CN102502916A - Method for photo-reduction of hexavalent chromium - Google Patents
Method for photo-reduction of hexavalent chromium Download PDFInfo
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- CN102502916A CN102502916A CN2011103362570A CN201110336257A CN102502916A CN 102502916 A CN102502916 A CN 102502916A CN 2011103362570 A CN2011103362570 A CN 2011103362570A CN 201110336257 A CN201110336257 A CN 201110336257A CN 102502916 A CN102502916 A CN 102502916A
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- hexavalent chromium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention relates to a method for reducing hexavalent chromium ions in aqueous solution by adding a photo-initiation agent on the condition of illumination. The method includes the steps of adding the photo-initiation agent in the aqueous solution containing hexavalent chromium, adjusting the solution to be acidic, achieving reduction of hexavalent chromium after mixing on the condition of sunlight or artificial light illumination, and reducing highly toxic hexavalent chromium to be trivalent chromium with low toxicity and small solubility. The method is an economical, simple, fast, effective and environment-friendly method for reducing hexavalent chromium, greatly lowers reduction treatment cost of hexavalent chromium ions in aqueous solution, and is capable of achieving the purpose of harmless treatment of hexavalent chromium waste water.
Description
Technical field
The present invention relates to waste water heavy metal ion process field, specifically, relate to a kind of chromic method in the light trigger reductive water solution of under illumination condition, utilizing.
Background technology
Chromium metal is a kind of common heavy metal contaminants, and mainly the form with sexavalent chrome (Cr (VI)) and trivalent chromium (Cr (III)) exists.Wherein, Cr (VI) is more common in the trade effluents such as Electroplate Factory, tannery, smeltery, printing and dyeing mill, pigment factory and textile mills.Cr (VI) transport property is big, oxidisability is strong, toxicity is high, belongs to three and causes material (carcinogenic, teratogenesis and cause prominent), if directly discharge, can cause serious harm to people, animal and plant etc.Therefore sexavalent chrome is an important indicator of water pollution control, and each state has all formulated the chromate waste water emission standard.As: EPA confirms as sexavalent chrome one of toxicant of 17 kinds of highly dangerous; European Union's issuing command requires to ban use of in Europe later on July 1st, 2007 sexavalent chrome and goods thereof; China will contain the refuse of Cr (VI) and classify " Hazardous wastes " register (numbering HW21) as, and in the existing wastewater discharge standard (GB8978-1996), the highest permission emission concentration of Cr (VI) is 0.5mg/L.Because the toxicity of Cr (III) reduces than Cr (VI) greatly, and the easy deposition removal of Cr (III), adopt method of reducing that the Cr (III) that high malicious Cr (VI) changes into low toxicity has been become important step in many chromate waste water treatment process.
Mode according to reduction chromium is different, mainly contains chemical reduction method and biological reducing method at present.Chemical reduction method is with chemical reducing agents such as S-WAT, inclined to one side hydrosulfate, ferrous sulfate or sulfurous gas Cr (VI) to be reduced to Cr (III), is to improve rate of reduction, needs heating sometimes, causes energy consumption cost high.And reaction process is wayward, and reduction efficiency is not high, and the adding of chemical reducing agent brings a large amount of secondary sludges easily, and the entire treatment technical process is tediously long, complicated; The reduction process that gases such as employing sulfurous gas are made reductive agent also needs in particular devices such as packed absorber, carry out, and facility investment is big, and running cost is high.The biological reducing method is the growth and breeding through bacterium, and the Cr in the chromate waste water (VI) is reduced to Cr (III), and the growth conditions that this method must the assurance function bacterium is good, and the proportioning of function yeast-waste water is also had strict demand.
CN 101519241A relates to the attenuation technology of a heavy metal wastewater.The Sewage Plant dewatered sludge is dried under 45～60 ℃ of conditions; The 0.45mm sieve is crossed in broken back; Screen underflow is biomass reductant; Adopt 0.1mol/L hydrochloric acid or sulphuric acid soln that reductive agent is carried out protonated pre-treatment, with the hexavalent chromium wastewater hybrid reaction, the hexavalent chrome reduction in the waste water is become trivalent chromium subsequently.The present invention is directed to the expensive of traditional chemical reductive agent and secondary pollution problem; Propose to adopt the Sewage Plant dewatered sludge as biomass reductant; Utilize in the mud sexavalent chrome in the organic reducing power reducing waste water; Have with low cost, wide material sources, equipment is simple, secondary pollution is little advantage, practical, have broad application prospects.
The said chromyl method of wastewater treatment of CN 102070261 A is that the sodium sulfite anhy 96 that adopts the Sodium Pyrosulfite hydrolysis to generate is made reductive agent, adopts the batch process technology to handle.Concrete treating processes is: 1. in waste water, add sulfuric acid, the pH value of waste water is adjusted in 2.0～3.0; 2. adding Sodium Pyrosulfite, is the hexavalent chrome reduction in the waste water trivalent chromium; The ratio that adds Sodium Pyrosulfite is 3.5～5: 1 weight ratio calculating by Sodium Pyrosulfite and chromic weight ratio.3. add sodium hydroxide at neutralization tank, the pH value of regulating waste water is between 8～9, makes trivalent chromium be completed into the deposition of chromium hydroxide; 4. utilize the cohesive force of polymeric flocculant SEPIGEL 305, by the effect of tube settler solid, liquid is separated after, discharge of wastewater, mud are concentrated after through the pressure filter press filtration and are stacked, then Unified Treatment according to the rules.
In view of existing hexavalent chrome reduction method exists cost height, complicated operation, brings secondary pollution and a series of problems such as be difficult to apply easily; Develop that a kind of cost is low, clearance is high, operation is simple, the hexavalent chrome reduction new technology of non-secondary pollution, the resource utilization of the Pollution abatement of water surrounding, chromium is utilized and promoted the industry and the harmonious development of environment all to have the important strategic meaning.
Summary of the invention
The present invention is directed to a series of problems that prior art exists, proposed a kind ofly under illumination condition, utilize light trigger hexavalent chromium to be reduced to the method for trivalent chromic ion.
To achieve these goals, the present invention realizes through following technical scheme:
A kind of method of photoreduction hexavalent chromium may further comprise the steps:
1) in containing the aqueous solution of hexavalent chromium, adds light trigger;
2) regulate above-mentioned solution to acid;
3) under illumination condition, above-mentioned solution is stirred, is fully mixed to hexavalent chromium be reduced into trivalent chromic ion.
The present invention can be used for handling the chromyl trade effluent that produces in plating, mining, smelting, process hides, the metal processing industry production process, or receives hexavalent chromium polluted former water, comprises river, lake and underground water.All can handle when hexavalent chromium concentration is 0.5～5000mg/L in the waste water, process range is wide, all can handle up hill and dale the waste water of lower or higher concentration.
Photoinitiator molecules ultraviolet region (250～400nm) or visible region (400～800nm) have certain extinction ability, and after directly or indirectly absorbing luminous energy, initiator molecule is scurried through between system and jumped to excited triplet state from the ground state transition to the excited singlet; After excited singlet or triplet experience unit molecule or bimolecular chemical action, generation can trigger monomer polymeric biologically active fragment, and these biologically active fragments can be radical, positively charged ion, negatively charged ion etc.Different according to triggering mechanism, light trigger can be divided into radical polymerization light trigger and cation light initiator.Light trigger preferable weight-average molecular weight of the present invention is 200～20000 polyoxyethylene glycol.
Nontoxic, the nonirritant of polyoxyethylene glycol series product has good water-solubility, and with many organic matter components good intermiscibility is arranged.They have excellent lubrication property, moisture retention, dispersiveness, cementability, static resistance and flexibility etc., in industries such as makeup, pharmacy, chemical fibre, rubber, plastics, papermaking, paint, plating, agricultural chemicals, metal processing and food-processing, all have very widely and use.The consumption of polyoxyethylene glycol according to the invention is to add 5～600g polyoxyethylene glycol in the 1L chromium-containing solution.
Step 2 according to the invention) regulator solution to acid used reagent is one or more in sulfuric acid, hydrochloric acid, nitric acid, the phosphoric acid, preferably sulfuric acid, hydrochloric acid, and further preferably sulfuric acid is adjusted to the pH value of solution value less than 6.
The light source that illumination condition according to the invention uses is sunshine or artificial light; Preferred halogen tungsten lamp of said artificial light or xenon lamp.Xenon lamp is a kind of xenon lamp that in the elliposoidal quartz bulb shell, is filled with 0.019～0.0266MPa high-pressure xenon, pole distance less than 10mm.Halogen tungsten lamp (halogen lamp) is that blanketing gas contains part haloid element or halid gas incandescent lamp.
Step 3) according to the invention is thorough mixing 20min at least under illumination condition, preferred 30～60min, further preferred 30min.
According to the chromic method of a kind of photoreduction provided by the invention, principle is: polyoxyethylene glycol excites the generation chargeseparated under the condition of illumination, and highly toxic sexavalent chrome is hypotoxic trivalent chromium in the conduction band electron reduction water body that utilization produces.
Compare with the prior art scheme, the present invention has following beneficial effect:
Method of the present invention can be carried out at normal temperatures, and is applied widely, utilizes sunshine or artificial light can realize hexavalent chrome reduction is trivalent chromium, and reducing power is strong, and reduction thoroughly.The polyoxyethylene glycol that is adopted has difficult combustion, characteristic such as not quick-fried, nontoxic, is a kind of safe, inexpensive bulk chemical, aspect industrialization promotion, has suitable advantage.Use this method to handle industrial chromium-containing waste water, simple to operate flexibly, process cost is few, simple to equipment requirements, can not produce secondary pollution, has wide popularizing application prospect.
Down in the face of further explain of the present invention.But following instance only is a simple and easy example of the present invention, does not represent or limits rights protection scope of the present invention, and interest field of the present invention is as the criterion with claims.
Embodiment
For the present invention is described better, be convenient to understand technical scheme of the present invention, typical case of the present invention but non-restrictive example is following:
Embodiment 1
In a Glass Containers, adding Cr (VI) concentration is the aqueous solution 20mL of 5000mg/L; The adding molecular weight is 2000 polyoxyethylene glycol 12g (consumption 600g/L chromium-containing solution); The pH value of using sulfuric acid to regulate chromium-containing solution is 0.5; Place mix solution 30min under the sunshine after, 98.7% sexavalent chrome can be reduced into trivalent chromium.
Embodiment 2
In a Glass Containers, adding Cr (VI) concentration is the aqueous solution 20mL of 0.5mg/L; The adding molecular weight is 20000 polyoxyethylene glycol 0.2g (consumption 10g/L chromium-containing solution); Use sulfuric acid to regulate the chromium-containing solution sulfuric acid concentration and be 6mol/L; Place mix solution 30min under the sunshine after, 96% sexavalent chrome can be reduced into trivalent chromium.
Embodiment 3
In a Glass Containers, adding Cr (VI) concentration is the aqueous solution 20mL of 200mg/L; The adding molecular weight is 400 polyoxyethylene glycol 3g (consumption 150g/L chromium-containing solution); The pH value of using hydrochloric acid to regulate chromium-containing solution is 5; Place to mix solution 30min under the sunshine, 99.3% sexavalent chrome can be reduced into trivalent chromium.
Embodiment 4
In a Glass Containers, adding Cr (VI) concentration is the aqueous solution 20mL of 500mg/L; The adding molecular weight is 200 polyoxyethylene glycol 4g (consumption 200g/L chromium-containing solution); Use sulfuric acid to regulate the chromium-containing solution sulfuric acid concentration and be 2mol/L; Place to mix solution 30min under the sunshine, 99.8% sexavalent chrome can be reduced into trivalent chromium.
Embodiment 5
In a Glass Containers, adding Cr (VI) concentration is the aqueous solution 20mL of 1000mg/L; The adding molecular weight is 10000 polyoxyethylene glycol 5g (consumption 250g/L chromium-containing solution); The pH value of using nitric acid to regulate chromium-containing solution is 4; Place under the 500W halogen tungsten light and mix solution 30min, 98.6% sexavalent chrome can be reduced into trivalent chromium.
Embodiment 6
In a Glass Containers, adding Cr (VI) concentration is the aqueous solution 20mL of 500mg/L; The adding molecular weight is 4000 polyoxyethylene glycol 3g (consumption 150g/L chromium-containing solution); Use sulfuric acid to regulate the chromium-containing solution sulfuric acid concentration and be 5mol/L; At once place under the sunshine and mix 30min, 100% sexavalent chrome can be reduced into trivalent chromium.
Embodiment 7
In a Glass Containers, adding Cr (VI) concentration is the aqueous solution 20mL of 1000mg/L; The adding molecular weight is 6000 polyoxyethylene glycol 5g (consumption 250g/L chromium-containing solution); The pH value of using nitric acid to regulate chromium-containing solution is 3; Place to mix solution 30min under the 300W xenon lamp, 99.2% sexavalent chrome can be reduced into trivalent chromium.
Embodiment 8
In a Glass Containers, adding Cr (VI) concentration is the aqueous solution 20mL of 500mg/L; The adding molecular weight is 4000 polyoxyethylene glycol 3g (consumption 150g/L chromium-containing solution); The pH value of using phosphoric acid to regulate chromium-containing solution is 6; Place to mix solution 30min under the sunshine, 96.4% sexavalent chrome can be reduced into trivalent chromium.
Embodiment 9
In a Glass Containers, adding Cr (VI) concentration is the aqueous solution 20mL of 500mg/L; The adding molecular weight is 2000 polyoxyethylene glycol 4g (consumption 200g/L chromium-containing solution); The pH value of using sulfuric acid to regulate chromium-containing solution is 1; Place to mix solution 30min under the sunshine, 99.3% sexavalent chrome can be reduced into trivalent chromium.
Embodiment 10
In a Glass Containers, adding Cr (VI) concentration is the aqueous solution 20mL of 500mg/L; The adding molecular weight is 8000 polyoxyethylene glycol 4g (consumption 200g/L chromium-containing solution); The pH value of using sulfuric acid to regulate chromium-containing solution is 2; Place to mix solution 30min under the sunshine, 99.7% sexavalent chrome can be reduced into trivalent chromium.
Embodiment 11
In a Glass Containers, adding Cr (VI) concentration is the aqueous solution 20mL of 10mg/L; The adding molecular weight is 200 polyoxyethylene glycol 0.1g (consumption 5g/L chromium-containing solution); Use sulfuric acid to regulate the chromium-containing solution sulfuric acid concentration and be 0.2mol/L; Place mix solution 20min under the sunshine after, 97.3% sexavalent chrome can be reduced into trivalent chromium.
Embodiment 12
In a Glass Containers, adding Cr (VI) concentration is the aqueous solution 20mL of 2300mg/L; The adding molecular weight is 600 polyoxyethylene glycol 10g (consumption 500g/L chromium-containing solution); The pH value of using sulfuric acid to regulate chromium-containing solution is 3.5; Place to mix solution 60min under the sunshine, 99.4% sexavalent chrome can be reduced into trivalent chromium.
Applicant's statement; The person of ordinary skill in the field is on the basis of the foregoing description, and is with the concrete point value of the foregoing description component, combined with the technical scheme of summary of the invention part; Thereby the new numerical range that produces; Also be one of record scope of the present invention, the application is no longer enumerated these numerical ranges for making specification sheets simple and clear.
Applicant's statement, the present invention explains method of reducing of the present invention through the foregoing description, but the present invention is not limited to above-mentioned method of reducing, does not mean that promptly the present invention must rely on above-mentioned method of reducing and could implement.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of reagent that the present invention selects for use and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. the method for a photoreduction hexavalent chromium is characterized in that, may further comprise the steps:
1) in the aqueous solution that contains hexavalent chromium, adds light trigger;
2) solution is transferred to acidity;
3) under illumination condition, above-mentioned solution is stirred, is fully mixed to hexavalent chromium be reduced into trivalent chromic ion.
2. the method for claim 1 is characterized in that, hexavalent chromium concentration is 0.5～5000mg/L in the said aqueous solution that contains hexavalent chromium.
3. according to claim 1 or claim 2 method is characterized in that the preferred polyoxyethylene glycol of said light trigger.
4. method as claimed in claim 3 is characterized in that, said polyoxyethylene glycol weight-average molecular weight is 200～20000.
5. like claim 3 or 4 described methods, it is characterized in that the consumption of said polyoxyethylene glycol is to add 5～600g polyoxyethylene glycol in the 1L chromium-containing solution.
6. like the described method of one of claim 1-5, it is characterized in that said step 2) solution is transferred to acid used reagent is in sulfuric acid, hydrochloric acid, nitric acid, the phosphoric acid one or more, preferably sulfuric acid, hydrochloric acid, further preferably sulfuric acid.
7. like the described method of one of claim 1-6, it is characterized in that said step 2) the pH value of solution value is adjusted to less than 6.
8. like the described method of one of claim 1-7, it is characterized in that the light source that said illumination condition uses is sunshine or artificial light; Preferred halogen tungsten lamp of said artificial light or xenon lamp.
9. like the described method of one of claim 1-8, it is characterized in that said step 3) is thorough mixing 20min at least under illumination condition, preferred 30～60min, further preferred 30min.
10. like the described method of one of claim 1-9; It is characterized in that; Said method can be used for handling the chromyl trade effluent that produces in plating, mining, smelting, process hides, the metal processing industry production process, or receives hexavalent chromium polluted former water, comprises river, lake and underground water.
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| CN201110336257.0A CN102502916B (en) | 2011-10-28 | 2011-10-28 | Method for photo-reduction of hexavalent chromium |
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| CN201110336257.0A CN102502916B (en) | 2011-10-28 | 2011-10-28 | Method for photo-reduction of hexavalent chromium |
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| CN102502916B CN102502916B (en) | 2014-02-26 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104487388A (en) * | 2012-07-06 | 2015-04-01 | 朗盛德国有限责任公司 | Method for reducing hexavalent chromium in oxidic solids |
| CN105731587A (en) * | 2015-12-18 | 2016-07-06 | 南京大学 | Method for reducing hexavalent chromium through micromolecular diketone-ultraviolet light |
| CN107352709A (en) * | 2017-07-17 | 2017-11-17 | 北京矿冶研究总院 | Method for removing and recovering chromium by membrane filtration coupling photoreduction |
| CN107473310A (en) * | 2017-07-17 | 2017-12-15 | 北京矿冶研究总院 | Method for extracting, removing and recovering chromium by photoreduction coupling film |
| CN107930551A (en) * | 2017-11-07 | 2018-04-20 | 安徽工程大学 | A kind of method for producing carbon dioxide radical anion, a kind of method of the processing containing hexavalent chromium wastewater |
-
2011
- 2011-10-28 CN CN201110336257.0A patent/CN102502916B/en not_active Expired - Fee Related
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104487388A (en) * | 2012-07-06 | 2015-04-01 | 朗盛德国有限责任公司 | Method for reducing hexavalent chromium in oxidic solids |
| CN104487388B (en) * | 2012-07-06 | 2017-04-12 | 朗盛德国有限责任公司 | Method for reducing hexavalent chromium in oxidic solids |
| US9725364B2 (en) | 2012-07-06 | 2017-08-08 | Lanxess Deutschland Gmbh | Method for reducing hexavalent chromium in oxidic solids |
| CN105731587A (en) * | 2015-12-18 | 2016-07-06 | 南京大学 | Method for reducing hexavalent chromium through micromolecular diketone-ultraviolet light |
| CN105731587B (en) * | 2015-12-18 | 2018-05-29 | 南京大学 | A kind of method using small molecule diketone-ultraviolet light reduction treatment Cr VI |
| CN107352709A (en) * | 2017-07-17 | 2017-11-17 | 北京矿冶研究总院 | Method for removing and recovering chromium by membrane filtration coupling photoreduction |
| CN107473310A (en) * | 2017-07-17 | 2017-12-15 | 北京矿冶研究总院 | Method for extracting, removing and recovering chromium by photoreduction coupling film |
| CN107352709B (en) * | 2017-07-17 | 2019-09-24 | 北京矿冶研究总院 | Method for removing and recovering chromium by membrane filtration coupling photoreduction |
| CN107930551A (en) * | 2017-11-07 | 2018-04-20 | 安徽工程大学 | A kind of method for producing carbon dioxide radical anion, a kind of method of the processing containing hexavalent chromium wastewater |
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| CN102502916B (en) | 2014-02-26 |
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