CN106540472B - The condensing method of rubber polymer condensing field and coacervation device and rubber polymer solution - Google Patents
The condensing method of rubber polymer condensing field and coacervation device and rubber polymer solution Download PDFInfo
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- CN106540472B CN106540472B CN201510607689.9A CN201510607689A CN106540472B CN 106540472 B CN106540472 B CN 106540472B CN 201510607689 A CN201510607689 A CN 201510607689A CN 106540472 B CN106540472 B CN 106540472B
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Abstract
The invention discloses a kind of rubber polymer condensing fields, the condensing field is for the solvent evaporation in rubber polymer solution and removes to obtain the micelle water containing rubber polymer, the condensing field includes: rubber polymer solution feed unit, for the mixture of rubber polymer solution and water to be imported into the condensing field；Steam feed unit, for steam to be imported into the condensing field to contact with the mixture；Water separative unit, for by the partial moisture in the material after the contact from and go out.The present invention also provides the coacervation devices of the rubber polymer solution using above-mentioned condensing field.And the present invention also provides the condensing methods of the rubber polymer solution using above-mentioned coacervation device.When carrying out the cohesion of polymer solution by using condensing field provided by the invention, concentrate is may be implemented in condensing field itself, is extended residence time of the micelle water in condensing field, is enhanced the solvent removal effect of polymer solution.
Description
Technical field
The present invention relates to the condensing methods of rubber polymer condensing field and coacervation device and rubber polymer solution.
Background technique
The production process of common rubber polymer generally includes the units such as polymerized unit, cohesion unit, post-processing.?
In polymerized unit, it is molten that one or more kinds of monomers obtains polymer with generation polymerization reaction under catalyst action in a solvent
Liquid；In cohesion unit, the solvent in the resulting polymer solution of polymerized unit is flashed using steam and water by elutriation method
Separation；The last handling processes such as the aqueous polymers drying that cohesion unit obtains obtain polymeric articles.Elutriation method is solidifying
Poly- process is under mechanical stirring, to be dispersed in water micelle in droplet-like, with steam is passed directly into, is condensed by some vapor
Latent heat is released to heat water, heat is by Water transport to micelle.At this point, the heated portions such as solvent, monomer in droplet-like glue
Gasification, solvent gas take condensing field out of by vapor, achieve the purpose that remove solvent.Rubber after solvent steams is in granular form analysis
Out, it is dispersed in water.
For the coacervation process of the prior art generally using double kettle cohesions or the cohesion of three kettles, more kettle cohesion operations can be improved solvent
The effect of removing.And it is water-cement ratio that another, which influences solvent removal effect and the influence factor of rubber quality, that is, first kettle
The ratio of middle water and glue, water-cement ratio is too small, and it is excessive on the one hand to may cause micelle density, so that micelle collision opportunity be made to increase
It is more, easily form bulk, causes condensing field, pump or line clogging；On the other hand since micelle becomes larger, to the solvent removal in micelle
It is unfavorable.The factor that third influences solvent removal effect is the residence time, and residence time of the material in condensing field is long, and solvent is just
What is removed is cleaner, therefore just uses the residence time for increasing the measures such as concentrate device equipment three kettles of extension in some technologies,
Increase the removal effect of solvent.
CN102382214A discloses a kind of cohesion process of polymerization product production, the invention be by the cohesion of three kettle differential pressures with
The technology that micelle concentrate technology combines, between the second condensing field and third condensing field install concentrate device to micelle water into
Row concentrate forms energy-saving type SBS cohesion new process, and energy conservation can be effectively relieved and lower consumption this to contradiction, it is molten to reach reduction
The purpose of agent consumption and steam consumption.The concentration of the shortcomings that the changing technology third condensing field that has been a concentrate, the effect of concentrate is limited,
In addition newly-increased concentrate device is also needed just to be able to achieve.
Summary of the invention
The purpose of the present invention is be to overcome to need lacking using concentrate device concentrate existing for existing polymer agglomerates technique
It falls into, a kind of rubber polymer condensing field for itself realizing concentrate and coacervation device and rubber polymer solution of capableing of is provided
Condensing method.
To achieve the goals above, the present invention provides a kind of rubber polymer condensing field, and the condensing field is poly- for rubber
Solvent evaporation in polymer solution is removed to obtain the micelle water containing rubber polymer, which includes: rubber polymer
Solution feed unit, for the mixture of rubber polymer solution and water to be imported into the condensing field；Steam feed unit,
For steam to be imported into the condensing field to contact with the mixture；Water separative unit is used for the contact
Part water in material afterwards is separated with the micelle water containing rubber polymer.
The present invention also provides a kind of coacervation device of rubber polymer solution, which includes concatenated 2 or more
Condensing field, wherein the first condensing field be used to contact the mixture of rubber polymer solution and water and steam progress first with
So that solvent evaporation removes, resulting micelle water carries out again after condensing field thereafter is used to contact in previous condensing field
Solvent evaporation removing；Wherein, at least one of condensing field which includes is above-mentioned condensing field.
The present invention also provides a kind of condensing method of rubber polymer solution, this method is connected by 3 above-mentioned condensing fields
Made of carry out in coacervation device, this method comprises:
(1) in the first condensing field, by the mixture of rubber polymer solution and the first water by rubber polymer solution into
Material unit is added and carries out first with the first steam being added by steam feed unit and contacts, and is connect by water separative unit by first
The partial moisture in material after touch from and go out, the second water isolated and separated the first micelle water after the water of part；
(2) in the second condensing field, by the first micelle water be added by rubber polymer solution feed unit and with by
The second steam that steam feed unit is added carries out the second contact, the portion in material after contacting by water separative unit by second
The separation of point water and go out, the third water isolated with separated the second micelle water after the water of part；
(3) in third condensing field, the second micelle water is added by rubber polymer solution feed unit, passes through water
Separative unit by partial moisture from and go out, the 4th water isolated and separated the third micelle water after the water of part.
When carrying out the cohesion of polymer solution by using condensing field provided by the invention, condensing field itself may be implemented to mention
Dense effect, so as to without concentrate device, extend residence time of the micelle water in condensing field, enhancing
The solvent removal effect of polymer solution.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is a kind of coacervation device of the polymer solution of embodiment according to the present invention.
Fig. 2 is a kind of front view of the condensing field of the polymer solution of embodiment according to the present invention.
Fig. 3 is a kind of top view of the condensing field of the polymer solution of embodiment according to the present invention.
Fig. 4 is the coacervation device that the method for comparative example 1 uses.
Description of symbols
1 --- blender；2 --- glue spraying pipe；3 --- the annular feed pipe with steam nozzle；
4 --- skimming baffle；5 --- micelle water outlet；6 --- water outlet；7 --- water inlet；
8 --- steam (vapor) outlet；M1 --- mixer；F1 --- the first condensing field；
F2 --- the second condensing field；F3 --- third condensing field；P1 --- the first micelle water pump；
P2 --- the first water pump；P3 --- the second micelle water pump；P4 --- the second water pump；
P5 --- third micelle water pump；P6 --- third water pump；J1 --- steam jet ejector；
S1 --- hot water；S2 --- rubber polymer solution；S3 --- low-pressure steam；
S4 --- micelle water goes to post-process；S5 --- steam goes condensing recovery；S6 --- steam blowing.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
In the present invention, the residence time refers to process stream in equipment from import to outlet mean time experienced
Between, it is commonly defined as τ (residence time)=V (equipment dischargeable capacity)/Q (equipment importation volume flow).
The present invention provides a kind of rubber polymer condensing field, and the condensing field is for the solvent vapour in rubber polymer solution
Change removing to obtain the micelle water containing rubber polymer, which includes:
Rubber polymer solution feed unit, for the mixture of rubber polymer solution and water to be imported into the cohesion
In kettle；
Steam feed unit, for steam to be imported into the condensing field to contact with the mixture；
Water separative unit, for by the partial moisture in the material after the contact from and go out.
According to the present invention, the rubber polymer solution feed unit can be this field conventionally used for by rubber polymer
The mixture of solution and water imported into the component in the condensing field, such as depicted in figs. 1 and 2, can use and agglomerate
The glue spraying pipe 2 in kettle is stretched on kettle wall, i.e., the described rubber polymer solution feed unit has glue spraying pipe 2, in condensing field
It is stretched in kettle obliquely on wall.When using the form of glue spraying pipe 2 as the rubber polymer solution feed unit, preferably make
It obtains glue spraying pipe 2 to stretch in kettle obliquely, more preferably making the angle of the wall of glue spraying pipe 2 and condensing field is 45-60 degree.
According to the present invention, condensing field provided by the invention and the maximum difference of the condensing field of the prior art are: described solidifying
Poly- kettle is provided with water separative unit so that the partial moisture in the material after the contact from and go out, to have been separated portion
The part water for dividing the micelle water containing rubber polymer of water and separating, to realize in condensing field to micelle water
The purpose of concentrate.Preferably, as shown in Figs. 1-3, the water separative unit is formed by skimming baffle 4, the skimming baffle 4
It is provided with through-hole, and is located at below rubber polymer solution feed unit, the through-hole being provided on the skimming baffle 4 to flow
The partial moisture contained in material after entering the contact of the condensing field lower part from and go out.It is highly preferred that in the separation
Baffle 4 covers and is provided with water outlet 6 on lower condensing field kettle wall, the through-hole separation that is provided with from the skimming baffle 4 and go out
Water is expelled to outside condensing field by water outlet 6.
According to the present invention, the through-hole on the skimming baffle 4 is therefore, described for separating micelle and part water
The size of through-hole on skimming baffle 4 can be selected (can specially pass water through, and micelle is not according to the size of micelle
Can pass through), such as can be 2-10mm.
According to the present invention, the skimming baffle 4 can use a variety of settings, as long as can be realized the effect of above-mentioned concentrate i.e.
Can, such as the edge of the skimming baffle 4 engages with the wall of the condensing field completely, so that the wall of the condensing field and institute
Skimming baffle 4 is stated to surround cavity (cavity refers to the cavity that the part water that contains in the material after the only contact enters, and empty
The outside of chamber is then the channel that condensing field is supplied to micelle water removing solvent), and the water outlet 6 is then located at where the cavity
On the wall of condensing field；Wherein, the side for defining the skimming baffle 4 towards the cavity is the outside of the skimming baffle 4, and
It is the inside of the skimming baffle 4 backwards to the cavity and towards the side of micelle water.
Skimming baffle 4 as water separative unit can be the lesser independent plate of area, in this way can be in the cohesion
More than one cavity surrounded by the wall of skimming baffle 4 and the condensing field (in this case, each cavity is formed at the lower part of kettle
Inside it is both provided with a water outlet), as long as the space of the condensing field left is sufficient to make the micelle water energy after having separated part water
Enough it is discharged by the micelle water outlet 5 of bottom.Preferably, as shown in Figures 2 and 3, the upper edge of the skimming baffle 4 with
The side wall of condensing field engages, and the lower edge of the skimming baffle 4 is engaged with the bottom of condensing field, thus by under the condensing field
Portion isolates the cavity that a circle is surrounded by the side wall of the skimming baffle 4 and condensing field, to accommodate through the skimming baffle 4
Through-hole separates and water out.In this case, the skimming baffle 4 forms a whole face, and with the wall of condensing field surround one it is complete
Whole cavity.Such skimming baffle 4 can form drum structure in condensing field, wherein engage with condensing field side wall upper
The face of edge to drum circumference can be plane, be also possible to inclined surface obliquely, preferably with the inclination as glue spraying pipe 2
Degree, i.e., the described skimming baffle 4 is by the first periphery (face for forming tubbiness i.e. in drum structure) and the second periphery (edge
Engaged with condensing field side wall, another side is along the face that engage with the upper edge of the first periphery) constitute, wherein the first periphery and
The wall surface of the condensing field is parallel, second periphery be one end and the first periphery upper peripheral edge (the first periphery it is upper
Edge) it combines, inclined surface of the other end in conjunction with the wall surface of the condensing field, and the inclined surface has as glue spraying pipe 2
Gradient.Preferably, the ratio of the diameter and condensing field internal diameter that drum structure are formed in condensing field by skimming baffle 4 is 0.4-
0.9:1, it can be understood as the lower edge of skimming baffle 4 engages at the point of the 0.1-0.6 of condensing field internal diameter with bottom.
According to the present invention, when the height of the condensing field is 3000-10000mm, it is preferable that glue spraying pipe 2 is located at height
For (vertical height i.e. from condensing field bottom up) at 1200-2500mm, then the upper edge of skimming baffle 4 is located at glue spraying pipe 2
At the 50-150mm of lower section.
According to the present invention, the size for the cavity that the skimming baffle 4 surrounds can be selected according to the effect of required concentrate
It selects, it is preferable that the 3-20 volume % in the space of condensing field is accounted for by the cavity that the side wall of the skimming baffle 4 and condensing field surrounds.
According to the present invention, the steam feed unit provides steam for condensing field, and using the steam as condensing field in
The heat source of reaction, therefore, there is no particular limitation to steam feed unit by the present invention, and can use this field routine is cohesion
The device of kettle offer steam, it is preferable that the steam feed unit is the annular feed pipe 3 with steam nozzle, and the annular
Inside of the feed pipe 3 around the skimming baffle 4 and the lower edge setting close to skimming baffle 4.Pass through steam feed list in this way
The steam that member provides can not only provide the solvent removal for micelle water, can be also used for purging the upper of the skimming baffle 4
Through-hole prevents blocking and kiss-coating to clear up it.
According to the present invention, the size of the steam nozzle on the annular feed pipe 3 with steam nozzle can be ability
The aperture of steam nozzle in the conventional selection in domain, such as the annular feed pipe 3 with steam nozzle is 2-4mm.
According to the present invention, as shown in Figures 2 and 3, the condensing field can also have the various configurations of this field routine,
Such as with blender 1, micelle water outlet 5 and steam (vapor) outlet 8 (being not shown in Fig. 2 and Fig. 3, have in Fig. 1 but unmarked),
In, the mixture of rubber polymer solution and water is injected into condensing field by glue spraying pipe 2, and (can have in blender 1
Single-layer or multi-layer impeller, such as layer 2-3 impeller) under the stirring that provides dispersion form micelle water, and with the ring with steam nozzle
The steam contact that shape feed pipe 3 sprays, so that solvent gasification is as steam is carried over and passes through steam (vapor) outlet 8 in rubber polymer
Discharge.
The present invention also provides a kind of coacervation device of rubber polymer solution, the coacervation device include concatenated 2 with
On condensing field, wherein the first condensing field F1 is used to first connect the mixture of rubber polymer solution and water and steam progress
Touching so that solvent evaporation removes, condensing field thereafter for resulting micelle water after being contacted in previous condensing field again
Carry out solvent evaporation removing；Wherein, at least one of condensing field which includes is above-mentioned condensing field.
Preferably, which includes concatenated 2-10 condensing fields, and more preferably 2-4 is a, still more preferably
It is 3, more preferably all condensing fields in the coacervation device are condensing field described above.In the coacervation device
Including under 3 concatenated condensing fields, definition agglomerates head kettle for the first condensing field F1, and followed by concatenated condensing field is second solidifying
Poly- kettle F2, concatenated condensing field is third condensing field F3 after following the second condensing field F2 closely, wherein the first condensing field F1 is used
It is contacted in the mixture of rubber polymer solution and water and steam are carried out first, the second condensing field F2 is used for described the
The one resulting micelle water of contact carries out second with steam and contacts.
Preferably, in the first condensing field F1, the second condensing field F2 and third condensing field F3 all above to be retouched
The condensing field stated.It will be appreciated by those skilled in the art that the first condensing field F1, the second condensing field F2 and third condensing field F3
For condensing field described above can according to each kettle it is respective effect and have the characteristics that it is different, but entirety function
Condensing field is essentially identical as described above for energy.
According to the present invention, the first condensing field F1 also referred to as agglomerates first kettle, is mainly used for rubber polymer
The mixture of solution and water carries out first with steam and contacts.Preferably, the coacervation device further includes having mixer M1, by this
Rubber polymer solution and water are mixed the mixture they are made, the mixer M1 and first cohesion by mixture M 1
The rubber polymer solution feed unit (can be glue spraying pipe, the position where glue spraying pipe 2 as shown in Figure 2) of kettle F1 is connected
It is logical, so as to which gained mixture is added in the first condensing field F1 by rubber polymer solution feed unit.
According to the present invention, the micelle water outlet of the first condensing field F1 is (where micelle water outlet as shown in Figure 25
Position) it with the rubber polymer solution feed unit of the second condensing field F2 (can be glue spraying pipe, glue spraying as shown in Figure 2
Position where pipe 2) connection, so that the micelle water of the first condensing field F1 outflow is gathered by the rubber of the second condensing field F2
Polymer solution feed unit enters in the second condensing field F2.Preferably, it is discharged in the micelle of the first condensing field F1
The rubber polymer solution of mouth (position where micelle water outlet 5 as shown in Figure 2) and the second condensing field F2 feed single
It is provided with the first micelle water pump P 1 on the pipeline of member connection, can control described in the inflow of micelle water by the first micelle water pump P 1
The flow of second condensing field F2.
According to the present invention, the micelle water outlet of the second condensing field F2 is (where micelle water outlet as shown in Figure 25
Position) it is connected to the rubber polymer solution feed unit of the third condensing field F3, so that the second condensing field F2 flows out
Micelle water by the third condensing field F3 rubber polymer solution feed unit (can be glue spraying pipe, spray as shown in Figure 2
Position where sebific duct 2) it enters in the third condensing field F3.Preferably, it is discharged in the micelle of the second condensing field F2
The rubber polymer solution of mouth (position where micelle water outlet 5 as shown in Figure 2) and the third condensing field F3 feed single
It is provided with the second micelle water pump P 3 on the pipeline of member connection, can control described in the inflow of micelle water by the second micelle water pump P 3
The flow of third condensing field F3.
In accordance with the present invention it is preferred that the top of the first condensing field F1 further includes water inlet 7, made by the water inlet 7
Obtain water outlet (6 institute of water outlet as shown in Figure 2 by the first condensing field F1, the second condensing field F2 and third condensing field F3
Position) discharge water enter in the first condensing field F1 to recycle.
According to the present invention, in order to enable going out by the first condensing field F1, the second condensing field F2 and third condensing field F3
The water of the mouth of a river (position where water outlet 6 as shown in Figure 2) discharge enters in the first condensing field F1, by described first
The water inlet that the top of the water outlet of condensing field F1, the second condensing field F2 and third condensing field F3 and the first condensing field F1 include
Mouth 7 is connected to, and is respectively excluding water from the water outlet of the first condensing field F1, the second condensing field F2 and third condensing field F3
Pipeline on be provided with the first water pump P 1, the second water pump P 4 and third water pump P 6.
It according to the present invention, further include steam outlet 8 at the top of the second condensing field F2 and third condensing field F3, it is described
Steam outlet 8 is connected to the steam feed device 3 of the first condensing field F1, so that the second condensing field F2 and third
The steam of the top discharge of condensing field F3 is by the steam feed unit of the first condensing field F1 (shown in preferably Fig. 2 and 3
Annular feed pipe 3 with steam nozzle) it enters in the first condensing field F1 to recycle.
Wherein, in order to enable the steam of the top of the second condensing field F2 and third condensing field F3 discharge passes through described the
The steam feed unit of one condensing field F1 enters in the first condensing field F1, the second condensing field F2 and third condensing field
The steam outlet 8 at the top of F3 is connected to the steam feed unit of the first condensing field F1, in order to promote by described
The steam of the top of second condensing field F2 and third condensing field F3 discharge is injected in the first condensing field F1, described second
The steam outlet 8 at the top of condensing field F2 and third condensing field F3 is connected to the steam feed unit of the first condensing field F1
Pipeline on be provided with steam jet ejector, it is especially solidifying in the steam outlet 8 at the top of third condensing field F3 and described first
It is provided with steam jet ejector J1 on the pipeline of the steam feed unit connection of poly- kettle F1, preferably third can be overcome to agglomerate in this way
Kettle F3 operating pressure is lower and is unfavorable for steam and enters the problems in first condensing field F1.
According to the present invention, the top of the first condensing field F1 also includes steam outlet (as shown in figure 1 described second
Position where the steam outlet 8 at the top of condensing field F2 and third condensing field F3), the steam for carrying solvent is discharged.
Preferably, in coacervation device provided by the invention, the steam feed unit can be in normal operation condition
Steam is provided for each condensing field, wherein steam mainly passes through the entrance of the second condensing field bottom, and the steam of the first condensing field is then
The steam returned from two kettles and three kettles, the major function of the steam feed pipe at third condensing field bottom are that purging and cleaning are made
With.
The present invention also provides a kind of condensing method of rubber polymer solution, this method is by 3 above-mentioned condensing field strings
It is carried out in coacervation device made of connection, this method comprises:
(1) in the first condensing field F1, by the mixture of rubber polymer solution and the first water by rubber polymer solution
Feed unit is added and carries out first with the first steam by two kettles and the return of three kettles and contacts, and is connect by water separative unit by first
The partial moisture in material after touch from and go out, the second water isolated and separated the first micelle water after the water of part；
(2) in the second condensing field F2, by the first micelle water be added by rubber polymer solution feed unit and with
Second contact is carried out by the second steam that steam feed unit is added, it will be in the material after the second contact by water separative unit
Partial moisture from and go out, the third water isolated and separated the second micelle water after the water of part；
(3) in third condensing field F3, the second micelle water is added by rubber polymer solution feed unit, is passed through
Water separative unit by partial moisture from and go out, the 4th water isolated and separated the third micelle water after the water of part.
The coacervation device is as described above, and details are not described herein.It will be appreciated by those skilled in the art that described solidifying
The condition setting of poly- device can be configured according to each condition for the coacervation device being outlined above, and the present invention is herein no longer
It repeats.
According to the present invention, wherein each step not only includes the process of respective condensing field removing solvent, also all includes
The process of the part water in material after removing contact in respective condensing field, the concentration of micelle water can be improved in this way, reach
To the purpose of concentrate, the micelle water after such concentrate can obtain the longer residence time when entering subsequent step.Material
After extended residence time in condensing field, solvent removal effect is more preferable, can be remained in micelle to avoid solvent in this way compared with
It mostly and brings post-processing unit into, causes the solvent removal load in subsequent processing units larger, and make a large amount of solvents of removing
It is difficult to recycle.
According to the present invention, the rubber polymer solution can pass through the preparation process of the rubber polymer of this field routine
It obtains, the rubber polymer solution is preferably the random total of conjugated diene homopolymers solution, conjugated diene and vinyl-arene
Block copolymer (such as the styrene-isoprene block polymer, benzene second of copolymer solution and conjugated diene and vinyl-arene
Alkene-butadiene block polymer etc.) one of solution or a variety of.Usually as molten used in such rubber polymer solution
Agent is one of alkane, cycloalkane and aromatic hydrocarbons or a variety of.It is highly preferred that in the rubber polymer solution polymer content
For 5-15 weight %.
According to the present invention, to the mixed proportion of the mixture of the rubber polymer solution S2 and the first water, there is no special
Restriction, can using this field routine ratio mixing, it is preferable that the mixture of the rubber polymer solution and the first water
In, in the unit time, the mass ratio of the first water and rubber polymer solution charging is 2-14:1.First water is hot water S1,
Preferably 70-95 DEG C of hot water.
According to the present invention, the dosage of the mixture and steam is not particularly limited, can be conventional with this field
Dosage, but method of the invention can also have the effect of reducing material consumption and energy consumption, realize that one kind of this effect is preferred
Embodiment is just that the steam by the second condensing field F2 steam being discharged and third condensing field F3 discharge returns to first
In condensing field F1, especially using the steam of the second condensing field F2 discharge and the steam of third condensing field F3 discharge as first
The first whole steam in condensing field F1 use.And in the method for the invention, the micelle water of third condensing field has reached
Enough concentrated effects and heating effect promote molten in polymer solution with sufficiently long residence time and enough heats
Agent further removes, and has been not necessarily to bottom purge steam to remove solvent, and a small amount of steam is only needed to keep off separation
Plate is cleaned or is disturbed the effect of micelle water, that is to say, that method of the invention preferably by substantially all of steam from
Enter in the steam feed unit of second condensing field, the steam of the second condensing field consumption is regarded as condensing method of the invention
Consumed steam total amount, in such cases it is preferred to which the mass flow ratio of ground, the mixture and the second steam is 8-
80:1.In the case where meeting such ratio, the mass flow of the mixture and the second steam can be according to different process scales
It makes appropriate choice, such as the mass flow of the mixture is 10000-150000kg/h, the mass flow of the second steam
For 1000-8300kg/h.
In the case of, according to the invention it is preferred to, the operating condition of the first condensing field F1 includes: that gauge pressure is 0.003-
0.03MPa, temperature are 83-92 DEG C.Wherein, the time of first contact refers to the mixed of rubber polymer solution and the first water
Close object relative retention time, also referred to as residence time in the first condensing field F1, wherein the residence time of first contact can
Think 8-60min, the residence time of first contact is preferably 20-60min.
In accordance with the present invention it is preferred that third water and step that the second water that step (1) is isolated, step (2) are isolated
(3) the 4th water isolated returns in the first condensing field F1, so that the mixture of the polymer solution and the first hot water
It contacts with the first steam progress first and is carried out in the presence of these water.That is, method of the invention further includes by step (1) point
The 4th water that the third water and step (3) that the second water for separating out, step (2) are isolated are isolated is added to where step (1)
In condensing field, to participate in the first contact.It should be understood that the water separated after above-mentioned each contact is all with higher
High-temperature-hot-water Returning utilization can be reduced the consumption of steam in this way by the hot water of temperature, so as to directly benefit as described above
It uses using the steam of the second condensing field F2 discharge and the steam of third condensing field F3 discharge as the first steam.
According to the present invention, by the second water that the step (1) is isolated and separated the first micelle water after the water of part from
The rate of condensing field extraction where it can be to adjust the residence time in step (2), it is preferable that the step (1) point
The second water for separating out and the mass flow ratio for having separated condensing field extraction of the first micelle water after the water of part where it are 1:
7-10.In the case where meeting such ratio, the second water and separated the first micelle water after the water of part that the step (1) is isolated
The mass flow of condensing field extraction where from it can be selected according to different process scales.
According to the present invention, in step (2), second steam provides source by the low-pressure steam S3 of outside setting and provides,
The present invention is not particularly limited this.Under preferable case, the operating condition of the second condensing field F2 includes: that gauge pressure is 0.06-
0.09MPa, temperature are 103-110 DEG C.Wherein, the residence time of second contact can be 15-80min, and described second connects
The residence time of touching is preferably 30-75min.
According to the present invention, by third water that the step (2) is isolated and separated the second micelle water after the water of part from
The rate of condensing field extraction where it can be to adjust the residence time in step (3), it is preferable that the step (2) point
The third water that separates out and the mass flow ratio for having separated condensing field extraction of the second micelle water after the water of part where it are 1:
5-10.In the case where meeting such ratio, third water and separated the second micelle water after the water of part that the step (2) is isolated
The mass flow of condensing field extraction where from it can be selected according to different process scales.
It is as described above, in third condensing field F3, due to have passed through the first and second condensing fields concentrate and with steaming
The contact of vapour, so that can have into the micelle water in third condensing field F3 temperature with higher and higher concentration
There are enough residence times, it can be solidifying using waste heat and third in the case where providing heat without being passed through steam and carrying
The pressure change of poly- kettle further removes the solvent of itself.Certainly, third condensing field F3 also has steam feed unit, but should
The effect that the effect that a small amount of steam that steam feed unit provides mainly plays is purging cleaning, prevents micelle from blocking.According to
The present invention, under preferable case, the operation of the third condensing field F3 includes: that gauge pressure is -0.001MPa to 0.005MPa, and temperature is
93-100℃.Wherein, the residence time of the third condensing field F3 can be 15-80min, the stop of the third condensing field F3
Time is preferably 30-75min.
According to the present invention, by the 4th water that the step (3) is isolated and separated the third micelle water after the water of part from
The rate of condensing field extraction where it can be to adjust the processing speed of entire coacervation process, wherein third micelle water is taken out
It can enter in the post-processing step of this field routine after out, coacervation process can be regarded as completion.Preferably, step (3) separation
The 4th water out and the mass flow ratio for having separated condensing field extraction of the third micelle water after the water of part where it are 1:5-
15.In the case where meeting such ratio, the 4th water that the step (3) is isolated and separated the third micelle water after the water of part from
The mass flow of condensing field extraction where it can be selected according to different process scales.
According to the present invention, the first condensing field F1, the second condensing field F2 and third condensing field F3 also have agitating device,
So that the material in three condensing fields can also carry out the removing of solvent under agitation, stirred in the first condensing field F1
The rate mixed can turn/min for 50-150, and the rate stirred in the second condensing field F2 can turn/min, institute for 50-120
/ min can be turned for 50-120 by stating the rate stirred in third condensing field F3.
The concentrate to polymer solution can be realized with itself by using the coacervation device of condensing field of the invention, so as to
The residence time for extending micelle water with more Shangdi enhances the removing of solvent, reduces material consumption and energy consumption.In environmental protection,
Implementation of the invention is also reduced since dissolvent residual enters the pollution caused by post-processing unit to environment.Cohesion of the invention
Device has longer controllability, the concentration of each condensing field micelle water can be adjusted and controlled according to process requirement, finally
Realize the adjusting to the residence time of micelle water in condensing field, therefore device operating flexibility is larger.In addition, condensing field of the invention
Self-cleaning function may be implemented, steam blowing, periodic cleaning can be used by the design of a circle steam jet in skimming baffle
Baffle, with prevent blocking, wall built-up situations such as generation.
In a preferred embodiment of the invention, relative to three traditional kettle cohesion process, by side of the invention
When method and device are applied to the agglomeration process of synthetic rubber such as SBS, SIS, the present processes can coagulate micelle water second
The extended residence time 9.1-20% of poly- kettle (it is existing to refer to that the difference of the residence time of residence time and the prior art of the invention account for
There is the percentage of the residence time of technology, the same below), the extended residence time 17.95-27.65% of third condensing field；Traditional work
Resid amount (i.e. organic solvent residue quantities) in the final dry glue of skill is 0.25 weight % or so, and uses the present processes most
The resid amount in resulting dry glue is 0.1 weight % hereinafter, solvent removal significant effect afterwards；Work is agglomerated relative to three traditional kettles
Skill, the present processes can reduce 10-20% steam consumption.
The present invention will be described in detail by way of examples below.
In following embodiment, used coacervation device is as shown in Figure 1, in which:
The height of first condensing field F1, the second condensing field F2 and third condensing field F3 are 5400mm, and glue spraying pipe is highly being
At the wall of the condensing field of 1800mm, the angle of the wall of glue spraying pipe and condensing field is 60 degree, and glue spraying pipe and condensing field tie point extremely divide
It is 100mm with a distance from baffle upper edge；Skimming baffle forms drum structure and its second plane and glue spraying pipe in condensing field
With same gradient, it is 0.75 that skimming baffle forms the diameter of drum structure and the ratio of condensing field internal diameter in condensing field:
1, so that the cavity that the side wall of the skimming baffle and condensing field surrounds accounts for the 14.6 volume % in the space of condensing field；Separation
The aperture in the hole on baffle is Ф 4mm；The aperture in the hole on the annular feed pipe with steam nozzle is Ф 2mm.
In following comparative example, used coacervation device as shown in figure 4, unlike coacervation device shown in FIG. 1,
Do not have skimming baffle in used condensing field, and the steam addition of condensing field F1 is be added from lower part and to be set in lower part
Be equipped with a steam entry port, and directly connect with the pipeline of conveying steam, rather than it is shown in FIG. 1 from bottom be with more
The steam feed device of the annular feed pipe of a steam nozzle is added；And the steam of condensing field F2 and F3 are sprayed into from bottom and bottom
It is provided with a steam entry port, and is directly connect with the pipeline of conveying steam, also there are multiple steam nozzles without using
The steam feed device of annular feed pipe.
In following embodiment and comparative example, rubber polymer solution is the hexane of styrene-isoprene block polymer
Solution, wherein the content of styrene-isoprene block polymer is 10 weight %.
Embodiment 1
The present embodiment is used to illustrate the condensing method of rubber polymer solution of the invention.
Rubber polymer solution is mixed with the flow of 5000kg/h and hot water (temperature for 90 DEG C, flow 40000kg/h)
It is sent into the first condensing field of Fig. 1 F1 with the flow of 45000kg/h from glue spraying pipe after conjunction, keeps bottom by steam feed device 3
Steam flow is 450kg/h (steam from the discharge of the kettle top of the second condensing field F2 and third condensing field F3), and kettle upper water enters
The water flow of mouth 7 is 5000kg/h；
Wherein, the operating pressure of the first condensing field F1 is 0.02~0.03MPa of gauge pressure, and temperature is 88~92 DEG C, micelle water
Residence time be 49.1min；
The operating pressure of second condensing field F2 is 0.06~0.09MPa of gauge pressure, and temperature is 103~110 DEG C, and micelle water stops
Staying the time is 57.9min；The steam flow of the feeding of steam feed device is 1200kg/h (from external low-pressure steam device
The steam of conveying)；
The operating pressure of third condensing field F3 is 0.001~0.005MPa of gauge pressure, and temperature is 95~100 DEG C, micelle water
Residence time is 64.6min；The a small amount of steam of the feeding of steam feed device is purge from clear (from external low-pressure steam
The steam of device conveying)；
The flow of P1 pump is 39792kg/h, and the flow of P2 pump is 5000g/h, and the flow of P3 pump is 35675kg/h, P4 pump
Flow be 5000g/h, P5 pump flow be 32542kg/h, P6 pump flow be 3000g/h.
The total residence time of condensed system is 2.86h, and system consumes the water of 32000kg and the steam of 1200kg in total,
The polymer solution for having handled 5000kg is collected to obtain the steam water of 5658kg from the steam (vapor) outlet of the first condensing field F1 kettle top
(hexane content is 79.44 weight %), the P5 of third condensing field F3 is pumped to post-processing and is dried to obtain dry glue 500kg, wherein dry
Hexane content is 0.1 weight % in glue.
Comparative example 1
By polymer solution with the flow of 5000kg/h and hot water (temperature for 90 DEG C, flow 40000kg/h) mixing after
It is sent into the first condensing field of Fig. 3 F1 with the flow of 45000kg/h from glue spraying pipe, the steam flow for keeping kettle lower part to provide is
450kg/h (steam from the discharge of the kettle top of the second condensing field F2 and third condensing field F3)；
Wherein, the operating pressure of the first condensing field F1 is 0.02~0.03MPa of gauge pressure, and temperature is 88~92 DEG C, micelle water
Residence time be 49.1min；
The operating pressure of second condensing field F2 is 0.06~0.09MPa of gauge pressure, and temperature is 103~110 DEG C, and micelle water stops
Staying the time is 53.4min；The steam flow of feeding is 1400kg/h (steam from external low-pressure steam device conveying)；
The operating pressure of third condensing field F3 is 0.001~0.005MPa of gauge pressure, and temperature is 95~100 DEG C, micelle water
Residence time is 53.6min；The steam flow of feeding is 100kg/h (steam from external low-pressure steam device conveying)；
The flow of P1 pump is 39832kg/h, and the flow of P3 pump is 40876.25kg/h, and the flow of P5 pump is
40843.25kg/h。
The total residence time of condensed system is 2.6h, and system consumes the water of 40000kg and the steam of 1500kg in total, is located
The polymer solution for having managed 5000kg is collected to obtain steam water (oneself of 5618kg from the steam (vapor) outlet of the first condensing field F1 kettle top
Alkane content is 79.3 weight %), the P5 of third condensing field F3 is pumped to post-processing and is dried to obtain dry glue 501.25kg, wherein dry
Hexane content is 0.25 weight % in glue.
By the Comparative result of embodiment 1 and comparative example 1 it is found that solvent, that is, hexane content in the resulting dry glue of embodiment 1
Only 0.1 weight %, comparative example 1 are then 0.25 weight %, and for comparative example 1, method of the invention enables to do
60% or more solvent content decline in glue, has better solvent removal effect, also, embodiment 1 makes than comparative example steam
Dosage reduces 20%, is to use less steam flow to obtain better solvent removal effect, thus side of the invention
Method material consumption and energy consumption are all relatively low, and cost is lower, more the value of industrial application.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (19)
1. a kind of rubber polymer condensing field, which is characterized in that the condensing field is for the solvent vapour in rubber polymer solution
Change removing to obtain the micelle water containing rubber polymer, which includes:
Rubber polymer solution feed unit, for the mixture of rubber polymer solution and water to be imported into the condensing field
In；
Steam feed unit, for steam to be imported into the condensing field to contact with the mixture；
Water separative unit, for by the partial moisture in the material after the contact from and go out；
Wherein, the water separative unit is formed by skimming baffle (4), wherein the upper edge of the skimming baffle (4) and cohesion
The side wall of kettle engages, and the lower edge of the skimming baffle (4) is engaged with the bottom of condensing field, thus by the lower part of the condensing field
The cavity that a circle is surrounded by the side wall of the skimming baffle (4) and condensing field is isolated, passes through the skimming baffle (4) to accommodate
Through-hole separation and go out water.
2. condensing field according to claim 1, wherein the sky surrounded by the side wall of the skimming baffle (4) and condensing field
Chamber accounts for the 3-20 volume % in the space of condensing field.
3. condensing field according to claim 1 or 2, wherein the steam feed unit is the annular with steam nozzle
Feed pipe (3), and inside of the annular feed pipe (3) around the skimming baffle (4) and the lower edge close to skimming baffle (4)
Setting.
4. condensing field according to claim 1 or 2, wherein the rubber polymer solution feed unit has glue spraying pipe
(2), it is stretched in kettle obliquely on condensing field wall.
5. condensing field according to claim 4, wherein the skimming baffle (4) is by the first periphery and the second periphery
It constitutes, wherein the first periphery is parallel with the wall surface of the condensing field, and second periphery is one end and the first periphery
Upper peripheral edge combines, inclined surface of the other end in conjunction with the wall surface of the condensing field, and the inclined surface has with glue spraying pipe (2) equally
Gradient.
6. according to claim 1, condensing field described in 2 or 5, wherein skimming baffle (4) covering is arranged with water outlet
(6), the through-hole being provided with from the skimming baffle (4) separates and water out, is expelled to condensing field by the water outlet (6)
Outside.
7. a kind of coacervation device of rubber polymer solution, which includes concatenated 2 or more condensing fields, wherein
First condensing field (F1) is used to the mixture of rubber polymer solution and water carrying out first with steam to contact so that solvent vapour
Change removing, condensing field thereafter carries out solvent evaporation for resulting micelle water after contacting in previous condensing field again and takes off
It removes；Wherein, at least one of condensing field which includes is cohesion described in any one of claim 1-6
Kettle.
8. coacervation device according to claim 7, wherein the coacervation device includes concatenated 2-10 condensing fields.
9. coacervation device according to claim 8, wherein the coacervation device includes concatenated 2-4 condensing field.
10. coacervation device according to claim 9, wherein the coacervation device includes concatenated 3 condensing fields.
11. coacervation device according to claim 10, wherein in the case where the coacervation device includes 3 concatenated condensing fields,
First condensing field (F1), the second condensing field (F2) and third condensing field (F3) are all for described in any one of claim 1-6
Condensing field.
12. coacervation device according to claim 11, wherein the top of first condensing field (F1) further includes water inlet
(7), made by the water inlet (7) by first condensing field (F1), the second condensing field (F2) and third condensing field (F3)
The water of water outlet discharge enters in first condensing field (F1) to recycle.
13. coacervation device according to claim 11 or 12, wherein second condensing field (F2) and third condensing field
It (F3) further include steam outlet (8) at the top of, the steam feed of the steam outlet (8) and first condensing field (F1)
Unit connection, so that the steam of the top of second condensing field (F2) and third condensing field (F3) discharge passes through described first
The steam feed unit of condensing field (F1) enters in first condensing field (F1) to recycle.
14. a kind of condensing method of rubber polymer solution, wherein this method is by any one of 3 claim 1-6 institute
It is carried out in the coacervation device that the condensing field stated is connected in series, this method comprises:
(1) in the first condensing field (F1), by the mixture of rubber polymer solution and the first water by rubber polymer solution into
Material unit is added and carries out first with the first steam being added by steam feed unit and contacts, and is connect by water separative unit by first
The partial moisture in material after touch from and go out, the second water isolated and separated the first micelle water after the water of part；
(2) in the second condensing field (F2), by the first micelle water be added by rubber polymer solution feed unit and with by
The second steam that steam feed unit is added carries out the second contact, the portion in material after contacting by water separative unit by second
The separation of point water and go out, the third water isolated with separated the second micelle water after the water of part；
(3) in third condensing field (F3), the second micelle water is added by rubber polymer solution feed unit, passes through water
Separative unit by partial moisture from and go out, the 4th water isolated and separated the third micelle water after the water of part.
15. condensing method according to claim 14, wherein the operating condition of first condensing field (F1) includes: table
Pressure is 0.003-0.03MPa, and temperature is 83-92 DEG C；The operating condition of second condensing field (F2) includes: that gauge pressure is 0.06-
0.09MPa, temperature are 103-110 DEG C；The operating condition of the third condensing field (F3) include: gauge pressure be -0.001MPa extremely
0.005MPa, temperature are 93-100 DEG C.
16. condensing method according to claim 14 or 15, wherein the second water for isolating step (1), step (2)
The 4th water that the third water and step (3) isolated are isolated returns in the first condensing field (F1).
17. condensing method according to claim 14 or 15, wherein by second condensing field (F2) discharge steam and
The steam of third condensing field (F3) discharge returns in the first condensing field (F1).
18. condensing method according to claim 14 or 15, wherein the rubber polymer solution is conjugated diene homopolymerization
The block copolymer of object solution, the random copolymer solution of conjugated diene and vinyl-arene and conjugated diene and vinyl-arene
One of solution is a variety of.
19. condensing method according to claim 18, wherein the content of rubber polymer in the rubber polymer solution
For 5-15 weight %.
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| CN114950270B (en) * | 2022-05-26 | 2023-05-16 | 宁波新溶聚企业管理合伙企业(有限合伙) | Four-kettle continuous production equipment and production method for producing solution polymerized styrene-butadiene rubber with low VOCs content |
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| CN202543122U (en) * | 2012-03-21 | 2012-11-21 | 中国石油化工股份有限公司 | Agglomeration equipment |
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| US6568663B1 (en) * | 2000-06-02 | 2003-05-27 | Uop Llc | Increased efficiency fractional distillation tray and process |
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| CN1510057A (en) * | 2002-12-26 | 2004-07-07 | 中国石油化工股份有限公司北京燕山分 | Method for eliminating fugitive component in 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 |
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