CN100563858C - A kind of TiO 2Method with polycyclic aromatic hydrocarbon compounds in the ultraviolet light combined degradation soil - Google Patents
A kind of TiO 2Method with polycyclic aromatic hydrocarbon compounds in the ultraviolet light combined degradation soil Download PDFInfo
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- CN100563858C CN100563858C CN 200610134208 CN200610134208A CN100563858C CN 100563858 C CN100563858 C CN 100563858C CN 200610134208 CN200610134208 CN 200610134208 CN 200610134208 A CN200610134208 A CN 200610134208A CN 100563858 C CN100563858 C CN 100563858C
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Abstract
The present invention relates to the degraded of polycyclic aromatic hydrocarbon pollution, specifically a kind of ultraviolet nanometer TiO of polycyclic aromatic hydrocarbon pollution
2The catalytic degradation method is with contaminated soil and nano-TiO
2Mixture in vessel, pave nano-TiO
2Addition and contaminated soil weight ratio be 0.2%-5%, place the ultraviolet lighting case to carry out illumination degrading, the illumination condition in the lighting box: the ultraviolet lighting wavelength is 210-365nm, sample is apart from light source 5-20cm, intensity of illumination is 500-10000 μ w/cm
2, temperature is 25-35 ℃, humidity is 30-50% in the Ventilation Control case, light application time 2-14 days.Advantage of the present invention is: the speed of removing pollutant is fast, efficient is high, easy operating, do not produce secondary pollution.
Description
Technical field
The present invention relates to the photocatalytic degradation of polycyclic aromatic hydrocarbon pollution, specifically a kind of TiO
2Method with polycyclic aromatic hydrocarbon compounds in the ultraviolet light combined degradation soil.
Background technology
Polycyclic aromatic hydrocarbon compounds (PAHs) is a ubiquitous class organic pollution in the environment.There are two aspects in its source: natural source and artificial source.Natural source mainly is the synthetic of forest and grassland big fire, volcanic eruption, plant and microorganism, and wherein synthetic, the colcanism of higher plant and microorganism are the main factors that produces the PAHs background value; Artificial source is from industrial production and processing (as the refining of production, crude oil and the derivative thereof of coke, carbon black and coal tar and fractionation etc.), and process such as organic imperfect combustion.In artificial source, artificial fuel combustion is the main contribution factor of industrially developed country and urban area PAHs, and the PAHs of exposure has brought huge health hazard for the people that live in developed regions, the world.Why PAHs as environmental contaminants is subjected to people's attention, at first is because secondly carcinogenic, the teratogenesis of some PAHs and mutagenesis are because PAHs stablizes, is difficult to degraded, is ever-increasing trend in environment.Adopt the rational recovery technique of economic benefit and environmental benefit to administer PAHs and pollute, be subject to people's attention more and more.
At present, comprise biological restoration, physics reparation and chemistry reparation about the PAHs pollution remediation technology.The biological restoration of PAHs has a lot of researchs at home and abroad, and biological restoration has many good qualities, and also comes with some shortcomings simultaneously, and is long as the cycle, and condition is difficult to be controlled etc.; Adopt physical methods such as heating and drip washing to remove, the expense height is handled not thorough.In recent years, UV-irradiation and semiconductor TiO
2Symphyogenetic photocatalytic process has been proved a new technology effective and the degradation treatment pollutant that is highly profitable by many achievements in research.
Summary of the invention
The object of the present invention is to provide that a kind of speed is fast, efficient is high, easy operating, do not produce the TiO of secondary pollution
2Method with polycyclic aromatic hydrocarbon compounds in the ultraviolet light combined degradation soil.
For achieving the above object, the technical solution used in the present invention is: with contaminated soil and nano-TiO
2Mixture in vessel, pave, place the ultraviolet lighting case to carry out illumination degrading, nano-TiO
2Addition be 0.2%-5% by weight percentage, the illumination condition in the lighting box: the ultraviolet lighting wavelength is 210-365nm, sample is apart from light source 5-20cm, intensity of illumination is 500-10000 μ w/cm
2, temperature is 20-38 ℃, humidity is 30-50% in the Ventilation Control case, light application time 2-14 days.
Described TiO
2Addition be 0.5%-4% by weight percentage, described ultraviolet lighting wavelength is 254-295nm, sample is apart from light source 5-15cm, intensity of illumination is 1000-3000 μ w/cm
2, temperature is 28-32 ℃, humidity is 35-40% in the Ventilation Control case, light application time 8-12 days.
The ultraviolet lighting dominant wavelength that described ultraviolet lighting case is selected for use is 254nm, 310nm or 365nm.Described nano-TiO
2Be anatase titanium dioxide, surface area is 50m
2g
-1, average diameter is 15-20nm.Described polycyclic aromatic hydrocarbon is BaP, pyrene or phenanthrene.Polycyclic aromatic hydrocarbon is 10-200mg/kg in the described contaminated soil.
The present invention has following advantage:
1. the speed of removal pollutant is fast, efficient is high.Polycyclic aromatic hydrocarbon is that a class persistent organism matter is generally hundreds of days to many decades in the time of nature permineralization, and the time that the intact gold of plant is repaired is more than 200 days.The present invention can be used for polycyclic aromatic hydrocarbons contaminated soil such as BaP, pyrene and phenanthrene.Do not adding TiO
2Situation under, the light degradation of polycyclic aromatic hydrocarbon needs 35-50 days.BaP, pyrene and luxuriant and rich with fragrance content are 40mg/kg in soil, and after handling through illumination in 8 days, BaP is at four kinds of different Ti O
2The degradation rate that adds concentration conditions (0.5%, 1%, 2% and 3%) is respectively 93.06%, 96.28%, 98.31% and 94.02%; After illumination in 12 days processing, pyrene is at four kinds of different Ti O
2The degradation rate that adds concentration conditions (0.5%, 1%, 2% and 3%) is respectively 94.29%, 91.03%, 90.48% and 84.72%; After illumination in 10 days processing, luxuriant and rich with fragrance at four kinds of different Ti O
2The degradation rate that adds concentration conditions (0.5%, 1%, 2% and 3%) is respectively 96.06%, 97.92%, 98.74% and 95.84%.Add a spot of TiO
2The light degradation of having accelerated polycyclic aromatic hydrocarbon greatly.
2. easy operating.The present invention makes the processing of contaminated soil simple, with low cost.Only need contaminated soil is carried out air-dry, the simple process of screening is with a spot of TiO
2Carry out mechanical mixture with contaminated soil, the device that then mixed soil is laid on the plane is placed on to shine under the ultraviolet source and gets final product.
3. do not produce secondary pollution.The invention belongs to photochemical degradating, a small amount of semiconductor that it adds in the contaminated soil is the material that itself has in the soil, toxic action can be do not produced to soil, thereby secondary pollution can not be caused, and be a kind of method of environmentally friendly processing contaminated soil.
The specific embodiment
The present invention is further described below in conjunction with embodiment.
Embodiment 1
Soil sample grinds at room-dry, crosses the 1mm sieve, and batch (-type) high pressure steam sterilization 2 times (each half an hour, 121 ℃) is behind the adding polycyclic aromatic hydrocarbon, air-dry standby.
The preparation of polycyclic aromatic hydrocarbon pollution: with in the soil sample of above-mentioned sterilization by weight 1: 1 ratio of volume ratio add methanol solution (the 1 gram soil: the methanol solution of 1ml polycyclic aromatic hydrocarbon) of polycyclic aromatic hydrocarbon, the BaP, pyrene or the phenanthrene that contain 10mg in the methanol solution of every 1000ml polycyclic aromatic hydrocarbon respectively, place ventilating kitchen 24h, the concentration of polycyclic aromatic hydrocarbon is 10mg/kg in the contaminated soil.
The preparation of polycyclic aromatic hydrocarbon methanol solution: accurately take by weighing 0.01 the gram BaP, pyrene and phenanthrene, respectively with methanol constant volume to 1000ml.
Nano-TiO
2Be anatase titanium dioxide, surface area: 50m
2g
-1, average diameter: 20nm.
With TiO
2Mix with polycyclic aromatic hydrocarbon pollution, mechanical agitation is to even.TiO
2Addition and contaminated soil weight ratio be 0.5%.
Take by weighing the above-mentioned soil sample of 5g and place the petri diss of 9cm diameter, pave, place lighting box to degrade.Irradiation is 8-12 days in lighting box, and soil is put into the 100ml centrifuge tube, adds the carrene of 25ml, ultrasonic water bath 2 hours, and the centrifugal 5min of 5000rmp crosses post, measures the content of the polycyclic aromatic hydrocarbon in the mixed liquor.
Illumination condition in the lighting box: ultraviolet lighting dominant wavelength is 254nm, and sample is apart from light source 15cm, and intensity of illumination is 1071 μ w/cm
2, temperature is 30 ± 1 ℃, humidity is 35% ± 2%.
Treatment effect: the degradation rate through BaP after 8 days the irradiation reaches 93.06%, reaches 94.29% through the degradation rate of pyrene after 12 days the irradiation, reaches 96.06% through degradation rate luxuriant and rich with fragrance after 10 days the irradiation.
Embodiment 2
Soil sample grinds at room-dry, crosses the 1mm sieve, and batch (-type) high pressure steam sterilization 2 times (each half an hour, 121 ℃) is behind the adding polycyclic aromatic hydrocarbon, air-dry standby then.
The preparation of polycyclic aromatic hydrocarbon pollution: with in the soil sample of above-mentioned sterilization by weight 1: 1 ratio of volume ratio add methanol solution (the 1 gram soil: the methanol solution of 1ml polycyclic aromatic hydrocarbon) of polycyclic aromatic hydrocarbon, the BaP, pyrene or the phenanthrene that contain 40mg in the methanol solution of every 1000ml polycyclic aromatic hydrocarbon respectively, place ventilating kitchen 24h, the concentration of polycyclic aromatic hydrocarbon is 40mg/kg in the contaminated soil.
The preparation of polycyclic aromatic hydrocarbon methanol solution: accurately take by weighing 0.04 the gram BaP, pyrene and phenanthrene, respectively with methanol constant volume to 1000ml.
Nano-TiO
2Be anatase titanium dioxide, surface area: 50m
2g
-1, average diameter: 20nm.
With TiO
2Mix by weight 1% with polycyclic aromatic hydrocarbon pollution, mechanical agitation is to evenly.
Take by weighing the above-mentioned soil sample of 5g and place the petri diss of 9cm diameter, pave, place lighting box to degrade.Irradiation is 8-12 days in lighting box, and soil is put into the 100ml centrifuge tube, adds the carrene of 25ml, ultrasonic water bath 2 hours, and the centrifugal 5min of 5000rmp crosses post, measures the content of the polycyclic aromatic hydrocarbon in the mixed liquor.
Illumination condition in the lighting box: ultraviolet lighting dominant wavelength is 254nm, and sample is apart from light source 5cm, and intensity of illumination is 680 μ w/cm
2, temperature is 30 ± 1 ℃, humidity is 45% ± 2%.
Treatment effect: the degradation rate through BaP after the irradiation of 2 days and 8 days reaches 26.17% and 96.28%, degradation rate through pyrene after the irradiation of 2 days and 12 days reaches 16.82% and 91.03%, reaches 20.61% and 97.92% through luxuriant and rich with fragrance degradation rate after the irradiation of 2 days and 10 days.
Embodiment 3
Soil sample grinds at room-dry, crosses the 1mm sieve, and batch (-type) high pressure steam sterilization 2 times (each half an hour, 121 ℃) is behind the adding polycyclic aromatic hydrocarbon, air-dry standby then.
The preparation of polycyclic aromatic hydrocarbon pollution: with (1 gram was native: the methanol solution of 1ml polycyclic aromatic hydrocarbon) in 1: 1 ratio in the soil sample of above-mentioned sterilization, the BaP, pyrene and the phenanthrene that add 40mg/1000ml respectively, place ventilating kitchen 24h, the concentration of polycyclic aromatic hydrocarbon is 40mg/kg in the contaminated soil.
The preparation of polycyclic aromatic hydrocarbon methanol solution: accurately take by weighing 0.04 the gram BaP, pyrene and phenanthrene, respectively with methanol constant volume to 1000ml.
Nano-TiO
2Be anatase titanium dioxide, surface area: 50m
2g
-1, average diameter: 15nm.
With TiO
2Mix by weight 2% with polycyclic aromatic hydrocarbon pollution, mechanical agitation is to evenly.
Take by weighing the above-mentioned soil sample of 5g and place the petri diss of 9cm diameter, pave, place lighting box to degrade.Irradiation is 8-12 days in lighting box, and soil is put into the 100ml centrifuge tube, adds the carrene of 25ml, ultrasonic water bath 2 hours, and the centrifugal 5min of 5000rmp crosses post, measures the content of the polycyclic aromatic hydrocarbon in the mixed liquor.
Illumination condition in the lighting box: ultraviolet lighting dominant wavelength is 365nm, and sample is apart from light source 20cm, and intensity of illumination is 9480 μ w/cm
2, temperature is 20 ± 1 ℃, humidity is 30% ± 2%.
Treatment effect: the degradation rate through BaP after 8 days the irradiation reaches 98.31%, reaches 90.48% through the degradation rate of pyrene after 12 days the irradiation, reaches 98.74% through degradation rate luxuriant and rich with fragrance after 10 days the irradiation.
Embodiment 4
Soil sample grinds at room-dry, crosses the 1mm sieve, and batch (-type) high pressure steam sterilization 2 times (each half an hour, 121 ℃) is behind the adding polycyclic aromatic hydrocarbon, air-dry standby then.
The preparation of polycyclic aromatic hydrocarbon pollution: with in the soil sample of above-mentioned sterilization by weight 1: 1 ratio of volume ratio add methanol solution (the 1 gram soil: the methanol solution of 1ml polycyclic aromatic hydrocarbon) of polycyclic aromatic hydrocarbon, the BaP, pyrene or the phenanthrene that contain 200mg in the methanol solution of every 1000ml polycyclic aromatic hydrocarbon respectively, place ventilating kitchen 24h, the concentration of polycyclic aromatic hydrocarbon is 200mg/kg in the contaminated soil.
The preparation of polycyclic aromatic hydrocarbon methanol solution: accurately take by weighing 0.2 the gram BaP, pyrene and phenanthrene, respectively with methanol constant volume to 1000ml.
Nano-TiO
2Be anatase titanium dioxide, surface area: 50m
2g
-1, average diameter: 20nm.
With TiO
2Mix by weight 3% with polycyclic aromatic hydrocarbon pollution, mechanical agitation is to evenly.
Take by weighing the above-mentioned soil sample of 5g and place the petri diss of 9cm diameter, pave, place lighting box to degrade.Irradiation is 8-12 days in lighting box, and soil is put into the 100ml centrifuge tube, adds the carrene of 25ml, ultrasonic water bath 2 hours, and the centrifugal 5min of 5000rmp crosses post, measures the content of the polycyclic aromatic hydrocarbon in the mixed liquor.
Illumination condition in the lighting box: ultraviolet lighting dominant wavelength is 310nm, and sample is apart from light source 15cm, and intensity of illumination is 3000 μ w/cm
2, temperature is 35 ± 1 ℃, humidity is 45% ± 2%.
Treatment effect: the degradation rate through BaP after 8 days the irradiation reaches 94.02%, reaches 84.72% through the degradation rate of pyrene after 12 days the irradiation, reaches 95.84% through degradation rate luxuriant and rich with fragrance after 10 days the irradiation.
Claims (6)
1. TiO
2Method with polycyclic aromatic hydrocarbon compounds in the ultraviolet light combined degradation soil is characterized in that: with contaminated soil and nano-TiO
2Mixture in vessel, pave, place the ultraviolet lighting case to carry out illumination degrading, nano-TiO
2Addition and contaminated soil weight ratio be 0.2%-5%, the illumination condition in the lighting box: the ultraviolet lighting wavelength is 210-365nm, sample is apart from light source 5-20cm, intensity of illumination is 500-10000 μ w/cm
2, temperature is 20-38 ℃, humidity is 30-50% in the Ventilation Control case, light application time 2-14 days.
2. according to the described TiO of claim 1
2Method with polycyclic aromatic hydrocarbon compounds in the ultraviolet light combined degradation soil is characterized in that: TiO
2Addition and contaminated soil weight ratio be 0.5%-4%, described ultraviolet lighting wavelength is 254-295nm, sample is apart from light source 5-15cm, intensity of illumination is 1000-3000 μ w/cm
2, temperature is 28-32 ℃, humidity is 35-40% in the Ventilation Control case, light application time 8-12 days.
3. according to the described TiO of claim 1
2Method with polycyclic aromatic hydrocarbon compounds in the ultraviolet light combined degradation soil is characterized in that: the ultraviolet lighting dominant wavelength that described ultraviolet lighting case is selected for use is 254nm, 310nm or 365nm.
4. according to the described TiO of claim 1
2Method with polycyclic aromatic hydrocarbon compounds in the ultraviolet light combined degradation soil is characterized in that: described nano-TiO
2Be anatase titanium dioxide, surface area is 50m
2g
-1, average diameter is 15-20nm.
5. according to the described TiO of claim 1
2Method with polycyclic aromatic hydrocarbon compounds in the ultraviolet light combined degradation soil is characterized in that: described polycyclic aromatic hydrocarbon is BaP, pyrene or phenanthrene.
6. according to the described TiO of claim 1
2Method with polycyclic aromatic hydrocarbon compounds in the ultraviolet light combined degradation soil is characterized in that: polycyclic aromatic hydrocarbon is 10-200mg/kg in the described contaminated soil.
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|---|---|---|---|
| CN 200610134208 CN100563858C (en) | 2006-11-08 | 2006-11-08 | A kind of TiO 2Method with polycyclic aromatic hydrocarbon compounds in the ultraviolet light combined degradation soil |
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|---|---|---|---|
| CN 200610134208 CN100563858C (en) | 2006-11-08 | 2006-11-08 | A kind of TiO 2Method with polycyclic aromatic hydrocarbon compounds in the ultraviolet light combined degradation soil |
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| CN100563858C true CN100563858C (en) | 2009-12-02 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260591A (en) * | 2011-07-01 | 2011-11-30 | 华南农业大学 | Method for removing benzopyrene from edible oil |
| CN105013799A (en) * | 2015-07-08 | 2015-11-04 | 上海大学 | Method for degrading benzopyrene/lead pollution in road dust through irradiation |
| CN105175384B (en) * | 2015-07-20 | 2017-09-05 | 宜春大海龟生命科学有限公司 | A kind of method that condensed-nuclei aromatics is removed from natural VE |
| CN109100318B (en) * | 2018-08-10 | 2022-01-14 | 辽宁大学 | Method for estimating photolysis quenching effect of pyrene by soluble organic matters in ice phase |
| CN109699867B (en) * | 2019-01-08 | 2022-07-12 | 华中农业大学 | Method for degrading patulin in fruit juice |
| CN112845565B (en) * | 2020-12-23 | 2022-09-02 | 中骏生态环境(上海)有限公司 | Application of graphene-based nanocomposite in petroleum hydrocarbon contaminated soil remediation |
| CN115368902A (en) * | 2021-05-18 | 2022-11-22 | 中国石油化工股份有限公司 | Kit with function of degrading organic pollutants and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1565762A (en) * | 2003-06-27 | 2005-01-19 | 中国科学院沈阳应用生态研究所 | Biological method for restoring polluted soil by oil and PAH5 |
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2006
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1565762A (en) * | 2003-06-27 | 2005-01-19 | 中国科学院沈阳应用生态研究所 | Biological method for restoring polluted soil by oil and PAH5 |
Non-Patent Citations (2)
| Title |
|---|
| "煤烟粒子中PAHs光化学降解的动力学"，王文兴等，1997-4-30煤烟粒子中PAHs光化学降解的动力学. 王文兴等.中国环境科学，第17卷第2期. 1997 * |
| 半导体光催化氧化有机物的研究现状及发展趋势. 货北平等.环境科学，第15卷第3期. 1994 * |
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