CN102976386A - Preparation method of nano-scale calcium peroxide for removing toluene in water body - Google Patents
Preparation method of nano-scale calcium peroxide for removing toluene in water body Download PDFInfo
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- CN102976386A CN102976386A CN201210513253XA CN201210513253A CN102976386A CN 102976386 A CN102976386 A CN 102976386A CN 201210513253X A CN201210513253X A CN 201210513253XA CN 201210513253 A CN201210513253 A CN 201210513253A CN 102976386 A CN102976386 A CN 102976386A
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Abstract
The invention relates to a preparation method of nano-scale calcium peroxide for removing toluene in a water body. The preparation method comprises the following steps of: grinding calcium hydroxide into slurry with the solid content of 15-30 percent by a ball mill, and adding the ground slurry to continuously-stirred hydrogen peroxide with the concentration of 30%; conducting a reaction in an ice-water bath and making a mixed solution which is prepared after the ground slurry is added to continuously react for 15-20minutes; adding hydrochloric acid to a mixed solution obtained after the reaction is finished to adjust pH to 6-7; and filtering and vacuum-drying the mixed solution subjected to pH adjustment to obtain the nano-scale calcium peroxide. The preparation method disclosed by the invention is used for preparing the nano-scale calcium peroxide at a low temperature, is simple and free of any additive and is low in cost of raw materials; and in addition, the nano-scale calcium peroxide prepared by using the preparation method is stable in property and favorable in environmental friendliness. Proved by a degradation experiment, the prepared nano-scale calcium peroxide has higher degradation capability on pollutants and is an extremely-promising environment repair material.
Description
Technical field
The present invention relates to the preparations of nanomaterials technology, particularly relate to a kind of preparation method of the nano level calcium peroxide for removing water body toluene.Belong to nano material and environmental science.
Background technology
Calcium peroxide is beige or white powder, odorless, nontoxic, be insoluble in water, be insoluble to ethanol, acetone and other organic solvent.Stable under the drying at room temperature condition, in humidity or water absorption course, decomposite gradually oxygen, its effective oxygen is 22.2%.Except stable oxygen release performance, calcium peroxide also has stronger sterilization, sterilization, bleachability, so calcium peroxide all is widely used at numerous areas such as aquaculture, herding, agriculturals.Can be used for removing heavy metal substance in the sewage at the environmental area calcium peroxide, copper, cadmium, lead, zinc etc. are all had higher clearance.In addition, research in recent years finds that calcium peroxide also has the character of oxidation organic pollutent, and the content of oxygen is excited by different conditions and can produce hydroxyl radical free radical, thereby pollutant oxidation is degraded up to 44% in the calcium peroxide in its water-soluble solution.
In recent years along with being widely used of oil and goods, because of accident and the oil that underground utilities are aging, transportation etc. causes reveal the pollution of soil and groundwater caused people's attention day by day.Of a great variety for the restorative procedure that is subjected to hydrocarbon contaminated soil and underground water, but excellent lacking, respectively arranged, and present a kind of New Solid oxygen-releasing compound injection method has caused increasing concern because of its efficient, cheap characteristics.This solid-state oxygen-releasing compound injection method mainly is by solid-state oxygen release material being comprised the contaminated zones of injection such as Magnesium peroxide, calcium peroxide degrade to pollutent, discharging simultaneously the Degradation that oxygen improves microbe in the surrounding environment.
Calcium peroxide is as a kind of oxygenant, in oxidize contaminants, can not bring disadvantageous effect to environment, oxygen is provided for simultaneously the microorganism in the environment, promote microbial growth, increase the Degradation of microbe, therefore be applied to have outstanding advantage in the reparation of polluted soil and underground water.But the calcium peroxide particle size of traditional non-nano level is excessive and be easy to reunite in actual applications, and difficulties in dispersion is difficult for flowing to specific restoring area in the underground water reparation is used, and remediation efficiency is lower.The nanometer calcium peroxide can increase the surface-area of calcium peroxide effectively, has accelerated the speed of reaction of calcium peroxide particle and pollutent, shortens to be used for the time that underground water is repaired, and has also reduced the amount for the calcium peroxide of repairing simultaneously.
The present invention as targeting substance, has studied prepared nanometer calcium peroxide to the degradation effect of toluene with the toluene in the petroleum-type pollutent.Toluene is as BTEX(benzene, toluene, ethylbenzene, xylenes) in a class essential substance, content is higher in oil, simultaneously, because the pollution of its generation has also caused increasing medical attention to the injury of human body.The maximum contaminant level that toluene allows in environment as a kind of carcinogens is 1ppm, but for the zone that is subjected to the petroleum-type contaminants, far super this limit value of the concentration of toluene.This pollutant of human body Long Term Contact will cause the damage of liver, kidney and central nervous system, severe patient even cause the canceration of body.This patent has been studied the removal for water body middle and high concentration toluene, synthetic calcium peroxide fast to degradation rate height and the degradation speed of toluene, obtained good effect.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who can be used for removing the nanometer calcium peroxide of toluene concentration thing in the water body.
The preparation method of a kind of nano level calcium peroxide for removing water body toluene of proposition of the present invention, concrete steps are as follows:
Take calcium hydroxide and hydrogen peroxide as raw material, it is 15% ~ 30% calcium hydroxide slurry that calcium peroxide and deionized water are made into solid content, through ball mill grinding 2 ~ 3h; Hydrogen peroxide is added in the beaker, and it is ice-water bath and the uniform stirring of 0-15 degree that beaker places temperature, slowly adds calcium hydroxide slurry in the hydrogen peroxide; The calcium hydroxide slurry that adds and hydrogen peroxide reaction 15 ~ 20min are beige to mixed solution, and the mol ratio of calcium hydroxide slurry and hydrogen peroxide is 1:(4.5 ~ 7.5); The pH value to 6 of mixed solution ~ 7 in the regulation system; Mixed solution is by 0.45 μ m filter membrane, gets that solid matter vacuum-drying to moisture evaporates fully on the film, namely gets desired product.
Among the present invention, described vacuum-drying temperature is 30 ~ 40 ℃.
Among the present invention, described hydrogen peroxide adopts 30% hydrogen peroxide.
Among the present invention, the pH value of mixed solution is regulated by adding hydrochloric acid in the system.
Among the present invention, the mol ratio of calcium hydroxide slurry and hydrogen peroxide is 1:(6.5 ~ 7.5).
The advantage of the prepared nanometer calcium peroxide of the present invention method is: prepared nanometer calcium peroxide has stronger degradation capability to pollutent, through experiment confirm the degraded of toluene is better than commercially available calcium peroxide to the removal ability of toluene.And preparation Raw cost is low, and the gained calcium peroxide has better stability and environment friendly.
Description of drawings
Fig. 1 is the XRD figure spectrum of embodiment 1 nanometer calcium peroxide;
Fig. 2, (a), (b) without the calcium hydroxide that grinds the SEM collection of illustrative plates of synthetic calcium peroxide;
(c), (d) is for the SEM collection of illustrative plates of embodiment 1 prepared nano level calcium peroxide.
Embodiment
Below in conjunction with the prepared nanometer calcium peroxide of the present invention the degraded of toluene is further specified the specific embodiment of the present invention.
Embodiment 1:
1, calcium hydroxide and deionized water being made into solid content is 15 ~ 30% slurries, through ball mill grinding 2 ~ 3h;
2, will be 1:(6.5 ~ 7.5 with the calcium hydroxide mol ratio) hydrogen peroxide add in the beaker, and place temperature to be lower than 15 ℃ ice-water bath;
3, add ground calcium hydroxide slurry while stirring;
4, after adding fully, solution continues reaction 15 ~ 20min;
5, add hydrochloric acid, regulator solution pH to 6 ~ 7;
6, mixed solution is by 0.45 μ m filter membrane, and solid matter is put into vacuum drying oven and is dried to moisture evaporates fully under 30 ~ 40 ℃, obtains the nanometer calcium peroxide powder.
As shown in Figure 1, the XRD figure spectrum for the prepared nano level calcium peroxide of the present invention through comparing with standard card, shows that prepared material is calcium peroxide.
As shown in Figure 2, (a) and (b) are the SEM collection of illustrative plates of the synthetic calcium peroxide of usual way; (c), (d) is the SEM collection of illustrative plates of the prepared nano level calcium peroxide of the present invention.The synthetic calcium peroxide size distribution of visible usual way institute is uneven from (a) and (b) figure, and most of grain diameter is all greater than 1um, part grain diameter even greater than 20um.The prepared calcium peroxide of usual way is adhered to one another, is agglomerated into piece.These character are the common calcium peroxide of impact key technical problems in the water body reparation is used.As seen, particle size is relatively even, is distributed between the 100-200nm from (c), (d) figure for the prepared nano level calcium peroxide of the present invention, is spherical or cubic.The particle monomer can clear identification out show that the prepared nano level calcium peroxide of the present invention has higher dispersiveness from figure.In the water body reparation is used, outstanding advantage is arranged.
Embodiment 2:
1, calcium hydroxide and deionized water being made into solid content is 15 ~ 30% slurries, through ball mill grinding 2 ~ 3h;
2, will be 1:(4.5 ~ 5.5 with the calcium hydroxide mol ratio) hydrogen peroxide add in the beaker, and place temperature to be lower than 15 ℃ ice-water bath;
3, add ground calcium hydroxide slurry while stirring;
4, after adding fully, solution continues reaction 15 ~ 20min;
5, add hydrochloric acid, regulator solution pH to 6 ~ 7;
6, mixed solution is by 0.45 μ m filter membrane, and solid matter is put into vacuum drying oven and be dried to moisture under 30 ~ 40 ℃
Application examples 1:
For gained mixed solution among the embodiment 1, add 460ppm toluene.Reaction 9d, and in the sampling of setting-up time point, measure the toluene residual volume, toluene is all removed in 3d after testing.Contrast simultaneously the hydrogen peroxide of same amount to the degraded of toluene, to get rid of the impact of hydrogen peroxide in the mixed solution, through identifying, without the removal effect, all the removal of toluene is because the effect of nanometer calcium peroxide of the present invention to hydrogen peroxide to toluene.
Application examples 2:
For gained mixed solution among the embodiment 2, add 460ppm toluene.Reaction 9d, and in the sampling of setting-up time point, measure the toluene residual volume, toluene is just removed fully in 7d after testing.
Comparative Examples 1:
Use the calcium peroxide that synthesizes by embodiment 1 same proportioning without the ordinary hydrogen calcium oxide that grinds, the toluene of adding and application examples same amount, all operations is consistent with embodiment 1, and only the pre-treatment of calcium hydroxide is different.The result shows that toluene still has remnants at 9d, and the clearance of 3d only is about 75%.
Comparative Examples 2:
With the ratio adding toluene of commercially available calcium peroxide by the same amount of substance of application examples, all operations is consistent with application examples.The result shows that toluene still has remnants at 9d, and the clearance of 3d only is 45%.
Claims (3)
1. preparation method who be used for to remove the nano level calcium peroxide of water body toluene is characterized in that concrete steps are as follows:
Take calcium hydroxide and hydrogen peroxide as raw material, it is 15% ~ 30% calcium hydroxide slurry that calcium peroxide and deionized water are made into solid content, through ball mill grinding 2 ~ 3h; Hydrogen peroxide is added in the beaker, and it is ice-water bath and the uniform stirring of 0-15 degree that beaker is placed temperature, slowly adds calcium hydroxide slurry in the hydrogen peroxide; The calcium hydroxide slurry that adds and hydrogen peroxide reaction 15 ~ 20min are beige to mixed solution, and the mol ratio of calcium hydroxide slurry and hydrogen peroxide is 1:(6.5 ~ 7.5); The pH value to 6 of mixed solution ~ 7 in the regulation system; Mixed solution is by 0.45 μ m filter membrane, gets that solid matter vacuum-drying to moisture evaporates fully on the film, namely gets desired product.
2. preparation method according to claim 1 is characterized in that described vacuum-drying temperature is 30 ~ 40 ℃.
3. preparation method according to claim 1 is characterized in that described hydrogen peroxide adopts 30% hydrogen peroxide.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601155A (en) * | 2013-11-18 | 2014-02-26 | 同济大学 | Method for preparing nano calcium peroxide by chemical modification |
| CN106966484A (en) * | 2017-03-31 | 2017-07-21 | 常州大学 | A kind of nanometer Fe3O4/CaO2The method for repairing the pollution of underground water benzene homologues |
| CN110182987A (en) * | 2019-03-22 | 2019-08-30 | 江苏长三角环境科学技术研究院有限公司 | A method of it repairing Automobile Service and place combined pollution underground water is electroplated |
| CN111115585A (en) * | 2019-12-26 | 2020-05-08 | 重庆新申世纪新材料科技有限公司 | Method for preparing high bulk density strontium peroxide and product thereof |
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|---|---|---|---|---|
| GB1108302A (en) * | 1964-02-26 | 1968-04-03 | Canadian Ind | Preparation of calcium peroxide |
| RU1778068C (en) * | 1990-06-12 | 1992-11-30 | Всесоюзный научно-исследовательский институт реактивов и химически чистых материалов для электронной техники | Method for producing calcium peroxide |
| JPH0733096A (en) * | 1993-07-22 | 1995-02-03 | Mitsubishi Heavy Ind Ltd | Overheat preventing device for propellant conduit |
| CN1104996A (en) * | 1993-11-18 | 1995-07-12 | 董国兴 | Calcium peroxide powder and its making method |
| CN1346787A (en) * | 2001-09-26 | 2002-05-01 | 陶华西 | Process for preparing calcium peroxide |
| RU2315708C1 (en) * | 2006-05-11 | 2008-01-27 | Ооо "Химновотех" | Method of production of calcium peroxide |
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2012
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1108302A (en) * | 1964-02-26 | 1968-04-03 | Canadian Ind | Preparation of calcium peroxide |
| RU1778068C (en) * | 1990-06-12 | 1992-11-30 | Всесоюзный научно-исследовательский институт реактивов и химически чистых материалов для электронной техники | Method for producing calcium peroxide |
| JPH0733096A (en) * | 1993-07-22 | 1995-02-03 | Mitsubishi Heavy Ind Ltd | Overheat preventing device for propellant conduit |
| CN1104996A (en) * | 1993-11-18 | 1995-07-12 | 董国兴 | Calcium peroxide powder and its making method |
| CN1346787A (en) * | 2001-09-26 | 2002-05-01 | 陶华西 | Process for preparing calcium peroxide |
| RU2315708C1 (en) * | 2006-05-11 | 2008-01-27 | Ооо "Химновотех" | Method of production of calcium peroxide |
Non-Patent Citations (2)
| Title |
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| ZHAI YONG-QING ET AL.: "Synthesis of CaO2 in Aqueous at Room Temperature and Its Application in Wastewater Treatment", 《中山大学学报（自然科学版）ACTA SCIENTIARUM NATURALIUM UNIVERSITATIS SUNYATSENI》, vol. 42, 30 June 2003 (2003-06-30), pages 122 - 125 * |
| 田从学: "过氧化钙(CaO2)的实验室制备研究", 《攀枝花大学学报》, vol. 18, no. 1, 31 March 2001 (2001-03-31), pages 76 - 79 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601155A (en) * | 2013-11-18 | 2014-02-26 | 同济大学 | Method for preparing nano calcium peroxide by chemical modification |
| CN106966484A (en) * | 2017-03-31 | 2017-07-21 | 常州大学 | A kind of nanometer Fe3O4/CaO2The method for repairing the pollution of underground water benzene homologues |
| CN110182987A (en) * | 2019-03-22 | 2019-08-30 | 江苏长三角环境科学技术研究院有限公司 | A method of it repairing Automobile Service and place combined pollution underground water is electroplated |
| CN111115585A (en) * | 2019-12-26 | 2020-05-08 | 重庆新申世纪新材料科技有限公司 | Method for preparing high bulk density strontium peroxide and product thereof |
| CN111115585B (en) * | 2019-12-26 | 2023-06-30 | 重庆新申世纪新材料科技有限公司 | Method for preparing high bulk density strontium peroxide and product thereof |
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