CN104016435B - The method of pentavalent inorganic arsenic in Adsorption water - Google Patents
The method of pentavalent inorganic arsenic in Adsorption water Download PDFInfo
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- CN104016435B CN104016435B CN201410234826.4A CN201410234826A CN104016435B CN 104016435 B CN104016435 B CN 104016435B CN 201410234826 A CN201410234826 A CN 201410234826A CN 104016435 B CN104016435 B CN 104016435B
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Abstract
The present invention is to provide the method for pentavalent inorganic arsenic in a kind of Adsorption water.(1) in containing the water of As (V), ferrous salt is dropped into; (2) in containing the water of As (V), carbide material is dropped into; (3) ferrous salt is fully mixed in water with carbide material.Fe
2+diffusion absorption is carried out on carbide material surface, with the complexing of carbide material surface group, for As in water (V) provides activated adsorption position, realize the efficient adsorption to the As contained in water body (V), thus reach the object effectively removing As (V) in water.The present invention does not need costliness and the preparation process of the metal-adsorbing material of complexity, secondary pollution can not be produced, the dearsenicating method provided, greatly can improve the arsenic removal usefulness of simple carbide material sorbing material, can be used for controlling the arsenic concentration in tap water, underground water, industrial arsenic-containing waste water and sewage secondary clarifier effluent, reach relevant national standard.
Description
Technical field
What the present invention relates to is a kind of water treatment method, specifically a kind of method removing As (V) in water.
Background technology
Arsenic (As) is the quasi-representative pollutent in water, and its pollution problem is mainly reflected in underground water.The arsenic of occurring in nature exists with the form of inorganic arsenic (arsenite and arsenate) usually, also containing the organoarsenic such as a small amount of first arsenic acid (MMA) and dimethyl arsenate (DMA).The toxicity size of these arsenides is followed successively by from high to low: inorganic arsenic (III) > organoarsenic (III) > inorganic arsenic (V) > organoarsenic (V), wherein, the toxicity of trivalent inorganic arsenic As (III) is 60 times of pentavalent inorganic arsenic As (V), also be the main existence form of arsenic in underground water, be easy to be converted into As (V) by mode of oxidizing As (III), therefore, in water treatment procedure, As (V) is the main arsenic pollutent controlled.
Systematic study shows, long-term exposure can cause body arsenicalism in low dosage containing arsenic tap water, and then cause the diseases such as heredity is poisoning, myocardial atrophy, diabetes, immunity system weakening, long-term exposure can cause skin carcinoma, lung cancer etc. in the arsenic tap water of high density, arsenic compound has been confirmed as carcinogens by the authoritative institutions such as the World Health Organization (WHO) and EPA (USEPA), therefore, in state's regulation tap water such as WHO, USEPA, European Union, Japan, China, the highest permission reduces to 10 μ g/L containing arsenic mass concentration by 50 original μ g/L.In recent years, the Chilean northern territory underground water of South America pollutes very serious by arsenic, be that in world wide, underground water pollutes country the most serious by arsenic, Supreme Procuratorate goes out concentration up to 21mg/L; The underground water of some countries of South East Asia and North America also receives the severe contamination of arsenic, and concentration is up to 10mg/L; High-arsenic underground water district of China is mainly distributed in 40 counties (flag, city) in province (autonomous region) districts such as Inner Mongol, Xinjiang, Shanxi, Taiwan, in underground water, Supreme Procuratorate goes out concentration and is about 2mg/L, and the high arsenic population of exposure that in drinking-water, arsenic content is greater than 50 μ g/L has exceeded nearly million people.These high arsenic pollute and cause a lot of endemic arseniasis event, become a large problem of world's drinking water safety.Country's " 12 " prevention and cure of endemic diseases planning clearly proposes to pollute region arsenic to fall arsenic engineering construction, guarantees that Drinking Water meets state health standards, visible, and the arsenic controlled in water pollutes, imperative.
The removal ability of conventional water treatment (coagulation, precipitation, filtration) process to As in water (V) is very limited.Adsorption technology is a kind of effective technology removing water pollutant, study about the absorption of arsenic in water at present, majority concentrates in metal oxide absorption, and this type of sorbent material has good arsenic removal usefulness, but there is the problems such as expensive, regeneration difficulty, operation expense are high in metal oxide absorption, be difficult to be applied in existing water factory, particularly high arsenic area is fallen behind for some, without potable water treatment plants, to be more difficultly used directly.Comparatively speaking, gac is a kind of well sorbing material, has been widely used in the removal of Organic substance in water and inorganics, adopts charcoal absorption to be considered to the effective technology controlling a kind of simple, economic of water pollutant and be convenient to practical application.Commercial gac has been in the news and has had certain adsorptive power to As (V), but comparatively other sorbing material such as metal oxide is poor for arsenic removal ability, therefore adopt gac direct absorption arsenic removal report less, more that the method for employing at carbon surface depositing metal oxide is to improve the adsorptive power of arsenic, but this mode can cause metal oxide uneven in activated carbon surface deposition distribution, and then cause the absorption of gac localized accumulated to be difficult to give full play to adsorptive power, affect (pH≤3 are best) greatly by system pH, reduction is to problems such as the removals of coexisted organic compounds, strongly limit the treatment efficiency of carried by active carbon metal oxide materials arsenic removal and actually to apply.Based on these problems, consider, seek a kind of method of efficient hardening charcoal absorption arsenic removal technology from Environmental capacity and technology application point, the arsenic controlled in water pollutes, and has profound significance.
Summary of the invention
The object of the present invention is to provide a kind of removal effect good, the method for pentavalent inorganic arsenic in the Adsorption water that cost is low.
The object of the present invention is achieved like this:
(1) in containing the water of As (V), ferrous salt is dropped into;
(2) in containing the water of As (V), carbide material is dropped into;
(3) ferrous salt is fully mixed in water with carbide material.
Above-mentioned steps (1) and (2) priority in out-of-order point, first can drop into ferrous salt, also first can drop into carbide material, also ferrous salt and carbide material can be fed in pending water simultaneously.
The present invention can also comprise:
1, described ferrous salt is iron protochloride or ferrous sulfate or its combination.The ferrous salt Fe dropped into
2+be 0.25:1 ~ 8:1 with the mol ratio of As in water (V).The ferrous salt Fe dropped into
2+4:1 is preferably with the mol ratio of As in water (V).
2, described carbide material is gac, carbon nanotube, carbon fiber or its combination.Fe in the quality of carbide material dropped into and ferrous salt
2+mass ratio be 20:1 ~ 1600:1.Fe in the quality of carbide material dropped into and ferrous salt
2+mass ratio be preferably 100:1.
The present invention is directed to conventional water treatment process poor to As in water (V) adsorption effect, the situations such as metal oxide adsorption technology is large by system parameter influence, cost is higher, regeneration is difficult, propose the method for As (V) in a kind of Adsorption water.
In Adsorption water of the present invention, the reaction mechanism of the method for As (V) is: when carbide material mixes by a certain percentage with ferrous salt, Fe
2+by diffusing into (micropore, mesopore, macropore) in the hole of carbide material, with the acid oxy radical complexing on carbide material surface, for As (V) provides more adsorption activity position, thus reach the efficient object except As (V).
The method of As (V) in Adsorption water of the present invention, relative to being conventionally used for the coagulation, precipitation, filtration, biological dearsenicating method etc. of removing As (V) in water at present, there is the advantages such as adsorption efficiency is high, with low cost, technique is simple, running maintenance is convenient; For metal oxide arsenic-removing adsorption agent and the application of current wide coverage, present method has efficient stable, regeneration with low cost, capable of washing, non-metallic ion stripping, the contaminant removal efficiency that coexists is high and be convenient to the features such as existing water factory application.
The present invention, by dropping into appropriate sorbent material (ferrous salt and carbide material) to containing in the pending water of As (V), stirs and sorbent material is fully adsorbed wherein.Fe
2+diffusion absorption is carried out on carbide material surface, with the complexing of carbide material surface group, for As in water (V) provides activated adsorption position, realize the efficient adsorption to the As contained in water body (V), thus reach the object effectively removing As (V) in water.The present invention does not need costliness and the preparation process of the metal-adsorbing material of complexity, secondary pollution can not be produced, the dearsenicating method provided, greatly can improve the arsenic removal usefulness of simple carbide material sorbing material, can be used for controlling the arsenic concentration in tap water, underground water, industrial arsenic-containing waste water and sewage secondary clarifier effluent, reach relevant national standard.
Accompanying drawing explanation
Fig. 1 is the removal rate profile of the method one of As (V) in Adsorption water of the present invention, and wherein █ is the adsorpting rate curve of method one, ▲ be the adsorpting rate curve of pure gac.
Fig. 2 is the removal rate profile of the method two of As (V) in Adsorption water of the present invention, and wherein █ is the adsorpting rate curve of method two, ▲ be the adsorpting rate curve of pure gac.
Fig. 3 is the removal rate profile of the method three of As (V) in Adsorption water of the present invention, and wherein █ is the adsorpting rate curve of method three, ▲ be the adsorpting rate curve of pure gac.
Fig. 4 is the removal rate curve comparison diagram of the method three of As (V) in Adsorption water of the present invention, method four, method five, wherein █ is the adsorpting rate curve of method three, ▲ be the adsorpting rate curve of method four, ● be the adsorpting rate curve of method five.
Fig. 5 is the removal rate profile of the method six of As (V) in Adsorption water of the present invention, and wherein █ is the adsorpting rate curve of method six, ▲ be the adsorpting rate curve of pure nano-carbon tube.
Fig. 6 is the removal rate profile of the method seven of As (V) in Adsorption water of the present invention, and wherein █ is the adsorpting rate curve of method seven, ▲ be the adsorpting rate curve of pure carbon fiber.
Fig. 7 is the removal rate profile of the method eight of As (V) in Adsorption water of the present invention, and wherein █ is the adsorpting rate curve of method eight, ▲ be pure gac and the adsorpting rate curve of carbon nanotube mass than 1:1 mixture.
Fig. 8 is the removal rate profile of the method nine of As (V) in Adsorption water of the present invention, wherein █ is the adsorpting rate curve of method nine, ▲ be the adsorpting rate curve of pure gac, carbon nanotube and carbon fiber mass ratio 2:2:1 mixture.
Embodiment
Technical solution of the present invention includes but not limited to following cited specific embodiment.
Method one: to pending containing (wherein the content of As (V) is 5mg/L) in As (V) water, add iron protochloride and gac, wherein the throwing amount of iron protochloride is according to Fe
2+be that 8:1 calculates and obtains with the mol ratio of As (V); The throwing amount of gac is according to gac and Fe
2+mass ratio be 20:1 calculate obtain; After mixing, the pH of solution controls near 7.0, and temperature controls near 25 DEG C, and under 150r/min condition, concussion mixing, makes sorbent material play one's part to the full in the solution, and after stable, in pending water, the clearance of As (V) is close to 100%.Be the process condition of As (V) in method one Adsorption water shown in Fig. 1, and with the contrast of pure charcoal absorption situation, visual method one is removed As in water (V) more former gac and is increased significantly.
Method two: to pending containing (wherein the content of As (V) is 5mg/L) in As (V) water, add iron protochloride and gac, wherein the throwing amount of iron protochloride is according to Fe
2+be that 0.25:1 calculates and obtains with the mol ratio of As (V); The throwing amount of gac is according to gac and Fe
2+mass ratio be 1600:1 calculate obtain; After mixing, the pH of solution controls near 7.0, and temperature controls near 25 DEG C, and under 150r/min condition, concussion mixing, makes sorbent material play one's part to the full in the solution, and after stable, in pending water, the clearance of As (V) is close to 60%.Be the process condition of As (V) in method two Adsorption water shown in Fig. 2, and with the contrast of pure charcoal absorption situation, visual method two is removed As in water (V) more former gac and is improved.
Method three: to pending containing (wherein the content of As (V) is 5mg/L) in As (V) water, add iron protochloride and gac, wherein the throwing amount of iron protochloride is according to Fe
2+be that 4:1 calculates and obtains with the mol ratio of As (V); The throwing amount of gac is according to gac and Fe
2+mass ratio be 100:1 calculate obtain; After mixing, the pH of solution controls near 7.0, and temperature controls near 25 DEG C, and under 150r/min condition, concussion mixing, makes sorbent material play one's part to the full in the solution, and after stable, in pending water, the clearance of As (V) is close to 100%.Be the process condition of As (V) in method three Adsorption water shown in Fig. 3, and with the contrast of pure charcoal absorption situation, visual method three is removed As in water (V) more former gac and is increased significantly.
Method four: to pending containing (wherein the content of As (V) is 5mg/L) in As (V) water, add iron protochloride and gac, wherein the throwing amount of iron protochloride is according to Fe
2+be that 4:1 calculates and obtains with the mol ratio of As (V); The throwing amount of gac is according to gac and Fe
2+mass ratio be 20:1 calculate obtain; After mixing, the pH of solution controls near 7.0, and temperature controls near 25 DEG C, and under 150r/min condition, concussion mixing, makes sorbent material play one's part to the full in the solution, and after stable, in pending water, the clearance of As (V) reaches 64%.
Method five: to pending containing (wherein the content of As (V) is 5mg/L) in As (V) water, add iron protochloride and gac, wherein the throwing amount of iron protochloride is according to Fe
2+be that 4:1 calculates and obtains with the mol ratio of As (V); The throwing amount of gac is according to gac and Fe
2+mass ratio be 1600:1 calculate obtain; After mixing, the pH of solution controls near 7.0, and temperature controls near 25 DEG C, and under 150r/min condition, concussion mixing, makes sorbent material play one's part to the full in the solution, and after stable, in pending water, the clearance of As (V) is close to 100%.
Adsorption rate correlation curve in the process of As (V) in the method three of As (V) in above-mentioned removal water, method four, method five Adsorption water is shown in Fig. 4.Can find out, Fe
2+throwing amount too high (i.e. method four), the clearance of As (V) is relatively low; Meanwhile, Fe
2+throwing amount too low (i.e. method five), although the clearance of As (V) is relatively high, high clearance may be caused by greater activity charcoal throwing amount, therefore uneconomical.
Method six: to pending containing (wherein the content of As (V) is 5mg/L) in As (V) water, add ferrous sulfate and carbon nanotube, wherein the throwing amount of ferrous sulfate is according to Fe
2+be that 4:1 calculates and obtains with the mol ratio of As (V); The throwing amount of carbon nanotube is according to carbon nanotube and Fe
2+mass ratio be 100:1 calculate obtain; After mixing, the pH of solution controls near 7.0, and temperature controls near 25 DEG C, and under 150r/min condition, concussion mixing, makes sorbent material play one's part to the full in the solution, and after stable, in pending water, the clearance of As (V) reaches 90%.Be the process condition of As (V) in method six Adsorption water shown in Fig. 5, and adsorb the contrast of situation with pure nano-carbon tube, visual method six is removed As in water (V) more former carbon nanotube and is increased significantly.
Method seven: to pending containing (wherein the content of As (V) is 5mg/L) in As (V) water, add iron protochloride, ferrous sulfate and carbon fiber, wherein Fe in water
2+be that 4:1 calculates and obtains with the mol ratio of contained As (V), iron protochloride and ferrous sulfate in molar ratio 1:1 add; The throwing amount of carbon fiber is that 100:1 calculates and obtains according to the mass ratio of Fe2+ total amount in carbon fiber and water; After mixing, the pH of solution controls near 7.0, and temperature controls near 25 DEG C, and under 150r/min condition, concussion mixing, makes sorbent material play one's part to the full in the solution, and after stable, in pending water, the clearance of As (V) reaches 95%.Be the process condition of As (V) in method seven Adsorption water shown in Fig. 6, and adsorb the contrast of situation with pure carbon fiber, visual method seven is removed As in water (V) more former carbon nanotube and is increased significantly.
Method eight: to pending containing (wherein the content of As (V) is 5mg/L) in As (V) water, add ferrous sulfate, gac and carbon nanotube, wherein the throwing amount of ferrous sulfate is according to Fe
2+be that 4:1 calculates and obtains with the mol ratio of As (V); The throwing amount of carbide is according to itself and Fe
2+mass ratio be that 100:1 calculates and obtains, carbide by gac and carbon nanotube in mass ratio 1:1 add and obtain; After mixing, the pH of solution controls near 7.0, and temperature controls near 25 DEG C, and under 150r/min condition, concussion mixing, makes sorbent material play one's part to the full in the solution, and after stable, in pending water, the clearance of As (V) is close to 100%.The process condition of As (V) in method eight Adsorption water is shown in Fig. 7, and adsorbing the contrast of situation than 1:1 mixture with pure gac and carbon nanotube mass, visual method eight is removed the more former pure gac of As in water (V) and is increased significantly than 1:1 mixture with carbon nanotube mass.
Method nine: to pending containing (wherein the content of As (V) is 5mg/L) in As (V) water, add iron protochloride, ferrous sulfate, gac, carbon nanotube and carbon fiber, wherein Fe in water
2+be that 4:1 calculates and obtains with the mol ratio of contained As (V), iron protochloride and ferrous sulfate in molar ratio 3:2 add; The throwing amount of carbide is according to itself and Fe
2+mass ratio be that 100:1 calculates and obtains, carbide by gac, carbon nanotube, carbon fiber three in mass ratio 2:2:1 add and obtain; After mixing, the pH of solution controls near 7.0, and temperature controls near 25 DEG C, and under 150r/min condition, concussion mixing, makes sorbent material play one's part to the full in the solution, and after stable, in pending water, the clearance of As (V) is close to 100%.The process condition of As (V) in method nine Adsorption water is shown in Fig. 8, and adsorbing the contrast of situation with pure gac, carbon nanotube and carbon fiber mass ratio 2:2:1 mixture, visual method nine is removed the more former pure gac of As in water (V), carbon nanotube and carbon fiber mass ratio 2:2:1 mixture and is increased significantly.
Claims (5)
1. the method for pentavalent inorganic arsenic in Adsorption water, is characterized in that:
(1) in containing the water of As (V), ferrous salt is dropped into, the ferrous salt Fe of input
2+be 0.25:1 ~ 8:1 with the mol ratio of As in water (V);
(2) in containing the water of As (V), drop into carbide material, described carbide material is gac, carbon nanotube, carbon fiber or its combination;
(3) ferrous salt is fully mixed in water with carbide material, Fe
2+by diffusing in the hole of carbide material, with the acid oxy radical complexing on carbide material surface, for As (V) provides adsorption activity position to remove pentavalent inorganic arsenic in water.
2. the method for pentavalent inorganic arsenic in Adsorption water according to claim 1, is characterized in that: described ferrous salt is iron protochloride or ferrous sulfate or its combination.
3. the method for pentavalent inorganic arsenic in Adsorption water according to claim 2, is characterized in that: the ferrous salt Fe of input
2+be 4:1 with the mol ratio of As in water (V).
4. the method for pentavalent inorganic arsenic in Adsorption water according to claim 3, is characterized in that: Fe in the quality of the carbide material of input and ferrous salt
2+mass ratio be 20:1 ~ 1600:1.
5. the method for pentavalent inorganic arsenic in Adsorption water according to claim 4, is characterized in that: Fe in the quality of the carbide material of input and ferrous salt
2+mass ratio be 100:1.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6461535B1 (en) * | 1999-12-03 | 2002-10-08 | Pan American Health Organization | Composition for arsenic removal from ground water |
| CN1506329A (en) * | 2002-12-10 | 2004-06-23 | 中国科学院生态环境研究中心 | Treating process of underground water with high arsenic content |
| CN101920191A (en) * | 2010-06-12 | 2010-12-22 | 华中农业大学 | Application of activated carbon modified material and application in removing arsenic from water |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6461535B1 (en) * | 1999-12-03 | 2002-10-08 | Pan American Health Organization | Composition for arsenic removal from ground water |
| CN1506329A (en) * | 2002-12-10 | 2004-06-23 | 中国科学院生态环境研究中心 | Treating process of underground water with high arsenic content |
| CN101920191A (en) * | 2010-06-12 | 2010-12-22 | 华中农业大学 | Application of activated carbon modified material and application in removing arsenic from water |
Non-Patent Citations (1)
| Title |
|---|
| "改进型除砷剂的研究";樊荣涛等;《中国卫生检验杂志》;20050930;第15卷(第9期);摘要、第1128页左栏第1行至1129页右栏第12行 * |
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