CN102559198A - Passivator for controlling pollutions of heavy metals copper, lead and cadmium on soil and applications thereof - Google Patents
Passivator for controlling pollutions of heavy metals copper, lead and cadmium on soil and applications thereof Download PDFInfo
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- CN102559198A CN102559198A CN201010595856XA CN201010595856A CN102559198A CN 102559198 A CN102559198 A CN 102559198A CN 201010595856X A CN201010595856X A CN 201010595856XA CN 201010595856 A CN201010595856 A CN 201010595856A CN 102559198 A CN102559198 A CN 102559198A
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Abstract
The invention belongs to the technical field of soil heavy metal pollution control and particularly relates to a passivator which is suitable for the in-situ control of the pollutions of heavy metals copper, lead and cadmium on soil and applications thereof. The passivator uses middle-grade and low-grade phosphate ore powder as the main raw material and the heavy metal passivator is prepared to passivate heavy metals in soil. The preparation method of the passivator comprises the following steps: smashing the middle-grade and low-grade phosphate ore of which P2O5 content is 20-30%, sieving with a 100 meshes of screen to obtain phosphate ore powder, mixing the phosphate ore powder with 0.1-0.7mol/L of oxalic acid according to the solid-to-liquid ratio of 1:1-1:20, activating at 28 DEG C for 6 days, and then drying at 50 DEG C for 20-24h to obtain the passivator. 3.97g of the prepared passivator is applied in 1kg of soil which is polluted by heavy metals; and the lettuce which grows for 120 days is harvested, and sampling is performed to measure the content of various forms of heavy metals in soil and the plant absorption amount. The passivator fully utilizes the middle-grade and low-grade phosphate ore resource which is difficult in use in China; and the passivator has the characteristics that the investment is low, the engineering quantity is low, the physicochemical properties of soil can not be damaged and secondary pollution can not be caused.
Description
Technical field
The invention belongs to heavy metal pollution of soil and administer technical field, be specifically related to a kind of passivator and application of administering heavy metal-polluted soil copper, lead, cadmium pollution.The present invention with in low-grade ground phosphate rock be main raw material, the preparation heavy metal deactivator come the passivation heavy metal-polluted soil.
Background technology
Heavy metal contamination is one of main type of soil pollution.Worldwide, because the excessive use of industrial and mineral three waste discharge and agrochemicals causes industrial district surrounding soil and agricultural soil toxic heavy metal excessive buildup, bring serious environmental and health risk (Xiao Pengfei etc., 2004).Therefore, the decontamination technology of heavy metal-polluted soil receives much concern.The improvement of heavy metal pollution of soil mainly contains methods such as physics, biological and chemical, and physical method is easy to operate, but cost is higher, only among a small circle, is suitable for; Mikrobe and phytoremediation technology cost are low, environmental friendliness, but because its target organism living weight is little, repair time is long, is not suitable for agricultural land soil; Chemistry original position deactivation method cost is low, easy to operate, though can not thoroughly remove the heavy metal in the soil, is applicable to large-scale farmland, and selecting suitable passivator then is the key of chemical process.
Closely during the last ten years, the investigator proposes with the phosphorus element as the passivator remediating lead-contaminated soil, compared with the method that pollutant in soil is removed of common employing; Not only economy but also Soil structure is not produced destructive (Hettiarachchi et al.2001); Many researchs show in soil add phosphorus modifying agent (comprising ground phosphate rock, Win 40350, phosphate fertilizer etc.) all can be effectively with the lead in the soil by non-residual form component (exchange state; The carbonate combined; The iron and manganese oxides combined with organically combine attitude) transform the lead in the fixed-contamination soil effectively, and keep secular stability to the residual form component.The plain kind of phosphorus is a lot, like ground phosphate rock etc., although higher-grade ground phosphate rock good passivation effect, resource-constrained, and low-grade phosphate ore is released the phosphorus poor effect, is difficult to bring into play its passivation effect.China's phosphate rock resource reserves are big; But in low-grade more; Ore dressing is difficult, so that the difficult performance due effect (Li Qingkui, 1992) in phosphatization industry of a large amount of phosphate rock resource; How will in apply contaminated soil after low-grade ground phosphate rock activation, come as passivator that heavy metal is a kind of practicable method (Cao et al.2002) in the passivation contaminated soil.
Existing related patent U.S. Patent No. has been reported the information that soil pollution is administered.A kind of plantation Thymifoious Euphorbia Herb is disclosed like Chinese invention patent application (200410027833.3); And inoculate the method that the heavy metallic activation bacterium comes restoration of soil polluted by heavy metal on this basis; But Soil structure, pH value, salinity, Pollutant levels and other toxicants possibly make the living weight of hyperaccumulative plant be restricted, and make it be difficult to promote.Chinese invention patent application (application number 200410082977.9) discloses the employing Secondary ammonium phosphate and the stalk ash makes the heavy metal fixing agent after a series of processing; And then use it for fixedly heavy metal cadmium, lead, copper, zinc; Although remediation efficiency is high; Starting material are simple and easy to, but the preparation process is loaded down with trivial details relatively.A kind of chemical leaching repairing method that is used for heavy metal cadmium, copper, lead, zinc and arsenic, mercury contaminated soil has been announced in Chinese invention patent application (application number is 200810198394.0), utilizes Na
2EDTA; Three kinds of combination of agents substeps of oxalic acid and KI ELUTION METHOD reaches the chemistry reparation to cadmium, copper, lead, zinc, arsenic and mercury etc. in the contaminated soil; Heavy metal reaches environmental safety standard in the contaminated soil thereby make; But the method for drip washing and leaching is better for the regional repairing effect of small area heavy metal severe contamination, unsuitable big area operation.
Summary of the invention
Method of the present invention is to overcome the deficiency that existing passivation heavy metal-polluted soil technology exists, provide a kind of raw material be easy to get, easy and simple to handle and can effective heavy metal-passivated copper, the method for lead, cadmium.Present method less investment, quantities is little, and technical requirements is not high, does not destroy soil physico-chemical property, and does not produce secondary pollution.
Technical scheme of the present invention is following:
A kind of passivator that is used for original position improvement heavy metal-polluted soil copper, lead, cadmium makes: with P as follows
2O
5Content be that the mid low grade phosphate rock stone flour of 20-30% was broken to 100 mesh sieves and obtains ground phosphate rock, with this ground phosphate rock and 0.1-0.7mol L
-1Oxalic acid be 1 by solid-to-liquid ratio: 1-1: 20 mix, and 28 ℃ of following activation 6 days, obtain passivator at 50 ℃ of 2 times dry 20-24h then.
As the prioritization scheme of technique scheme, wherein said oxalic acid addition is 0.5mol L
-1
The present invention proposes the application method of above-mentioned passivator in administering heavy metal-polluted soil copper, lead, cadmium, its main points are that passivator with the present invention's preparation is with 3.97g kg
-1Soil applies the soil that receives heavy metal contamination, planting vegetable lettuce on this soil, and results after 120 days, the content of each form of sampling and measuring heavy metal in soil and plant absorbed dose, thus reach the effect of administering heavy metal-polluted soil copper, lead, cadmium.
The method of passivation heavy metal-polluted soil of the present invention; Its key problem in technology is to be raw material with the mid low grade phosphate rock powder that exists in a large number in China; Be prepared into passivator after selecting for use certain density oxalic acid with its activation; Select suitable passivator and soil quality ratio for use, can accomplish in the short period of time the particularly passivation of copper, lead, cadmium of heavy metal in soil.The present invention has changed the shortcoming of passivator in the existing method, has improved ground phosphate rock P
2O
5Utilising efficiency, described passivator is environmentally friendly, technology is easy, is suitable for suitability for industrialized production, cost is low, the cycle is short, operation efficiency is high, the method for the passivation heavy metal in soil of a kind of simple and feasible of can yet be regarded as.
Embodiment
The preparation of embodiment 1 passivator
Supply three kinds of ground phosphate rock of examination to originate from hubei baokang, Nanzhang and Zhongxiang City respectively, its P
2O
5Content is followed successively by 26.1%, 24.2% and 23.2%.The about 0.25g of ground phosphate rock that took by weighing 100 mesh sieves (particle diameter is 0.15mm) adds 5mL concentration respectively and is 0.1,0.2,0.3,0.4,0.5molL in the 50mL centrifuge tube
-1Oxalic acid, in 40 ± 0.5 ℃ thermostat container, cultivate activation 6 days, 50 ℃ are drying to obtain activating phosphorite powder.Below be these three kinds of ground phosphate rock P after the oxalic acid activation
2O
5The detection data (table 1) of %.
Available phosphorus content (the P of table 1 different concns oxalic acid activating phosphorite powder
2O
5%)
The preparation of embodiment 2 passivator
The ground phosphate rock 5,2.5,1,0.5,0.25g that took by weighing 100 mesh sieves are in the 50mL centrifuge tube, and adding 5mL concentration respectively is 0.5molL
-1Oxalic acid, in the thermostat container of (40 ± 0.5) ℃, cultivate activation 6 days, 50 ℃ are drying to obtain activating phosphorite powder.Below be these three kinds of ground phosphate rock after the oxalic acid activation, P
2O
5The detection data (seeing table 2) of %.
Table 2 different solid is than the available phosphorus content (P of activating phosphorite powder
2O
5%)
The preparation of embodiment 3 passivator
The ground phosphate rock 0.25g that takes by weighing different-grain diameter is in the 50mL centrifuge tube, and adding 5mL concentration respectively is 0.5molL
-1Oxalic acid, in 40 ± 0.5 ℃ thermostat container, cultivate activation 6 days, under 50 ℃, be drying to obtain activating phosphorite powder.Below be three kinds of ground phosphate rock after the oxalic acid activation, P
2O
5The detection data (table 3) of %.
Available phosphorus content (the P of table 3 different-grain diameter activating phosphorite powder
2O
5%)
Embodiment 4 application implementations example
According to the result of embodiment 1,2,3, confirm that the best approach of preparation passivator is following: the Rock Phosphate (72Min BPL) and the 0.5mol L that will cross 100 mesh sieves
-1Oxalic acid be to mix at 1: 10 by solid-to-liquid ratio, 28 ℃ of following activation 6 days, in 50 ℃ down dry 20-24h obtain.The passivator that is adopted in the following application example all adopts this method preparation.Through measuring P in the passivator that the Rock Phosphate (72Min BPL) place of production is hubei baokang, Nanzhang and Zhongxiang City
2O
5Content is followed successively by 19.2%, 17.4%, 16.9%.
Supplying examination soil is the drab soil that picks up from the Zaoyang City, Hubei Province, the latosol of Dengmai County, Hainan Province and the red soil of Daye City, Hubei Province, measures its pH and is respectively 6.80,4.15 and 6.18, and content of tatal phosphorus is followed successively by 0.19,0.50 and 0.92g kg in the soil
-1, available phosphorus contents is 7.99,8.96 and 38.5mg kg
-1, the full lead content 238.8mg of drab soil kg
-1, the full lead content 231.6mgkg of latosol
-1, the full copper content of red soil 337.5mg kg
-1, full cadmium content 4.47mg kg
-1
With the artifact pollution of analytical pure lead nitrate, make in the soil Pb content drab soil and latosol to 200mg kg
-1, the down aging 30d of normal temperature (25 ℃) applies different concns (0,0.11,1.1 and 4.6gP with aging good soil
2O
5Kg
-1Soil) ground phosphate rock and passivator static cultivation 30d.Behind the 30d, analyze Pb metamorphosis in the soil (see Table 4 with table 5) with the Tessier continuous extraction.
Table 4 applies exchange state lead content variation (mg kg in ground phosphate rock and the passivator drab soil
-1)
Annotate: contained P in ground phosphate rock that 1 representative is applied or the passivator
2O
5Amount be 0.11g P
2O
5Kg
-1Soil; The contained P of 2 representatives
2O
5Amount be 1.1g P
2O
5Kg
-1Soil; The contained P of 3 representatives
2O
5Amount be 4.6g P
2O
5Kg
-1Soil, table 5 are together
Table 5 applies behind ground phosphate rock and the passivator that the exchange state lead content changes (mg kg in the latosol
-1)
Embodiment 5 application implementations example
In the plastic flowerpot of 20 * 30cm, adorn native 2kg, apply nitrogenous fertilizer (0.9g urea/basin) and potash fertilizer (0.8g KCl/ basin) in every basin, handle as follows every basin culture transferring two strains.Apply ground phosphate rock and passivator, the amount of ground phosphate rock and passivator needs phosphorus amount (0.15g P to satisfy plant growth
2O
5/ kg soil) amount that is scaled ground phosphate rock is (with full dose P
2O
5Meter) be Schwellenwert, amount concentration (0.30g P in establishing then
2O
5/ kg is native) and a large amount concentration (0.60g P
2O
5/ kg soil).Assurance is applied to the identical of full phosphorus amount contained in the passivator of every basin and ground phosphate rock.
Table 6 applies lettuce over-ground part Cu behind ground phosphate rock and the passivator, Cd content (mg kg
-1)
Annotate: CK does not apply the pedotheque of ground phosphate rock and passivator; PR1 applies ground phosphate rock 0.15g P
2O
5Kg
-1Soil; PR2 applies ground phosphate rock 0.30g P
2O
5Kg
-1Soil; PR3 applies ground phosphate rock 0.60g P
2O
5Kg
-1Soil; PR4 applies passivator 0.15g P
2O
5Kg
-1Soil; PR5 applies passivator 0.30g P
2O
5Kg
-1Soil; PR6 applies passivator 0.60g P
2O
5Kg
-1Soil, table 7,8,9 together.
Table 7 applies lettuce root Cu behind ground phosphate rock and the passivator, Cd content (mg kg
-1)
Table 8 applies soil Cu form classification (mg/kg) behind Baokang ground phosphate rock and the passivator
Table 9 applies soil Cd form classification (mg/kg) behind Baokang ground phosphate rock and the passivator
Reference:
1. Li Qing road. the agricultural use of Chinese phosphorus ore [M]. Nanjing: Jiangsu science tech publishing house, 1992.
2. Xiao Peng flies etc. heavy metal pollution of soil and phytoremediation research [J] thereof. and Liaoning University's journal (natural science edition), 2004,31 (3): 279-283.
3.Hettiarachchi?G.M.，Pierzynski?G.M.，Ransom?M.D..In?situ?stabilization?of?soil?Lead?usingphosphorus[J].Journal?of?Environmental?Quality.2001，30：1214-1221.
4.Cao?X.D.，Ma?L.Q.，Chen?M.，Singh?S.R.，Harris?W.G..Impacts?of?phosphate?amendments?on?leadbiogeochemistry?at?a?contaminated?site[J].Environmental?Science?and?Technology.2002，36(24)：5296-5304.
Claims (3)
1. a passivator of administering heavy metal-polluted soil copper, lead, cadmium pollution is characterized in that, makes as follows:
With P
2O
5The content of % is that the mid low grade phosphate rock stone of 20-30% was broken to 100 mesh sieves and obtains ground phosphate rock, with this ground phosphate rock and 0.1-0.7mol L
-1Oxalic acid be 1 by solid-to-liquid ratio: 1-1: 20 mix, 28 ℃ of following activation 6 days, then 50 ℃ down dry 20-24h obtain passivator.
2. passivator according to claim 1 is characterized in that: described oxalic acid is 0.5mol L
-1
3. claim 1 or 2 described passivator are administered the application in heavy metal-polluted soil copper, lead, the cadmium pollution in position, it is characterized in that, with claim 1 or 2 the preparation passivator with 3.97g kg
-1The use level of soil applies the said soil that receives heavy metal contamination, and the planting vegetable lettuce was gathered in the crops after 120 days, the content of each form of sampling and measuring heavy metal in soil and plant absorbed dose.
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|---|---|---|---|
| CN201010595856XA CN102559198A (en) | 2010-12-14 | 2010-12-14 | Passivator for controlling pollutions of heavy metals copper, lead and cadmium on soil and applications thereof |
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| CN102962250A (en) * | 2012-12-17 | 2013-03-13 | 浙江省农业科学院 | Method for remedying cadmium (Cd) and lead (Pb) polluted soil by alum pulp in situ |
| CN103084384A (en) * | 2013-01-08 | 2013-05-08 | 四川农业大学 | Application of oxalic acid in removal of soil cadmium pollution |
| CN108262351A (en) * | 2018-01-22 | 2018-07-10 | 佛山市诺瓦安评检测有限公司 | Heavy metal ion in five-step approach extraction soil |
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| CN102962250A (en) * | 2012-12-17 | 2013-03-13 | 浙江省农业科学院 | Method for remedying cadmium (Cd) and lead (Pb) polluted soil by alum pulp in situ |
| CN103084384A (en) * | 2013-01-08 | 2013-05-08 | 四川农业大学 | Application of oxalic acid in removal of soil cadmium pollution |
| CN108262351A (en) * | 2018-01-22 | 2018-07-10 | 佛山市诺瓦安评检测有限公司 | Heavy metal ion in five-step approach extraction soil |
| CN108949180A (en) * | 2018-07-19 | 2018-12-07 | 盐城英贝吉环保科技有限公司 | A kind of cadmium nickel contamination soil-repairing agent and preparation method |
| CN109370596A (en) * | 2018-11-20 | 2019-02-22 | 大连理工大学 | A kind of in-situ passivation the reparation medicament, preparation method and application of cadmium arsenic combined pollution agricultural land soil |
| CN109517600A (en) * | 2018-11-26 | 2019-03-26 | 北京南科大蓝色科技有限公司 | It is a kind of for the soil-repairing agent and its application method of heavy metal pollution and application |
| CN109513740A (en) * | 2018-11-26 | 2019-03-26 | 北京南科大蓝色科技有限公司 | One kind is for alkaline heavy metal contaminated soil renovation agent and its application method and application |
| CN109588080A (en) * | 2018-12-05 | 2019-04-09 | 湖南博川农业发展有限责任公司 | A kind of high altitude localities preventing from heavy metal Alfalfa Growing method |
| CN111229777A (en) * | 2020-01-16 | 2020-06-05 | 陈赫然 | Soil remediation material based on phosphate tailings and preparation and application methods thereof |
| CN111632577A (en) * | 2020-06-08 | 2020-09-08 | 中国科学院城市环境研究所 | Ammonium oxalate modified phosphate tailing adsorbing material, preparation method and application |
| CN111632577B (en) * | 2020-06-08 | 2023-05-30 | 中国科学院城市环境研究所 | Ammonium oxalate modified phosphate tailing adsorption material, preparation method and application |
| CN112094786A (en) * | 2020-10-26 | 2020-12-18 | 四川省地质矿产勘查开发局四0五地质队 | Method for reducing heavy metal lead and cadmium in plants in river sand |
| CN113528141A (en) * | 2021-07-09 | 2021-10-22 | 贵州雏阳生态环保科技有限公司 | Modified natural mineral soil conditioner and preparation method thereof |
| CN117181799A (en) * | 2023-09-08 | 2023-12-08 | 中国科学院地球化学研究所 | Solid waste improvement material combining plant stabilization and soil heavy metal fixation and soil improvement method |
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Application publication date: 20120711 |