CN102924642B - Apparatus for increasing acrylonitrile conversion rate in styrene-acrylonitrile copolymerization reaction - Google Patents
Apparatus for increasing acrylonitrile conversion rate in styrene-acrylonitrile copolymerization reaction Download PDFInfo
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- CN102924642B CN102924642B CN201210173350.9A CN201210173350A CN102924642B CN 102924642 B CN102924642 B CN 102924642B CN 201210173350 A CN201210173350 A CN 201210173350A CN 102924642 B CN102924642 B CN 102924642B
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Abstract
The present invention relates to a petroleum chemical industry apparatus, especially to an apparatus for increasing an acrylonitrile conversion rate in a styrene-acrylonitrile copolymerization reaction. According to the apparatus, at a late stage of a copolymerization reaction, two reactors connected in series are respectively added with a forced reflux pipeline, part of materials are forced to reflux to the reactor so as to enhance reactant mixing o in the reactor, such that the materials in the reactor are uniformly mixed, an acrylonitrile conversion rate is more than 75% and can reach 80%, production capacity is improved, single line production capacity of the apparatus is increased to 80000 ton/year, production operation is stable, mixing degree of the materials in the reactor is uniform, and the product quality is at the international advanced level. According to the present invention, residual amounts of monomers and solvents are reduced after the reaction, a monomer yield is improved, cost of monomer and solvent recovery is saved, equipment investment cost of the production unit is saved, and operation cost of the apparatus is saved so as to reduce product production cost.
Description
Technical field
The present invention relates to a kind of device of petrochemical complex, particularly a kind of device of acrylonitrile-styrene copolymerized reaction.
Background technology
Acrylonitritrile-styrene resin, also claims SAN or AS, is a kind of by vinyl cyanide and the styrene copolymerized macromolecular compound forming.Acrylonitritrile-styrene resin has thermoplasticity, not easy to change, be not subject to the impact of diluted acid, diluted alkaline, rare alcohol and gasoline, there is good thermotolerance and solvent resistance, for the manufacture of oil resistant mechanical component, meter housing, panel board, cell box, tractor fuel tank, battery cell case, packaging vessel, daily necessities etc., or a kind of main blend composition as production ABS resin.
In suitability for industrialized production implementation process, first-generation emulsion polymerization has been experienced in synthesizing of styrene-acrylonitrile copolymer in industrializing implementation, and the s-generation is hanged newborn polymerization, third generation continuous bulk polymerization method.Described emulsion polymerization is due to complex manufacturing, and cost height has been on the verge of to eliminate.The product poor transparency that described outstanding newborn polymerization is produced, can only be for the ABS resin of base-material blending.It is pure that the styrene-acrylonitrile copolymer that described continuous bulk polymerization method makes has product, and transparency is high, oil resistant, the good feature of chemical resistance, is the synthetic method of styrene-acrylonitrile copolymer the most frequently used in industry.Continuous bulk polymerization method adopts thermal initiation continuous bulk polymerization technology, and take vinylbenzene, vinyl cyanide is monomer, adds a small amount of ethylbenzene and carrys out synthesizing styrene-acrylonitrile copolymer as diluting solvent.
Mass polymerization is produced in styrene-acrylonitrile copolymer technique, and the subject matter of existence is vinyl cyanide low conversion rate.The styrene-acrylonitrile copolymer viscosity generating due to reaction is very large, and when reaction occurred after for some time, reactant mixes inhomogeneous, the contact difficulty between reactant, even if the augmenting response residence time, vinyl cyanide transformation efficiency also can only reach 50%～70%wt.If by strengthening stir speed (S.S.), material in reactor is mixed, can cause breakdown of emulsion, affect quality product.So existing mass polymerization is produced in the technique of styrene-acrylonitrile copolymer, generally adopt the tandem reactor of two small volumes.Nonetheless, second reactor exit, vinyl cyanide transformation efficiency also only can reach 70%wt.
Vinyl cyanide low conversion rate, can cause following adverse consequences: first, National Games cause raw material availability low, poor product quality; Secondly, this can reduce the single line throughput of styrene-acrylonitrile copolymer, and ton product-specific investments increases; In addition, this also can increase in follow-up unreacted monomer and solvent recovery unit, the amount of unreacted monomer and solvent, facility investment and the process cost of increase unreacted monomer and solvent recovery unit.This is urgent problem during styrene-acrylonitrile copolymer is produced.
Summary of the invention
The object of this invention is to provide a kind of device that improves vinyl cyanide transformation efficiency in acrylonitrile-styrene copolymerized reaction and improve product single line throughput.
Technical scheme of the present invention, according to the acrylonitrile-styrene copolymerized reaction later stage, material in reactor viscosity is very large, the feature of the contact difficulty between reactant, after the reactor of two series connection, add respectively a forced refluence pipeline, by partial material forced refluence in reactor, strengthen the mixing of reactant in reactor, can not cause under the condition of breakdown of emulsion, make the interior mixing of materials of reactor even, to improve the transformation efficiency of vinyl cyanide.
A kind of device that improves vinyl cyanide transformation efficiency in styrene-acrylonitrile copolyreaction, reaction mass has vinyl cyanide, vinylbenzene, thinner, molecular weight regulator, thinner is ethylbenzene, molecular weight regulator is lauryl mercaptan, the material ratio of copolyreaction, vinyl cyanide: vinylbenzene: ethylbenzene: lauryl mercaptan=(20%～30%): (50%～70%): (10%～35%): (0～2%), by weight percentage, is expressed as %wt, vinyl cyanide and reaction mass are through 1# reactor feed mouth, enter 1# reactor, temperature of reaction is at 140～160 ℃, reacting kettle inner pressure 0.16～0.3MPa, reaction time is 1.8～2.0 hours, product and unreacted reactant are through 1# reactor discharging pump, a part is sent into 2# reactor, another part is through 1# reactor content refluxing opening, turn back to 1# reactor, reflux ratio is 0.28～0.35, on 1# reactor return wire, be provided with 1# reactor pressure control valve, in 2# reactor feed line, be provided with 1# reactor level control valve, in 1# reactor head, be provided with 1# reactor condenser, the gaseous component volatilizing in 1# reactor, after its condensation, be back in 1# reactor, withdraw from reaction heat, when the transformation efficiency of 1# reactor bottom vinyl cyanide reaches 60%, send into 2# reactor, material enters 2# reactor through 2# reactor feed mouth, 140～160 ℃ of temperature of reaction, reacting kettle inner pressure 0.16～0.3MPa, 1.8～2.0 hours reaction times, reaction product and unreacted reactant, through the 2# of 2# reactor bottom reactor discharging pump, a part is sent into subsequent products centrifugal station, another part is by reflux pipeline, from 2# reactor feed refluxing opening, return to 2# reactor, reflux ratio is 0.28～0.4, on the return wire of 2# reactor, be provided with a 2# reactor pressure control valve, going on the pipeline of centrifugal station, to be provided with 2# reactor level control valve, in 2# reactor head, be provided with a 2# reactor condenser, the gaseous component volatilizing in 2# reactor, after its condensation, be back in 2# reactor, when the vinyl cyanide transformation efficiency of 2# reactor bottom reaches 80%, material in 2# reactor is sent into centrifugal station.
The invention has the advantages that, by reactant forced-flow, strengthen mixing, improve the degree of uniformity of mixing of materials in reactor, and increase the residence time of material in reactor, the transformation efficiency of reactor outlet vinyl cyanide, by 50%～70%wt, is brought up to 75～80%wt.The backflow of liquid, makes the mixing of material in reactor more even, therefore can adopt the reactor that volume is larger, under the prerequisite of transformation efficiency that does not reduce vinyl cyanide, the single line throughput of acrylonitrile-styrene polymkeric substance is improved.Because transformation efficiency has improved 10%～30%wt, after reaction, unreacted monomer and solvent residual content are few.Like this, can reduce the yield of unreacted monomer and solvent, save investment cost and the working cost of this part unit equipment, thus the energy consumption of saving reduce product cost.
Accompanying drawing explanation
Fig. 1 is device general flow chart of the present invention.
Wherein: 1# reactor 1, 1# reactor discharging pump 2, 1# reactor condenser 3, 1# reactor pressure control valve 4, 1# reactor level control valve 5, 1# reactor agitator 6, 1# reactor feed mouth 7, 1# reactor discharge port 8, 1# reactor agitator motor 9, 1# reactor content refluxing opening 10, 2# reactor 11, 2# reactor discharging pump 12, 2# reactor condenser 13, 2# reactor pressure control valve 14, 2# reactor level control valve 15, 2# reactor agitator 16, 2# reactor feed mouth 17, 2# reactor discharge port 18, 2# reactor agitator motor 19, 2# reactor content refluxing opening 20, 1# reactor jacket 21, 2# reactor jacket 22.
Embodiment
Below in conjunction with accompanying drawing 1 and specific embodiment, the present invention is described in detail.
A kind of device of acrylonitrile-styrene copolymerized reaction of two series connection, the material of reaction has vinyl cyanide, vinylbenzene, thinner, molecular weight regulator, thinner is ethylbenzene, molecular weight regulator is lauryl mercaptan, the material ratio of copolyreaction, vinyl cyanide: vinylbenzene: ethylbenzene: lauryl mercaptan=(20%～30%): (50%～70%): (10%～35%): (0～2%), by weight percentage, is expressed as %wt; Vinyl cyanide, vinylbenzene through 1# reactor feed mouth 7, enter 1# reactor 1 respectively, to deep fat in reactor jacket 21, are heated to 110 ℃, enter thermal initiation.Because reaction is heat radiation reaction, the temperature of carrying out with reaction can constantly raise, for preventing implode, start to react rear employing recirculated water and remove heat, to guarantee that temperature of reaction is between 140～160 ℃, by regulating reactor top condenser quantity of reflux to keep reacting kettle inner pressure between 0.16～0.3MPaG, reaction time is 1.8～2.0 hours.Product and unreacted reactant are through 1# reactor discharging pump 2, and a part is sent into 2# reactor 11, and another part, through 1# reactor content refluxing opening 10, turns back to 1# reactor 1, and reflux ratio is 0.28～0.35.On 1# reactor 1 return wire, a 1# reactor pressure control valve 4 is installed, a 1# reactor level control valve 5 is installed on 2# reactor 11 feeding lines.When the pressure of 1# reactor discharging pump 2, in the time of not in setting range, regulate the aperture of 1# reactor pressure control valve 4 on return wire, make pump discharge pressure return to setting range.Now, in 1# reactor 1, liquid level can change accordingly, regulates the aperture of 1# reactor level control valve 5 on 2# reactor 11 feeding lines, makes 1# reactor 1 liquid level return to setting range.At 1# reactor 1 top, be provided with a 1# reactor condenser 3, the gaseous component volatilizing in 1# reactor 1 is back in 1# reactor 1 after its condensation, withdraws from reaction heat.By controlling height and the reaction time of liquid level in 1# reactor 1, control the transformation efficiency of vinyl cyanide in 1# reactor 1.When the transformation efficiency of 1# reactor 1 bottom vinyl cyanide reaches 60%, send into 2# reactor 11.
Material enters 2# reactor 11 through 2# reactor feed mouth 17, to passing into deep fat in reactor jacket 22, is heated to 110 ℃, enters thermal initiation.Because reaction is heat radiation reaction, the temperature of carrying out with reaction can constantly raise, in order to prevent implode, start to react rear employing recirculated water and remove heat, to guarantee that temperature of reaction is between 140～160 ℃, by regulating reactor top condenser quantity of reflux to keep reacting kettle inner pressure between 0.16～0.3MPaG, reaction time is 1.8～2.0 hours.Reaction product and unreacted reactant, through the 2# reactor discharging pump 12 of 2# reactor 11 bottoms, a part is sent into subsequent products centrifugal station, another part is by reflux pipeline, from 2# reactor content refluxing opening 20, return to 2# reactor 11, reflux ratio is 0.28～0.4.At 2# reactor 11, a 2# reactor pressure control valve 14 is installed on return wire, going that a 2# reactor level control valve 15 is installed on the pipeline of centrifugal station.When the pressure of 2# reactor discharging pump 12, in the time of not in setting range, regulate the aperture of 2# reactor pressure control valve 14 on return wire, make pump discharge pressure return to setting range.Now, in 2# reactor 11, liquid level can change accordingly, regulates the aperture of 2# reactor level control valve 15, makes 2# reactor 11 liquid levels return to setting range.At 2# reactor 11 tops, be provided with a 2# reactor condenser 13, the gaseous component volatilizing in 2# reactor 11 is back in 2# reactor 11 after its condensation.By controlling height and the reaction time of liquid level in 2# reactor 11, control the transformation efficiency of vinyl cyanide in 2# reactor 11.When the vinyl cyanide transformation efficiency of 2# reactor 11 bottoms reaches 80%, the material in 2# reactor 11 is sent into centrifugal station.
Specific embodiment below, as shown in table 1:
Certain device of the present invention, after the reactor of two series connection, add respectively a forced refluence pipeline, partial material forced refluence, in reactor, is strengthened to the mixing of reactant in reactor, make the interior mixing of materials of reactor even, the transformation efficiency of vinyl cyanide is more than 75%, reach 80%, its throughput improves
Table 1
The single line throughput of device is brought up to 80,000 tons/year, and production operation is stable, and in reactor, mixing of materials degree is even, and quality product is in the leading level in the world.After reaction of the present invention, monomer and solvent residual content reduce, monomer yield is improved, and the cost of monomer and solvent recuperation is saved, and the facility investment expense of productive unit is saved, the working cost of device is saved, thereby has reduced the production cost of product.
Claims (1)
1. a device that improves vinyl cyanide transformation efficiency in styrene-acrylonitrile copolyreaction, it is characterized in that, the material of reaction has vinyl cyanide, vinylbenzene, thinner, molecular weight regulator, thinner is ethylbenzene, molecular weight regulator is lauryl mercaptan, the material ratio of copolyreaction, vinyl cyanide: vinylbenzene: ethylbenzene: lauryl mercaptan=(20%～30%): (50%～70%): (10%～35%): (0～2%), by weight percentage, sum is 100%, vinyl cyanide and reaction mass are through 1# reactor feed mouth (7), enter 1# reactor (1), temperature of reaction is between 140～160 ℃, reacting kettle inner pressure 0.16～0.3MPa, reaction time is 1.8～2.0 hours, product and unreacted reactant are through 1# reactor discharging pump (2), a part is sent into 2# reactor (11), another part is through 1# reactor content refluxing opening (10), turn back to 1# reactor (1), reflux ratio is 0.28～0.35, on 1# reactor (1) return wire, be provided with 1# reactor pressure control valve (4), on 2# reactor (11) feeding line, be provided with 1# reactor level control valve (5), at 1# reactor (1) top, be provided with 1# reactor condenser (3), the gaseous component volatilizing in 1# reactor (1), after its condensation, be back in 1# reactor (1), withdraw from reaction heat, when the transformation efficiency of 1# reactor (1) bottom vinyl cyanide reaches 60%, send into 2# reactor (11), material enters 2# reactor (11) through 2# reactor feed mouth (17), 140～160 ℃ of temperature of reaction, reacting kettle inner pressure 0.16～0.3MPa, 1.8～2.0 hours reaction times, reaction product and unreacted reactant, through the 2# reactor discharging pump (12) of 2# reactor (11) bottom, a part is sent into subsequent products centrifugal station, and another part is by reflux pipeline, from 2# reactor content refluxing opening (20), return to 2# reactor (11), reflux ratio is 0.28～0.4, on the return wire of 2# reactor (11), be provided with a 2# reactor pressure control valve (14), going on the pipeline of centrifugal station, to be provided with 2# reactor level control valve (15), at 2# reactor (11) top, be provided with a 2# reactor condenser (13), the gaseous component volatilizing in 2# reactor (11), after its condensation, be back in 2# reactor (11), when the vinyl cyanide transformation efficiency of 2# reactor (11) bottom reaches 80%, material in 2# reactor (11) is sent into centrifugal station.
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| CN104628925B (en) * | 2013-11-08 | 2017-10-27 | 中国石油天然气股份有限公司 | A kind of method that two kettles series polymerizations produce SAN resins |
| CN105781954A (en) * | 2016-04-25 | 2016-07-20 | 张家港市华昌新材料科技有限公司 | Propylene pump delivery constant pressure regulating method |
| TWI707876B (en) * | 2019-01-07 | 2020-10-21 | 台灣化學纖維股份有限公司 | Equipment for preparing styrene-acrylonitrile copolymer |
| CN113307903B (en) * | 2021-07-07 | 2022-10-18 | 邢台学院 | Poly (styrene-acrylonitrile) copolymer microsphere and preparation method thereof |
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| CN85101103A (en) * | 1984-03-29 | 1987-01-17 | 钟渊化学工业株式会社 | The preparation method of multipolymer |
| CN85106459A (en) * | 1983-09-21 | 1987-02-18 | 考斯顿技术公司 | Make the method for styrenic-alkenylnitrile copolymers |
| CN1144810A (en) * | 1995-07-03 | 1997-03-12 | Basf公司 | Continuous preparation of polymers and apparatus therefor |
| CN1368983A (en) * | 1998-12-18 | 2002-09-11 | Lg化学株式会社 | Process for preparing acrylonitrile-styrene copolymer |
| CN102086254A (en) * | 2010-04-08 | 2011-06-08 | 上海领智化工科技有限公司 | Method for preparing high impact resistant ACS polymer |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85106459A (en) * | 1983-09-21 | 1987-02-18 | 考斯顿技术公司 | Make the method for styrenic-alkenylnitrile copolymers |
| CN85101103A (en) * | 1984-03-29 | 1987-01-17 | 钟渊化学工业株式会社 | The preparation method of multipolymer |
| CN1144810A (en) * | 1995-07-03 | 1997-03-12 | Basf公司 | Continuous preparation of polymers and apparatus therefor |
| CN1368983A (en) * | 1998-12-18 | 2002-09-11 | Lg化学株式会社 | Process for preparing acrylonitrile-styrene copolymer |
| CN102086254A (en) * | 2010-04-08 | 2011-06-08 | 上海领智化工科技有限公司 | Method for preparing high impact resistant ACS polymer |
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