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WO2017143976A1 - 一种乳液聚合树脂生产中废水污染物削减或控制方法 - Google Patents

一种乳液聚合树脂生产中废水污染物削减或控制方法 Download PDF

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Publication number
WO2017143976A1
WO2017143976A1 PCT/CN2017/074323 CN2017074323W WO2017143976A1 WO 2017143976 A1 WO2017143976 A1 WO 2017143976A1 CN 2017074323 W CN2017074323 W CN 2017074323W WO 2017143976 A1 WO2017143976 A1 WO 2017143976A1
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wastewater
demulsification
latex
chloride
treatment
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French (fr)
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周岳溪
宋玉栋
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Chinese Research Academy of Environmental Sciences
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Chinese Research Academy of Environmental Sciences
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Priority to US16/079,197 priority Critical patent/US10335760B2/en
Priority to DE112017000939.1T priority patent/DE112017000939B4/de
Publication of WO2017143976A1 publication Critical patent/WO2017143976A1/zh
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    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/04—Breaking emulsions
    • B01D17/042—Breaking emulsions by changing the temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/04—Breaking emulsions
    • B01D17/047—Breaking emulsions with separation aids
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    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
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    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
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    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
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    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • C08F6/22—Coagulation
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    • B01J2219/00765—Baffles attached to the reactor wall
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    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
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    • C02F2101/32—Hydrocarbons, e.g. oil
    • C02F2101/325—Emulsions
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    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
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    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
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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
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Definitions

  • the present invention relates to a method for reducing or controlling wastewater contaminants in the production of emulsion polymerized resins.
  • Emulsion polymerization is an important synthetic resin production method, and is also a mainstream production process for synthetic resins such as ABS resin, polyvinyl chloride, polytetrafluoroethylene, polyvinyl alcohol, and polymethyl methacrylate. Since the emulsion polymerized resin is formed into a medium by using water as a medium, and then the polymer is separated from water to further process the product, the amount of waste water is large, the concentration of the pollutant is high, and the high concentration of the refractory polymer and the toxicity are strong. Polymer monomer is very difficult to handle.
  • the wastewater in the production of emulsion polymer resin mainly comes from the emulsion polymerization section and the coagulation drying section where the polymer is separated from the emulsion.
  • the emulsion polymerization section wastewater mainly comes from the latex filter cleaning wastewater and the reaction kettle cleaning wastewater.
  • the pollutants are mainly latex, the latex particle size is small, and the separation is difficult.
  • the coagulation drying section wastewater (or "coagulation drying wastewater”) is usually acidic high-temperature wastewater, has a high content of dissolved pollutants, and contains a relatively large particle size polymer powder.
  • the wastewater with different characteristics described above is mixed and subjected to terminal treatment, and the impact load is high, the treatment is difficult, the effluent is unstable, and the treatment cost is high.
  • methods for producing emulsion polymerized resins include:
  • the monomer is polymerized in the reaction vessel to obtain an emulsion in which the polymer and the aqueous phase are mixed;
  • the polymer-containing emulsion obtained in the step 1 is filtered through a latex filter to obtain a polymer
  • the polymer obtained by the filtration in step 2 is grafted in a reaction vessel to obtain an emulsion in which a graft polymer and an aqueous phase are mixed;
  • the emulsion containing the graft polymer obtained in the step 3 is filtered through a latex filter
  • the obtained polymer is coagulated and dried.
  • Steps 3 and 4 above are optional steps, that is, steps that are selected when needed.
  • the invention provides a method for reducing or controlling wastewater pollutants produced by an emulsion polymerization resin, comprising the following steps:
  • Step (A) can prolong the cycle of the reactor and reduce the discharge of waste water and pollutants.
  • step (A) of the method of the invention is prevented or by at least one of the following Reduce the adhesion of the polymer on the wall of the kettle: add a scraper on the stirring paddle of the reactor, the scraper can scrape off the polymer adhering near the wall of the kettle during the polymerization process; the use can promote the between the center of the reactor and the wall of the kettle a mass transfer heat transfer plate frame and/or a pusher agitator; and/or a baffle baffle mounted adjacent the wall to prevent the mixture from swirling as a whole.
  • the wastewater contaminant reduction method of the present invention further comprises treating the wastewater in each step of the emulsion polymerization resin production before the wastewater collection, and reducing the pollutants in the collected wastewater.
  • the method of the invention can adopt a filter for reducing the amount of latex loss of the filter cleaning and the concentration of the cleaning waste water pollutant, such as a nitrogen-discharge type low residual liquid latex filter (ie, after the filter is normally filtered, the nitrogen gas will be used.
  • the residual liquid in the filter is discharged from the filter to ensure a low amount of residual liquid before the filter is cleaned.
  • a nitrogen inlet may be provided in the upper part of the nitrogen-discharge type low residual liquid latex filter, and a filtrate discharge port may be provided in the lower part.
  • the method further comprises at least one of the following steps:
  • (B) performing a demulsification degumming treatment (such as breaking milk) on the wastewater discharged from the latex filter cleaning to reduce the amount of pollutants discharged from the wastewater; when graft polymerization is present, preferably, the monomer (such as The wastewater discharged after the polymerization of 1,3-diene (referred to as latex wastewater) is mixed with the wastewater discharged after the graft polymerization, and then subjected to emulsion degumming.
  • a demulsification degumming treatment such as breaking milk
  • the method further comprises at least one of the following steps:
  • the effluent after coagulation and air flotation treatment uses biological treatment process to remove organic matter, nitrogen and phosphorus.
  • step (B) means that the monomer (such as 1,3-diene) polymerized latex and the optional graft polymer latex are subjected to a filtration operation of the latex filter before the next process, and the latex filter is cleaned. Waste water is treated.
  • the method of breaking the milk that is, using steam heating, adding a medicament to achieve demulsification, and forming a rubber block, and then removing the rubber block, the pollutants in the discharged waste water are reduced.
  • the demulsification of the latex filter washing wastewater in the method of the present invention includes, but is not limited to, the following methods: heating with steam to 25-80 ° C, adding calcium chloride, magnesium chloride, polyaluminum chloride, polyferric chloride, polysulfuric acid A demulsifier such as iron or sulfuric acid is added in an amount of 100 to 5000 mg/L; polyacrylamide can be used as a coagulant.
  • the demulsification degumming of the clearing water can be at least two ways One kind of realization: (1) directly add the demulsifier to the clearing waste water in the reactor and stir the demulsification, and install a self-priming air mixer in the venting port of the reaction kettle to inhale the air when the demulsification wastewater is emptied (0.25 ⁇ 1 times the volume of wastewater), forms microbubbles and adheres to the latex flocs; the wastewater mixed with air enters the flotation tank to separate the latex from the water.
  • the reaction vessel clearing wastewater directly enters the separate demulsification flotation tank, and the demulsification agent is demulsified, and the separation of the latex and the water is realized in the flotation tank.
  • the amount of air added is 0.25 to 1 times the volume of wastewater.
  • the flotation cell used may include a water inlet zone, a flap mixing demulsification zone, a water distribution zone, a flotation zone, a water outlet zone, and a pharmaceutical dosing system.
  • the demulsifier may be selected from calcium chloride or polyaluminum chloride, wherein the dosage of calcium chloride is 200-700 mg/L, and the dosage of polyaluminium chloride is 25-75 mg/L; polyacrylamide is a coagulant. The dosage is 1 to 10 mg/L, and the demulsification temperature is 35 to 70 °C.
  • the demulsification after the graft polymerization wastewater is mixed with the monomer (1,3-diene) polymerized latex wastewater may be selected from the group consisting of calcium chloride, magnesium chloride, polyaluminum chloride or a combination thereof. Demulsifier.
  • the post-demulsified latex wastewater is mixed with the coagulated dry wastewater for coagulation air flotation treatment, and the coagulating agent which can be used is selected from the group consisting of polyaluminum chloride, polyferric chloride, aluminum sulfate, and chlorination. Calcium or their combination with ferric chloride and ferric sulfate.
  • the dosage of the medicament is 50-300 mg/L, and polyacrylamide is used as a coagulant.
  • the dosage is 1-10 mg/L, the temperature is 20-60 °C, the flocculation removal rate of the polymer is over 90%, and the phosphorus removal rate is 80. %the above.
  • the effluent after the coagulation air flotation treatment according to the present invention uses a biological treatment process to remove organic matter, nitrogen and phosphorus, and the biological treatment reactor contains a region in which dissolved oxygen is above 0.4 and dissolved oxygen is 0.2.
  • the mixed liquid in the reactor circulates, the circulation flow rate is 2 to 6 times of the influent flow rate, and the hydraulic retention time is 30 to 48 hours.
  • the source of pollutants is reduced, resources are recovered and the difficulty and cost of wastewater treatment are reduced.
  • the concentration of pollutants in the reactor is high and the discharge is large, which is one of the main sources of wastewater pollutants in the emulsion polymerization section.
  • part of the reaction kettle clearing cycle is less than 30 batches, and 3 batches are reacted every day, and the kettle is cleaned once every 10 days, which affects the production efficiency of the reactor, discharges a large amount of pollutants and causes waste of raw materials.
  • the cleaning cycle can be extended to more than 100 batches, and accordingly, the cleaning waste water and pollutants are reduced by more than 70%.
  • the latex filter cleans the wastewater with small amount of water and intermittent discharge, but the concentration of pollutants is up to several hundred thousand mg/L, and the pollutants are mainly latex, which has resource value.
  • the latex in the wastewater can be agglomerated into a rubber block, which can be resourced by taking out the take-out, reducing the impact load of the wastewater and reducing the difficulty of subsequent wastewater treatment.
  • High concentration of waste water The concentration of dyes is high, the single discharge is large, and the pollutants are mainly latex, which is easy to generate impact load on the subsequent coagulation air flotation-bioprocessing unit, which affects the stability of the effluent water quality.
  • the high-concentration latex in the wastewater can be removed by demulsification flotation to prevent the impact load.
  • the graft polymerization wastewater and the polymerization (for example, 1,3-diene polymerization) latex wastewater are both latex wastewater, but the characteristics of the emulsion are quite different.
  • the compounding coagulating agent is used to achieve the removal of the high concentration of phosphorus while reducing the processing load of the subsequent biological processing unit while achieving the removal of the latex and the powder.
  • emulsion polymerization resin production wastewater may also contain high concentrations of nitrogen and phosphorus pollutants. Although there are mature biological nitrogen and phosphorus removal processes, the removal of phosphorus is often limited by the easily degradable carbon source in the wastewater, and a large amount of excess sludge is produced, and the sludge yield is high.
  • the present invention therefore proposes a coagulating agent that simultaneously achieves the removal of organic polymers and phosphorus in wastewater.
  • Figure 1 is a schematic diagram of a wastewater treatment process in the production of a conventional emulsion polymerization resin.
  • Figure 3 is a schematic view of a demulsification flotation cell.
  • Figure 4 is a schematic diagram of a reaction vessel with a self-priming air mixer.
  • Figure 5 is a schematic view of a nitrogen-discharge type low residual liquid filter.
  • the inner part of the ABS graft polymerization reactor was modified.
  • the stirrer was replaced by a frame stirrer and replaced with a frame stirrer.
  • a rectangular baffle baffle was installed near the wall to prevent the mixture from swirling.
  • the internal parts of the butadiene polymerization reactor were modified, and the agitator was added with an adaptive blade on the basis of the original ribbon agitator. During the stirring, the blade was kept close to the reaction vessel, and the butadiene was optimized after stirring and optimization.
  • the polymerization reactor cleaning cycle was extended from 30 batches to 112 batches, and the amount of waste water and pollutants generated by the tank was reduced by at least 73%.
  • the inner part of the ABS graft polymerization reactor was modified, and the stirrer was replaced with a double-belly mixer to push-type.
  • a rectangular baffle was installed near the wall to prevent the mixture from swirling.
  • the ABS graft polymerization reactor is extended from 28 batches to 102 batches.
  • the waste water and pollutants can be reduced by at least 73%, and the latex filter cleaning frequency is reduced from 4 times/month to 2 times. /month.
  • the traditional cage filter is transformed into a nitrogen discharge low residual liquid filter, single filter cleaning
  • the latex emissions of the operation can be reduced by at least 82%.
  • the filter is used to clean the wastewater, calcium chloride is used as a demulsifier, the dosage is 5000mg/L, and the emulsion is broken at 40°C.
  • the COD of the wastewater can be reduced by at least 95% before the emulsion breaking. .
  • the high-concentration clearing wastewater is made of polyaluminum chloride or calcium chloride as a demulsifier, the dosage is 1000mg/L, and the dosage of PAM is 2mg/L, which is floated by a separate flap.
  • Demulsification flotation at 70 °C, the COD of wastewater can be reduced by at least 80% before demulsification.
  • the mixed wastewater of butadiene polymerization wastewater and ABS graft polymerization wastewater is first treated with calcium chloride for demulsification, the dosage is 75mg/L, the temperature is 20 °C, and then mixed with coagulated dry wastewater to carry out coagulation gas.
  • Floating treatment using a composite coagulant containing polyaluminum chloride, calcium chloride and ferric chloride (weight ratio 50:40:10), the dosage is 100mg / L, PAM is a coagulant, the dosage is 5mg / L, temperature is 50 ° C, COD removal of 43%, TP removal of 86%, than butadiene polymerization wastewater, ABS graft polymerization wastewater and coagulation drying wastewater mixed with polyaluminum chloride as a coagulant for coagulation Floating, the cost of the drug can be reduced by at least 56% when the same treatment effect is achieved.
  • the coagulated air flotation water of Example 7 is treated by an A/O activated sludge reactor, and the dissolved oxygen in the aerobic zone is controlled to be 1.0 mg/L, the dissolved oxygen in the anoxic zone is 0.1 mg/L, and the hydraulic retention time is 48 h.
  • the effluent TN is less than 15 mg/L, the ammonia nitrogen is less than 5 mg/L, and the TP is less than 0.5 mg/L.
  • the peak COD of the device drainage is reduced from 6000 mg/L to less than 2000 mg/L, which reduces the number of subsequent processing units. Impact and effluent stability increase; COD source of latex wastewater is reduced by more than 70%; wastewater treatment cost is reduced by more than 50% (such as 51%).

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Abstract

一种乳液聚合树脂生产中废水污染物的削减或控制方法，包括以下步骤：(1)通过乳液聚合反应釜优化延长反应釜清釜周期，减少清釜废水及污染物排放量；(2)胶乳过滤器清洗废水破乳捞胶减少污染物排放量；(3)高浓度清釜废水破乳浮选回收；(4)接枝聚合废水与1,3-二烯聚合废水混合后破乳；(5)破乳后胶乳废水与凝聚干燥废水混合进行混凝气浮处理；(6)混凝气浮出水采用生物处理工艺去除有机物、氮、磷。该方法具有源头减排污染物、提高产品收率、节约资源、废水分质处理、处理成本低的特点。

Description

一种乳液聚合树脂生产中废水污染物削减或控制方法 技术领域
本发明涉及乳液聚合树脂生产中废水污染物的削减或控制方法。
背景技术
乳液聚合是重要的合成树脂生产方法，也是ABS树脂、聚氯乙烯、聚四氟乙烯、聚乙烯醇、聚甲基丙烯酸甲酯等合成树脂的主流生产工艺。由于乳液聚合树脂生产过程中以水为介质形成乳液，然后聚合物与水分离以进一步加工产品，因此废水产生量大、污染物浓度高，且含有高浓度的难降解聚合物和毒性较强的聚合物单体，处理难度很大。
乳液聚合树脂生产中的废水主要来自乳液聚合工段和聚合物从乳液中分离出来的凝聚干燥工段。乳液聚合工段废水主要来自胶乳过滤器清洗废水和反应釜清釜废水，污染物以胶乳为主，胶乳粒径小，分离困难。凝聚干燥工段废水(或称为“凝聚干燥废水”)通常为酸性高温废水，溶解态污染物含量高，并含有粒径相对较大的聚合物粉料。现有处理方法多将上述不同特性的废水混合之后进行末端处理，冲击负荷高、处理难度大，出水不稳定，处理成本高。
发明内容
本发明的目的在于提供一种用于实现乳液聚合树脂生产中废水污染物的削减或控制方法。
通常，乳液聚合树脂生产的方法包括：
1.单体在反应釜中发生聚合反应，得到聚合物和水相混合的乳液；
2.将步骤1得到的含聚合物的乳液经过胶乳过滤器过滤，得到聚合物；
3.将步骤2过滤得到的聚合物在反应釜中进行接枝反应，得到接枝聚合物和水相混合的乳液；
4.将步骤3得到的含接枝聚合物的乳液经过胶乳过滤器过滤；
5.将得到的聚合物进行凝聚干燥。
以上步骤3和步骤4是任选的步骤，即在需要时则选用的步骤。
本发明提供的一种乳液聚合树脂生产的废水污染物削减或控制方法，包括以下步骤：
(A)防止或减少反应釜中聚合物在釜壁的粘附。
步骤(A)可延长反应釜清釜周期，减少清釜废水及污染物排放量。
根据本发明的一些实施方式，本发明方法的步骤(A)是通过以下至少一种方式防止或 减少聚合物在釜壁的粘附：在反应釜搅拌桨上增加刮片，刮片能使聚合过程中釜壁附近粘附的聚合物及时刮走；采用能够促进反应釜中心与釜壁之间混合液传质传热的板框和/或推进式搅拌器；和/或在釜壁附近安装折流挡板，防止混合液整体打旋。
本发明的废水污染物削减方法还包括，在废水汇集之前，对乳液聚合树脂生产的各步骤中的废水进行处理，减少汇集后废水中的污染物。
本发明的方法可采用减少过滤器清洗的胶乳损失量和清洗废水污染物浓度的过滤器，如采用氮气排液式低残液胶乳过滤器(即，过滤器正常过滤操作结束后，用氮气将过滤器内残液排出过滤器，从而保证过滤器清洗前残液量低)。如图5所示。具体地，可以在氮气排液式低残液胶乳过滤器上部设有氮气入口，下部设有滤液排口。当过滤操作停止时，向过滤器内缓慢通入氮气，将过滤器内残液压入滤液排口，然后再进行过滤器清洗操作。
根据本发明的一些实施方式，所述方法还包括以下至少一个步骤：
(B)对胶乳过滤器清洗而排出的废水进行破乳脱胶处理(如破乳捞胶)，以减少废水中的污染物排放量；当存在接枝聚合时，优选地，将单体(如1,3-二烯)聚合后排出的废水(称为胶乳废水)与接枝聚合后排出的废水混合后进行破乳脱胶。
(C)对反应釜中排出的清釜废水进行破乳脱胶处理(如破乳浮选)，以减少废水中的污染物排放量；
(D)将胶乳过滤器清洗而排出的废水和反应釜中排出的清釜废水混合后破乳脱胶，以减少废水中的污染物排放量。
根据本发明的一些实施方式，所述方法还包括以下至少一个步骤：
(E)上述(B)、(C)或(D)步骤得到的处理后废水与凝聚干燥废水混合进行混凝气浮处理；和
(F)混凝气浮处理后的出水采用生物处理工艺去除有机物、氮、磷。
上述步骤(B)是指单体(如1,3-二烯)聚合胶乳和任选的接枝聚合胶乳在进入下一道工艺处理之前进行胶乳过滤器的过滤操作，对胶乳过滤器清洗产生的废水进行处理。例如采用破乳捞胶方式，即采用蒸汽加热、投加药剂的方式实现破乳，并形成胶块，然后将胶块捞出，使排出的废水中的污染物减少。
本发明的方法中的胶乳过滤器清洗废水的破乳包括但不限于以下方式：用蒸汽加热至25～80℃，投加氯化钙、氯化镁、聚合氯化铝、聚合氯化铁、聚合硫酸铁或硫酸等破乳剂，投加量为100～5000mg/L；可采用聚丙烯酰胺为助凝剂。
上述步骤(C)中，所述清釜废水的破乳脱胶(如破乳浮选)可通过以下两种方式至少 之一种实现：(1)向反应釜内清釜废水中直接加入破乳剂并搅拌破乳，在反应釜放空口安装自吸式空气混合器，使破乳后废水放空时吸入空气(0.25～1倍废水体积)，形成微气泡并与胶乳絮体粘附；混入空气的废水进入浮选槽，实现胶乳与水的分离。(2)反应釜清釜废水直接进入单独的破乳浮选槽，投加破乳药剂破乳，并在浮选槽内实现胶乳与水的分离。空气投加量为0.25～1倍废水体积。所使用的浮选槽可包括进水区、折板混合破乳区、布水区、浮选区、出水区和药剂投加系统。上述破乳剂可选自氯化钙或聚合氯化铝，其中氯化钙投加量为200～700mg/L，聚合氯化铝投加量为25～75mg/L；聚丙烯酰胺为助凝剂，投加量为1～10mg/L，破乳温度为35～70℃。
在步骤(D)中，接枝聚合废水与单体(1,3-二烯)聚合胶乳废水混合后的破乳可采用的破乳剂选自氯化钙、氯化镁、聚合氯化铝或其组合的破乳剂。
在步骤(E)中，所述破乳后胶乳废水与凝聚干燥废水混合进行混凝气浮处理，其可采用的混凝药剂选自聚合氯化铝、聚合氯化铁、硫酸铝、氯化钙或它们与氯化铁、硫酸铁的复配药剂。药剂投加量为50～300mg/L，采用聚丙烯酰胺为助凝剂，投加量为1～10mg/L，温度为20～60℃，聚合物絮凝去除率90％以上，磷去除率80％以上。
在步骤(F)中，本发明所述的混凝气浮处理后的出水采用生物处理工艺去除有机物、氮、磷，生物处理反应器内同时含有溶解氧在0.4以上的区域以及溶解氧在0.2以下的区域，反应器内混合液循环流动，循环流量为进水流量的2～6倍，水力停留时间为30～48h。
本发明的乳液聚合树脂生产中废水污染物控制的方法具有至少以下之一的优点：
(1)通过生产设备与工艺优化，实现污染物的源头削减，回收资源并降低废水处理难度和成本。反应釜清釜过程中污染物浓度高，排放量大，是乳液聚合工段废水污染物主要排放源之一。现有方法的部分反应釜清釜周期在30批以下，按照每天反应3批，10天就要清釜一次，影响了反应釜的生产效率，排放大量污染物并造成原料浪费。采用本发明所述方法，可将清釜周期延长至100批以上，相应地，清釜废水及污染物削减70％以上。
(2)采用本发明提出的氮气排液式胶乳过滤器代替传统的胶乳过滤器，过滤器清洗前的残液量可大幅减少，从而减少胶乳消耗量和清洗废水中的污染物浓度。
(3)废水分质处理，在保证污染物去除效果的同时，降低废水处理成本。胶乳过滤器清洗废水，水量小，间歇排放，但污染物浓度高达几十万mg/L，且污染物以胶乳为主，具有资源化价值。通过破乳，可使废水中胶乳凝聚为胶块，捞取外卖可实现资源化，减小废水的冲击负荷，降低后续废水处理的难度。高浓度清釜废水污 染物浓度高，单次排水量大，污染物以胶乳为主，易对后续混凝气浮-生物处理单元产生冲击负荷，影响出水水质的稳定性。通过破乳浮选可实现废水中高浓度胶乳的去除，防止冲击负荷的产生。接枝聚合废水与聚合(例如1,3-二烯聚合)胶乳废水均为胶乳废水，但乳液特性差异较大，发明人发现两种废水混合处理的破乳难度和所需破乳药剂投加量显著低于单独破乳，因此两种废水宜混合破乳，然后再与凝聚干燥工段废水进行混合处理。
(4)采用复配混凝药剂，在实现胶乳及粉料去除的同时，实现高浓度磷的去除，减小后续生物处理单元处理负荷。乳液聚合树脂生产废水中除含有高浓度有机聚合物外，还可能含有高浓度的氮、磷污染物。尽管目前已有成熟的生物脱氮、除磷工艺，但磷的去除往往受到废水中易降解碳源的限制，且产生大量剩余污泥，污泥产率高。由于乳液聚合废水都具有混凝气浮单元，在混凝气浮阶段去除有机聚合物的同时，实现磷的去除，将显著降低后续生物处理单元的负荷。因此本发明提出了同时实现废水中有机聚合物和磷去除的混凝药剂。
下面结合附图对本发明一种乳液聚合树脂生产装置废水污染物源头削减与控制方法作进一步说明。
附图说明
图1为传统的乳液聚合树脂生产中废水处理工艺路线。
图2为采用本发明方法时乳液聚合树脂生产中废水污染物源头削减与控制的工艺路线。
图3为破乳浮选槽示意图。
图4为一种带自吸式空气混合器的反应釜示意图。
图5为一种氮气排液式低残液过滤器示意图。
具体实施方式
以下通过具体实施例示例说明本申请的方法，但本申请的保护范围并不受限于实施例。
实施例1：
对ABS接枝聚合反应釜釜内件进行改造，搅拌器由锚式搅拌器更换为框式搅拌器，在釜壁附近安装矩形折流挡板，以防止混合液整体打旋。经搅拌改造优化后ABS接枝聚合反应釜清釜周期由60批延长至100批，清釜废水及污染物产生量可至少削减40％。
实施例2：
对丁二烯聚合反应釜釜内件进行改造，搅拌器在原有螺带搅拌器基础上增加自适应刮片，搅拌期间，刮片一直紧贴反应釜上，经搅拌改造优化后，丁二烯聚合反应釜清釜周期由30批延长至112批，清釜废水及污染物产生量可至少削减73％。
实施例3：
对ABS接枝聚合反应釜釜内件进行改造，搅拌器由双螺带搅拌器更换为推进式，在釜壁附近安装矩形折流挡板，以防止混合液整体打旋。经搅拌改造优化后ABS接枝聚合反应釜清釜周期由28批延长至102批，清釜废水及污染物产生量可至少削减73％，胶乳过滤器清洗频率由4次/月降低到2次/月。
实施例4：
乳液聚合工艺(如ABS接枝聚合、聚丁二烯乳液聚合、聚四氟乙烯乳液聚合等)中，将传统笼型过滤器改造为氮气排液式低残液过滤器，单次过滤器清洗操作的胶乳排放量可至少削减82％。
实施例5：
聚丁二烯乳液聚合工艺中，过滤器清洗废水，以氯化钙为破乳剂，投加量为5000mg/L，40℃下通过破乳捞胶，废水COD较破乳前可至少降低95％。
实施例6：
在ABS接枝聚合工艺中，高浓度清釜废水，以聚合氯化铝或氯化钙为破乳剂，投加量为1000mg/L，PAM投加量为2mg/L，采用单独的折板浮选槽70℃下破乳浮选，废水COD较破乳前可至少降低80％。
实施例7：
丁二烯聚合废水及ABS接枝聚合废水的混合废水先用含有氯化钙进行破乳处理，投加量为75mg/L，温度为20℃，然后再与凝聚干燥废水混合后进行混凝气浮处理，采用含聚合氯化铝、氯化钙和氯化铁的复合混凝剂(重量比50:40:10)，投加量为100mg/L，PAM为助凝剂，投加量为5mg/L，温度为50℃，COD去除43％，TP去除86％，比丁二烯聚合废水、ABS接枝聚合废水及凝聚干燥废水混合后以聚合氯化铝为混凝剂进行混凝气浮，在达到同等处理效果的情况下，药剂成本可至少降低56％。
实施例8：
实施例7所述混凝气浮出水采用A/O活性污泥反应器进行处理，控制好氧区溶解氧1.0mg/L，缺氧区溶解氧0.1mg/L，水力停留时间为48h，出水TN达15mg/L以下，氨氮达5mg/L以下，TP达0.5mg/L以下。
实施例9：
采用本发明按照实施例1、2或2、3以及实施例4～8对ABS树脂生产装置进行改造后，装置排水峰值COD由6000mg/L降至2000mg/L以下，减少了对后续处理单元的冲击，出水稳定性提高；胶乳废水COD源头削减70％以上；废水处理成本下降50％以上(如51％)。
以上所述实施例仅是对本发明优选实施方式进行描述，并非对本发明的范围进行限定，在不脱离本发明设计精神的前提下，本领域普通技术人员对本发明的技术方案作出的各种变形和改进，均应落入本发明权利要求书确定的保护范围内。

Claims (14)

  1. 一种乳液聚合树脂生产中废水污染物削减或控制方法，其包括以下步骤：
    (A)防止或减少反应釜中聚合物在釜壁的粘附。
  2. 根据权利要求1所述的方法，其中所述步骤(A)是通过以下至少一种方式实现的：(1)在反应釜搅拌桨上增加刮片；(2)采用能够促进反应釜中心与釜壁之间混合液传质传热的板框和/或推进式搅拌器；(3)和/或在釜壁附近安装折流挡板，防止混合液整体打旋。
  3. 根据权利要求1或2所述的方法，其中，所述方法还包括以下至少之一的步骤：
    (B)对胶乳过滤器清洗而排出的废水进行破乳脱胶处理；
    (C)对反应釜中排出的清釜废水进行破乳脱胶处理；
    (D)将胶乳过滤器清洗而排出的废水和反应釜中排出的清釜废水混合后进行破乳脱胶处理。
  4. 根据权利要求3所述的方法，其中所述方法还包括以下至少一个步骤：
    (E)步骤(B)、(C)或(D)得到的处理后废水与凝聚干燥废水混合进行混凝气浮处理；和
    (F)混凝气浮处理后的出水采用生物处理工艺去除有机物、氮、磷。
  5. 根据权利要求3所述的方法，其中，所述胶乳过滤器为氮气排液式低残液过滤器。
  6. 根据权利要求3所述的方法，其中，当乳液聚合中存在接枝聚合时，将单体聚合的胶乳废水与接枝聚合后排出的废水混合后进行破乳脱胶。
  7. 根据权利要求1-6中任意一项所述的方法，其中，所述步骤(B)中的胶乳过滤器清洗废水的破乳是通过以下方式实现的：用蒸汽加热至25～80℃，并投加氯化钙、氯化镁、聚合氯化铝、聚合氯化铁、聚合硫酸铁或硫酸破乳剂。
  8. 根据权利要求3-7中任意一项所述的方法，其中所述步骤(C)中的清釜废水的破乳脱胶是通过以下两种方式至少之一种而实现：(1)向反应釜内清釜废水中直接加入破乳剂并搅拌破乳，在反应釜放空口安装自吸式空气混合器，使破乳后废水放空时吸入空气，形成微气泡并与胶乳絮体粘附；混入空气的废水进入浮选槽，实现胶乳与水的分离；(2)反应釜清釜废水直接进入单独的破乳浮选槽，投加破乳药剂破乳，并在浮选槽内实现胶乳与水的分离。
  9. 根据权利要求8所述的方法，其中所述清釜废水的破乳所采用的破乳剂选自氯化钙或聚合氯化铝，其中氯化钙投加量为200～700mg/L，聚合氯化铝投加量为25～75mg/L。
  10. 根据权利要求8或9所述的方法，其中所述破乳浮选槽包括进水区、折板混合破乳区、布水区、浮选区、出水区和药剂投加系统。
  11. 根据权利要求6所述的方法，其中所述破乳采用的破乳剂选自氯化钙、氯化镁、聚 合氯化铝或其复合破乳剂，投加量为20～100mg/L，温度为20～70℃。
  12. 根据权利要求4所述的方法，其中所述步骤(E)中需采用混凝药剂进行混凝，所述混凝药剂选自聚合氯化铝、聚合氯化铁、硫酸铝、氯化钙或它们与氯化铁、硫酸铁的复配药剂。
  13. 根据权利要求4所述的方法，其中在进行所述步骤(F)中的生物处理时，其生物处理反应器内同时含有溶解氧在0.4以上的区域以及溶解氧在0.2以下的区域，反应器内混合液在这两个区域间循环流动。
  14. 根据权利要求1-13中任意一项所述的方法，其中所述树脂选自ABS树脂、聚氯乙烯、聚四氟乙烯、聚乙烯醇或聚甲基丙烯酸甲酯。
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