CN101475252A - Integrated method for processing arsenic-containing wastewater by using iron composite bentonite - Google Patents
Integrated method for processing arsenic-containing wastewater by using iron composite bentonite Download PDFInfo
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- CN101475252A CN101475252A CNA2008101622548A CN200810162254A CN101475252A CN 101475252 A CN101475252 A CN 101475252A CN A2008101622548 A CNA2008101622548 A CN A2008101622548A CN 200810162254 A CN200810162254 A CN 200810162254A CN 101475252 A CN101475252 A CN 101475252A
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Abstract
The invention discloses an integrated method for treating arsenous wastewater through iron composite bentonite. The method comprises the following steps that: (1) an oxidant is added into the arsenous wastewater for pre-oxygenation; (2) a molysite solid is directly thrown into the arsenous wastewater; and the molar ratio of Fe to As is between 5 and 50; (3) the PH value of the wastewater is regulated between 4 and 7 by lime; an iron carbonyl adsorbent is formed; and the molar ratio of OH<-> to Fe is between 0.5 and 5.0; and (4) bentonite is directly thrown into the pretreated arsenous wastewater; the mass-volume ratio of the bentonite to the arsenous wastewater is between 1g : 100mL and 1g : 20,000mL; the wastewater is stirred; simultaneously the synthesis of the iron composite bentonite and high-efficient removal of arsenic pollutant in the wastewater are realized; the precipitation of iron carbonyl is accelerated; and the wastewater reaches the emission standard. The method can be used for wastewater treatment and emergency treatment of accidents of arsenic leakage and pollution in the arsenous industry.
Description
Technical field
The present invention relates to water technology and application, relate in particular to a kind of integral method of processing arsenic-containing wastewater by using iron composite bentonite.
Background technology
Arsenic is a kind of element of serious harm human health.The purposes of arsenic is very extensive, relates to the every aspect of human being's production, life, the use of weedicide, sterilant, wood preservative, and process such as mining, metallurgy, electronic industry, semiconductor production all can relate to the discharging of arsenic.Arsenic and all arsenical compounds all are deleterious, and are material carcinogenic, teratogenesis mostly.Arsenic can be accumulated on the positions such as the liver, kidney, lung, spleen, uterus, placenta, skeleton, muscle of human body, particularly in hair, the nail, thereby causes arsenicalism, reaches several years latent period even decades.Owing to contain a large amount of uses of arsenic chemical and the discharging of metallurgical and chemical industry arsenic-containing waste water waste residue, caused arsenic accumulation in a large number in soil and water body deposit.Arsenic Contamination in Groundwater is the problem that recent two decades exposes to the open air out, according to statistics: all there is the Arsenic Contamination in Groundwater problem in the many countries and regions comprising China as Bangladesh, India, Thailand, Chile, Argentina, Mexico, Canada and the U.S. etc.Data show: Bangladesh has 5,000 ten thousand people approximately, and China has the positive working concentration of 6 million peoples to surpass the tap water of 50 μ g/L approximately, and estimation population quantity surpasses 100,000,000 five thousand ten thousand in the world wide.Water body and arsenic in soil pollute and are just causing that people more and more pay close attention to.Serious threat drinking water safety, food safety and population health constantly take place in the arsenic contamination accident recently, as Guizhou Province fertilizer plant's discharging arsenic-containing waste water take place once, cause downstream occurrence of large-area arseniasis; Yunnan Yang Zonghai arsenic contamination incident in 2008 causes the contaminated water body total amount of Yang Zonghai to reach 6.04 billion cubic meters.Still none overlaps the science way that a large amount of arsenic of effective improvement leak the field condition emergency processing that causes river severe contamination accident both at home and abroad at present.
The quality standard of arsenic is more and more stricter in the environment.U.S. environment protection general administration (U.S.EPA) just proposed and the arsenic drinking water standard of 50 original μ g/L will be reduced to 10 μ g/L as far back as calendar year 2001, and its long-term goal is 2 μ g/L.The World Health Organization also fixed tentatively the arsenic concentration of tap water at 10 μ g/L in 1993.
The removal method of arsenic contamination is the same with other metal in the water, and conventional treatment method is divided three classes, i.e. physics method, chemical method and biochemical process.In addition, at present domestic and international relevant industrial is handled the emerging treatment process of arsenic waste water, many reports are also arranged, mainly contain the precipitator method, flocculence, filtration method, absorption method, oxidation style, ion exchange method, membrane separation process, electrolytic process and biological process etc., but these methods and be not suitable for and administer a large amount of arsenic and leak the field condition emergency processing that causes river severe contamination accident.
The technology such as charcoal absorptions and chemical coagulation and precipitation that adopt were handled arsenic-containing waste water more during common engineering was used and studied, but had shortcomings such as long flow path, complex process and expense height.Therefore, seeking new efficient low expense and the simple sorbent material of technical process and treatment process has great importance to the processing and the research of such waste water.
Utilizing the molysite arsenic removal is the treatment process of using always, and iron(ic) chloride and alum are commonly used for flocculation agent and add water body.Under the higher pH value condition, iron(ic) chloride can produce great amount of hydroxy group iron, and arsenate in the solution and ironic hydroxide also adsorption coprecipitation can take place, thereby can obtain higher arsenic removal efficiency.Iron carbonyl will be much larger than the removal effect to As (III) to the removal effect of As (V), and the increase of concentration of iron helps the removal of As (V), but little to the removal effect influence of As (III).Therefore need the As in the waste water (III) be oxidized to As (V) by preoxidation, the arsenic in iron carbonyl and the waste water is worked.
Wilkinite is to be the tonstein of main component with the montmorillonite, is one of nonmetallic minerals that is most widely used.Montmorillonite mainly is made up of aqueous aluminium silicate mineral, and its unit cell is made up of two-layer silicon-oxy tetrahedron folder layer of aluminum hydrogen-oxygen tetrahedron; Al in the montmorillonite octahedron
3+(or) Si in the tetrahedron
4+Often part (or all) by other cation replacement, has high cation exchange capacity.According to exchangeable sodium and calcium ion content, wilkinite is divided into sodium bentonite and calcium-base bentonite etc.Wilkinite not only can produce certain adsorption to arsenic, and can quicken to adsorb the precipitation of the iron carbonyl after the arsenic.China's bentonite resource is very abundant, occupies first place in the world, and total standing stock are 77.4 hundred million tons; 17.2 hundred million tons of proven reserve; sodium bentonite with higher utility value reaches 5.86 hundred million tons, and wherein industrial reserves is 2.05 hundred million tons, particularly is with a wide range of applications in the processing of waste water in environment protection.By retrieval, existing iron(ic) chloride is used for the relevant patent that arsenic-containing waste water is handled, as contains treatment process (the patent of invention publication number: CN1733616A) of As groundwater.But do not see the patent report of relevant iron composite bentonite integral method processing arsenic-containing waste water.
Summary of the invention
The integral method that the purpose of this invention is to provide a kind of processing arsenic-containing wastewater by using iron composite bentonite.
The integral method of processing arsenic-containing wastewater by using iron composite bentonite comprises the steps:
(1) in arsenic-containing waste water, adds oxygenant and carry out preoxidation;
(2) the molysite solid directly is added in the arsenic-containing waste water, the mol ratio of Fe and As is 5～50;
(3) regulating waste water ph with lime is 4～7, forms the iron carbonyl sorbent material, OH
-With the mol ratio of Fe be 0.5～5.0;
(4) wilkinite directly is added in the pretreated arsenic-containing waste water, the mass volume ratio of wilkinite and arsenic-containing waste water is 1g:100mL～1g:20000mL, through stirring, realizes simultaneously that the arsenic contamination object height is imitated in the synthetic and waste water of iron composite bentonite to remove, acceleration iron carbonyl precipitation, discharged wastewater met the national standard.
Described oxygenant comprises ozone, pure oxygen, air, H
2O
2Or MnO
2Molysite is iron(ic) chloride or ferric sulfate.The mol ratio of Fe and As is preferably 20～40.Waste water ph is preferably 5～7.OH
-Be preferably 2～4 with the mol ratio of Fe.Wilkinite is the calcium-base bentonite original soil.Adding the product that oxygenant carries out after the preoxidation in the arsenic-containing waste water is H
2AsO
4 -, HAsO
4 2-Or/and AsO
4 3-
Molysite that purifying method of the present invention adopts and natural mineral, raw material is easy to get.China's bentonite resource is very abundant, occupies first place in the world, and total reserves is greater than 7,000,000,000 tons.This method technology is simple, technical requirements is low, solid-liquid separates rapidly, and treatment effect is good, and running cost is low; And, be particularly suitable for the emergency processing of waste water containing arsenic processing, arsenic leakage pollution accident through simple process.
Embodiment
Embodiment 1
(1) in arsenic-containing waste water, adds ozone and carry out preoxidation;
(2) the iron(ic) chloride solid directly is added in the arsenic-containing waste water, the mol ratio of Fe and As is 10;
(3) regulating waste water ph with lime is 4～5, forms the iron carbonyl sorbent material, and the mol ratio of OH-and Fe is 2.5;
(4) wilkinite directly is added in the pretreated arsenic-containing waste water, the mass volume ratio of wilkinite and arsenic-containing waste water is 1g:100mL, through stirring, realize simultaneously that the arsenic contamination object height is imitated in the synthetic and waste water of iron composite bentonite and remove, clearance〉95%, quicken the iron carbonyl precipitation, discharged wastewater met the national standard.
Embodiment 2
(1) in arsenic-containing waste water, adds ozone and carry out preoxidation;
(2) the iron(ic) chloride solid directly is added in the arsenic-containing waste water, the mol ratio of Fe and As is 20;
(3) regulating waste water ph with lime is 6-7, forms the iron carbonyl sorbent material, OH
-With the mol ratio of Fe be 2.5;
(4) wilkinite directly is added in the pretreated arsenic-containing waste water, the mass volume ratio of wilkinite and arsenic-containing waste water is 1g:1000mL, through stirring, realize simultaneously that the arsenic contamination object height is imitated in the synthetic and waste water of iron composite bentonite and remove, clearance〉95%, acceleration iron carbonyl precipitation, discharged wastewater met the national standard.
Embodiment 3
(1) in arsenic-containing waste water, adds air and carry out preoxidation;
(2) the ferric sulfate solid directly is added in the arsenic-containing waste water, the mol ratio of Fe and As is 15;
(3) regulating waste water ph with lime is 4～5, forms the iron carbonyl sorbent material, OH
-With the mol ratio of Fe be 1.5;
(4) wilkinite directly is added in the pretreated arsenic-containing waste water, the mass volume ratio of wilkinite and arsenic-containing waste water is 1g:1000mL, through stirring, realize simultaneously that the arsenic contamination object height is imitated in the synthetic and waste water of iron composite bentonite and remove, clearance〉95%, acceleration iron carbonyl precipitation, discharged wastewater met the national standard.
Embodiment 4
(1) in arsenic-containing waste water, adds air and carry out preoxidation;
(2) the ferric sulfate solid directly is added in the arsenic-containing waste water, the mol ratio of Fe and As is 30;
(3) regulating waste water ph with lime is 6-7, forms the iron carbonyl sorbent material, OH
-With the mol ratio of Fe be 3.0;
(4) wilkinite directly is added in the pretreated arsenic-containing waste water, the mass volume ratio of wilkinite and arsenic-containing waste water is 1g:10000mL, through stirring, realize simultaneously that the arsenic contamination object height is imitated in the synthetic and waste water of iron composite bentonite and remove, clearance〉95%, acceleration iron carbonyl precipitation, discharged wastewater met the national standard.
Embodiment 5
(1) in arsenic-containing waste water, adds H
2O
2Carry out preoxidation;
(2) the ferric sulfate solid directly is added in the arsenic-containing waste water, the mol ratio of Fe and As is 25;
(3) regulating waste water ph with lime is 5～6, forms the iron carbonyl sorbent material, OH
-With the mol ratio of Fe be 3.5;
(4) wilkinite directly is added in the pretreated arsenic-containing waste water, the mass volume ratio of wilkinite and arsenic-containing waste water is 1g:5000mL, through stirring, realize simultaneously that the arsenic contamination object height is imitated in the synthetic and waste water of iron composite bentonite and remove, clearance〉95%, acceleration iron carbonyl precipitation, discharged wastewater met the national standard.
Embodiment 6
(1) in arsenic-containing waste water, adds H
2O
2Carry out preoxidation;
(2) the ferric sulfate solid directly is added in the arsenic-containing waste water, the mol ratio of Fe and As is 50;
(3) regulating waste water ph with lime is 6-7, forms the iron carbonyl sorbent material, OH
-With the mol ratio of Fe be 3.5;
(4) wilkinite directly is added in the pretreated arsenic-containing waste water, the mass volume ratio of wilkinite and arsenic-containing waste water is 1g:20000mL, through stirring, realize simultaneously that the arsenic contamination object height is imitated in the synthetic and waste water of iron composite bentonite and remove, clearance〉95%, acceleration iron carbonyl precipitation, discharged wastewater met the national standard.
Embodiment 7
0.4kg iron(ic) chloride solid directly is added to 1 ton of pH=7 contains in 5mg/L As (V) waste water, stir 1h, the arsenic in the waste water is removed in absorption.The 1kg calcium-base bentonite directly is added in the arsenic-containing waste water, and remaining arsenic in the waste water is removed in absorption, quickens the iron carbonyl precipitation simultaneously, and the clearance of As in the waste water (V) is reached 97%, discharged wastewater met the national standard.
Embodiment 8
0.4kg iron(ic) chloride solid directly is added to 1 ton of pH=7 through preoxidation contains in the 5mg/LAs waste water, stir 1h, the arsenic in the waste water is removed in absorption.The 1kg calcium-base bentonite directly is added in the arsenic-containing waste water, and remaining arsenic in the waste water is removed in absorption, quickens the iron carbonyl precipitation simultaneously, and the clearance of As in the waste water is reached 97%, discharged wastewater met the national standard.
Claims (8)
1. the integral method of a processing arsenic-containing wastewater by using iron composite bentonite is characterized in that comprising the steps:
(1) in arsenic-containing waste water, adds oxygenant and carry out preoxidation;
(2) the molysite solid directly is added in the arsenic-containing waste water, the mol ratio of Fe and As is 5～50;
(3) regulating waste water ph with lime is 4～7, forms the iron carbonyl sorbent material, OH
-With the mol ratio of Fe be 0.5～5.0;
(4) wilkinite directly is added in the pretreated arsenic-containing waste water, the mass volume ratio of wilkinite and arsenic-containing waste water is 1g:100mL～1g:20000mL, through stirring, realizes simultaneously that the arsenic contamination object height is imitated in the synthetic and waste water of iron composite bentonite to remove, acceleration iron carbonyl precipitation, discharged wastewater met the national standard.
2. the integral method of a kind of processing arsenic-containing wastewater by using iron composite bentonite according to claim 1 is characterized in that described oxygenant comprises ozone, pure oxygen, air, H
2O
2Or MnO
2
3. the integral method of a kind of processing arsenic-containing wastewater by using iron composite bentonite according to claim 1 is characterized in that described molysite is iron(ic) chloride or ferric sulfate.
4. the integral method of a kind of processing arsenic-containing wastewater by using iron composite bentonite according to claim 1, the mol ratio that it is characterized in that described Fe and As is 20～40.
5. the integral method of a kind of processing arsenic-containing wastewater by using iron composite bentonite according to claim 1 is characterized in that described waste water ph is 5～7.
6. the integral method of a kind of processing arsenic-containing wastewater by using iron composite bentonite according to claim 1 is characterized in that described OH
-With the mol ratio of Fe be 2～4.
7. the integral method of a kind of processing arsenic-containing wastewater by using iron composite bentonite according to claim 1 is characterized in that described wilkinite is the calcium-base bentonite original soil.
8. the integral method of a kind of processing arsenic-containing wastewater by using iron composite bentonite according to claim 1, it is characterized in that adding in the described arsenic-containing waste water product that oxygenant carries out after the preoxidation is H
2AsO
4 -, HAsO
4 2-Or/and AsO
4 3-
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| CN102765800A (en) * | 2012-08-13 | 2012-11-07 | 常州大学 | Treatment method of organic wastewater through synthesis-free heterogeneous Fenton treatment |
| CN102764759A (en) * | 2012-07-31 | 2012-11-07 | 湖南永清环境修复有限公司 | Remediation agent for treating arsenic contaminated soil and usage of remediation agent |
| CN102872825A (en) * | 2012-09-04 | 2013-01-16 | 常州大学 | Composite adsorption material for removing arsenic ions from natural water and preparation method for adsorption material |
| CN103663779A (en) * | 2013-11-19 | 2014-03-26 | 苏州丹百利电子材料有限公司 | Method for safely and efficiently treating arsenic waste water generated from arsenic hydride production |
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| CN102764759B (en) * | 2012-07-31 | 2013-11-13 | 永清环保股份有限公司 | Remediation agent for treating arsenic contaminated soil and usage of remediation agent |
| CN102765800A (en) * | 2012-08-13 | 2012-11-07 | 常州大学 | Treatment method of organic wastewater through synthesis-free heterogeneous Fenton treatment |
| CN102872825A (en) * | 2012-09-04 | 2013-01-16 | 常州大学 | Composite adsorption material for removing arsenic ions from natural water and preparation method for adsorption material |
| CN103663779A (en) * | 2013-11-19 | 2014-03-26 | 苏州丹百利电子材料有限公司 | Method for safely and efficiently treating arsenic waste water generated from arsenic hydride production |
| CN105233838A (en) * | 2015-11-09 | 2016-01-13 | 广东省环境科学研究院 | Preparation method of O3/H2O2 catalyst using activated bentonite as carrier, catalyst and application thereof |
| CN105645635A (en) * | 2016-01-12 | 2016-06-08 | 浙江大学 | Physicochemical treatment method of disperse dye wastewater |
| CN105668897A (en) * | 2016-03-18 | 2016-06-15 | 昆明冶金研究院 | Method for dearsenization of arsenic containing waste water generated in regeneration process of vanadium, tungsten and titanium denitration catalyst |
| CN106219921A (en) * | 2016-08-31 | 2016-12-14 | 新奥生态环境治理有限公司 | The processing means of heavy metal arsenic in water sludge |
| CN106380048A (en) * | 2016-08-31 | 2017-02-08 | 新奥生态环境治理有限公司 | Harmless arsenic treatment technology |
| CN106380048B (en) * | 2016-08-31 | 2019-05-28 | 新奥生态环境治理有限公司 | The technique of harmless treatment arsenic |
| CN106219921B (en) * | 2016-08-31 | 2019-05-28 | 新奥生态环境治理有限公司 | The processing unit of heavy metal arsenic in water sludge |
| CN107188292A (en) * | 2017-05-19 | 2017-09-22 | 山东国大黄金股份有限公司 | A kind of utilization silver extraction by cyanidation waste residue purifies the method containing arsenic waste solution |
| CN108249625A (en) * | 2017-10-29 | 2018-07-06 | 中国有色集团（广西）平桂飞碟股份有限公司 | A kind of method of flue gas during smelting spray liquid plural serial stage absorption arsenic removal |
| CN108217895A (en) * | 2018-03-02 | 2018-06-29 | 武汉理工大学 | A kind of method of efficient process arsenic-containing waste water |
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| CN115259454B (en) * | 2022-07-15 | 2023-08-29 | 浙大城市学院 | Treatment method of arsenic-containing acidic wastewater in wide pH range |
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Open date: 20090708 |