CN1623696A - Process for reducing pollution of hexa covalent chromium ion - Google Patents
Process for reducing pollution of hexa covalent chromium ion Download PDFInfo
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- CN1623696A CN1623696A CN 200410052084 CN200410052084A CN1623696A CN 1623696 A CN1623696 A CN 1623696A CN 200410052084 CN200410052084 CN 200410052084 CN 200410052084 A CN200410052084 A CN 200410052084A CN 1623696 A CN1623696 A CN 1623696A
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- hexavalent chromium
- furnace slag
- ground blast
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- chromium
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- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
A process for dicreasing the pollution of 6-valence Cr ions features that the slags of blast furnace are ground and then proportionally mixed with the Cr-contained aqueous solution or solid waste for reducing the 6-valence Cr ions to become low-valence non-toxic Cr ions and then solidifying them. Its advantages are high efficiency, durably stability and no by-effect.
Description
Technical field
The invention belongs to field of environment protection, be specifically related to a kind of method that hexavalent chromium pollutes that reduces.
Background technology
There are some researches show, flyash, incinerator ash and some other trade waste, all exist the stripping phenomenon of heavy metal and toxic metals component (general designation harmful constituent) even in the cement, the stripping of the hexavalent chromium that toxicity is bigger is exactly one of them major issue.Hexavalent chromium belongs to water-soluble, under the effect of rainwater, underground water etc., is easy to stripping, produces ecological hazard and by water and biological chain, food chain human body is produced harm.With regard to control and the stripping problem that reduces hexavalent chromium, external at present general reducing process, chemosetting method and the absorption method etc. of adopting, as add ferrous sulfate (reducing process, volume is about 1%) and active carbon (absorption method) etc., its current effect is fine, is difficult to deficiencies such as mixing and long-time stability difference in cost height, the large volume material but exist.The long-time stability difference is meant under some environmental condition, is reduced into chromium ion at a low price and is oxidized to Cr VI again, and the bounce-back of working the mischief property, this is a big defective that has method at present now.
Summary of the invention
The present invention is intended to overcome the defective that above-mentioned prior art exists, a kind of method that hexavalent chromium pollutes that reduces is provided, promptly reduce the method that hexavalent chromium concentration in the chromium-containing solution and minimizing contain hexavalent chromium stripping in chromium solid obsolete material such as flyash or the incinerator ash, make poisonous hexavalent chromium be reduced into nontoxic at a low price chromium ion and solidify.
Blast-furnace cinder forms in strong reducing atmosphere, has very strong reproducibility, and simultaneously, levigate blast-furnace cinder has higher specific surface area, has certain adsorption capacity and higher hydration activity.The present invention utilizes the above-mentioned character of levigate blast-furnace cinder just, poisonous hexavalent chromium is reduced into nontoxic at a low price chromium ion and curing, with concentration that reduces hexavalent chromium in the chromium-containing solution and the stripping that reduces hexavalent chromium in the solid obsolete material.
Under the effect of grinding aid, be 300～800m through grinding to Blain specific surface
2The ground blast-furnace slag of/kg (hereinafter to be referred as the modification ground blast-furnace slag) can effectively reduce hexavalent chromium concentration in the chromium-containing solution and reduce the stripping that contains hexavalent chromium in chromium solid obsolete material such as flyash or the incinerator ash, and modification ground blast-furnace slag fineness is big more, volume is many more, and action effect is good more.
In content of 6-valence Cr ions was chromium-containing solution below the 2mg/L, adding 3～30% Blain specific surface by the solid-liquid mass ratio was 300～800m
2Behind the modification ground blast-furnace slag of/kg,, leave standstill, hexavalent chromium concentration is reduced to below the 0.05mg/L, reach China's environmental standard setting: underground water-III class＜0.05mg/L (GB/T14848-93, health a reference value) through stirring.
In containing chromium solid obsolete material such as flyash or incinerator ash, be 300～800m by the Portland cement of mass ratio adding 3～5% and 3～10% Blain specific surface
2Behind the modification ground blast-furnace slag of/kg, adding water stirs and to make the mud hardenite or stiffly to hit behind the real hardenite demoulding maintenance to 28 day, can make that the stripping quantity of hexavalent chromium is reduced to below the 0.05mg/L in the hardenite, reach the requirement of above-mentioned China standard GB/T14848-93.
Modification ground blast-furnace slag of the present invention can be used as a kind of admixture and is used for construction material production, plays the effect that reduces and prevent the hexavalent chromium stripping.
The present invention compares with reducing process, chemosetting method and the absorption method etc. that abroad generally adopt at present and has following beneficial effect:
(1) using method of the present invention and technological process are simple, the efficient height, can directly the modification ground blast-furnace slag be mixed in pending waste liquid or the solid obsolete material, or it is used for construction material production as a kind of admixture, play the effect that reduces and prevent the hexavalent chromium stripping;
(2) because blast-furnace cinder is a kind of industrial slag, can turn waste into wealth, reach the useless purpose of energy-conservation profit, and raw material sources of the present invention be extensive, production cost is low;
(3) volume of modification ground blast-furnace slag of the present invention can in very large range be regulated, mix easily, and because the particle characteristics of slag powders, and the reproducibility length of holding time, long-time stability are good, and have no side effect.
The specific embodiment
Embodiment 1
In hexavalent chromium concentration is in the aqueous solution of 0.03mg/L, and mixing 5% specific area by the solid-liquid mass ratio is 450m
2Behind the modification ground blast-furnace slag of/kg, through stirring, leave standstill, hexavalent chromium concentration just reduces to below the 0.010mg/L, reaches the requirement of China standard GB/T14848-93.
Embodiment 2
In hexavalent chromium concentration is in the aqueous solution of 0.08mg/L, and mixing 10% specific area by the solid-liquid mass ratio is 450m
2Behind the modification ground blast-furnace slag of/kg, through stirring, leave standstill, hexavalent chromium concentration just reduces to below the 0.010mg/L, reaches the requirement of China standard GB/T14848-93.
Embodiment 3
In hexavalent chromium concentration is in the aqueous solution of 0.15mg/L, and mixing 30% specific area by the solid-liquid mass ratio is 450m
2Behind the modification ground blast-furnace slag of/kg, through stirring, leave standstill, hexavalent chromium concentration just reduces to below the 0.010mg/L, reaches the requirement of China standard GB/T14848-93.
Embodiment 4
In hexavalent chromium concentration is in the aqueous solution of 0.05mg/L, and mixing 3% specific area by the solid-liquid mass ratio is 300m
2Behind the modification ground blast-furnace slag of/kg, through stirring, leave standstill, hexavalent chromium concentration just reduces to below the 0.022mg/L, reaches the requirement of China standard GB/T14848-93.
Embodiment 5
In hexavalent chromium concentration is in the aqueous solution of 0.80mg/L, and mixing 6% specific area by the solid-liquid mass ratio is 780m
2Behind the modification ground blast-furnace slag of/kg, through stirring, leave standstill, hexavalent chromium concentration just reduces to below the 0.022mg/L, reaches the requirement of China standard GB/T14848-93.
Embodiment 6
In hexavalent chromium concentration is in the aqueous solution of 2mg/L, and mixing 20% specific area by the solid-liquid mass ratio is 800m
2Behind the modification ground blast-furnace slag of/kg, through stirring, leave standstill, hexavalent chromium concentration just reduces to below the 0.022mg/L, reaches the requirement of China standard GB/T14848-93.
Embodiment 7
Solubility hexavalent chromium content in certain flyash is 1.2mg/kg, itself and water is stirred make sealed maintenance behind the mud hardenite that divergence is 220mm, and during the 28 day length of time, the hexavalent chromium stripping quantity is 0.072mg/L; If in examination when body formed, in flyash, mix 3% normal portland cement and 3% specific area is 300m by mass ratio
2The modification ground blast-furnace slag of/kg, under the same test conditions, the stripping quantity of hexavalent chromium will reduce to 0.034mg/L.
Embodiment 8
In embodiment 7,, in flyash, mix 5% normal portland cement and 5% specific area is 450m by mass ratio if in examination when body formed
2The modification ground blast-furnace slag of/kg, under the same test conditions, the stripping quantity of hexavalent chromium will reduce to 0.015mg/L.
Embodiment 9
In embodiment 7,, in flyash, mix 3% normal portland cement and 5% specific area is 800m by mass ratio if in examination when body formed
2The modification ground blast-furnace slag of/kg, under the same test conditions, the stripping quantity of hexavalent chromium will reduce to 0.014mg/L.
Embodiment 10
If modification ground blast-furnace slag addition content is brought up to 10%, then the stripping quantity of hexavalent chromium will be reduced to below the 0.010mg/L among the embodiment 9.
Embodiment 11
For (hexavalent chromium stripping quantity＞0.1mg/L) and mixing water are that divergence that 0.10mg/L hexavalent chromium solution is made is a sealed maintenance behind the mud hardenite of 220mm, and during the 28 day length of time, the hexavalent chromium stripping quantity is 0.13mg/L with certain flyash; If in examination when body formed, in flyash, mix 3% normal portland cement and 3% specific area is 450m by mass ratio
2The modification ground blast-furnace slag of/kg, the stripping quantity of hexavalent chromium will reduce to 0.028mg/L.
Embodiment 12
In embodiment 11,, in flyash, mix 3% normal portland cement and 3% specific area is 800m by mass ratio if in examination when body formed
2The modification ground blast-furnace slag of/kg, the stripping quantity of hexavalent chromium will reduce to 0.020mg/L.
Embodiment 13
In embodiment 11,, in flyash, mix 3% normal portland cement and 6% specific area is 300m by mass ratio if in examination when body formed
2The modification ground blast-furnace slag of/kg, the stripping quantity of hexavalent chromium will reduce to 0.011mg/L.
Embodiment 14
In embodiment 11,, in flyash, mix 3% normal portland cement and 6% specific area is 780m by mass ratio if in examination when body formed
2The modification ground blast-furnace slag of/kg, the stripping quantity of hexavalent chromium will reduce to 0.009mg/L.
Embodiment 15
For with incinerator ash (hexavalent chromium stripping quantity＞0.1mg/L), be that mixing water is made and stiffly hit real hardenite (water consumption is an optimum moisture content with the pure water, try to achieve by country's " Standard for test methods of earthworks ") the back sealed maintenance, during the 28 day length of time, the hexavalent chromium stripping quantity is 0.150mg/L; If in examination when body formed, in incinerator ash, mix 3% normal portland cement and 3% specific area is 300m by mass ratio
2The modification ground blast-furnace slag of/kg, the stripping quantity of hexavalent chromium will reduce to 0.030mg/L.
Embodiment 16
In embodiment 15,, in incinerator ash, mix 3% normal portland cement and 3% specific area is 800m by mass ratio if in examination when body formed
2The modification ground blast-furnace slag of/kg, the stripping quantity of hexavalent chromium will reduce to 0.025mg/L.
Embodiment 17
In embodiment 15,, in incinerator ash, mix 5% normal portland cement and 10% specific area is 450m by mass ratio if in examination when body formed
2The modification ground blast-furnace slag of/kg, the stripping quantity of hexavalent chromium will reduce to 0.015mg/L.
Embodiment 18
In embodiment 15,, in incinerator ash, mix 5% normal portland cement and 10% specific area is 780m by mass ratio if in examination when body formed
2The modification ground blast-furnace slag of/kg, the stripping quantity of hexavalent chromium will reduce to 0.008mg/L.
From the above, modification ground blast-furnace slag fineness is big more, volume is many more, and action effect is good more.
Technological process of the present invention is simple, can directly the modification ground blast-furnace slag be mixed in pending waste liquid or the solid obsolete material, or it is used for construction material as a kind of admixture produces, play the effect that reduces and prevent the hexavalent chromium stripping, and modification ground blast-furnace slag volume can in very large range regulate, mix easily, and because the particle characteristics of modification ground blast-furnace slag, the reproducibility length of holding time is so long-time stability are good.
Claims (6)
1. one kind is reduced the method that hexavalent chromium pollutes, and it is characterized in that, in containing chromium solid obsolete material, mixes 3～5% Portland cement and 3～10% Blain specific surface is 300～800m by mass ratio
2The modification ground blast-furnace slag of/kg adds water then and stirs moulding, demoulding maintenance to 28 day.
2. the method that minimizing hexavalent chromium according to claim 1 pollutes is characterized in that, described modification ground blast-furnace slag is to be 300～800m by blast-furnace cinder grinding to Blain specific surface under the effect of grinding aid
2The ground blast-furnace slag of/kg.
3. the method that minimizing hexavalent chromium according to claim 1 pollutes is characterized in that, described to contain chromium solid obsolete material be flyash.
4. the method that minimizing hexavalent chromium according to claim 1 pollutes is characterized in that, described to contain chromium solid obsolete material be incinerator ash.
5. one kind is reduced the method that hexavalent chromium pollutes, and it is characterized in that, in chromium-containing solution, adding 3～30% Blain specific surface by the solid-liquid mass ratio is 300～800m
2Behind the modification ground blast-furnace slag of/kg,, leave standstill through stirring.
6. the method that minimizing hexavalent chromium according to claim 5 pollutes is characterized in that, described modification ground blast-furnace slag is to be 300～800m by blast-furnace cinder grinding to Blain specific surface under the effect of grinding aid
2The ground blast-furnace slag of/kg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410052084 CN1285424C (en) | 2004-11-05 | 2004-11-05 | Process for reducing pollution of hexa covalent chromium ion |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410052084 CN1285424C (en) | 2004-11-05 | 2004-11-05 | Process for reducing pollution of hexa covalent chromium ion |
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| CN1623696A true CN1623696A (en) | 2005-06-08 |
| CN1285424C CN1285424C (en) | 2006-11-22 |
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| CN 200410052084 Expired - Fee Related CN1285424C (en) | 2004-11-05 | 2004-11-05 | Process for reducing pollution of hexa covalent chromium ion |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295933A (en) * | 2011-07-01 | 2011-12-28 | 浙江大学 | Special stabilizing agent for chromium polluted soil |
| CN102718440A (en) * | 2011-03-29 | 2012-10-10 | 鞍钢股份有限公司 | Modified cement solidification body with blast furnace slag and method for treating chromium slag thereof |
| CN103831080A (en) * | 2014-03-12 | 2014-06-04 | 福州大学 | Nickel slag adsorbing material for recovering heavy metal ions in wastewater and preparation method thereof |
| JP2017087190A (en) * | 2015-11-17 | 2017-05-25 | 太平洋セメント株式会社 | Insolubilization material and method of suppressing elution of hexavalent chromium |
| CN115368036A (en) * | 2022-08-30 | 2022-11-22 | 攀枝花钢城集团有限公司 | Doping material for reducing water-soluble hexavalent chromium of cement and preparation method and application thereof |
-
2004
- 2004-11-05 CN CN 200410052084 patent/CN1285424C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718440A (en) * | 2011-03-29 | 2012-10-10 | 鞍钢股份有限公司 | Modified cement solidification body with blast furnace slag and method for treating chromium slag thereof |
| CN102718440B (en) * | 2011-03-29 | 2014-09-03 | 鞍钢股份有限公司 | Modified cement solidification body with blast furnace slag and method for treating chromium slag thereof |
| CN102295933A (en) * | 2011-07-01 | 2011-12-28 | 浙江大学 | Special stabilizing agent for chromium polluted soil |
| CN102295933B (en) * | 2011-07-01 | 2013-06-05 | 浙江大学 | Special stabilizing agent for chromium polluted soil |
| CN103831080A (en) * | 2014-03-12 | 2014-06-04 | 福州大学 | Nickel slag adsorbing material for recovering heavy metal ions in wastewater and preparation method thereof |
| CN103831080B (en) * | 2014-03-12 | 2016-03-30 | 福州大学 | For reclaiming nickel slag sorbing material and the preparation thereof of heavy metal ions in wastewater |
| JP2017087190A (en) * | 2015-11-17 | 2017-05-25 | 太平洋セメント株式会社 | Insolubilization material and method of suppressing elution of hexavalent chromium |
| CN115368036A (en) * | 2022-08-30 | 2022-11-22 | 攀枝花钢城集团有限公司 | Doping material for reducing water-soluble hexavalent chromium of cement and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1285424C (en) | 2006-11-22 |
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Granted publication date: 20061122 Termination date: 20131105 |