WO2015165234A1 - 一种离子交换树脂脱附液的无害化处置与资源化利用方法 - Google Patents

一种离子交换树脂脱附液的无害化处置与资源化利用方法 Download PDF

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WO2015165234A1
WO2015165234A1 PCT/CN2014/090598 CN2014090598W WO2015165234A1 WO 2015165234 A1 WO2015165234 A1 WO 2015165234A1 CN 2014090598 W CN2014090598 W CN 2014090598W WO 2015165234 A1 WO2015165234 A1 WO 2015165234A1
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resin
ion exchange
desorption solution
anode
cathode
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PCT/CN2014/090598
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English (en)
French (fr)
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李爱民
王柏俊
王长明
江野立
朱兆连
宋海欧
王骏
陈讯
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南京大学
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Priority to US15/305,429 priority Critical patent/US20170044031A1/en
Publication of WO2015165234A1 publication Critical patent/WO2015165234A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • 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
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • 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
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • 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
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C02F2001/46142—Catalytic coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/46115—Electrolytic cell with membranes or diaphragms

Definitions

  • the invention relates to a method for resource utilization of an ion exchange resin desorption liquid, in particular to a method for harmless disposal and resource utilization of an ion exchange resin desorption liquid, which is an anion exchange resin for biochemical tail water A method of detoxification treatment and resource utilization of the resin desorption liquid produced after the deep treatment.
  • China is a country with scarce water resources.
  • the per capita water resources is only one-fourth of the world's water resources per capita, and it is unevenly distributed and has low utilization rate.
  • the demand for water is increasing, and the contradiction between water shortage and social economic development is more prominent. It is necessary to carry out advanced treatment and reuse of wastewater to alleviate the tension of China's water resources.
  • the advanced treatment methods include physical methods such as filtration, adsorption, membrane separation, evaporation and concentration, chemical methods such as ion exchange, coagulation, advanced oxidation, and biological methods such as biological nitrogen removal and dephosphorization.
  • the ion exchange method is a widely used advanced treatment method.
  • the ion exchange method filters the raw water with an ion exchange resin, and ions in the water are exchanged with ions fixed on the resin.
  • the surface of the secondary effluent organic material is mostly negatively charged, so the application of the anion exchange resin is more extensive.
  • NDMP resin is a new magnetic acrylic anion exchange resin developed by Nanjing University.
  • the resin has the characteristics of small particle size, fast adsorption, easy sedimentation and easy regeneration. It can not only adsorb organic matter in water, but also greatly reduce the levels of COD and UV254, and remove salt ions such as nitrate, fluoride and sulfate ions in water by ion exchange.
  • the ion exchange method has the advantages of good purification effect, low operating cost, and simple operation.
  • the ion exchange method produces a small amount of resin desorption liquid during application, and the desorption liquid has the characteristics of high salt content, high concentration, complex composition, high toxicity, poor biodegradability, and deep color.
  • the desorption liquid contains a relatively large amount of resin regenerant, and if it is improperly disposed, it will cause secondary pollution while causing waste of resources.
  • Advanced oxidation methods include ozone oxidation, Fenton oxidation, electrocatalytic oxidation, etc., ozone oxidation has no secondary pollution, but low ozone utilization rate and high power consumption; Fenton Oxidation technology has the advantages of simple and flexible operation and easy control, but also has the disadvantage that liquid hydrogen peroxide is inconvenient for storage and transportation and relatively high in cost.
  • Electrocatalytic oxidation is increasingly showing its unique advantages in wastewater treatment technology, such as high environmental compatibility, relatively simple electrochemical system equipment, small floor space, low operating and maintenance costs, and can effectively avoid secondary pollution and reaction.
  • the degree of control is high, and it is easy to realize the advantages of industrial automation. Therefore, electrochemical technology is also known as "environmentally friendly" technology, and has gradually become a useful tool to effectively solve the problem of water pollution.
  • electrochemical methods have been widely used in the treatment of organic wastewater such as dyes, paper, textiles, chemicals, leather, and bio-pharmaceuticals.
  • Electrocatalytic oxidation is used for the treatment of the resin desorption liquid, and there is no such literature in the field of desorption liquid treatment.
  • a small amount of resin desorption liquid is generated in the process of application of the ion exchange resin, and the desorption liquid has the characteristics of high salt content, high concentration, complex composition, high toxicity, poor biodegradability and deep color; and at the same time, desorption
  • the liquid contains a relatively large amount of resin regenerant. If it is improperly disposed, it will cause secondary pollution while causing waste of resources, which becomes a bottleneck restricting the application of resin in various industries.
  • the invention provides a method for harmless disposal and resource utilization of an ion exchange resin desorption liquid, wherein the content of organic substances in the desorption liquid is greatly reduced by the electrocatalytic oxidation method, and most of the regenerant is retained. After replenishing a certain amount of regenerant, the desorption liquid is re-established with good resin regeneration performance, thereby achieving the recycling of the desorption liquid, so that the amount of desorption liquid generated is greatly reduced.
  • the electrochemical reactor used includes a steady current power source, an electrolysis cell, an anode, and a cathode; and the electrolysis cell can separate the cathode chamber and the anode through a cation exchange membrane
  • the anode and the cathode are respectively located in the anode chamber and the cathode chamber, and the anode and the cathode are respectively connected to the steady current power source;
  • the electrolytic tank includes a water inlet and a water outlet;
  • the cathode adopts a graphite plate, a titanium plate, a titanium plate supporting cerium oxide or cerium oxide;
  • the anode is a titanium-based stable electrode, and the coating is cerium oxide Or bismuth oxide.
  • the anode and cathode have a current density of 5-50 mA/cm 2 , and the resin desorption liquid has a reaction time of 0.5-3 h in the electrolytic cell; the anode and cathode spacing is 1.5-5cm; direct oxidation reaction occurs on the surface of the anode.
  • Organic pollutants are oxidatively degraded by electron transfer on the surface of the electrode.
  • H 2 O is electrochemically oxidized to form O 3 or OH ⁇ , and the desorption solution contains a large amount of Cl.
  • the amount of sodium chloride added in the step (c) is such that the mass fraction of sodium chloride in the resin desorption solution is increased to 12-15%.
  • the cathode chamber and the anode chamber are separated by a cation exchange membrane to reduce the interference of the cathode reduction on the electrocatalytic oxidation and improve the oxidation performance.
  • the current density in the step (b) is adjusted to 20 mA/cm 2 and the reaction time is 2 h.
  • the pH of the resin desorption solution is adjusted to be neutral or weakly acidic prior to electrocatalytic oxidation in step (b).
  • a certain amount of NaOH is added in the step (c).
  • the invention discloses a method for harmless disposal and resource utilization of an ion exchange resin, wherein the COD of the desorption liquid after electrocatalytic oxidation treatment in step (b) is reduced by 30-70%, and the treated desorption liquid
  • the TOC is reduced by 25-50%
  • the chroma of the treated desorption solution is reduced by 95-99%
  • the UV 254 of the treated desorption solution is decreased by 50-70%
  • the B/C of the desorbed solution after treatment is lowered by 0.02 up to 0.13-0.20
  • lethal concentration Daphnia magna (LD 50) decreased from about 2% to 3%.
  • the method Compared with the existing resin desorption liquid disposal method, the method has the advantages of simple operation, no chemical addition, no secondary pollution, wide pH application range, and avoiding waste of regenerant in the desorption liquid.
  • the amount of desorption liquid is greatly reduced, and the reuse of the resin desorption liquid is realized, thereby saving ion exchange.
  • Replacing the resin cost of the desorbent produced by the resin reduces the technical cost.
  • the method can be widely applied to the treatment of the resin desorption liquid generated in the deep purification process of water quality by using an ion exchange resin.
  • the electrocatalytic oxidation device is used to treat the ion exchange resin desorption solution, and the electrocatalytic oxidation device comprises a steady current power source, an electrolysis cell, an anode and a cathode; the electrolysis cell comprises a water inlet and a water outlet, and the electrolysis cell is exchanged with a cation
  • the membrane separates the cathode chamber and the anode chamber, wherein the anode and the cathode are respectively located in the anode chamber and the cathode chamber, the cathode is a graphite plate; the anode is a titanium-based stable electrode, and the coating is a cerium oxide;
  • the ion exchange resin desorption solution is added to the electrocatalytic oxidation device.
  • the current density of the anode and cathode of the electrocatalytic oxidation device is 5 mA/cm 2 , the electrode spacing between the anode and the cathode is 5 cm, and the reaction time in the electrolysis cell is 0.5 h.
  • the post-COD removal rate was 42%, the TOC removal rate was 26%, the UV 254 removal rate was 55%, and the chroma removal rate was 95%.
  • the mass fraction of NaCl is 12%, and no NaCl is added.
  • As a resin regenerant the efficiency of regenerating the saturated resin is 90% of the fresh regenerant. After repeated use for 3 times, the regeneration efficiency is reduced to less than 60% of the fresh regenerant. Dispose of the desorption solution. At this point, the desorption liquid was reduced to 1/4 of the conventional method.
  • the desorption solution is treated by an electrocatalytic oxidation device, and the treatment equipment is the same as that of Embodiment 1, except that the cathode is a titanium plate; the anode is a titanium-based stable electrode, and the coating is barium oxide; the current density is 20 mA/ Cm 2 , electrode spacing 4 cm, treatment for 2 h, COD removal rate was 51%, TOC removal rate was 29%, UV 254 removal rate was 58%, and chroma removal rate was 97%.
  • the mass fraction of NaCl is 11%, and NaCl is added to a mass fraction of 12%.
  • As a resin regenerant the efficiency of regenerating the saturated resin is 92% of the fresh regenerant. After repeated use for 4 times, the regeneration efficiency drops to the fresh regenerant. Dispose of the desorption solution below 60%. At this point, the desorption solution was reduced to 1/5 of the conventional method.
  • a municipal wastewater After a municipal wastewater is treated in a conventional process, it is subjected to deep purification treatment with an ion exchange resin. After the resin treatment reached the adsorption saturation, it was regenerated with the regeneration liquid for 30 minutes under normal temperature and normal pressure. After regeneration, the regenerant becomes a desorption solution.
  • the desorption solution is treated by an electrocatalytic oxidation apparatus.
  • the treatment equipment is the same as that of Embodiment 1, except that the cathode is a titanium plate loaded with cerium oxide; the anode is a titanium-based stable electrode, and the coating is cerium oxide.
  • the current density was 30 mA/cm 2 , the electrode spacing was 3 cm, the treatment was 2 h, the COD removal rate was 54%, the TOC removal rate was 34%, the UV 254 removal rate was 62%, and the chroma removal rate was 97%.
  • the mass fraction of NaCl is 11%, and NaCl is added to a mass fraction of 12%.
  • the efficiency of regenerating the saturated resin is 94% of the fresh regenerant.
  • the regeneration efficiency is reduced to the fresh regenerant.
  • a municipal wastewater After a municipal wastewater is treated in a conventional process, it is subjected to deep purification treatment with an ion exchange resin. After the resin treatment reached the adsorption saturation, it was regenerated with the regeneration liquid for 30 minutes under normal temperature and normal pressure. After regeneration, the regenerant becomes a desorption solution.
  • the desorption solution is treated by an electrocatalytic oxidation apparatus.
  • the treatment equipment is the same as that of Embodiment 1, except that the cathode is a titanium plate loaded with cerium oxide; the anode is a titanium-based stable electrode, and the coating is cerium oxide.
  • the current density was 40 mA/cm 2 , the electrode spacing was 2 cm, the treatment was 2 h, the COD removal rate was 62%, the TOC removal rate was 40%, the UV 254 removal rate was 68%, and the chroma removal rate was 99%.
  • the mass fraction of NaCl is 10%, and NaCl is added to a mass fraction of 14%.
  • the efficiency of regenerating the saturated resin is 95% of the fresh regenerant. After repeated use for 6 times, the regeneration efficiency is reduced to the fresh regenerant. Dispose of the desorption solution below 60%. At this point, the desorption liquid was reduced to 1/7 of the conventional method.
  • a municipal wastewater After a municipal wastewater is treated in a conventional process, it is subjected to deep purification treatment with an ion exchange resin. After the resin treatment reached the adsorption saturation, it was regenerated with the regeneration liquid for 30 minutes under normal temperature and normal pressure. After regeneration, the regenerant becomes a desorption solution.
  • the desorption solution is treated by an electrocatalytic oxidation device, and the treatment equipment is the same as that of Embodiment 1, except that the cathode is a graphite plate; the anode is a titanium-based stable electrode, and the coating is a cerium oxide.
  • the current density was 50 mA/cm 2 , the electrode spacing was 1.5 cm, the treatment was 3 h, the COD removal rate was 64%, the TOC removal rate was 42%, the UV 254 removal rate was 70%, and the chroma removal rate was 99%.
  • the mass fraction of NaCl is 9%, and NaCl is added to the mass fraction of 12%.
  • the efficiency of regenerating the saturated resin is 96% of the fresh regenerant. After repeated use for 6 times, the regeneration efficiency is reduced to the fresh regenerant. Dispose of the desorption solution below 60%. At this point, the desorption liquid was reduced to 1/7 of the conventional method.
  • the other operations were the same as in Example 5.
  • the COD removal rate was 64%
  • the TOC removal rate was 42%
  • the UV 254 removal rate was 70%
  • the chroma removal rate was 99%.
  • the mass fraction of NaCl is 9%
  • NaCl is added to a mass fraction of 14%.
  • the efficiency of regenerating the saturated resin is 98% of the fresh regenerant.
  • the regeneration efficiency is reduced to the fresh regenerant.
  • the other operations were the same as in Example 5.
  • the COD removal rate was 64%
  • the TOC removal rate was 42%
  • the UV 254 removal rate was 70%
  • the chroma removal rate was 99%.
  • the mass fraction of NaCl is 9%
  • NaCl is added to the mass fraction of 15%
  • NaOH with a mass fraction of 0.5% is added.
  • the efficiency of regenerating the saturated resin is 99% of the fresh regenerant.
  • the regeneration efficiency was reduced to less than 60% of the fresh regenerant, and the desorption solution was disposed. At this point, the desorption liquid was reduced to 1/8 of the conventional method.
  • a printing and dyeing wastewater is subjected to a deep purification treatment with an ion exchange resin after a conventional process. After the resin treatment reached the adsorption saturation, it was regenerated with the regeneration liquid for 30 minutes under normal temperature and normal pressure. After regeneration, the regenerant becomes a desorption solution.
  • the electrocatalytic oxidation device is used to treat the ion exchange resin desorption solution, and the electrocatalytic oxidation device comprises a steady current power source, an electrolysis cell, an anode and a cathode; the electrolysis cell comprises a water inlet and a water outlet, and the electrolysis cell is exchanged with a cation
  • the membrane separates the cathode chamber and the anode chamber, wherein the anode and the cathode are respectively located in the anode chamber and the cathode chamber, the cathode is a graphite plate; the anode is a titanium-based stable electrode, and the coating is a cerium oxide;
  • the ion exchange resin desorption solution is added to the electrocatalytic oxidation device.
  • the current density of the anode and cathode of the electrocatalytic oxidation device is 20 mA/cm 2 , the distance between the anode and the cathode electrode is 2 cm, and the reaction time of the electrolysis cell is 3 h, and the COD removal rate is 60. %, the TOC removal rate was 39%, the UV 254 removal rate was 66%, and the chroma removal rate was 97%.
  • the mass fraction of NaCl is 9%, and the mass fraction of NaCl added to the resin desorption solution is 12%.
  • As a resin regenerant the efficiency of regenerating the saturated resin is 94% of the fresh regenerant. After repeated use for 4 times, The regeneration efficiency is reduced to less than 60% of the fresh regenerant, and the desorption solution is disposed of. At this point, the desorption solution was reduced to 1/5 of the conventional method.
  • Example 8 The other operations were the same as in Example 8.
  • the COD removal rate was 60%, the TOC removal rate was 39%, the UV 254 removal rate was 66%, and the chroma removal rate was 97%.
  • the mass fraction of NaCl is 9%, and NaCl is added to a mass fraction of 15%.
  • the efficiency of regenerating the saturated resin is 98% of the fresh regenerant.
  • the regeneration efficiency is reduced to the fresh regenerant.
  • Example 8 The other operations were the same as in Example 8.
  • the COD removal rate was 60%, the TOC removal rate was 39%, the UV 254 removal rate was 66%, and the chroma removal rate was 97%.
  • the mass fraction of NaCl is 9%, NaCl is added to the mass fraction of 15%, and NaOH with a mass fraction of 0.5% is added.
  • As a resin regenerant the efficiency of regenerating the saturated resin is 99% of the fresh regenerant, and the reuse is repeated 5 After that, the regeneration efficiency was reduced to less than 60% of the fresh regenerant, and the desorption solution was disposed. At this point, the desorption liquid was reduced to 1/6 of the conventional method.

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Abstract

本发明公开了一种离子交换树脂脱附液的无害化处置和资源化利用的方法，属于树脂脱附液的再生领域。其方法为将树脂脱附液引入两侧分别设有进出水口的电解槽中，阳极与阴极分别与稳流电源连接，通过阳极的直接氧化和间接氧化作用降解脱附液中的有机物，再补充再生剂，使脱附液重新具备很好的树脂再生性能，从而实现脱附液的循环使用，避免了脱附液中再生剂的浪费，使得脱附液的产生量大大减少。该方法有着操作简单，不外加化学药剂，不产生二次污染，pH适用范围广等优点。本发明实现了树脂脱附液的再生与回用，满足了树脂脱附液无害化、减量化、资源化的要求。

Description

一种离子交换树脂脱附液的无害化处置与资源化利用方法 技术领域
本发明涉及的是一种离子交换树脂脱附液的资源化利用的方法，具体涉及一种离子交换树脂脱附液的无害化处置与资源化利用方法，是用阴离子交换树脂对生化尾水进行深度处理后产生的树脂脱附液的无害化处置和资源化利用的方法。
背景技术
我国是一个水资源匮乏的国家，水资源人均占有量仅为世界水资源人均占有量的1/4，而且分布不均、利用率低。随着社会经济发展，水的需求量不断增加，水资源短缺和社会经济发展的矛盾更加突出，开展废水深度处理及回用对缓解我国水资源的紧张形势十分必要。
深度处理的方法包括过滤、吸附、膜分离、蒸发浓缩等物理方法，离子交换、混凝、高级氧化等化学方法以及生物脱氮、脱磷法等生物方法。
离子交换法是一种被广泛应用的深度处理方法，离子交换法是以离子交换树脂过滤原水，水中的离子会与固定在树脂上的离子交换。二级出水有机物表面大多带有负电，因此阴离子交换树脂的应用更为广泛。
NDMP树脂是南京大学自行开发的新型磁性丙烯酸系阴离子交换树脂，该树脂具有粒径小、吸附快、易沉降、易再生的特点。不仅可以吸附水中有机物，大大降低COD、UV254水平，而且通过离子交换，去除水中的硝酸根、氟离子、硫酸根离子等盐离子。离子交换法与其它技术相比，具有净化效果好、运行成本低、操作简单等优点。但是，离子交换法在应用的过程中会产生少量的树脂脱附液，这种脱附液具有高盐分、高浓度、成分复杂、毒性大、可生化性差、色度深的特点。同时，脱附液中含有较大量的树脂再生剂，如果处置不当，在造成资源浪费的同时也会引起二次污染。
常用的脱附液处置方法有固化填埋、蒸发浓缩焚烧、强化混凝、膜滤、高级氧化等。固化填埋只是转移了污染物且会占用土地。蒸发浓缩焚烧处理彻底，但能耗大、成本高。强化混凝药剂用量大、污泥产量大且难以直接达标。膜滤容易造成膜污染且污染物分离后仍需进行处理。高级氧化法包括臭氧氧化、Fenton氧化、电催化氧化等，臭氧氧化无二次污染，但臭氧利用率低、电耗高；Fenton 氧化技术具有操作简单灵活，易于控制等优点，但也有着液体过氧化氢对贮存及运输不便、成本相对较高的缺点。
电催化氧化在废水处理技术中正日益显示出其独特的优越性，如环境兼容性高、电化学系统设备相对简单、占地面积小、操作维护费用较低、能有效避免二次污染、反应可控程度高、便于实现工业自动化等优势。因此电化学技术也被称为“环境友好型”技术，并且逐渐成为有效解决水污染问题的一种有利工具。目前，电化学法已广泛应用在染料、造纸、纺织、化工、皮革、生物制药等有机废水的处理方面。将电催化氧化用于树脂脱附液进行处理，脱附液处理领域还没有这样的文献。
对于本领域技术人员而言，如何去除树脂脱附液中较高浓度的有机物，从而利用其中残留的较高浓度的树脂再生剂，进而削减脱附液处置成本、减少脱附液产生量，一直是困扰的难题。
发明内容
1.发明需要解决的技术问题
针对离子交换树脂在应用的过程中会产生少量的树脂脱附液，这种脱附液具有高盐分、高浓度、成分复杂、毒性大、可生化性差、色度深的特点；同时，脱附液中含有较大量的树脂再生剂，如果处置不当，在造成资源浪费的同时也会引起二次污染，成为限制树脂在各行各业应用的一个瓶颈。本发明提供了一种离子交换树脂脱附液的无害化处置和资源化利用的方法，通过电催化氧化方法，使脱附液中的有机物含量大大降低，而保留绝大部分的再生剂，在补充一定量的再生剂后，使脱附液重新具备很好的树脂再生性能，从而实现脱附液的循环使用，使得脱附液的产生量大大减少。
2.技术方案
一种离子交换树脂脱附液的资源化回收再利用的方法，其具体步骤如下：
(a)向电催化氧化装置内加入树脂脱附液；所采用的电化学反应器包括稳流电源、电解槽、阳极和阴极；所述的电解槽可以通过阳离子交换膜隔开阴极室和阳极室；所述的阳极和阴极分别位于阳极室和阴极室中，阳极与阴极分别与稳流电源连接；所述的电解槽包括进水口和出水口；所述的阴极采用石墨板、钛板、负载钌氧化物或铱氧化物的钛板；所述的阳极为钛基形稳电极，涂层为钌氧化物 或铱氧化物。
(b)开始电催化氧化处理，所述的阳极和阴极的电流密度为5-50mA/cm2，树脂脱附液在电解槽的反应时间为0.5-3h；所述的阳极和阴极的间距为1.5-5cm；阳极表面发生直接氧化反应，有机污染物在电极表面通过电子的转移从而被氧化降解，另外，H2O通过电化学氧化生成O3或者OH·，脱附液中含有大量的Cl-，Cl-离子首先电解生成Cl2，然后生成HClO和ClO-，O3、OH·、Cl2、HClO和ClO-均是强氧化物，在溶液中能较好地降解有机污染物，为间接氧化反应；溶液中的O2在阴极表面被还原成H2O2后再生成OH·，也起到一定的氧化效果；经过电催化氧化处理，脱附液的色度大大降低，UV254、TOC、COD等指标都明显下降。
(c)向处理过的树脂脱附液中补充一定量的氯化钠，配制成离子交换树脂再生剂用于再生饱和的离子交换树脂，其脱附性能为新鲜再生剂的90-99％。
步骤(c)中添加氯化钠的量为使得树脂脱附液中氯化钠质量分数提升至12-15％。
优选地，所述步骤(a)中的电解槽中间用阳离子交换膜隔开阴极室和阳极室，降低阴极还原作用对电催化氧化的干扰，提升氧化性能。
优选地，所述步骤(b)中电流密度调节为20mA/cm2，反应时间为2h。
优选地，所述步骤(b)中电催化氧化之前将树脂脱附液的pH调节为中性或弱酸性。
优选地，所述步骤(c)中添加一定量的NaOH。
3.有益效果
本发明公开了一种离子交换树脂的无害化处置和资源化利用的方法，经过步骤(b)中电催化氧化处理后的脱附液的COD降低30-70％，处理后的脱附液的TOC降低25-50％，处理后的脱附液的色度降低95-99％，处理后的脱附液的UV254降低50-70％，处理后的脱附液的B/C降低由0.02提升至0.13-0.20；大型蚤的半致死浓度(LD50)由2％下降至约3％。
与现有的树脂脱附液处置方法相比，该方法有着操作简单，不外加化学药剂，不产生二次污染，pH适用范围广的优点，并且避免了脱附液中再生剂的浪费，同时大大削减了脱附液的产生量，实现了树脂脱附液的重复利用，节约了离子交 换树脂产生的脱附液的树脂费用，降低了技术成本。该方法可以广泛应用于利用离子交换树脂进行水质深度净化过程中产生的树脂脱附液的处置。
具体实施方式
以下通过具体实施案例进一步说明本发明
实施例1
某市政污水在常规工艺处理后，用离子交换树脂进行深度净化处理。在树脂处理达到吸附饱和后，在常温常压下，用再生液(NaCl溶液)再生30min。再生后，再生液成为脱附液。用电催化氧化装置处理离子交换树脂脱附液，所采用的电催化氧化装置包括稳流电源、电解槽、阳极和阴极；所述的电解槽包括进水口和出水口，电解槽中间用阳离子交换膜隔开阴极室和阳极室，所述的阳极和阴极分别位于阳极室和阴极室中，所述的阴极采用石墨板；所述的阳极为钛基形稳电极，涂层为钌氧化物；向电催化氧化装置加入离子交换树脂脱附液，电催化氧化装置的阳极和阴极的电流密度为5mA/cm2，阳极和阴极的电极间距5cm，在电解槽的反应时间0.5h，经过上述处理后COD去除率为42％，TOC去除率为26％，UV254去除率为55％，色度去除率为95％。处理后NaCl质量分数为12％，不添加NaCl，作为树脂再生剂使用，再生饱和树脂的效率为新鲜再生剂的90％，重复使用3次后，再生效率下降至新鲜再生剂的60％以下，将脱附液处置。至此，脱附液减量化为常规方法的1/4。
实施例2
某市政污水在常规工艺处理后，用离子交换树脂进行深度净化处理。在树脂处理达到吸附饱和后，在常温常压下，用再生液再生30min。再生后，再生液成为脱附液。用电催化氧化装置处理脱附液，处理设备同实施例1，不同在于所述的阴极采用钛板；所述的阳极为钛基形稳电极，涂层为铱氧化物；电流密度为20mA/cm2，电极间距4cm，处理2h，COD去除率为51％，TOC去除率为29％，UV254去除率为58％，色度去除率为97％。处理后NaCl质量分数为11％，添加NaCl至质量分数为12％，作为树脂再生剂使用，再生饱和树脂的效率为新鲜再生剂的92％，重复使用4次后，再生效率下降至新鲜再生剂的60％以下，将脱附液处置。至此，脱附液减量化为常规方法的1/5。
实施例3
某市政污水在常规工艺处理后，用离子交换树脂进行深度净化处理。在树脂 处理达到吸附饱和后，在常温常压下，用再生液再生30min。再生后，再生液成为脱附液。用电催化氧化装置处理脱附液，处理设备同实施例1，不同在于所述的阴极采用负载钌氧化物的钛板；所述的阳极为钛基形稳电极，涂层为铱氧化物。电流密度为30mA/cm2，电极间距3cm，处理2h，COD去除率为54％，TOC去除率为34％，UV254去除率为62％，色度去除率为97％。处理后NaCl质量分数为11％，添加NaCl至质量分数为12％，作为树脂再生剂使用，再生饱和树脂的效率为新鲜再生剂的94％，重复使用5次后，再生效率下降至新鲜再生剂的60％以下，将脱附液处置。至此，脱附液减量化为常规方法的1/6。
实施例4
某市政污水在常规工艺处理后，用离子交换树脂进行深度净化处理。在树脂处理达到吸附饱和后，在常温常压下，用再生液再生30min。再生后，再生液成为脱附液。用电催化氧化装置处理脱附液，处理设备同实施例1，不同在于所述的阴极采用负载铱氧化物的钛板；所述的阳极为钛基形稳电极，涂层为铱氧化物。电流密度为40mA/cm2，电极间距2cm，处理2h，COD去除率为62％，TOC去除率为40％，UV254去除率为68％，色度去除率为99％。处理后NaCl质量分数为10％，添加NaCl至质量分数为14％，作为树脂再生剂使用，再生饱和树脂的效率为新鲜再生剂的95％，重复使用6次后，再生效率下降至新鲜再生剂的60％以下，将脱附液处置。至此，脱附液减量化为常规方法的1/7。
实施例5
某市政污水在常规工艺处理后，用离子交换树脂进行深度净化处理。在树脂处理达到吸附饱和后，在常温常压下，用再生液再生30min。再生后，再生液成为脱附液。用电催化氧化装置处理脱附液，处理设备同实施例1，不同在于所述的阴极采用石墨板；所述的阳极为钛基形稳电极，涂层为钌氧化物。电流密度为50mA/cm2，电极间距1.5cm，处理3h，COD去除率为64％，TOC去除率为42％，UV254去除率为70％，色度去除率为99％。处理后NaCl质量分数为9％，添加NaCl至质量分数为12％，作为树脂再生剂使用，再生饱和树脂的效率为新鲜再生剂的96％，重复使用6次后，再生效率下降至新鲜再生剂的60％以下，将脱附液处置。至此，脱附液减量化为常规方法的1/7。
实施例6
其他操作同实例5，COD去除率为64％，TOC去除率为42％，UV254去除率为70％， 色度去除率为99％。处理后NaCl质量分数为9％，添加NaCl至质量分数为14％，作为树脂再生剂使用，再生饱和树脂的效率为新鲜再生剂的98％，重复使用7次后，再生效率下降至新鲜再生剂的60％以下，将脱附液处置。至此，脱附液减量化为常规方法的1/8。
实施例7
其他操作同实例5，COD去除率为64％，TOC去除率为42％，UV254去除率为70％，色度去除率为99％。处理后NaCl质量分数为9％，添加NaCl至质量分数为15％，并添加质量分数为0.5％的NaOH，作为树脂再生剂使用，再生饱和树脂的效率为新鲜再生剂的99％，重复使用7次后，再生效率下降至新鲜再生剂的60％以下，将脱附液处置。至此，脱附液减量化为常规方法的1/8。
实施例8
某印染废水在常规工艺处理后，用离子交换树脂进行深度净化处理。在树脂处理达到吸附饱和后，在常温常压下，用再生液再生30min。再生后，再生液成为脱附液。用电催化氧化装置处理离子交换树脂脱附液，所采用的电催化氧化装置包括稳流电源、电解槽、阳极和阴极；所述的电解槽包括进水口和出水口，电解槽中间用阳离子交换膜隔开阴极室和阳极室，所述的阳极和阴极分别位于阳极室和阴极室中，所述的阴极采用石墨板；所述的阳极为钛基形稳电极，涂层为钌氧化物；向电催化氧化装置加入离子交换树脂脱附液，电催化氧化装置的阳极和阴极的电流密度为20mA/cm2，阳极和阴极电极间距2cm，在电解槽的反应时间3h，COD去除率为60％，TOC去除率为39％，UV254去除率为66％，色度去除率为97％。处理后NaCl质量分数为9％，添加NaCl至树脂脱附液中的NaCl质量分数为12％，作为树脂再生剂使用，再生饱和树脂的效率为新鲜再生剂的94％，重复使用4次后，再生效率下降至新鲜再生剂的60％以下，将脱附液处置。至此，脱附液减量化为常规方法的1/5。
实施例9
其他操作同实例8，COD去除率为60％，TOC去除率为39％，UV254去除率为66％，色度去除率为97％。处理后NaCl质量分数为9％，添加NaCl至质量分数为15％，作为树脂再生剂使用，再生饱和树脂的效率为新鲜再生剂的98％，重复使用5次后，再生效率下降至新鲜再生剂的60％以下，将脱附液处置。至此，脱附液减量化为常规方法的1/6。
实施例10
其他操作同实例8，COD去除率为60％，TOC去除率为39％，UV254去除率为66％，色度去除率为97％。处理后NaCl质量分数为9％，添加NaCl至质量分数为15％，并添加质量分数为0.5％的NaOH，作为树脂再生剂使用，再生饱和树脂的效率为新鲜再生剂的99％，重复使用5次后，再生效率下降至新鲜再生剂的60％以下，将脱附液处置。至此，脱附液减量化为常规方法的1/6。

Claims (5)

  1. 一种离子交换树脂脱附液的无害化处置与资源化利用方法，其步骤包括：
    (a)向电催化氧化装置内加入树脂脱附液；所采用的电催化氧化装置包括稳流电源、电解槽、阳极和阴极；所述的电解槽包括进水口和出水口，所述的阴极采用石墨板、钛板、负载钌氧化物或铱氧化物的钛板；所述的阳极为钛基形稳电极，涂层为钌氧化物或铱氧化物；
    (b)树脂脱附液开始电催化氧化处理，所述的阳极和阴极的电流密度为5-50mA/cm2，树脂脱附液在电解槽的反应时间为0.5-3h；所述的阳极和阴极的间距为1.5-5cm。
  2. 根据权利要求1所述的离子交换树脂脱附液的无害化处置与资源化利用方法，其特征在于，还包括步骤(c)，其步骤为：向步骤(b)处理过的树脂脱附液中补充氯化钠，补充氯化钠之后，树脂脱附液中氯化钠质量分数提升至12-15％，配制成离子交换树脂再生剂用于再生饱和的离子交换树脂。
  3. 根据权利要求1所述的离子交换树脂脱附液的无害化处置与资源化利用方法，其特征在于，所述步骤(a)中的电解槽中间用阳离子交换膜隔开阴极室和阳极室，所述的阳极和阴极分别位于阳极室和阴极室中。
  4. 根据权利要求1或2所述的离子交换树脂脱附液的无害化处置与资源化利用方法，其特征在于，所述步骤(b)中电流密度调节为20mA/cm2，反应时间为2h。
  5. 根据权利要求2所述的离子交换树脂脱附液的无害化处置与资源化利用方法，其特征在于，还包括在所述步骤(c)树脂脱附液中添加NaOH。
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