CN1050138C - Method and apparatus for removing residual volatile component from polymer system - Google Patents
Method and apparatus for removing residual volatile component from polymer system Download PDFInfo
- Publication number
- CN1050138C CN1050138C CN97113303A CN97113303A CN1050138C CN 1050138 C CN1050138 C CN 1050138C CN 97113303 A CN97113303 A CN 97113303A CN 97113303 A CN97113303 A CN 97113303A CN 1050138 C CN1050138 C CN 1050138C
- Authority
- CN
- China
- Prior art keywords
- volatile component
- heating
- residual volatile
- devolatilization
- stirring rake
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Images
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a method and an apparatus for removing a residual volatile component from a polymer system. The apparatus comprises a heater, a built-in heating distributor, a stirring paddle and a volatile component removing tank of a distribution plate, wherein the heater is increased step by step. After polymer passes through the multi-stage heater expanded step by step, the polymer enters the volatile component removing tank, and the residual volatile component is removed by a separator. In order to increase an application range of the process, the apparatus is additionally provided with an auxiliary fluid addition unit. The present invention is adapted to a volatile component removing system with a high volatile component boiling point and great requirements for a process volatile component removing rate, such as the removal of a non-reaction monomer in the styrene body polymerization process. Residual monomer content can reach below 200 ppm, and the quality of the polymer is obviously enhanced. The present invention can be used for the fields of chemical industrial process, macromolecule industry, paint, etc.
Description
The present invention relates to remove behind the polymer polymerizing method and apparatus of volatile matter.
A large amount of experiment and facts have proved that the residual volatile component major part in the polymkeric substance is all harmful also influences the material use properties simultaneously, therefore must remove deleterious in the production process of polymkeric substance or influences healthy residual volatile component.Produce in the continuous polymerization method of phenylethylene polymer composition with mass polymerization or solution polymerization process, devolatilization method and device are one of them key links, because the general viscosity ratio of system is higher, and cinnamic boiling point is again than higher, so devolatilization is a thorny difficult problem in styrene series resin production process and the technological development always.Existing apparatus generally takes single-stage devolatilization of bar formula or multistage devolatilization, as US4294652, Te Kaiping 6-157640, the spy opens clear 61-203102, and the spy opens clear 61-203103, DE3409066 etc., but for devolatilization than (ratio of import fugitive constituent and outlet fugitive constituent index) mass polymerization systems such as vinylbenzene up to three orders of magnitude, the general bar formula device that falls, the energy expenditure of single-stage devolatilization is very big, and the burden of vacuum system is also very heavy; And the general multistage devolatilization technology that adopts, the problem that a large amount of devolatilization processes that generate bubble do not have consideration the fugitive constituent in the bubble is overflowed fast in early stage causes the not high and frequent blocking of vacuum system of devolatilization efficient.Therefore present devolatilization device all is in the situation of high energy consumption, inefficient operation to some extent, a lot of devices reach the single residual content index by prolongation operating time, reduction equipment service ability, usually cause the number of polymers degraded, influence quality, perhaps operation of equipment elasticity is very little, be difficult to regulate and control, perhaps process makes very complicated.
The objective of the invention is: provide a kind of and both made in the polymkeric substance residual volatile component reach high standard to remove, make process have the removal methods and the device of residual volatile component in the elastic polymer system of excellent operation again, can solve the problem that exists in the background technology field.
To achieve the above object of the invention, the technical solution used in the present invention is: come the polymkeric substance in the autoreactor, enter with heating medium heating and temperature and be controlled in 80～300 ℃ the well heater, after the relief valve pressure regulation, send in the devolatilization groove by the heating medium insulation, pressure-controlling in the devolatilization groove is at＜100mmHg, the heating sparger of polymkeric substance logical heating medium through the middle part, the heat that consumes that bubbles rapidly can in time be replenished, the space that needs is provided, polymkeric substance from the distribution orifice flow of heating sparger bottom through stirring rake, under the stirring action of stirring rake, fugitive constituent in the bubble escapes into vacuum system rapidly, reaches quick, high efficiency separation.Polymkeric substance has the grid distributor in many distributions hole again below stirring rake, further slough residual volatile component after, flow to the bottom of devolatilization groove, with the high viscosity fluid pump polymkeric substance is discharged.During in order to the devolatilization of upper level method in the well heater temperature preferably be controlled at 80～260 ℃, the pressure in the devolatilization groove preferably is controlled at＜30mmHg.
During with the two step method devolatilization, the temperature in the well heater is controlled at 80～300 ℃, preferably is controlled at 80～200 ℃; Pressure-controlling in the devolatilization groove preferably is controlled at＜50mmHg at＜100mmHg, and the polymkeric substance of discharging from the high viscosity fluid pump enters the Surface Renewal type separator.Temperature in the Surface Renewal type separator is controlled at 100～300 ℃, preferably is controlled at 150～260 ℃, and pressure-controlling preferably is controlled at＜30mmHg at＜100mmHg; By the Surface Renewal effect, make it to slough all the other residual volatile components rapidly again and escape into vacuum system, polymkeric substance is discharged from separator.
Under the situation that does not increase the well heater total volume, adopt 2～3 grades of expansible well heaters step by step, single-phase to adapt to, heterogeneous operation, when adopting the one-level devolatilization, the well heater of She Zhiing can have the function of pre-devolatilizer simultaneously like this.Between the bottom of devolatilization groove and high viscosity fluid pump, establish auxiliary fluid and add the unit, inject water or C
4Auxiliary fluids such as following alcohol or ketone are to strengthen the devolatilization effect.
In the polymer system residual volatile component remove device, it mainly comprises well heater, the devolatilization groove, the high viscosity fluid pump, well heater is generally 2～3 grades for becoming big step by step; In the devolatilization groove, the heating tube of the logical heating medium in middle part is housed from top to down successively, the heating sparger of the logical outward polymkeric substance of heating tube wall, bottom have and stirring rake are housed below the heating sparger in many distributions hole, and the grid distributor in many distributions hole is housed out below the stirring rake.Surface Renewal type separator can be housed below the high viscosity fluid pump.Also can between the bottom of devolatilization groove and high viscosity fluid pump, set up auxiliary fluid and add the unit.
Its profile of heating sparger is Polygons or circle, and the distribution hole on heating sparger bottom and the grid distributor can be square hole, delthyrium, circular hole, other polygonal hole, can have pointed tooth, Polygons tooth in these holes.
Stirring rake is 1～3 layer, stirring rake can be ribbon stirring rake, flat oar, sawtooth oar etc., the diameter of stirring rake is controlled at 50～80% of devolatilization groove internal diameter, have many distributions hole on the stirring rake, can be square hole, delthyrium, circular hole, other polygonal hole, or in these holes, have pointed tooth, Polygons tooth.
The present invention compares with background technology, and the useful effect that is had is:
1. heating sparger, stirring rake and grid distributor are housed in the devolatilization groove, adapt to process characteristics and the requirement of devolatilization ratio up to the highly difficult foaming devolatilization of three orders of magnitude, devolatilization equipment is strengthened, turndown ratio increases, devolatilization efficient height, the vacuum system stable operation;
2. adopt relief valve to regulate the foaming degree of fugitive constituent in the may command well heater, the devolatilization requirement of the polymer system under the adaptive response process differentiated yields situation behind the well heater;
3. adopt the multistage well heater of expansible gradually, the turndown ratio of well heater is increased, be adapted to single-phase or heterogeneous operation, cooperate with relief valve to have controlled pre-devolatilization function;
4. use the two-stage devolatilization, turndown ratio is increased again, be convenient to reduce process cost, process optimization, reach single residual content below 500ppm,, set up auxiliary fluid and add the unit in order to increase the scope of application of process.
It is higher that the present invention is adapted to the fugitive constituent boiling point, and the process devolatilization is than the devolatilization system of having relatively high expectations, and as the characteristics and the requirement of the subtractive process of the unreacted monomer of vinylbenzene mass polymerization engineering, single residual content can reach below the 200ppm, and the quality of polymkeric substance is obviously improved.Can use in fields such as chemical process, polymer industry, coating, fine chemistry industries.
Fig. 1, structural representation of the present invention;
A kind of structural representation of Fig. 2, heating sparger;
The another kind of structural representation of Fig. 3, heating sparger;
Hole shape exemplary plot on Fig. 4, the heating sparger;
Fig. 5, stirring rake structural representation;
The layout drawing in hole on Fig. 6, the grid distributor.
Provide details of the present invention and embodiment below in conjunction with accompanying drawing.
As shown in Figure 1, when adopting the devolatilization of one-level method, in the polymer system residual volatile component remove device, it mainly comprises well heater 1, devolatilization groove 7, high viscosity fluid pump 15.Come the polymkeric substance 14 of autoreactor to enter well heater 1, well heater 1 is under the situation that does not increase the heating tube total volume, become big on from descending step by step, be generally 2～3 grades (among the figure being 3 grades), the pressure of control relief valve, make the fugitive constituent in the polymkeric substance in every grade of well heater constantly form bubble, expand step by step.The terminal relief valve 2 of polymkeric substance heater via enters devolatilization groove 7, the heating tube of the logical heating medium in middle part is housed from top to down successively, the heating tube wall is the heating sparger 3 (it is shaped as circle or Polygons) of logical polymkeric substance outward, 3 times harness of heating sparger that the bottom has many distributions hole have the stirring rake of strong regeneration function, the grid distributor 10 in many distributions hole is housed out below the stirring rake, has on the devolatilization groove 7 and vacuumize hole 11.
As shown in Figure 2, heating sparger 3 its profiles are circular, heating medium is from import 19 to heating tube in 16, pipeline through inside, heating medium flows out from exporting 21, the import 20 of polymkeric substance 18 outside heating tube wall 17 is to heating sparger 3, the bottom (in polymkeric substance is arranged) of heating sparger 3 has many distributions hole (not drawing among the figure), the distribution hole can be square hole, delthyrium, circular hole, other polygonal hole, as a, b, c, d, e among Fig. 4, or in these holes, be furnished with various pointed tooths or Polygons tooth, the number of teeth can be 1 to multi-disc, with 3～6 for well.
As shown in Figure 3, heating sparger 3 its profiles are square, heating medium is from import 19 to heating tube in 16, pipeline through inside, heating medium flows out from exporting 21, the import 20 of polymkeric substance 18 outside heating tube wall 17 is to heating sparger 3, the bottom (in polymkeric substance is arranged) of heating sparger 3 has many distributions hole 22, the distribution hole can be square hole, delthyrium, circular hole, other polygonal hole equally, as a, b, c, d, e among Fig. 4, or in these holes, be furnished with various pointed tooths, Polygons tooth, the number of teeth can be 1 to multi-disc, with 3～6 for well.
As shown in Figure 5, the stirring rake with strong regeneration function is driven by motor 12, and it can be ribbon stirring rake, flat oar, sawtooth oar (Fig. 5 be a sawtooth oar 24) etc., stirring rake can be 1 layer also but multilayer, 4,5,6 is stirring rake among Fig. 1.Have the distribution hole on the stirring rake, it can be square hole 23, delthyrium, circular hole, other polygonal hole equally, as a, b, c, d, e among Fig. 4, or is furnished with various pointed tooths, Polygons tooth in these holes, and the number of teeth can be 1 to multi-disc, with 3～6 for well.
As shown in Figure 6, grid distributor 10 is arranged below the stirring rake, to strengthen devolatilization, distribution hole in this plate can be circular hole 25, square hole, delthyrium, other polygonal hole too, as a, b, c, d, e among Fig. 4, or in these holes, be furnished with various pointed tooths, Polygons tooth, the number of teeth can be 1 to multi-disc, with 3～6 for well.
As shown in Figure 1, when adopting the two step method devolatilization, Surface Renewal type separator 9 is housed below high viscosity fluid pump 15,,, makes it to slough all the other residual volatile components rapidly, reach suitable requirement by the Surface Renewal effect as adopting vented extruder.Sometimes in order to adapt to edible Application for Field, or in order to increase the turndown ratio of process, set up auxiliary fluid at the bottom of devolatilization groove 7 and 15 of high viscosity fluid pumps and add unit 8, according to the needs of concrete system, inject water or C
4Auxiliary fluids such as following alcohol or ketone are to strengthen the devolatilization effect.Polymkeric substance after the devolatilization is discharged from exporting 13.
Embodiment 1:
Do not enable auxiliary fluid and add unit operation, the heating sparger is the form of Fig. 3, stirring rake is the form of Fig. 5, grid distributor is the form of Fig. 6, handling the autoreactor transformation efficiency is vinylbenzene/polystyrene material of 59%, flow is 500ml/min, temperature is controlled at 100～150 ℃ in the well heater, devolatilization groove pressure-controlling is at 50mmHg, temperature is controlled at 150～260 ℃ in the vented extruder, pressure-controlling is below 10mmHg, and after two step method devolatilization device was handled, the exit fugitive constituent was reduced to 380ppm.
Embodiment 2:
Enable auxiliary fluid and add unit operation, handling the autoreactor transformation efficiency is vinylbenzene/polystyrene material of 59%, flow is 500ml/min, and temperature is controlled at 100～150 ℃ in the well heater, and devolatilization groove pressure-controlling is at 50mmHg, temperature is controlled at 150～260 ℃ in the vented extruder, pressure-controlling uses water as auxiliary fluid below 10mmHg, adding speed is 3ml/min, after two step method devolatilization device was handled, the exit fugitive constituent was reduced to 180ppm.
Embodiment 3:
Do not enable auxiliary fluid and add unit operation, handling the autoreactor transformation efficiency is vinylbenzene/polystyrene material of 59%, flow is 500ml/min, temperature is controlled at 200～260 ℃ in the well heater, devolatilization groove pressure-controlling is below 10mmHg, after one-level method devolatilization device was handled, the exit fugitive constituent was reduced to 490ppm.
Claims (9)
1. the removal methods of residual volatile component in the polymer system, it is characterized in that: come the polymkeric substance in the autoreactor, enter with heating medium heating and temperature and be controlled in 80～300 ℃ the well heater, after the relief valve pressure regulation, send in the devolatilization groove by the heating medium insulation, pressure-controlling in the devolatilization groove is at＜100mmHg, the heating sparger of polymkeric substance logical heating medium through the middle part, the heat that consumes that bubbles rapidly can in time be replenished, the space that needs is provided, polymkeric substance from the distribution orifice flow of heating sparger bottom through stirring rake, under the stirring action of stirring rake, fugitive constituent in the bubble escapes into vacuum system rapidly, reach quick, high efficiency separation, polymkeric substance has the grid distributor in many distributions hole again below stirring rake, after further sloughing residual volatile component, flow to the bottom of devolatilization groove, polymkeric substance is discharged or enter temperature with the high viscosity fluid pump and be controlled at 100～300 ℃ from the polymkeric substance that the high viscosity fluid pump is discharged, pressure-controlling is at the Surface Renewal type separator of＜100mmHg, by the Surface Renewal effect, make it to slough rapidly all the other residual volatile components and the people's vacuum system of escaping, polymkeric substance is discharged from separator.
2. the removal methods of residual volatile component in the polymer system according to claim 1 is characterized in that: temperature is controlled at 80～260 ℃ in the well heater, and the pressure-controlling in the devolatilization groove is at＜30mmHg.
3. the removal methods of residual volatile component in the polymer system according to claim 1, it is characterized in that: the temperature in the well heater is controlled at 80～200 ℃, pressure-controlling in the devolatilization groove is at＜50mmHg, temperature in the Surface Renewal type separator is controlled at 150～260 ℃, and pressure-controlling is at＜30mmHg.
4. the removal methods of residual volatile component in the polymer system according to claim 1 is characterized in that: under the situation that does not increase the well heater total volume, adopt 2～3 grades of expansible well heaters step by step; Between the bottom of devolatilization groove and high viscosity fluid pump, set up auxiliary fluid and add the unit, inject water or C
4Following alcohol or ketone auxiliary fluid are to strengthen the devolatilization effect.
5. employed device in the removal methods of residual volatile component in the polymer system according to claim 1, it comprises well heater, devolatilization groove [7], high viscosity fluid pump [15] is characterized in that:
1) well heater [1] adopts 2～3 grades for becoming big step by step;
2) in the devolatilization groove [7], the heating tube [16] of the logical heating medium in middle part is housed from top to down successively, the heating sparger [3] of the outer logical polymkeric substance of heating tube wall [17], the bottom has is equipped with stirring rake below the heating sparger [3] in many distributions hole, the grid distributor [10] that has many distributions hole is housed below the stirring rake.
6. in the polymer system according to claim 5 residual volatile component remove device, it is characterized in that: Surface Renewal type separator [9] is housed below high viscosity fluid pump [15].
7. according to the device that removes of residual volatile component in claim 5 or the 6 described polymer systems, it is characterized in that: between the bottom of devolatilization groove [7] and high viscosity fluid pump [15], set up auxiliary fluid and add unit [8].
8. residual volatile component removes device in the polymer system according to claim 5, it is characterized in that: its profile of heating sparger [3] is Polygons or circle, distribution hole on heating sparger [3] bottom and the grid distributor [10] is square hole, delthyrium, circular hole, other polygonal hole, or has pointed tooth or Polygons tooth in these holes.
9. residual volatile component removes device in the polymer system according to claim 5, it is characterized in that: stirring rake is 1～3 layer, stirring rake is ribbon stirring rake, flat oar, sawtooth oar, the diameter of stirring rake is controlled at 50～80% of devolatilization groove internal diameter, have many distributions hole on the stirring rake, these holes are square hole, delthyrium, circular hole, other polygonal hole, or are furnished with pointed tooth, Polygons tooth in these holes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97113303A CN1050138C (en) | 1997-05-22 | 1997-05-22 | Method and apparatus for removing residual volatile component from polymer system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97113303A CN1050138C (en) | 1997-05-22 | 1997-05-22 | Method and apparatus for removing residual volatile component from polymer system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1167772A CN1167772A (en) | 1997-12-17 |
| CN1050138C true CN1050138C (en) | 2000-03-08 |
Family
ID=5172612
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97113303A Expired - Lifetime CN1050138C (en) | 1997-05-22 | 1997-05-22 | Method and apparatus for removing residual volatile component from polymer system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1050138C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101024674B (en) * | 2007-01-11 | 2010-06-02 | 宁波大发化纤有限公司 | Method for separating regenerated polymer low-molecular impurity and vacuum separating tower thereof |
| CN102093590B (en) * | 2010-12-01 | 2012-05-30 | 宁波大发化纤有限公司 | Waste plastic conditioning and viscosity modifying system |
| CN106397641B (en) * | 2015-07-28 | 2019-05-03 | 中国石油天然气股份有限公司 | Remove the device and method of fugitive constituent in polymer powders |
| US10358540B2 (en) * | 2017-06-09 | 2019-07-23 | GM Global Technology Operations LLC | Process and system for reducing volatile compound emissions from a product |
| CN113304492A (en) * | 2021-07-06 | 2021-08-27 | 江苏永大化工机械有限公司 | Devolatilization device |
| CN113769423A (en) * | 2021-09-29 | 2021-12-10 | 华东理工大学 | Cyclic supplement type devolatilization device and process |
| CN114478849A (en) * | 2021-11-05 | 2022-05-13 | 广州创特技术有限公司 | Polymer material devolatilization device |
-
1997
- 1997-05-22 CN CN97113303A patent/CN1050138C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1167772A (en) | 1997-12-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Effect of interfacial phenomena on the development of particle morphology in a polymer latex system | |
| CN1050138C (en) | Method and apparatus for removing residual volatile component from polymer system | |
| EP0359432B1 (en) | Devolatilization of liquid composition containing polymer and volatile constituents | |
| WO1996040427A1 (en) | A polymerization process, apparatus and polymer | |
| EP1437174A3 (en) | Continuous slurry polymerisation volatile removal | |
| CA2452887A1 (en) | Process and apparatus for preparing emulsion polymers | |
| WO2000000280A1 (en) | TAYLOR REACTOR FOR MATERIALS CONVERSION IN THE COURSE OF WHICH A CHANGE IN VISCOSITY ξ OF THE REACTION MEDIUM OCCURS | |
| EP2481476A1 (en) | Continuous polymerization apparatus and process for producing polymer composition | |
| Tirrell et al. | Polymerization reactors | |
| Shen et al. | Continuous atom transfer radical block copolymerization of methacrylates | |
| SG181219A1 (en) | Continuous polymerization apparatus and process for producing polymer composition | |
| EP2481477A1 (en) | Continuous polymerization apparatus and process for producing polymer composition | |
| CN1295583A (en) | Method for removing volatile matter from polymer solution composition | |
| RU2004106026A (en) | MONOVINYLIDENAROMATIC POLYMERS BASED ON HIGH-LINE HIGH-MOLECULAR POLYBUTADIENE RUBBERS AND METHOD FOR PRODUCING THEM | |
| CN1050137C (en) | Method and apparatus for removing volatile component from thermoplastic polymer | |
| EA014494B1 (en) | Process of polymerisation olephin monomer and a loop reactor of continuous construction | |
| Alduncin et al. | Molecular-weight distributions in the miniemulsion polymerization of styrene initiated by oil-soluble initiators | |
| US6117939A (en) | Free radical miniemulsion polymerization with low shear and heat exchanger | |
| US7651670B2 (en) | Method for continuously polymerizing in mass quantities and taylor reactor for carrying out this method | |
| Barandiaran et al. | Emulsion polymerization | |
| DE19960389A1 (en) | Taylor reactor, e.g. for producing (co)polymer, polycondensate, polyadduct, core-shell latex, dispersion, modified polymer, unsaturated curable material or mesophase, includes mixing aggregate connected to dosing units | |
| Tuncel et al. | Emulsion copolymerization of styrene and methacrylic acid in the presence of a polyethylene oxide based-polymerizable stabilizer with a shorter chain length | |
| JPH04218512A (en) | Production of styrene-based resin | |
| Van Den Boomen et al. | Continuous emulsion copolymerisation of styrene and methyl acrylate | |
| EP1344563A3 (en) | Continuous slurry polymerisation volatile removal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20000308 |
|
| CX01 | Expiry of patent term |