CN106882854A - The method for efficiently removing hexavalent chromium in chromate waste water - Google Patents
The method for efficiently removing hexavalent chromium in chromate waste water Download PDFInfo
- Publication number
- CN106882854A CN106882854A CN201710119782.4A CN201710119782A CN106882854A CN 106882854 A CN106882854 A CN 106882854A CN 201710119782 A CN201710119782 A CN 201710119782A CN 106882854 A CN106882854 A CN 106882854A
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- CN
- China
- Prior art keywords
- waste water
- hexavalent chromium
- water solution
- tio
- ionising radiation
- 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.)
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Classifications
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/307—Treatment of water, waste water, or sewage by irradiation with X-rays or gamma radiation
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention provides a kind of method of hexavalent chromium in efficient removal chromate waste water, add nano semiconductor material in waste water solution to be catalyzed and carry out ionising radiation to waste water solution, using the reducing power of ionising radiation generation strong hydroperoxyl radical H and aqueous electron eaq ‑, promote Cr in waste water solution（Ⅵ）Cr (III) is reduced into, Cr (III) is converted into Cr under neutral or alkalescence condition（OH）3Precipitation, finally makes precipitation be separated from waste water solution.Profit of the invention adds appropriate nano-TiO on the basis of with gamma-ray radiation method processing waste water containing chrome2, the clearance that makes hexavalent chromium is higher, treatment effect more preferably, while the irradiation dose needed for wastewater treatment can be reduced.
Description
Technical field
The present invention relates to gamma-ray irradiation technical applications, in specifically a kind of efficiently removal chromate waste water Cr VI from
The method of son.
Background technology
Cr VI is the property swallowed poisonous substance/imbedibility poisonous substance, and skin contact may cause sensitivity；More likely cause heredity base
Because of defect, suction is potentially carcinogenic, and has lasting danger to environment.But these are the characteristic of Cr VI, chromium metal, trivalent or tetravalence
Chromium ion does not simultaneously have these toxicity.Cr VI is easy to be absorbed by the body, it can by digestion, respiratory tract, skin and
Mucous membrane invades human body.Have been reported that there is different degrees of hoarse, nose to glue during by breathing in air the chromic anhybride containing various concentrations
Film atrophy, can also make perforation of nasal septum and bronchiectasis etc. when serious, can be caused vomiting when being invaded through alimentary canal, abdomen pain, warp
Skin can produce dermatitis and eczema when invading, that endangers maximum has carcinogenic danger when being and contacting or suck in long or short term.
The toxicity of chromium is relevant with the valence state that it is present, it is generally recognized that the toxicity of Cr VI is higher by 100 times, sexavalence than trivalent chromium
Chromium is more easily absorbed by the body and accumulates in vivo.China is defined as Cr VI to implement one of index of overall control, root
According to《Integrated wastewater discharge standard》Primary standard：Total Cr concentration must not be higher than 1.5mg/L, Cr（Ⅵ）Concentration must not be higher than 0.5mg/
L, and necessary treatment can not be replaced with dilution method；Chromium content must not exceed 0.05mg/L in Drinking Water.
The pollution source of chromium is mainly the industries such as metallurgical industry, Treatment of Metal Surface, leather tanning, pigment, printing and dyeing.Chromium
The common valence state of compound has trivalent and sexavalence, in water body, Cr（Ⅵ）Typically with tri- kinds of the moon of CrO42-, Cr2O72-, HCrO4-
Ionic species is present, and under certain condition, the compound of trivalent chromium and Cr VI can mutual inversion of phases.The salt of trivalent chromium can be
Hydrolyzed in neutral or weakly alkaline solution, generate water insoluble chromium hydroxide and sink under water.Generally for Cr's in water (VI)
Removal, is generally first reduced to the relatively low Cr of toxicity (III) by Cr (VI), and Cr is converted under neutral or alkalescence condition（OH）3It is heavy
Form sediment, it is separated from solution.Conventional reduction Cr (VI) method mainly has photo catalytic reduction, electrolysis and chemistry
Reducing process etc., these methods need the certain chemical agent of consumption, while also there are secondary pollution problems, thus by certain
Limitation.
The content of the invention
The present invention is in order to solve problem of the prior art, there is provided hexavalent chromium in a kind of efficient removal chromate waste water
Method, using adding appropriate nano-TiO on the basis of gamma-ray radiation method processing waste water containing chrome2, make hexavalent chromium
Clearance is higher, treatment effect is more preferable, while the irradiation dose needed for can reducing wastewater treatment.
The method that the present invention is used is：Ionising radiation is carried out to waste water solution, the reducing power produced using ionising radiation
Strong hydroperoxyl radical H and aqueous electron eaq -, promote Cr in waste water solution（Ⅵ）Cr (III) is reduced into, then at neutral or alkaline bar
Cr (III) is set to be converted into Cr under part（OH）3Precipitation, finally makes precipitation be separated from waste water solution.
Further improve, before waste water solution carries out ionising radiation, addition nano semiconductor material is carried out in waste water solution
Catalysis.Nano-TiO is added in waste water2Catalysis Cr（Ⅵ）Reduction removal, while adsorb fixed solution in Cr（Ⅵ）, can have
Effect promotes Cr in waste water solution（Ⅵ）Removal, improve reaction rate, reduce waste water radiation treatment needed for absorbed dose of radiation, reduce
Cost.
Further improve, described nano semiconductor material is TiO2.Titanium dioxide has high stability, high activity in itself
With polymolecularity, nontoxicity, it is widely present in environment, adds a certain amount of titanium dioxide not bring secondary dirt to water environment
Dye.
Further improve, described TiO2It is diameter 10nm solid powders, addition is 1g/L.
Further improve, described ionising radiation is gamma-ray irradiation reduction, and gamma-rays is produced by radionuclide 60Co,
Close rate is 0.89kGy/h, and irradiation dose is 0-35.6kGy.
Beneficial effect of the present invention is：Using the reducing power of ionising radiation generation strong hydroperoxyl radical H and eaq -, promote
Cr (VI) in waste water is reduced into Cr (III), and nano-TiO is added in waste water2The reduction of Cr VI is catalyzed, while nano-TiO2Have
Larger specific surface area, has certain absorption fixation to Cr VI, and follow-up waste water solution only needs the filtration treatment just to make
Cr in waste water（Ⅵ）Concentration reach the discharge standard of national regulation.Titanium dioxide has high stability, high activity and height in itself
Dispersiveness, nontoxicity.Itself all contain titanium elements in nearly all biology, rock, water body and soil, add a certain amount of two
Titanium oxide will not bring secondary pollution to water environment.
Brief description of the drawings
Fig. 1 for the waste water solution of concentration 4mg/L carry out ionising radiation when, dose of radiation and residue Cr（Ⅵ）Concentration and Cr
（Ⅵ）The relation of clearance.
Fig. 2 for the waste water solution of concentration 20mg/L carry out ionising radiation when, dose of radiation and residue Cr（Ⅵ）Concentration and
Cr（Ⅵ）The relation of clearance.
Fig. 3 for the waste water solution of concentration 40mg/L carry out ionising radiation when, dose of radiation and residue Cr（Ⅵ）Concentration and
Cr（Ⅵ）The relation of clearance.
Specific embodiment
The invention will be further described with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1：
1st, voluntarily configuration concentration is the Cr of 4mg/L to take 20ml（Ⅵ）The aqueous solution, is added to the resistance to spoke equipped with 1-3 μm of silica wool of diameter
According to glass container, being placed in central duct carries out radiation treatment；
2nd, voluntarily configuration concentration is the Cr of 4mg/L to take 20ml（Ⅵ）The aqueous solution, is added to the resistance to spoke equipped with 1-3 μm of silica wool of diameter
According in glass container, the TiO of a diameter of 10nm of 0.02g is added2Solid powder, makes its concentration for 1g/L, and concussion shakes up, and makes TiO2
Uniform adsorption is placed in central duct and carries out radiation treatment in silica wool silk table face, by glass container.
3、Cr（Ⅵ）The aqueous solution passes through60The gamma-radiation radiation treatment that Co sources provide, close rate is 0.89kGy/h, irradiates agent
Measure as 0,7.12,14.24,21.36,28.48kGy.
4th, the solution that will have been irradiated carries out filtration treatment, determines residue Cr in solution（Ⅵ）Concentration, and calculate Cr
（Ⅵ）Clearance, as shown in Figure 1.Under conditions of gamma-ray irradiation, when irradiation dose is 7.12kGy, it is distributed with solution
The TiO of 1g/L2Experimental group hexavalent chromium removal rate is 100%, without TiO2Blank control group hexavalent chromium removal rate be 72%.
Embodiment 2：
1st, voluntarily configuration concentration is the Cr of 20mg/L to take 20ml（Ⅵ）The aqueous solution, is added to equipped with the resistance to of 1-3 μm of silica wool of diameter
In irradiation glass container, being placed in central duct carries out radiation treatment；
2nd, voluntarily configuration concentration is the Cr of 20mg/L to take 20ml（Ⅵ）The aqueous solution, is added to equipped with the resistance to of 1-3 μm of silica wool of diameter
In irradiation glass container, the TiO of a diameter of 10nm of 0.02g is added2Solid powder, makes its concentration for 1g/L, and concussion shakes up, makes
TiO2Uniform adsorption is placed in central duct and carries out radiation treatment in silica wool silk table face, by glass container.
3、Cr（Ⅵ）The gamma-radiation radiation treatment that the aqueous solution is provided by 60Co sources, close rate is 0.89kGy/h, irradiation
Dosage be 0,7.12,14.24,21.36,35.6kGy.
4th, the solution that will have been irradiated carries out filtration treatment, determines residue Cr in solution（Ⅵ）Concentration, and calculate Cr
（Ⅵ）Clearance, as shown in Figure 2.Under conditions of gamma-ray irradiation, when irradiation dose is 14.24kGy, it is distributed with solution
The TiO of 1g/L2Experimental group hexavalent chromium removal rate is 91%, without TiO2Blank control group hexavalent chromium removal rate be 33%.
Embodiment 3：
1st, voluntarily configuration concentration is the Cr of 40mg/L to take 20ml（Ⅵ）The aqueous solution, is added to equipped with the resistance to of 1-3 μm of silica wool of diameter
In irradiation glass container, being placed in central duct carries out radiation treatment；
2nd, voluntarily configuration concentration is the Cr of 40mg/L to take 20ml（Ⅵ）The aqueous solution, is added to equipped with the resistance to of 1-3 μm of silica wool of diameter
In irradiation glass container, the TiO of a diameter of 10nm of 0.02g is added2Solid powder, makes its concentration for 1g/L, and concussion shakes up, makes
TiO2 uniform adsorptions are placed in central duct and carry out radiation treatment in silica wool silk table face, by glass container.
3、Cr（Ⅵ）The gamma-radiation radiation treatment that the aqueous solution is provided by 60Co sources, close rate is 0.89kGy/h, irradiation
Dosage be 0,7.12,14.24,21.36,35.6kGy.
4th, the solution that will have been irradiated carries out filtration treatment, determines residue Cr in solution（Ⅵ）Concentration, and calculate Cr
（Ⅵ）Clearance, as shown in Figure 3.Under conditions of gamma-ray irradiation, when irradiation dose is 35.6kGy, it is distributed with solution
The TiO of 1g/L2Experimental group hexavalent chromium removal rate is 67.1%, without TiO2Blank control group hexavalent chromium removal rate be 32%.
Concrete application approach of the present invention is a lot, and the above is only the preferred embodiment of the present invention, it is noted that for
For those skilled in the art, under the premise without departing from the principles of the invention, some improvement can also be made, this
A little improvement also should be regarded as protection scope of the present invention.
Claims (4)
1. it is a kind of it is efficient removal chromate waste water in hexavalent chromium method, it is characterised in that：Nanometer is added in waste water solution
Semi-conducting material is catalyzed and is carried out ionising radiation to waste water solution, using the strong hydrogen of the reducing power of ionising radiation generation certainly
By base H and aqueous electron eaq -, promote Cr in waste water solution（Ⅵ）Cr (III) is reduced into, Cr is made under neutral or alkalescence condition
(III) it is converted into Cr（OH）3Precipitation, finally makes precipitation be separated from waste water solution.
2. it is according to claim 1 it is efficient removal chromate waste water in hexavalent chromium method, it is characterised in that：Described
Nano semiconductor material is TiO2。
3. it is according to claim 2 it is efficient removal chromate waste water in hexavalent chromium method, it is characterised in that：Described
TiO2It is diameter 10nm solid powders, addition is 1g/L.
4. in the efficient removal chromate waste water according to claim 1 or 3 hexavalent chromium method, it is characterised in that：Institute
The ionising radiation stated is reduced for gamma-ray irradiation, and gamma-rays is produced by radionuclide 60Co, and close rate is 0.89kGy/h, spoke
It is 0-35.6kGy according to dosage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710119782.4A CN106882854A (en) | 2017-03-02 | 2017-03-02 | The method for efficiently removing hexavalent chromium in chromate waste water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710119782.4A CN106882854A (en) | 2017-03-02 | 2017-03-02 | The method for efficiently removing hexavalent chromium in chromate waste water |
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| Publication Number | Publication Date |
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| CN106882854A true CN106882854A (en) | 2017-06-23 |
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| CN201710119782.4A Pending CN106882854A (en) | 2017-03-02 | 2017-03-02 | The method for efficiently removing hexavalent chromium in chromate waste water |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107459125A (en) * | 2017-09-08 | 2017-12-12 | 水利部交通运输部国家能源局南京水利科学研究院 | A kind of sewage disposal reaction unit |
| CN113735163A (en) * | 2021-09-28 | 2021-12-03 | 北京大学 | Porous titanium dioxide material containing oxygen vacancies and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1587094A (en) * | 2004-09-21 | 2005-03-02 | 南京大学 | Process for removing sexavalent chromium in low concentration waste water containing chromium |
-
2017
- 2017-03-02 CN CN201710119782.4A patent/CN106882854A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1587094A (en) * | 2004-09-21 | 2005-03-02 | 南京大学 | Process for removing sexavalent chromium in low concentration waste water containing chromium |
Non-Patent Citations (2)
| Title |
|---|
| RYUJI NAGAISHI 等: "《Radiation-induced catalytic reduction of chromium(VI) in aqueous solution containing TiO2, Al2O3 or SiO2 fine particles》", 《RADIATION PHYSICS AND CHEMISTRY》 * |
| 徐蕾 等: "《负载型多酸光催化材料及应用》", 31 March 2015, 东北师范大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107459125A (en) * | 2017-09-08 | 2017-12-12 | 水利部交通运输部国家能源局南京水利科学研究院 | A kind of sewage disposal reaction unit |
| CN113735163A (en) * | 2021-09-28 | 2021-12-03 | 北京大学 | Porous titanium dioxide material containing oxygen vacancies and preparation method and application thereof |
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Application publication date: 20170623 |