CN104289708B - Nitrate or the method for chlorine disinfection by-product in a kind of deoxidization, degradation water - Google Patents
Nitrate or the method for chlorine disinfection by-product in a kind of deoxidization, degradation water Download PDFInfo
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- CN104289708B CN104289708B CN201410482530.4A CN201410482530A CN104289708B CN 104289708 B CN104289708 B CN 104289708B CN 201410482530 A CN201410482530 A CN 201410482530A CN 104289708 B CN104289708 B CN 104289708B
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Abstract
The invention discloses nitrate or the alfer powder body material of chlorine disinfection by-product in a kind of deoxidization, degradation water, it is prepared by following steps: ingot iron and fine aluminium are added heat fusing 1 2h at 1000～1800 DEG C by a.；B. cool down melted ferroaluminium and crushed, obtaining alfer powder body material.The invention also discloses nitrate or the method for chlorine disinfection by-product in a kind of deoxidization, degradation water, by the pending water containing nitrate or chlorine disinfection by-product by loading the filter post of above-mentioned alfer powder body material.The present invention has economical and efficient, advantage simple to operate, has good economy and environmental benefit.
Description
Technical field
The invention belongs to water treatment field, be specifically related to a kind of deoxidization, degradation and process nitrate and the new material of chlorine disinfection by-product and method in water.
Background technology
Along with improving constantly of industrialized level, the whole world water body more than 25% is contaminated, and how to process polluted water body and makes it be converted into safe drinking water, become we mankind have to faced by a significant task.
Former water enters after water factory while using disinfectant to carry out sterilizing, and the substance reaction such as disinfectant chlorine and natural organic matter, humic acid and the man-made pollutant in former water produces disinfection byproduct (DBP)----carbon tetrachloride, chloroform, the trichloroacetic acid etc. to human health.Nervous system, liver or the kidney etc. of human or animal, with healthy, caused damage and have " three cause " effect (carcinogenic, teratogenesis, mutagenesis) by these chlorine disinfection by-products harm Environmental security.According to national drinking water standard, carbon tetrachloride content in water body must not exceed 2 μ g/L, and chloroform content in water body must not exceed 60 μ g/L, and trichloroacetic acid content in water body must not exceed 100 μ g/L.
In water, azotate pollution is mainly produced by human being's production and life, and agricultural fertilizer, sanitary sewage, industrial wastewater etc. enter body of groundwater after oozing under leaching.Subsoil water after drinking by azotate pollution can serious harm health.Nitrate is reduced to nitrite under nitrate reduction bacterium and metabolism in people's intestinal, may result in " blue baby is sick "；Additionally, nitrate also easily induced tumor disease.World Health Organization's regulation Nitrate In Drinking Water content should be less than 50mg/L, and content of nitrite is less than 3mg/L, and (nitrate concentration/50+ nitrite concentration/3)≤1mg/L.U.S. Environmental Protection Agency (EPA) and Canada's environmental organization regulation nitrate ceiling value are 10mg-N/L, and nitrite ceiling value is 1mg-N/L.
Remove the main method of disinfection byproduct (DBP) in water both at home and abroad and have physical method and the electronation edman degradation Edmans such as vaporizing extract process, extraction, absorption method.Chemical reduction method commonly utilizes the reproducibility organic chlorine-containing compound of degraded of metal self, thus is removed one by one by the chlorine element in organic chlorine-containing compound so that it is become nontoxic chloride ion and hydro carbons.Simple substance iron powder is cheap, has stronger reproducibility, is widely used in the chlorine organic in deoxidization, degradation water body.Helland et al. uses fe powder body material to remove the carbon tetrachloride of 1.5-5.5 μM in water, finds under anaerobic, and it can quickly be removed by Zero-valent Iron, and therein 49% is converted into chloroform.But, particle diameter is that the Zero-valent Iron of micron or millimeter is relatively low to some chlorinated organics reactivity, and degraded not exclusively, has substantial amounts of iron ion to generate during degraded, and its surface can form passivation layer, thus cause the decline of degradation rate.Pure aluminum light weight, reproducibility is strong, but the aluminum oxide film of its surface compact has been passivated the reactivity of aluminum, and application is extremely restricted.There is scholar will prepare the degraded of Fe-Al bimetallic material using aluminum as inner layer metal and remove carbon tetrachloride in water, this material prevents the corrosion product deposition of material surface ferrum using Al as electron donor thus keeps ironing surface more new state, but the Fe-Al bimetallic material prepared is the deposition of iron surface at alumina particles, course of reaction easily comes off, causes treatment effect unstable.Additionally, it is stubborn problem that nano material separates in engineer applied with water body, the impact of the secondary pollution of the water body nano material that it causes can not be ignored.
In water, the minimizing technology of nitrate currently mainly has physical-chemical process, biological denitrification method and chemical reduction method.In metal deoxidization removal water, nitrate is swift in response compared with bioanalysis, technique is simple, it is small-sized to be suitable to and dispersion processes.Zero-valent metal, such as Zero-valent Iron, aluminum etc., can effectively remove nitrate in water.Aluminum can effectively remove nitrate in water in the basic conditions.Under weak basic condition (pH=8), alumina particles Surface Creation protective sull, cover in metal surface.Along with pH raises, metal surface protection thin film gradually dissolves, nitrate in the removable water of metallic aluminium exposed.When pH=10.25, aluminum is selectively removed nitrate in water, to the nitrate of 100mg/L in 10min clearance up to 70%.During groundwater remediation frequently with permeable reactive wall technology, i.e. insert in contaminated underground water body Zero-valent Iron as body of wall in reducing agent.When Zero-valent Iron removes nitrate in water, metallic iron surface can gradually form one layer of iron oxides or hydroxide passivating layer, thus reduces the further reduction even stoping ferrum to nitrate.Zero-valent Iron is generally applied to the removal of nitrate in water when low pH.Metallic iron removes nitrate in water, having many problems demand to solve, must carry out in acid condition including reaction, the nitrogen selective of product is the highest, ferrum dissolution causes colourity in water outlet to exceed standard, and the generation of oxidation on metal surface thing and hydroxide stops the problems such as reaction is carried out further.
United States Patent (USP) US 5,069,800 of Murphy discloses a kind of to the chemical method of denitrogenation of water, nitrate during alternative removes water when the method has sulfate and chloride ion to coexist in alkaline solution, and aluminum and water react the material consumed and can almost ignore；Needed for solution reaction, pH value is higher, is applied to be restricted when water factory processes the former water that pH value is neutral range.The Chinese patent CN102744041A of Li Fulin et al. discloses permeable reactive barrier packing material removing nitrate and preparation method thereof, react iron powder, activated carbon and coarse sand that the pretreatment that packing material within the walls is volume ratio 3:1:6 is arrived, for the repairing and treating of high concentration nitrate IA.The Chinese patent CN 103570114A of Lu Yongsheng et al. discloses a kind of method of nitrate in reduction treatment water, puts into patina class material and react in containing nitrate wastewater, removes the nitrate of more than 95% in 4h；Nitrogen removal rate 35%.
The problem using aluminum or ferrum simple substance to be primarily present during removing pollutant at present is that material surface easily generates metal-oxide or hydroxide stops reaction to carry out further；Therefore, pure aluminum and fe typically require and carry out under specific pH value (alkalescence or acid), to avoid the problem of passivation of metal surfaces as far as possible, and need to be adjusted a large amount of pending waste water the work of pH value in practice, wasting time and energy, cost improves.Additionally, with pure aluminum or fe reduce nitrate time, in nitrate reduction product, ammonia nitrogen proportion is higher, and the nitrate transformation of even more than 90% is ammonia nitrogen；Disinfection byproduct (DBP) deoxidization, degradation speed is slower.
Summary of the invention
Present invention aims to the deficiencies in the prior art, it is provided that nitrate and the material of chlorine disinfection by-product and method in a kind of deoxidization, degradation water.The present invention utilizes the reproducibility of alfer, under near-neutral sulfite deinking, nitrate is reduced, process the water body by azotate pollution；Under condition of different pH, chlorine disinfection by-product is carried out deoxidization, degradation, processes the water body polluted by chlorine disinfection by-product.
One aspect of the present invention relates to nitrate and the alfer powder body material of chlorine disinfection by-product in a kind of deoxidization, degradation water, and it is prepared by following steps:
A. ingot iron and fine aluminium are added heat fusing 1-2h at 1000～1800 DEG C；
B. cool down melted ferroaluminium and crushed, obtaining alfer granule.
Described melting process can be carried out in electric furnace, and whole preparation process can be carried out under air atmosphere.
In preferred embodiments, in described material, the mass ratio of total aluminum and total ferrum is (40%～90%): (60%～10%).
In preferred embodiments, described alfer has ferromagnetism.
In preferred embodiments, the density of described alfer is 1.9～4.7g/cm3。
In preferred embodiments, may be screened after crushing.Such as, the particle diameter of described alfer powder body material can be 0.3～3.0mm.
Second aspect present invention relates to nitrate or the method for chlorine disinfection by-product in a kind of deoxidization, degradation water, it includes contacting the alfer powder body material of the water containing nitrate or chlorine disinfection by-product with nitrate in above-mentioned deoxidization, degradation water or chlorine disinfection by-product, comes nitrate described in deoxidization, degradation or disinfection byproduct (DBP).
In preferred embodiments, described chlorine disinfection by-product includes chloroform, carbon tetrachloride or trichloroacetic acid.
Wherein when described method nitrate in the deoxidization, degradation water, by the water containing nitrate in a looping fashion, such as flow through the reaction column equipped with described alfer powder body material by peristaltic pump: wherein the initial concentration of nitrate in terms of nitrogen in the range of 10～100mg/L；React under the near-neutral sulfite deinking that pH is 6.5～8.0；The dosage of alfer is 100～400g/L.Flow velocity can be 2.5～3.5ml/s.
Wherein when described method trichloroacetic acid disinfection byproduct (DBP) in the deoxidization, degradation water, by the water containing disinfection byproduct (DBP) trichloroacetic acid in a looping fashion, such as the reaction column equipped with described alfer powder body material is flowed through by peristaltic pump: wherein the initial concentration of trichloroacetic acid is in the range of 1～20mg/L；Do not regulate the initial pH of solution to react；The dosage of alfer is 100～400g/L.Flow velocity can be 2.5～3.5ml/s
Wherein when the described method little molecule disinfection byproduct (DBP) in the deoxidization, degradation water, water containing little molecule disinfection byproduct (DBP) is flowed through the reaction column equipped with described alfer powder body material in the way of disposable post excessively: wherein the initial concentration of carbon tetrachloride is less than 20 μ g/L, and the initial concentration of chloroform is less than 200 μ g/L；Do not regulate the initial pH of solution to react；The dosage of alfer is 100～400g/L.Wherein, described little molecule disinfection byproduct (DBP) includes carbon tetrachloride or chloroform.Flow velocity can be 1～1.5ml/s
In the present invention, when the water body containing nitrate or disinfection byproduct (DBP) passes through the Filter column equipped with alfer powder body material or filtering ponds with certain flow velocity, in water, nitrate and disinfection byproduct (DBP) are removed by alloy powder material deoxidization, degradation.During deoxidization, degradation, being nitrogen, nitrite and ammonia nitrogen by nitrate transformation, the chlorine that such as chloroform, carbon tetrachloride and trichloroacetic acid etc. contain by disinfection byproduct (DBP) removes successively.Water body leads to Filter column or time filter tank flow velocity is 2.5～3.5ml/s in a looping fashion, can remove the nitrate of more than 99% in 1h, and nitrogen removal rate reaches more than 45%, and trichloroacetic acid clearance is up to 70%；When water body disposably leads to Filter column, and time of contact, < during 2min, carbon tetrachloride clearance was up to more than 50%, and chloroform clearance is up to 23%.
Wherein, nitrogen removal rate computing formula is as follows:
Nitrogen total amount in the front nitrate of the total amount/reaction of various nitrogen forms in solution after the reaction of nitrogen removal rate=1.
From this formula, nitrogen removal rate is the highest, and the nitrate being converted into nitrogen is the most.
The shortcoming that materials A l existing in prior art, Fe and Al-Fe bimetallic nano are existed, and compared with prior art beneficial effects of the present invention is shown in Table 1:
Table 1
The present invention utilizes the corrosion resistance of alfer material high, considerably reducing the corrosion rate using traditional fe powder body as reduction filtering material, the aluminium ion produced because of the trace dissolution of aluminum and ferrum in alloy material in water body and iron ion meet the national standard of correlation water.And the alfer powder body material of the present invention, either reduction nitrate still reduces chlorine disinfection by-product, can play a role under near-neutral sulfite deinking, therefore without pending waste water being carried out preconditioning pH step.Additionally, the alfer material of the present invention can reduce removes almost all of nitrate, and in reduzate, ammonia nitrogen ratio is substantially reduced.Therefore, the present invention is a kind of economical and efficient, simple to operate, and have good economy and environmental benefit removes nitrate or the method for chlorine disinfection by-product in water.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further illustrated, but should not be construed as limitation of the present invention.
Embodiment 1
Cast iron and aluminium ingot are added in smelting furnace with total weight of iron ratio for 40%:60% according to total aluminum, at 1500 DEG C, adds heat fusing.Come out of the stove after cooling, sieve after the alloy breaks down that will obtain, obtain the Al-Fe alloy powder material of particle diameter 10-20 mesh (0.3mm-3mm).Deionized water is used to soak with activated metal material surface Al-Fe alloy material.After filtration, Al-Fe alloy powder material is inserted as filtrate in the lucite post of internal diameter 40mm.
Under room temperature, measuring the aqueous solution that 200ml nitrate concentration is 100mg/L and be placed in conical flask, pH regulator is 7.8 ± 0.1.Peristaltic pump is used to be circulated through the pillar equipped with Al-Fe alloy material filtrate with the flow velocity of 3.0ml/s.Initial reaction stage interval 5min extracts water sample, and after 30min, interval 10min extracts water sample.Each water sample is by, after 0.22 μm filter membrane, being analyzed nitrate, nitrite, ammonia nitrogen, aluminium ion and iron concentration in water.Result shows, reaction only carries out 4min, and in water, the clearance of nitrate reaches 31%, and nitrogen removal rate reaches 31%；After 1h, in water, the clearance of nitrate reaches 100%, and nitrogen removal rate reaches 45%, and in water body, metal ion aluminium ion, iron concentration detect through ICP-MS, concentration < 0.1mg/L.
Embodiment 2
Cast iron and aluminium ingot are added in smelting furnace with total weight of iron ratio for 80%:20% according to total aluminum, at 1300 DEG C, adds heat fusing.Come out of the stove after cooling, sieve after the alloy breaks down that will obtain, obtain the Al-Fe alloy powder material of particle diameter 10-20 mesh (0.3mm-3mm).Deionized water is used to soak with activated metal material surface Al-Fe alloy material.After filtration, Al-Fe alloy powder material is inserted as filtrate in the tool core glass column of internal diameter 35mm.
Under room temperature, measure the solution that 100ml Carbon Tetrachloride Concentration is 10 μ g/L, in the way of disposable post excessively, flow through the filtrate of thickness 7cm.After solution passes through completely, measure 5ml water sample and add in 25ml cillin bottle, after sealing of jumping a queue, keep 1h, extraction upper gas 20 μ L to carry out gas chromatographic detection in 45 DEG C of water-baths.Result shows, after solution crosses post completely, carbon tetrachloride clearance is 38.5%；Metal ion in solution aluminium ion, iron concentration detects through ICP-MS, concentration < 0.1mg/L.
Embodiment 3
Cast iron and aluminium ingot are added in smelting furnace with total weight of iron ratio for 90%:10% according to total aluminum, at 1000 DEG C, adds heat fusing.Come out of the stove after cooling, sieve after the alloy breaks down that will obtain, obtain the Al-Fe alloy powder material of particle diameter 10-20 mesh (0.3mm-3mm).Deionized water is used to soak with activated metal material surface Al-Fe alloy material.After filtration, Al-Fe alloy powder material is inserted as filtrate in the tool core glass column of internal diameter 35mm.
Under room temperature, measure the solution that 100ml chloroform concentration is 100 μ g/L, in the way of disposable post excessively, flow through the filtrate of thickness 7cm.After solution passes through completely, measure 5ml water sample and add in 25ml cillin bottle, after sealing of jumping a queue, keep 1h, extraction upper gas 20 μ L to carry out gas chromatographic detection in 45 DEG C of water-baths.Result shows, after solution crosses post completely, chloroform clearance is 23%；Metal ion in solution aluminium ion, iron concentration detects through ICP-MS, concentration < 0.1mg/L.
Embodiment 4
Cast iron and aluminium ingot are added in smelting furnace with total weight of iron ratio for 90%:10% according to total aluminum, at 1000 DEG C, adds heat fusing.Come out of the stove after cooling, sieve after the alloy breaks down that will obtain, obtain the Al-Fe alloy powder material of particle diameter 10-20 mesh (0.3mm-3mm).Deionized water is used to soak with activated metal material surface Al-Fe alloy material.After filtration, Al-Fe alloy powder material is inserted as filtrate in the lucite post of internal diameter 40mm.
Under room temperature, measure the solution of trichloroacetic acid that 250ml concentration is 20mg/L and be placed in conical flask, do not regulate solution original ph.Peristaltic pump is used to be circulated through the pillar equipped with Al-Fe alloy powder material with the flow velocity of 3.5ml/s.Initial reaction stage interval 5min extracts water sample, and after 30min, interval 10min extracts water sample.Water sample is by, after 0.22 μm filter membrane, being analyzed trichloroacetic acid, aluminium ion and iron concentration in water.Result shows, after 1h, in water, the clearance of trichloroacetic acid reaches 70%, and in water body, metal ion aluminium ion, iron concentration detect through ICP-MS, concentration < 0.1mg/L.
From embodiment, the alfer powder body material of the present invention is good for nitrate in water and chlorine disinfection by-product removal effect, and in use metal dissolving is little in alfer, corrosion resistance is strong, therefore, the present invention is a kind of economical and efficient, simple to operate, and have good economy and environmental benefit removes nitrate or the method for chlorine disinfection by-product in water.
Claims (6)
1. nitrate or a method for chlorine disinfection by-product in deoxidization, degradation water, it includes containing nitrate
Or the water of chlorine disinfection by-product contacts with alfer powder body material, wherein said alfer powder body material
Prepared by following steps:
A. ingot iron and fine aluminium are added heat fusing 1-2h at 1000～1800 DEG C；
B. cool down melted ferroaluminium and crushed, sieve, obtaining alfer powder body material；
Wherein total aluminum is (40%～90%) with the mass ratio of total ferrum: (60%～10%).
Method the most according to claim 1, wherein said chlorine disinfection by-product includes chloroform, four chlorinations
Carbon or trichloroacetic acid.
Method the most according to claim 1, wherein when described method nitrate in the deoxidization, degradation water,
Water containing nitrate is flowed through in a looping fashion the reaction column equipped with described alfer powder body material: its
The initial concentration of middle nitrate in terms of nitrogen in the range of 10～100mg/L；PH be 6.5～8.0 near in
React under the conditions of property；The dosage of alfer is 100～400g/L.
Method the most according to claim 1, the wherein trichloroacetic acid in described method is used for deoxidization, degradation water
During disinfection byproduct (DBP), the water containing disinfection byproduct (DBP) trichloroacetic acid is flowed through in a looping fashion equipped with described aluminum
The reaction column of ferroalloy powder body material: wherein the initial concentration of trichloroacetic acid is in the range of 1～20mg/L；
Do not regulate the initial pH of solution to react；The dosage of alfer is 100～400g/L.
Method the most according to claim 1, wherein includes tetrachloro when described method in the deoxidization, degradation water
Change carbon or chloroform are when interior little molecule disinfection byproduct (DBP), by the water containing little molecule disinfection byproduct (DBP)
The reaction column equipped with described alfer powder body material is flowed through in the way of post: wherein four chlorination by disposable mistake
The initial concentration of carbon is less than 20 μ g/L, and the initial concentration of chloroform is less than 200 μ g/L；Do not regulate molten
The initial pH of liquid reacts；The dosage of alfer is 100～400g/L.
Method the most according to claim 1, the particle diameter of wherein said alfer powder body material is
0.3～3.0mm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410482530.4A CN104289708B (en) | 2014-09-19 | Nitrate or the method for chlorine disinfection by-product in a kind of deoxidization, degradation water |
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| CN201410482530.4A CN104289708B (en) | 2014-09-19 | Nitrate or the method for chlorine disinfection by-product in a kind of deoxidization, degradation water |
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| CN104289708A CN104289708A (en) | 2015-01-21 |
| CN104289708B true CN104289708B (en) | 2017-01-04 |
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