heat conduction oil circulation system and a heat conduction oil intelligent temperature control system. The heat-conducting oil intelligent temperature control system is formed by mutually connecting a heat-conducting oil pipeline with an inner coil pipe and an outer jacket of the reactor to form a heat-conducting oil circulating system. Under normal conditions, the temperature of the polymerization reactor is controlled by the circulation of heat conducting oil of the inner coil pipe and the outer jacket, reaction heat generated by polymerization reaction is removed in time, and when necessary, the temperature of materials in the polymerization reactor can be rapidly cooled by cold heat conducting oil.
The heat conduction oil intelligent temperature control system is formed by sequentially connecting a heat conduction oil storage tank 801, a cold heat conduction oil storage tank 802, a hot oil furnace heater 803 and a heat conduction oil cooler 804 to form a cycle.
The total heat conduction oil system provides heat conduction hot oil with the temperature not more than 280 ℃ and cold heat conduction oil with the temperature not more than 90 ℃, the heat conduction hot oil and the cold heat conduction oil are supplied to the polymerization system and the devolatilization system through the conveying pipeline for use, and the heat exchange with the materials is carried out and then the heat exchange returns to the total heat conduction oil system. In addition, a heat conducting oil delivery pump 807 and a control valve 808 are arranged on a circulating pipeline of the heat conducting oil intelligent temperature control system, and temperature controllers are arranged on the hot oil furnace heater 803 and the heat conducting oil cooler 804. The devolatilization preheater 53, the first-stage devolatilizer 61 and the second-stage devolatilizer 62 directly use hot oil from a total heat-conducting oil system to heat materials of the devolatilizers, and simultaneously keep the temperatures of the first-stage devolatilizer 61 and the second-stage devolatilizer 62, so that the devolatilization temperature is ensured to completely remove unreacted styrene monomers and other volatile matters, and the quality of products is ensured.
The heat-conducting oil which takes away the heat of polymerization reaction from the polymerization reactor can be used as the oil supply of the pre-polymerization preheater, the medium-temperature oil from the polymerization reactor returns to the heat-conducting oil which can enter the heat-conducting oil circulation system of the pre-polymerization preheater with the heat-conducting oil of the heat-conducting oil supply pipeline through the control valve, and the required temperature for preheating the styrene is provided. Under the normal operation condition, the energy consumption of production can be saved by preheating the styrene feed liquid by utilizing the polymerization heat of the polymerization reactor. The temperature of the polymer in the polymerization reactor is controlled by temperature controllers which control the supply control valves of heat conducting oil and cold conducting oil from the total heat conducting oil system, the control valves put the required amount of heat conducting oil or cold conducting oil into the heat conducting oil circulating system, and the polymerization reactor circularly adds cold conducting oil through an inner coil and an outer jacket in the polymerization reactor to remove reaction heat so as to keep the temperature set by the polymerization reactor.
Claims (8)
1. A production system of medium impact polystyrene resin is characterized by comprising a sol tank (21), a mixed feeding tank (22), an ultrafine powder mixing tank (11), an ultrafine powder feeding tank (12), a prepolymerization preheater (51), a first-stage prepolymerization reactor (31), a second-stage prepolymerization reactor (32), a multi-stage polymerization reactor, a devolatilization preheater (53), a first-stage devolatilization device (61), a second-stage devolatilization device (62), a third-stage vacuum pump (7), a circulating condenser (55), a collecting tank (63) and a granulator (9), the sol tank (21), the mixed feeding tank (22), the superfine powder batching tank (11), the superfine powder feeding tank (12), the first-stage prepolymerization reactor (31), the second-stage prepolymerization reactor (32), the multistage polymerization reactor, the first-stage devolatilization device (61), the second-stage devolatilization device (62) and the collecting tank (63) are respectively and independently provided with a metering conveying pump; the sol tank (21), the mixed feeding tank (22), the first-stage prepolymerization reactor (31), the second-stage prepolymerization reactor (32), the multistage polymerization reactor, the first-stage devolatilization device (61), the second-stage devolatilization device (62) and the granulator (9) are sequentially connected in series, and the ultrafine powder mixing tank (11) is connected with the ultrafine powder feeding tank (12) in series and then connected with an inlet of the first-stage polymerization reactor of the multistage polymerization reactor; the pre-polymerization preheater (51) is arranged on a pipeline between the mixed feeding tank (22) and the first-stage pre-polymerization reactor (31); the devolatilization preheater (53) is arranged on a pipeline between the last-stage polymerization reactor and the first-stage devolatilization reactor (61) of the multi-stage polymerization reactors; in addition, the upper parts of the end parts of the first-stage devolatilizer (61) and the second-stage devolatilizer (62) are connected in series through a conveying pipeline and are connected with a circulating condenser (55), a collecting tank (63) is connected to the bottom of the circulating condenser (55), the outlet at the bottom of the collecting tank (63) is connected with the inlet of a prepolymerization preheater (51), and a third-stage vacuum pump (7) is arranged on the conveying pipelines of the devolatilizer and the circulating condenser (55);
the production system of the medium impact polystyrene resin also comprises a total heat conducting oil system and a three-level vacuum system;
the system comprises a total heat conduction oil system, a heat conduction oil circulation system, a heat conduction oil intelligent temperature control system and a heat conduction oil control system, wherein the heat conduction oil intelligent temperature control system is connected with inner coil pipes and outer jackets of all levels of prepolymerization reactors and polymerization reactors by heat conduction oil pipelines to form the heat conduction oil circulation system;
the three-stage vacuum system comprises a primary vacuum pump, a secondary vacuum pump (8) and a tertiary vacuum pump (7); the top outlet pipeline of the second-stage prepolymerization reactor (32) is connected in parallel with the top outlet pipelines of the first-stage devolatilization device (61) and the second-stage devolatilization device (62) through a first reflux condenser (52), and then is connected with a first-stage vacuum pump after being connected with a second-stage vacuum pump (8) through a circulating condenser (55); a second reflux condenser (54) and a third-stage vacuum pump (7) are arranged on a connecting pipeline of an outlet pipeline of the second-stage devolatilizer (62) and the circulating condenser (55).
2. The production system according to claim 1, wherein the multistage polymerization reactor consists of four stages of plug flow reactors connected in series one after the other.
3. The production system of claim 1, wherein each of the prepolymerization reactor and the polymerization reactor is internally provided with an inner coil pipe which can be controlled in a sectional manner, and externally provided with an outer jacket, and the outer jacket is provided with a heat-conducting oil inlet and a heat-conducting oil outlet.
4. The production system of claim 1, wherein the heat-conducting oil intelligent temperature control system is formed by sequentially connecting a heat-conducting hot oil storage tank (801), a cold-conducting oil storage tank (802), a hot oil furnace heater (803) and a heat-conducting oil cooler (804) to form a cycle.
5. The production system according to claim 4, wherein a heat-conducting oil delivery pump (807) and a control valve (808) are arranged on the circulation pipeline of the heat-conducting oil intelligent temperature control system; and temperature controllers are arranged on the hot oil furnace heater (803) and the heat conducting oil cooler (804).
6. The production system according to claim 1, wherein a first reflux condenser (52) is provided on the second stage prepolymerization reactor (32).
7. The production system according to claim 1, wherein the first stage prepolymerization reactor (31) and the second stage prepolymerization reactor (32) are both continuous stirred tank full mixed flow reactors; the continuous stirring kettle type full mixing flow reactor is provided with a stirrer, the stirrer comprises a stirring power assembly and a stirring shaft which are fixedly connected in a detachable mode, and the stirring shaft is provided with a plurality of combined stirring blades.
8. The production system according to claim 1, wherein each of the prepolymerization reactor and the polymerization reactor is provided with a real-time detection device, and the real-time detection devices comprise a viscosity detector, a pressure detector, a temperature detector, a liquid level detector, an alarm for sending an alarm signal and a control system electrically connected with the alarm; the lower sections of the temperature detector and the viscosity detector extend into the reaction liquid; the viscosity detector, the pressure detector, the temperature detector and the liquid level detector are respectively electrically connected with the control system.
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| CN112694571A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Elastomer modified styrene polymer and preparation method and preparation device thereof |
| CN112724296A (en) * | 2020-12-28 | 2021-04-30 | 江苏可立特工程设计研究有限公司 | Transparent polystyrene with capacity of more than 5 ten thousand tons and production equipment and process thereof |
| CN112661910A (en) * | 2020-12-28 | 2021-04-16 | 江苏可立特工程设计研究有限公司 | Impact-resistant polystyrene with capacity of more than 5 ten thousand tons and equipment and production process thereof |
| CN114685721A (en) * | 2022-04-18 | 2022-07-01 | 北京鑫美格工程设计有限公司 | Device and method for preparing ABS |
| CN115960286B (en) * | 2022-12-23 | 2023-11-03 | 常州瑞华化工工程技术股份有限公司 | Control system and control method for reaction sampling of expanded polystyrene |
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| CN102675550A (en) * | 2012-05-10 | 2012-09-19 | 华东理工大学 | High-impact-resistance polystyrene polymer and preparation method thereof |
| CN104558430A (en) * | 2015-01-27 | 2015-04-29 | 北方华锦化学工业集团有限公司 | Method of preparing mass ABS (acrylonitrile-butadiene-styrene) resin with high impact resistance |
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| JPH07138329A (en) * | 1993-11-19 | 1995-05-30 | Daicel Chem Ind Ltd | Production of high-impact styrenic resin |
| CN102675550A (en) * | 2012-05-10 | 2012-09-19 | 华东理工大学 | High-impact-resistance polystyrene polymer and preparation method thereof |
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