CN1276944C - Treatment method of waste liquid containing emulsion polymerized polymer - Google Patents
Treatment method of waste liquid containing emulsion polymerized polymer Download PDFInfo
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- CN1276944C CN1276944C CNB031051642A CN03105164A CN1276944C CN 1276944 C CN1276944 C CN 1276944C CN B031051642 A CNB031051642 A CN B031051642A CN 03105164 A CN03105164 A CN 03105164A CN 1276944 C CN1276944 C CN 1276944C
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- Prior art keywords
- waste liquid
- polymer
- aggregate
- polymer coagulant
- letex polymerization
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The present invention provided a treatment method for emulsion polymerization-based polymer-containing waste liquid which can improve the collection efficiency of flocculation of emulsion polymerization based polymers by increasing the particle size of the flocculate and reduce the content of organic substances in the waste water to be discharged. In this treatment method for flocculating the emulsion polymerization based polymers and separating them from the emulsion polymerization based polymer-containing waste liquid, aluminum sulfate is added to the emulsion polymerization based polymer-containing waste liquid, a first polymer coagulant is added to the waste liquid to which the aluminum sulfate has been added, and a second polymer coagulant having an electric charge different from that of the first polymer coagulant is added to the waste liquid added with the first polymer coagulant.
Description
Technical field
The present invention relates to make the letex polymerization base polymer the time waste liquid that contains letex polymerization base polymer, emulsifying agent etc. of discharging treatment process.
Background technology
Always, the letex polymerization base polymer is through contained the polymerization process of the polymer emulsion of polymkeric substance by the emulsion polymerization preparation, the operation of solidifying with the cohesion becoming of the polymkeric substance in polymer emulsion polymkeric substance raw material, wash repeatedly and dewater and from the polymkeric substance raw material, remove simultaneously and anhydrate and thereby flocculation agent finally obtains the washing and the dehydration procedure of the low dehydrate of moisture rate, and make the dehydrate drying become the drying process of powder body and make.
When preparation letex polymerization base polymer, the waste liquid that contains letex polymerization base polymer and emulsifying agent etc. that discharge is produced by washing and dehydration procedure, in addition, behind preparation letex polymerization base polymer, because the washing of the device of each operation, discharge the waste liquid of the emulsion that contains the letex polymerization base polymer and latex etc.
In these waste liquids, contain many polymkeric substance, these polymkeric substance have become to cause the major cause of the water quality deterioration of COD etc., therefore it intactly can not be discharged into the outside as general draining, but must reclaim polymkeric substance through liquid waste disposal such as coagulative precipitation processing.
Always, to the coagulative precipitation treating processes that contains letex polymerization base polymer waste liquid be: behind the letex polymerization base polymer in the cohesion waste liquid, precipitation aggregate, separation supernatant and the aggregate, supernatant is discharged into the outside as general draining, make the condensation product dehydration on the other hand, as offal treatment.
In addition, the condensing method of the letex polymerization base polymer in the waste liquid can take to add the method for inorganic flocculants such as aluminium salt, magnesium salts, molysite in waste liquid; Perhaps in waste liquid, add inorganic flocculant, again to wherein adding from anionic the cationic method that waits a kind of polymer coagulant selecting in the polymer agglomeration agent.
Yet, in waste liquid, only add inorganic flocculant, or add inorganic flocculant and a kind of polymer coagulant, promptly enable the particle diameter that the cohesion of letex polymerization base polymer reaches the degree that can precipitate, the cohesion of aggregate also is inadequate, is easy to divide the aggregate that forms small particle size.This small particle size aggregate is difficult to precipitation, separates, and might remain in the supernatant, thereby generation need be condensed once more to supernatant, the situation of liquid waste disposal.
In addition, in the factory that makes the letex polymerization base polymer etc., the production line of letex polymerization base polymer has many mostly, and mostly the emulsifier type that contains in the waste liquid of being discharged by these production lines is to have nothing in common with each other.In order to make the letex polymerization base polymer become the aggregate of big particle diameter, the ionic of polymer coagulant of adding to usually in the waste liquid adapted by suitable being chosen as with the ionic of emulsifying agent, but in waste liquid, contain under the situation of several ionic different emulsifying agents, if it is only corresponding with it and do not limit with a kind of polymer coagulant, then be difficult to obtain the aggregate of big particle diameter, the small particle size aggregate might remain in the supernatant.
Summary of the invention
Therefore, the purpose of this invention is to provide a kind of treatment process that contains letex polymerization base polymer waste liquid, this method can make the particle diameter of the aggregate of letex polymerization base polymer increase, and the organic efficiency of aggregate is improved, and the organic content in the draining of discharging is reduced.
Promptly, the treatment process that contains letex polymerization base polymer waste liquid of the present invention is cohesion, a separating emulsions polymeric type polymkeric substance from the waste liquid that contains the letex polymerization base polymer, it is characterized in that, in the waste liquid that contains the letex polymerization base polymer, add Tai-Ace S 150, in the waste liquid that has added Tai-Ace S 150, add first polymer coagulant then, in the waste liquid that has added first polymer coagulant, add second polymer coagulant that has with the different electric charges of first polymer coagulant again.
In addition, in the treatment process that contains letex polymerization base polymer waste liquid of the present invention, preferably the pH value of having added the waste liquid of Tai-Ace S 150 is adjusted in the scope of 7-10.
In addition, aforesaid 2 kinds of polymer coagulant preferred mass molecular-weight average are that the anionic polymer coagulant of 1,000 ten thousand-1,500 ten thousand polyacrylamide and quality molecular-weight average are the cationic high-molecular flocculation agent of 3,500,000-5,000,000 polyacrylate(s).
Embodiment
Below the present invention is made detailed description.
The treatment process that contains letex polymerization base polymer waste liquid of the present invention is characterised in that, in the waste liquid that has added Tai-Ace S 150, add the first different separately polymer coagulant of electric charge and second polymer coagulant (below, their notes are made 2 types polymer coagulant) again.
Among the present invention, since good to the cohesion ability of letex polymerization base polymer, use Tai-Ace S 150 as inorganic flocculant.
Addition to Tai-Ace S 150 is not done special qualification, is good with the degree that can make the cohesion of letex polymerization base polymer form aggregate, with respect to the letex polymerization base polymer in the waste liquid (dividing Gu form) 100 mass parts, is the scope of 0.3-1.0 mass parts usually.
Added the waste liquid of Tai-Ace S 150, be the cohesion of promotion letex polymerization base polymer, and formed the aggregate of big particle diameter easily, preferably regulated the scope of the pH value of waste liquid for 7-10.When the pH of waste liquid value less than 7 the time, a little less than the cohesion of letex polymerization base polymer, probably be difficult to generate the aggregate of big particle diameter, on the other hand, when the pH of waste liquid value surpasses 10, the same aggregate of worrying to be difficult to generate big particle diameter.PH the value more preferably scope of 7.5-9.5, the more preferably scope of 8.0-9.0 of the waste liquid of Tai-Ace S 150 have been added.
Because the waste liquid that adds behind the Tai-Ace S 150 becomes acidity, so, can use the alkaline aqueous solution such as aqueous sodium hydroxide solution in order again the pH value of this waste liquid to be adjusted in the scope of 7-10.
As two types polymer coagulant, use the different polymer coagulant of each self charge, i.e. anionic polymer coagulant and cationic high-molecular flocculation agent.
As the anionic polymer coagulant, for example can enumerate: acrylamide adds acrylic amide polymer coagulants such as water decomposition thing with (methyl) vinylformic acid, 2-acrylamide-2-methyl propane sulfonic acid, vinyl sulfonic acid or the multipolymer of their salt, the part of polyacrylamide; Polyacrylic acid bases polymer coagulant that obtains by vinylformic acid and sodium hydroxide etc.
Wherein, the anionic polymer coagulant of polyacrylamide is because its cohesion ability to the letex polymerization base polymer is good and more suitable.In addition, the quality molecular-weight average of the anionic polymer coagulant of polyacrylamide is preferably 1,000 ten thousand-1,500 ten thousand scope.When the quality molecular-weight average less than 1,000 ten thousand the time, the cohesive force deficiency is easy to form the aggregate of small particle size.On the other hand, when the quality molecular-weight average surpassed 1,500 ten thousand, same cohesive force deficiency also was easy to form the aggregate of small particle size.Addition to the anionic polymer coagulant is not done special qualification, and this addition is the scope of 0.2-10000ppm with respect to waste liquid usually.
As the cationic high-molecular flocculation agent, can enumerate: contain disassociation and become the acrylic compound of cationic as the polyacrylate(s) polymer coagulant of monomeric unit, polyamine family macromolecule flocculation agent, Dyhard RU 100 family macromolecule flocculation agent etc.
Wherein, the cationic high-molecular flocculation agent of polyacrylate(s) is because its cohesion ability to the letex polymerization base polymer is good and more suitable.In addition, the quality molecular-weight average of the cationic high-molecular flocculation agent of polyacrylamide acid esters class is preferably 3,500,000-5,000,000 scope.When the quality molecular-weight average less than 3,500,000 the time, the cohesive force deficiency is easy to form the aggregate of small particle size.On the other hand, when the quality molecular-weight average surpassed 5,000,000, same cohesive force deficiency also was easy to form the aggregate of small particle size.Addition to the cationic high-molecular flocculation agent is not done special qualification, and this addition is the scope of 0.2-10000ppm with respect to waste liquid usually.
Anionic polymer coagulant and cationic high-molecular flocculation agent are to add in waste liquid individually, rather than add simultaneously.To the order of adding, promptly no matter with anionic and cationic in anyly do not do special qualification as second polymer coagulant as first polymer coagulant with any among them, but preferably make decision according to the ionic of the emulsifying agent that contains in the waste liquid.Promptly, the emulsifying agent that contains in the waste liquid be anionic property or waste liquid in the emulsifying agent that contains be under the many situations of the emulsifier content of multiple and anionic property, consider from aggregation efficiency, preferably at first in waste liquid, add the cationic high-molecular flocculation agent, then add the anionic polymer flocculation agent.In addition, the emulsifying agent that contains in waste liquid is a cationic, or the emulsifying agent that contains in the waste liquid is under the emulsifier content situation how of multiple and cationic, consider from aggregation efficiency, preferably at first in waste liquid, add the anionic polymer coagulant, then add the cation high molecular flocculation agent.
As the emulsifying agent that contains in the waste liquid, for example can enumerate: anionic property, cationic, both sexes and non-ionic tenside.As the tensio-active agent of anionic property, for example can enumerate: soap type, sulfuric acid type, sulfonate type, phosphate ester salt type etc.As the tensio-active agent of cationic, for example can enumerate: alkylamine salt type, quarternary ammonium salt type etc.As amphoterics, for example can enumerate: alkyl betaine-type, amine oxide type etc.As non-ionic tenside, for example can enumerate: poly-hydroxyl ethylene type, sorbitol ester type, phosphate ester salt type etc.
The Tai-Ace S 150 2 kind polymer coagulants different with electric charge are added individually separately, generation be the waste liquid of the aggregate of main component with the letex polymerization base polymer, can supernatant be separated with aggregate by known method.Separation method for example can be enumerated: the settling methods of gravity settling, centrifugal method of enrichment and membrane separation process etc.
This isolating aggregate is dehydrated, and as final waste and processed.The dewatering of aggregate can use for example known method such as belt press (ベ Le と プ レ ス) evaporation, centrifuge dehydration method, screw press evaporation, filter-press dehydration method.
In the treatment process of the waste liquid that contains the letex polymerization base polymer of above explanation, at first in the waste liquid that contains the letex polymerization base polymer, add Tai-Ace S 150, the cohesion of letex polymerization base polymer generates the aggregate than small particle size.Then, add first polymer coagulant in the waste liquid that has added Tai-Ace S 150, the aggregate of small particle size reassociates and generates the aggregate of greater particle size.Again in the waste liquid that has added first polymer coagulant, add second polymer coagulant that has with the different electric charges of first polymer coagulant, this second polymer coagulant and the first polymer coagulant ionic bond that enters in the aggregate, play effect, thereby form the aggregate of huge aggregate as the linking agent between aggregate.
The aggregate of this aggregate is because settling velocity is fast, so the efficient of liquid waste disposal is very good.In addition, the aggregate of this aggregate is gathered difficult the division because the ionic bond of 2 kinds of different polymer coagulants of electric charge is arranged strongly.Therefore, can suppress to be difficult to precipitate, the generation of the aggregate of isolating small particle size, can improve the organic efficiency of aggregate, and reduce the organic content in the draining of discharging.
In addition, owing to added two kinds of different polymer coagulants of electric charge in the waste liquid, even so contain ionic different numerous emulsifiers in the waste liquid, the cohesion ability of polymer coagulant can not reduce yet, can improve the organic efficiency of aggregate in view of the above, and reduce the organic content in the draining of discharging.
Embodiment
Below the present invention will be described with embodiment, but the present invention is not subjected to the qualification of these embodiment.In addition, in the present invention, " part " and " % " refers to " mass parts " and " quality % " as not special explanation.
In addition, in the present embodiment, the size of aggregate is represented with the settling velocity of the aggregate that following method is measured.
Settling velocity
Form the discharge water of aggregate with the graduated cylinder collection of 500ml, leave standstill then, to reach the complete isolating time of aggregate and water as settling velocity.
In addition, in the present embodiment, the waste liquid that contains the letex polymerization base polymer uses following waste liquid.
(waste liquid A)
It is the waste liquid (draining) of when making methyl methacrylate as the letex polymerization base polymer/butadiene/styrene copolymers, discharging, contain 1.2% the outstanding absurd creature matter (being designated hereinafter simply as SS) of swimming, the anion surfactant of 1500ppm (flower king (strain) system, KS ソ one プ MR) as the soap type of emulsifying agent.
(waste liquid B)
It is the waste liquid (draining) of when making, discharging as the methyl methacrylate/butadiene/styrene copolymers of letex polymerization base polymer and silicon rubber, contain 1.8% SS, the anion surfactant of 130ppm (flower king (strain) system as the soap type of emulsifying agent, KS ソ one プ MR) and the anion surfactant of the sulfonate type of 350ppm (flower king (strain) system, KS ソ one プ MR).
(waste liquid C)
Be in the waste liquid (draining) of when making methyl methacrylate/butadiene/styrene copolymers as the letex polymerization base polymer, silicon rubber and acrylic rubber, discharging, contain 2.8% SS, the anion surfactant of 110ppm (flower king (strain) system as the soap type of emulsifying agent, KS ソ one プ MR), the anion surfactant of the sulfonate type of 380ppm (flower king (strain) system, KS ソ one プ MR) and the nonionogenic tenside of the phosphate ester salt type of 200ppm (eastern nation chemistry system, Off オ ス Off ア ノ one Le LO-529).
Embodiment 1
At first, add 2 parts of Tai-Ace S 150 in 100 parts of waste liquid A, again to the aqueous sodium hydroxide solution that wherein adds 2%, regulating the pH value is 7.5, stirs 5 minutes.
Then, in the waste liquid that has added Tai-Ace S 150, add the cationic high-molecular flocculation agent (ダ イ ヤ Off ロ Star Network (strain) system, KP-204B, quality molecular-weight average 4,000,000) of the polyacrylate(s) of 500ppm again, stirred 1 minute.
Then, in this waste liquid, add the anionic polymer coagulant (ダ イ ヤ Off ロ Star Network (strain) system, AP-120, quality molecular-weight average 1,100 ten thousand) of the polyacrylamide of 500ppm, stirred 1 minute.
Measure the settling velocity of the aggregate in the waste liquid, show the result in table 1.
Embodiment 2
Except waste liquid A is changed to the waste liquid B, carry out the liquid waste disposal identical with embodiment 1, measure the settling velocity of the aggregate in the waste liquid, show the result in table 1.
Embodiment 3
Except waste liquid A is changed to the waste liquid C, carry out the liquid waste disposal identical with embodiment 1, measure the settling velocity of the aggregate in the waste liquid, show the result in table 1.
Comparative Examples 1
Except not adding cationic and anionic polymer coagulant, carry out the liquid waste disposal identical with embodiment 3, measure the settling velocity of the aggregate in the waste liquid, it the results are shown in table 1.
Comparative Examples 2
Except not adding cationic flocculation agent, and the addition of anionic polymer coagulant is outside the 1000ppm, carries out the liquid waste disposal identical with embodiment 3, measures the settling velocity of the aggregate in the waste liquid, shows the result in table 1.
Comparative Examples 3
Except not adding the anionic polymer coagulant, and the addition of cationic high-molecular flocculation agent is outside the 1000ppm, carries out the liquid waste disposal identical with embodiment 3, measures the settling velocity of the aggregate in the waste liquid, shows the result in table 1.
Comparative Examples 4
Except not adding Tai-Ace S 150, and the addition that changes the cationic high-molecular flocculation agent is that the addition of 1000ppm and anionic polymer coagulant is outside the 1000ppm, carry out the liquid waste disposal identical, measure the settling velocity of the aggregate in the waste liquid, show the result in table 1 with embodiment 3.
Table 1
| Embodiment | Comparative Examples | ||||||
| 1 | 2 | 3 | 1 | 2 | 3 | 4 | |
| The kind of waste liquid | A | B | C | C | C | C | C |
| Tai-Ace S 150 | Add | Add | Add | Add | Add | Add | - |
| The cationic high-molecular flocculation agent | Add | Add | Add | - | - | Add | Add |
| The anionic polymer coagulant | Add | Add | Add | - | Add | - | Add |
| The settling velocity of aggregate (second) | 8 | 9 | 7 | 59 | 62 | 86 | 32 |
As described above, the treatment process that contains the waste liquid of letex polymerization base polymer of the present invention is to add Tai-Ace S 150 in the waste liquid that contains the letex polymerization base polymer, in the waste liquid that is added with Tai-Ace S 150, add first polymer coagulant then, in the waste liquid that is added with first polymer coagulant, add second polymer coagulant that has with the different electric charges of first polymer coagulant again, therefore can make the particle diameter of the aggregate of letex polymerization base polymer become big, the organic efficiency of aggregate is improved, the organic content in the draining of discharging is reduced.
In addition,, just can promote the cohesion of letex polymerization base polymer, be easy to generate the aggregate of big particle diameter, and improve the efficient of liquid waste disposal if adjust the scope of the pH value of the waste liquid that has added Tai-Ace S 150 at 7-10.
In addition, if 2 types above-mentioned polymer coagulant is the quality molecular-weight average is the anionic polymer coagulant of 1,000 ten thousand-1,500 ten thousand polyacrylamide, with the quality molecular-weight average be the cationic high-molecular flocculation agent of 3,500,000-5,000,000 polyacrylate(s), just can make with the polymkeric substance of discharging in the manufacturing of emulsification base polymer is that the outstanding absurd creature of swimming of main component condenses with high-level efficiency, form the aggregate of big particle diameter, thus the efficient of the wastewater treatment that increases substantially.
Claims (2)
1. a treatment process that contains the waste liquid of letex polymerization base polymer by cohesion, separating emulsions polymeric type polymkeric substance in the waste liquid that contains the letex polymerization base polymer, is characterized in that,
In the waste liquid that contains the letex polymerization base polymer, add Tai-Ace S 150, in the waste liquid that has added Tai-Ace S 150, add first polymer coagulant then, in the waste liquid that has added first polymer coagulant, add second polymer coagulant that has with the different electric charges of first polymer coagulant again
Adjustment has been added the pH value of waste liquid of Tai-Ace S 150 in the scope of 7-10.
2. the treatment process that contains the waste liquid of letex polymerization base polymer according to claim 1, it is characterized in that, described 2 types polymer coagulant is that the quality molecular-weight average is that the anionic polymer coagulant of 1,000 ten thousand-1,500 ten thousand polyacrylamide and quality molecular-weight average are the cationic high-molecular flocculation agent of 3,500,000-5,000,000 polyacrylate(s).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002059245A JP3740423B2 (en) | 2002-03-05 | 2002-03-05 | Method for treating waste liquid containing emulsion polymerization polymer |
| JP200259245 | 2002-03-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1442443A CN1442443A (en) | 2003-09-17 |
| CN1276944C true CN1276944C (en) | 2006-09-27 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031051642A Expired - Fee Related CN1276944C (en) | 2002-03-05 | 2003-03-03 | Treatment method of waste liquid containing emulsion polymerized polymer |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3740423B2 (en) |
| CN (1) | CN1276944C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4177354B2 (en) * | 2004-05-26 | 2008-11-05 | 三洋化成工業株式会社 | Treatment method of waste water containing resin particles |
| JP5350870B2 (en) * | 2009-04-20 | 2013-11-27 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Method for reducing CODCr of waste liquid generated during production of silicone monomer |
| JP6644607B2 (en) * | 2016-03-30 | 2020-02-12 | 住友重機械エンバイロメント株式会社 | Wastewater treatment system |
| CN110015735B (en) * | 2019-04-10 | 2022-03-22 | 深圳市松柏实业发展有限公司 | Composite flocculant, flocculation method thereof, recycling method and recycling system |
-
2002
- 2002-03-05 JP JP2002059245A patent/JP3740423B2/en not_active Expired - Fee Related
-
2003
- 2003-03-03 CN CNB031051642A patent/CN1276944C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003251364A (en) | 2003-09-09 |
| JP3740423B2 (en) | 2006-02-01 |
| CN1442443A (en) | 2003-09-17 |
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