CN103056156A - Method for fixing chlorobenzene volatile organic pollutants by straw biomass charcoal - Google Patents
Method for fixing chlorobenzene volatile organic pollutants by straw biomass charcoal Download PDFInfo
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Abstract
A method for fixing chlorobenzene volatile organic pollutants by straw biomass charcoal comprises the following steps: shearing straws into fragmentations, drying the fragmentations at the temperature of 80 DEG C, then, transferring the fragmentations to a retort for charing, wherein the initial retort temperature is 200 DEG C, and the retort temperature is increased to 30 DEG C and then to 500 DEG C through temperature programming, lasting for 1.5 hours, naturally cooling and then grinding the fragmentations, screening the fragmentations by a 0.25 mm sieve to obtain biomass charcoal; and enabling the the biomass charcoal to be uniformly mixed with chlorobenzene polluted soil at a ratio of 0.1 to 2 percent of the dry weight of the soil, standing for 4 to 12 weeks, and finishing the fixation. The straws are wheat straws. After biomass charcoal is added in the soil, the volatilization loss of chlorobenzene only accounts for 4.49 to 15.58 percent of that of chlorobenzen when no biomass charcoal is added in the soil, and the bio-concentration of earthworms to chlorobenzene in the soil only accounts for 2.83 to 3.78 percent of that of earthworms to chlorobenzene when no biomass charcoal is added in the soil, so that the environment risk of the volatile pollutants is reduced remarkably. The crop straws resource is rich, is cheap and easily obtained, and the method opens up a novel way for using the straws to restore the polluted soil.
Description
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Technical field
The invention belongs to contaminated soil and repair the field, relate to the application process that utilizes chlorobenzene class volatile organic contaminant in the straw biomass charcoal fixing soil.
Background technology
Soil pollution, especially persistence organic pollutant pollute, and have become one of global important environmental problem.Chlorobenzene belongs to persistence organic pollutant, and China is major country of production and the supply country of global chlorobenzene product, and in some industrial areas, the pollution problem of soil chlorobenzene highlights.For example, in Beijing Craft in Chemical Industrial Area, all there is chlorobenzene to detect [Zhou Xia in the soil and plant medium, Yu Gang, Huang Jun, Zhang Zulin, Hu Hongying. the residual and distribution characteristics of chlorobenzene type organic in the Southeastern Suburb of Beijing Craft in Chemical Industrial Area soil and plant. environmental science, 2007,28 (2): 249-254.], the chlorobenzene pollution level reaches 71.06-716.57 ng/g [Song, Y. in the vegetable soil of certain chlorobenzene production factory periphery, Wang, F., Bian, Y.R., Zhang, Y.P., Jiang, X. Chlorobenzenes and organochlorinated pesticides in vegetable soils from an industrial site, China. Journal of Environmental Sciences. 2012,24 (3): 362-369.].Therefore, particularly important to the reparation of industrial area periphery chlorobenzene polluted farmland soil.Chlorobenzene belongs to volatile organic contaminant, at present, repair mode to VOCs-contaminated Soils mainly comprises the materialization recovery technique [Liu Shasha such as thermal desorption, light degradation, Soil leaching, Dong Jiahua, Chen Zhiliang, Peng Xiaochun, Wu Yanyu, Xu Yuxin. VOCs-contaminated Soils recovery technique progress. the Agriculture of Anhui science. 2012,40 (12): 7130-7132.].But this class Technology Need dystopy is processed, quantities is large, soil texture and soil productivity are produced destruction, is the contaminated soil of site of high concentration, small size mainly for target, is not suitable for and repairs large-area farmland pollution soil.Microbial degradation also is a kind of mode of repairing VOCs-contaminated Soils, but for chlorobenzene class persistence, volatility, toxic pollutant, screen relatively difficulty of its specific degradation bacteria, and the degradation bacteria that filters out is inoculated into and is difficult to survival behind the soil, thereby repairing effect is also not good.Owing to having volatility, chlorobenzene is easy to volatilize to atmosphere from soil, and pollutant atmosphere, and long-distance migration are so that contaminated soil becomes one of source of atmospheric pollution.Therefore, under the prerequisite that does not change the original productivity of soil, this pollutant original position is fixed in the soil, reduces it to the migration of atmosphere and crop system and to reduce its biological effectiveness will be the repair mode best to the agricultural land soil of large tracts of land slight pollution.
Original position immobilization reparation is a kind of of original position reparation, it is to add the chemical substances such as modifying agent, inhibitor or passivator in contaminated soil, reduce water-soluble, diffusivity and the biological effectiveness of pollutant in soil, thereby make pollutant be converted into mobility or the lower chemical form of toxicity, reduce the migration of polluting from soil to crop system, with the harm of pollution abatement thing to ecosystem environment.Adding sorptive material in the soil is one of important channel of fixed-contamination thing.The biomass carbon that agricultural crop straw is prepared under the anaerobic in low temperature condition has higher specific area and microcellular structure, and has abundant oxygen-containing functional group, and it has stronger adsorption capacity to pollutant.CN 102351271 A disclose the method for utilizing biomass carbon to process the heavy metal copper in the electroplating wastewater.CN 102204436 A disclose the method for utilizing heavy metal cadmium in the biomass carbon fixing soil.Though biomass carbon has report [Chun to the absorption of organic pollution such as polycyclic aromatic hydrocarbon, herbicide etc., Y., Sheng, G.Y., Chiou, C.T., Xing, B.S. Compositions and sorptive properties of crop residue-derived chars. Environmental Science ﹠amp; Technology, 2004,38 (17): 4649-4655; Yang, Y.N., Sheng, G.Y. Enhanced pesticide sorption by soils containing particulate matter from crop residue burns. Environmental Science ﹠amp; Technology, 2003a, 37 (16): 3635-3639.], but utilize the volatile organic contaminant in fixing of the biomass carbon rehabilitating soil to yet there are no report.Simultaneously, biomass carbon is added in the soil as sorbing material, fixing volatile organic contaminant not only, and can increase soil fertility, improve soil organic carbon, reduce greenhouse gas emission.
Summary of the invention
The technical problem that solves:
For soil volatile organic contaminant pollution situation, in order to reduce the environmental risk of volatile organic contaminant in the agricultural land soil of industrial area, the invention provides a kind of method of utilizing chlorobenzene class organic pollution in the straw biomass charcoal fixing soil, the method can reduce the biological effectiveness of chlorobenzene in the soil effectively.
Technical scheme:A kind of method of utilizing chlorobenzene class volatile organic contaminant in the straw biomass charcoal fixing soil, step is: stalk is cut into broken section and at 80 ℃ of lower oven dry 12 h, then be transferred to charing in the retort, 200 ℃ of initial furnace temperature, ℃ then temperature programming to 300 is to 500 ℃ and keep 1.5 h, naturally grind after the cooling, cross 0.25 mm sieve series and get biomass carbon; Again with the gained biomass carbon to account for 0.1 ~ 2% ratio and chlorobenzene contaminated soil mixing of soil dry weight, left standstill for 4-12 weeks, finish fixing.
Described stalk is wheat stalk.
Described chlorobenzene is trichloro-benzenes, tetrachlorobenzene or pentachlorobenzene.
Beneficial effect:
The invention discloses a kind of method of utilizing chlorobenzene class volatile organic contaminant in the straw biomass charcoal fixing soil.Its useful achievement comprises: after adding biomass carbon in (1) soil, chlorobenzene has been fixed in absorption, has reduced the volatilization of chlorobenzene in the atmosphere, add biomass carbon process in the volatilization loss of chlorobenzene only account for do not add that biomass carbon processes 4.49 ~ 15.58%.(2) add biomass carbon in the soil after, reduced the biological effectiveness of chlorobenzene in the soil, add biomass carbon process in the Soil of Earthworms biological concentration of chlorobenzene only account for do not add that biomass carbon processes 2.83 ~ 3.78%, significantly reduced the environmental risk of volatile contaminant; (3) add not only fixing volatile organic contaminant of straw biomass charcoal in the soil, and can improve soil, environmental protection can not produce secondary pollution.China's crop material aboundresources but dispose difficulty, the method is that a new way has been opened up in the utilization of stalk in the contaminated soil reparation.
Description of drawings
Fig. 1 is in the different disposal soil 1,2,4-trichloro-benzenes residual;
Fig. 2 is in the different disposal 1,2, the accumulation volatile quantity of 4-trichloro-benzenes;
Fig. 3 is in the different disposal soil 1,2, and the butanols of 4-trichloro-benzenes extracts the percentage that accounts for total amount;
Fig. 4 is pentachlorobenzene residual in the soil under the different biomass carbon additions;
Fig. 5 is the volatilization of pentachlorobenzene in the soil under the different biomass carbon additions;
Fig. 6 be under the different biomass carbon additions in the soil butanols of pentachlorobenzene extract the percentage account for total amount;
Fig. 7 is under the different biomass carbon additions in the soil 1,2,4,5-tetrachlorobenzene residual;
Fig. 8 is under the different biomass carbon additions in the soil 1,2,4, the volatilization of 5-tetrachlorobenzene;
Fig. 9 is under the different biomass carbon additions in the soil 1,2,4, and the butanols of 5-tetrachlorobenzene extracts the percentage that accounts for total amount;
Figure 10 is under the different biomass carbon additions in the soil 1,2,4-trichloro-benzenes residual;
Figure 11 is under the different biomass carbon additions in the soil 1,2, the volatilization of 4-trichloro-benzenes;
Figure 12 is under the different biomass carbon additions in the soil 1,2, and the butanols of 4-trichloro-benzenes extracts the percentage that accounts for total amount;
Figure 13 is the biological concentration factor of chlorobenzene in the Soil of Earthworms under aging 1 week and the 24 weeks rear different biomass carbon additions.
The specific embodiment
Further specify by the following examples the present invention, used biomass carbon is made by following methods among the embodiment: wheat stalk is cut into broken section and at 80 ℃ of lower oven dry 12 h, then be transferred to charing in the retort, 200 ℃ of initial furnace temperature, be warming up to 300 ℃, then to 500 ℃ and keep 1.5 h, naturally grind after the cooling, cross 0.25 mm sieve series and get biomass carbon.
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Biomass carbon, active carbon, clay mineral are joined 300 g 1,2 with 1% the addition that accounts for the soil dry weight respectively, and 4-trichloro-benzenes concentration is 7 μ g g
1Contaminated soil in, fully stir and evenly mix, then be transferred in the 1-L wide-mouth bottle, regulating soil moisture content is 28%, compacting soil to density is 1.3 g cm
3, with having the rubber stopper seal of air inlet and gas outlet, cultivate 25 ℃ of lower lucifuges.Not add the contrast that is treated to of any material.In the 1st, 2,4,8,12,24 weeks of cultivating, with airtight capturing device ventilation, ventilation finishes, and gathers soil, and employing n-hexane-accelerated solvent extraction and analysis is the total amount of chlorobenzene wherein, and with the biological effectiveness of chlorobenzene in the butanols extraction and analysis soil.
As shown in Figure 1, that adds trichloro-benzenes in clay mineral and the control treatment does not residually dynamically have a significant difference, and after adding biomass carbon and active carbon, the residual concentration of trichloro-benzenes increases in the soil, and it is the highest to cultivate the processing trichloro-benzenes residual concentration that adds biomass carbon when finishing.As shown in Figure 2, through cultivating in 24 weeks, trichloro-benzenes accumulation volatilization loss is maximum in the control treatment, secondly processes for adding clay mineral, the trichloro-benzenes volatilization was minimum during the interpolation biomass carbon was processed, only account for 5.61% of control treatment volatilization loss, as shown in Figure 3, cultivated for 24 weeks after, butanols to add biomass carbon process in 1, the recovery rate of 2,4-trichloro-benzenes is minimum, only accounts for 46.94% of control treatment.This embodiment illustrates that adding biomass carbon can significantly fix trichloro-benzenes in the soil, reduce its biological effectiveness, and effect is better than active carbon.
Biomass carbon is joined 300 g pentachlorobenzene concentration as 1 μ g g take 0.1% the addition that accounts for the soil dry weight
1Contaminated soil in, fully stir and evenly mix, then be transferred in the 1-L wide-mouth bottle, regulating soil moisture content is 28%, compacting soil to density is 1.3 g cm
3, with having the rubber stopper seal of air inlet and gas outlet, cultivate 25 ℃ of lower lucifuges.It is the same that 0.5%wt, 1% wt and 2% wt biomass carbon addition are processed operation, is treated to contrast (0% wt) with what do not add biomass carbon.In the 1st, 2,4,8,12,24 weeks of cultivating, with airtight capturing device ventilation, ventilation finishes, and gathers soil, and employing n-hexane-accelerated solvent extraction and analysis is the total amount of chlorobenzene wherein, and with the biological effectiveness of chlorobenzene in the butanols extraction and analysis soil.
As shown in Figure 4, behind the interpolation biomass carbon, the residual concentration of pentachlorobenzene increases in the soil, and the biomass carbon that adds is more, and they are residual also more.As shown in Figure 5, add biomass carbon and reduced the volatilization loss of pentachlorobenzene from soil to atmosphere, 2% addition is processed lower, and the volatilization loss of pentachlorobenzene only accounts for 15.58% of control treatment.As shown in Figure 6, butanols significantly is lower than contrast to the recovery rate that adds pentachlorobenzene in the biomass carbon processing, and butanols only accounted for 52.48 ~ 58.43% of control treatment to the recovery rate of pentachlorobenzene during 2% wt addition was processed.
Embodiment 3
Biomass carbon is joined 300 g 1,2,4 with 0.1% the addition that accounts for the soil dry weight, and 5-tetrachlorobenzene concentration is 0.9 μ g g
1Contaminated soil in, fully stir and evenly mix, then be transferred in the 1-L wide-mouth bottle, regulating soil moisture content is 28%, compacting soil to density is 1.3 g cm
3, with having the rubber stopper seal of air inlet and gas outlet, cultivate 25 ℃ of lower lucifuges.It is the same that 0.5%wt, 1% wt and 2% wt biomass carbon addition are processed operation, is treated to contrast (0% wt) with what do not add biomass carbon.In the 1st, 2,4,8,12,24 weeks of cultivating, with airtight capturing device ventilation, ventilation finishes, and gathers soil, and employing n-hexane-accelerated solvent extraction and analysis is the total amount of chlorobenzene wherein, and with the biological effectiveness of chlorobenzene in the butanols extraction and analysis soil.
As shown in Figure 7, behind the interpolation biomass carbon, the residual concentration of tetrachlorobenzene increases in the soil, and the biomass carbon that adds is more, and they are residual also more.As shown in Figure 8, add biomass carbon and reduced the volatilization loss of tetrachlorobenzene from soil to atmosphere, 2% addition is processed lower, and the volatilization loss of tetrachlorobenzene only accounts for 14.58% of control treatment.As shown in Figure 9, butanols significantly is lower than contrast to the recovery rate that adds tetrachlorobenzene in the biomass carbon processing, and butanols only accounted for 47.71 ~ 56.74% of control treatment to the recovery rate of tetrachlorobenzene during 2% wt addition was processed.
Biomass carbon is joined 300 g 1,2 with 0.1% the addition that accounts for the soil dry weight, and 4-trichloro-benzenes concentration is 8 μ g g
1Contaminated soil in, fully stir and evenly mix, then be transferred in the 1-L wide-mouth bottle, regulating soil moisture content is 28%, compacting soil to density is 1.3 g cm
3, with having the rubber stopper seal of air inlet and gas outlet, cultivate 25 ℃ of lower lucifuges.It is the same that 0.5% wt, 1% wt and 2% wt biomass carbon addition are processed operation, is treated to contrast (0% wt) with what do not add biomass carbon.In the 1st, 2,4,8,12,24 weeks of cultivating, with airtight capturing device ventilation, ventilation finishes, and gathers soil, and employing n-hexane-accelerated solvent extraction and analysis is the total amount of chlorobenzene wherein, and with the biological effectiveness of chlorobenzene in the butanols extraction and analysis soil.
As shown in figure 10, behind the interpolation biomass carbon, the residual concentration of trichloro-benzenes increases in the soil, and the biomass carbon that adds is more, and they are residual dense more.As shown in figure 11, add biomass carbon and reduced the volatilization loss of trichloro-benzenes from soil to atmosphere, 2% wt addition is processed lower, and the volatilization loss of trichloro-benzenes only accounts for 4.49% of control treatment.As shown in figure 12, butanols significantly is lower than contrast to the recovery rate that adds trichloro-benzenes in the biomass carbon processing, and butanols only accounted for 32.98 ~ 38.65% of control treatment to the recovery rate of trichloro-benzenes during 2% addition was processed.
Biomass carbon is joined in the 300 g chlorobenzene contaminated soils with 0.1% the addition that accounts for the soil dry weight, fully stir and evenly mix, then be transferred in the 1-L wide-mouth bottle, regulating soil moisture content is 28%, and compacting soil to density is 1.3 g cm
3, with having the rubber stopper seal of air inlet and gas outlet, cultivate 25 ℃ of lower lucifuges.It is the same that 0.5% wt, 1% wt and 2% wt biomass carbon addition are processed operation, is treated to contrast (0% wt) with what do not add biomass carbon.After the 1st week of cultivating and 24 weeks, respectively 15 earthworms are joined in the blake bottle, with the aluminium foil sealing that has punched, illumination cultivation 14 days.Cultivate and finish earthworm is taken out from soil, measure the enrichment factor to chlorobenzene.
As shown in figure 13, earthworm significantly is lower than contrast to the enrichment of adding chlorobenzene in the biomass carbon processing, after cultivating for 24 weeks, during 0.1% wt addition is processed, earthworm is to pentachlorobenzene, the biological concentration factor of tetrachlorobenzene and trichloro-benzenes significantly is lower than control treatment and only accounts for respectively 55.9% of control treatment, 5.2% and 6%, and earthworm is lower to the biological concentration factor of chlorobenzene in the processing of 2% wt addition, slip reaches 97% compared with the control, explanation is in 0.1-2% wt addition scope, and biomass carbon is the chlorobenzene in the fixing soil effectively, significantly reduces its biological effectiveness.In sum, by adding the well chlorobenzene in the fixed-contamination soil of 0.1-2% ratio straw biomass charcoal, reduce its in the atmosphere volatilization and reduce the biological effectiveness of chlorobenzene in soil, thereby reduce environmental risk.
Claims (3)
1. method of utilizing chlorobenzene class volatile organic contaminant in the straw biomass charcoal fixing soil, it is characterized in that step is: stalk is cut into broken section and at 80 ℃ of lower oven dry 12 h, then be transferred to charing in the retort, 200 ℃ of initial furnace temperature, ℃ then temperature programming to 300 is to 500 ℃ and keep 1.5 h, naturally grind after the cooling, cross 0.25 mm sieve series and get biomass carbon; Again with the gained biomass carbon to account for 0.1 ~ 2% ratio and chlorobenzene contaminated soil mixing of soil dry weight, left standstill for 4-12 weeks, finish fixing.
2. a kind of method of utilizing chlorobenzene class volatile organic contaminant in the straw biomass charcoal fixing soil according to claim 1 is characterized in that described stalk is wheat stalk.
3. a kind of method of utilizing chlorobenzene class volatile organic contaminant in the straw biomass charcoal fixing soil according to claim 1 is characterized in that described chlorobenzene is trichloro-benzenes, tetrachlorobenzene or pentachlorobenzene.
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| CN103394506A (en) * | 2013-08-12 | 2013-11-20 | 湖南省烟草公司郴州市公司 | Comprehensive remediation method of 2-methyl-4-chlorophenoxyacetic acid herbicide contaminated soil in tobacco-rice rotation zones |
| CN103394508A (en) * | 2013-08-12 | 2013-11-20 | 湖南省烟草公司郴州市公司 | Comprehensive remediation method of quinclorac herbicide contaminated soil in tobacco-rice rotation zones |
| CN104550209A (en) * | 2014-12-01 | 2015-04-29 | 中国科学院南京土壤研究所 | Biological carbon-plant joint repairing method of chlorobenzene volatile organic compound-contaminated soil |
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| CN104823585A (en) * | 2015-04-15 | 2015-08-12 | 中国科学院东北地理与农业生态研究所 | Paddy field fertilizing method for in situ reduction of non-point source pollutant herbicide |
| CN106582514A (en) * | 2015-10-14 | 2017-04-26 | 天津众华鑫环保科技有限公司 | Method for recycling biological waste in biomass charcoal |
| CN114307955A (en) * | 2021-11-29 | 2022-04-12 | 生态环境部南京环境科学研究所 | Method for restoring organic pollutants in farmland soil by combining biological carbon with biological degradation |
| CN115108740A (en) * | 2022-05-23 | 2022-09-27 | 临沂中联水泥有限公司 | Cement clinker for treating polluted soil of coking plant |
| CN115232625A (en) * | 2021-09-30 | 2022-10-25 | 黄芸 | Treatment method and application of soil organic pollutants |
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| CN103394506A (en) * | 2013-08-12 | 2013-11-20 | 湖南省烟草公司郴州市公司 | Comprehensive remediation method of 2-methyl-4-chlorophenoxyacetic acid herbicide contaminated soil in tobacco-rice rotation zones |
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| CN115232625A (en) * | 2021-09-30 | 2022-10-25 | 黄芸 | Treatment method and application of soil organic pollutants |
| CN114307955A (en) * | 2021-11-29 | 2022-04-12 | 生态环境部南京环境科学研究所 | Method for restoring organic pollutants in farmland soil by combining biological carbon with biological degradation |
| CN114307955B (en) * | 2021-11-29 | 2022-08-26 | 生态环境部南京环境科学研究所 | Method for restoring organic pollutants in farmland soil by combining biological carbon with biological degradation |
| CN115108740A (en) * | 2022-05-23 | 2022-09-27 | 临沂中联水泥有限公司 | Cement clinker for treating polluted soil of coking plant |
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Application publication date: 20130424 |