CN102502911A - Method for adsorbing and degrading perchlorate in water - Google Patents
Method for adsorbing and degrading perchlorate in water Download PDFInfo
- Publication number
- CN102502911A CN102502911A CN2011103432056A CN201110343205A CN102502911A CN 102502911 A CN102502911 A CN 102502911A CN 2011103432056 A CN2011103432056 A CN 2011103432056A CN 201110343205 A CN201110343205 A CN 201110343205A CN 102502911 A CN102502911 A CN 102502911A
- Authority
- CN
- China
- Prior art keywords
- perchlorate
- water
- described step
- patina
- sorbent material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the technical field of water treatment, and relates to a method for adsorbing and degrading perchlorate in water. The method comprises the following steps of: (1) adding an adsorbent into water to be treated; (2) adsorbing and degrading perchlorate in water with an adsorbent at a certain rotating speed and certain temperature; and (3) after adsorbing, intercepting, separating and treating the adsorbent in water. In the method, perchlorate in water is adsorbed and degraded by using patina, the effects of synchronous adsorption and degradation of perchlorate into harmless chlorine ions are represented, adsorption time is short, over 90 percent of perchlorate can be adsorbed within 6 hours, degradation rate is over 75 percent, and good economic benefit and environmental benefit are achieved.
Description
Technical field
The invention belongs to water-treatment technology field, relate to the method for perchlorate in a kind of absorption degradation water.
Background technology
The perchlorate is an inert ion extremely stable in the water; Wherein the Oxidation Number of chlorine is+7, the strong oxidation capacity of tool, but the activation energy of reaction is very high; So that it is highly stable under big multiple environmental conditions; Only the high density perchlorate just has strong oxidizing property under dense strong acid condition, and the lower concentration perchlorate has very high chemistry and electrochemical stability, can not be by general reductive agent reduction.Because perchlorate's electric charge and ionic radius and iodide ion are very approaching; It and iodide ion competition get into the Tiroidina of human body, thereby hinder the absorption of iodine, cause the minimizing of Triiodothyronine T3 and T4 resultant quantity; The human thyroglobulin function there is restraining effect, finally influences the growth of human body.
The removal of perchlorate and the technology that pollute to repair adopts mainly contain anionresin and adsorbents adsorb, chemical reduction, electrochemical reduction, biological reducing, membrane separation technique etc.Absorption method and reduction method are the main means of perchlorate removal technology in the water.But it is limited to the perchlorate loading capacity that conventional charcoal absorption method exists, and be prone to cause secondary pollution problems after the absorption; And because the perchlorate rate of reduction is slow, be that the metallic reducing method of representative exists processing efficiency not high again with the Zero-valent Iron, the shortcoming of length consuming time; The biological reducing method need be cultivated the reduction bacterium, length not only consuming time, and can't ensure drinking water safety; Adopt the membrane separation technique cost of equipment high, the quality of film will directly influence removal effect, need in time clean and change film simultaneously, therefore in the popularization of actual production, be restricted.Therefore ripe reasonably perchlorate degradation technique is not arranged at present as yet.
Discovering in recent years under neutrality or alkaline condition, in fe or the ferrous oxidation nitrogen process, can form emerald green or bottle-green powdery substance, and this material is called as patina.It is very easily oxidized in air, is the intermediate product of iron rot, and final product possibly be pyrrhosiderite, lepidocrokile or magnetite.The molecular formula of patina is [Fe
II 6-xFe
III x(OH)
12]
X+[(A)
X/aYH
2O]
X-, be Fe
2+And Fe
3+Oxyhydroxide and the mixture of hydrate, also be the intermediate product of ferrite preparation, have very strong reductibility.The factor that influences the patina reducing power has: specific surface area, interlayer configuration, interlayer charge amount and (Fe
II/ Fe
III).
Domestic and international many scholars have research to the absorption and the reduction characteristic of patina.People such as Ph Refait, Ding Ming think that patina has extremely strong adsorptive power, can reduce some negatively charged ion in the solution, like chromate, nitrate radical, selenate radical etc.Hansen etc. think that the nitrate salt in soil and the throw out percolate is except being changed into N by the microbiological anaerobic denitrification
2O/N
2, also can be reduced into ammonia by the patina in the soil.Reports such as Satapanajaru, directly dechlorination of patina, but active Fe (II) and reactive behavior point can be provided in reaction process, can significantly promote Zero-valent Iron reduction metolachlor.
Chinese patent CN 101481163A, Chinese patent CN 101481155A and Chinese patent CN 101601992A all adopt substance modification gacs such as hydrous iron oxide and tensio-active agent to remove perchlorate in the tap water, have material modified easy desorption and reach absorption deficiency such as can not regenerate after saturated.
Utilize the method for perchlorate in the patina absorption degradation water still not to be reported at present.
Summary of the invention
The objective of the invention is to provide the method for perchlorate in a kind of absorption degradation water to the defective of prior art.
For realizing above-mentioned purpose, the present invention adopts following technical scheme:
The patina that adopts among the present invention has extremely strong absorption property, can be used for handling the water body that receives perchlorate contaminated.
The method of perchlorate in a kind of absorption degradation water comprises following steps:
(1) sorbent material is joined in the pending water:
(2) under certain rotating speed and temperature, the perchlorate in the water is carried out absorption degradation through sorbent material;
(3) after absorption is accomplished, the sorbent material in the water is held back separating treatment.
Described perchlorate is water-soluble perchlorate, one or more in preferred sodium perchlorate, potassium perchlorate or the lithium perchlorate etc.
The starting point concentration of the perchlorate in the described step (1) in the pending water is 200～5000 μ g/L.
The mass ratio of sorbent material and pending water is 1: 50～1: 8 in the described step (1).
Sorbent material is fresh patina (FeFe in the described step (1)
2(SO
4)
4(H
2O)
2), be no more than 24 hours its storage period.
The pH of pending water is 5～10 in the described step (1).
The adsorption time of described step (2) is 15min～6h.
The adsorption temp of described step (2) is 5～35 ℃.
The rotating speed of described step (2) is 120～200rpm.
Sorbent material in the described step (3) is removed through membrane treatment process, and membrane pore size is 0.22～0.45 μ m.
Patina (FeFe of the present invention
2(SO
4)
4(H
2O)
2) synthesize according to the prior art coprecipitation method, that is:
(1) foundation of reaction unit: institute responds and all under anaerobic carries out, and can in the operation box that nitrogen is full of, accomplish.There-necked flask is as the main reaction container, in the bottle air with nitrogen purging after, pour divalence, the ferric iron mixing solutions of certain proportioning into flask.Three bottlenecks connect constant pressure funnel, pH electrode and nitrogen respectively and feed mouth, and the soft rubber ball jam-pack is used in the junction, adopts magnetic agitation, and entire reaction is carried out under nitrogen atmosphere.
(2) the NaOH solution of deoxidation deionized water configuration 0.1mol/L is transferred in the constant pressure funnel.Under anaerobic, continuous magnetic agitation, the flow velocity of alkali lye makes that the mixing solutions pH value in the there-necked flask remains on 6.0 ± 0.1 in the control constant pressure funnel.
(3) dropwise after, continue dripping alkali liquid in solution, observe solution colour simultaneously and change, be 7 up to the pH of solution value, the reaction end.
(4) behind the thermostatic crystallization 24h, filter, promptly obtain patina, in anaerobic environment, preserve.
Described divalence and trivalent iron salt are vitriol, and [Fe
2+]/[Fe
3+]=3 (molar ratio).
The said crystallization temperature of described step (4) is 75 ℃, and crystallization time is 6h.
Be filtered in the described step (4) and use the quantitative paper suction filtration, and cause no iron ion with the deoxidation deionized water rinsing and detect.
Anaerobic environment is preserved in the described step (4), and is kept in the deoxidation deionized water that pours continuously under the high pure nitrogen.
Compared with prior art; The present invention has significant advantage, adopts the perchlorate in the patina absorption degradation water, shows synchronous absorption and the degraded perchlorate effect for harmless cl ions; And adsorption time is short; 6h is adsorbable perchlorate more than 90%, and degradation rate reaches more than 75%, has good economic benefit and environmental benefit.
Embodiment
Embodiment 1
(1) all medicaments are analytical pure, and experimental water is the deoxidation deionized water.Patina preparation and absorption degradation experiment are all accomplished in the operation box that anaerobic condition or nitrogen are full of.
(2) take by weighing 1.3903g FeSO47H2O and 1g Fe
2(SO
4)
3In the 200mL beaker, add 50mL deoxidation deionized water, make [Fe
2+]/[Fe
3+]=3, and pouring in the there-necked flask that nitrogen purging crosses, vigorous stirring makes it fully dissolve on magnetic stirring apparatus, the NaOH solution of configuration 0.1mol/L, and alkali lye is transferred to constant pressure funnel.Three bottlenecks connect constant pressure funnel, pH electrode and nitrogen respectively and feed mouth, and the soft rubber ball jam-pack is used in the junction.Subsequently, dripping alkali liquid dropwise, and through control alkali lye flow rate control pH value of solution value about 6.0.After reaction finishes, continue dripping alkali liquid in solution, observe solution colour simultaneously and change, drip to pH value of solution value 7 and after keeping for some time, reaction finishes.At 75 ℃ of following crystallization 6h, obtain the patina crystal.Filter with quantitative paper, and do not detect to there being iron ion with the deoxidation deionized water rinsing, the material on the filter paper promptly is required patina.
(3) quantitatively be flushed to patina in the 250mL tool plug bottle and add the deoxidation deionized water to 250mL, subsequent use.
(4) get the patina solution that 10ml prepares and join ClO
4 -Starting point concentration is (mass ratio of patina and pending water is 1: 15) in 2000 μ g/L, the 150ml sodium perchlorate solution, need not regulator solution pH value (about 7.0), and 25 ℃ of following constant temperature are as for 160rpm concussion in the shaking table.
(5) 15min, 30min, 1h, 3h, 6h sampling are got the 5mL adsorption liquid respectively and are crossed 0.45 μ m membrane filtration, ion-chromatographic determination solution residue perchlorate concentration.The result shows that absorption 30min can remove the perchlorate more than 75%, and absorption reaches balance basically behind the absorption 3h, and clearance reaches more than 90%.Increase through measuring with adsorption time, Cl-concentration constantly increases in the solution, shows that the perchlorate of absorption is reduced to harmless cl ions in succession, and behind the absorption 6h, the perchlorate of degradable about 70% is harmless cl ions.
Embodiment 2
With embodiment 1 step (1)～(3).
(4) the serial perchlorate's starting point concentration of configuration is that 2000 μ g/L, pH value of solution value are 6 150ml solution, in solution, adds 3,5,10,15 under 25 ℃ respectively, 20ml patina solution (mass ratio of patina and pending water was respectively 1: 50,1: 30,1: 15,1: 10,1: 8).25 ℃ of following constant temperature are as for shaking with rotating speed 160rpm in the shaking table.
(5) behind the reaction 6h, get the 5mL adsorption liquid respectively and cross 0.45 μ m membrane filtration.Dosage is respectively 3,5,10,15, the patina solution of 20ml is respectively 77.81%, 82.31%, 90.35%, 91.28% and 94.67% to the clearance of perchlorate.
Embodiment 3
With embodiment 1 step (1)～(3).
(4) the serial perchlorate's starting point concentration of configuration is that 2000 μ g/L, pH value of solution value are respectively each 150ml of solution of 3,4,5,6,8,10,12, in solution, adds 10ml patina solution (mass ratio of patina and pending water is 1: 15) respectively.25 ℃ of following constant temperature are as for shaking with rotating speed 160rpm in the shaking table
(5) behind the reaction 6h, get the 5mL adsorption liquid respectively and cross 0.45 μ m membrane filtration.Recording the pH value is respectively 3,4,5,6,8,10,12 times patinas the clearance of perchlorate is respectively 20.26%, 60.25%, 68.19%, 90.21%, 93.15%, 93.79% and 59.47%.This is because along with the redox potential of the rising patina of pH value reduces the reducing power enhancing.
Embodiment 4
With embodiment 1 step (1)～(3).
(4) the serial perchlorate starting point concentration of configuration is 200,500,1000,2000,5000 each 150ml of μ g/L solution, in solution, adds 10ml patina solution (mass ratio of patina and pending water is 1: 15) respectively.25 ℃ of following constant temperature of room temperature are as for shaking with rotating speed 160rpm in the shaking table.
(5) behind the reaction 6h; Get the 5mL adsorption liquid respectively and cross 0.45 μ m membrane filtration, record different starting point concentration 200,500,1000,2000,5000 μ g/L sorbent materials the perchlorate clearance is respectively 96.27%, 94.32%, 94.84%, 90.35%, 87.6%.
Embodiment 5
With embodiment 1 step (1)～(3).
(4) the serial perchlorate starting point concentration of configuration is the solution 150ml of 2000 μ g/L; Add 10ml patina (mass ratio of patina and pending water is 1: 15); This moment, the pH value of solution value was about 7, under 5,15,25,35 ℃, put into shaking table constant temperature, 160rpm concussion respectively.
(5) behind the reaction 6h, get the 5mL adsorption liquid respectively and cross 0.45 μ m membrane filtration, recording under the differing temps 5,15,25,35 ℃ of patinas is 9321%, 91.36%, 90.35%, 84.22% to the clearance of perchlorate.
The above-mentioned description to embodiment is can understand and use the present invention for ease of the those of ordinary skill of this technical field.The personnel of skilled obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (10)
1. the method for perchlorate in the absorption degradation water is characterized in that: comprise following steps:
(1) sorbent material is joined in the pending water:
(2) under certain rotating speed and temperature, the perchlorate in the water is carried out absorption degradation through sorbent material;
(3) after absorption is accomplished, the sorbent material in the water is held back separating treatment.
2. method according to claim 1 is characterized in that: described perchlorate is water-soluble perchlorate, one or more in preferred sodium perchlorate, potassium perchlorate or the lithium perchlorate.
3. method according to claim 1 is characterized in that: the starting point concentration of the perchlorate in the described step (1) in the pending water is 200～5000 μ g/L.
4. method according to claim 1 is characterized in that: the mass ratio of sorbent material and pending water is 1: 50～1: 8 in the described step (1).
5. method according to claim 1 is characterized in that: sorbent material is fresh patina FeFe in the described step (1)
2(SO
4)
4(H
2O)
2, be no more than 24 hours its storage period.
6. method according to claim 1 is characterized in that: the pH of pending water is 5～10 in the described step (1).
7. method according to claim 1 is characterized in that: the adsorption time of described step (2) is 15min～6h.
8. method according to claim 1 is characterized in that: the adsorption temp of described step (2) is 5～35 ℃.
9. method according to claim 1 is characterized in that: the rotating speed of described step (2) is 120～200rpm.
10. method according to claim 1 is characterized in that: the sorbent material in the described step (3) is removed through membrane treatment process, membrane pore size≤0.45 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103432056A CN102502911A (en) | 2011-11-03 | 2011-11-03 | Method for adsorbing and degrading perchlorate in water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103432056A CN102502911A (en) | 2011-11-03 | 2011-11-03 | Method for adsorbing and degrading perchlorate in water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102502911A true CN102502911A (en) | 2012-06-20 |
Family
ID=46215062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011103432056A Pending CN102502911A (en) | 2011-11-03 | 2011-11-03 | Method for adsorbing and degrading perchlorate in water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102502911A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105776493A (en) * | 2016-03-19 | 2016-07-20 | 上海大学 | Preparation method of lamellar metal compound for treating organic pollutants in wastewater |
| CN105906072A (en) * | 2016-06-22 | 2016-08-31 | 同济大学 | Method for removing perchlorate in water |
| CN111153492A (en) * | 2020-01-10 | 2020-05-15 | 广东省生态环境技术研究所 | Rust material for fixing anaerobic lake sediment phosphate and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481163A (en) * | 2009-03-03 | 2009-07-15 | 同济大学 | Method for removing perchlorate ion in water and preparation of adsorption material |
| CN101481155A (en) * | 2009-03-03 | 2009-07-15 | 同济大学 | Composite material for water treatment, and preparation and use thereof |
| US20100000924A1 (en) * | 2004-04-26 | 2010-01-07 | Mitsubishi Materials Corporation | Reducing water purification material, method for producing reducing water purification material, method for treating wastewater, and wastewater treatment apparatus |
-
2011
- 2011-11-03 CN CN2011103432056A patent/CN102502911A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100000924A1 (en) * | 2004-04-26 | 2010-01-07 | Mitsubishi Materials Corporation | Reducing water purification material, method for producing reducing water purification material, method for treating wastewater, and wastewater treatment apparatus |
| CN101481163A (en) * | 2009-03-03 | 2009-07-15 | 同济大学 | Method for removing perchlorate ion in water and preparation of adsorption material |
| CN101481155A (en) * | 2009-03-03 | 2009-07-15 | 同济大学 | Composite material for water treatment, and preparation and use thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105776493A (en) * | 2016-03-19 | 2016-07-20 | 上海大学 | Preparation method of lamellar metal compound for treating organic pollutants in wastewater |
| CN105906072A (en) * | 2016-06-22 | 2016-08-31 | 同济大学 | Method for removing perchlorate in water |
| CN111153492A (en) * | 2020-01-10 | 2020-05-15 | 广东省生态环境技术研究所 | Rust material for fixing anaerobic lake sediment phosphate and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108160048B (en) | Large-scale preparation method of high-stability cesium removal adsorbent, and product and application thereof | |
| CN101386424B (en) | Method for preparing modification forming magnalium hydrotalcite and application | |
| CN103086460B (en) | Phosphorus-removing method based on nano-grade iron | |
| CN101428929B (en) | Method for direct advanced treatment for heavy metal wastewater with biological agent | |
| CN102190345A (en) | Method for enriching low-concentration heavy metal in water by recyclable magnesium hydroxide adsorbent | |
| CN101920190B (en) | Zeolite modifying method and application thereof in removing arsenic in water | |
| CN103506065A (en) | Magnetic heavy metal adsorbent with casing-core structure and preparation method thereof | |
| Sun et al. | Recovering rare earth elements via immobilized red algae from ammonium-rich wastewater | |
| CN102626605A (en) | Material for removing radioactive elements from water and preparation and use methods thereof | |
| WO2012161216A1 (en) | Complex and uses thereof | |
| CN109650492A (en) | A kind of iron-carbon micro-electrolysis filler and preparation method thereof | |
| CN102502911A (en) | Method for adsorbing and degrading perchlorate in water | |
| WO2021042599A1 (en) | Method for preparing water-purifying charcoal composite material with low loading amount of nano zero-valent iron and nano silver | |
| CN101857282A (en) | Method for selectively absorbing and separating thiocyanates and thiosulfates in water solution | |
| CN103418341B (en) | Method for preparing activated carbon used for liquid phase adsorption | |
| CN103949226A (en) | Preparation and application methods of magnetic polyvinyl alcohol-chitosan particles | |
| CN103578594B (en) | A kind of use nanometer Fe3O4-CeO2The method of radionuclide removed by material | |
| Zhang et al. | Selective removal of phosphate by magnetic NaCe (CO3) 2/Fe3O4 nanocomposites: Performance and mechanism | |
| Yu et al. | Cr (VI) removal by biogenic schwertmannite in continuous flow column | |
| JP2012192359A (en) | Selenium containing water reduction treatment apparatus and selenium containing water reduction treatment method | |
| CN108393061A (en) | A kind of ion sieve and preparation method thereof of selective removal ammonium | |
| CN102886240B (en) | Adsorbent for removing toxic element arsenic in water and application thereof | |
| CN102145945A (en) | Method for removing trace cadmium in high salt wastewater by combining polymer chelation with adsorption | |
| CN107162215A (en) | A kind of biochemical process for handling arsenic-containing waste water | |
| CN101613148B (en) | Method for removing nitrate nitrogen, corresponding combination preparation, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120620 |