WO2025156331A1 - 基于电子束辐照工艺去除焦化废水反渗透浓缩液中有机污染物的方法与系统 - Google Patents

基于电子束辐照工艺去除焦化废水反渗透浓缩液中有机污染物的方法与系统

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Publication number
WO2025156331A1
WO2025156331A1 PCT/CN2024/076305 CN2024076305W WO2025156331A1 WO 2025156331 A1 WO2025156331 A1 WO 2025156331A1 CN 2024076305 W CN2024076305 W CN 2024076305W WO 2025156331 A1 WO2025156331 A1 WO 2025156331A1
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Prior art keywords
electron beam
beam irradiation
organic pollutants
purified water
dose
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PCT/CN2024/076305
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English (en)
French (fr)
Inventor
王建龙
王诗宗
周月东
谭国庆
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Tsinghua University
CGN Dasheng Electron Accelerator Technology Co Ltd
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Tsinghua University
CGN Dasheng Electron Accelerator Technology Co Ltd
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Publication of WO2025156331A1 publication Critical patent/WO2025156331A1/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
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/305—Treatment of water, waste water, or sewage by irradiation with electrons
    • 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
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4691—Capacitive deionisation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical

Definitions

  • the present invention relates to the technical field of wastewater treatment, and in particular to a method and system for removing organic pollutants in reverse osmosis concentrated liquid of coking wastewater based on an electron beam irradiation process.
  • Coking wastewater is a difficult industrial wastewater to treat, characterized by its complex pollutant composition, high concentrations, and resistance to biodegradation.
  • Biochemical treatment is one of the most widely used processes in industrial wastewater treatment.
  • biological treatment processes are unable to effectively remove toxic, harmful, and recalcitrant organic pollutants in coking wastewater. This results in the treated effluent not meeting requirements for direct discharge.
  • Electron beam irradiation is a new type of advanced oxidation technology.
  • the main principle of its wastewater treatment is to remove pollutants by the direct effect of electron beam (energy deposition) and the indirect effect of active species generated by its excitation of activated water molecules.
  • electron beam energy deposition
  • it has the advantages of good treatment effect, short treatment time and no need to add chemicals.
  • using electron beam irradiation alone to treat membrane concentrate is not very effective. Due to the presence of high salt in the membrane concentrate, a very high irradiation dose is usually required to achieve the ideal treatment effect, resulting in a significant increase in treatment costs.
  • the present invention provides a method and system for removing organic pollutants in the reverse osmosis concentrated liquid of coking wastewater based on an electron beam irradiation process, which couples electron beam irradiation with electric adsorption to treat the concentrated liquid to achieve the removal of organic pollutants and the recovery of salts in the reverse osmosis concentrated liquid of coking wastewater.
  • the present invention provides a method for removing organic pollutants in reverse osmosis concentrate of coking wastewater based on an electron beam irradiation process, the process comprising:
  • the reverse osmosis concentrate is passed through a high-dose electron beam irradiation unit, whereby some salt substances are ionized under the action of the electron beam irradiation to generate hydrated electrons and oxidative free radicals; the hydrated electrons charge some organic pollutants, and the oxidative free radicals decompose some organic pollutants, thereby obtaining primary pre-purified water;
  • H2O2 generated during the irradiation process is activated by the anode of the electric adsorption treatment unit to form hydroxyl radicals, and the hydroxyl radicals decompose the organic pollutants adsorbed on the electrode surface, thereby obtaining secondary pre-purified water;
  • the tertiary pre-purified water is returned to the electric adsorption treatment unit for circulation treatment until the COD of the effluent from the low-dose electron beam irradiation unit is less than or equal to 10 mg/L, thereby completing the removal of organic pollutants in the reverse osmosis concentrated liquid of the coking wastewater.
  • the reverse osmosis concentrated liquid 150 mg/L ⁇ COD ⁇ 500 mg/L, 10000 us/cm ⁇ conductivity ⁇ 100000 us/cm.
  • the high-dose electron beam irradiation dose is between 20 and 100 kGy.
  • the water inlet flow rate of the electric adsorption unit is between 1 m 3 /h and 20 m 3 /h.
  • the voltage applied by the electrosorption processing unit is between 1.2V and 1.7V.
  • the anode of the electrosorption treatment unit is composed of a carbon-wrapped iron-nickel material
  • the cathode of the electric adsorption treatment unit is composed of a titanium plate or a carbon material.
  • the carbon-wrapped iron-nickel material includes a combination of one or more of a graphene-wrapped iron-nickel material, a biochar-wrapped iron-nickel material, a modified graphene-wrapped iron-nickel material, and a modified biochar-wrapped iron-nickel material.
  • the low-dose electron beam irradiation dose is between 1 and 10 kGy.
  • the cyclic treatment is repeated 1-20 times.
  • the present invention provides a system for removing organic pollutants from reverse osmosis concentrate of coking wastewater based on electron beam irradiation, wherein the system is applicable to the method described in the first aspect above, comprising:
  • a high-dose electron beam irradiation unit is used to ionize salt substances in the reverse osmosis concentrated liquid into hydrated electrons and oxidative free radicals; the hydrated electrons charge a portion of organic pollutants, and the oxidative free radicals decompose a portion of organic pollutants, thereby obtaining primary pre-purified water;
  • an electric adsorption treatment unit for adsorbing salt ions and a portion of the charged organic pollutants in the primary pre-purified water; and activating H2O2 generated by irradiation into hydroxyl radicals, which decompose the organic pollutants adsorbed on the electrode surface, thereby obtaining secondary pre-purified water;
  • the low-dose electron beam irradiation unit is used to decompose organic pollutants in the secondary pre-purified water to obtain purified water.
  • the present invention has the following advantages:
  • the present invention provides a method for removing organic pollutants in reverse osmosis concentrated liquid of coking wastewater based on electron beam irradiation process.
  • the method directly acts high-dose electron beam irradiation on the reverse osmosis concentrated liquid of coking wastewater, so that the salt substances in the concentrated liquid are directly ionized into hydrated electrons and corresponding oxidative free radicals, thereby reducing the quenching effect of the salt substances on the active species in the water and increasing the concentration of the active species in the system, thereby increasing the system's ability to remove organic pollutants in the concentrated liquid;
  • the water irradiated by the high-dose electron beam is subjected to electrosorption treatment, and a carbon-coated iron-nickel material is used as the anode material of the electrosorption treatment unit (the surface of the carbon material co-modified with iron and nickel forms obvious positive and negative charge areas, which is conducive to the adsorption of salt ions in the system), thereby better achieving brine separation; in addition, a certain
  • the organic pollutants attached to the concentrate can be further removed; the low-concentration organic pollutants remaining in the concentrate after electro-adsorption treatment are further decomposed and removed under the action of low-dose electron beam irradiation. If the effluent COD is greater than 10 mg/L, the effluent can be returned to the electro-adsorption treatment unit and circulated through the electro-adsorption treatment unit and the low-dose electron beam irradiation unit until the effluent COD is less than 10 mg/L.
  • the present invention provides a method for removing organic pollutants from reverse osmosis concentrate of coking wastewater based on electron beam irradiation.
  • the method is simple to operate and does not require the addition of chemical substances. While reducing the organic pollutants in the membrane concentrate, it is also conducive to the recovery and utilization of salt.
  • the method has broad application prospects in the field of RO concentrated water treatment of coking wastewater.
  • FIG1 shows a flow chart of a method for removing organic pollutants from reverse osmosis concentrate of coking wastewater based on an electron beam irradiation process according to an embodiment of the present invention
  • FIG2 shows a schematic diagram of the structure of a system for removing organic pollutants in reverse osmosis concentrate of coking wastewater based on an electron beam irradiation process provided by an embodiment of the present invention.
  • the indirect effect of electron beam irradiation is mainly used in wastewater treatment in research and practical applications, and the direct effect of electron beam irradiation is not considered.
  • the concentration of organic pollutants in the concentrate is low, the salt substances are much greater than the concentration of organic pollutants, which makes the electron beam irradiation process
  • the generated active species react more with salt substances and cannot effectively remove low-concentration organic pollutants. If electron beam irradiation is used alone to remove low-concentration organic pollutants in concentrated liquids, a much higher irradiation dose than theoretically required is usually required, which significantly increases the treatment cost.
  • Electrosorption uses an electric field to cause ions in water to migrate toward oppositely charged electrodes, where they are adsorbed and stored within the double layer. Research has shown that electrosorption can separate salt and water. However, it cannot remove organic pollutants from water. Furthermore, the choice of electrode material is crucial for electrosorption separation of salt and water.
  • the present invention aims to achieve the removal of organic pollutants in the coking wastewater reverse osmosis concentrate by coupling electron beam irradiation with electrosorption treatment.
  • the specific implementation content is as follows:
  • the present invention provides a method for removing organic pollutants from a reverse osmosis concentrate of coking wastewater based on an electron beam irradiation process.
  • FIG1 shows a flow chart of a method for removing organic pollutants from a reverse osmosis concentrate of coking wastewater based on an electron beam irradiation process according to an embodiment of the present invention. As shown in FIG1 , the method comprises:
  • the embodiment of the present invention utilizes the direct effect of high-dose electron beam irradiation to directly ionize some salt substances, generating corresponding hydrated electrons and oxidative free radicals, wherein the oxidative free radicals include but are not limited to O 2 ⁇ - , Cl ⁇ , SO 4- ⁇ , and NO 3 ⁇ .
  • the conversion of salt substances reduces their quenching effect on active species, while the generated active species can also enhance the oxidation ability of organic pollutants in the concentrated solution.
  • the high-dose electron beam irradiation dose is between 20 and 100 kGy; on the other hand, the electron beam can ...
  • hydrated electrons and oxidative free radicals generating corresponding hydrated electrons and oxidative free radicals, generating corresponding hydrated electrons and oxidative free radicals, generating corresponding hydrated electrons and oxidative free radicals, generating corresponding hydrated electrons and oxidative free radicals, generating corresponding hydrated electrons and oxidative free radicals, generating corresponding hydrated electrons and oxidative free radicals, generating corresponding hydrated electrons and oxidative free radicals, generating corresponding hydrated electrons and oxidative free radicals, generating corresponding hydrated electrons and oxidative free radicals, generating corresponding hydrated electrons and oxidative free radicals, generating corresponding hydrated electrons and oxidative free radicals, generating corresponding hydrated electrons and oxidative free radicals, generating corresponding hydrated electrons and oxidative free radicals, generating corresponding hydrated electrons and oxidative free radicals, generating corresponding hydrated electrons and oxidative free radicals, generating
  • the present invention uses carbon-wrapped iron-nickel material as the positive electrode material of the electrosorption treatment unit, which has a good adsorption effect on H2O2 generated during the electron beam irradiation process and activates it into hydroxyl radicals. Hydroxyl radicals can be used to remove organic pollutants adsorbed on the electrode surface, improve the purity of salt substances adsorbed by the electrode material, and improve the recovery value of salt substances.
  • any remaining low-concentration organic pollutants in the effluent can be removed by low-dose electron beam irradiation at the rear end. If the COD of the effluent after low-dose electron beam irradiation is greater than 10 mg/L, the effluent can be returned to the electro-adsorption unit and circulated through the electro-adsorption unit and low-dose electron beam irradiation unit until the effluent COD is less than 10 mg/L.
  • the present invention can effectively remove organic pollutants from the membrane concentrate, ultimately achieving resource utilization of experimental salt.
  • the present invention can treat high-salt coking wastewater reverse osmosis concentrate, where the salt content, expressed as solution conductivity, can reach a maximum of 100,000 ⁇ s/cm and a minimum of no less than 10,000 ⁇ s/cm. Furthermore, the treatment process provided by the present invention is suitable for RO concentrates with organic matter concentrations ranging from 150 mg/L to ⁇ COD and from ⁇ 500 mg/L.
  • the anode of the electrosorption treatment unit is composed of a carbon-wrapped iron-nickel material; and the cathode of the electrosorption treatment unit is composed of a titanium plate or a carbon material.
  • Preferred carbon-wrapped iron-nickel materials include: a combination of one or more of graphene-wrapped iron-nickel materials, biochar-wrapped iron-nickel materials, modified graphene-wrapped iron-nickel materials, and modified biochar-wrapped iron-nickel materials. Since H 2 O 2 is generated during the electron beam irradiation process, the carbon-wrapped iron-nickel material is used as the electrode anode for electrosorption.
  • the iron-nickel modification increases the active sites on the electrode surface, enhances its ability to adsorb salts in sewage, and also reduces the energy barrier required for the activation of H 2 O 2 (oxidant) present in the system, activating H 2 O 2 into hydroxyl radicals.
  • Hydroxyl radicals can remove organic pollutants adsorbed on the electrode surface, improve the purity of salt substances adsorbed by the electrode material, and thereby improve the recovery value of the salt substances.
  • the addition of thiourea introduces sulfur and nitrogen into the electrode material at the same time. Sulfur, a multivalent element with abundant electrons, enhances the electron transfer and exchange capabilities of electrode materials, further promoting the activation of adsorbed oxidants.
  • a biochar-coated iron-nickel material can be prepared by the following preparation method: 20 ml of a 0.1 M potassium ferricyanide solution is dropwise added to 20 ml of a 0.15 M solution. After aging in air for 12 hours, the mixture is filtered and washed three times with deionized water to obtain a Prussian blue analog. The mixture is then dried in a 60°C oven for 12 hours. 0.5 g of the dried Prussian blue solid and 1.5 g of chitosan are placed in 50 ml of deionized water, ultrasonicated for 10 minutes, stirred for 1 hour, and then dried in an 80°C oven for 12 hours.
  • 1 g of the dried solid is mixed with 10 g of thiourea solid and ground uniformly.
  • the ground powder is placed in a tube furnace. Under nitrogen conditions, the temperature is increased at 3°C/min to 550°C and held for 1 hour, then increased at 5°C/min to 900°C and held for 1 hour. After cooling naturally, the resulting solid is washed three times with deionized water and dried in a 60°C oven. The resulting solid is the carbon-coated iron-nickel material.
  • a graphene-wrapped iron-nickel material can be prepared by the following preparation method: 20 ml of a 0.1 M potassium ferricyanide solution is dropwise added to 20 ml of a 0.2 M solution. After aging in air for 10 hours, the mixture is filtered and washed three times with deionized water to obtain a Prussian blue analog. The mixture is then dried in an 80°C oven for 12 hours. 0.5 g of the dried Prussian blue solid and 2 g of the modified graphene are placed in 50 ml of deionized water, ultrasonicated for 10 minutes, stirred for 1 hour, and then dried in an 80°C oven for 12 hours.
  • 1 g of the dried solid is mixed with 15 g of thiourea solid and ground uniformly.
  • the ground powder is placed in a tube furnace. Under nitrogen conditions, the temperature is increased at 3°C/min to 550°C and held for 1 hour, then increased at 5°C/min to 900°C and held for 1 hour. After cooling naturally, the obtained solid is washed three times with deionized water and dried in a 60°C oven. The resulting solid is the carbon-wrapped iron-nickel material.
  • the tertiary pre-purified water is returned to the electric adsorption treatment unit for 5-20 cycles, and the COD in the effluent is ⁇ 10 mg/L.
  • the present invention provides a system for removing organic pollutants from reverse osmosis concentrate of coking wastewater based on an electron beam irradiation process.
  • the system is applicable to the method described in the first aspect above.
  • FIG2 shows a schematic structural diagram of a system for removing organic pollutants from reverse osmosis concentrate of coking wastewater based on an electron beam irradiation process provided by an embodiment of the present invention. As shown in FIG2 , the system comprises:
  • High-dose electron beam irradiation unit used to ionize salt substances in reverse osmosis concentrate into hydrated Electrons and oxidative free radicals; hydrated electrons charge some organic pollutants, and oxidative free radicals decompose some organic pollutants, thereby obtaining primary pre-purified water;
  • the electro-adsorption treatment unit is used to adsorb salt ions and some charged organic pollutants in the primary pre-purified water; and activate the H2O2 generated by irradiation into hydroxyl radicals, which decompose the organic pollutants adsorbed on the electrode surface, thereby obtaining secondary pre-purified water;
  • the low-dose electron beam irradiation unit is used to decompose organic pollutants in the secondary pre-purified water to obtain purified water.
  • the specific treatment method for coking wastewater is as follows: RO concentrated water first passes through the first electron beam irradiation treatment unit (high-dose electron beam irradiation unit), the effluent enters the electric adsorption treatment unit, and finally enters the second electron beam irradiation treatment unit (low-dose electron beam irradiation unit).
  • the effluent is directly discharged (COD in the effluent is less than 10 mg/L), or returns to the electric adsorption treatment unit for multiple cycles. After the effluent COD of the low-dose electron beam irradiation unit is less than 10 mg/L, it is discharged, and the treatment of the membrane concentrate is finally completed.
  • RO concentrate from a coking plant in Hebei province had an initial COD of 247 mg/L and a conductivity of 17,500 ⁇ s/cm.
  • the electrosorption unit's anode consisted of iron-nickel modified coconut shell carbon, the cathode was a titanium plate, and the flow rate was 1 m3 /h.
  • the first stage of electron beam irradiation was 30 kGy, and the second stage was 5 kGy. After three cycles of treatment, the effluent COD was ⁇ 10 mg/L.
  • RO concentrate from a coking plant in Hebei province had an initial COD of 247 mg/L and a conductivity of 17,500 ⁇ s/cm.
  • the electrosorption unit's anode consisted of iron-nickel modified coconut shell carbon, the cathode was a titanium plate, and the flow rate was 1 m3 /h.
  • the first stage of electron beam irradiation was 50 kGy, and the second stage was 10 kGy. After two cycles of treatment, the effluent COD was ⁇ 10 mg/L.
  • RO concentrate from a coking plant in Hebei province had an initial COD of 376 mg/L and a conductivity of 77,500 ⁇ s/cm.
  • the electrosorption unit's anode consisted of iron-nickel modified coconut shell carbon, the cathode was a titanium plate, and the flow rate was 1 m3 /h.
  • the first stage of electron beam irradiation received a dose of 70 kGy, and the second stage received a dose of 10 kGy. After six cycles of treatment, the effluent COD was ⁇ 10 mg/L.
  • RO concentrate from a coking plant in Hebei province had an initial COD of 247 mg/L and a conductivity of 17,500 ⁇ s/cm. It was treated with a single electron beam irradiation dose of 150 kGy, resulting in a effluent COD of 134 mg/L.
  • RO concentrate from a coking plant in Hebei province had an initial COD of 376 mg/L and a conductivity of 77,500 ⁇ s/cm. It was treated with a single electron beam irradiation dose of 150 kGy, resulting in a effluent COD of 277 mg/L.
  • electron beam irradiation coupled with electrosorption can effectively reduce the impact of high salt concentrations. Since no chemicals are added during the entire treatment process, the final salt purity is relatively high. Therefore, electron beam irradiation coupled with electrosorption offers the advantages of simple operation, excellent treatment results, and high salt purity.
  • references herein to "one embodiment,” “an embodiment,” or “one or more embodiments” mean that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present disclosure. Furthermore, please note that instances of the phrase “in one embodiment” do not necessarily all refer to the same embodiment.
  • any reference signs placed between parentheses shall not be construed as limiting the claim.
  • the word “comprising” does not exclude the presence of elements or steps not listed in the claim.
  • the word “a” or “an” preceding an element does not exclude the presence of a plurality of such elements.
  • the present disclosure may be implemented by means of hardware comprising several different elements and by means of a suitably programmed computer. In a unit claim enumerating several means, several of these means may be embodied by the same item of hardware.
  • the use of the words first, second, and third etc. does not indicate any order. These words may be interpreted as names.

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Abstract

提供一种基于电子束辐照工艺去除焦化废水反渗透浓缩液中有机污染物的方法与系统，包括：将RO浓缩液依次通过高剂量电子束辐照单元、电吸附处理单元以及低剂量电子束辐照单元，在通过高剂量电子束辐照单元时，RO浓缩液中的盐类物质被高剂量辐照电离为水合电子和氧化性自由基，有效减少了盐类物质对辐照过程中产生的氧化性自由基的猝灭，同时增强了对反渗透浓缩液中有机污染物的去除，出水通过电吸附处理单元时，在电场作用下，盐类离子被吸附去除；出水进一步通过低剂量电子束辐照单元时，其中的有机污染物被低剂量电子束辐照分解去除，出水可进一步返回至电吸附处理单元做循环处理，直至低剂量电子束辐照单元的出水中COD≤10mg/L。

Description

基于电子束辐照工艺去除焦化废水反渗透浓缩液中有机污染物的方法与系统
相关申请的交叉引用
本公开要求在2024年01月26日提交中国专利局、申请号为202410116948.7、名称为“基于电子束辐照工艺去除焦化废水反渗透浓缩液中有机污染物的方法与系统”的中国专利申请的优先权，其全部内容通过引用结合在本公开中。
技术领域
本发明涉及废水处理技术领域，特别涉及一种基于电子束辐照工艺去除焦化废水反渗透浓缩液中有机污染物的方法与系统。
背景技术
焦化废水具有污染物组成成分复杂、浓度高和难生物降解的特点，是一种难处理的工业废水。生化处理法是工业废水处理领域应用最为广泛的处理工艺之一。但生物处理工艺无法有效去除焦化废水中的有毒、有害、难降解的有机污染物。这导致处理后的出水无法满足直接排放的要求。
针对上述问题，目前通常在生化处理后增加深度处理工艺来提高处理效果。高级氧化工艺，例如Fenton和臭氧氧化，是常用的深度处理工艺之一。尽管高级氧化工艺可以进一步降低生化出水中的有机污染物，但出水指标仍然不能满足回用的要求。为了提高废水回用率及达到“零排放”的目标，实际中常用高级氧化技术耦合膜工艺。膜工艺的使用会产生膜浓缩液。膜浓缩液具有高盐和高COD的特点。对膜浓缩液的处理又面临高盐的存在显著影响膜浓缩液中有机污染物的去除问题，导致现有的废水处理工艺对膜浓缩液的处理效果不明显。
电子束辐照是一种新型的高级氧化技术。其废水处理的主要原理是依靠电子束的直接作用(能量沉积)和其激发活化水分子产生的活性物种的间接作用去除污染物。与传统的高级氧化工艺比较，具有处理效果好、处理时间短以及无需添加化学物质的优势。但单独采用电子束辐照处理膜浓缩液，由 于膜浓缩液中高盐的存在，要达到理想的处理效果，通常需要很高的辐照剂量，导致处理成本显著增加。
因此，如何降低膜浓缩液中高盐对电子束辐照去除有机污染物的影响，以及，在考虑去除膜浓缩液中有机污染物的同时，实现膜浓缩液中盐的回收利用，最终实现盐的资源化利用，是目前亟需解决的问题。
概述
针对现有技术中存在的上述问题，本发明提供一种基于电子束辐照工艺去除焦化废水反渗透浓缩液中有机污染物的方法与系统，以电子束辐照耦合电吸附处理浓缩液，以实现焦化废水反渗透浓缩液中有机污染物的去除和盐类的回收。
具体发明内容如下：
第一方面，本发明提供一种基于电子束辐照工艺去除焦化废水反渗透浓缩液中有机污染物的方法，所述工艺包括：
将所述反渗透浓缩液通入高剂量电子束辐照单元，部分盐类物质在电子束辐照作用下电离产生水合电子和氧化性自由基；所述水合电子使一部分有机污染物带电，所述氧化性自由基使一部分有机污染物分解，从而得到一次预净化水；
将所述一次预净化水通入电吸附处理单元，使得所述一次净化水在电场作用下，其中的盐类离子和一部分所述带电的有机污染物被电吸附去除；其中辐照过程中产生的H2O2被电吸附处理单元的阳极活化为羟基自由基，所述羟基自由基使吸附于电极表面的有机污染物分解，从而得到二次预净化水；
将所述二次预净化水通入低剂量电子束辐照单元，以去除二次预净化水中有机污染物，得到三次预净化水；
将所述三次预净化水返回至所述电吸附处理单元做过循环处理，直至所述低剂量电子束辐照单元的出水中COD≤10mg/L时，完成焦化废水反渗透浓缩液中有机污染物的去除。
可选地，所述反渗透浓缩液中，150mg/L≤COD≤500mg/L，10000us/cm≤电导率≤100000us/cm。
可选地，所述高剂量电子束辐照剂量介于20～100kGy。
可选地，所述电吸附单元进水流速介于1m3/h～20m3/h。
可选地，所述电吸附处理单元施加的电压介于1.2～1.7V。
可选地，所述电吸附处理单元的阳极由碳包裹铁镍材料组成；
所述电吸附处理单元的阴极由钛板或碳材料组成。
可选地，所述碳包裹铁镍材料包括：石墨烯包裹铁镍材料、生物炭包裹铁镍材料、改性石墨烯包裹铁镍材料和改性生物炭包裹铁镍材料中的一种或多种的组合。
可选地，所述低剂量电子束辐照剂量介于1～10kGy。
可选地，所述循环处理次数为1-20次。
第二方面，本发明提供一种基于电子束辐照去除焦化废水反渗透浓缩液中有机污染物的系统，所述系统适用于上述第一方面所述的方法，包括：
高剂量电子束辐照单元，用于将所述反渗透浓缩液中的盐类物质电离为水合电子和氧化性自由基；所述水合电子使一部分有机污染物带电，所述氧化性自由基使一部分有机污染物分解，从而得到一次预净化水；
电吸附处理单元，用于吸附所述一次预净化水中的盐类离子和一部分所述带电的有机污染物；以及，将辐照产生的H2O2活化为羟基自由基，所述羟基自由基使吸附于电极表面的有机污染物分解，从而得到二次预净化水；
低剂量电子束辐照单元，用于分解所述二次预净化水中的有机污染物，得到净化水。
与现有技术相比，本发明具有以下优点：
本发明提供的一种基于电子束辐照工艺去除焦化废水反渗透浓缩液中有机污染物的方法，通过将高剂量电子束辐照直接作用于焦化废水反渗透浓缩液，使浓缩液中的盐类物质直接电离为水合电子和相应的氧化性自由基，减少了盐类物质对水中活性物种猝灭作用的同时，增加了体系中的活性物种的浓度，进而增加了体系对浓缩液中有机污染物的去除能力；进一步地，对高剂量电子束辐照出水进行电吸附处理，并以碳包裹铁镍材料作为电吸附处理单元的阳极材料(铁镍共修饰的碳材料表面形成了明显的正电荷和负电荷区域，有利于吸附体系中的盐类离子)，进而更好的实现盐水分离；此外，电子束辐照条件处理后的浓缩液中存在一定量的H2O2，碳包裹铁镍材料可以很好的吸附H2O2，并将其活化为羟基自由基，羟基自由基用于去除电极表面吸 附的有机污染物，可进一步去除浓缩液中有机污染物；经电吸附处理后浓缩液中残留的低浓度有机污染物进一步在低剂量电子束辐照作用下，被分解除去，若出水COD大于10mg/L，可将出水返回电吸附处理单元，经电吸附处理单元与低剂量电子束辐照单元的循环处理，直至出水COD小于10mg/L。
本发明提供的一种基于电子束辐照去除焦化废水反渗透浓缩液中有机污染物方法操作简单，无需添加化学物质，在降低膜浓缩液中有机污染物的同时，有利于实现盐的回收利用，在焦化废水RO浓水处理领域具有广泛的应用前景。
附图说明
为了更清楚地说明本公开实施例或相关技术中的技术方案，下面将对实施例或相关技术描述中所需要使用的附图作一简单地介绍，显而易见地，下面描述中的附图是本公开的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1示出了本发明实施例提供的基于电子束辐照工艺去除焦化废水反渗透浓缩液中有机污染物的方法流程图；
图2示出了本发明实施例提供的基于电子束辐照工艺去除焦化废水反渗透浓缩液中有机污染物的系统结构示意图。
具体实施例
提供下述实施例是为了更好地进一步理解本发明，并不局限于所述最佳实施方式，不对本发明的内容和保护范围构成限制，任何人在本发明的启示下或是将本发明与其他现有技术的特征进行组合而得出的任何与本发明相同或相近似的产品，均落在本发明的保护范围之内。
实施例中未注明具体实验步骤或者条件，按照本领域内的现有技术所描述的常规实验步骤的操作或条件即可进行。所用试剂以及其他仪器未注明生产厂商者，均为可以通过市购获得的常规试剂产品。
目前研究和实际应用中主要采用的是电子束辐照的间接作用进行废水处理，并没有考虑电子束辐照的直接作用。此外，当浓缩液中有机污染物浓度较低时，由于盐类物质远远大于有机污染物浓度，这使得电子束辐照过程中 产生的活性物种更多的与盐类物质反应，而不能有效去除浓度较低的有机污染物。如果单独使用电子束辐照去除浓缩液中低浓度有机污染物，通常需要用比理论需要高的多的多的辐照剂量，这显著增加了处理成本。
电吸附是利用电场的作用使水中离子分别向带相反电荷的电极迁移，并被电极吸附并储存在双电层内。研究表明：利用电吸附可以实现盐分和水的分离。但电吸附无法去除水中的有机污染物。并且，电极材料的选择是电吸附分离盐分和水的关键。
基于上述考虑，本发明希望实现电子束辐照耦合电吸附处理浓缩液，以实现焦化废水反渗透浓缩液中有机污染物的去除。具体实施内容如下：
第一方面，本发明提供一种基于电子束辐照工艺去除焦化废水反渗透浓缩液中有机污染物的方法，图1示出了本发明实施例提供的基于电子束辐照工艺去除焦化废水反渗透浓缩液中有机污染物的方法流程图，如图1所示，所述方法包括：
S1、将反渗透浓缩液通入高剂量电子束辐照单元，部分盐类物质在电子束辐照作用下电离产生水合电子和氧化性自由基；水合电子使一部分有机污染物带电，氧化性自由基使一部分有机污染物分解，从而得到一次预净化水；
S2、将一次预净化水通入电吸附处理单元，使得一次净化水在电场作用下，其中的盐类离子和一部分带电的有机污染物被电吸附去除；其中辐照过程中产生的H2O2被电吸附处理单元的阳极活化为羟基自由基，羟基自由基使吸附于电极表面的有机污染物分解，从而得到二次预净化水；
S3、将二次预净化水通入低剂量电子束辐照单元，以去除二次预净化水中有机污染物，得到三次预净化水；
S4、将三次预净化水返回至电吸附处理单元做过循环处理，直至低剂量电子束辐照单元的出水中COD≤10mg/L时，完成焦化废水反渗透浓缩液中有机污染物的去除。
具体实施时，本发明实施例一方面利用高剂量电子束辐照的直接作用，使部分盐类物质直接电离，产生相应的水合电子和氧化性自由基，其中，氧化性自由基包括且不限于O2·-、Cl·、SO4 -·和NO3·等。盐类物质的转化减少了其对活性物种猝灭作用的同时，生成的活性物种还能增强对浓缩液中有机污染物的氧化能力，高剂量电子束辐照剂量介于20～100kGy；另一方面，电 子束辐照过程中还产生水合电子，使原本呈中性的有机污染物带电，进而致使电吸附能去除浓缩液中的部分有机污染物。
当电子束辐照作用于RO浓缩液的剂量介于20～100kGy时，浓缩液中的部分盐类物质被电离分解，部分有机污染物在电离产物的作用下被分解，进一步采用电吸附手段，可实现剩余盐类物质和水的分离。电吸附过程施加的电压介于1.2～1.7V。并且，本发明采用碳包裹铁镍材料作为电吸附处理单元的正极材料，其对电子束辐照过程中产生的H2O2具有很好的吸附作用，并将其活化为羟基自由基。羟基自由基可以用于去除电极表面吸附的有机污染物，提高电极材料吸附的盐类物质的纯度，提高盐类物质的回收价值。
电吸附处理单元处理后的出水中，剩余的低浓度有机污染物可以通过后端低剂量电子束辐照去除，若低剂量电子束辐照处理后的出水COD大于10mg/L，可将出水返回电吸附处理单元，经电吸附处理单元与低剂量电子束辐照单元的循环处理，直至出水COD小于10mg/L。本发明通过电子束辐照和电吸附的协同作用，可以有效去除膜浓缩液中有机污染物，最终实验盐的资源化利用。
具体实施时，由于高剂量电子束辐照可直接将RO浓缩液中的一部分盐类物质直接电离为水合电子和氧化性自由基，剩余盐类物质继续经电吸附处理单元吸附除去。因此，本发明可处理高含盐量的焦化废水反渗透浓缩液，其中的盐含量以溶液电导率表示，其最高值可达100000us/cm，最低值不小于10000us/cm。并且，本发明提供的处理工艺适用于RO浓缩液中有机物浓度在150mg/L≤COD≤500mg/L。
在一些实施方式中，电吸附处理单元的阳极由碳包裹铁镍材料组成；电吸附处理单元的阴极由钛板或碳材料组成。优选的碳包裹铁镍材料包括：石墨烯包裹铁镍材料、生物炭包裹铁镍材料、改性石墨烯包裹铁镍材料和改性生物炭包裹铁镍材料中的一种或多种的组合。由于电子束辐照过程生成H2O2，碳包裹铁镍材料作为电吸附用电极阳极，铁镍修饰增加了电极表面的活性位点，增强了其对污水中的盐分吸附能力，同时还降低了活化体系中存在的H2O2(氧化剂)所需要的能垒，将H2O2活化为羟基自由基，羟基自由基可以去除电极表面吸附的有机污染物，提高电极材料吸附的盐类物质的纯度，进而提高盐类物质的回收价值。此外，硫脲的添加使电极材料中同时引入了硫和氮， 硫是多价态元素，具备丰富的电子，可提升电极材料的电子传递能力和电子交换能力，从而进一步促进对吸附的氧化剂的活化。使电极材料不仅具备良好的分盐性能，同时具有吸附和活化氧化剂的能力。氮的存在使复合材料中的铁镍与氮络合，形成更稳定的结构，有效防止复合材料在实际使用过程中铁镍溶出造成的材料损失或失效。
在一些实施方式中，生物炭包裹铁镍材料可通过如下制备方法获得：20ml0.1M铁氰化钾溶液逐滴加入到20ml 0.15M溶液中，在空气中老化12h后，经过滤、去离子水洗涤3次，获得普鲁士蓝类似物。然后，置于60℃烘箱中干燥12h。取干燥后的普鲁士蓝固体0.5g和壳聚糖1.5g置于50ml去离子水中，超声10min后搅拌1h，然后在80℃烘箱中干燥12h。取干燥后的固体1g与10g硫脲固体混合，研磨均匀。将研磨后的粉末放入管式炉中。在氮气条件下，以3℃/min升温至550℃保持1h，然后以5℃/min升温至900℃保持1h，自然降温后，获得的固体采用去离子水洗涤3次后置于60℃烘箱中烘干，所获的固体即为碳包裹铁镍材料。
在一些实施方式中，石墨烯包裹铁镍材料可通过如下制备方法获得：20ml0.1M铁氰化钾溶液逐滴加入到20ml 0.2M溶液中，在空气中老化10h后，经过滤、去离子水洗涤3次，获得普鲁士蓝类似物。然后，置于80℃烘箱中干燥12h。取干燥后的普鲁士蓝固体0.5g和改性石墨烯2g置于50ml去离子水中，超声10min后搅拌1h，然后在80℃烘箱中干燥12h。取干燥后的固体1g与15g硫脲固体混合，研磨均匀。将研磨后的粉末放入管式炉中。在氮气条件下，以3℃/min升温至550℃保持1h，然后以5℃/min升温至900℃保持1h，自然降温后，获得的固体采用去离子水洗涤3次后置于60℃烘箱中烘干，所获的固体即为碳包裹铁镍材料。
在一些实施方式中，三次预净化水在返回至电吸附处理单元做循环处理的次数在5-20次后，实现出水中COD≤10mg/L。
第二方面，本发明提供一种基于电子束辐照工艺去除焦化废水反渗透浓缩液中有机污染物的系统，所述系统适用于上述第一方面所述的方法，图2示出了本发明实施例提供的基于电子束辐照工艺去除焦化废水反渗透浓缩液中有机污染物的系统结构示意图，如图2所示，包括：
高剂量电子束辐照单元，用于将反渗透浓缩液中的盐类物质电离为水合 电子和氧化性自由基；水合电子使一部分有机污染物带电，氧化性自由基使一部分有机污染物分解，从而得到一次预净化水；
电吸附处理单元，用于吸附一次预净化水中的盐类离子和一部分带电的有机污染物；以及，将辐照产生的H2O2活化为羟基自由基，羟基自由基使吸附于电极表面的有机污染物分解，从而得到二次预净化水；
低剂量电子束辐照单元，用于分解二次预净化水中的有机污染物，得到净化水。
为使本领域技术人员更加清楚地理解本发明，现通过以下实施例对本发明所述的一种基于电子束辐照工艺去除焦化废水反渗透浓缩液中有机污染物的方法与系统进行详细说明。
焦化废水的具体处理方法为：RO浓水首先经过第1段电子束辐照处理单元(高剂量电子束辐照单元)，出水进入电吸附处理单元，最后进入第2段电子束辐照处理单元(低剂量电子束辐照单元)，出水直接排放(出水中COD小于10mg/L)，或返回至电吸附处理单元经过多次循环后，低剂量电子束辐照单元出水COD小于10mg/L后排放，最终完成对膜浓缩液的处理。
实施例1
取河北某焦化厂RO浓缩液，初始COD为247mg/L，电导率17500μs/cm。电吸附单元的阳极为铁镍修饰椰壳炭，阴极为钛板，流速为1m3/h。第1段电子束辐照剂量为30kGy，第2段电子束辐照剂量为5kGy，循环处理3次后出水COD<10mg/L。
实施例2
取河北某焦化厂RO浓缩液，初始COD为247mg/L，电导率17500μs/cm。电吸附单元的阳极为铁镍修饰椰壳炭，阴极为钛板，流速为1m3/h。第1段电子束辐照剂量为50kGy，第2段电子束辐照剂量为10kGy，循环处理2次后出水COD<10mg/L。
实施例3
取河北某焦化厂RO浓缩液，初始COD为376mg/L，电导率77500μs/cm。电吸附单元的阳极为铁镍修饰椰壳炭，阴极为钛板，流速为1m3/h。第1段电子束辐照剂量为70kGy，第2段电子束辐照剂量为10kGy，循环处理6次后出水COD<10mg/L。
对比例1
取河北某焦化厂RO浓缩液，初始COD为247mg/L，电导率17500μs/cm。采用单独电子束辐照处理，辐照剂量为150kGy，处理后出水COD为134mg/L。
对比例2
取河北某焦化厂RO浓缩液，初始COD为376mg/L，电导率77500μs/cm。采用单独电子束辐照处理，辐照剂量为150kGy，处理后出水COD为277mg/L。
由上述实施例可以看出，电子束辐照耦合电吸附技术可以有效减少高盐的影响，由于整个处理过程中未添加化学物质，最终盐的纯度较高。因此，电子束辐照耦合电吸附技术具有操作简单、处理效果好和提盐纯度高的优点。
本文中所称的“一个实施例”、“实施例”或者“一个或者多个实施例”意味着，结合实施例描述的特定特征、结构或者特性包括在本公开的至少一个实施例中。此外，请注意，这里“在一个实施例中”的词语例子不一定全指同一个实施例。
在此处所提供的说明书中，说明了大量具体细节。然而，能够理解，本公开的实施例可以在没有这些具体细节的情况下被实践。在一些实例中，并未详细示出公知的方法、结构和技术，以便不模糊对本说明书的理解。
在权利要求中，不应将位于括号之间的任何参考符号构造成对权利要求的限制。单词“包含”不排除存在未列在权利要求中的元件或步骤。位于元件之前的单词“一”或“一个”不排除存在多个这样的元件。本公开可以借助于包括有若干不同元件的硬件以及借助于适当编程的计算机来实现。在列举了若干装置的单元权利要求中，这些装置中的若干个可以是通过同一个硬件项来具体体现。单词第一、第二、以及第三等的使用不表示任何顺序。可将这些单词解释为名称。
最后应说明的是：以上实施例仅用以说明本公开的技术方案，而非对其限制；尽管参照前述实施例对本公开进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本公开各实施例技术方案的精神和范围。

Claims (10)

  1. 一种基于电子束辐照工艺去除焦化废水反渗透浓缩液中有机污染物的方法，其特征在于，所述工艺包括：
    将所述反渗透浓缩液通入高剂量电子束辐照单元，部分盐类物质在电子束辐照作用下电离产生水合电子和氧化性自由基；所述水合电子使一部分有机污染物带电，所述氧化性自由基使一部分有机污染物分解，从而得到一次预净化水；
    将所述一次预净化水通入电吸附处理单元，使得所述一次净化水在电场作用下，其中的盐类离子和一部分所述带电的有机污染物被电吸附去除；其中辐照过程中产生的H2O2被电吸附处理单元的阳极活化为羟基自由基，所述羟基自由基使吸附于电极表面的有机污染物分解，从而得到二次预净化水；
    将所述二次预净化水通入低剂量电子束辐照单元，以去除二次预净化水中有机污染物，得到三次预净化水；
    将所述三次预净化水返回至所述电吸附处理单元做过循环处理，直至所述低剂量电子束辐照单元的出水中COD≤10mg/L时，完成焦化废水反渗透浓缩液中有机污染物的去除。
  2. 根据权利要求1所述的方法，其特征在于，所述反渗透浓缩液中，150mg/L≤COD≤500mg/L，10000us/cm≤电导率≤100000us/cm。
  3. 根据权利要求1所述的处理工艺，其特征在于，所述高剂量电子束辐照剂量介于20～100kGy。
  4. 根据权利要求1所述的方法，其特征在于，所述电吸附单元进水流速介于1m3/h～20m3/h。
  5. 根据权利要求1所述的方法，其特征在于，所述电吸附处理单元施加的电压介于1.2～1.7V。
  6. 根据权利要求1所述的方法，其特征在于，所述电吸附处理单元的阳极由碳包裹铁镍材料组成；
    所述电吸附处理单元的阴极由钛板或碳材料组成。
  7. 根据权利要求6所述的方法，其特征在于，所述碳包裹铁镍材料包括：石墨烯包裹铁镍材料、生物炭包裹铁镍材料、改性石墨烯包裹铁镍材料和改性生物炭包裹铁镍材料中的一种或多种的组合。
  8. 根据权利要求1所述的方法，其特征在于，所述低剂量电子束辐照剂量介于1～10kGy。
  9. 根据权利要求1所述的方法，其特征在于，所述循环处理次数为1-20次。
  10. 一种基于电子束辐照工艺处理焦化废水反渗透浓缩液中有机污染物的系统，其特征在于，所述系统适用于上述权利要求1-9任一所述的方法，包括：
    高剂量电子束辐照单元，用于将所述反渗透浓缩液中的盐类物质电离为水合电子和氧化性自由基；所述水合电子使一部分有机污染物带电，所述氧化性自由基使一部分有机污染物分解，从而得到一次预净化水；
    电吸附处理单元，用于吸附所述一次预净化水中的盐类离子和一部分所述带电的有机污染物；以及，将辐照产生的H2O2活化为羟基自由基，所述羟基自由基使吸附于电极表面的有机污染物分解，从而得到二次预净化水；
    低剂量电子束辐照单元，用于分解所述二次预净化水中的有机污染物，得到净化水。
PCT/CN2024/076305 2024-01-26 2024-02-06 基于电子束辐照工艺去除焦化废水反渗透浓缩液中有机污染物的方法与系统 Pending WO2025156331A1 (zh)

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