CN112142881A - ABS graft latex coagulating method and device thereof - Google Patents
ABS graft latex coagulating method and device thereof Download PDFInfo
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- CN112142881A CN112142881A CN202011129944.0A CN202011129944A CN112142881A CN 112142881 A CN112142881 A CN 112142881A CN 202011129944 A CN202011129944 A CN 202011129944A CN 112142881 A CN112142881 A CN 112142881A
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- 239000004816 latex Substances 0.000 title claims abstract description 36
- 229920000126 latex Polymers 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000001112 coagulating effect Effects 0.000 title claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 49
- 230000003068 static effect Effects 0.000 claims abstract description 23
- 238000005345 coagulation Methods 0.000 claims abstract description 20
- 230000015271 coagulation Effects 0.000 claims abstract description 20
- 238000009826 distribution Methods 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000701 coagulant Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000001110 calcium chloride Substances 0.000 claims description 6
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000001723 curing Methods 0.000 abstract description 20
- 239000002245 particle Substances 0.000 abstract description 15
- 239000000843 powder Substances 0.000 abstract description 10
- 238000010924 continuous production Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 abstract description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 42
- 239000002002 slurry Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
- C08F6/22—Coagulation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/40—Static mixers
- B01F25/42—Static mixers in which the mixing is affected by moving the components jointly in changing directions, e.g. in tubes provided with baffles or obstructions
- B01F25/421—Static mixers in which the mixing is affected by moving the components jointly in changing directions, e.g. in tubes provided with baffles or obstructions by moving the components in a convoluted or labyrinthine path
- B01F25/423—Static mixers in which the mixing is affected by moving the components jointly in changing directions, e.g. in tubes provided with baffles or obstructions by moving the components in a convoluted or labyrinthine path by means of elements placed in the receptacle for moving or guiding the components
- B01F25/4233—Static mixers in which the mixing is affected by moving the components jointly in changing directions, e.g. in tubes provided with baffles or obstructions by moving the components in a convoluted or labyrinthine path by means of elements placed in the receptacle for moving or guiding the components using plates with holes, the holes being displaced from one plate to the next one to force the flow to make a bending movement
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
- B01F35/20—Measuring; Control or regulation
- B01F35/22—Control or regulation
- B01F35/221—Control or regulation of operational parameters, e.g. level of material in the mixer, temperature or pressure
- B01F35/2215—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F2101/00—Mixing characterised by the nature of the mixed materials or by the application field
- B01F2101/2805—Mixing plastics, polymer material ingredients, monomers or oligomers
Abstract
The invention relates to a method and a device for coagulating ABS graft latex, and aims to provide a method and a device for coagulating ABS graft latex into powder with uniform particle size by adopting a static mixing mode and a circular tube type continuous reactor. The method of the invention adopts a static mixing and curing method to coagulate the ABS graft latex into powder, has short coagulation process flow, does not need to rotate and stir, has uniform coagulated powder particles, and can realize continuous production.
Description
Technical Field
The invention belongs to the technical field of ABS synthetic resin production processes, relates to a coagulation method of ABS graft latex and a device used by the coagulation method, and particularly relates to a coagulation method of static mixing four-section temperature control loop type continuous reaction.
Technical Field
The ABS resin is a thermoplastic resin material prepared by copolymerizing three monomers, namely butadiene, styrene and acrylonitrile, has the characteristics of rubber and resin, has better comprehensive mechanical properties, is wide in application field, and is an important engineering high polymer material. The emulsion grafting-bulk SAN blending method is the most widely applied process technology for ABS resin production at present, and the method adopts emulsion polymerization technology to produce polydiene latex, then graft-copolymerizes the polydiene latex with styrene and acrylonitrile to prepare ABS graft latex, then utilizes coagulation and drying process technology to prepare the ABS graft latex into ABS graft powder, and mixes the ABS graft powder with SAN resin to extrude and produce ABS resin, and the coagulation process is the process of separating solid matters from liquid phase in the ABS graft latex. Usually, ABS agglomeration is performed by adopting multi-kettle series semi-continuous production, because the volume of a single kettle is large, an agglomerating agent is added, materials are mixed unevenly, operating parameters of each kettle are different, the particle size distribution of agglomerated ABS powder is uneven, the stability of a downstream process is influenced, and the performance of a final ABS resin product is fluctuated due to uneven particle distribution.
Disclosure of Invention
The invention changes the traditional ABS agglomeration process method, and provides a static mixing four-section temperature control loop type continuous agglomeration reaction device and a method for producing ABS powder with uniform particle size.
The technical scheme of the invention is as follows:
a static mixing four-section temperature control circular tube type continuous reaction device for ABS graft latex condensation comprises four continuous parts, namely a mixing section, a dispersing section, a flow guide section and a curing section, wherein the mixing section is a cylindrical tube body with the length-diameter ratio (L1: D1) of (5-10:1), a static mixing dispersion disc is arranged in the mixing section, the dispersing section is in the shape of an arc cavity cylinder, the arc angle is 120-145 degrees, the flow guide section is in the shape of an inclined tube, the curing section is in the shape of a cavity cylinder, and the length-diameter ratio (L4: D4) is (1-3: 1).
The static mixing dispersion plate of the mixing section is arranged in a cross shape by adopting a single layer of stainless steel sheets, and each layer is arranged in a staggered mode.
The flow guide section inclined tubular distribution disc is formed by tightly arranging hexagonal steel pipes.
The port of the mixing section is a material inlet.
The mixing section, the dispersing section, the flow guide section and the curing section are all provided with steam inlets.
And a discharge port is arranged at the tail end of the curing section.
The ABS graft latex, a coagulant and desalted water are added into a loop reactor according to the mass ratio of 1 (0.001-0.005) to (0.2-1) based on the dry basis of the ABS graft latex, and the temperature is controlled by adjusting the steam flow, so that the internal temperature of the mixing section is controlled to be 60-80 ℃; controlling the internal temperature of the dispersion section to be 75-85 ℃; controlling the temperature of the flow guide section to be 80-95 ℃; controlling the temperature of the curing section to be 80-95 ℃.
Wherein the coagulant is a mixture of multivalent metal ion strong acid salt or multivalent metal ion strong acid salt and medium strong acid with concentration of 10-40%, including MgSO4Solution, MgSO4Mixed solution with acetic acid, MgSO4Mixed with sulfuric acid, CaCl2Solution, CaCl2Mixed with acetic acid, CaCl2Mixed with sulfuric acid, H2SO4One of the solutions.
As an optimization scheme, static mixing is adopted in the method, and the flow velocity of static mixed materials is 2-5 m/s.
The method has the advantages that the ABS graft latex is coagulated into powder by adopting the method, the static mixing four-section temperature control annular tube type coagulation process is adopted, stirring is not needed, rotating equipment is not needed, the coagulation process of the traditional batch type reaction kettle is broken through, continuous coagulation production can be realized, the particle size and appearance difference of the ABS powder among batches are avoided, and the particle size and appearance color of the coagulated ABS powder are uniform.
Drawings
FIG. 1 is a front view of an apparatus for coagulating an ABS graft latex according to the present invention.
FIG. 2 is a top view of a static mixing dispersion plate of a mixing section of the device for the coagulation method of the ABS graft latex of the present invention.
FIG. 3 is a top view of an inclined tube distribution plate of a diversion section of an apparatus for a method for coagulating ABS graft latex according to the present invention.
In the figure: ABS graft latex feed inlet A, coagulant feed inlet B, desalted water feed inlet C, steam inlet D, steam inlet E, steam inlet F, steam inlet G, steam inlet H, ABS slurry feed outlet I.
1 mixing section, 2 dispersing section, 3 solidifying section, 4 curing section, 5 static mixing dispersing disc and 6 inclined tube distributing disc.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Other features, objects and advantages of the present invention will become more apparent from the following detailed description of non-limiting embodiments thereof, which proceeds with reference to the accompanying drawings.
As shown in FIGS. 1 to 3, the static mixing four-section temperature control loop type continuous reaction device for ABS graft latex coagulation provided by the invention comprises four continuous parts, namely a mixing section 1, a dispersing section 2, a flow guide section 3 and a curing section 4. The mixing section 1 is a columnar pipe body with the length-diameter ratio (L1: D1) of (5-10:1), a static mixing dispersion disc 5 is arranged in the mixing section 1, the stainless steel sheets are distributed in a single-layer cross shape, the stainless steel sheets are arranged in a staggered mode among layers, the stainless steel sheets can efficiently shear ABS slurry, and the staggered distribution can change the direction of fluid to achieve the purpose of rapid dispersion. The dispersion section is cylindrical with an arc-shaped cavity, and the arc angle is 120-145 degrees. The guide flow section is an inclined tubular distribution disc 6, the inside of the guide flow section is a hexagonal steel pipe with the diameter of 50mm, the guide flow section is closely arranged, the dispersed slurry enables the flow direction of the fluid to be uniform through the guide flow section runner, and the fluid is guaranteed to stably enter the curing section to form spiral rising and discharge after being sufficiently cured. The curing section is in a hollow cylindrical shape, and the length-diameter ratio (L4: D4) is (1-3: 1).
The port of the mixing section is a material inlet, ABS graft latex, a coagulant and desalted water are added into the reaction device from the port, the mixing section, the dispersing section, the flow guide section and the curing section are all provided with steam inlets for controlling the temperature of each section, the tail end of the curing section is provided with a discharge hole, and ABS slurry is discharged from the discharge hole.
Example 1
ABS graft latex solid content 40%, coagulant 10% MgSO4Adding the solution and desalted water into a ring-tube reactor according to the ratio of 1:0.001:0.2 and the flow rate of 2m/s, adjusting the steam flow, controlling the temperature of a mixing section to be 60 ℃, the temperature of a dispersing section to be 75 ℃, the temperature of a curing section to be 85 ℃, the temperature of a curing section to be 95 ℃, and measuring the particle size distribution of the ABS slurry at the discharge port of the coagulation device, wherein the particle size distribution is shown in Table 1.
Example 2
ABS graft latex solid content 45%, coagulant 15% MgSO4The mixed solution and acetic acid, desalted water were added into a loop reactor at a flow rate of 3m/s at a ratio of 1:0.002:0.3, the steam flow was adjusted, the temperature of the mixing section was controlled to 70 ℃, the temperature of the dispersing section was controlled to 85 ℃, the temperature of the curing section was controlled to 90 ℃, the temperature of the aging section was controlled to 92 ℃, and the measured particle size distribution of the ABS slurry at the discharge port of the coagulation apparatus is shown in Table 1.
Example 3
50 percent of solid content of ABS graft latex and 20 percent of CaCl of coagulant2Adding the solution and desalted water into a ring-tube reactor according to the ratio of 1:0.003:0.5 and the flow rate of 5m/s, adjusting the steam flow, controlling the temperature of a mixing section to be 70 ℃, the temperature of a dispersing section to be 85 ℃, the temperature of a curing section to be 92 ℃, the temperature of a curing section to be 95 ℃, and measuring the particle size distribution of the ABS slurry at the discharge port of the coagulation device, wherein the particle size distribution is shown in Table 1.
Example 4
40 percent of solid content of ABS graft latex and 30 percent of CaCl of coagulant2The solution and the sulfuric acid mixed solution, desalted water were added into the loop reactor at a flow rate of 4m/s at a ratio of 1:0.004:0.8, the steam flow was adjusted, the temperature of the mixing section was controlled at 72 ℃, the temperature of the dispersing section at 80 ℃, the temperature of the curing section at 85 ℃, the temperature of the aging section at 95 ℃, and the measured particle size distribution of the ABS slurry at the discharge port of the coagulation apparatus is shown in Table 1.
Example 5
The ABS graft latex has a solid content of 43 percent, a coagulant of 40 percent of sulfuric acid solution and desalted water are added into a loop reactor according to a ratio of 1:0.005:1 and a flow rate of 3m/s, the steam flow is adjusted, the temperature of a mixing section is controlled to be 75 ℃, the temperature of a dispersing section is controlled to be 85 ℃, the temperature of a curing section is controlled to be 90 ℃, the temperature of a curing section is controlled to be 95 ℃, and the measured particle size distribution of the ABS slurry at the discharge port of the coagulation device is shown in Table 1.
TABLE 1 ABS sizing agent particle size distribution Table
Claims (8)
1. A static mixing four-section temperature control circular tube type continuous reaction device for ABS graft latex condensation is characterized by comprising four continuous parts, namely a mixing section, a dispersing section, a flow guide section and a curing section, wherein the mixing section is a cylindrical tube body with the length-diameter ratio (L1: D1) of 5-10:1, a static mixing dispersing disc is arranged in the mixing section, the dispersing end is cylindrical with an arc-shaped cavity, the arc-shaped angle is 120-145 degrees, the flow guide section is an inclined tube-shaped distribution disc, the curing section is cylindrical with the cavity, and the length-diameter ratio (L4: D4) is 1-3: 1.
2. The static mixing four-stage temperature-controlled loop type continuous reaction device for the coagulation of the ABS graft latex according to claim 1, wherein the static mixing dispersion plate of the mixing stage is arranged in a single-layer cross shape by stainless steel sheets, and each layer is arranged in a staggered manner.
3. The static mixing four-stage temperature-controlled loop type continuous reaction device for ABS graft latex condensation as claimed in claim 2, wherein the flow guide section inclined tubular distribution plate is formed by closely arranging hexagonal steel tubes.
4. The static mixing four-stage temperature-controlled loop type continuous reaction device for the coagulation of the ABS graft latex according to claim 3, wherein the port of the mixing stage is a material inlet.
5. The static mixing four-stage temperature-controlled loop type continuous reaction device for the coagulation of the ABS graft latex according to claim 4, wherein the mixing stage, the dispersing stage, the flow guiding stage and the curing stage are provided with steam inlets.
6. The static mixing four-stage temperature-controlled loop type continuous reaction device for the coagulation of the ABS graft latex according to claim 5, wherein the end of the curing stage is provided with a discharge port.
7. A method for coagulating ABS graft latex by using the static mixing four-stage temperature-controlled loop-type continuous reaction device as defined in claim 6, characterized in that the ABS graft latex, a coagulating agent and desalted water are added into the loop-type reactor in a mass ratio of 1 (0.001-0.005): (0.2-1) based on the dry basis of the ABS graft latex, and the internal temperature of the mixing stage is controlled to be 60-80 ℃ by adjusting the steam flow to control the temperature; controlling the internal temperature of the dispersion section to be 75-85 ℃; controlling the temperature of the flow guide section to be 80-95 ℃; controlling the temperature of the curing section to be 80-95 ℃,
wherein the coagulant is a mixture of multivalent metal ion strong acid salt or multivalent metal ion strong acid salt and medium strong acid with concentration of 10-40%, including MgSO4Solution, MgSO4Mixed solution with acetic acid, MgSO4Mixed with sulfuric acid, CaCl2Solution, CaCl2Mixed with acetic acid, CaCl2Mixed with sulfuric acid, H2SO4One of the solutions.
8. The method for coagulating an ABS graft latex according to claim 7, wherein the flow rate of the material is 2 to 5 m/s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011129944.0A CN112142881B (en) | 2020-10-21 | Method for agglomerating ABS grafted latex and device used by same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011129944.0A CN112142881B (en) | 2020-10-21 | Method for agglomerating ABS grafted latex and device used by same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112142881A true CN112142881A (en) | 2020-12-29 |
| CN112142881B CN112142881B (en) | 2024-05-03 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112876586A (en) * | 2021-01-18 | 2021-06-01 | 万华化学(四川)有限公司 | Method for coagulating ABS graft latex |
| CN113416267A (en) * | 2021-07-28 | 2021-09-21 | 万华化学(四川)有限公司 | ABS graft latex coagulation method for improving biodegradability of process sewage |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4890929A (en) * | 1987-04-21 | 1990-01-02 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Method and apparatus for manufacturing coagulated grains from polymer latex |
| CN101570588A (en) * | 2008-04-30 | 2009-11-04 | 中国石油天然气股份有限公司 | Method for preparing bimodal distribution ABS |
| CN103193940A (en) * | 2012-01-10 | 2013-07-10 | 李祎山 | Production technology of ABS resin |
| KR20190052613A (en) * | 2017-11-08 | 2019-05-16 | 주식회사 엘지화학 | Apparatus and method for preparing of polymer latex |
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4890929A (en) * | 1987-04-21 | 1990-01-02 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Method and apparatus for manufacturing coagulated grains from polymer latex |
| CN101570588A (en) * | 2008-04-30 | 2009-11-04 | 中国石油天然气股份有限公司 | Method for preparing bimodal distribution ABS |
| CN103193940A (en) * | 2012-01-10 | 2013-07-10 | 李祎山 | Production technology of ABS resin |
| KR20190052613A (en) * | 2017-11-08 | 2019-05-16 | 주식회사 엘지화학 | Apparatus and method for preparing of polymer latex |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112876586A (en) * | 2021-01-18 | 2021-06-01 | 万华化学(四川)有限公司 | Method for coagulating ABS graft latex |
| CN113416267A (en) * | 2021-07-28 | 2021-09-21 | 万华化学(四川)有限公司 | ABS graft latex coagulation method for improving biodegradability of process sewage |
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