CN104072643B - The method containing intermingle with polymer desolvation - Google Patents
The method containing intermingle with polymer desolvation Download PDFInfo
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Abstract
The invention discloses a kind of method containing intermingle with polymer desolvation, the method be by contain intermingle with polymer be heated to 110～130 DEG C carry out flash distillation after, pumping into steam temperature is 96～100 DEG C, pressure be 0.05～0.09MPa condensing field I in desolvation；Again the glue granule obtained after desolvation in condensing field I and hot water being pumped into steam temperature is 98～102 DEG C, pressure be 0～0.09MPa condensing field II in be condensed；After having condensed, it is dried；The method low energy consumption, low material consumption, low cost, can effectively remove the solvent in polymer, can extensive industrial applications.
Description
Technical field
The present invention relates to the method containing intermingle with polymer desolvation, particularly lithium series of polymer and the method for depriving solvent for cis-polybutadiene, belongs to macromolecule technical field of purification.
Background technology
Polymerisation in solution is a kind of important synthetic method during Polymer Synthesizing, monomer and initiator is dissolved in appropriate solvent, the polyreaction carried out under solution state.In polymerisation in solution device, separation and the recycling of solvent are important chemical units, are divided into elutriation method and two kinds of methods of dry method devolatilization.
Elutriation method coacervation process is under mechanical stirring, make glue be droplet distribution in the hot water, it is passed directly into steam, the latent heat released by some vapor condensation carrys out heat hot water, heat passes to glue by hot water, enter the initial stage of hot water at glue, owing to solvent is high, be therefore the constant speed coacervation process of a large amount of solvents controlled by boil-off rate and rate of heat transfer；In the later stage, owing to being vaporized of a large amount of free solvent steams and gradually concentrate so that forming solid particle, the solvent of polymeric inner is to external diffusion, diffusion velocity the deceleration coacervation process controlled.
Chinese Patent Application No. 200910197591.5 describes a kind of method of depriving solvent for cis-polybutadiene, comprised the following steps by employing: a) material I containing rubber glue and hot water injects from the top of the first condensing field, aqueous and solvent material II is discharged from the top of the first condensing field, discharging material III from the overflow pipe of the first condensing field sidepiece, wherein the flow of material III is by tank level control system control；B) logistics III gas-phase space position from the second condensing field enters, and after aqueous and solvent material is extracted out by vaccum-pumping equipment, together enters bottom the first condensing field with supplementary live steam；The logistics containing butadiene rubber after being condensed bottom second condensing field；C), after aqueous and solvent logistics II is separated, described solvent is obtained.The method optimum be solvent naphtha consumption be 50kg/ ton rubber, steam consumption is 1.3 ton/ton rubber, solvent naphtha consume bigger.
Chinese Patent Application No. 200710159354.0 describes the condensing method of a kind of solution polymerized rubber, it is to make the energy with steam, using superheated water as separating medium, glue and 115-130 DEG C of superheated water is allowed to be sufficiently mixed the non-homogeneous mixture obtaining glue-hot water, then during the condensing field of 93-100 DEG C of hot water is injected in injection, under glue continues to stir in condensing field, the control time of staying is 40～50 minutes, i.e. completes elutriation method coacervation process.The method water and glue mixing, and long in the condensing field time of staying, steam consumption is bigger.
Summary of the invention
When the present invention is directed to prior art contain intermingle with polymer except solvent, energy consumption is big, solvent naphtha consumes the defect big, cost is high, purpose is to provide a kind of and has the method containing intermingle with polymer desolvation that low energy consumption, low material consumption, low cost, desolvation are effective simultaneously, the method is particularly well-suited to lithium series of polymer and depriving solvent for cis-polybutadiene, can extensive industrial applications.
The invention provides the method containing intermingle with polymer desolvation, the method be by contain intermingle with polymer be heated to 110～130 DEG C carry out flash distillation after, pumping into steam temperature is 96～100 DEG C, pressure be-0.05～0.09MPa condensing field I in desolvation；Again the glue granule obtained after desolvation in condensing field I and hot water being pumped into steam temperature is 98～102 DEG C, pressure be 0～0.09MPa condensing field II in be condensed；After having condensed, it is dried.
The described desolvation time is 10～30min.
Described pool time is 10～30min.
The solvent removed by flash distillation in the inventive method is accounted for and contains intermingle with 20～60wt% of solvent in polymer.
Described condensing field I adds dry glue quality 0.2～the dispersant of 0.5%.
Described dispersant is one or more in polybasic carboxylic acid sodium, calcium stearate, polybasic carboxylic acid calcium, polybasic carboxylic acid barium, magnesium stearate, barium stearate, enuatrol, magnesium oleate, barium oleate, sodium palmitate, palmitic acid magnesium or palmitic acid barium (dispersant of the present invention is all commercially available conventional reagent).
The present invention contains intermingle with the method for polymer desolvation, it is before glue enters condensing field, by one group of heat exchanger, the temperature of glue is increased to 110～130 DEG C, first flash away the solvent of 20～60wt%, removing the residual solvent of about 98wt% again in condensing field I, remove the solvent of residual in condensing field II, detailed process is as follows:
I), after polymerisation in solution completes, glue passes through one group of heat exchanger, glue is heated to 110～130 DEG C and carries out flash distillation；
II) high temperature glue is squeezed into condensing field I by glue solution pump, and in condensing field I, steam temperature is at 96～100 DEG C, and dispersant addition is the 0.2～0.5% of dry glue quality, and glue is 10～30min in the condensing field I time of staying；
III) by II) sol particle of step gained and hot water squeezes into condensing field II by granule pump, and in condensing field II, steam temperature is 98～102 DEG C, and the time of staying is 10～30min；
IV), after having condensed, sol particle is sent into and is dried post.
The technological difficulties of the present invention and know-why: the energy-saving and cost-reducing theoretical research of elutriation method cohesion proves, the consumption of solvent consumption and steam is the conflict conditioned each other.Domestic each rubber plant existing cohesion mode, it is all that the glue of 60～90 DEG C is pumped in condensing field, glue is become little micelle by the shearing of steam Yu stirring in glue still, the least micelle absorbs heat from the water/vapour mixture of condensing field, in micelle, solvent evaporation is in water/steam, but there is inefficient shortcoming with the process of solvent evaporation in this heat exchange, because the surface temperature of micelle is higher than the inside of micelle, therefore solvent is first from surface evaporation, and micelle surface forms comparatively dense solid layer after losing solvent, after micelle surface forms compacted zone, solvent inside micelle to be evaporated and to must pass through Surface absorption heat, therefore the exchange efficiency of heat is low, solvent is the most smooth from micelle diffusion inside to surface channel simultaneously, the efficiency of solvent evaporation is low；Needing the longer time of staying for the solvent in removing micelle in this case, steam enters the chance of condenser to be increased, and material consumption to be reduced (i.e. reducing the content of the solvent of product) just necessarily increases energy consumption (steam), and vice versa.
For solving this contradiction, effort through inventor is thought deeply and research discovery, before the glue needing cohesion is entered condensing field, by one group of heat exchanger, glue temperature is increased to 110～130 DEG C, first flashes away the solvent of 20～60wt%, solvent relative high pressure and at a temperature of diffuse out from each position of micelle, forming substantial amounts of oil-gas diffusion passage, when being conducive to next step to condense, the solvent within colloid volatilizees；Then the glue of high temperature pumps into temperature is 98 ± 2 DEG C, pressure is in the condensing field of-0.05～0.09MPa, owing to glue temperature is high, until the temperature of micelle just takes heat from condensing field less than its ambient temperature, so shortening the time of heat exchange, the gas channel simultaneously formed when micelle flash distillation adds heat and mass transfer area, and the efficiency of organic gas gasification is high, both having shortened the solvent that pool time in turn ensure that in micelle effectively to be removed, therefore energy consumption declines with material consumption.
Research also finds by the temperature of glue after heat exchanger at 110～130 DEG C of optimums, and temperature is the highest, and the motive force of solvent evaporation is the highest, and solvent consumption is the least；But the too high requirement to heat exchanger of glue temperature is the highest, and the requirement to the corollary equipment such as pipeline, pump is the highest, corresponding equipment investment is the highest；When the flash distillation amount of solvent is maintained at 20～60wt% optimal, the highest by the flash distillation amount of solvent during heat exchanger, due to evaporation is neat solvent, it is only necessary to the heat of vaporization of solvent just can, heat utilization ratio height, steam consumption is the lowest；But solvent flash distillation amount is excessive, the solid content of high temperature glue is high, and the viscosity of glue is big, flow difficulties；In order to ensure the seriality of coacervation process, condensing field II is identical with the time of staying of condensing field I and the retention time is relatively low at 10～30min costs, and glue is short in the time of staying of condensing field, and solvent consumption is the highest, if the time of staying is long, steam consumption is the highest.
Beneficial effects of the present invention: under conditions of the method for the present invention can keep low energy consumption and low material consumption simultaneously, effectively removing contains intermingle with the solvent being polymerized in micelle, with low cost；Especially more preferable to the solvent removal effect being lithium series of polymer and butadiene rubber, can be the most useful industrially.
Accompanying drawing explanation
[Fig. 1] is the inventive method process flow diagram.
Detailed description of the invention
Further illustrate the present invention below in conjunction with cohesion embodiment, but be not to limit the scope of the present invention.
Embodiment is with as a example by lithium series of polymer SBS, and solvent is hexamethylene, and hexamethylene thermal capacitance is 1.68kJ/ (kg DEG C), and hexamethylene enthalpy of vaporization is 4.27 × 102KJ/kg, is 68.95 DEG C with the azeotropic point of water, and its cyclohexane accounts for weight ratio 91.6%.
Embodiment 1
Being polymerized rear glue 70～80 DEG C, by heat exchanger, glue is warming up to 120 DEG C, and the flash distillation amount of solvent is 40wt%, by 35m3/ h flow squeezes into condensing field I, still is dispersant built with polybasic carboxylic acid sodium, enuatrol or the sodium stearate of dry glue quality about 0.4%, stops 20min at condensing field I, then squeezes into condensing field II with granule pump, stopping 20min at condensing field II, micelle sends into post processing dried.Controlling condensing field I temperature is 98 DEG C, and pressure is-0.05～0.09MPa, and controlling condensing field II temperature is 101 DEG C, and pressure is 0～0.09MPa.
Result is: solvent naphtha consumption is 15Kg/ ton rubber, and steam consumption is 2.8 ton/ton rubber.
Embodiment 2
Rising to 130 DEG C by heat exchanger glue temperature, other condition is same as in Example 1.
Result is: solvent naphtha consumption is 13Kg/ ton rubber, and steam consumption is 2.95 ton/ton rubber.
Embodiment 3
Rising to 110 DEG C by heat exchanger glue temperature, other condition is same as in Example 1.
Result is: solvent naphtha consumption is 18Kg/ ton rubber, and steam consumption is 2.7 ton/ton rubber.
Embodiment 4
Micelle is 15min in the time of staying of condensing field I and condensing field II, and other condition is same as in Example 1.
Result is: solvent naphtha consumption is 18Kg/ ton rubber, and steam consumption is 2.5 ton/ton rubber.
Embodiment 5
Micelle is 30min in the time of staying of condensing field I and condensing field II, and other condition is same as in Example 1.
Result is: solvent naphtha consumption is 11Kg/ ton rubber, and steam consumption is 3.4 ton/ton rubber.
Embodiment 6
Glue solvent flash distillation amount when by heat exchanger is 20wt%, and other condition is same as in Example 1.
Result is: solvent naphtha consumption is 20Kg/ ton rubber, and steam consumption is 3.2 ton/ton rubber.
Embodiment 7
Glue solvent flash distillation amount when by heat exchanger is 30wt%, and other condition is same as in Example 1.
Result is: solvent naphtha consumption is 18Kg/ ton rubber, and steam consumption is 3.0 ton/ton rubber.
Embodiment 8
Glue solvent flash distillation amount when by heat exchanger is 50wt%, and other condition is same as in Example 1.
Result is: solvent naphtha consumption is 12Kg/ ton rubber, and steam consumption is 2.6 ton/ton rubber.
Embodiment 9
Glue solvent flash distillation amount when by heat exchanger is 60wt%, and other condition is same as in Example 1.
Result is: solvent naphtha consumption is 10Kg/ ton rubber, and steam consumption is 2.5 ton/ton rubber.
Comparative example 1
Rear glue 70～80 DEG C are polymerized it, by 35m3/ h flow directly squeezes into the first condensing field, stops 30min at the first condensing field, then squeezes into the second condensing field with granule pump, stops 30min at the second condensing field, and micelle sends into post processing dried.Controlling the first condensing field temperature is 98 DEG C, and pressure is-0.05～0.09MPa, and controlling the second condensing field temperature is 101 DEG C, and pressure is 0～0.09MPa.
Result is: solvent naphtha consumption is 84Kg/ ton rubber, and steam consumption is 4.9 ton/ton rubber.
Comparative example 2
Micelle is 45min in the time of staying of the first condensing field and the second condensing field, and other condition is identical with comparative example 1.
Result is: solvent naphtha consumption is 72Kg/ ton rubber, and steam consumption is 6.0 ton/ton rubber.
Comparative example 3
Micelle is 20min in the time of staying of the first condensing field and the second condensing field, and other condition is identical with comparative example 1.
Result is: solvent naphtha consumption is 146Kg/ ton rubber, and steam consumption is 3.8 ton/ton rubber.
Claims (5)
1. the method containing intermingle with polymer desolvation, it is characterised in that polymer will be contained intermingle with and added by heat exchanger
After heat carries out flash distillation to 110～130 DEG C, pumping into steam temperature is 96～100 DEG C, and pressure is-0.05～0.09MPa
Condensing field I in desolvation；Again the glue granule obtained after desolvation in condensing field I and hot water are pumped into water
Vapor (steam) temperature is 98～102 DEG C, pressure be 0～0.09MPa condensing field II in be condensed；After having condensed,
It is dried；
Wherein, the solvent removed by flash distillation is accounted for and contains intermingle with 20～60wt% of solvent in polymer.
2. the method for claim 1, it is characterised in that the described desolvation time is 10～30min.
3. the method for claim 1, it is characterised in that described pool time is 10～30min.
4. the method for claim 1, it is characterised in that add dry glue quality in described condensing field I
0.2～the dispersant of 0.5%.
5. method as claimed in claim 4, it is characterised in that described dispersant is polybasic carboxylic acid sodium, tristearin
Acid calcium, polybasic carboxylic acid calcium, polybasic carboxylic acid barium, magnesium stearate, barium stearate, enuatrol, magnesium oleate, oleic acid
In barium, sodium palmitate, palmitic acid magnesium or palmitic acid barium one or more.
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| CN105777945B (en) * | 2014-12-17 | 2017-06-06 | 中国石油化工股份有限公司 | A kind of method of polyolefin glue cohesion |
| CN104961846B (en) * | 2015-07-03 | 2017-03-08 | 新疆蓝德精细石油化工股份有限公司 | Improve device and its using method of cohesion process rubber oil separating effect |
| CN107987187A (en) * | 2018-01-29 | 2018-05-04 | 山东贝隆杜仲生物工程有限公司 | A kind of eucommia ulmoides refined glue cohesion process |
| CN110144073A (en) * | 2019-05-31 | 2019-08-20 | 益凯新材料有限公司 | A kind of the high speed condensing method and production technology of rubber |
| CN111234058A (en) * | 2020-03-17 | 2020-06-05 | 北京诺维新材科技有限公司 | Method for treating polymer solution |
| CN111793153A (en) * | 2020-06-30 | 2020-10-20 | 北京诺维新材科技有限公司 | Preparation method and preparation device of rubber |
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| CN101235105A (en) * | 2007-12-30 | 2008-08-06 | 中国石油大庆石油化工总厂 | Method for agglomerating solution-polymerized rubber |
| CN102040676A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工股份有限公司 | Method for depriving solvent for cis-polybutadiene |
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| IT1391942B1 (en) * | 2008-11-14 | 2012-02-02 | Polimeri Europa Spa | PROCEDURE FOR OBTAINING AN ELASTOMER IN THE SOLID STAGE STARTING FROM ITS POLYMERIC SOLUTION |
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| CN1214341A (en) * | 1997-10-15 | 1999-04-21 | 北京燕山石油化工公司研究院 | Method for removal of volatile component from polymer solution |
| CN101235105A (en) * | 2007-12-30 | 2008-08-06 | 中国石油大庆石油化工总厂 | Method for agglomerating solution-polymerized rubber |
| CN102040676A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工股份有限公司 | Method for depriving solvent for cis-polybutadiene |
Non-Patent Citations (1)
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