CN112225306B - Method for removing organic pollutants in water by activating sulfite with organic peroxyacid - Google Patents
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 40
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 150000004967 organic peroxy acids Chemical class 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000003213 activating effect Effects 0.000 title claims abstract description 9
- 230000015556 catabolic process Effects 0.000 claims abstract description 23
- 238000006731 degradation reaction Methods 0.000 claims abstract description 23
- -1 sulfate radicals Chemical class 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 8
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 38
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 34
- NTHXOOBQLCIOLC-UHFFFAOYSA-N iohexol Chemical compound OCC(O)CN(C(=O)C)C1=C(I)C(C(=O)NCC(O)CO)=C(I)C(C(=O)NCC(O)CO)=C1I NTHXOOBQLCIOLC-UHFFFAOYSA-N 0.000 claims description 30
- 229960001025 iohexol Drugs 0.000 claims description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 14
- 239000004098 Tetracycline Substances 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 9
- 229960002180 tetracycline Drugs 0.000 claims description 9
- 229930101283 tetracycline Natural products 0.000 claims description 9
- 235000019364 tetracycline Nutrition 0.000 claims description 9
- 150000003522 tetracyclines Chemical class 0.000 claims description 9
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 8
- 235000010265 sodium sulphite Nutrition 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 2
- 235000019252 potassium sulphite Nutrition 0.000 claims description 2
- 238000007171 acid catalysis Methods 0.000 claims 3
- 239000000203 mixture Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000012190 activator Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 150000003254 radicals Chemical class 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 9
- 238000001994 activation Methods 0.000 description 7
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- ZEYOIOAKZLALAP-UHFFFAOYSA-M sodium amidotrizoate Chemical compound [Na+].CC(=O)NC1=C(I)C(NC(C)=O)=C(I)C(C([O-])=O)=C1I ZEYOIOAKZLALAP-UHFFFAOYSA-M 0.000 description 4
- 229910001428 transition metal ion Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229940079826 hydrogen sulfite Drugs 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Removal Of Specific Substances (AREA)
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Abstract
本发明公开了一种有机过氧酸活化亚硫酸盐去除水中有机污染物的方法，通过有机过氧酸活化亚硫酸盐产生硫酸根自由基和羟基自由基降解水中有机污染物，包括如下步骤：(1)将含有有机污染物的待处理水体的pH调节至3～10；(2)将亚硫酸盐以及有机过氧酸加入含有有机污染物的待处理水体中，在室温条件下搅拌反应5～60min，即可实现有机污染物的有效降解。本发明采用有机过氧酸作为活化剂，具有高效、低成本和无有毒副产物等优点，无需提供额外的能源，操作简单可靠。本发明适用于多种有机污染物的降解，具有自由基产率高、有机污染物去除效率高的特点，在水中有机污染物降解领域具有较好的优势。
The invention discloses a method for activating sulfite by organic peroxy acid to remove organic pollutants in water. The organic peroxy acid activates sulfite to generate sulfate radicals and hydroxyl radicals to degrade organic pollutants in water. The method comprises the following steps: (1) adjusting the pH of the water body to be treated containing organic pollutants to 3-10; (2) adding sulfite and organic peroxyacid to the water body to be treated containing organic pollutants, and stirring reaction 5 at room temperature ~60min, the effective degradation of organic pollutants can be achieved. The invention adopts the organic peroxy acid as the activator, has the advantages of high efficiency, low cost, no toxic by-products and the like, does not need to provide additional energy, and is simple and reliable in operation. The invention is suitable for the degradation of various organic pollutants, has the characteristics of high free radical yield and high removal efficiency of organic pollutants, and has good advantages in the field of organic pollutant degradation in water.
Description
技术领域technical field
本发明属于水污染处理技术领域，具体涉及一种有机过氧酸活化亚硫酸盐去除水中有机污染物的方法。The invention belongs to the technical field of water pollution treatment, and in particular relates to a method for removing organic pollutants in water by activating sulfite with an organic peroxyacid.
背景技术Background technique
高级氧化技术主要是利用氧化剂分解成高活性自由基(羟基自由基和硫酸根自由基等)，快速降解水中的有机污染物，其中硫酸根自由基具有氧化还原电位高(2.5～3.1V)、反应活性受pH值影响小、半衰期长(30～40μs)、与有机污染物的反应速率高(106～109M-1s-1)、选择性高等独特的性质，反应受水质背景物质影响较小，使得硫酸根自由基受到许多研究者的关注。目前过硫酸盐和亚硫酸盐是生成硫酸根自由基的主要来源。应用基于硫酸根自由基的高级氧化技术的关键是寻找高效活化过硫酸盐和亚硫酸盐产生硫酸根自由基的方法。Advanced oxidation technology mainly uses oxidants to decompose into highly reactive free radicals (hydroxyl radicals and sulfate radicals, etc.) to rapidly degrade organic pollutants in water. Among them, sulfate radicals have high redox potential (2.5-3.1V), The reactivity is less affected by pH value, the half-life is long (30-40μs), the reaction rate with organic pollutants is high (10 6 ～ 10 9 M -1 s -1 ), and the selectivity is high. The effect is small, which makes sulfate radicals attract the attention of many researchers. Currently, persulfate and sulfite are the main sources of sulfate radicals. The key to applying advanced oxidation technology based on sulfate radicals is to find a method for efficiently activating persulfate and sulfite to generate sulfate radicals.
目前基于过硫酸盐的活化方法存在以下不足：一是过硫酸盐的成本较高；二是通过外加能源活化过硫酸盐会增加设备投资和运行成本；三是采用过渡金属离子活化过硫酸盐存在金属离子释放的问题，有一定的环境风险。相比较而言，亚硫酸盐廉价易得，但是亚硫酸盐自氧化速率较慢，通常可采用过渡金属离子活化、非均相活化剂的方法促进亚硫酸盐自氧化过程来高活性自由基降解水中的有机污染物。均相过渡金属离子活化剂具有技术难度低、活化效能高、耗能少的优点，但是其存在金属离子释放的问题，有一定的环境风险。采用非均相活化剂具有能够重复利用且无二次污染的有点，但是存在活化效能低、有机污染物去除效率较低的问题。且在这些活化过程中往往存在适应pH范围窄，需要外加能量、运行成本高等问题，限制了亚硫酸盐高级氧化工艺在实际工艺中的应用。因此有必要研发新型活化亚硫酸盐体系，将这种体系用于构建产生高活性自由基的高级氧化体系，对于有机污染物降解具有重要的价值。The current activation methods based on persulfate have the following shortcomings: first, the cost of persulfate is relatively high; second, activation of persulfate by external energy will increase equipment investment and operating costs; third, the use of transition metal ions to activate persulfate exists The problem of metal ion release has certain environmental risks. In comparison, sulfites are cheap and easy to obtain, but the rate of auto-oxidation of sulfites is slow. Usually, transition metal ion activation and heterogeneous activators can be used to promote the auto-oxidation process of sulfites to degrade highly active free radicals. Organic pollutants in water. Homogeneous transition metal ion activators have the advantages of low technical difficulty, high activation efficiency, and low energy consumption, but they have the problem of metal ion release and certain environmental risks. The use of heterogeneous activators has the advantage of being reusable and free of secondary pollution, but there are problems of low activation efficiency and low removal efficiency of organic pollutants. And in these activation processes, there are often problems such as narrow pH range, additional energy, and high operating costs, which limit the application of the advanced sulfite oxidation process in practical processes. Therefore, it is necessary to develop a new type of activated sulfite system, which is used to construct an advanced oxidation system that generates highly reactive free radicals, which is of great value for the degradation of organic pollutants.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于克服现有技术的不足之处，提供了一种有机过氧酸活化亚硫酸盐去除水中有机污染物的方法，解决了上述背景技术中亚硫酸盐活化的问题。The object of the present invention is to overcome the deficiencies of the prior art, and provides a method for activating sulfites with organic peroxyacids to remove organic pollutants in water, which solves the problem of sulfite activation in the above-mentioned background technology.
本发明解决其技术问题所采用的技术方案是：提供了一种有机过氧酸活化亚硫酸盐去除水中有机污染物的方法，通过有机过氧酸活化亚硫酸盐产生硫酸根自由基和羟基自由基降解水中有机污染物，包括如下步骤：The technical scheme adopted by the present invention to solve the technical problem is as follows: a method for removing organic pollutants in water by activating sulfite by organic peroxyacid is provided, and sulfate radicals and hydroxyl radicals are generated by activating sulfite by organic peroxyacid Degradation of organic pollutants in water, including the following steps:
(1)将含有有机污染物的待处理水体的pH调节至3～10；(1) Adjust the pH of the water body to be treated containing organic pollutants to 3-10;
(2)将亚硫酸盐以及有机过氧酸加入含有有机污染物的待处理水体中，在室温条件下搅拌反应5～60min，实现有机污染物的降解；(2) adding sulfite and organic peroxy acid to the water body to be treated containing organic pollutants, and stirring and reacting at room temperature for 5-60 minutes to realize the degradation of organic pollutants;
其中，待处理水体中的有机污染物、有机过氧酸和亚硫酸盐的摩尔浓度比为1∶10～100∶50～500。Wherein, the molar concentration ratio of organic pollutants, organic peroxyacids and sulfites in the water body to be treated is 1:10-100:50-500.
本技术方案与背景技术相比，它具有如下优点：Compared with the background technology, the technical solution has the following advantages:
1、本发明采用亚硫酸盐替代传统的过硫酸盐，通过有机过氧酸活化亚硫酸盐产生硫酸根自由基和羟基自由基降解水中有机污染物，有效克服了需要投加过渡金属离子的问题，具有高效、无有毒副产物等优点，无需提供额外的能源，操作简单可靠避免二次污染，且无需外加能源，从而降低成本；1. The present invention adopts sulfite to replace traditional persulfate, and generates sulfate radical and hydroxyl radical to degrade organic pollutants in water by activating sulfite by organic peroxyacid, effectively overcoming the problem of adding transition metal ions , has the advantages of high efficiency, no toxic by-products, no need to provide additional energy, simple and reliable operation to avoid secondary pollution, and no additional energy, thereby reducing costs;
2.本发明活化产生硫酸根自由基的强氧化活性自由基，能够实现水中亚硫酸盐和有机污染物的协同转化，也适用于无机亚硫酸盐和有机污染物共污染水体的修复；2. The present invention activates strong oxidative active radicals that generate sulfate radicals, can realize the synergistic transformation of sulfites and organic pollutants in water, and is also suitable for the restoration of water bodies co-contaminated by inorganic sulfites and organic pollutants;
3.本发明在常温常压下即可实现，适用pH范围广，处理效果好，操作简便。3. The invention can be realized at normal temperature and pressure, has a wide applicable pH range, good treatment effect and easy operation.
附图说明Description of drawings
图1为实施例1中各体系下碘海醇的降解曲线，其中，■为亚硫酸盐体系对碘海醇的去除效果曲线；●为过氧乙酸体系对碘海醇的去除效果曲线；
图2为实施例2中不同pH条件下碘海醇的降解效率图。Figure 2 is a graph of the degradation efficiency of iohexol under different pH conditions in Example 2.
图3为实施例3中不同pH条件下泛影酸钠的降解效率图。Figure 3 is a graph showing the degradation efficiency of sodium diatrizoate under different pH conditions in Example 3.
图4为实施例4中不同pH条件下四环素的降解效率图。FIG. 4 is a graph showing the degradation efficiency of tetracycline under different pH conditions in Example 4. FIG.
具体实施方式Detailed ways
本发明中，所述亚硫酸盐为亚硫酸钠和/或亚硫酸钾，所述室温条件指25℃。In the present invention, the sulfite is sodium sulfite and/or potassium sulfite, and the room temperature condition refers to 25°C.
所述有机过氧酸包括过氧甲酸、过氧乙酸、过氧丙酸中的至少一种，实施例中采用的有机过氧酸均采用对应酸与过氧化氢制备在硫酸催化下制备而成：The organic peroxyacids include at least one of peroxyformic acid, peroxyacetic acid, and peroxypropionic acid. The organic peroxyacids used in the examples are prepared from corresponding acids and hydrogen peroxide under the catalysis of sulfuric acid. :
1、过氧甲酸是采用甲酸与过氧化氢在硫酸催化下制备的，其中甲酸与过氧化氢的摩尔比为1～4∶1，充分搅拌，避光室温下静置24h。1. Peroxyformic acid is prepared by using formic acid and hydrogen peroxide under the catalysis of sulfuric acid, wherein the molar ratio of formic acid and hydrogen peroxide is 1 to 4:1, fully stirred, and allowed to stand for 24 hours at room temperature in the dark.
2、过氧乙酸是采用乙酸与过氧化氢在硫酸催化下制备的，其中乙酸与过氧化氢的摩尔比1～4∶1，浓硫酸质量分数为1.0％～6.0％，充分搅拌，避光室温下静置24h。2. Peracetic acid is prepared by using acetic acid and hydrogen peroxide under the catalysis of sulfuric acid, wherein the molar ratio of acetic acid and hydrogen peroxide is 1～4:1, and the mass fraction of concentrated sulfuric acid is 1.0%～6.0%. Stir well and keep away from light. Stand at room temperature for 24h.
3、过氧丙酸是采用丙酸与过氧化氢在硫酸催化下制备的，其中丙酸与过氧化氢的摩尔比为3.5～7∶1，浓硫酸质量分数为10％～40％，温度控制60℃，充分搅拌，避光室温下静置24h。3. Peroxypropionic acid is prepared by using propionic acid and hydrogen peroxide under the catalysis of sulfuric acid, wherein the molar ratio of propionic acid and hydrogen peroxide is 3.5 to 7:1, the mass fraction of concentrated sulfuric acid is 10% to 40%, and the temperature Control at 60°C, stir well, and let stand for 24h at room temperature in the dark.
实施例1Example 1
室温条件下，向有机污染物为碘海醇的待处理水体中投加过氧乙酸，随后采用氢氧化钠和硫酸将待处理水体pH值调节为4，采用搅拌器搅拌均匀并反应。其中待处理水体中碘海醇、过氧乙酸和亚硫酸钠的摩尔浓度比为1∶40∶400。反应过程中，在不同的反应时间点(0、1、3、5、10、15、20、30min)，取水样测定水体中碘海醇的剩余浓度，绘制不同反应时间条件下碘海醇的降解曲线。At room temperature, peracetic acid was added to the water to be treated with iohexol as the organic pollutant, and then the pH value of the water to be treated was adjusted to 4 by using sodium hydroxide and sulfuric acid, and the agitator was used to stir evenly and react. The molar concentration ratio of iohexol, peracetic acid and sodium sulfite in the water body to be treated is 1:40:400. During the reaction, at different reaction time points (0, 1, 3, 5, 10, 15, 20, 30min), water samples were taken to measure the remaining concentration of iohexol in the water body, and iohexol was drawn under different reaction time conditions. degradation curve.
分别采用亚硫酸盐体系对碘海醇的去除效果、过氧乙酸体系对碘海醇的去除效果、过氧化氢/亚硫酸盐体系对碘海醇的去除效果作为对比，与本实施例过氧乙酸活化亚硫酸盐体系对碘海醇的去除效果，绘制碘海醇的降解曲线如图1。The removal effect of sulfite system on iohexol, the removal effect of peroxyacetic acid system on iohexol, and the removal effect of hydrogen peroxide/sulfite system on iohexol were respectively used as comparisons. The removal effect of iohexol by acetic acid activated sulfite system, and the degradation curve of iohexol is drawn as shown in Figure 1.
由图1可知，在亚硫酸钠体系和过氧乙酸体系中，碘海醇几乎没有降解。由于过氧乙酸溶液中存在一定量的过氧化氢，需要排除过氧化氢的影响，过氧化氢活化亚硫酸盐体系不能有效降解碘海醇。相比较而言，过氧乙酸活化亚硫酸盐体系显著加速了碘海醇的降解。随着反应进行，待处理水体中碘海醇的浓度逐渐降低；反应5min后，碘海醇的剩余浓度基本没有检出，说明过氧乙酸活化亚硫酸盐体系对碘海醇具有较高的去除效能。It can be seen from Figure 1 that in the sodium sulfite system and the peracetic acid system, iohexol is almost not degraded. Due to the presence of a certain amount of hydrogen peroxide in the peracetic acid solution, the influence of hydrogen peroxide needs to be excluded, and the hydrogen peroxide-activated sulfite system cannot effectively degrade iohexol. In contrast, the peracetic acid-activated sulfite system significantly accelerated the degradation of iohexol. As the reaction proceeds, the concentration of iohexol in the water to be treated gradually decreases; after 5 minutes of reaction, the remaining concentration of iohexol is basically not detected, indicating that the peracetic acid-activated sulfite system has a higher removal of iohexol. efficacy.
实施例2Example 2
室温条件下，向有机污染物为碘海醇的待处理水体中投加过氧乙酸，随后采用氢氧化钠和硫酸将待处理水体pH值调节为3、4、5、6、7，采用搅拌器搅拌均匀并反应30min。其中待处理水体中碘海醇、过氧乙酸和亚硫酸钠的摩尔浓度比为1∶40∶400。反应结束后取水样测定水体中碘海醇的剩余浓度，绘制不同pH条件下碘海醇的降解效率图，实验结果如图2所示。Under room temperature conditions, add peracetic acid to the water body to be treated whose organic pollutant is iohexol, and then use sodium hydroxide and sulfuric acid to adjust the pH value of the water body to be treated to 3, 4, 5, 6, and 7, and use stirring. The device was stirred evenly and reacted for 30 min. The molar concentration ratio of iohexol, peracetic acid and sodium sulfite in the water body to be treated is 1:40:400. After the reaction, a water sample was taken to measure the remaining concentration of iohexol in the water body, and a graph of the degradation efficiency of iohexol under different pH conditions was drawn. The experimental results are shown in Figure 2.
由图2可知，纵坐标表示碘海醇的去除效率，pH值为3～7均能实现碘海醇的高效降解，其降解效率为80％以上，尤其在pH值为3～5时，反应30min后，待处理水体中碘海醇的剩余浓度基本没有检出，说明过氧乙酸活化亚硫酸盐体系在较宽的pH范围内对碘海醇具有较好的去除效能。It can be seen from Figure 2 that the ordinate represents the removal efficiency of iohexol, and the high-efficiency degradation of iohexol can be achieved at pH values of 3 to 7, and its degradation efficiency is over 80%, especially when the pH value is 3 to 5. After 30 minutes, the residual concentration of iohexol in the water to be treated was basically not detected, indicating that the peracetic acid-activated sulfite system had better removal efficiency for iohexol in a wide pH range.
实施例3Example 3
室温条件下，向有机污染物为泛影酸钠的待处理水体中投加过氧乙酸，随后采用氢氧化钠和硫酸将待处理水体pH值调节为3、4、5、6、7，采用搅拌器搅拌均匀并反应30min。其中待处理水体中泛影酸钠、过氧乙酸和亚硫酸钠的摩尔浓度比为1∶40∶400。反应结束后取水样测定水体中泛影酸钠的剩余浓度，绘制不同pH条件下泛影酸钠的降解效率图，实验结果如图3所示。At room temperature, peracetic acid was added to the water to be treated whose organic pollutant was sodium diatrizoate, and then sodium hydroxide and sulfuric acid were used to adjust the pH of the water to be treated to 3, 4, 5, 6, and 7. The stirrer stirred uniformly and reacted for 30min. The molar concentration ratio of sodium diatrizoate, peracetic acid and sodium sulfite in the water to be treated is 1:40:400. After the reaction, water samples were taken to measure the remaining concentration of sodium diadate in the water, and the degradation efficiency of sodium diadate under different pH conditions was drawn. The experimental results are shown in Figure 3.
由图3可知，纵坐标表示泛影酸钠的去除效率，pH值为3～7均能实现泛影酸钠的高效降解，其降解效率为85％以上。说明过氧乙酸活化亚硫酸盐体系在较宽的pH范围内对泛影酸钠具有较好的去除效能。It can be seen from Figure 3 that the ordinate represents the removal efficiency of sodium diadate, and the pH value of 3-7 can achieve efficient degradation of sodium diadate, and the degradation efficiency is above 85%. It shows that the peracetic acid activated sulfite system has better removal efficiency for sodium diatrizoate in a wide pH range.
实施例4Example 4
室温条件下，向有机污染物为四环素的待处理水体中投加过氧乙酸，随后采用氢氧化钠和硫酸将待处理水体pH值调节为3、4、5、6、7，采用搅拌器搅拌均匀并反应30min。其中待处理水体中四环素、过氧乙酸和亚硫酸钠的摩尔浓度比为1∶40∶400。反应结束后取水样测定水体中四环素的剩余浓度，绘制不同pH条件下四环素的降解效率图，实验结果如图4所示。Under the condition of room temperature, add peracetic acid to the water to be treated whose organic pollutant is tetracycline, and then use sodium hydroxide and sulfuric acid to adjust the pH of the water to be treated to 3, 4, 5, 6, and 7, and stir with a stirrer. Homogeneous and reacted for 30min. The molar concentration ratio of tetracycline, peracetic acid and sodium sulfite in the water to be treated is 1:40:400. After the reaction, water samples were taken to measure the remaining concentration of tetracycline in the water, and a graph of the degradation efficiency of tetracycline under different pH conditions was drawn. The experimental results are shown in Figure 4.
由图4可知，纵坐标表示四环素的去除效率，pH值为3～7均能实现四环素的高效降解，其降解效率为88％以上。说明过氧乙酸活化亚硫酸盐体系在较宽的pH范围内对四环素具有良好的去除效能。It can be seen from FIG. 4 that the ordinate represents the removal efficiency of tetracycline, and the high-efficiency degradation of tetracycline can be achieved at pH values of 3 to 7, and the degradation efficiency is above 88%. This indicated that the peracetic acid-activated sulfite system had good removal efficiency for tetracycline in a wide pH range.
以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，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，或者对其中部分或者全部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发明各实施例技术方案的范围。The above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that the foregoing embodiments can still be used for The recorded technical solutions are modified, or some or all of the technical features thereof are equivalently replaced; and these modifications or replacements do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
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