WO2023020038A1 - 一种含氯及有机物废水的处理工艺 - Google Patents

一种含氯及有机物废水的处理工艺 Download PDF

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WO2023020038A1
WO2023020038A1 PCT/CN2022/092456 CN2022092456W WO2023020038A1 WO 2023020038 A1 WO2023020038 A1 WO 2023020038A1 CN 2022092456 W CN2022092456 W CN 2022092456W WO 2023020038 A1 WO2023020038 A1 WO 2023020038A1
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treatment
wastewater
treatment process
sulfate
chlorine
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PCT/CN2022/092456
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French (fr)
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陈琪
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无锡中天固废处置有限公司
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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
    • C02F9/00—Multistage treatment of water, waste water or sewage

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  • the embodiment of the present application relates to the technical field of wastewater treatment and recycling, for example, a process for treating wastewater containing chlorine and organic matter.
  • CN112960757A discloses a method for removing organic matter in chlorine-containing wastewater, said method comprising the following steps: adding hypochlorite, catalyst and ozone to chlorine-containing wastewater to form a diversified oxidation system, utilizing the ozone produced in the process of catalytic oxidation Hydroxyl radicals react with chlorine to oxidize and degrade organic matter in sewage.
  • This method uses chloride ions in high-salt wastewater to achieve low-cost and high-efficiency removal of organic matter.
  • chlorine-containing compounds are added in the process of removing organic matter, and excess chloride ions in wastewater are not removed, which has a negative impact on the environment. Pollution still exists.
  • CN110255799A discloses a chlorine removal agent and its method and application for dechlorinating polluted acid wastewater.
  • the chlorine removal agent includes persulfuric acid and its salt compounds.
  • the chlorine removal method includes the following steps: Heating, adding an appropriate amount of chlorine removal agent, heating and stirring for a certain period of time can remove the chloride ions in the polluted acid wastewater, and the chlorine gas generated during the reaction process is absorbed by the lye.
  • This dechlorination method converts chlorine ions in wastewater into chlorine gas and recycles them to avoid direct discharge and pollute the environment.
  • hypochlorite ions still exist in the solution during the dechlorination process, and the complete removal of chloride ions has not been achieved.
  • An embodiment of the present application provides a treatment process for wastewater containing chlorine and organic matter.
  • the treatment process can simultaneously remove chloride ions and organic matter in the waste water, and solve the reverse rise of chloride ion content in the process of chlorine removal, further improving the Chloride ion removal rate.
  • An embodiment of the present application provides a treatment process for wastewater containing chlorine and organic matter.
  • the treatment process includes the following steps: performing synergistic oxidation treatment and ozone aeration treatment on the wastewater containing chlorine and organic matter at the same time.
  • sulfuric acid needs to be added to the wastewater to adjust the pH before the coordinated oxidation treatment.
  • the pH is adjusted to ⁇ 1, such as 0.1, 0.3, 0.5, 0.7 or 0.9, but not limited to the listed values, and other unlisted values within the range of values are also applicable.
  • the coordinated oxidation treatment includes adding an oxidant and a catalyst to the wastewater.
  • the oxidizing agent is a persulfate.
  • the persulfate includes any one or a combination of at least two of sodium persulfate, potassium persulfate or ammonium persulfate, the typical but non-limiting examples of the combination are: sodium persulfate and potassium persulfate Combination, combination of sodium persulfate and ammonium persulfate or combination of potassium persulfate and ammonium persulfate, etc.
  • the mass volume ratio of the added amount of the oxidant to the waste water is (0.25-1): 10g/mL, such as 0.25: 10g/mL, 0.45: 10g/mL, 0.65: 10g/mL, 0.85 : 10g/mL, 0.95: 10g/mL or 1: 10g/mL, etc., but not limited to the listed values, other unlisted values within the range of values are also applicable.
  • the catalyst is a transition metal sulfate.
  • the transition metal sulfate includes any one or a combination of at least two of ferric sulfate, ferrous sulfate, cobalt sulfate or copper sulfate, the typical but non-limiting examples of the combination are: iron sulfate and cobalt sulfate Combination, combination of ferrous sulfate and copper sulfate or combination of ferric sulfate and ferrous sulfate, etc.
  • the mass volume ratio of the amount of catalyst added to the waste water is (0.025-0.1): 10g/mL, such as 0.025: 10g/mL, 0.045: 10g/mL, 0.065: 10g/mL, 0.085 : 10g/mL, 0.095: 10g/mL or 0.1: 10g/mL, etc., but not limited to the listed values, other unlisted values within the range of values are also applicable.
  • the coordinated oxidation treatment is carried out under heating conditions.
  • the heating temperature is 85-95°C, such as 85°C, 87°C, 89°C, 91°C, 93°C or 95°C, etc., but not limited to the listed values, and other values not listed within the range values are also applicable.
  • the co-oxidation process is carried out under stirring conditions.
  • the stirring rate is 300-500rpm, such as 300rpm, 350rpm, 400rpm, 450rpm or 500rpm, etc., but not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the stirring time is 30-150 min, such as 30 min, 60 min, 90 min, 120 min or 150 min, etc., but not limited to the listed values, and other unlisted values within the range of values are also applicable.
  • the volume ratio of the amount of ozone introduced into the wastewater to the wastewater in the ozone aeration treatment is (0.05-2) mL/min: 1 mL, for example, it can be 0.05 mL/min: 1 mL, 0.08 mL/min: 1mL, 0.59mL/min: 1mL, 1.2mL/min: 1mL, 1.6mL/min: 1mL or 2mL/min: 1mL, etc., but not limited to the listed values, other unlisted values within the value range The same applies.
  • chlorine gas is removed through tail gas absorption in the coordinated oxidation treatment and the ozone aeration treatment.
  • the selection of the absorption liquid and the specific absorption method in the tail gas absorption can be selected according to the actual production situation, and no specific limitation is made here.
  • the obtained sulfate solution is recovered after the ozone aeration treatment.
  • the recovery treatment includes adding alkali to the sulfate solution to neutralize it, and evaporating and crystallizing the obtained liquid phase after solid-liquid separation to obtain the product.
  • the sulfate solution is neutralized to a pH of 5-6, such as 5, 5.1, 5.3, 5.5, 5.7, 5.9 or 6, etc., but not limited to the listed values, other values not included in the range of values The listed values also apply.
  • the alkali includes any one or a combination of at least two of sodium hydroxide, potassium hydroxide or ammonia water.
  • Typical but non-limiting examples of the combination include: a combination of sodium hydroxide and potassium hydroxide, hydroxide A combination of sodium and ammonia or a combination of potassium hydroxide and ammonia, etc.
  • the precipitate is recycled for the coordinated oxidation.
  • the transition metal sulfate obtained after the precipitation is dissolved by sulfuric acid can be recycled as a catalyst for the synergistic oxidation treatment.
  • the treatment process specifically includes the following steps: adjusting the chlorine and organic waste water to pH ⁇ 1 with sulfuric acid, adding persulfate and transition metal sulfate to synergistically oxidize the waste water, wherein, the added The mass-volume ratio of persulfate to the waste water is (0.25-1): 10g/mL, and the mass-volume ratio of the added transition metal sulfate to the waste water is (0.025-0.1): 10g/mL, heated to Stirring at 300-500rpm for 30-150min at 85-95°C, while performing ozone aeration treatment, the volume ratio of the amount of ozone introduced in the ozone aeration treatment to the waste water is (0.05-2)mL/min : 1mL, the chlorine gas produced in the process of synergistic oxidation treatment and ozone aeration treatment is absorbed and removed by tail gas, the sulfate solution obtained is neutralized with alkali after the
  • a kind of treatment process of chlorine-containing and organic waste water provided by the embodiment of the present application can remove organic matter and chloride ions in the waste water simultaneously, and can obtain sulfate products. It improves the recycling and reuse of resources, and has good economic and environmental benefits;
  • a treatment process for chlorine-containing and organic waste water provided in the embodiment of the present application, the treatment process simultaneously carries out ozone aeration treatment in the coordinated oxidation process, avoiding the reverse dissolution of chlorine gas in water and peroxidation in the dechlorination process phenomenon, which solves the problem of reverse rise of chloride ions in the related technology, thereby further improving the removal rate of chloride ions, and the content of chloride ions in the solution after chlorine removal can be as low as 7ppm.
  • Fig. 1 is a schematic flow chart of a treatment process for wastewater containing chlorine and organic matter provided in a specific embodiment of the present application.
  • This embodiment provides a treatment process for wastewater containing chlorine and organic matter.
  • the process flow of the treatment process is shown in Figure 1.
  • the treatment process includes the following steps: 100 mL of waste water with a chlorine concentration of 3847 ppm and a COD content of 4381 ppm Add it to the container, adjust the pH of the wastewater to 0.5 with sulfuric acid, add 5g of sodium persulfate and 0.5g of copper sulfate to synergistically oxidize the wastewater, heat it to 90°C, stir at 300rpm for 90min, and carry out ozone aeration treatment at the same time, ozone
  • the input volume is 0.2mL/min: 1mL
  • the chlorine gas produced in the process of synergistic oxidation treatment and ozone aeration treatment is removed by tail gas absorption, and the sulfate solution obtained after ozone aeration treatment is added to sodium hydroxide And the solution, adjust the pH to 5.5, and then carry out solid-liquid separation treatment
  • This embodiment provides a treatment process for wastewater containing chlorine and organic matter.
  • the process flow of the treatment process is shown in Figure 1.
  • the treatment process includes the following steps: 100 mL of waste water with a chlorine concentration of 3847 ppm and a COD content of 4381 ppm Add it to the container, adjust the pH of the wastewater to 0.7 with sulfuric acid, add 10g of sodium persulfate and 1g of copper sulfate to synergistically oxidize the wastewater, heat it to 85°C, stir at 400rpm for 120min, and carry out ozone aeration treatment at the same time.
  • the feed rate is 2mL/min:1mL, and other process parameters are the same as in Example 1.
  • This embodiment provides a treatment process for wastewater containing chlorine and organic matter.
  • the process flow of the treatment process is shown in Figure 1.
  • the treatment process includes the following steps: 100 mL of waste water with a chlorine concentration of 3847 ppm and a COD content of 4381 ppm Add it to the container, adjust the pH of the wastewater to 0.3 with sulfuric acid, add 2.5g of sodium persulfate and 0.025g of copper sulfate to synergistically oxidize the wastewater, heat it to 95°C, stir at 500rpm for 60min, and perform ozone aeration treatment at the same time.
  • the feed rate of ozone is 0.05mL/min:1mL, and other processing parameters are identical with embodiment 1.
  • This embodiment provides a treatment process for wastewater containing chlorine and organic matter.
  • the process flow of the treatment process is shown in Figure 1.
  • the treatment process includes the following steps: 100 mL of waste water with a chlorine concentration of 3847 ppm and a COD content of 4381 ppm Add in the container, the pH of waste water is adjusted to 2 with sulfuric acid, and other processing parameters are identical with embodiment 1.
  • This embodiment provides a treatment process for wastewater containing chlorine and organic matter.
  • the process flow of the treatment process is shown in Figure 1.
  • the treatment process includes the following steps: 100 mL of waste water with a chlorine concentration of 3847 ppm and a COD content of 4381 ppm Add in the container, the pH of waste water is adjusted to 7 with sulfuric acid, and other processing parameters are identical with embodiment 1.
  • This embodiment provides a treatment process for wastewater containing chlorine and organic matter.
  • the process flow of the treatment process is shown in Figure 1.
  • the treatment process includes the following steps: 100 mL of waste water with a chlorine concentration of 3847 ppm and a COD content of 4381 ppm Add in the container, the pH of waste water is adjusted to 12 with sodium hydroxide, and other processing parameters are identical with embodiment 1.
  • This embodiment provides a treatment process for wastewater containing chlorine and organic matter.
  • the process flow of the treatment process is shown in Figure 1.
  • the treatment process includes the following steps: 100 mL of waste water with a chlorine concentration of 3847 ppm and a COD content of 4381 ppm Add it to the container, adjust the pH of the wastewater to 0.5 with sulfuric acid, add 5g of sodium persulfate and 0.5g of copper sulfate to synergistically oxidize the wastewater, stir at 300rpm for 90min, and perform ozone aeration treatment at the same time, and the amount of ozone introduced is 0.2 mL/min: 1mL, other processing parameters are identical with embodiment 1.
  • This embodiment provides a treatment process for wastewater containing chlorine and organic matter.
  • the process flow of the treatment process is shown in Figure 1.
  • the treatment process includes the following steps: 100 mL of waste water with a chlorine concentration of 3847 ppm and a COD content of 4381 ppm Add it to the container, adjust the pH of the wastewater to 0.6 with sulfuric acid, add 9g of sodium persulfate and 1g of copper sulfate to synergistically oxidize the wastewater, heat it to 80°C, stir at 300rpm for 90min, and carry out ozone aeration treatment at the same time.
  • the input volume is 0.2mL/min: 1mL.
  • the chlorine gas generated during the process of synergistic oxidation treatment and ozone aeration treatment is absorbed and removed by tail gas, and the sulfate solution obtained after ozone aeration treatment is neutralized by adding sodium hydroxide. solution, adjust the pH to 6, and other process parameters are the same as in Example 1.
  • This embodiment provides a treatment process for wastewater containing chlorine and organic matter.
  • the process flow of the treatment process is shown in Figure 1.
  • the treatment process includes the following steps: 100 mL of waste water with a chlorine concentration of 3847 ppm and a COD content of 4381 ppm Add it to the container, adjust the pH of the wastewater to 0.9 with sulfuric acid, add 8g of potassium persulfate and 0.4g of cobalt sulfate to synergistically oxidize the wastewater, heat it to 95°C, stir at 350rpm for 100min, and perform ozone aeration treatment at the same time, ozone
  • the amount of feed is 0.3mL/min: 1mL, the chlorine gas generated during the process of synergistic oxidation treatment and ozone aeration treatment is removed by tail gas absorption, and the sulfate solution obtained after ozone aeration treatment is added to potassium hydroxide And the solution, adjust the pH to 5, and then carry out solid-liquid separation treatment,
  • This embodiment provides a treatment process for wastewater containing chlorine and organic matter.
  • the process flow of the treatment process is shown in Figure 1.
  • the treatment process includes the following steps: 100 mL of waste water with a chlorine concentration of 3847 ppm and a COD content of 4381 ppm Add it to the container, adjust the pH of the wastewater to 0.4 with sulfuric acid, add 8g of ammonium persulfate and 0.7g of ferric sulfate to synergistically oxidize the wastewater, heat it to 85°C, stir at 400rpm for 130min, and carry out ozone aeration treatment at the same time, ozone
  • the input volume is 0.3mL/min: 1mL
  • the chlorine gas produced in the process of synergistic oxidation treatment and ozone aeration treatment is removed by tail gas absorption, and the sulfate solution obtained after ozone aeration treatment is added with ammonia water neutralization solution , adjust the pH to 5.5, and then carry out solid
  • This embodiment provides a treatment process for wastewater containing chlorine and organic matter.
  • the process flow of the treatment process is shown in Figure 1.
  • the treatment process includes the following steps: 100 mL of waste water with a chlorine concentration of 3847 ppm and a COD content of 4381 ppm Add it to the container, adjust the pH of the wastewater to 0.9 with sulfuric acid, add 3g of sodium persulfate, 3g of potassium persulfate, 0.2g of copper sulfate, 0.2g of cobalt sulfate to synergistically oxidize the wastewater, and heat to 90°C, stirring at 300rpm 90min, carry out ozone aeration treatment at the same time, the input rate of ozone is 0.4mL/min: 1mL, the chlorine gas produced in the process of synergistic oxidation treatment and ozone aeration treatment is absorbed and removed by tail gas, and the obtained after ozone aeration treatment Sulphate solution, add sodium hydroxide and potassium hydro
  • This embodiment provides a treatment process for wastewater containing chlorine and organic matter.
  • the process flow of the treatment process is shown in Figure 1.
  • the treatment process includes the following steps: 100 mL of waste water with a chlorine concentration of 3847 ppm and a COD content of 4381 ppm Add it to the container, adjust the pH of the wastewater to 0.9 with sulfuric acid, add 3g of potassium persulfate, 3g of ammonium persulfate, 0.2g of cobalt sulfate, 0.2g of iron sulfate to synergistically oxidize the wastewater, and heat to 95°C, stirring at 500rpm 60min, carry out ozone aeration treatment at the same time, the input amount of ozone is 0.4mL/min: 1mL, the chlorine gas produced in the process of synergistic oxidation treatment and ozone aeration treatment is absorbed and removed by tail gas, and the obtained after ozone aeration treatment Sulphate solution, add potassium hydroxide and
  • potassium sulfate and ammonium sulfate solution is evaporated and crystallized, potassium sulfate and ammonium sulfate products are obtained, and the obtained hydrogen Cobalt oxide and iron hydroxide precipitates are dissolved in sulfuric acid to obtain reusable cobalt sulfate and iron sulfate catalysts.
  • This comparative example provides a kind of treatment process of chlorine-containing and organic waste water, and the process flow of described treatment process is as shown in Figure 1, and described treatment process comprises the following steps: the 100mL waste water that chlorine concentration is 3847ppm and COD content is 4381ppm Add it to the container, adjust the pH of the wastewater to 0.5 with sulfuric acid, add 5g of sodium persulfate and 0.5g of copper sulfate to synergistically oxidize the wastewater, heat to 90°C, stir at 300rpm for 90min, and perform air aeration treatment at the same time.
  • the input volume is 0.2mL/min: 1mL
  • the chlorine gas produced in the process of synergistic oxidation treatment and air aeration treatment is removed by tail gas absorption, and the sulfate solution obtained after air aeration treatment is added to sodium hydroxide And solution, adjust the pH to 5.5, then carry out solid-liquid separation treatment, obtain sodium sulfate product after evaporation and crystallization treatment of sodium sulfate solution, the copper hydroxide precipitation after solid-liquid separation treatment is dissolved in sulfuric acid to obtain reusable copper sulfate catalyst.
  • This comparative example provides a kind of treatment process of chlorine-containing and organic waste water, and the process flow of described treatment process is as shown in Figure 1, and described treatment process comprises the following steps: the 100mL waste water that chlorine concentration is 3847ppm and COD content is 4381ppm Add it to the container, adjust the pH of the wastewater to 0.5 with sulfuric acid, add 5g of sodium persulfate and 0.5g of copper sulfate to synergistically oxidize the wastewater, and heat to 90°C, stir at 300rpm for 90min, without aeration treatment, other process parameters Same as Example 1.
  • This comparative example provides a kind of treatment process of chlorine-containing and organic waste water, and the process flow of described treatment process is as shown in Figure 1, and described treatment process comprises the following steps: the 100mL waste water that chlorine concentration is 3847ppm and COD content is 4381ppm Add it to the container, adjust the pH of the wastewater to 0.5 with sulfuric acid, add 5g of sodium persulfate and 0.5g of copper sulfate to synergistically oxidize the wastewater, heat to 90°C, stir at 300rpm for 90min, and perform air aeration treatment after the oxidation process , the feed rate of air is 0.2mL/min:1mL, and other processing parameters are identical with embodiment 1.
  • This comparative example provides a kind of treatment process of chlorine-containing and organic waste water, and the process flow of described treatment process is as shown in Figure 1, and described treatment process comprises the following steps: the 100mL waste water that chlorine concentration is 3847ppm and COD content is 4381ppm Add it to the container, adjust the pH of the wastewater to 0.5 with sulfuric acid, heat it to 90°C, stir at 300rpm for 90min, and perform ozone aeration treatment. The amount of ozone introduced is 0.2mL/min: 1mL. The chlorine gas produced in the process is removed by tail gas absorption.
  • This comparative example provides a kind of treatment process of chlorine-containing and organic waste water, and the process flow of described treatment process is as shown in Figure 1, and described treatment process comprises the following steps: the 100mL waste water that chlorine concentration is 3847ppm and COD content is 4381ppm Add it to the container, adjust the pH of the wastewater to 2 with sulfuric acid, add 7g of sodium persulfate and 0.5g of copper sulfate to synergistically oxidize the wastewater, heat it to 90°C, stir at 300rpm for 90min, and carry out air aeration treatment at the same time, the air The feeding rate is 0.2mL/min:1mL, and other processing parameters are the same as in Example 1.
  • This comparative example provides a kind of treatment process of chlorine-containing and organic waste water, and the process flow of described treatment process is as shown in Figure 1, and described treatment process comprises the following steps: the 100mL waste water that chlorine concentration is 3847ppm and COD content is 4381ppm Add it to the container, adjust the pH of the wastewater to 7 with sulfuric acid, add 10g of sodium persulfate and 0.75g of copper sulfate to synergistically oxidize the wastewater, heat it to 90°C, stir at 300rpm for 90min, and carry out air aeration treatment at the same time.
  • the feeding rate is 0.2mL/min:1mL, and other processing parameters are the same as in Example 1.
  • the chloride ion content in the solution will be measured three times, and the chloride ion content is measured immediately after the aeration respectively; after the aeration, the chlorine ion content is measured after standing overnight; Measure the chloride ion content after 2h.
  • the chloride ion content in the solution was also measured three times.
  • the chloride ion content was measured immediately after oxidation; the chloride ion content was measured after standing overnight; ion content.
  • the application provides a treatment process for wastewater containing chlorine and organic matter. Under pH ⁇ 1 and heating conditions, ozone aeration treatment can be carried out simultaneously in the synergistic oxidation process to remove organic matter and chloride ions in the wastewater.
  • the residual chlorine ion after gas is less than 12ppm, and the residual COD is lower than 214ppm.
  • Example 1 and Examples 4-6 In conjunction with Example 1 and Examples 4-6, it can be seen that when pH>1, it is not conducive to the removal of chlorine ions and organic matter in the wastewater, and the higher the pH, the lower the removal efficiency; it can be seen in combination with Example 1 and Example 7 , It is also not conducive to the removal of chloride ions and organic matter in wastewater without heating; thus it is shown that the present application helps the removal of chloride ions and organic matter in wastewater under the preferred pH range and heating conditions.
  • Example 1 (4) In conjunction with Example 1 and Comparative Examples 2-3, it can be seen that aeration treatment is carried out after no aeration treatment or synergistic oxidation treatment, although the residual chloride ion measured immediately after the experiment is lower, but after standing overnight Sodium sulfite was added to the solution as a reducing agent, and the residual amount of chloride ions measured rose, indicating that chlorine gas inversion and peroxidation existed in the chlorine removal process; thus, it was shown that in the process of wastewater treatment, aeration treatment was carried out simultaneously in the process of synergistic oxidation It is an important step to ensure that chlorine gas back-dissolution and peroxidation do not occur during the dechlorination process.
  • the application provides a treatment process for wastewater containing chlorine and organic matter, which can remove organic matter and chloride ions in the wastewater at the same time; in the process of synergistic oxidation, ozone aeration treatment is carried out at the same time, avoiding the chlorine removal process.
  • the reverse dissolution of chlorine gas in water and the phenomenon of peroxidation solve the problem of reverse rise of chlorine ions in the related technology, thereby further improving the removal rate of chloride ions.
  • the content of chloride ions in the solution can be as low as 7ppm.

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Abstract

本文公布一种含氯及有机物废水的处理工艺，所述处理工艺包括：对所述含氯及有机物废水进行协同氧化处理以及臭氧曝气处理。所述处理工艺可以实现废水中有机物与氯离子的同步去除，并回收硫酸盐产品。本申请处理后的废水中氯离子浓度低至10ppm以下，不仅解决了废水中氯离子完全去除的难题，而且工艺流程简单，成本低廉，并实现了资源的回收再利用。

Description

一种含氯及有机物废水的处理工艺 技术领域
本申请实施例涉及废水处理与回收利用技术领域，例如一种含氯及有机物废水的处理工艺。
背景技术
随着工业水平的迅速发展和自然资源的快速消耗，采矿、石油化工、食品加工、有色金属冶金、造纸、纺织、油漆和机械制造等行业排放的工业废水在过去几十年中显著增加。工业废水中常含有高浓度的氯离子和有机物，不仅会对污染环境、危害人体健康及动植物生长，也会严重腐蚀建筑物、生产及环保设备，甚至引发生产安全以及环境风险事故。因此含有高浓度氯和有机物的工业废水的去除是目前研究的重点和难点。
CN112960757A公开了一种去除含氯废水中有机物的方法，所述方法包括以下步骤：向含氯废水中加入次氯酸盐、催化剂和臭氧，构成多样化氧化体系，利用臭氧催化氧化过程中产生的羟基自由基与氯反应，氧化降解污水中的有机物。该方法利用高盐废水中的氯离子，实现了有机物的低成本、高效去除，但在去除有机物的过程中投加了含氯化合物，也并未去除废水中多余的氯离子，其对环境的污染依然存在。
CN110255799A公开了一种除氯药剂及利用其对污酸废水进行除氯的方法和应用，所述除氯药剂包括过硫酸及其盐类化合物，除氯方法包括如下步骤以下步骤：将污酸废水加热，加入适量除氯药剂，加热搅拌一定时间可去除污酸废水中的氯离子，且反应过程中产生的氯气通过碱液吸收。该除氯方法的将废水中的氯离子转化为氯气并回收利用，避免直接排放污染环境，但其在除氯过程中溶液中仍存在着次氯酸根离子，并未实现氯离子的完全去除。
鉴于上述技术存在的问题，工业废水中氯离子和有机物的同步去除仍然存在着较大的技术难题，为了实现废水资源化利用，减少废水排放对环境造成的伤害，开发一种高效、操作简单和成本低廉的去除废水中氯离子和有机物的工艺是十分必要的。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本申请一实施例提供一种含氯及有机物废水的处理工艺，所述处理工艺能同时去除废水中的氯离子及有机物，并解决了除氯过程中氯离子含量的反升现象，进一步提高了氯离子的去除率。
本申请一实施例提供了一种含氯及有机物废水的处理工艺，所述处理工艺包括以下步骤：对所述含氯及有机物废水同时进行协同氧化处理以及臭氧曝气处理。
本申请中，由于含氯废水在除氯过程中，产生的氯气未及时排出会重新溶于水中变为氯离子和次氯酸根离子，其产生的氯离子又被氧化，最后溶液中只会存在次氯酸根离子，导致出现氯气反溶和过氧化的现象。本申请通过在协同氧化过程中加入臭氧曝气处理，将产生的氯气从溶液中吹出，解决了溶液中氯离子的反升问题，从而进一步提高了氯离子的去除率。
作为本申请优选的技术方案，所述废水在协同氧化处理前需加入硫酸调节pH。
优选地，所述pH调节至＜1，例如可以是0.1、0.3、0.5、0.7或0.9等，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
作为本申请优选的技术方案，所述协同氧化处理包括向所述废水中加入氧化剂和催化剂。
优选地，所述氧化剂为过硫酸盐。
优选地，所述过硫酸盐包括过硫酸钠、过硫酸钾或过硫酸铵中的任意一种或至少两种组合，所述组合典型但非限制性实例有：过硫酸钠和过硫酸钾的组合、过硫酸钠和过硫酸铵的组合或过硫酸钾和过硫酸铵的组合等。
优选地，所述氧化剂的加入量与所述废水的质量体积比为(0.25-1):10g/mL，例如可以是0.25:10g/mL、0.45:10g/mL、0.65:10g/mL、0.85:10g/mL、0.95:10g/mL或1:10g/mL等，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
优选地，所述催化剂为过渡金属硫酸盐。
优选地，所述过渡金属硫酸盐包括硫酸铁、硫酸亚铁、硫酸钴或硫酸铜中的任意一种或至少两种组合，所述组合典型但非限制性实例有：硫酸铁和硫酸 钴的组合、硫酸亚铁和硫酸铜的组合或硫酸铁和硫酸亚铁的组合等。
优选地，所述催化剂的加入量与所述废水的质量体积比为(0.025-0.1):10g/mL，例如可以是0.025:10g/mL、0.045:10g/mL、0.065:10g/mL、0.085:10g/mL、0.095:10g/mL或0.1:10g/mL等，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
作为本申请优选的技术方案，所述协同氧化处理在加热条件下进行。
优选地，所述加热的温度为85-95℃，例如可以是85℃、87℃、89℃、91℃、93℃或95℃等，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
优选地，所述协同氧化过程在搅拌条件下进行。
优选地，所述搅拌的速率为300-500rpm，例如可以是300rpm、350rpm、400rpm、450rpm或500rpm等，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
优选地，所述搅拌的时间为30-150min，例如可以是30min、60min、90min、120min或150min等，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
作为本申请优选的技术方案，所述臭氧曝气处理中臭氧的通入量与所述废水的体积比为(0.05-2)mL/min:1mL，例如可以是0.05mL/min:1mL、0.08mL/min:1mL、0.59mL/min:1mL、1.2mL/min:1mL、1.6mL/min:1mL或2mL/min:1mL等，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
作为本申请优选的技术方案，所述协同氧化处理以及所述臭氧曝气处理中通过尾气吸收除去氯气。
本申请中，所述尾气吸收中吸收液以及具体的吸收方式的选择，可根据实际的生产情况进行选择，在此不做具体限定。
作为本申请优选的技术方案，所述臭氧曝气处理后对得到的硫酸盐溶液进行回收处理。
优选地，所述回收处理包括，对所述硫酸盐溶液加碱中和，固液分离后对得到的液相进行蒸发结晶后得到产品。
优选地，对所述硫酸盐溶液进行中和至pH为5-6，例如可以是5、5.1、5.3、 5.5、5.7、5.9或6等，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
优选地，所述碱包括氢氧化钠、氢氧化钾或氨水中的任意一种或至少两种组合，所述组合典型但非限制性实例有：氢氧化钠和氢氧化钾的组合、氢氧化钠和氨水的组合或氢氧化钾和氨水的组合等。
作为本申请优选的技术方案，所述固液分离后对沉淀进行回收处理用于所述协同氧化。
本申请中，所述沉淀通过硫酸溶解后得到的过渡金属硫酸盐，可作为催化剂循环用于所述协同氧化处理。
作为本申请优选的技术方案，所述处理工艺具体包括如下步骤：将含氯及有机物废水用硫酸调节至pH＜1，投加过硫酸盐和过渡金属硫酸盐协同氧化废水，其中，投加的过硫酸盐与所述废水的质量体积比为(0.25-1):10g/mL，投加的过渡金属硫酸盐与所述废水的质体积比为(0.025-0.1):10g/mL，加热至85-95℃下在300-500rpm下搅拌30-150min，同时进行臭氧曝气处理，所述臭氧曝气处理中臭氧的通入量与所述废水的体积比为(0.05-2)mL/min:1mL，将协同氧化处理以及臭氧曝气处理的过程中产生的氯气通过尾气吸收去除，对臭氧曝气处理后对得到的硫酸盐溶液加碱中和，固液分离处理后对得到的液相进行蒸发结晶后得到硫酸盐产品，得到的沉淀用硫酸溶解后回用于所述协同氧化处理。
与相关技术相比，本申请实施例具有以下有益效果：
(1)本申请实施例提供的一种含氯及有机物废水的处理工艺，可将废水中的有机物与氯离子同时除去，并可得到硫酸盐产品，所述处理工艺流程简单、成本低廉，实现了资源的回收再利用，具有良好的经济和环境效益；
(2)本申请实施例提供的一种含氯及有机物废水的处理工艺，所述处理工艺在协同氧化过程中同时进行臭氧曝气处理，避免了除氯过程中氯气反溶于水中和过氧化现象，解决了相关技术中氯离子反升的问题，从而进一步提高了氯离子的去除率，除氯后溶液中的氯离子含量可低至7ppm。
在阅读并理解了附图和详细描述后，可以明白其他方面。
附图说明
附图用来提供对本文技术方案的进一步理解，并且构成说明书的一部分，与本申请的实施例一起用于解释本文的技术方案，并不构成对本文技术方案的限制。
图1是本申请一具体实施方式中提供的一种含氯及有机物废水的处理工艺的流程示意图。
具体实施方式
下面结合附图并通过具体实施方式来进一步说明本申请的技术方案。但下述的实例仅仅是本申请的简易例子，并不代表或限制本申请的权利保护范围，本申请的保护范围以权利要求书为准。
实施例1
本实施例提供了一种含氯及有机物废水的处理工艺，所述处理工艺的流程如图1所示，所述处理工艺包括以下步骤：将含氯浓度为3847ppm和COD含量为4381ppm的100mL废水加到容器中，用硫酸将废水的pH调节为0.5，投加5g过硫酸钠和0.5g硫酸铜协同氧化废水，并加热至90℃，在300rpm下搅拌90min，同时进行臭氧曝气处理，臭氧的通入量为0.2mL/min:1mL，将协同氧化处理以及臭氧曝气处理的过程中产生的氯气通过尾气吸收除去，对臭氧曝气处理后得到的硫酸盐溶液，投加氢氧化钠中和溶液，调节pH至5.5，之后进行固液分离处理，得到的硫酸钠溶液蒸发结晶处理后获得硫酸钠产品，得到的氢氧化铜沉淀使用硫酸溶解后得到可重复使用的硫酸铜催化剂。
实施例2
本实施例提供了一种含氯及有机物废水的处理工艺，所述处理工艺的流程如图1所示，所述处理工艺包括以下步骤：将含氯浓度为3847ppm和COD含量为4381ppm的100mL废水加到容器中，用硫酸将废水的pH调节为0.7，投加10g过硫酸钠和1g硫酸铜协同氧化废水，并加热至85℃，在400rpm下搅拌120min，同时进行臭氧曝气处理，臭氧的通入量为2mL/min:1mL，其他工艺参数与实施例1相同。
实施例3
本实施例提供了一种含氯及有机物废水的处理工艺，所述处理工艺的流程如图1所示，所述处理工艺包括以下步骤：将含氯浓度为3847ppm和COD含量 为4381ppm的100mL废水加到容器中，用硫酸将废水的pH调节为0.3，投加2.5g过硫酸钠和0.025g硫酸铜协同氧化废水，并加热至95℃，在500rpm下搅拌60min，同时进行臭氧曝气处理，臭氧的通入量为0.05mL/min:1mL，其他工艺参数与实施例1相同。
实施例4
本实施例提供了一种含氯及有机物废水的处理工艺，所述处理工艺的流程如图1所示，所述处理工艺包括以下步骤：将含氯浓度为3847ppm和COD含量为4381ppm的100mL废水加到容器中，用硫酸将废水的pH调节为2，其他工艺参数与实施例1相同。
实施例5
本实施例提供了一种含氯及有机物废水的处理工艺，所述处理工艺的流程如图1所示，所述处理工艺包括以下步骤：将含氯浓度为3847ppm和COD含量为4381ppm的100mL废水加到容器中，用硫酸将废水的pH调节为7，其他工艺参数与实施例1相同。
实施例6
本实施例提供了一种含氯及有机物废水的处理工艺，所述处理工艺的流程如图1所示，所述处理工艺包括以下步骤：将含氯浓度为3847ppm和COD含量为4381ppm的100mL废水加到容器中，用氢氧化钠将废水的pH调节为12，其他工艺参数与实施例1相同。
实施例7
本实施例提供了一种含氯及有机物废水的处理工艺，所述处理工艺的流程如图1所示，所述处理工艺包括以下步骤：将含氯浓度为3847ppm和COD含量为4381ppm的100mL废水加到容器中，用硫酸将废水的pH调节为0.5，投加5g过硫酸钠和0.5g硫酸铜协同氧化废水，在300rpm下搅拌90min，同时进行臭氧曝气处理，臭氧的通入量为0.2mL/min:1mL，其他工艺参数与实施例1相同。
实施例8
本实施例提供了一种含氯及有机物废水的处理工艺，所述处理工艺的流程如图1所示，所述处理工艺包括以下步骤：将含氯浓度为3847ppm和COD含量为4381ppm的100mL废水加到容器中，用硫酸将废水的pH调节为0.6，投加9g过硫酸钠和1g硫酸铜协同氧化废水，并加热至80℃，在300rpm下搅拌90min， 同时进行臭氧曝气处理，臭氧的通入量为0.2mL/min:1mL，将协同氧化处理以及臭氧曝气处理的过程中产生的氯气通过尾气吸收除去，对臭氧曝气处理后得到的硫酸盐溶液，投加氢氧化钠中和溶液，调节pH至6，其他工艺参数与实施例1相同。
实施例9
本实施例提供了一种含氯及有机物废水的处理工艺，所述处理工艺的流程如图1所示，所述处理工艺包括以下步骤：将含氯浓度为3847ppm和COD含量为4381ppm的100mL废水加到容器中，用硫酸将废水的pH调节为0.9，投加8g过硫酸钾和0.4g硫酸钴协同氧化废水，并加热至95℃，在350rpm下搅拌100min，同时进行臭氧曝气处理，臭氧的通入量为0.3mL/min:1mL，将协同氧化处理以及臭氧曝气处理的过程中产生的氯气通过尾气吸收除去，对臭氧曝气处理后得到的硫酸盐溶液，投加氢氧化钾中和溶液，调节pH至5，之后进行固液分离处理，得到的硫酸钾溶液蒸发结晶处理后获得硫酸钾产品，得到的氢氧化钴沉淀使用硫酸溶解后得到可重复使用的硫酸钴催化剂。
实施例10
本实施例提供了一种含氯及有机物废水的处理工艺，所述处理工艺的流程如图1所示，所述处理工艺包括以下步骤：将含氯浓度为3847ppm和COD含量为4381ppm的100mL废水加到容器中，用硫酸将废水的pH调节为0.4，投加8g过硫酸铵和0.7g硫酸铁协同氧化废水，并加热至85℃，在400rpm下搅拌130min，同时进行臭氧曝气处理，臭氧的通入量为0.3mL/min:1mL，将协同氧化处理以及臭氧曝气处理的过程中产生的氯气通过尾气吸收除去，对臭氧曝气处理后得到的硫酸盐溶液，投加氨水中和溶液，调节pH至5.5，之后进行固液分离处理，得到的硫酸铵溶液蒸发结晶处理后获得硫酸铵产品，得到的氢氧化铁沉淀使用硫酸溶解后得到可重复使用的硫酸铁催化剂。
实施例11
本实施例提供了一种含氯及有机物废水的处理工艺，所述处理工艺的流程如图1所示，所述处理工艺包括以下步骤：将含氯浓度为3847ppm和COD含量为4381ppm的100mL废水加到容器中，用硫酸将废水的pH调节为0.9，投加3g过硫酸钠、3g过硫酸钾和0.2g硫酸铜、0.2g硫酸钴协同氧化废水，并加热至90℃，在300rpm下搅拌90min，同时进行臭氧曝气处理，臭氧的通入量为 0.4mL/min:1mL，将协同氧化处理以及臭氧曝气处理的过程中产生的氯气通过尾气吸收除去，对臭氧曝气处理后得到的硫酸盐溶液，投加氢氧化钠和氢氧化钾中和溶液，调节pH至5.5，之后进行固液分离处理，得到的的硫酸钠和硫酸钾溶液蒸发结晶处理后获得硫酸钠和硫酸钾产品，得到的氢氧化铜和氢氧化钴沉淀使用硫酸溶解后得到可重复使用的硫酸铜和硫酸钴催化剂。
实施例12
本实施例提供了一种含氯及有机物废水的处理工艺，所述处理工艺的流程如图1所示，所述处理工艺包括以下步骤：将含氯浓度为3847ppm和COD含量为4381ppm的100mL废水加到容器中，用硫酸将废水的pH调节为0.9，投加3g过硫酸钾、3g过硫酸铵和0.2g硫酸钴、0.2g硫酸铁协同氧化废水，并加热至95℃，在500rpm下搅拌60min，同时进行臭氧曝气处理，臭氧的通入量为0.4mL/min:1mL，将协同氧化处理以及臭氧曝气处理的过程中产生的氯气通过尾气吸收除去，对臭氧曝气处理后得到的硫酸盐溶液，投加氢氧化钾和氨水中和溶液，调节pH至5.5，之后进行固液分离处理，得到的硫酸钾和硫酸铵溶液蒸发结晶处理后获得硫酸钾和硫酸铵产品，得到的氢氧化钴和氢氧化铁沉淀使用硫酸溶解后得到可重复使用的硫酸钴和硫酸铁催化剂。
对比例1
本对比例提供了一种含氯及有机物废水的处理工艺，所述处理工艺的流程如图1所示，所述处理工艺包括以下步骤：将含氯浓度为3847ppm和COD含量为4381ppm的100mL废水加到容器中，用硫酸将废水的pH调节为0.5，投加5g过硫酸钠和0.5g硫酸铜协同氧化废水，并加热至90℃，在300rpm下搅拌90min，同时进行空气曝气处理，空气的通入量为0.2mL/min:1mL，将协同氧化处理以及空气曝气处理的过程中产生的氯气通过尾气吸收除去，对空气曝气处理后得到的硫酸盐溶液，投加氢氧化钠中和溶液，调节pH至5.5，之后进行固液分离处理，得到的硫酸钠溶液蒸发结晶处理后获得硫酸钠产品，固液分离处理后的氢氧化铜沉淀使用硫酸溶解后得到可重复使用的硫酸铜催化剂。
对比例2
本对比例提供了一种含氯及有机物废水的处理工艺，所述处理工艺的流程如图1所示，所述处理工艺包括以下步骤：将含氯浓度为3847ppm和COD含量为4381ppm的100mL废水加到容器中，用硫酸将废水的pH调节为0.5，投加 5g过硫酸钠和0.5g硫酸铜协同氧化废水，并加热至90℃，在300rpm下搅拌90min，无曝气处理，其他工艺参数与实施例1相同。
对比例3
本对比例提供了一种含氯及有机物废水的处理工艺，所述处理工艺的流程如图1所示，所述处理工艺包括以下步骤：将含氯浓度为3847ppm和COD含量为4381ppm的100mL废水加到容器中，用硫酸将废水的pH调节为0.5，投加5g过硫酸钠和0.5g硫酸铜协同氧化废水，并加热至90℃，在300rpm下搅拌90min，氧化过程后进行空气曝气处理，空气的通入量为0.2mL/min:1mL，其他工艺参数与实施例1相同。
对比例4
本对比例提供了一种含氯及有机物废水的处理工艺，所述处理工艺的流程如图1所示，所述处理工艺包括以下步骤：将含氯浓度为3847ppm和COD含量为4381ppm的100mL废水加到容器中，用硫酸将废水的pH调节为0.5，并加热至90℃，在300rpm下搅拌90min，进行臭氧曝气处理，臭氧的通入量为0.2mL/min:1mL，臭氧曝气处理的过程中产生的氯气通过尾气吸收除去。
对比例5
本对比例提供了一种含氯及有机物废水的处理工艺，所述处理工艺的流程如图1所示，所述处理工艺包括以下步骤：将含氯浓度为3847ppm和COD含量为4381ppm的100mL废水加到容器中，用硫酸将废水的pH调节为2，投加7g过硫酸钠和0.5g硫酸铜协同氧化废水，并加热至90℃，在300rpm下搅拌90min，同时进行空气曝气处理，空气的通入量为0.2mL/min:1mL，其他工艺参数与实施例1相同。
对比例6
本对比例提供了一种含氯及有机物废水的处理工艺，所述处理工艺的流程如图1所示，所述处理工艺包括以下步骤：将含氯浓度为3847ppm和COD含量为4381ppm的100mL废水加到容器中，用硫酸将废水的pH调节为7，投加10g过硫酸钠和0.75g硫酸铜协同氧化废水，并加热至90℃，在300rpm下搅拌90min，同时进行空气曝气处理，空气的通入量为0.2mL/min:1mL，其他工艺参数与实施例1相同。
实施例与对比例中将测量三次溶液中的氯离子含量，分别在曝气后立即测 氯离子含量；曝气后静置过夜后测氯离子含量；静置过夜后加入亚硫酸钠作为还原剂，反应2h后测氯离子含量。
没有曝气处理的对比例也测量三次溶液中的氯离子含量，在氧化后立即测氯离子含量；静置过夜后测氯离子含量；静置过夜后加入亚硫酸钠作为还原剂，反应2h后测氯离子含量。
实验中氯离子含量通过滴定法测量；COD含量通过重铬酸钾法测量。
表1
Figure PCTCN2022092456-appb-000001
从表1可以看出以下几点：
(1)本申请提供的一种含氯及有机物废水的处理工艺，在pH<1、加热条件下，在协同氧化过程中同时进行臭氧曝气处理可同时去除废水中的有机物与 氯离子，曝气后氯离子残留低于12ppm，COD残留低于214ppm。
(2)结合实施例1与实施例4-6可知，当pH>1时不利于去除废水中的氯离子和有机物的去除且pH越高去除效率越低；结合实施例1与实施例7可知，在不加热条件下也不利于去除废水中的氯离子和有机物；由此表明，本申请在优选的pH范围和加热条件下，有助于废水中氯离子和有机物的去除。
(3)结合实施例1与对比例1可知，当用空气曝气替代臭氧曝气后，实验后测得的氯离子和COD残留量较高；由此表明，空气曝气效果不如臭氧曝气。
(4)结合实施例1与对比例2-3可知，无曝气处理或协同氧化处理后再进行曝气处理，虽然实验后立即测得的氯离子残留量较低，但对静置过夜后的溶液加入亚硫酸钠为还原剂，测得的氯离子残留量反升，说明除氯过程存在氯气反溶和过氧化现象；由此表明，在处理废水过程中，协同氧化过程中同时进行曝气处理是保证除氯过程中不出现氯气反溶和过氧化现象的重要步骤。
(5)结合实施例1与对比例4可知，在处理废水过程中不进行协同氧化处理，无法实现废水中氯离子和有机物的去除；由此表明，在处理废水过程中，协同氧化处理是保证废水中氯离子和有机物去除的重要步骤。
综上所述，本申请提供的一种含氯及有机物废水的处理工艺，可将废水中的有机物与氯离子同时除去；在协同氧化过程中同时进行臭氧曝气处理，避免了除氯过程中氯气反溶于水中和过氧化现象，解决了相关技术中氯离子反升的问题，从而进一步提高了氯离子的去除率，除氯后溶液中的氯离子含量可低至7ppm。
申请人声明，以上所述仅为本申请的具体实施方式，但本申请的保护范围并不局限于此，所属技术领域的技术人员应该明了，任何属于本技术领域的技术人员在本申请揭露的技术范围内，可轻易想到的变化或替换，均落在本申请的保护范围和公开范围之内。

Claims (12)

  1. 一种含氯及有机物废水的处理工艺，其包括以下步骤：对所述含氯及有机物废水进行协同氧化处理以及臭氧曝气处理。
  2. 根据权利要求1所述的处理工艺，其中，所述废水在协同氧化处理前需加入硫酸调节pH。
  3. 根据权利要求2所述的处理工艺，其中，所述pH调节至＜1。
  4. 根据权利要求1-3任一项所述的处理工艺，其中，所述协同氧化处理包括向所述废水中加入氧化剂和催化剂。
  5. 根据权利要求4所述的处理工艺，其中，所述氧化剂为过硫酸盐；
    优选地，所述过硫酸盐包括过硫酸钠、过硫酸钾或过硫酸铵中的任意一种或至少两种组合；
    优选地，所述氧化剂的加入量与所述废水的质量体积比为(0.25-1)：10g/mL。
  6. 根据权利要求4所述的处理工艺，其中，所述催化剂为过渡金属硫酸盐；
    优选地，所述过渡金属硫酸盐包括硫酸铁、硫酸亚铁、硫酸钴或硫酸铜中的任意一种或至少两种组合；
    优选地，所述催化剂的加入量与所述废水的质量体积比为(0.025-0.1)：10g/mL。
  7. 根据权利要求1-6任一项所述的处理工艺，其中，所述协同氧化处理在加热条件下进行；
    优选地，所述加热的温度为85-95℃；
    优选地，所述协同氧化处理在搅拌条件下进行；
    优选地，所述搅拌的速率为300-500rpm；
    优选地，所述搅拌的时间为30-150min。
  8. 根据权利要求1-7任一项所述的处理工艺，其中，所述臭氧曝气处理中臭氧的通入量与所述废水的体积比为(0.05-2)mL/min：1mL。
  9. 根据权利要求1-8任一项所述的处理工艺，其中，所述协同氧化处理以及所述臭氧曝气处理的过程中通过尾气吸收除去氯气。
  10. 根据权利要求1-9任一项所述的处理工艺，其中，所述臭氧曝气处理后对得到的硫酸盐溶液进行回收处理；
    优选地，所述回收处理包括：对所述硫酸盐溶液加碱中和，固液分离处理 后对液相进行蒸发结晶后得到产品；
    优选地，对所述硫酸盐溶液加碱中和至pH为5-6；
    优选地，所述碱包括氢氧化钠、氢氧化钾或氨水中的任意一种或至少两种组合。
  11. 根据权利要求10所述的处理工艺，其中，所述固液分离处理后对沉淀进行回收处理用于所述协同氧化处理。
  12. 根据权利要求1-11任一项所述的处理工艺，其包括如下步骤：
    使用硫酸将含氯及有机物废水调节至pH＜1，投加过硫酸盐和过渡金属硫酸盐对所述废水进行协同氧化处理，所述过硫酸盐的加入量与所述废水的质量体积比为(0.25-1)：10g/mL，所述催化剂的加入量与所述废水的质量体积比为(0.025-0.1)：10g/mL；加热至85-95℃下在300-500rpm下搅拌30-150min，同时进行臭氧曝气处理，所述臭氧曝气处理中臭氧的通入量与所述废水的体积比为(0.05-2)mL/min：1mL；将协同氧化处理以及臭氧曝气处理的过程中产生的氯气通过尾气吸收去除，对臭氧曝气处理后得到的硫酸盐溶液加碱中和，固液分离处理后对得到的液相进行蒸发结晶后得到产品，对沉淀进行回收处理用于所述协同氧化处理。
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