CN100463723C - Iodine reducing laminar material and method for processing iodine-enrichment water - Google Patents
Iodine reducing laminar material and method for processing iodine-enrichment water Download PDFInfo
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- CN100463723C CN100463723C CNB2005100863505A CN200510086350A CN100463723C CN 100463723 C CN100463723 C CN 100463723C CN B2005100863505 A CNB2005100863505 A CN B2005100863505A CN 200510086350 A CN200510086350 A CN 200510086350A CN 100463723 C CN100463723 C CN 100463723C
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- roasting
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Abstract
The invention provides a layered material for degrading iodine and the method for treating iodine-containing water, belonging to the water treatment technique. The inventive layered material is the layered bi-hydroxy composite metallic oxide LDHs and its sintered product CLDH, whose chemical formula is [M2+1-xM3+x (OH) 2] x+ (An-) x/2*yH2O). The invention has following advantages that: it can be directly used the LDHs into the treatment of industry acid iodine-containing waster water, or using its sintered product CLDH into the treatment of iodine-containing waste water, while said material can process the high iodine-containing drinking water to reach the standard iodine content of 10-125 mug/L suggested by nation. The invention can be regenerated in the sodium carbonate or sodium-hydroxide solution with a certain concentration. And said material can be used to recover the iodine. The invention has better iodine-degradation effect, while the treatment agent can be regenerated to be used.
Description
Technical field
The invention belongs to water-treatment technology field, a kind of method of falling iodine with stratified material and processing high iodine-containing water thereof particularly is provided.
Background technology
Iodine is the requisite trace element of human body, atomic weight 53.Reserves account for 47 on earth.Occurring in nature rock, soil, water and air all contain micro iodine.Sodium nitrate contains iodine and is up to 450mg/kg in the rock, is sedimentary rock and igneous rock secondly.Soil iodine generally is lower than 5mg/kg; Seawater iodine is 50～60 μ g/L, and stable content, far above river (5～20 μ g/L); It is very few to contain iodine in the air.It is the highest to contain iodine with marine product in the organic matter, is egg, milk products and meat secondly; It is minimum that grain and vegetables contain iodine.The content of iodine of liver and adipose tissue is higher than fresh-water fishes in the ocean fish.Iodine is a kind of human body to be had the material of important physiologic meaning, and iodine deficiency will make the adult suffer from endemicgoiter, make the infant symptoms such as cerebral agenesis, health severe deformities occur.The source of human body iodine mainly by food supply (comprising the land product, marine product), accounts for 80%～90% of iodine intake every day.Secondly be water iodine, account for 10%～20%.Air iodine can suck or the skin absorption through respiratory tract, but its amount only accounts for 5%～10%, and relevant with the residence environment, and it is many slightly that operation on the sea or coastal resident inhale iodine, and interior ground resident is then less.
Grain nutrition office of American Academy of Sciences proposes the requirement of human body to iodine, and the concrete standard of supplying with is: adult's minimal requirement is 75 μ g/d, but quantity delivered is its 2 times, reaches 150 μ g/d; The minimum quantity delivered of children (1～3 years old) is 70 μ g/d, and the minimum quantity delivered of children (4～6 years old) is 90 μ g/d, and the minimum quantity delivered of children (7～10 years old) is 120 μ g/d.It is generally acknowledged that the safe range of Iodine intake is 50～1000 μ g/d, low iodine and high iodine all have harmful effect to human body.
The swollen illness rate of water iodine and first all is " U " type curved line relation, has two-phase.Its conclusion is: water iodine is below 5 μ g/L, and the few more thyroid gland illness rate of iodine is high more; And when 200 μ g/L were above, iodine many thyroid glands illness rate more was high more, so water iodine safe range is 7.0～220 μ g/L, and the swollen illness rate of first this moment＜3.0% (China is decided to be non-lesion).
It has been established that, and all there is the high iodine problem of water in tens counties of provinces (district) such as China Shandong, Shanxi, Hebei, Xinjiang.The investigation about " Shandong high iodine endemicgoiter epidemiology characteristics " in 1994 has confirmed that there is high iodine district in Shandong Inland Areas, and has high iodine ground first swollen popular.With the Wudi County, Shandong that is located in bank, the Bohai Sea is example, in beating more than 50 in dark motor-pumped well in 1998 altogether, after testing, also severe overweight of the motor-pumped well water iodide content more than 90% wherein, generally all reached about 1mg/L, that have even up to 2mg/L, substantially exceed the standard amount of iodine of 10～125 μ g/L of country's suggestion.Fluorinated volume also exceed standard (generally about 2.0mg/L, reaching as high as 3.8mg/L) simultaneously.
At present, relevant height contains more deep that the reducing fluoride method of fluorine drinking water studied.But, because the high iodine of water area worldwide distributes less, except the electroosmose process that acquires a certain degree of difficulty at aspects such as operational administratives, adopt the powdered ceramics material of ultra-fine micropore to fall outside the iodine in domestic 1999 disclosed patent (CN 1225336A), find no close the high iodine-containing drinking water the report of iodine falls with stratified material.Such material has the iodine removal amount big, renewable recycling advantage.
Layered di-hydroxyl composite metal oxidate also claims houghite (LDHs) and product of roasting (CLDH) thereof, is the important inorganic functional material of a class.Because of it has the adjustable sex change of layer structure, laminate element and the interchangeability of interlayer anion, have a wide range of applications, on academic and industrial research, caused people's extensive concern at present.
Summary of the invention
The purpose of this invention is to provide a kind of method of falling iodine, make high iodine-containing water reach the method for national recommended standard scope concentration after treatment with stratified material and processing high iodine-containing water thereof.
The iodine stratified material that falls of the present invention is laminar dual hydroxy composite metal oxygen thing (LayeredDouble Hydroxides is called for short LDHs) and product of roasting (Calcined Layered DoubleHydroxides is called for short CLDH) thereof, and the chemical general formula of LDHs is:
[M
2+ 1-xM
3+ x(OH)
2]
x+(A
n-)
x/n·yH
2O)，
M wherein
2+Represent bivalent metal ion Mg
2+, Ca
2+, Sr
2+, Ba
2+, Zn
2+, Ni
2+, Fe
2+, Cu
2+, Mn
2+In any, that preferable is Mg
2+, Ca
2+Or Ba
2+M
3+Represent trivalent metal ion Al
3+, Cr
3+, Fe
3+, V
3+, Co
3+, Ga
3+, Ti
3+In any 1～2 kind, that preferable is Al
3+02≤x≤0.4,0≤y≤2; A
N-Be interlayer anion CO
3 2-, SO
4 2-, PO
4 3-, Cl
-, NO
3 -In any.
The product of roasting of LDHs (CLDH) is the product that above any LDHs obtained 200～1000 ℃ of following roastings in 1～12 hour.
High iodine-containing water of the present invention comprises and contains iodine waste water and high iodine-containing drinking water.
It is as follows that the present invention handles the concrete grammar of high iodine-containing water:
A, layered di-hydroxyl composite metal oxidate or its product of roasting are joined in the high iodine-containing water, stir, reacted 0.5～8 hour, reaction temperature is controlled at 20～80 ℃.The iodide ion initial concentration that contains iodine aqueous solution is 1～2000mg/L, and the layered di-hydroxyl composite metal oxidate consumption is 0.01～20g/L.Iodide ion concentration is reduced to 0.01～0.1mg/L scope, reaches the standard amount of iodine of 10～125 μ g/L of country's suggestion.
B, will react the layered di-hydroxyl composite metal oxidate that reclaimed Na with 0.01～1M
2CO
3Or the NaOH processing of regenerating.Biodine after the exchange uses the suitable oxidizing agent with I
-Be oxidized to I
2, the iodine resource is reclaimed.
Processing I under the present invention
-Oxidant be an amount of chlorine or rare nitric acid.
Layered di-hydroxyl composite metal oxidate described in the step a, M
2+Be Mg
2+, Ca
2+, Zn
2+, Ni
2+, Fe
2+, Mn
2+In any 1～2 kind, that preferable is Mg
2+, Ca
2+, Fe
2+Or Ba
2+M
3+Be Al
3+, Cr
3+, Fe
3+, V
3+, Co
3+, Ga
3+, Ti
3+In any 1～2 kind, that preferable is Al
3+Or Fe
3+, A
N-Be CO
3 2-, SO
4 2-, NO
3 -, Cl
-In any, its CO
3 2-, NO
3 -Preferable.
Layered di-hydroxyl composite metal oxidate product of roasting described in the step a be LDHs at 1～12 hour product of 200～1000 ℃ of following roastings, preferable sintering temperature is 200～800 ℃, more excellent sintering temperature is 400～600 ℃; Preferable roasting time is 1～6 hour, and more excellent roasting time is 2～4 hours.
The invention has the advantages that: by directly LDHs being applied to the processing that acidity contains iodine waste water, also its product of roasting CLDH can be applied to contain the processing of iodine waste water, this stratified material can also be handled high iodine drinking water, reaches national drinking water content of iodine recommended standard.This inorganic agent can be regenerated in certain density sodium carbonate liquor or sodium hydroxide solution.This material also can be used for the recovery of iodine.It is effective that the present invention has the iodine of falling, the advantage of the renewable recycling of inorganic agent.
The specific embodiment
Embodiment 1: at the 1000mL iodide ion concentration is in the aqueous solution of 2000mg/L, add a certain amount of LDHs (10.0g), constant temperature water bath (30 ℃), salpeter solution with 1% or sodium hydroxide solution control pH value are a steady state value (as 6.0), reacted 6 hours, filtered and recycled LDHs, filtrate iodide ion concentration are 0.1mg/L.
Embodiment 2: at the 1000mL iodide ion concentration is in the aqueous solution of 100mg/L, add a certain amount of LDHs (1.0g), constant temperature water bath (30 ℃), salpeter solution with 1% or sodium hydroxide solution control pH value are a steady state value (as 6.0), reacted 1 hour, filtered and recycled LDHs, filtrate iodide ion concentration are 0.1mg/L.
Embodiment 3: at the 2000mL iodide ion concentration is in the aqueous solution of 100mg/L, adds a certain amount of CLDH (2.0g), and constant temperature water bath (30 ℃) reacted 6 hours, and filtered and recycled is handled material, and the filtrate iodide ion concentration is 0.1mg/L.
Embodiment 4: at the 2000mL iodide ion concentration is the high iodine drinking water of 10mg/L, adds a certain amount of CLDH (1.0g), reacts 6 hours, and filtered and recycled is handled material, and the filtrate iodide ion concentration is below the 0.1mg/L.This stratified material can also be removed the harmful substances such as fluorine ion in the water simultaneously.
Embodiment 5: at the 2000mL iodide ion concentration is the high iodine drinking water of 1mg/L, adds a certain amount of CLDH (0.1g), reacts the filtered and recycled inorganic agent 2 hours.Iodide ion concentration is finally reduced to 0.02mg/L.This stratified material can also be removed the harmful substances such as fluorine ion in the water simultaneously.
Embodiment 6: at the Na of 0.1M
2CO
3Add in the solution and reclaim the stratified material that obtains, stirred 6 hours, carry out structure regeneration.
Embodiment 7: add in the NaOH of 0.1M solution and reclaim the stratified material that obtains, stirred 6 hours, carry out structure regeneration.
Embodiment 8: at the 1000mL iodide ion concentration is the aqueous solution of 1000mg/L, adds the LDHs (6.0g) after a certain amount of regeneration, and salpeter solution with 1% or sodium hydroxide solution control pH value are a steady state value (as 6.0), react filtered and recycled LDHs 6 hours.The iodide ion ultimate density is 0.1mg/L。
Embodiment 9: at the 2000mL iodide ion concentration is the aqueous solution of 100mg/L, adds the CLDH (2.0g) after a certain amount of regeneration, reacts 6 hours, and filtered and recycled stratified material, iodide ion concentration finally are 0.1mg/L.
Embodiment 10: at the 2000mL iodide ion concentration is the high iodine drinking water of 10mg/L, and constant temperature water bath (30 ℃) adds the CLDH (0.2g) after a certain amount of regeneration, reacts the filtered and recycled stratified material 6 hours.The iodide ion ultimate density is 0.1mg/L.
Embodiment 11: at the 2000mL iodide ion concentration is the high iodine drinking water of 1mg/L, and constant temperature water bath (30 ℃) adds the CLDH (0.1g) after a certain amount of regeneration, reacts the filtered and recycled stratified material 2 hours.The iodide ion ultimate density is 0.02mg/L.
Claims (3)
1. one kind is fallen iodine and handles the method for high iodine-containing water with stratified material, and it is characterized in that: concrete processing step is:
A, layered di-hydroxyl composite metal oxidate LDHs or its product of roasting CLDH joined contain in the iodine water, stir, reacted 0.5-8 hour, the layered di-hydroxyl composite metal oxidate consumption is 0.1～10g/L, the iodide ion initial concentration is 1～2000mg/L, iodide ion concentration is reduced to 0.01～0.2mg/L, reaches country and contains the iodine water quality standard; The described iodine stratified material that falls is layered di-hydroxyl composite metal oxidate LDHs or its product of roasting CLDH, and the chemical general formula of LDHs is:
[M
2+ 1-xM
3+ x(OH)
2]
X+(A
N-)
X/nYH
2O), M wherein
2+Represent bivalent metal ion Ca
2+, Mg
2+, Sr
2+, Ba
2+, Zn
2+, Ni
2+, Fe
2+, Cu
2+, Mn
2+In any; M
3+Represent trivalent metal ion Al
3+, Cr
3+, Fe
3+, V
3+, Co
3+, Ga
3+, Ti
3+In any; 0.2≤x≤0.4,0≤y≤2; A
N-Be interlayer anion CO
3 2-, SO
4 2-, PO
4 3-, Cl
-, NO
3 -In any; The product of roasting of LDHs is the product that above any LDHs obtained 200～1000 ℃ of following roastings in 1～12 hour;
B, will react the layered di-hydroxyl composite metal oxidate that reclaimed Na with 0.01～1M
2CO
3Or the NaOH processing of regenerating; Biodine after the exchange, with oxidant with I
-Be oxidized to I
2, the iodine resource is reclaimed described processing I
-Oxidant be chlorine or rare nitric acid.
2. method according to claim 1 is characterized in that: the sintering temperature of LDHs is 200～800 ℃, and roasting time is 1～6 hour.
3. method according to claim 1 is characterized in that: the sintering temperature of LDHs is 400～600 ℃; Roasting time is 2～4 hours.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100863505A CN100463723C (en) | 2005-09-05 | 2005-09-05 | Iodine reducing laminar material and method for processing iodine-enrichment water |
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|---|---|---|---|
| CNB2005100863505A CN100463723C (en) | 2005-09-05 | 2005-09-05 | Iodine reducing laminar material and method for processing iodine-enrichment water |
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| Publication Number | Publication Date |
|---|---|
| CN1768960A CN1768960A (en) | 2006-05-10 |
| CN100463723C true CN100463723C (en) | 2009-02-25 |
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| CN101890329B (en) * | 2010-07-21 | 2012-08-29 | 北京化工大学 | Thiophene adsorbents and application thereof |
| CN103191695A (en) * | 2013-04-16 | 2013-07-10 | 北京化工大学 | Renewable thiosulfate selective adsorbent and method for treating waste water by using renewable thiosulfate selective adsorbent |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1184084A (en) * | 1997-09-02 | 1999-03-26 | Co-Op Chem Co Ltd | Removal method for radioactive iodine |
| CN1275442A (en) * | 1999-05-26 | 2000-12-06 | 中国科学院大连化学物理研究所 | Waterlike talc solid catalyst for production of triethyl glycol monoethers |
| CN1486784A (en) * | 2003-07-10 | 2004-04-07 | 复旦大学 | Zeolite deiodination adsorbent with high silver carrying amount and its prepn process |
| CN1623647A (en) * | 2003-12-02 | 2005-06-08 | 北京化工大学 | Process for separating organic isomer using inorganic laminated material |
-
2005
- 2005-09-05 CN CNB2005100863505A patent/CN100463723C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1184084A (en) * | 1997-09-02 | 1999-03-26 | Co-Op Chem Co Ltd | Removal method for radioactive iodine |
| CN1275442A (en) * | 1999-05-26 | 2000-12-06 | 中国科学院大连化学物理研究所 | Waterlike talc solid catalyst for production of triethyl glycol monoethers |
| CN1486784A (en) * | 2003-07-10 | 2004-04-07 | 复旦大学 | Zeolite deiodination adsorbent with high silver carrying amount and its prepn process |
| CN1623647A (en) * | 2003-12-02 | 2005-06-08 | 北京化工大学 | Process for separating organic isomer using inorganic laminated material |
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| CN1768960A (en) | 2006-05-10 |
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