WO2021164489A1 - Method for removing organic arsenic in water by means of synchronous oxidation and in-situ adsorption - Google Patents

Method for removing organic arsenic in water by means of synchronous oxidation and in-situ adsorption Download PDF

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WO2021164489A1
WO2021164489A1 PCT/CN2021/073037 CN2021073037W WO2021164489A1 WO 2021164489 A1 WO2021164489 A1 WO 2021164489A1 CN 2021073037 W CN2021073037 W CN 2021073037W WO 2021164489 A1 WO2021164489 A1 WO 2021164489A1
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arsenic
water
removal
organic arsenic
organic
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PCT/CN2021/073037
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French (fr)
Chinese (zh)
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马军
王盼新
江进
程海军
何旭
纪润灵
丁健
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哈尔滨工业大学
哈尔滨工业大学水资源国家工程研究中心有限公司
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Publication of WO2021164489A1 publication Critical patent/WO2021164489A1/en

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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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • C02F2101/103—Arsenic 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
    • C02F2101/38—Organic compounds containing nitrogen

Definitions

  • the present invention relates to a treatment method for water containing organic arsenic, in particular to a method for removing organic arsenic represented by p-aminophenylarsonic acid, especially an application method for removing trace and trace amounts of organic arsenic from drinking water.
  • Organic arsenic such as p-aminophenylarsonic acid (arsanic acid), 3-nitro-4-hydroxyphenylarsonic acid (roxarsone), etc., are used as synthetic antibacterial agents and have been widely used as additives for pig, chicken and other livestock and poultry feeds. They have the effect of killing bacteria, protozoa and spirochetes, and can promote the growth of livestock and poultry and improve feed efficiency.
  • these organic arsenic will hardly be decomposed in animals, and most of them will be excreted through feces. Most of the aquaculture wastewater is simply treated or discharged directly without treatment, resulting in more than several thousand tons of organic arsenic discharged into the environment every year.
  • the detected concentration of organic arsenic is as high as 771 ⁇ g/kg, which is significantly higher than other regions.
  • arsanic acid and roxarsone have low toxicity as organic arsenic, they can be biodegraded in the environment or oxidized to trivalent, pentavalent and other highly toxic inorganic arsenic, resulting in arsenic enrichment in natural water bodies, which is harmful to the ecological environment. And human survival pose a great threat.
  • the oxidation + adsorption method Compared with the anaerobic treatment process, the oxidation + adsorption method has the advantages of short time and simple process. However, the optimal environmental conditions (such as pH, etc.) required by the oxidation process and the adsorption process are often inconsistent. Constantly adjusting the reaction conditions of the two stages will result in higher costs and lower feasibility of the process during practical applications.
  • optimal environmental conditions such as pH, etc.
  • the patent publication number is CN 109942070 A, and the patent name is "A method for removing arsenic from water using a sulfite and iron salt catalytic oxidation system".
  • the patent application discloses adding sulfite and iron salt to the arsenic-containing water to be treated. Adjust the pH value to 4-6, then stir the reaction, and then stand still at room temperature to obtain effluent.
  • the invention has a small dosage, high treatment efficiency and stable effect, and can remove more than 95% of organic arsenic and more than 98% of inorganic arsenic within 60 minutes.
  • iron ions in a slightly acidic aerobic solution, iron ions (Fe 3+ ) can catalyze the reaction of oxygen and sulfite (SO 3 2- ) to produce sulfur oxygen radicals, which can efficiently oxidize positive trivalent arsenic in water (As 3+ ) or arsenic-containing organic matter (ASA), can efficiently convert positive trivalent arsenic (As 3+ ) into positive pentavalent arsenic (As 5+ ) and remove it by the adsorption of iron ions in a short time.
  • SO 3 2- sulfur oxygen radicals
  • the patent publication number is CN 103342410 B, and the patent name is "A water treatment method for strengthening the removal of arsenic from zero-valent iron".
  • Sulfate produces strong oxidizing sulfate radical (SO 4 ⁇ – ), and its redox potential is 2.5–3.1V, which is higher than hydroxyl radical (OH ⁇ ) (1.9–2.0V) under neutral or alkaline conditions ), which is similar to OH ⁇ (2.4–2.7V) under acidic conditions.
  • SO 4 ⁇ – can efficiently and quickly oxidize As(III) in water to As(V).
  • the surface of zero-valent iron is oxidized to new ecological iron oxide by persulfate and SO 4 ⁇ – , which can adsorb As more efficiently (V).
  • the addition of ferrous ions and ferrous ions in the persulfate synergistic agent can promote the faster decomposition of persulfate and produce more SO 4 ⁇ – , so that the degradation rate of As(III) is faster.
  • the zero-valent iron used in this patent is more difficult to store, and the amount converted into the new ecological trivalent iron is small.
  • This patent uses zero-valent iron as a catalyst. According to the content of the patent, it is suitable for the removal of inorganic arsenic. For organic arsenic, the scheme of this patent cannot realize the partial oxidation of organic arsenic to pentavalent arsenic (As(V)). Completely removed. Similarly, the patent requires complete oxidation of organic arsenic to pentavalent arsenic (As(V)) before arsenic can be removed.
  • the purpose of the present invention is to solve the problem that organic arsenic pollutants in water, especially large-scale drinking water arsenic removal water plant source water cannot achieve simultaneous oxidation and in-situ adsorption removal, and provide a simple operation, high performance, and economical It is feasible and easy to be applied on a large scale in the project to utilize the simultaneous oxidation of divalent iron salt and persulfate and the method of in-situ adsorption and removal of organic arsenic in water.
  • the method of the present invention for simultaneous oxidation and in-situ adsorption and removal of organic arsenic in water is carried out according to the following steps:
  • the divalent iron salt and persulfate are added to the water containing arsenic to achieve simultaneous oxidative degradation and in-situ adsorption and removal of organic arsenic from the water.
  • the molar ratio of the divalent iron salt and the persulfate is 1:0.8-4.
  • the divalent iron salt includes one or more of ferrous sulfate, ferrous nitrate, and ferrous chloride.
  • organic arsenic includes p-aminophenylarsonic acid (arsanic acid) and/or 3-nitro-4-hydroxyphenylarsonic acid (roxarsone).
  • the concentration of the organic arsenic is 0.1 ⁇ M-100 ⁇ M.
  • the divalent iron salt includes one or more of ferrous sulfate, ferrous nitrate, and ferrous chloride.
  • the persulfate includes permonosulfate and/or peroxodisulfate.
  • the peroxymonosulfate salt includes one or two of potassium peroxymonosulfate and potassium peroxymonosulfate.
  • the peroxodisulfate salt includes one or more of potassium peroxodisulfate, sodium peroxodisulfate, and ammonium peroxodisulfate.
  • the pH value of the arsenic-containing water is controlled within the range of 3-8, preferably within the range of 5-7.
  • the temperature of the arsenic-containing water is 5°C-40°C.
  • the preferred temperature is 20°C to 30°C.
  • divalent iron salt and persulfate salt are added to the water containing organic arsenic at the same time or successively at intervals of 30 seconds.
  • divalent iron salt and persulfate salt are directly added to the water containing organic arsenic.
  • the water containing arsenic is aquaculture wastewater, factory sewage or drinking water.
  • divalent iron ions Fe 2+
  • Fe 2+ divalent iron ions
  • Fe(IV) intermediate tetravalent iron
  • the arsenate group of organic arsenic is oxidized to make it fall from the benzene ring and eventually become inorganic pentavalent arsenic (As(V));
  • the ferrous ion is simultaneously oxidized to hydroxyl group-rich hydroxyl group Iron oxide (FeOOH)
  • the amorphous iron oxyhydroxide produced in situ can quickly and efficiently adsorb pentavalent arsenic (As(V)) and incompletely oxidized organic arsenic on its surface through electrostatic attraction and hydroxyl bonding. Separate and remove arsenic from the water phase to purify water quality.
  • the present invention adopts the simultaneous oxidation of divalent iron salt and persulfate and in-situ adsorption to remove organic arsenic in water, without additional light, without heating, without adding auxiliary reagents, and the system itself can produce high oxidation active intermediate iron and/ Or free radicals, which strip the arsenic group in the organic arsenic from the organic group and become the inorganic arsenic which is more easily adsorbed.
  • the present invention adopts the simultaneous oxidation of divalent iron salt and persulfate and in-situ adsorption to remove organic arsenic from water. No additional adsorbent is needed, and the system itself will produce iron oxyhydroxide adsorbent in situ, and the hydroxyl oxyhydroxide produced in situ will be oxidized. Iron is rich in hydroxyl groups, has a small particle size, and has a large specific surface area. It can efficiently adsorb and remove inorganic arsenic and has a strong ability to adsorb organic arsenic.
  • the method of the present invention realizes the simultaneous progress of the organic arsenic degradation process and removal. While the persulfate oxidizes the organic arsenic, the in-situ production of iron oxyhydroxide can adsorb the oxidized arsenic (the adsorption includes two parts: non-oxidized The remaining organic arsenic and the inorganic arsenic products produced after oxidation), see Figures 2 and 3. This is a unique feature of the present invention and is also unattainable by existing methods.
  • the raw materials (ferric salt and persulfate) used in the present invention are low in price, stable in physical and chemical properties, and easy to transport and store.
  • the raw materials do not need pretreatment and can be directly added to the water body without additional equipment, saving space, without changing the original treatment process of the water plant, easy to operate, and capable of large-scale application.
  • ferrous sulfate 500g, 12 yuan; Sinopharm
  • zero-valent iron reduced iron powder, 500g, 71 yuan; Sinopharm
  • Ferrous sulfate is stable in nature and can be stored stably.
  • the present invention can be applied to the pretreatment, coagulation and other links of the conventional treatment process, and can also be used in the membrane filtration front-end link of the membrane-containing process water plant, and has a wide range of applications.
  • the invention has high removal efficiency of organic arsenic, and the total arsenic removal rate can reach more than 99.1%; the time is short, and the stable and efficient removal effect can be achieved within 30 minutes.
  • the present invention is also applicable to the removal of inorganic arsenic (As(III), As(V)) in water, and the removal of arsenic in the case of the coexistence of inorganic arsenic and organic arsenic.
  • Figure 1A is the degradation kinetics diagram of organic arsenic in Example 1-4 of the present invention
  • the ordinate C t /C 0 represents the residual organic arsenic concentration (C t ) and the initial organic arsenic concentration (C 0 ) at different treatment times Ratio, the smaller the ratio, the higher the degradation rate of total organic arsenic; among them, Is the degradation curve of Example 1, Is the degradation curve of Example 2, Is the degradation curve of Example 3, Is the degradation curve of Example 4;
  • FIG. 1B is the corresponding total arsenic removal rate of organic arsenic in Example 1-4 of the present invention.
  • Example 2 is an LC-ICP-MS diagram of the oxidative degradation of p-aminophenylarsonic acid and the formation of inorganic arsenic with the reaction time in Example 3 of the present invention
  • Figure 3 is the LC-ICP-MS diagram of the simultaneous oxidation of p-aminophenylarsonic acid and the in-situ produced iron oxyhydroxide for the simultaneous adsorption of organic arsenic and inorganic arsenic by divalent iron salt and persulfate in Example 3 of the present invention;
  • the dotted line is the image before filtering, and the solid line is the image after filtering;
  • Figure 4 is a comparison diagram of the removal rate of organic arsenic (para-aminophenylarsonic acid) under the same Fe dosage of the present invention and traditional Fe 3+ (FeCl 3 ); where A is the removal of PDS+Fe 2+ in the present invention Curve, B is the traditional Fe 3+ (FeCl 3 ) removal curve;
  • Figure 5 is an SEM image of iron oxyhydroxide produced in situ in Example 4 of the present invention.
  • Specific implementation mode 1 The method for simultaneous oxidation and in-situ adsorption and removal of organic arsenic in water of this embodiment is carried out according to the following steps:
  • the divalent iron salt and persulfate are added to the water containing arsenic to achieve simultaneous oxidative degradation and in-situ adsorption and removal of organic arsenic from the water.
  • the molar ratio of the divalent iron salt and the persulfate is 1:0.8-4.
  • the total arsenic concentration can be detected by inductively coupled plasma atomic emission spectrometer (ICP-OES) or inductively coupled plasma mass spectrometer (ICP-MS), and the separation and determination of organic arsenic and inorganic arsenic can be determined by high performance liquid chromatography. Combined with inductively coupled plasma mass spectrometer (LC-ICP-MS) detection.
  • ICP-OES inductively coupled plasma atomic emission spectrometer
  • ICP-MS inductively coupled plasma mass spectrometer
  • LC-ICP-MS inductively coupled plasma mass spectrometer
  • ferric salt Fe 2+
  • ferrous salt and persulfate are directly added to the organic arsenic-containing water for agitation treatment.
  • the dosage of ferrous and persulfate depends on the concentration of organic arsenic in the water.
  • the removal efficiency of wastewater containing organic arsenic is very high in the range of 3-8, and the optimal pH range is 6-7.
  • this embodiment is different from specific embodiment one in that the water containing arsenic is organic arsenic and/or inorganic arsenic. Others are the same as the first embodiment.
  • the method of this embodiment is mainly aimed at organic arsenic, but the method is also applicable to inorganic arsenic or a mixture of the two, and can still achieve the technical effect of the present invention.
  • the method for simultaneous oxidation and in-situ adsorption and removal of organic arsenic in water of this embodiment includes the following steps: adding 100 ⁇ mol of ferrous sulfate and 75 ⁇ mol of potassium peroxodisulfate to 1L of water containing para-aminophenylarsonic acid, The concentration of aminophenylarsine acid is 5 ⁇ mol/L, pH is 3, temperature is 25°C, after stirring for 30min, adjust the pH to 6, and filter through 0.22 ⁇ m cellulose acetate membrane to complete the removal of arsenic in water.
  • the organic arsenic removal can be completed within 30 minutes.
  • the method for simultaneous oxidation and in-situ adsorption and removal of organic arsenic in water of this embodiment includes the following steps: adding 100 ⁇ mol of ferrous sulfate and 150 ⁇ mol of potassium peroxymonosulfate to a volume of 1L of water containing p-aminophenylarsonic acid, The concentration of aminophenylarsine acid is 5 ⁇ mol/L, pH is 3, temperature is 25°C, after stirring for 30min, adjust the pH to 6, and filter through 0.22 ⁇ m cellulose acetate membrane to complete the removal of arsenic in water.
  • the method for simultaneous oxidation and in-situ adsorption and removal of organic arsenic in water of this embodiment includes the following steps: adding 100 ⁇ mol of ferrous sulfate and 150 ⁇ mol of sodium peroxodisulfate to 1L of water containing p-aminophenylarsonic acid, The concentration of aminophenylarsine is 5 ⁇ mol/L, pH is 6, and temperature is 25°C. After stirring for 30min, it is filtered through 0.22 ⁇ m cellulose acetate membrane to complete the removal of arsenic in water.
  • the removal rate of total arsenic is much higher than that of CN 109942070A patent, and the remaining total arsenic content is less than CN 109942070A patent. It can be seen that the organic arsenic degradation process and the removal of the organic arsenic in this embodiment are simultaneously performed. While persulfate oxidizes the organic arsenic, the in-situ generation of iron oxyhydroxide can adsorb the oxidized arsenic (the adsorption includes two parts: unoxidized The remaining organic arsenic and the inorganic arsenic products produced after oxidation). It is precisely because of the above-mentioned effects of this application that the effects of this embodiment can be achieved.
  • the excess acid salt used in this example is 100 ⁇ mol
  • the sulfite used in the CN 109942070 A patent is 1000 ⁇ mol. Because these two substances eventually become sulfates, the sulfate produced in this embodiment is 1/of the CN 109942070 A patent. 10. Drinking water also has regulations on sulfate, which cannot exceed 300mg/L.
  • the persulfate of this embodiment has stronger oxidation performance and can degrade organic arsenic more without adjusting the pH. So as to achieve a higher total arsenic removal rate.
  • the new ecological trivalent iron salt of this embodiment has stronger arsenic adsorption performance than directly added Fe 3+ iron salt (see Figure 4).
  • the method for simultaneous oxidation and in-situ adsorption and removal of organic arsenic in water of this embodiment includes the following steps: adding 100 ⁇ mol of ferrous chloride and 150 ⁇ mol of sodium peroxodisulfate to 1L of water containing para-aminophenylarsonic acid, The concentration of p-aminophenylarsine is 5 ⁇ mol/L, the pH is 6, the temperature is 25°C, after stirring for 30min, centrifugal precipitation is performed to complete the removal of arsenic from the water.
  • the degradation kinetic diagram of organic arsenic in Examples 1-4 the ordinate C t /C 0 represents the ratio of the concentration of residual organic arsenic (C t ) to the initial concentration of organic arsenic (C 0 ) at different treatment times, the smaller the ratio is , The higher the total organic arsenic degradation rate;
  • Figure 1B is the corresponding total arsenic removal rate of organic arsenic in Examples 1-4. It can be seen from Figure 1 that the methods of Examples 1 to 4 can quickly reach a high removal rate. The oxidation basically balances (ends) within 10 minutes, and the adsorption is a fast process, so it can reach a high level in a short time. The removal rate. The above effects can be achieved mainly due to: 1.
  • the production rate of new ecological iron is fast.
  • Ferrous sulfate or ferrous chloride can complete the conversion of new ecological iron within 10 minutes.
  • the new ecological iron is positively charged, it has a nanometer size and a large specific surface area.
  • Arsenic is negatively charged in the water and is easily adsorbed by the new ecological iron under the action of electrostatic gravity, and the adsorption of arsenic promotes the agglomeration of the new ecological iron, so that the new ecological iron cannot be filtered or not precipitated from the initial formation.
  • the small nano-particles of the required size quickly agglomerate and grow into large particles, reaching a size that can be filtered or precipitated, and finally complete the removal of arsenic.
  • the new ecological iron has a faster agglomeration rate, a stronger adsorption capacity, and a shorter time to reach the adsorption equilibrium, completing the advantage of removing the total arsenic.
  • the method for simultaneous oxidation and in-situ adsorption and removal of organic arsenic in water of this embodiment includes the following steps: adding 100 ⁇ mol of ferrous sulfate and 150 ⁇ mol of sodium peroxodisulfate to 1L of water containing p-aminophenylarsonic acid, The concentration of aminophenylarsine is 5 ⁇ mol/L, pH is 7, temperature is 25°C, after stirring for 30min, it is filtered through 0.22 ⁇ m cellulose acetate membrane to complete the removal of arsenic in water.
  • the method for simultaneous oxidation and in-situ adsorption and removal of organic arsenic in natural water of this embodiment includes the following steps: adding 140 ⁇ mol of ferrous sulfate and 210 ⁇ mol of sodium peroxodisulfate to a volume of 1L of surface water containing p-aminophenylarsonic acid
  • concentration of p-aminophenylarsonic acid is 5 ⁇ mol/L
  • pH pH is 7.96
  • temperature is 25°C
  • after stirring for 30min it is filtered through 0.22 ⁇ m cellulose acetate membrane to complete the removal of arsenic in water.
  • the method for simultaneous oxidation and in-situ adsorption and removal of inorganic arsenic in natural water of this embodiment includes the following steps: adding 100 ⁇ mol of ferrous sulfate and 150 ⁇ mol of sodium peroxodisulfate to a volume of 1L containing trivalent arsenic (As(III) ) In the water, the concentration of trivalent arsenic is 5 ⁇ mol/L, the pH is 6, and the temperature is 25°C. After stirring for 30min, it is filtered through a 0.22 ⁇ m cellulose acetate membrane to complete the removal of arsenic in the water.
  • the method for simultaneous oxidation and in-situ adsorption and removal of inorganic arsenic in natural water of this embodiment includes the following steps: adding 100 ⁇ mol of ferrous sulfate and 150 ⁇ mol of sodium peroxodisulfate to a volume of 1L containing pentavalent arsenic (As(V) ) In the water, the concentration of pentavalent arsenic is 5 ⁇ mol/L, the pH is 6, and the temperature is 25°C. After stirring for 30min, it is filtered through a 0.22 ⁇ m cellulose acetate membrane to complete the removal of arsenic in the water. After testing, the total arsenic removal rate is about 99.9%, and the remaining total arsenic content is 0.37 ⁇ g/L, which is lower than the limit of arsenic concentration in water (10 ⁇ g/ L).
  • the method for simultaneous oxidation and in-situ adsorption to remove organic arsenic and inorganic arsenic in natural water of this embodiment includes the following steps: adding 100 ⁇ mol of ferrous sulfate and 150 ⁇ mol of sodium peroxodisulfate to a volume of 1L containing p-aminophenylarsonic acid And trivalent arsenic (As(III)) water, the concentration of p-aminophenylarsonic acid and trivalent arsenic are 5 ⁇ mol/L and 2 ⁇ mol/L, respectively, pH is 6, temperature is 25°C, after stirring for 30min, after 0.22 ⁇ m acetic acid Fiber membrane filtration completes the removal of arsenic in water.
  • the method for simultaneous oxidation and in-situ adsorption to remove organic arsenic and inorganic arsenic in natural water of this embodiment includes the following steps: adding 100 ⁇ mol of ferrous sulfate and 150 ⁇ mol of sodium peroxodisulfate to a volume of 1L containing p-aminophenylarsonic acid And pentavalent arsenic (As(V)) water, the concentrations of p-aminophenylarsonic acid and pentavalent arsenic are 5 ⁇ mol/L and 2 ⁇ mol/L, respectively, the pH is 6, the temperature is 25°C, after stirring for 30min, after 0.22 ⁇ m acetic acid Fiber membrane filtration completes the removal of arsenic in water.

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Abstract

A method for removing organic arsenic in water by means of synchronous oxidation and in-situ adsorption. The present invention relates to a treatment method for water containing organic arsenic. In the present invention, the problem that organic arsenic pollutants in water, particularly, organic arsenic in water source water of large-scale drinking water arsenic removal water plants could not be removed by means of synchronous oxidation and in-situ adsorption is solved. The method comprises: adding a ferrous salt and persulfate into water containing organic arsenic to achieve synchronous oxidative degradation and in-situ adsorption for removing organic arsenic in water, the molar ratio of ferrous salt to persulfate being 1 : 0.8 - 4. The method of the present invention is simple in process operation, applicable for a wide water quality condition, capable of efficiently removing representative organic arsenic, p-arsanilic acid contained in water, and particularly suitable for removing organic arsenic in water source water of large-scale drinking water arsenic removal water plants. The present invention is applied to the field of arsenic removal.

Description

一种同步氧化及原位吸附去除水中有机砷的方法Method for simultaneous oxidation and in-situ adsorption and removal of organic arsenic in water 技术领域Technical field
本发明涉及含有有机砷水的处理方法，特别涉及以对氨基苯胂酸为代表的有机砷的去除方法，尤其是在饮用水中去除微量及痕量有机砷的应用方法。The present invention relates to a treatment method for water containing organic arsenic, in particular to a method for removing organic arsenic represented by p-aminophenylarsonic acid, especially an application method for removing trace and trace amounts of organic arsenic from drinking water.
背景技术Background technique
对氨基苯胂酸(阿散酸)，3-硝基-4-羟基苯胂酸(洛克沙胂)等有机砷作为合成抗菌剂,已经被广泛用作猪、鸡等畜禽饲料的添加剂，它们具有杀灭细菌，原虫及螺旋体的作用，并且能够促进畜禽生长，提高饲料效率。但是这些有机砷在动物体内几乎不会被分解，大部分会通过粪便排出。养殖废水大部分经过简单处理或未处理直接排放，导致每年有超过几千吨的有机砷排放到环境中。在中国南部的珠江三角洲的养猪场周围的土壤中，有机砷的检出浓度高达771μg/kg,明显高于其他地区。尽管阿散酸，洛克沙胂作为有机砷，毒性较低，但是在环境中能够被生物降解或者环境氧化成三价、五价等高毒性的无机砷，导致自然水体富砷化，对生态环境和人体生存产生极大的威胁。Organic arsenic such as p-aminophenylarsonic acid (arsanic acid), 3-nitro-4-hydroxyphenylarsonic acid (roxarsone), etc., are used as synthetic antibacterial agents and have been widely used as additives for pig, chicken and other livestock and poultry feeds. They have the effect of killing bacteria, protozoa and spirochetes, and can promote the growth of livestock and poultry and improve feed efficiency. However, these organic arsenic will hardly be decomposed in animals, and most of them will be excreted through feces. Most of the aquaculture wastewater is simply treated or discharged directly without treatment, resulting in more than several thousand tons of organic arsenic discharged into the environment every year. In the soil around pig farms in the Pearl River Delta in southern China, the detected concentration of organic arsenic is as high as 771μg/kg, which is significantly higher than other regions. Although arsanic acid and roxarsone have low toxicity as organic arsenic, they can be biodegraded in the environment or oxidized to trivalent, pentavalent and other highly toxic inorganic arsenic, resulting in arsenic enrichment in natural water bodies, which is harmful to the ecological environment. And human survival pose a great threat.
砷污染对人类健康的危害已广为人知,长期饮用含高砷的水源,会发生肺癌、皮肤癌、肾癌和肌肉萎缩等疾病。因此,我国规定废水中砷的排放标准为0.5mg/L,我国最新《生活饮用水卫生标准》(GB5749-2006)对砷的浓度限值做出了严格的规定，要求饮用水中砷的最大浓度必须低于10μg/L。因此已经有大量文献和专利对无机砷(As(III)和As(V))的去除进行了研究报道，主要包括吸附剂吸附法、中和沉淀法、絮凝沉淀法、铁氧体法、硫化物沉淀法等。但由于有机砷含有复杂的有机官能团，常见的无机砷的去除方法很难高效的去除有机砷。截止目前，已经公开报道的有机砷的去除方法并不是很多，可以概括为厌氧处理工艺和氧化+吸附工艺。相比于厌氧处理工艺，氧化+吸附方法，具有所用时间短，工艺简单等优势。但是氧化过程和吸附过程所要求的最适环境条件(如pH等)往往不一致，不断调节两个阶段的反应条件会导致该工艺在实际应用过程中成本变高，可行性降低。The harm of arsenic pollution to human health has been widely known. Long-term drinking of high arsenic water can cause diseases such as lung cancer, skin cancer, kidney cancer and muscle atrophy. Therefore, my country stipulates that the discharge standard of arsenic in wastewater is 0.5mg/L. my country’s latest "Drinking Water Hygiene Standard" (GB5749-2006) has made strict regulations on the concentration limit of arsenic, requiring the maximum arsenic in drinking water. The concentration must be less than 10μg/L. Therefore, there have been a large number of literatures and patents on the removal of inorganic arsenic (As(III) and As(V)), which mainly include adsorbent adsorption method, neutralization precipitation method, flocculation precipitation method, ferrite method, sulfide Substance precipitation method and so on. However, because organic arsenic contains complex organic functional groups, common inorganic arsenic removal methods are difficult to efficiently remove organic arsenic. Up to now, there are not many methods for removing organic arsenic that have been publicly reported, which can be summarized as an anaerobic treatment process and an oxidation + adsorption process. Compared with the anaerobic treatment process, the oxidation + adsorption method has the advantages of short time and simple process. However, the optimal environmental conditions (such as pH, etc.) required by the oxidation process and the adsorption process are often inconsistent. Constantly adjusting the reaction conditions of the two stages will result in higher costs and lower feasibility of the process during practical applications.
专利公开号为CN 109942070 A，专利名称为《一种利用亚硫酸盐与铁盐催化氧化体系去除水中砷的方法》专利申请，公开了向含砷待处理水中加入亚硫酸盐和铁盐，再将pH值调节至4～6，再搅拌反应，再在室温下静置，得到出水。本发明与单纯吸附法相比、本发明用药量少且处理效率高，效果稳定，可在60分钟内完成95％以上的有机砷去除，98％以上无机砷的去除。The patent publication number is CN 109942070 A, and the patent name is "A method for removing arsenic from water using a sulfite and iron salt catalytic oxidation system". The patent application discloses adding sulfite and iron salt to the arsenic-containing water to be treated. Adjust the pH value to 4-6, then stir the reaction, and then stand still at room temperature to obtain effluent. Compared with the simple adsorption method, the invention has a small dosage, high treatment efficiency and stable effect, and can remove more than 95% of organic arsenic and more than 98% of inorganic arsenic within 60 minutes.
该专利在偏酸性的有氧溶液中，铁离子(Fe 3+)可催化氧气与亚硫酸根(SO 3 2-)反应产生 硫氧自由基，该自由基可高效氧化水中正三价态的砷(As 3+)或含砷有机物(ASA)，可高效将正三价态的砷(As 3+)转化为正五价砷(As 5+)并在短时间内通过铁离子的吸附作用除去。 In this patent, in a slightly acidic aerobic solution, iron ions (Fe 3+ ) can catalyze the reaction of oxygen and sulfite (SO 3 2- ) to produce sulfur oxygen radicals, which can efficiently oxidize positive trivalent arsenic in water (As 3+ ) or arsenic-containing organic matter (ASA), can efficiently convert positive trivalent arsenic (As 3+ ) into positive pentavalent arsenic (As 5+ ) and remove it by the adsorption of iron ions in a short time.
但是该方法所使用的亚硫酸盐用量较大，且需要加入氧气的参与，还需要调节pH才能完成反应。最主要的是该专利不能实现有机砷部分氧化成五价砷(As(V))，部分未氧化的情况下，将有机砷完全去除。该专利需要将有机砷完全氧化成五价砷(As(V))后，才能去除有机砷。However, the amount of sulfite used in this method is relatively large, and oxygen needs to be added, and pH needs to be adjusted to complete the reaction. The most important thing is that the patent cannot realize the partial oxidation of organic arsenic to pentavalent arsenic (As(V)), and the organic arsenic is completely removed when part of it is not oxidized. This patent requires the complete oxidation of organic arsenic to pentavalent arsenic (As(V)) before the organic arsenic can be removed.
专利公开号为CN 103342410 B，专利名称为《一种强化零价铁除砷的水处理方法》，公开了通过加入过硫酸盐和其协同药剂强化零价铁除砷，零价铁可以催化过硫酸盐产生强氧化性的硫酸根自由基(SO 4·–)，其氧化还原电位为2.5–3.1V，在中性或碱性条件下高于羟基自由基(OH·)(1.9–2.0V)，在酸性条件下与OH·(2.4–2.7V)相近。SO 4·–可以高效快速地将水中的As(III)氧化成As(V)，同时，零价铁表面被过硫酸盐和SO 4·–氧化为新生态氧化铁，可以更高效的吸附As(V)。过硫酸盐协同药剂中的铁离子和亚铁离子的加入可以促进过硫酸盐更快的分解，产生更多的SO 4·–，从而使As(III)的降解速度更快。 The patent publication number is CN 103342410 B, and the patent name is "A water treatment method for strengthening the removal of arsenic from zero-valent iron". Sulfate produces strong oxidizing sulfate radical (SO 4·– ), and its redox potential is 2.5–3.1V, which is higher than hydroxyl radical (OH·) (1.9–2.0V) under neutral or alkaline conditions ), which is similar to OH·(2.4–2.7V) under acidic conditions. SO 4·– can efficiently and quickly oxidize As(III) in water to As(V). At the same time, the surface of zero-valent iron is oxidized to new ecological iron oxide by persulfate and SO 4·– , which can adsorb As more efficiently (V). The addition of ferrous ions and ferrous ions in the persulfate synergistic agent can promote the faster decomposition of persulfate and produce more SO 4·– , so that the degradation rate of As(III) is faster.
该专利所选用的零价铁较难存储，转变成新生态三价铁的量少。该专利是利用零价铁作为催化剂使用。从该专利内容可以，其适用于无机砷的去除，对于有机砷，该专利的方案并不能实现有机砷部分氧化成五价砷(As(V))，部分未氧化的情况下，将有机砷完全去除。同样，该专利需要将有机砷完全氧化成五价砷(As(V))后，才能去除砷。The zero-valent iron used in this patent is more difficult to store, and the amount converted into the new ecological trivalent iron is small. This patent uses zero-valent iron as a catalyst. According to the content of the patent, it is suitable for the removal of inorganic arsenic. For organic arsenic, the scheme of this patent cannot realize the partial oxidation of organic arsenic to pentavalent arsenic (As(V)). Completely removed. Similarly, the patent requires complete oxidation of organic arsenic to pentavalent arsenic (As(V)) before arsenic can be removed.
发明内容Summary of the invention
本发明的目的针对水中的有机砷污染物，尤其是大规模饮用水除砷水厂水源水中的有机砷无法实现同步氧化及原位吸附去除的问题，而提供一种操作简单，性能高效，经济可行，易于在工程中大规模应用的利用二价铁盐和过硫酸盐同步氧化及原位吸附去除水中有机砷的方法。The purpose of the present invention is to solve the problem that organic arsenic pollutants in water, especially large-scale drinking water arsenic removal water plant source water cannot achieve simultaneous oxidation and in-situ adsorption removal, and provide a simple operation, high performance, and economical It is feasible and easy to be applied on a large scale in the project to utilize the simultaneous oxidation of divalent iron salt and persulfate and the method of in-situ adsorption and removal of organic arsenic in water.
本发明的一种同步氧化及原位吸附去除水中有机砷的方法，它是按照以下步骤进行的：The method of the present invention for simultaneous oxidation and in-situ adsorption and removal of organic arsenic in water is carried out according to the following steps:
将二价铁盐和过硫酸盐加入到含砷的水中，以实现同步氧化降解及原位吸附去除水中有机砷，其中二价铁盐和过硫酸盐的摩尔比为：1:0.8～4。The divalent iron salt and persulfate are added to the water containing arsenic to achieve simultaneous oxidative degradation and in-situ adsorption and removal of organic arsenic from the water. The molar ratio of the divalent iron salt and the persulfate is 1:0.8-4.
进一步地，所述的二价铁盐包括硫酸亚铁，硝酸亚铁，氯化亚铁的一种或多种。Further, the divalent iron salt includes one or more of ferrous sulfate, ferrous nitrate, and ferrous chloride.
进一步地，所述有机砷包括对氨基苯胂酸(阿散酸)和/或3-硝基-4-羟基苯胂酸(洛克沙胂)。Further, the organic arsenic includes p-aminophenylarsonic acid (arsanic acid) and/or 3-nitro-4-hydroxyphenylarsonic acid (roxarsone).
进一步地，所述有机砷浓度为0.1μM～100μM。Further, the concentration of the organic arsenic is 0.1 μM-100 μM.
进一步地，所述二价铁盐包括硫酸亚铁，硝酸亚铁，氯化亚铁的一种或多种。Further, the divalent iron salt includes one or more of ferrous sulfate, ferrous nitrate, and ferrous chloride.
进一步地，所述过硫酸盐包括过一硫酸盐和/或过二硫酸盐。Further, the persulfate includes permonosulfate and/or peroxodisulfate.
进一步地，所述过一硫酸盐包括过一硫酸钾和过一硫酸氢钾中的一种或两种。Further, the peroxymonosulfate salt includes one or two of potassium peroxymonosulfate and potassium peroxymonosulfate.
进一步地，所述过二硫酸盐包括过二硫酸钾、过二硫酸钠和过二硫酸铵中的一种或多种。Further, the peroxodisulfate salt includes one or more of potassium peroxodisulfate, sodium peroxodisulfate, and ammonium peroxodisulfate.
进一步地，所述含砷水的pH值控制在3～8范围内，优选的，控制在5～7范围内。Further, the pH value of the arsenic-containing water is controlled within the range of 3-8, preferably within the range of 5-7.
进一步地，所述含砷水的温度为5℃～40℃。优选的温度为20℃～30℃。Further, the temperature of the arsenic-containing water is 5°C-40°C. The preferred temperature is 20°C to 30°C.
进一步地，所述二价铁盐和过硫酸盐同时或者间隔30s先后加入到含有机砷的水中。Further, the divalent iron salt and persulfate salt are added to the water containing organic arsenic at the same time or successively at intervals of 30 seconds.
进一步地，所述二价铁盐和过硫酸盐直接加入到含有有机砷的水中。Further, the divalent iron salt and persulfate salt are directly added to the water containing organic arsenic.
进一步地，所述的含砷的水为养殖废水、工厂污水或饮用水。Further, the water containing arsenic is aquaculture wastewater, factory sewage or drinking water.
本发明方案的原理：The principle of the scheme of the present invention:
本发明在酸性和近中性条件的溶液中，二价铁离子(Fe 2+)可催化过硫酸盐产生强氧化性硫酸根自由基和/或中间态四价铁(Fe(IV))，将有机砷的砷酸根基团氧化，使其从苯环上掉落下来并最终变成无机的五价砷(As(V))；二价铁离子同时被氧化成富含羟基基团的羟基氧化铁(FeOOH),原位产生的无定型羟基氧化铁可快速高效地将五价砷(As(V))和未被完全氧化的有机砷通过静电引力及羟基键合作用吸附在自身表面，将砷从水相分离去除，净化水质。 In the solution of the present invention under acidic and near-neutral conditions, divalent iron ions (Fe 2+ ) can catalyze persulfate to produce strong oxidizing sulfate radicals and/or intermediate tetravalent iron (Fe(IV)), The arsenate group of organic arsenic is oxidized to make it fall from the benzene ring and eventually become inorganic pentavalent arsenic (As(V)); the ferrous ion is simultaneously oxidized to hydroxyl group-rich hydroxyl group Iron oxide (FeOOH), the amorphous iron oxyhydroxide produced in situ can quickly and efficiently adsorb pentavalent arsenic (As(V)) and incompletely oxidized organic arsenic on its surface through electrostatic attraction and hydroxyl bonding. Separate and remove arsenic from the water phase to purify water quality.
本发明包含以下有益效果：The present invention contains the following beneficial effects:
一、本发明采用二价铁盐和过硫酸盐同步氧化及原位吸附去除水中有机砷，无需额外光照，无需加热，无需添加辅助试剂，体系自身就可以产生高氧化活性中间价态铁和/或自由基，将有机砷中的砷基团从有机基团上剥离出来，变成更容易被吸附的无机砷。1. The present invention adopts the simultaneous oxidation of divalent iron salt and persulfate and in-situ adsorption to remove organic arsenic in water, without additional light, without heating, without adding auxiliary reagents, and the system itself can produce high oxidation active intermediate iron and/ Or free radicals, which strip the arsenic group in the organic arsenic from the organic group and become the inorganic arsenic which is more easily adsorbed.
二、本发明采用二价铁盐和过硫酸盐同步氧化及原位吸附去除水中有机砷，无需额外投加吸附剂，体系自身就会原位产生羟基氧化铁吸附剂，原位产生的羟基氧化铁富含羟基，粒径较小，比表面积大，能高效吸附去除无机砷，同时具有很强的吸附有机砷的能力。2. The present invention adopts the simultaneous oxidation of divalent iron salt and persulfate and in-situ adsorption to remove organic arsenic from water. No additional adsorbent is needed, and the system itself will produce iron oxyhydroxide adsorbent in situ, and the hydroxyl oxyhydroxide produced in situ will be oxidized. Iron is rich in hydroxyl groups, has a small particle size, and has a large specific surface area. It can efficiently adsorb and remove inorganic arsenic and has a strong ability to adsorb organic arsenic.
本发明的方法的实现了有机砷降解过程及被去除的同步进行，在过硫酸盐氧化有机砷的同时，原位产生羟基氧化铁能够将氧化后的砷吸附(吸附包括两部分：未被氧化的剩余有机砷和被氧化后产生的无机砷产物)，见附图2和3。这是本发明独有的特点，也是现有方法无法达到的。The method of the present invention realizes the simultaneous progress of the organic arsenic degradation process and removal. While the persulfate oxidizes the organic arsenic, the in-situ production of iron oxyhydroxide can adsorb the oxidized arsenic (the adsorption includes two parts: non-oxidized The remaining organic arsenic and the inorganic arsenic products produced after oxidation), see Figures 2 and 3. This is a unique feature of the present invention and is also unattainable by existing methods.
三、本发明所采用的原料(二价铁盐和过硫酸盐)，价格低廉，物理化学性能稳定，易于运输和储存。原料无需预处理，可直接投加到水体，无需额外增加设备，节省空间，不改变水厂原有处理工艺，易于操作，能够进行大规模应用。3. The raw materials (ferric salt and persulfate) used in the present invention are low in price, stable in physical and chemical properties, and easy to transport and store. The raw materials do not need pretreatment and can be directly added to the water body without additional equipment, saving space, without changing the original treatment process of the water plant, easy to operate, and capable of large-scale application.
与CN 103342410 B的零价铁过硫酸盐对比：Compared with CN 103342410 B's zero-valent iron persulfate:
硫酸亚铁价格(500g,12元；国药)相比于零价铁(还原铁粉，500g,71元；国药)，价格更低，可以降低成本；还原铁粉容易被空气氧化变质，降低效率，所以在实际操作，应用，储存过程中都比较复杂。硫酸亚铁性质稳定，可以稳定存储。The price of ferrous sulfate (500g, 12 yuan; Sinopharm) is lower in price than zero-valent iron (reduced iron powder, 500g, 71 yuan; Sinopharm), which can reduce costs; reduced iron powder is easily oxidized and deteriorated by air, reducing efficiency , So the actual operation, application, and storage process are more complicated. Ferrous sulfate is stable in nature and can be stored stably.
四、本发明可应用于常规处理工艺的预处理，混凝等环节，也可用于含膜工艺水厂的膜滤前端环节，适用范围广。4. The present invention can be applied to the pretreatment, coagulation and other links of the conventional treatment process, and can also be used in the membrane filtration front-end link of the membrane-containing process water plant, and has a wide range of applications.
五、本发明可直接应用于近中性(pH＝5.5～7.5)的含有机砷水体而无需调节pH,与其他先降低pH氧化有机砷再升高pH吸附砷方法相比，节约成本60％左右，尤其适用于给水厂含砷水源水的处理。5. The present invention can be directly applied to near-neutral (pH=5.5～7.5) water containing organic arsenic without adjusting the pH. Compared with other methods of first reducing the pH to oxidize organic arsenic and then raising the pH to adsorb arsenic, it can save 60% of the cost. It is especially suitable for the treatment of arsenic-containing source water in water supply plants.
六、本发明去除有机砷效率高，总砷去除率可达99.1％以上；所用时间短，30分钟内即可达到稳定高效的去除效果。6. The invention has high removal efficiency of organic arsenic, and the total arsenic removal rate can reach more than 99.1%; the time is short, and the stable and efficient removal effect can be achieved within 30 minutes.
七、本发明同样适用于水中的无机砷(As(III),As(V))的去除,以及无机砷与有机砷共存的情况下砷的去除。7. The present invention is also applicable to the removal of inorganic arsenic (As(III), As(V)) in water, and the removal of arsenic in the case of the coexistence of inorganic arsenic and organic arsenic.
附图说明Description of the drawings
图1A为本发明实施例1-4中有机砷的降解动力学图；纵坐标C t/C 0表示在不同处理时间残留有机砷砷浓度(C t)与有机砷初始浓度(C 0)的比值，比值越小，总有机砷降解率越高；其中，
Figure PCTCN2021073037-appb-000001
为实施例1降解曲线，
Figure PCTCN2021073037-appb-000002
为实施例2降解曲线，
Figure PCTCN2021073037-appb-000003
为实施例3降解曲线，
Figure PCTCN2021073037-appb-000004
为实施例4降解曲线； Figure 1A is the degradation kinetics diagram of organic arsenic in Example 1-4 of the present invention; the ordinate C t /C 0 represents the residual organic arsenic concentration (C t ) and the initial organic arsenic concentration (C 0 ) at different treatment times Ratio, the smaller the ratio, the higher the degradation rate of total organic arsenic; among them,
Figure PCTCN2021073037-appb-000001
Is the degradation curve of Example 1,
Figure PCTCN2021073037-appb-000002
Is the degradation curve of Example 2,
Figure PCTCN2021073037-appb-000003
Is the degradation curve of Example 3,
Figure PCTCN2021073037-appb-000004
Is the degradation curve of Example 4;
图1B为本发明实施例1-4中有机砷相应的总砷去除率；FIG. 1B is the corresponding total arsenic removal rate of organic arsenic in Example 1-4 of the present invention;
图2为本发明实施例3中对氨基苯胂酸随反应时间被氧化降解及无机砷的生成的LC-ICP-MS图；2 is an LC-ICP-MS diagram of the oxidative degradation of p-aminophenylarsonic acid and the formation of inorganic arsenic with the reaction time in Example 3 of the present invention;
图3为本发明实施例3中二价铁盐和过硫酸盐同步氧化对氨基苯胂酸及原位产生的羟基氧化铁同步吸附有机砷和无机砷的LC-ICP-MS图；其中，图中虚线为过滤前图，实线为过滤后图；Figure 3 is the LC-ICP-MS diagram of the simultaneous oxidation of p-aminophenylarsonic acid and the in-situ produced iron oxyhydroxide for the simultaneous adsorption of organic arsenic and inorganic arsenic by divalent iron salt and persulfate in Example 3 of the present invention; The dotted line is the image before filtering, and the solid line is the image after filtering;
图4为本发明与传统Fe 3+(FeCl 3)在相同Fe投量情况下对有机砷(对氨基苯胂酸)的去除率对比图；其中，A为本发明PDS+Fe 2+的去除曲线，B为传统Fe 3+(FeCl 3)去除曲线； Figure 4 is a comparison diagram of the removal rate of organic arsenic (para-aminophenylarsonic acid) under the same Fe dosage of the present invention and traditional Fe 3+ (FeCl 3 ); where A is the removal of PDS+Fe 2+ in the present invention Curve, B is the traditional Fe 3+ (FeCl 3 ) removal curve;
图5为本发明实施例4中原位产生的羟基氧化铁的SEM图。Figure 5 is an SEM image of iron oxyhydroxide produced in situ in Example 4 of the present invention.
具体实施方式Detailed ways
具体实施方式一：本实施方式的一种同步氧化及原位吸附去除水中有机砷的方法，它是按照以下步骤进行的：Specific implementation mode 1: The method for simultaneous oxidation and in-situ adsorption and removal of organic arsenic in water of this embodiment is carried out according to the following steps:
将二价铁盐和过硫酸盐加入到含砷的水中，以实现同步氧化降解及原位吸附去除水中有机砷，其中二价铁盐和过硫酸盐的摩尔比为：1:0.8～4。The divalent iron salt and persulfate are added to the water containing arsenic to achieve simultaneous oxidative degradation and in-situ adsorption and removal of organic arsenic from the water. The molar ratio of the divalent iron salt and the persulfate is 1:0.8-4.
本实施方式中，总砷浓度可采用电感耦合等离子体原子发射光谱仪(ICP-OES)或者电感耦合等离子体质谱仪(ICP-MS)检测，有机砷和无机砷的分离测定可采用高效液相色谱与电感耦合等离子体质谱仪联用(LC-ICP-MS)检测。In this embodiment, the total arsenic concentration can be detected by inductively coupled plasma atomic emission spectrometer (ICP-OES) or inductively coupled plasma mass spectrometer (ICP-MS), and the separation and determination of organic arsenic and inorganic arsenic can be determined by high performance liquid chromatography. Combined with inductively coupled plasma mass spectrometer (LC-ICP-MS) detection.
本实施方式采用二价铁盐(Fe 2+)活化过硫酸盐处理含有机砷的水中的有机砷，将二价铁盐和过硫酸盐直接加入到含有机砷水中进行搅拌处理。二价铁盐和过硫酸盐的用量根据水中有机砷浓度而定。含有机砷废水的pH在3-8范围内去除效率均很高，最佳pH范围内为6～7。 In this embodiment, ferric salt (Fe 2+ ) is used to activate persulfate to treat organic arsenic in water containing organic arsenic, and the ferrous salt and persulfate are directly added to the organic arsenic-containing water for agitation treatment. The dosage of ferrous and persulfate depends on the concentration of organic arsenic in the water. The removal efficiency of wastewater containing organic arsenic is very high in the range of 3-8, and the optimal pH range is 6-7.
具体实施方式二：本实施方式与具体实施方式一不同的是：含砷的水为有机砷和/或无机砷。其它与具体实施方式一相同。Specific embodiment two: this embodiment is different from specific embodiment one in that the water containing arsenic is organic arsenic and/or inorganic arsenic. Others are the same as the first embodiment.
本实施方式的方法主要针对有机砷，但是该方法同样适用于无机砷或者二者的混合，仍然能够达到本发明所述的技术效果。The method of this embodiment is mainly aimed at organic arsenic, but the method is also applicable to inorganic arsenic or a mixture of the two, and can still achieve the technical effect of the present invention.
通过以下实施例验证本发明的有益效果：The beneficial effects of the present invention are verified through the following examples:
实施例1：Example 1:
本实施例的一种同步氧化及原位吸附去除水中有机砷的方法，包括以下步骤：将100μmol硫酸亚铁和75μmol过二硫酸钾加入到体积为1L的含对氨基苯胂酸的水中，对氨基苯胂酸的浓度为5μmol/L，pH为3，温度为25℃，搅拌30min后，调节pH到6，经0.22μm醋酸纤维膜过滤，完成水中砷的去除。经检测，90.3％的对氨基苯胂酸被氧化降解，总砷的去除率为99.4％，剩余总砷的含量为2.25μg/L，低于《生活饮用水卫生标准》(GB5749-2006)中规定的水中砷浓度的限值(10μg/L)。The method for simultaneous oxidation and in-situ adsorption and removal of organic arsenic in water of this embodiment includes the following steps: adding 100 μmol of ferrous sulfate and 75 μmol of potassium peroxodisulfate to 1L of water containing para-aminophenylarsonic acid, The concentration of aminophenylarsine acid is 5μmol/L, pH is 3, temperature is 25℃, after stirring for 30min, adjust the pH to 6, and filter through 0.22μm cellulose acetate membrane to complete the removal of arsenic in water. After testing, 90.3% of para-aminophenylarsonic acid was oxidized and degraded, the removal rate of total arsenic was 99.4%, and the content of remaining total arsenic was 2.25μg/L, which was lower than the "Sanitary Standard for Drinking Water" (GB5749-2006) The prescribed limit of arsenic concentration in water (10μg/L).
与CN 109942070 A专利相比，本实施例的pH＝3条件，CN 109942070 A专利最低pH＝4，可以说明本实施例适应的pH的范围更宽。本实施例可以在30min时间内完成有机砷去除。Compared with the CN 109942070 A patent, the pH=3 condition of this embodiment and the lowest pH of the CN 109942070 A patent=4 can indicate that the pH range of this embodiment is wider. In this embodiment, the organic arsenic removal can be completed within 30 minutes.
实施例2：Example 2:
本实施例的一种同步氧化及原位吸附去除水中有机砷的方法，包括以下步骤：将100μmol硫酸亚铁和150μmol过一硫酸钾加入到体积为1L的含对氨基苯胂酸的水中，对氨 基苯胂酸的浓度为5μmol/L，pH为3，温度为25℃，搅拌30min后，调节pH到6，经0.22μm醋酸纤维膜过滤，完成水中砷的去除。经检测，100％的对氨基苯胂酸被氧化降解，总砷的去除率为99.6％,剩余总砷的含量为1.50μg/L,低于《生活饮用水卫生标准》(GB5749-2006)中规定的水中砷浓度的限值(10μg/L)。The method for simultaneous oxidation and in-situ adsorption and removal of organic arsenic in water of this embodiment includes the following steps: adding 100 μmol of ferrous sulfate and 150 μmol of potassium peroxymonosulfate to a volume of 1L of water containing p-aminophenylarsonic acid, The concentration of aminophenylarsine acid is 5μmol/L, pH is 3, temperature is 25℃, after stirring for 30min, adjust the pH to 6, and filter through 0.22μm cellulose acetate membrane to complete the removal of arsenic in water. After testing, 100% of p-aminophenylarsine is oxidized and degraded, the removal rate of total arsenic is 99.6%, and the content of remaining total arsenic is 1.50μg/L, which is lower than the "Sanitary Standard for Drinking Water" (GB5749-2006) The prescribed limit of arsenic concentration in water (10μg/L).
实施例3：Example 3:
本实施例的一种同步氧化及原位吸附去除水中有机砷的方法，包括以下步骤：将100μmol硫酸亚铁和150μmol过二硫酸钠加入到体积为1L的含对氨基苯胂酸的水中，对氨基苯胂酸的浓度为5μmol/L，pH为6，温度为25℃，搅拌30min后，经0.22μm醋酸纤维膜过滤，完成水中砷的去除。经检测，49.4％的对氨基苯胂酸被氧化降解，总砷的去除率为99.1％，剩余总砷的含量为3.37μg/L，低于《生活饮用水卫生标准》(GB5749-2006)中规定的水中砷浓度的限值(10μg/L)。The method for simultaneous oxidation and in-situ adsorption and removal of organic arsenic in water of this embodiment includes the following steps: adding 100 μmol of ferrous sulfate and 150 μmol of sodium peroxodisulfate to 1L of water containing p-aminophenylarsonic acid, The concentration of aminophenylarsine is 5μmol/L, pH is 6, and temperature is 25℃. After stirring for 30min, it is filtered through 0.22μm cellulose acetate membrane to complete the removal of arsenic in water. After testing, 49.4% of p-aminophenylarsonic acid was oxidatively degraded, the removal rate of total arsenic was 99.1%, and the content of remaining total arsenic was 3.37μg/L, which was lower than the "Sanitary Standard for Drinking Water" (GB5749-2006) The prescribed limit of arsenic concentration in water (10μg/L).
采用与CN 109942070 A专利的方法对本实施例的含对氨基苯胂酸的水进行处理，具体操作如下：The method of CN 109942070 A patent is used to process the water containing p-aminophenylarsonic acid of this embodiment, and the specific operations are as follows:
100μmol三价铁，1000μmol亚硫酸钠，对氨基苯胂酸5μmol/L，pH为6，温度为25℃，搅拌30min后，经0.22μm醋酸纤维膜过滤，完成水中砷的去除。经检测，18.3％的对氨基苯胂酸被氧化降解，总砷的去除率为<90％，剩余总砷的含量为>10μg/L,高于《生活饮用水卫生标准》(GB5749-2006)中规定的水中砷浓度的限值(10μg/L)。100μmol of trivalent iron, 1000μmol of sodium sulfite, 5μmol/L of p-aminophenylarsine, pH of 6, temperature of 25℃, stirred for 30min, filtered through 0.22μm cellulose acetate membrane to complete the removal of arsenic in water. After testing, 18.3% of p-aminophenylarsonic acid was oxidatively degraded, the removal rate of total arsenic was <90%, and the content of remaining total arsenic was >10μg/L, which was higher than the "Sanitary Standard for Drinking Water" (GB5749-2006) The limit of arsenic concentration in water (10μg/L) specified in the.
经比较发现，本实施例被氧化降解的对氨基苯胂酸量原大于CN 109942070A专利。Through comparison, it is found that the amount of p-aminophenylarsonic acid that is oxidatively degraded in this embodiment is greater than that of the CN 109942070A patent.
且总砷的去除率也远大于CN 109942070A专利，剩余总砷含量小于CN 109942070A专利。由此可知说明本实施例有机砷降解过程及被去除的同步进行，在过硫酸盐氧化有机砷的同时，原位产生羟基氧化铁能够将氧化后的砷吸附(吸附包括两部分：未被氧化的剩余有机砷和被氧化后产生的无机砷产物)。正是由于本申请的上述作用，才能实现本实施例的效果。Moreover, the removal rate of total arsenic is much higher than that of CN 109942070A patent, and the remaining total arsenic content is less than CN 109942070A patent. It can be seen that the organic arsenic degradation process and the removal of the organic arsenic in this embodiment are simultaneously performed. While persulfate oxidizes the organic arsenic, the in-situ generation of iron oxyhydroxide can adsorb the oxidized arsenic (the adsorption includes two parts: unoxidized The remaining organic arsenic and the inorganic arsenic products produced after oxidation). It is precisely because of the above-mentioned effects of this application that the effects of this embodiment can be achieved.
而且，本实施例所用过量酸盐为100μmol，CN 109942070 A专利所用亚硫酸盐为1000μmol，因为这两种物质最终都变成硫酸盐，本实施例产生的硫酸盐是CN 109942070 A专利的1/10，而饮用水对硫酸盐也有规定，不能超过300mg/L。Moreover, the excess acid salt used in this example is 100 μmol, and the sulfite used in the CN 109942070 A patent is 1000 μmol. Because these two substances eventually become sulfates, the sulfate produced in this embodiment is 1/of the CN 109942070 A patent. 10. Drinking water also has regulations on sulfate, which cannot exceed 300mg/L.
本实施例的过硫酸盐氧化性能更强，能在不调节pH的条件下，更多的降解有机砷。从而达到更高的总砷去除率。The persulfate of this embodiment has stronger oxidation performance and can degrade organic arsenic more without adjusting the pH. So as to achieve a higher total arsenic removal rate.
本实施例的新生态三价铁盐比直接投加的Fe 3+铁盐，吸附砷的性能更强(见附图4)。 The new ecological trivalent iron salt of this embodiment has stronger arsenic adsorption performance than directly added Fe 3+ iron salt (see Figure 4).
本实施例直观的展现了有机砷降解过程及被去除的机理，(吸附包括两部分：未被氧 化的剩余有机砷和被氧化后产生的无机砷产物)，见附图2和3。This embodiment intuitively demonstrates the degradation process of organic arsenic and the mechanism of its removal (the adsorption includes two parts: the remaining organic arsenic that has not been oxidized and the inorganic arsenic product produced after being oxidized), see Figures 2 and 3.
实施例4：Example 4:
本实施例的一种同步氧化及原位吸附去除水中有机砷的方法，包括以下步骤：将100μmol氯化亚铁和150μmol过二硫酸钠加入到体积为1L的含对氨基苯胂酸的水中，对氨基苯胂酸的浓度为5μmol/L，pH为6，温度为25℃，搅拌30min后，离心沉淀，完成水中砷的去除。经检测，49.4％的对氨基苯胂酸被氧化降解，总砷的去除率为98.9％,剩余总砷的含量为4.12μg/L，低于《生活饮用水卫生标准》(GB5749-2006)中规定的水中砷浓度的限值(10μg/L)。The method for simultaneous oxidation and in-situ adsorption and removal of organic arsenic in water of this embodiment includes the following steps: adding 100 μmol of ferrous chloride and 150 μmol of sodium peroxodisulfate to 1L of water containing para-aminophenylarsonic acid, The concentration of p-aminophenylarsine is 5μmol/L, the pH is 6, the temperature is 25℃, after stirring for 30min, centrifugal precipitation is performed to complete the removal of arsenic from the water. After testing, 49.4% of p-aminophenylarsonic acid was oxidatively degraded, the removal rate of total arsenic was 98.9%, and the content of remaining total arsenic was 4.12μg/L, which was lower than the "Sanitary Standard for Drinking Water" (GB5749-2006) The prescribed limit of arsenic concentration in water (10μg/L).
实施例1-4中有机砷的降解动力学图，纵坐标C t/C 0表示在不同处理时间残留有机砷砷浓度(C t)与有机砷初始浓度(C 0)的比值，比值越小，总有机砷降解率越高；图1B为实施例1-4中有机砷相应的总砷去除率。由图1可知，实施例1至4的方法可以很快达到较高的去除率，氧化在10分钟就基本平衡(结束)了，而吸附是个快速过程，所以能在较短时间内达到很高的去除率。能够达到以上效果主要归功于：1.氧化速率快(10分钟内氧化结束)，2.新生态氧化铁的强吸附能力。所以最终决定多长时间能到达最终吸附平衡(即吸附稳定，或者吸附结束)，取决于新生态铁(原位产生的三价铁)的形成速率和团聚速率。而CN 109942070A专利达到所要求去除率(95％以上的有机砷去除)需要60分钟：达到氧化平衡所需时间约为30分钟，然后是30分钟吸附平衡。实施例1至4只需30分钟，就可以完成氧化加吸附。 The degradation kinetic diagram of organic arsenic in Examples 1-4, the ordinate C t /C 0 represents the ratio of the concentration of residual organic arsenic (C t ) to the initial concentration of organic arsenic (C 0 ) at different treatment times, the smaller the ratio is , The higher the total organic arsenic degradation rate; Figure 1B is the corresponding total arsenic removal rate of organic arsenic in Examples 1-4. It can be seen from Figure 1 that the methods of Examples 1 to 4 can quickly reach a high removal rate. The oxidation basically balances (ends) within 10 minutes, and the adsorption is a fast process, so it can reach a high level in a short time. The removal rate. The above effects can be achieved mainly due to: 1. Fast oxidation rate (oxidation ends within 10 minutes), 2. Strong adsorption capacity of new ecological iron oxide. Therefore, the final decision on how long it takes to reach the final adsorption equilibrium (that is, the adsorption is stable, or the adsorption is over) depends on the formation rate and agglomeration rate of virgin iron (ferric iron produced in situ). The CN 109942070A patent requires 60 minutes to reach the required removal rate (removal of more than 95% of organic arsenic): it takes about 30 minutes to reach the oxidation equilibrium, and then the adsorption equilibrium is 30 minutes. In Examples 1 to 4, it only takes 30 minutes to complete the oxidation plus adsorption.
实施例1-4中新生态铁产生速率快，硫酸亚铁或者氯化亚铁可以在10分钟内完成新生态铁的全部转化，由于新生态铁带正电，具有纳米尺寸，比表面积大，而砷在水中带负电，在静电引力作用下，很容易被新生态铁吸附，而对砷的吸附又促进了新生态铁的团聚，使新生态铁从最初形成时不能被过滤或者未达到沉淀所需尺寸的纳米级小颗粒，快速团聚增长为大颗粒，达到能被过滤或者沉淀的尺寸，最终完成砷的去除。与CN 109942070A专利相比具有新生态铁团聚速率更快，吸附能力更强，更短时间达到吸附平衡，完成总砷的去处优势。In Examples 1-4, the production rate of new ecological iron is fast. Ferrous sulfate or ferrous chloride can complete the conversion of new ecological iron within 10 minutes. Because the new ecological iron is positively charged, it has a nanometer size and a large specific surface area. Arsenic is negatively charged in the water and is easily adsorbed by the new ecological iron under the action of electrostatic gravity, and the adsorption of arsenic promotes the agglomeration of the new ecological iron, so that the new ecological iron cannot be filtered or not precipitated from the initial formation. The small nano-particles of the required size quickly agglomerate and grow into large particles, reaching a size that can be filtered or precipitated, and finally complete the removal of arsenic. Compared with the CN 109942070A patent, the new ecological iron has a faster agglomeration rate, a stronger adsorption capacity, and a shorter time to reach the adsorption equilibrium, completing the advantage of removing the total arsenic.
实施例5：Example 5:
本实施例的一种同步氧化及原位吸附去除水中有机砷的方法，包括以下步骤：将100μmol硫酸亚铁和150μmol过二硫酸钠加入到体积为1L的含对氨基苯胂酸的水中，对氨基苯胂酸的浓度为5μmol/L，pH为7，温度为25℃，搅拌30min后，经0.22μm醋酸纤维膜过滤，完成水中砷的去除。经检测，38.3％的对氨基苯胂酸被氧化降解，总砷的去除 率为98.6％，剩余总砷的含量为5.24μg/L，低于《生活饮用水卫生标准》(GB5749-2006)中规定的水中砷浓度的限值(10μg/L)。The method for simultaneous oxidation and in-situ adsorption and removal of organic arsenic in water of this embodiment includes the following steps: adding 100 μmol of ferrous sulfate and 150 μmol of sodium peroxodisulfate to 1L of water containing p-aminophenylarsonic acid, The concentration of aminophenylarsine is 5μmol/L, pH is 7, temperature is 25℃, after stirring for 30min, it is filtered through 0.22μm cellulose acetate membrane to complete the removal of arsenic in water. After testing, 38.3% of p-aminophenylarsenic acid was oxidized and degraded, the removal rate of total arsenic was 98.6%, and the content of remaining total arsenic was 5.24μg/L, which was lower than the "Sanitary Standard for Drinking Water" (GB5749-2006) The prescribed limit of arsenic concentration in water (10μg/L).
实施例6：Example 6:
本实施例的一种同步氧化及原位吸附去除天然水中有机砷的方法，包括以下步骤：将140μmol硫酸亚铁和210μmol过二硫酸钠加入到体积为1L的含对氨基苯胂酸的地表水中，对氨基苯胂酸的浓度为5μmol/L，pH为7.96，温度为25℃，搅拌30min后，经0.22μm醋酸纤维膜过滤，完成水中砷的去除。经检测，34.9％的对氨基苯胂酸被氧化降解，总砷的去除率为98.8％，剩余总砷的含量为4.50μg/L，低于《生活饮用水卫生标准》(GB5749-2006)中规定的水中砷浓度的限值(10μg/L)。The method for simultaneous oxidation and in-situ adsorption and removal of organic arsenic in natural water of this embodiment includes the following steps: adding 140 μmol of ferrous sulfate and 210 μmol of sodium peroxodisulfate to a volume of 1L of surface water containing p-aminophenylarsonic acid The concentration of p-aminophenylarsonic acid is 5μmol/L, pH is 7.96, temperature is 25℃, after stirring for 30min, it is filtered through 0.22μm cellulose acetate membrane to complete the removal of arsenic in water. After testing, 34.9% of p-aminophenylarsonic acid was oxidatively degraded, the removal rate of total arsenic was 98.8%, and the content of remaining total arsenic was 4.50μg/L, which was lower than the "Sanitary Standard for Drinking Water" (GB5749-2006) The prescribed limit of arsenic concentration in water (10μg/L).
实施例7：Example 7:
本实施例的一种同步氧化及原位吸附去除天然水中无机砷的方法，包括以下步骤：将100μmol硫酸亚铁和150μmol过二硫酸钠加入到体积为1L的含三价砷(As(III))水中，三价砷的浓度为5μmol/L，pH为6，温度为25℃，搅拌30min后，经0.22μm醋酸纤维膜过滤，完成水中砷的去除。经检测，100％的三价砷被氧化成五价砷(As(V))，总砷的去除率为99.8％,剩余总砷的含量为0.75μg/L，低于《生活饮用水卫生标准》(GB5749-2006)中规定的水中砷浓度的限值(10μg/L)。The method for simultaneous oxidation and in-situ adsorption and removal of inorganic arsenic in natural water of this embodiment includes the following steps: adding 100 μmol of ferrous sulfate and 150 μmol of sodium peroxodisulfate to a volume of 1L containing trivalent arsenic (As(III) ) In the water, the concentration of trivalent arsenic is 5μmol/L, the pH is 6, and the temperature is 25℃. After stirring for 30min, it is filtered through a 0.22μm cellulose acetate membrane to complete the removal of arsenic in the water. After testing, 100% of trivalent arsenic is oxidized to pentavalent arsenic (As(V)), the removal rate of total arsenic is 99.8%, and the content of remaining total arsenic is 0.75μg/L, which is lower than the "Sanitary Standard for Drinking Water" 》(GB5749-2006) The limit of arsenic concentration in water (10μg/L).
实施例8：Example 8:
本实施例的一种同步氧化及原位吸附去除天然水中无机砷的方法，包括以下步骤：将100μmol硫酸亚铁和150μmol过二硫酸钠加入到体积为1L的含五价砷(As(V))水中，五价砷的浓度为5μmol/L，pH为6，温度为25℃，搅拌30min后，经0.22μm醋酸纤维膜过滤，完成水中砷的去除。经检测，总砷的去除率约为99.9％，剩余总砷的含量为0.37μg/L，低于《生活饮用水卫生标准》(GB5749-2006)中规定的水中砷浓度的限值(10μg/L)。The method for simultaneous oxidation and in-situ adsorption and removal of inorganic arsenic in natural water of this embodiment includes the following steps: adding 100 μmol of ferrous sulfate and 150 μmol of sodium peroxodisulfate to a volume of 1L containing pentavalent arsenic (As(V) ) In the water, the concentration of pentavalent arsenic is 5μmol/L, the pH is 6, and the temperature is 25℃. After stirring for 30min, it is filtered through a 0.22μm cellulose acetate membrane to complete the removal of arsenic in the water. After testing, the total arsenic removal rate is about 99.9%, and the remaining total arsenic content is 0.37μg/L, which is lower than the limit of arsenic concentration in water (10μg/ L).
实施例9：Example 9:
本实施例的一种同步氧化及原位吸附去除天然水中有机砷及无机砷的方法，包括以下步骤：将100μmol硫酸亚铁和150μmol过二硫酸钠加入到体积为1L的含对氨基苯胂酸和三价砷(As(III))水中，对氨基苯胂酸与三价砷的浓度分别为5μmol/L和2μmol/L,pH为6，温度为25℃，搅拌30min后，经0.22μm醋酸纤维膜过滤，完成水中砷的去除。经检测，48.7％的对氨基苯胂酸被氧化降解，100％的三价砷被氧化成五价砷(As(V))，总砷的去除率为98.8％,剩余总砷的含量为6.3μg/L，低于《生活饮用水卫生标准》(GB5749-2006)中规定的水中砷浓度的限值(10μg/L)。The method for simultaneous oxidation and in-situ adsorption to remove organic arsenic and inorganic arsenic in natural water of this embodiment includes the following steps: adding 100 μmol of ferrous sulfate and 150 μmol of sodium peroxodisulfate to a volume of 1L containing p-aminophenylarsonic acid And trivalent arsenic (As(III)) water, the concentration of p-aminophenylarsonic acid and trivalent arsenic are 5μmol/L and 2μmol/L, respectively, pH is 6, temperature is 25℃, after stirring for 30min, after 0.22μm acetic acid Fiber membrane filtration completes the removal of arsenic in water. After testing, 48.7% of p-aminophenylarsonic acid was oxidized and degraded, 100% of trivalent arsenic was oxidized to pentavalent arsenic (As(V)), the removal rate of total arsenic was 98.8%, and the content of remaining total arsenic was 6.3 μg/L, which is lower than the limit of arsenic concentration in water (10μg/L) specified in the "Sanitary Standards for Drinking Water" (GB5749-2006).
实施例10：Example 10:
本实施例的一种同步氧化及原位吸附去除天然水中有机砷及无机砷的方法，包括以下步骤：将100μmol硫酸亚铁和150μmol过二硫酸钠加入到体积为1L的含对氨基苯胂酸和五价砷(As(V))水中，对氨基苯胂酸与五价砷的浓度分别为5μmol/L和2μmol/L，pH为6，温度为25℃，搅拌30min后，经0.22μm醋酸纤维膜过滤，完成水中砷的去除。经检测，49.2％的对氨基苯胂酸被氧化降解，总砷的去除率为98.9％,剩余总砷的含量为5.8μg/L，低于《生活饮用水卫生标准》(GB5749-2006)中规定的水中砷浓度的限值(10μg/L)。The method for simultaneous oxidation and in-situ adsorption to remove organic arsenic and inorganic arsenic in natural water of this embodiment includes the following steps: adding 100 μmol of ferrous sulfate and 150 μmol of sodium peroxodisulfate to a volume of 1L containing p-aminophenylarsonic acid And pentavalent arsenic (As(V)) water, the concentrations of p-aminophenylarsonic acid and pentavalent arsenic are 5μmol/L and 2μmol/L, respectively, the pH is 6, the temperature is 25℃, after stirring for 30min, after 0.22μm acetic acid Fiber membrane filtration completes the removal of arsenic in water. After testing, 49.2% of p-aminophenylarsonic acid was oxidatively degraded, the removal rate of total arsenic was 98.9%, and the content of remaining total arsenic was 5.8μg/L, which was lower than the "Sanitary Standard for Drinking Water" (GB5749-2006) The prescribed limit of arsenic concentration in water (10μg/L).
对于本领域技术人员而言，显然本发明不限于上述示范性实施例的细节，而且在不背离本发明的精神或基本特征的情况下，能够以其他的具体形式实现本发明。因此，无论从哪一点来看，均应将实施例看作是示范性的，而且是非限制性的，本发明的范围由所附权利要求而不是上述说明限定，因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。不应将权利要求中的任何附图标记视为限制所涉及的权利要求。For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description, and therefore it is intended to fall within the claims. All changes within the meaning and scope of the equivalent elements of are included in the present invention. Any reference signs in the claims should not be regarded as limiting the claims involved.
此外，应当理解，虽然本说明书按照实施方式加以描述，但并非每个实施方式仅包含一个独立的技术方案，说明书的这种叙述方式仅仅是为清楚起见，本领域技术人员应当将说明书作为一个整体，各实施例中的技术方案也可以经适当组合，形成本领域技术人员可以理解的其他实施方式。In addition, it should be understood that although this specification is described in accordance with the implementation manners, not each implementation manner only includes an independent technical solution. This narration in the specification is only for the sake of clarity, and those skilled in the art should regard the specification as a whole The technical solutions in the various embodiments can also be appropriately combined to form other implementations that can be understood by those skilled in the art.
本发明不限于以上对实施例的描述，本领域技术人员根据本发明揭示的内容，在本发明基础上不必经过创造性劳动所进行的改进和修改，都应该在本发明的保护范围之内。The present invention is not limited to the above description of the embodiments. According to the content disclosed by the present invention, those skilled in the art make improvements and modifications without creative work on the basis of the present invention, and all should fall within the protection scope of the present invention.

Claims (10)

  1. 一种同步氧化及原位吸附去除水中有机砷的方法，其特征在于，它是按照以下步骤进行的：A method for simultaneous oxidation and in-situ adsorption and removal of organic arsenic in water is characterized in that it is carried out according to the following steps:
    将二价铁盐和过硫酸盐加入到含砷的水中，以实现同步氧化降解及原位吸附去除水中有机砷，其中二价铁盐和过硫酸盐的摩尔比为：1:0.8～4。The divalent iron salt and persulfate are added to the water containing arsenic to achieve simultaneous oxidative degradation and in-situ adsorption and removal of organic arsenic from the water. The molar ratio of the divalent iron salt and the persulfate is 1:0.8-4.
  2. 根据权利要求1所述的一种同步氧化及原位吸附去除水中有机砷的方法，其特征在于，所述的二价铁盐包括硫酸亚铁，硝酸亚铁，氯化亚铁的一种或多种。The method for simultaneous oxidation and in-situ adsorption and removal of organic arsenic in water according to claim 1, wherein the divalent iron salt includes one of ferrous sulfate, ferrous nitrate, and ferrous chloride. Many kinds.
  3. 根据权利要求1所述的一种同步氧化及原位吸附去除水中有机砷的方法，其特征在于，所述的过硫酸盐为过一硫酸盐和/或过二硫酸盐。The method for simultaneous oxidation and in-situ adsorption and removal of organic arsenic in water according to claim 1, wherein the persulfate is persulfate and/or peroxodisulfate.
  4. 根据权利要求3所述的一种同步氧化及原位吸附去除水中有机砷的方法，其特征在于，所述的过一硫酸盐为过一硫酸钾和过一硫酸氢钾中的一种或两种。The method for simultaneous oxidation and in-situ adsorption and removal of organic arsenic in water according to claim 3, wherein the peroxymonosulfate is one or both of potassium persulfate and potassium persulfate. kind.
  5. 根据权利要求3所述的一种同步氧化及原位吸附去除水中有机砷的方法，其特征在于，所述的过二硫酸盐包括过二硫酸钾、过二硫酸钠和过二硫酸铵中的一种或多种。The method for simultaneous oxidation and in-situ adsorption and removal of organic arsenic in water according to claim 3, wherein the peroxodisulfate comprises potassium peroxodisulfate, sodium peroxodisulfate and ammonium peroxodisulfate. One or more.
  6. 根据权利要求1～5中任一项所述的一种同步氧化及原位吸附去除水中有机砷的方法，其特征在于，所述含砷水的pH值控制在3～8范围内，和/或所述含砷废水的温度为5℃～40℃。The method for simultaneous oxidation and in-situ adsorption and removal of organic arsenic from water according to any one of claims 1 to 5, characterized in that the pH value of the arsenic-containing water is controlled within the range of 3-8, and/ Or the temperature of the arsenic-containing wastewater is 5°C-40°C.
  7. 根据权利要求1～5中任一项所述的一种同步氧化及原位吸附去除水中有机砷的方法，其特征在于，所述含砷水中含有有机砷的浓度为0.1μM～100μM。The method for simultaneous oxidation and in-situ adsorption and removal of organic arsenic from water according to any one of claims 1 to 5, wherein the concentration of organic arsenic contained in the arsenic-containing water is 0.1 μM-100 μM.
  8. 根据权利要7所述的一种同步氧化及原位吸附去除水中有机砷的方法，其特征在于，含砷水为有机砷和/或无机砷。The method for simultaneous oxidation and in-situ adsorption and removal of organic arsenic from water according to claim 7, wherein the arsenic-containing water is organic arsenic and/or inorganic arsenic.
  9. 根据权利要1所述的一种同步氧化及原位吸附去除水中有机砷的方法，其特征在于，所述二价铁盐和过硫酸盐同时或者间隔30s先后加入到含砷的水中。The method for simultaneous oxidation and in-situ adsorption and removal of organic arsenic in water according to claim 1, characterized in that the divalent iron salt and persulfate are added to the arsenic-containing water at the same time or successively at an interval of 30 seconds.
  10. 根据权利要1所述的一种同步氧化及原位吸附去除水中有机砷的方法，其特征在于，所述的含砷的水为养殖废水、工厂污水或饮用水。The method for simultaneous oxidation and in-situ adsorption and removal of organic arsenic in water according to claim 1, wherein the water containing arsenic is aquaculture wastewater, factory sewage or drinking water.
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