CN105728426A - Method for promoting reduction of Cr(VI) in chromium core deposits by utilizing nano-material - Google Patents
Method for promoting reduction of Cr(VI) in chromium core deposits by utilizing nano-material Download PDFInfo
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- CN105728426A CN105728426A CN201610065069.1A CN201610065069A CN105728426A CN 105728426 A CN105728426 A CN 105728426A CN 201610065069 A CN201610065069 A CN 201610065069A CN 105728426 A CN105728426 A CN 105728426A
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- nano
- ore deposit
- chrome ore
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 13
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 title abstract 9
- 230000001737 promoting effect Effects 0.000 title abstract 2
- 239000011651 chromium Substances 0.000 claims abstract description 70
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 20
- 239000002105 nanoparticle Substances 0.000 claims abstract description 20
- 239000002893 slag Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012153 distilled water Substances 0.000 claims abstract description 10
- 238000012360 testing method Methods 0.000 claims abstract description 3
- 239000008187 granular material Substances 0.000 claims description 14
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 230000003068 static effect Effects 0.000 claims description 6
- 238000006392 deoxygenation reaction Methods 0.000 claims description 5
- 239000008246 gaseous mixture Substances 0.000 claims description 5
- 238000005273 aeration Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000005070 sampling Methods 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 125000006267 biphenyl group Chemical group 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000004098 cellular respiration Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 201000007048 respiratory system cancer Diseases 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a method for promoting reduction of Cr(VI) in chromium core deposits by utilizing a nano-material, and relates to a Cr(VI) pollutant treatment method. The method provided by the invention comprises the following steps: dispersing polluted chromium core deposits around a chromium slag heap by utilizing distilled water, dissolving out Cr(VI), and then adding nano-particles; performing anaerobic treatment on various samples; placing a reactor into an incubator in a standing manner; and performing sampling at different time points, testing the Cr(VI) concentrations of the samples, and taking out the reactor till the Cr(VI) concentrations reach zero, so as to complete the reduction of Cr(VI) in the chromium core deposits. The method has advantages that the utilized nano-particles are nontoxic and harmless, cheap, easy to obtain, and small in adding amount; the effect on the reduction of Cr(VI) in the chromium core deposits is remarkable; the total reduction amount of Cr(VI) is obviously improved; and the environmental friendliness and the economic feasibility are achieved.
Description
Technical field
The present invention relates to the processing method of Cr (VI) pollutant, especially relate to one and utilize nano material to promote the method that in chrome ore deposit, Cr (VI) reduces.
Background technology
It is an important sources of deposit pollution of chromium that chromium slag muck is put, and generally, often produces 1 ton of big appointment 10 tons of chromium slag of discharge of crome metal, often produces 1 ton of chromic salts and can discharge the high toxicity chromium slag (regenerated resources research, 2004,6,34-38) of 2.5～3 tons.In chromium slag, the Transport And Transformation of chromium is very active, and it can migrate between air, water body, Soil sediment and plant, and ecological environment causes serious pollution.Mainly there is (EnvironmentPollution, 2000,107,263-283) with the form of oxidation state Cr (III) two kinds stable and Cr (VI) in the chromium in nature.Cr (III) is the most stable of form of chromium, it is easy to forming stable complex, toxicity is little, and the toxicity of Cr (VI) is 100 times of Cr (III), can cause respiratory system cancer (TaiYuan Industry University, 1988,7,30-33).The toxicity of chromium pollutant mostlys come from Cr (VI), therefore, reduces pollution of chromium and first has to reduce the pollution of Cr (VI).
The method of reducing of Cr (VI) has the methods such as chemical method (environmental project journal, 2015,9,3077-3085) and microbial method (EnvironmentMicrobiology, 2004,6,851-860).The shortcoming of chemical method is complicated operation, and cost is high, and the reagent of employing is poisonous, is easily generated secondary pollution etc..Though the patent that publication number is CN105039726A adopts the cyclone furnace high-temperature detoxification poisonous chromium slag of reduction that chromium slag can be made to be recycled utilization, but cost of equipment is high, operates more complicated.Microbial method is to rely on Cellular respiration by provided electron transmission of electron donor such as organic matters to terminal electron acceptor Cr (VI) method making it reduce.The reaction condition of bioanalysis is gentle, but reaction rate is slower.Finding through research, nano-particle can promote the reducing power of heavy metal ion.Wang Yuanpeng etc. report through nanometer Fe2O3Granule or nanometer Fe3O4After particle disposal, in deposit, the rate of reduction of arsenic is greatly improved (EnvironmentalScience&Techonology, 2014,48,7,469 7476).
Summary of the invention
It is an object of the invention to provide the method that one nano material promotes that in chrome ore deposit, Cr (VI) reduces.
The present invention comprises the following steps:
1) make the chrome ore deposit breakup that chromium slag muck periphery pollutes, dissolution Cr (VI) with distilled water, add nano-particle；
2) each sample is carried out anaerobic treatment；
3) reactor is static is placed in calorstat；
4) sample in different time points, Cr (VI) concentration in test sample, when Cr (VI) concentration is 0, take out reactor, namely complete Cr (VI) reduction in chrome ore deposit.
In step 1) in, the chrome ore deposit that described chromium slag muck periphery pollutes is retrieved from the chrome ore deposit that Qujing of Yunnan chromium slag muck periphery pollutes；The proportioning of described distilled water, chrome ore deposit and nano-particle can be 24ml: (19～21) g: 0.2g, and wherein, distilled water is calculated by volume, and chrome ore deposit and nano-particle are calculated in mass；The mass concentration of described dissolution Cr (VI) can be 286～356mg/L；Described nano-particle is selected from Nano-meter SiO_22Granule, nanometer Fe2O3Granule, nanometer Fe3O4One in granule etc.；The granularity of described nano-particle can be 100nm.
In step 2) in, in described anaerobic treatment, the gas for deoxygenation can be N2And CO2Gaseous mixture, by volume percentage ratio N2∶CO2=80%: 20%, aeration time can be 40min.
In step 3) in, the temperature of calorstat can be 30 DEG C, and the time of described placement can be 20.5～25.5 days.
The present invention is simple to operate, first makes chrome ore deposit be completely dispersed with distilled water, adds nano-particle, adopts N after shaking up2With CO2Gaseous mixture sample is carried out deoxygenation, then sample is positioned in calorstat, makes Cr (VI) in chrome ore deposit be reduced.The present invention analyzes Cr (VI) concentration in different time points sample, and result shows to add the reduction that nano-particle has been obviously promoted in chrome ore deposit Cr (VI).
The invention discloses one utilizes nano-particle to promote the method for Cr (VI) in chrome ore deposit.The method is containing adding Nano-meter SiO_2 in chromium deposit to common2Granule or nanometer Fe2O3Granule or nanometer Fe3O4One in granule, and matched group is set above-mentioned nano-particle is promoted, and Cr (VI) reduction is verified in chrome ore deposit.Relative to simple chemical reduction method, the method experiment condition requires low, and experiment reagent is nontoxic to be easy to get, and has environment friendly.It addition, after nano-particle processes, the rate of reduction of Cr (VI) is high with reducing degree in chrome ore deposit, provide a kind of novelty, feasible method for processing Cr (VI) pollutant in chrome ore deposit.
Accompanying drawing explanation
Fig. 1 is that the embodiment of the present invention 1～4 measures Cr (VI) concentration curve.
Detailed description of the invention
Below by drawings and Examples, the present invention will be further described.
Embodiment 1
20 ± 1g chrome ore deposit is made to be completely dispersed with 24ml distilled water, by volume percentage ratio N2∶CO2The gaseous mixture of=80%: 20%, to sample aeration 40min, is then placed in 30 DEG C of calorstats 25.5 days by static for sample.By diphenyl phosphinylidyne two hydrazine spectrophotography, measure Cr (VI) concentration in different time sample.Curve a in Fig. 1 is Cr (VI) concentration changes with time curve in the sample without nano-particle process.
Embodiment 2
Make 20 ± 1g chrome ore deposit be completely dispersed with 24ml distilled water, add 0.2g Nano-meter SiO_22Granule, uses N2∶CO2The gaseous mixture of=80%: 20%, to sample aeration 40min, is then placed in 30 DEG C of calorstats 25.5 days by static for sample.By diphenyl phosphinylidyne two hydrazine spectrophotography, measure Cr (VI) concentration in different time sample.Curve b in Fig. 1 is through Nano-meter SiO_22Cr (VI) concentration changes with time curve in the sample of particle disposal.
Embodiment 3
0.2g nanometer Fe 2O is added according to the equal step of embodiment 23Particle disposal is containing chromium deposit, according to the same deoxygenation condition of embodiment 1, is then placed in 30 DEG C of calorstats 20.5 days by static for sample.By diphenyl phosphinylidyne two hydrazine spectrophotography, measure Cr (VI) concentration in different time sample.Curve c in Fig. 1 is through nanometer Fe2O3Cr (VI) concentration changes with time curve in the sample of particle disposal.
Embodiment 4
0.2g nanometer Fe is added according to the equal step of embodiment 23O4Particle disposal is containing chromium deposit, according to the same deoxygenation of embodiment 1 and condition, by diphenyl phosphinylidyne two hydrazine spectrophotography, measures Cr (VI) concentration in different time sample, is then placed in 30 DEG C of calorstats 20.5 days by static for sample.Curve d in Fig. 1 is through nanometer Fe3O4Cr (VI) concentration changes with time curve in the sample of particle disposal.
Nano-meter SiO_2 used by the present invention2Granule, nanometer Fe2O3Granule, nanometer Fe3O4Granule is nontoxic, cheap and easy to get, and addition is few, and in chrome ore deposit, the reduction effect of Cr (VI) is notable, and the reduction total amount of Cr (VI) is obviously improved.The method that nano-particle promotes that in chrome ore deposit, Cr (VI) reduces is utilized to have environmental friendliness and economic feasibility.
Claims (8)
1. promote, by nano material, the method that in chrome ore deposit, Cr (VI) reduces, it is characterised in that comprise the following steps:
1) make the chrome ore deposit breakup that chromium slag muck periphery pollutes, dissolution Cr (VI) with distilled water, add nano-particle；
2) each sample is carried out anaerobic treatment；
3) reactor is static is placed in calorstat；
4) sample in different time points, Cr (VI) concentration in test sample, when Cr (VI) concentration is 0, take out reactor, namely complete Cr (VI) reduction in chrome ore deposit.
2. promote, by nano material, the method that in chrome ore deposit, Cr (VI) reduces as claimed in claim 1, it is characterized in that in step 1) in, the proportioning of described distilled water, chrome ore deposit and nano-particle is 24ml: (19～21) g: 0.2g, wherein, distilled water is calculated by volume, and chrome ore deposit and nano-particle are calculated in mass.
3. promote, by nano material, the method that in chrome ore deposit, Cr (VI) reduces as claimed in claim 1, it is characterised in that in step 1) in, the mass concentration of described dissolution Cr (VI) is 286～356mg/L.
4. promote, by nano material, the method that in chrome ore deposit, Cr (VI) reduces as claimed in claim 1, it is characterised in that in step 1) in, described nano-particle is selected from Nano-meter SiO_22Granule, nanometer Fe2O3Granule, nanometer Fe3O4One in granule.
5. promote, by nano material, the method that in chrome ore deposit, Cr (VI) reduces as claimed in claim 1, it is characterised in that in step 1) in, the granularity of described nano-particle is 100nm.
6. promote, by nano material, the method that in chrome ore deposit, Cr (VI) reduces as claimed in claim 1, it is characterised in that in step 2) in, in described anaerobic treatment, the gas for deoxygenation is N2And CO2Gaseous mixture, by volume percentage ratio N2∶CO2=80%: 20%, aeration time is 40min.
7. promote, by nano material, the method that in chrome ore deposit, Cr (VI) reduces as claimed in claim 1, it is characterised in that in step 3) in, the temperature of calorstat is 30 DEG C.
8. promote, by nano material, the method that in chrome ore deposit, Cr (VI) reduces as claimed in claim 1, it is characterised in that in step 3) in, the time of described placement is 20.5～25.5 days.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610065069.1A CN105728426A (en) | 2016-01-29 | 2016-01-29 | Method for promoting reduction of Cr(VI) in chromium core deposits by utilizing nano-material |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610065069.1A CN105728426A (en) | 2016-01-29 | 2016-01-29 | Method for promoting reduction of Cr(VI) in chromium core deposits by utilizing nano-material |
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| CN105728426A true CN105728426A (en) | 2016-07-06 |
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| CN201610065069.1A Pending CN105728426A (en) | 2016-01-29 | 2016-01-29 | Method for promoting reduction of Cr(VI) in chromium core deposits by utilizing nano-material |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5990373A (en) * | 1996-08-20 | 1999-11-23 | Kansas State University Research Foundation | Nanometer sized metal oxide particles for ambient temperature adsorption of toxic chemicals |
| US20030029803A1 (en) * | 2001-04-16 | 2003-02-13 | Korea Institute Of Geoscience And Mineral Resources | Method for treating wastewater containing heavy metals with used iron oxide catalyst |
| WO2005016828A2 (en) * | 2003-08-13 | 2005-02-24 | Crane Company | Metal-treated particles for remediation |
| CN101306862A (en) * | 2008-07-01 | 2008-11-19 | 浙江大学 | Method for preparing nano-level Fe<0>/Fe3O4 and uses thereof |
| CN103949469A (en) * | 2014-04-21 | 2014-07-30 | 山西霍尼韦尔水处理工程有限公司 | Method for restoring hexavalent-chromium-polluted underground water by virtue of stable zero-valent iron nanoparticles |
| CN103962110A (en) * | 2014-04-29 | 2014-08-06 | 浙江大学 | Multifunctional Fe3O4 magnetic nanometer material, as well as preparation method and application thereof |
-
2016
- 2016-01-29 CN CN201610065069.1A patent/CN105728426A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5990373A (en) * | 1996-08-20 | 1999-11-23 | Kansas State University Research Foundation | Nanometer sized metal oxide particles for ambient temperature adsorption of toxic chemicals |
| US20030029803A1 (en) * | 2001-04-16 | 2003-02-13 | Korea Institute Of Geoscience And Mineral Resources | Method for treating wastewater containing heavy metals with used iron oxide catalyst |
| WO2005016828A2 (en) * | 2003-08-13 | 2005-02-24 | Crane Company | Metal-treated particles for remediation |
| CN101306862A (en) * | 2008-07-01 | 2008-11-19 | 浙江大学 | Method for preparing nano-level Fe<0>/Fe3O4 and uses thereof |
| CN103949469A (en) * | 2014-04-21 | 2014-07-30 | 山西霍尼韦尔水处理工程有限公司 | Method for restoring hexavalent-chromium-polluted underground water by virtue of stable zero-valent iron nanoparticles |
| CN103962110A (en) * | 2014-04-29 | 2014-08-06 | 浙江大学 | Multifunctional Fe3O4 magnetic nanometer material, as well as preparation method and application thereof |
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| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Li Qingbiao Inventor after: Han Kezeng Inventor after: Zhang Yaxian Inventor after: Wang Yuanpeng Inventor before: Li Qingbiao Inventor before: Zhang Yaxian Inventor before: Wang Yuanpeng |
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Application publication date: 20160706 |