CN110963612A - Method for co-processing lead and arsenic composite pollutants in underground water by adopting pre-oxidation - Google Patents
Method for co-processing lead and arsenic composite pollutants in underground water by adopting pre-oxidation Download PDFInfo
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- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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Abstract
The invention discloses a method for treating lead-arsenic composite pollutants in underground water by adopting preoxidation and synergism. The invention has the advantages that: the toxicity of the underground water can be effectively reduced and the removal rate of the underground water can be improved by increasing pre-oxidation, the removal rate reaches over 95 percent, the arsenic and lead concentration of the treated underground water is lower than 10ppb, and the underground water is harmless to the health of human bodies; the COD in the wastewater is also removed to a certain extent; secondary pollution to underground water is avoided; the method is suitable for acid-base wastewater; the process flow is simple, and the matched device is simple and easy to control.
Description
Technical Field
The invention belongs to the technical field of ex-situ treatment of polluted water, and particularly relates to a method for treating underground water lead-arsenic composite pollutants by adopting preoxidation.
Background
At present, the mature method for treating the arsenic-containing wastewater mainly comprises the following steps: ferrite method, lime iron salt neutralization method, lime aluminum salt neutralization method, lime magnesium salt neutralization method, sulfuration method and neutralization oxidation method, and the pH value needs to be controlled between 5 and 9 in the treatment process. As for the lead-containing wastewater, the lead-containing wastewater is relatively mature and widely applied, such as a chemical precipitation method, an ion exchange method, an electrolytic method, a physical adsorption method, a biological method, a membrane separation method and the like, and the pH value needs to be controlled between 8 and 10 in the treatment process. Because the difference between the treatment process and the treatment condition is large, in the field of groundwater remediation of lead-arsenic combined pollution, a synergistic treatment example is reported at present, and the arsenic-lead concentration of the remediated groundwater cannot meet the strict limit requirement of the groundwater.
Disclosure of Invention
The invention aims to provide a method for treating lead-arsenic composite pollutants in underground water by adopting preoxidation and synergism.
The purpose of the invention is realized by the following technical scheme:
a method for co-processing lead-arsenic composite pollutants in underground water by adopting pre-oxidation is characterized by comprising the following steps:
(1) pumping the underground polluted water to a primary sedimentation tank to settle silt, and pumping the underground polluted water to a reaction device;
(2) adding an oxidizing agent into the reaction device, and carrying out stirring reaction for 5-10 minutes, wherein the added oxidizing agent accounts for 0.1-0.5% of the underground polluted water by mass;
(3) adding a trivalent ferric salt solution with the mass concentration of 0.5-1.0% into the underground polluted water treated in the step (2) until the mass concentration of the trivalent ferric salt in the underground polluted water reaches 0.1-0.5%, controlling the pH of the underground polluted water to be 5-7 by using an acid-base regulator, and stirring for 10-20 minutes;
(4) putting a strong alkali solution with the mass fraction of 10% into the underground polluted water treated in the step (3) until the PH of the underground polluted water is stabilized between 8 and 9, and stirring for reacting for 10 to 20 minutes;
(5) adding a flocculating agent with the mass fraction of 5-200ppm into the underground polluted water treated in the step (4), and stirring for reacting for 5-10 minutes;
(6) standing the underground polluted water treated in the step (5) for 1-2 hours until the flocculation reaction is complete, performing solid-liquid separation to obtain sludge and effluent, filtering the effluent to obtain underground water reaching the standard after lead and arsenic are removed, and bagging the sludge after filter pressing.
The standard hydrogen electrode potential of the oxidant is +1.23V, and is Na2S2O8One of Fenton reagent, sodium hypochlorite, potassium permanganate, potassium dichromate and ozone.
In the step (3), the acid-base regulator used for the underground polluted water with the original acidity is a strong alkali solution; and for the underground polluted water with the original alkalinity, the acid-base regulator is an acid solution.
The strong alkali solution is one or a combination of a calcium hydroxide solution, a strong sodium oxide solution and a strong potassium oxide solution.
The flocculating agent is one or a combination of more of polyacrylamide, polyaluminium chloride and polyferric sulfate.
The speed of the stirring reaction is controlled between 50 and 200 r/min.
The invention has the advantages that:
(1) as (III) has toxicity and mobility higher than those of As (V), but As (III) usually exists in a neutral molecular form in a pH range of 3-10, so that the removal rate of As (III) by a plurality of technologies is far lower than that of As (V); therefore, the toxicity of the underground water can be effectively reduced and the removal rate of the underground water can be improved by increasing pre-oxidation, the removal rate reaches over 95 percent, the arsenic and lead concentration of the treated underground water is lower than 10ppb, and the underground water is harmless to the health of human bodies;
(2) the COD in the wastewater is also removed to a certain extent;
(3) the groundwater environment is complex and sensitive, different from industrial wastewater, and has high requirements on secondary pollution prevention and control during treatment, and the method uses a medicament which is polymerized in the sediment to avoid secondary pollution to the groundwater;
(4) is suitable for acid-base waste water.
(5) The process flow is simple, and the matched device is simple and easy to control.
Drawings
FIG. 1 is a schematic flow chart of a method for treating underground water lead-arsenic composite pollutants by using preoxidation in cooperation with treatment;
FIG. 2 is a schematic diagram of the addition of agents to the test group E1-E16 according to the present invention;
FIG. 3 is a graph showing the lead and arsenic removal rate curves of the underground contaminated water of the test groups E1-E16 in accordance with the present invention;
FIG. 4 is a schematic diagram of the drug addition in test group A1-A7 of the present invention;
FIG. 5 is a schematic diagram of the drug addition in test groups A1 and B1 of the present invention.
Detailed Description
The features of the present invention and other related features are described in further detail below by way of example in conjunction with the following drawings to facilitate understanding by those skilled in the art:
example (b): as shown in fig. 1, in this embodiment, a method for treating a lead-arsenic composite pollutant in groundwater by using preoxidation in cooperation is specifically provided, in which an oxidant, a ferric salt, an alkali solution and a flocculant are sequentially added to underground polluted water at a certain concentration, and under the condition that the pH environment of a reaction system is well controlled, the reaction time and the stirring rate are set so as to allow the underground polluted water to react sufficiently, thereby achieving the purpose of synchronously removing the lead-arsenic pollutant from the underground polluted water. The method specifically comprises the following steps:
(1) pumping underground polluted water into a primary sedimentation tank to settle silt, and pumping the underground polluted water to a reaction device.
(2) Adding an oxidizing agent into a reaction device, and carrying out stirring reaction for 5-10 minutes, wherein the mass ratio of the added oxidizing agent to the polluted water under the floor is 0.1-0.5%; oxidizing agent is all standard hydrogen electrode potentials>+1.23V strong oxidizing agent, which may be Na2S2O8One or more of fenton reagent, sodium hypochlorite, potassium permanganate, potassium dichromate and ozone.
(3) Adding a trivalent ferric salt solution with the mass concentration of 0.5-1.0% into the underground polluted water treated in the step (2) until the mass concentration of the trivalent ferric salt in the underground polluted water reaches 0.1-0.5%, controlling the pH of the underground polluted water to be between 5 and 7 by using an acid-base regulator, and stirring for 10-20 minutes; wherein the ferric salt refers to a compound containing iron ions (Fe)3+) A salt; the pH is controlled within the range of 5-7, the pH is further reduced by adding ferric salt to the original acidic underground polluted water, the adjustment can be carried out by using the strong base solution in the step (4), and the adjustment can be carried out by using an acid solution to the original alkaline underground polluted water.
(4) Putting 10% by mass of strong alkali solution into the underground polluted water treated in the step (3) until the PH of the underground polluted water is stabilized between 8 and 9, and stirring for reaction for 10 to 20 minutes; wherein the strong alkali solution is one or more of calcium hydroxide, strong sodium oxide and strong potassium oxide solution.
(5) Adding a flocculating agent with the mass fraction of 5-200ppm into the underground polluted water treated in the step (4), and stirring for reacting for 5-10 minutes; wherein the flocculating agent is a polymer flocculant, and can be one or a combination of polyacrylamide, polyaluminium chloride and polyferric sulfate.
(6) Standing the underground polluted water treated in the step (5) for 1-2 hours until the flocculation reaction is complete, performing solid-liquid separation to obtain sludge and effluent, filtering the effluent to obtain underground water reaching the standard after lead and arsenic are removed, and bagging the sludge after filter pressing.
It should be noted that the stirring reaction in each step is controlled at a rate of 50-200 r/min.
To verify the beneficial effects of the method in this example, the following comparative tests with multiple subjects were used respectively:
first, different medicament proportioning tests of specific experimental group
In this set of experiments, the high-efficiency oxidizing agent is exemplified by sodium persulfate, the ferric salt is exemplified by ferric chloride, the strong alkaline solution is exemplified by calcium hydroxide, and the flocculating agent is exemplified by polyacrylamide:
(1) subpackaging underground polluted water into 16 500ml conical flask containers, and determining the background values of untreated underground water heavy metal arsenic and lead to be 528 mug/L and 375 mug/L respectively by using an HJ700-2004 method;
(2) according to the method steps in the embodiment, chemical agents participating in the reaction are added according to the mass fractions set in the table of FIG. 2, the chemical agents are divided into 16 groups, and the serial numbers of the groups are respectively E1, E2, E3, E15 and E16;
(3) adding sodium persulfate into each group of underground polluted water samples to be tested, stirring for 10 minutes, adding ferric chloride, fully stirring for reaction for 10 minutes, adding calcium hydroxide to adjust the pH value to 8-9, stirring for 10 minutes, standing for 30 minutes, adding PAM (polyacrylamide) for flocculation and precipitation, taking supernate, testing the residual amounts of As and Pb, and obtaining data shown in the following table;
a lead and arsenic removal rate curve of the treated underground polluted water is shown in fig. 3;
according to the above experimental data, the following are summarized:
① and E1-E16 test groups have certain removal rate of lead and arsenic, wherein the removal rate of lead is 82.9-99.5% and the removal rate of arsenic is 76.1-98.9%.
②, in the experimental group with the same mass fractions of sodium persulfate, ferric salt and calcium hydroxide, the addition of 8ppm and 16ppm polyacrylamide had substantially no effect on the removal rate, indicating that a flocculant concentration of 8ppm was sufficient.
③, in the experimental group added with the same mass fraction of sodium persulfate and ferric salt, when the pH value of the solution system is adjusted to 8 by calcium hydroxide, the metal removal rate is generally higher than that when the pH value is 9, which shows that the pH value is increased in a small range and is not beneficial to the precipitation of lead and arsenic metal.
④, the groups E5/E6, E9/E10 and E13/E14 have the best removal effect, and when the method is used for guiding practical application, economic and practical medicament proportions can be comprehensively considered according to site characteristics, pollution remediation targets and the like.
Comparison between different oxidants, ferric salts, and strong base solutions
(1) Adding 4 kinds of oxidants, 2 kinds of ferric iron salts, 2 kinds of strong alkali solution and 2 kinds of flocculating agents according to the types of chemical agents set in the table in the figure 4; the total number of the groups is 7, and the serial numbers of the groups are A1, A2, A3, A4, A5, A6 and A7;
(2) the following test data, i.e., the remaining amounts of As and Pb, were obtained after the following treatments, performed in sequence according to the method steps in this example:
according to the above experimental data, the following are summarized:
①, in the experimental group, different ferric salts and strong alkali solutions are selected to have no influence on the removal rate.
②, the removal rate of the two types of metals is higher than that of the PAC group by adopting an organic polymeric flocculant PAM group.
③ comparison of different oxidants Na2S2O8、 NaClO、kMnO4In the case of Fenton's reagent, Na was found in the test2S2O8The group treatment effect is optimal.
Comparison of Pre-Oxidation with non-Oxidation
(1) According to the followingThe chemical agent types are added according to the table in figure 5, wherein the oxidant is Na2S2O8And kMnO4(ii) a Dividing into B1 group and A1 group, wherein B1 group is not pre-oxidized;
(2) two sets of tests were performed according to the method steps in this example, respectively, to obtain the test data after treatment, i.e. the residual amounts of As and Pb, As shown in the following table:
through the two groups of tests, the group which is not subjected to pre-oxidation can be found to have lower arsenic removal rate for underground water.
Claims (6)
1. A method for co-processing lead-arsenic composite pollutants in underground water by adopting pre-oxidation is characterized by comprising the following steps:
(1) pumping the underground polluted water to a primary sedimentation tank to settle silt, and pumping the underground polluted water to a reaction device;
(2) adding an oxidizing agent into the reaction device, and carrying out stirring reaction for 5-10 minutes, wherein the added oxidizing agent accounts for 0.1-0.5% of the underground polluted water by mass;
(3) adding a trivalent ferric salt solution with the mass concentration of 0.5-1.0% into the underground polluted water treated in the step (2) until the mass concentration of the trivalent ferric salt in the underground polluted water reaches 0.1-0.5%, controlling the pH of the underground polluted water to be 5-7 by using an acid-base regulator, and stirring for 10-20 minutes;
(4) putting a strong alkali solution with the mass fraction of 10% into the underground polluted water treated in the step (3) until the PH of the underground polluted water is stabilized between 8 and 9, and stirring for reacting for 10 to 20 minutes;
(5) adding a flocculating agent with the mass fraction of 5-200ppm into the underground polluted water treated in the step (4), and stirring for reacting for 5-10 minutes;
(6) standing the underground polluted water treated in the step (5) for 1-2 hours until the flocculation reaction is complete, performing solid-liquid separation to obtain sludge and effluent, filtering the effluent to obtain underground water reaching the standard after lead and arsenic are removed, and bagging the sludge after filter pressing.
2. The method of claim 1, wherein the oxidizing agent has a standard hydrogen electrode potential of > +1.23V, Na2S2O8One of Fenton reagent, sodium hypochlorite, potassium permanganate, potassium dichromate and ozone.
3. The method for the cooperative disposal of lead and arsenic complex pollutants in underground water by pre-oxidation as claimed in claim 1, wherein in the step (3), the pH regulator used for the underground polluted water with original acidity is a strong alkaline solution; and for the underground polluted water with the original alkalinity, the acid-base regulator is an acid solution.
4. The method of claim 1, wherein the strong alkaline solution is one or more of calcium hydroxide solution, strong sodium oxide solution and strong potassium oxide solution.
5. The method for the synergistic treatment of the lead-arsenic complex pollutants in the underground water by the pre-oxidation according to claim 1, wherein the flocculant is one or more of polyacrylamide, polyaluminium chloride and polyferric sulfate.
6. The method for the cooperative disposal of lead-arsenic complex pollutants in underground water by pre-oxidation as claimed in claim 1, wherein the stirring reaction rate is controlled to be between 50 and 200 r/min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112122334A (en) * | 2020-09-08 | 2020-12-25 | 浙江省冶金研究院有限公司 | Method for repairing organic-heavy metal combined contaminated soil by coupling chemical oxidation with biochar and strengthening microorganisms |
| CN114349214A (en) * | 2022-01-04 | 2022-04-15 | 湖南云河信息科技有限公司 | Efficient arsenic removal process and device for underground water |
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| CN103043812A (en) * | 2011-10-13 | 2013-04-17 | 中国科学院过程工程研究所 | Advanced treatment method for arsenic-containing wastewater |
| JP2014087731A (en) * | 2012-10-30 | 2014-05-15 | Okumura Corp | Processing device and processing method for waste water containing heavy metal |
| CN104556472A (en) * | 2014-12-05 | 2015-04-29 | 安徽华盛科技控股股份有限公司 | Treatment method and system for CIT heavy metal-containing sulfuric acid wastewater |
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| CN1295031A (en) * | 2000-12-05 | 2001-05-16 | 易求实 | Method of eliminating As, Pb, Cr and Hg from drinking water |
| CN1733617A (en) * | 2004-08-11 | 2006-02-15 | 巨化集团公司 | Processing method of waste water containing fluorine arsenic and lead |
| CN103043812A (en) * | 2011-10-13 | 2013-04-17 | 中国科学院过程工程研究所 | Advanced treatment method for arsenic-containing wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112122334A (en) * | 2020-09-08 | 2020-12-25 | 浙江省冶金研究院有限公司 | Method for repairing organic-heavy metal combined contaminated soil by coupling chemical oxidation with biochar and strengthening microorganisms |
| CN114349214A (en) * | 2022-01-04 | 2022-04-15 | 湖南云河信息科技有限公司 | Efficient arsenic removal process and device for underground water |
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