CN108298609A - A kind of efficient hexavalent chromium removal agent and preparation method thereof - Google Patents
A kind of efficient hexavalent chromium removal agent and preparation method thereof Download PDFInfo
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- CN108298609A CN108298609A CN201810187133.2A CN201810187133A CN108298609A CN 108298609 A CN108298609 A CN 108298609A CN 201810187133 A CN201810187133 A CN 201810187133A CN 108298609 A CN108298609 A CN 108298609A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention relates to water treatment fields, and in particular to a kind of efficient hexavalent chromium removal agent, raw material constituent are made of following ratio by weight：The sponge iron of 1~3mm of grain size, 20 parts；The copper sulphate of 0.1~0.5mm of grain size, 3~12 parts；The oxalic acid of 0.3~0.8mm of grain size, 1~4 part；In addition, the invention also provides the preparation methods of above-mentioned efficient hexavalent chromium removal agent.The present invention remover have many advantages, such as that cheap and easy to get, production method is simple, ecological security is good, service life is long, by hexavalent chromium polluted plant chimney stalk, river, lake, underground water repair process in play an important role.
Description
Technical field
The present invention relates to water treatment fields, and in particular to a kind of efficient hexavalent chromium removal agent and preparation method thereof.
Background technology
Chromium is a kind of important strategic resources, basis of the chromic salts series of products as the advanced alloy material of chemical industry-light industry-
Raw material, using and its extensively, be related to the range of goods of national economy 15%.On the one hand the utilization of a large amount of chromium improve its people
Living standard, on the other hand also result in the generation of a large amount of chromium slags and chromium-containing waste gas.Since 1958, China, which has accumulated, filled out
More than 600 ten thousand tons of high toxicity chromium slags are buried, and annual 600000 tons newly-increased.The processing of chromium slag is considered as Chrome Salt Industry hard nut to crack,
It is also worldwide the difficult problem of environmental protection, is much to seek a real cost-effective chromic wastes disposal technology so far.
Main harmful substance is calcium chromate and water soluble hexavalent chromium in chromium slag, and stacking field in chromium slag does not comply fully with
In the case of the requirement of " ne-leakage, nothing scatter, without loss ", Cr VI is easy to the eluviation through rainwater and enters underground water,
And then pollute water-bearing layer nearby.For the human body, Cr VI has irritation, corrosivity and mutagenesis, teratogenesis, carcinogenic
Three cause effect.The Cr VI limit value of drinking water is set to by China at " standards for drinking water quality " (GB 5749-2006)
0.05mg/L；Cr VI was just included in " priority monitoring and the pollutant of control in water " by U.S. EPA in 1977；2011
Year, international environment health risk assessment mechanism Blacksmith Institute are according to the size of contaminants range and potential
The quantity of aggrieved crowd has carried out quantitative evaluation to global toxic pollutant event and has sorted, and researches show that developing countries number
Million crowds are exposed in the environment of pollution of chromium.Therefore, very urgent for the improvement of Cr VI.
At present in water Cr VI improvement mainly by redox make high toxicity, high migration sexavalence
Chromium is reduced into hypotoxicity, the difficult trivalent chromium migrated1.Usually use nano zero valence iron, iron filings, ferrous sulfate, sulfide etc. opposite
Cheap reducing agent can be added directly into as repair materials in the water or soil of contaminated site, be a kind of easy to operate fast
Prompt method.But currently a popular nano zero valence iron have aoxidized in air, reunite inactivation phenomena such as, therefore study people
For member often Nanoscale Iron to be supported on high molecular material, it is complex that this often leads to preparation process.Some sulfide restore
Agent is also possible to that secondary pollution occurs.Therefore, physical condition carries out above-mentioned material the removal influence of hexavalent chromium pollutant in water
It is larger.
Sponge iron not only has excellent redox property, also as a kind of artificial synthesized Zero-valent Iron metal charge
Have the characteristics that with loose porous, large specific surface area.Can electronation not only be carried out to the Cr VI in water, but also carry out physics
Absorption is Cr VI material in the ideal processing water of one kind.Wu Jifeng removes Cr to sponge iron6+It is summarized, it is believed that in acid
Fe and Fe under the conditions of property2+Electron donor is can be used as, as electron acceptor micro-electrolysis reaction occurs for the complex anion of Cr VI.With
The progress of micro-electrolysis reaction, hydrogen ion constantly consumes in water, and pH value of solution and OH- concentration gradually increase, and it is difficult to be generated in solution
The flocculation sediments such as molten iron hydroxide and chromium hydroxide, to remove chromium ion in water.Hamid Reza Zafarani are in temperature
It it is 27 DEG C, pH 3.7,5.5g sponge iron can be by the 10mg/L CrO of 25mL at 15 minutes380% or more solution reduction2,
It can be seen that this is a kind of excellent hexavalent chromium removal agent.
From the point of view of domestic and international present Research, for the restorative procedure of Cr VI in water mainly have chemical precipitation, physical absorption,
Chemical cleaning method, microbial remediation method, ion exchange, UF membrane, hyperfiltration technique, chemical reduction method etc..
Chemical precipitation method3It is by the way that the substances such as lime, EDTA are added into the solution containing heavy metal, make heavy metal ion
Flocculation sediment occurs.This method is although easy to operate, but often greatly changes water pH value, and introduces new pollutant,
After-treatment is needed in actual application.Physisorphtion4It is using high porosities and specific surface areas such as activated carbon, expanded graphites
Material carry out physical absorption, this absorption is difficult selective, and processing often reduces and makes containing more polymictic aqueous solution
Use effect.Chemical cleaning method5It is to push cleaning solution to clear pollution out by contaminated site using hydraulic pressure, then again
To the cleaning containing chromium, cleaning solution is either certain complexing agent, it is also possible to be exactly clear water.But the treatment effect of this method is past
It is past to depend on soil pH value, it is larger using limiting.Microbial remediation method6、7It is a kind of environmentally friendly, simple in-situ treatment method, field
Geomicrobes just can be applied to site remediation by domestication.Content of 6-valence Cr ions reaches 1800mg/ in French Rhone-Alpes soil
G, microorganism can be carried out reduction reaction after nutritional ingredient is added, show huge reparative potential.Though this method
It so has a extensive future, but still is frequently subjected to actual place bacterium colony population and is difficult to tame and need to add the limitation of nutriment.From
Son exchanges8、9、10It is often made with ion exchange resin or is easy to the method progress Water quality restoration that the organic matter degraded passes through ion exchange.
UF membrane11Technology mainly carries out ion exchange using osmotic pressure, and heavy metal ion is stayed in the side of semi-permeable membrane, will be clean
Water penetration is to the other side.Hyperfiltration technique12Mainly using the material adsorbing hexavalent chromium that can actively adsorb heavy metal, to reach
Purpose of purifying the water quality.These three kinds researchs are at the early-stage, although often having the characteristics that removal efficiency is high, cost is excessively high,
Speed limits it and is widely used slowly excessively.
Existing recovery technique often exist it is with high costs, complicated for operation, be difficult to preserve, treatment effect is relatively slow, does not have needle
To property and generate one or several disadvantages such as secondary pollution, it is difficult to effectively be handled the Cr VI in water.
Bibliography：
1Lv X,Zhang Y,Fu W,et al.Zero-valent iron nanoparticles embedded into
reduced graphene oxide-alginate beads for efficient chromium(VI)removal[J].J
Colloid Interface Sci,2017,506:633-643.
2Zafarani H R,Bahrololoom M E,Javidi M,et al.Removal of chromate ion
from aqueous solutions by sponge iron[J].Desalination&Water Treatment,2014,52
(37-39):7154-7162.
3Kurniawan,Tonni Agustiono,et al."Physico–chemical treatment
techniques for wastewater laden with heavy metals."Chemical Engineering
Journal 118.1–2(2006):83-98.
4Mohan,D,and P.C.Jr."Activated carbons and low cost adsorbents for
remediation of tri-and hexavalent chromium from water."Journal of Hazardous
Materials 137.2(2006):762-811.
5Pichtel J,Pichtel T M.Comparison of Solvents for Ex Situ Removal of
Chromium and Lead from Contaminated Soil[J].Environmental Engineering
Science,1997,14(2):97-104
6Desjardin V,Bayard R,Huck N,et al.Effect of microbial activity on
the mobility of chromium in soils.[J].Waste Management,2002,22(2):195-200.
7Cifuentes,F.R,Lindemann,et al.CHROMIUM SORPTION AND REDUCTION IN
SOIL WITH IMPLICATIONS TO BIOREMEDIATION.[J].Soil Science,1996,161(4):233-
241.
8Bachmann,R.T.,et al."Feasibility study on the recovery of hexavalent
chromium from a simulated electroplating effluent using Alamine 336and
refined palm oil."Separation&Purification Technology 75.3(2010):303-309.
9Edebali,Serpil,and E.Pehlivan."Evaluation of Amberlite IRA96and
Dowex 1×8ion-exchange resins for the removal of Cr(VI)from aqueous
solution."Chemical Engineering Journal 161.1(2010):161-166.
10Cavaco,S.A.,et al."Removal of chromium from electroplating industry
effluents by ion exchange resins."Journal of Hazardous Materials144.3(2007):
634.
11The such as Xiaojing " Fabrication of asymmetric poly (m-phenylene
Isophthalamide) nanofiltration membrane for chromium (VI) removal. " ACTA Scientiae Circumstantiaes
(English edition) 22.9 (2010):1335-1341.
12Ghosh,Gargi,and P.K.Bhattacharya."Hexavalent chromium ion removal
through micellar enhanced ultrafiltration."Chemical Engineering Journal 119.1
(2006):45-53.
Invention content
In view of this, providing a kind of efficient hexavalent chromium removal agent and its system the invention aims to overcome above insufficient
Preparation Method.
In order to solve the above technical problems, the present invention uses following technical scheme：
A kind of efficient hexavalent chromium removal agent, includes the raw material of following mass fraction：
20 parts of sponge iron, 3~12 parts of copper sulphate and 1~4 part of oxalic acid.
The grain size of the sponge iron is 1~3mm.
0.1~0.5mm of grain size of the copper sulphate.
0.3~0.8mm of grain size of the oxalic acid.
The preparation method of the efficient hexavalent chromium removal agent of the present invention, includes the following steps：
Step A, first the sponge iron hydrochloric acid of 1mol/L is rinsed, removes the oxidation film on surface, then uses ultrapure water
Fall the ironing surface hydrochloric acid of sponge；
Step B, copper sulphate is mixed again with sponge iron, is added in 1L deionized waters, and be 200W, place in ultrasonic power
Reason temperature vibrates half an hour under conditions of being 20 DEG C；
Step C, oxalic acid is added, waits for that aubergine spot occurs in material surface, is placed in -50 DEG C, is lyophilized under vacuum condition, must produce
Object.
The above-mentioned technical proposal of the present invention has the beneficial effect that：
This remover overcome previous repair materials it is easy reunite, easy in inactivation and reaction speed is slow, removal efficiency is low feelings
Condition, while non-secondary pollution, the water quality safety that improves that treated.Make as main component go in larger particles (1~3mm)
Except in agent, only remover of the invention can completely remove the hexavalent chromium wastewater of 30mg/L in 0.5h.And because its
It is mainly made of bulky grain so that easy to operate, easy keeping, the present invention will play important in the water process containing heavy metal
Effect.
Waste water containing Cr VI can effectively make hexavalent chromium concentration up to standard after the efficient remover of the present invention
Or completely remove, safety easy to operate, it reduces in the past to the processing cost of Cr VI in water.Present invention also avoids impurity
Influence, repair materials inactivation or the case where generate secondary pollution, be it is a kind of efficiently, good novel multiple of economy, ecological security
With hexavalent chromium removal agent.
Specific implementation mode
To keep the technical problem to be solved in the present invention, technical solution and advantage clearer, below in conjunction with specific implementation
Example is described in detail.
Contrast experiment：
Respectively select phase homogenous quantities 1~3mm sponge iron, 3-5mm sponge iron, scoria, expanded graphite, vitamin C,
The materials such as loess, fine sand, activated carbon and oxalic acid carry out hexavalent chromium removal experimental study in water.The result shows that in hexavalent chromium concentration
For 30mg/L when, react 6h, 1~3mm sponge iron and oxalic acid respectively reach 84% He to the removal efficiency highest of hexavalent chromium solution
90%.Other processing material results are 50% hereinafter, its medium-fine sand effect is worst, less than 5%.
In view of the clean-up effect of water can be further increased, the reaction time is reduced, according to galvanic corrosion theory, to sponge
Iron carries out copper plating treatment (Eq (1)), and is compounded with oxalic acid.It is hexavalent chromium polluted that purification is greatly reduced after three kinds of material compoundings
Aqueous solution time, removal effect can reach 100% in 0.5h, greatly improve the removal rate of Cr VI.
Fe0+Cu2+→Cu0+Fe2+ Eq.(1)
Embodiment 1
A kind of efficient hexavalent chromium removal agent, raw material constituent are made of following ratio in parts by weight：1~3mm of grain size
20 parts of sponge iron, 3 parts of 0.1~0.5mm copper sulphate, 4 parts of 0.1~0.5mm oxalic acid.
It is 56.3% in 20 DEG C, action time 10min, 10mg/L hexavalent chromium solution removal rates.
Embodiment 2
A kind of efficient hexavalent chromium removal agent, raw material constituent are made of following ratio in parts by weight：1~3mm of grain size
20 parts of sponge iron, 3 parts of 0.1~0.5mm copper sulphate, 1 part of 0.1~0.5mm oxalic acid.
It is 61.6% in 20 DEG C, action time 10min, 10mg/L hexavalent chromium solution removal rates.
Embodiment 3
A kind of efficient hexavalent chromium removal agent, raw material constituent are made of following ratio in parts by weight：1~3mm of grain size
20 parts of sponge iron, 3 parts of 0.1~0.5mm copper sulphate, 2 parts of 0.1~0.5mm oxalic acid.
It is 50.8% in 20 DEG C, action time 10min, 10mg/L hexavalent chromium solution removal rates.
Embodiment 4
A kind of efficient hexavalent chromium removal agent, raw material constituent are made of following ratio in parts by weight：1~3mm of grain size
20 parts of sponge iron, 6 parts of 0.1~0.5mm copper sulphate, 2 parts of 0.1~0.5mm oxalic acid.
It is 52.7% in 20 DEG C, action time 10min, 10mg/L hexavalent chromium solution removal rates.
Embodiment 5
A kind of efficient hexavalent chromium removal agent, raw material constituent are made of following ratio in parts by weight：1~3mm of grain size
20 parts of sponge iron, 9 parts of 0.1~0.5mm copper sulphate, 2 parts of 0.1~0.5mm oxalic acid.
It is 47.4% in 20 DEG C, action time 10min, 10mg/L hexavalent chromium solution removal rates.
Embodiment 6
A kind of efficient hexavalent chromium removal agent, raw material constituent are made of following ratio in parts by weight：1~3mm of grain size
20 parts of sponge iron, 12 parts of 0.1~0.5mm copper sulphate, 2 parts of 0.1~0.5mm oxalic acid.
It is 45.5% in 20 DEG C, action time 10min, 10mg/L hexavalent chromium solution removal rates.
The preparation method of efficient hexavalent chromium removal agent in Examples 1 to 6, includes the following steps：
Step A, first the sponge iron hydrochloric acid of 1mol/L is rinsed, removes the oxidation film on surface, then uses ultrapure water
Fall the ironing surface hydrochloric acid of sponge；
Step B, copper sulphate is mixed again with sponge iron, is added in 1L deionized waters, and be 200W, place in ultrasonic power
Reason temperature vibrates half an hour under conditions of being 20 DEG C；
Step C, oxalic acid is added, waits for that aubergine spot occurs in material surface, be placed in -50 DEG C, under vacuum condition freeze-drying to get
Product.
This remover overcome previous repair materials it is easy reunite, easy in inactivation and reaction speed is slow, removal efficiency is low feelings
Condition, while non-secondary pollution, the water quality safety that improves that treated.Larger particles (1~3mm) be remover it is main at
In point, only the present invention can completely remove the hexavalent chromium wastewater of 30mg/L in 0.5h.And because it is mainly by big
Grain is constituted so that easy to operate, keeping is easy, and the present invention will play an important role in the water process containing heavy metal.
Waste water containing Cr VI can effectively make hexavalent chromium concentration up to standard after the efficient remover of the present invention
Or completely remove, safety easy to operate, it reduces in the past to the processing cost of Cr VI in water.Present invention also avoids impurity
Influence, repair materials inactivation or the case where generate secondary pollution, be it is a kind of efficiently, good novel multiple of economy, ecological security
With hexavalent chromium removal agent.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principles of the present invention, several improvements and modifications can also be made, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (5)
1. a kind of efficient hexavalent chromium removal agent, which is characterized in that include the raw material of following mass fraction：
20 parts of sponge iron, 3~12 parts of copper sulphate and 1~4 part of oxalic acid.
2. efficient hexavalent chromium removal agent according to claim 1, which is characterized in that the grain size of the sponge iron be 1~
3mm。
3. efficient hexavalent chromium removal agent according to claim 1, which is characterized in that the grain size 0.1 of the copper sulphate~
0.5mm。
4. efficient hexavalent chromium removal agent according to claim 1, which is characterized in that the grain size 0.3 of the oxalic acid~
0.8mm。
5. the preparation method of efficient hexavalent chromium removal agent according to claims 1 to 4, which is characterized in that including walking as follows
Suddenly：
Step A, first the sponge iron hydrochloric acid of 1mol/L is rinsed, removes the oxidation film on surface, then falls sea with ultrapure water
Continuous ironing surface hydrochloric acid；
Step B, copper sulphate is mixed again with sponge iron, is added in 1L deionized waters, and be 200W, processing temperature in ultrasonic power
Degree vibrates half an hour under conditions of being 20 DEG C；
Step C, oxalic acid is added, waits for that aubergine spot occurs in material surface, is placed in -50 DEG C, is lyophilized under vacuum condition, obtain product.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113264708A (en) * | 2021-06-24 | 2021-08-17 | 邢台建德水泥有限公司 | Hexavalent chromium reducing agent for high-reducibility cement and preparation method thereof |
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| CN107176644A (en) * | 2016-03-09 | 2017-09-19 | 株式会社神户制钢所 | Purifying agent and purifying treatment method |
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2018
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| CN101244864A (en) * | 2008-03-17 | 2008-08-20 | 中山大学 | Method for improving zero-valent iron dechromisation catalytic reduction liveness in neutrality condition |
| CN102671614A (en) * | 2012-04-24 | 2012-09-19 | 中国环境科学研究院 | Double-metal macromolecule permeable reactive barrier stuffing material and preparation method thereof |
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Application publication date: 20180720 |