CN103331299A - Composite ecomaterial for solidified soil polluted by heavy metal - Google Patents
Composite ecomaterial for solidified soil polluted by heavy metal Download PDFInfo
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- 239000004021 humic acid Substances 0.000 claims description 2
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- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
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Abstract
The invention relates to an improver for polluted soil, and in particular relates to a composite ecomaterial for solidified soil polluted by heavy metal, which is prepared from two or more of a humic material, a polymer material, a coal-based composite material and a powdery mineral material through mixing and evenly blending. The composite ecomaterial is added in the soil, and four weeks later, crops can be planted in the soil. Compared with the prior art, the composite ecomaterial disclosed by the invention has an obvious improvement effect on the solidified soil due to pollution of the heavy metal such as lead and cadmium; the selected materials contain no substances harmful to the environment and the health. At the same time, the materials of the composite ecomaterial are cheap, and the effective repair can be carried out with few human and material resources.
Description
Technical field
The present invention relates to the modifying agent of contaminated soil, particularly a kind of combinational environment material of curing soil heavy metal pollution.
Background technology
Soil refers to grow in can the grow loose and porous structure top layer of green plants of earth top, is part very important in the ecosystem, also is the most important natural resources of human society.In recent years, the heavy metal pollution of soil problem is comparatively outstanding.Heavy metal pollution of soil refers to because mankind's activity makes heavy metal in soil content apparently higher than original content, and causes the phenomenon that soil environment quality descends and farmland ecological environment worsens.Along with industrial expansion, human in creation economy, promotion social development, bring also for survival environment gradually and destroy and pollution.Nearly decades, more and more serious because of the loss that heavy metal pollution brings in the world, China also faces increasingly serious situation.
China is subjected to nearly 2,000 ten thousand hm of cultivated area of heavy metal pollutions such as Cd, As, Cr, Pb at present
2, accounting for 1/5 of total area under cultivation, heavy metal Cd is polluted 1,130,000 hm that plough
2, relate to 25 areas of 11 provinces and cities; Contain Pb amount in the grain and also have 11 greater than the place of production of 110mg/kg.Ever-increasing heavy metal pollution has caused the large tracts of land soil can not farming.In 320 emphasis contaminated areas in the very fast area of economic developments such as 24 provinces of China (city) outskirts of a town, sewage irrigation district, industrial and mineral, the agricultural output that content of beary metal exceeds standard and area account for pollutant more than 80% of agricultural product total amount and the gross area that exceeds standard, and be especially outstanding with Pb, Cd, Hg, Cu and combined pollution thereof.In addition, China's sewage irrigation district area is about 1,400,000 hm
2, suffer the land area of heavy metal pollution to account for dirty 64.8% of the gross area of irritating, Cd, Cr in the foods such as many local grains, vegetables, fruit, content of beary metal such as As, Pb exceed standard or near critical value.Cadmium and lead are non-nutrients, plant there is tangible toxic action, can influences the plant cell metabolism and grow the morphosis of change plant, and can jeopardize the health of human and other animals along with food chain, so heavy metal lead, cadmium pollution have become a serious environmental problem.
In order to alleviate serious day by day heavy metal pollution of soil, the heavy metal pollution of soil recovery technique more and more is subjected to people and payes attention to.But characteristics such as heavy metal pollution of soil tool disguise, chronicity and consequence seriousness cause the limitation aspect improvement.
More at the method kind of heavy metal pollution of soil reparation at present, roughly can be divided into physical method, chemical method and biological method by repairing principle.
Physical method mainly is to administer heavy metal in soil by physics or physicochemical principle.Concrete measure has heat treating process, electrodynamics method, soil moved in to improve the original, soil replacement method etc.But this measure common engineering amount is bigger, wastes time and energy, and only is suitable for small size severe contamination area and uses.
Biological restoration mainly refers to phytoremediation.Plant is mainly removed the heavy metal ion in the soil or reduces its biologically active by modes such as phytovolatilization, plant passivation, the extractions of root filter plant.So far, the research of heavy metal pollution of soil phytoremediation has decades, though obtained many achievements and progress, also exists many problems to keep punching simultaneously.Mainly show: difficulty is used greatly and the uncertainty of effect in the field; Need prevent " alien species invasion " problem during from external introduction super enriching plant and when using super enriching plant to repair polluted soil, how effectively prevent secondary pollution problems.
Chemistry reparation mainly comprises elution method, chemical fixation etc.Though used material is drawn materials conveniently in this method, quick result, the composition of material itself is indeterminate, even just contains heavy metal element in the material or water body is caused eutrophication, in the repair process of contaminated site environment is caused secondary pollution.
Nineteen ninety, the good professor in Tokyo Univ Japan Yamamoto proposes the concept (also claiming ecological environment material nd) of " environmentally conscious materials " first in investigation of materials, refer to when the exploitation new material, not only require to consider its excellent serviceability, will consider that also material must keep and the harmony of ball ecological environment in the overall process for preparing, circulates, uses and discard.It is one of effective for repairing mode that the environmentally conscious materials repairing heavy metal in soil pollutes, utilize environmentally conscious materials to the influence research of crops production and soil, help to widen heavy metal pollution of soil and repair the field, for environmentally conscious materials applying in the soil pollution reparation provides theoretical foundation and practical advice.
The inventive method can be included in the chemical repairing method to heavy metal pollution.This method mainly is to add environmentally conscious materials as modifying agent in soil, to reduce transfer ability and the biological effectiveness of heavy metal in environment, alleviates them to the harm of the ecosystem.These environmentally conscious materialses are by changing physicochemical properties such as soil pH, Eh and EC, make the effects such as heavy metal generation oxidation, reduction, precipitation, absorption, inhibition and antagonism in the soil, reach the biological effectiveness effect that reduces heavy metal, it is effective using at soil light, moderate heavy metal pollution.Modifying agent commonly used at present has inorganic amendment and organic amendment, and wherein inorganic amendment mainly is mineral materials such as lime, calcium carbonate, hydroxyapatite, ground phosphate rock, calcium monohydrogen phosphate, and organic amendment comprises organic fertilizer such as farm manure, green manure, the peat composed of rotten mosses.
Material therefor is environmentally friendly material among the present invention, carries out in the soil environment not being become secondary pollution when the heavy metal pollution original position repairs guaranteeing that it adds to as chemical improvement agent.
Summary of the invention
The present invention is a kind of compound environmentally conscious materials, this environmentally conscious materials can carry out the original position reparation to heavy metal lead, cadmium pollution place, can bring into play that the chemical improvement agent method is with low cost as a kind of based technique for in-situ remediation, the advantage of easy operating, can not cause secondary pollution to institute's repairing environment again.
The technical solution adopted for the present invention to solve the technical problems is: comprise humic class material, macromolecular material, coal-based composite and opaque mineral material.
Described environmentally conscious materials can by in four kinds of materials any three kinds or any two kinds combine.
Humus class material is humic acid.
Macromolecular material is granularity 100 purpose polyacrylates.
Coal-based composite is flyash, is that 91% silty sand grain and 9% clay are formed by weight ratio, and surface color is grey, pH value 8.36.
The opaque mineral material is zeolite, granularity 100 orders.
Step 1) is carried out mixing and stirring with the described four kinds of materials of claim 1 or three kinds of materials or two kinds of materials.
Step 2) is added in the soil.
Question responses such as step 3) begin to plant crops after 4 weeks.
In terms of existing technologies, the environmentally conscious materials combination among the present invention is remarkable to the improved effect of heavy metal lead, cadmium pollution, and does not contain the material that endangers Environmental Health in the material of selecting for use.Simultaneously, the composition material of environmentally conscious materials combination is with low cost, and needs less human and material resources just can carry out effective for repairing.
For above-mentioned purpose of the present invention, feature can be become apparent more, the present invention is further detailed explanation below in conjunction with the drawings and specific embodiments.
Description of drawings
Fig. 1 is that environmentally conscious materials is to the influence of soybeans top Pb, Cd content.
The specific embodiment
Humus class material material (HA), macromolecular material (SAP), coal-based composite (FM) and opaque mineral material (FS) are hereinafter all represented with code name.HA is provided by Inner Mongol Huo Linhe Coal Industry Group Co., Ltd; SAP is provided by Tangshan Bo Yake skill Group Co.,Ltd; FM is provided by colliery, Datong Group Co.,Ltd; Huaihe River, Xinyang, FS effluent south industry Mineralka D. O. O. provides.
Embodiment 1: the leaching experiment of environmentally conscious materials curing soil heavy metal
Experiment is handled: according to used environmentally conscious materials setting
D1-humus class material (0.25g ﹒ kg
-1Soil);
D2-macromolecular material (2g ﹒ kg
-1);
D3-fly ash material (50g ﹒ kg
-1);
D4-opaque mineral material (10g ﹒ kg
-1);
F1-four kind of environmentally conscious materials combination (HA+SAP+FM+FS);
F2-three kind of environmentally conscious materials combination (HA+SAP+FM);
F3-three kind of environmentally conscious materials combination (HA+SAP+FS);
Any environmentally conscious materials of CT1-do not add.
Be respectively 500mg ﹒ kg for Pb, Cd concentration in the examination soil
-1, 20mg ﹒ kg
-1Experiment is provided with 8 processing (each handles three repetitions) altogether: (1) D1; (2) D2; (3) D3; (4) D4; (5) F1; (6) F2; (7) F3; (8) CT1.Add mixing in proportion when mixing leaching with soil and get final product, each material usage is identical with the single consumption of material in the combination.
Experimental result:
(1) Pb content and consolidation effect thereof in the leaching liquor:
Table 1 leaching result shows that D1 and F3 processing leaching go out the Pb amount and be lower than contrast, and namely D1 and F3 handle the fixed effect of Pb is handled significantly than other.The migration of the Pb ion of environmentally conscious materials HA has the greatest impact, and the Pb amount that D1 processing leaching goes out illustrates that for 40.6% of contrast CT1 processing the adsorption capacity of HA colloid is higher than other colloid in the soil.The chelation of the metal of HA is simultaneous with the exchange suction-operated.It is generally acknowledged, when concentration of metal ions is high, be adsorbed as the master with exchange; When concentration is low, based on chelation.
Known by experimental result, tried soil after adding FM and these two kinds of environment functional materials of HA, all promoted soil fixing Pb.This is relevant with two kinds of material self structure, the thin light weight of FM grain, loose porous, and the surface can be high, has certain activity group and stronger adsorption capacity, can remove harmful substance by synergies such as absorption, neutralization, flocculation, filtrations.And in HA colloid molecule, carboxyl (COOH), the hydroxyl (OH) H of functional group
+Can exchange with metal cation, have certain complex performance, can delay or weaken heavy metal pollution.
Pb content μ g/kg in the leaching liquor of the different leaching number of times of table 1
Annotate: the different letter representation group differences of same column are (following table together) significantly
(2) Cd content and consolidation effect thereof in the leaching liquor:
Table 2 demonstration, D2 and combination F3 handle the Cd leaching are played inhibitory action, and the Cd amount that institute's leaching goes out is respectively 55.32%, 78.13% of contrast CT1 processing, and Cd is played remarkable consolidation effect.Outside this and the used environmentally conscious materials heterogeneity, also with special electrically relevant of soil colloids, because special molecule, atom or the ion that electrically can adsorb surrounding medium to some extent makes the concentration of these molecules, atom or ion at surface enrichment.
Table 2 is handled Cd content μ g/k in the leaching liquor of back
Embodiment 2: potted plant experiment
According to used environmentally conscious materials set handling
S1---humus class material (0.25g ﹒ kg
-1);
S2---macromolecular material (2g ﹒ kg
-1);
S3---fly ash material (50g ﹒ kg
-1);
S4---zeolitic material (10g ﹒ kg
-1);
C1---two kinds of environmentally conscious materials combinations (HA+SAP);
C2---two kinds of environmentally conscious materials combinations (SAP+FM);
C3---two kinds of environmentally conscious materials combinations (SAP+FS);
C4---three kinds of environmentally conscious materials combinations (HA+SAP+FM);
C5---three kinds of environmentally conscious materials combinations (HA+SAP+FS);
C6---three kinds of environmentally conscious materials combinations (SAP+FM+FS);
C7---four kinds of environmentally conscious materials combinations (HA+SAP+FM+FS);
CT2---add heavy metal, do not add any environmentally conscious materials.
Setting is plumbous in the experiment, (Pb, Cd concentration are respectively 500mg ﹒ kg to cadmium combined pollution soil
-1, 10mg ﹒ kg
-1), in 25cm * 25cm plastic tub, adorn native 8kg, plant soybean and corn respectively, each is handled 3 times and repeats, and the material addition adds mixing in proportion when mixing soil, and each material usage is identical with the homogenous material consumption in the combination.
As shown in Table 3, environmentally conscious materials influences milpa top lead, cadmium content: known that by table 3 in the harvest corn phase, S3 handles content for 68.92% of contrast, illustrates that the P in soil b solidification effect of FM is obvious; Milpa top Pb content under C6 and C7 handle reaches significant difference for 65.67% and 64.21% of contrast CT2.Illustrate that used environmentally conscious materials has suppressed heavy metal in soil Pb and moved to corn, single FM, combination S AP+FM+FS and HA+SAP+FM+FS fixed effect are remarkable.
Milpa top Cd content was 15.64mg ﹒ kg during contrast CT2 handled
-1, the milpa top Cd content that adds material processed all significantly is lower than contrast, and the milpa top Cd content that S4 handles is minimum, reaches 10.31mg ﹒ kg
-1, be 65.92% of CT2; The content that C1 handles milpa top Cd is 10.89mg ﹒ kg
-1, be 69.63% of contrast CT2; The milpa top Cd content that C6 handles is 10.39mg ﹒ kg
-1, be 66.43% of contrast CT2.FM, FS and F33(SAP+FM+FS) the corn C d content handled significantly is lower than contrast, and effect illustrates that obviously in other processing these three kinds of materials play remarkable inhibitory action to heavy metal in soil Cd to the corn migration.
Table 3 is handled back milpa top Pb harvest time, Cd content
Fig. 1 shows that environmentally conscious materials influences soybeans top lead, cadmium content: in the soybean harvest phase, soybeans top Pb content is 16.43mg ﹒ kg among the contrast CT2
-1, the soybeans top Pb content that four kinds of homogenous materials and combination C5, C6 handle significantly is lower than contrast, and wherein S1 handles obviously to the Pb fixed effect, and content is 9.88mg ﹒ kg
-1, be 60.13% of contrast; C5 handles remarkable to the Pb fixed effect, and content is 10.82mg ﹒ kg
-1, be 65.86% of contrast; Illustrate that material therefor has suppressed heavy metal-polluted soil Pb and moved to soybean, especially the S1 treatment effect is the most obvious, illustrates that its adsorption capacity is higher than other colloid in the soil, in HA colloid molecule, and carboxyl (COOH), the hydroxyl (OH) H of functional group
+Can exchange with metal cation, have certain complexing power, can delay or weaken heavy metal pollution.
Soybeans top Cd content under contrast CT2 handles is 9.46mg ﹒ kg
-1, add material processed soybeans top Cd content all be lower than contrast, effect is remarkable.The Cd content that S1 handles is minimum, reaches 3.36mg ﹒ kg
-1, be 35.52% of contrast; The content of the soybeans top Cd of combination C5 correspondence is 4.92mg ﹒ kg
-1, for contrasting 52.01%, effect is all significantly in other processing.Illustrate that the two can significantly suppress heavy metal in soil Cd and move to soybean.Each handles the influence to the migration of soybeans top to P in soil b, Cd contrast, and S1 and combination C5 effect are all very remarkable, and the fixed effect of two heavy metal species obviously in other, and is reached significant difference with CT2, and the two has suppressed Pb, Cd moves to soybean.
Used specific embodiment herein principle of the present invention and embodiment are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; Simultaneously, for one of ordinary skill in the art, according to thought of the present invention, part in specific embodiments and applications all can change.In sum, this description should not be construed as limitation of the present invention.
Claims (7)
1. the combinational environment material of a curing soil heavy metal pollution is characterized in that: comprise humic class material, macromolecular material, coal-based composite and opaque mineral material.
2. a kind of curing soil combinational environment material according to claim 1, it is characterized in that: described environmentally conscious materials can combine by four kinds in four kinds of materials, three kinds or two kinds.
3. a kind of curing soil combinational environment material according to claim 1, it is characterized in that: humus class material is humic acid.
4. the combinational environment material of a kind of curing soil heavy metal pollution according to claim 1, it is characterized in that: macromolecular material is granularity 100 purpose polyacrylates.
5. the combinational environment material of a kind of curing soil heavy metal pollution according to claim 1 is characterized in that: coal-based composite is that 91% silty sand grain and 9% clay are formed by weight ratio, and surface color is grey, pH value 8.36.
6. the combinational environment material of a kind of curing soil heavy metal pollution according to claim 1, it is characterized in that: the opaque mineral material is zeolite, granularity 100 orders.
7. the using method of the combinational environment material of a kind of curing soil heavy metal pollution according to claim 1 is characterized in that:
Step 1) is carried out mixing and stirring with the described four kinds of materials of claim 1 or three kinds of materials or two kinds of materials.
Step 2) is added in the soil.
Question responses such as step 3) begin to plant crops after 4 weeks.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103736717A (en) * | 2013-12-26 | 2014-04-23 | 江苏盖亚环境工程有限公司 | Method for stabilizing heavy metal pollutants in soil by using macromolecule modification polymers |
| CN105001874A (en) * | 2015-06-25 | 2015-10-28 | 红云红河烟草(集团)有限责任公司 | Curing agent for inhibiting tobacco from absorbing cadmium and lead elements in soil and application thereof |
| CN107699249A (en) * | 2017-10-25 | 2018-02-16 | 中国矿业大学(北京) | A kind of passivator of farmland soil heavy metals pollution and its preparation method and application |
| CN108034426A (en) * | 2017-12-20 | 2018-05-15 | 袁阔 | A kind of agent for preserving soil moisture and its preparation method and application |
| CN109604319A (en) * | 2018-12-27 | 2019-04-12 | 广西博世科环保科技股份有限公司 | The combined governance packet of fortification of plants extraction repairing heavy metal pollution farming land |
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| CN103736717A (en) * | 2013-12-26 | 2014-04-23 | 江苏盖亚环境工程有限公司 | Method for stabilizing heavy metal pollutants in soil by using macromolecule modification polymers |
| CN105001874A (en) * | 2015-06-25 | 2015-10-28 | 红云红河烟草(集团)有限责任公司 | Curing agent for inhibiting tobacco from absorbing cadmium and lead elements in soil and application thereof |
| CN105001874B (en) * | 2015-06-25 | 2020-04-14 | 红云红河烟草(集团)有限责任公司 | Curing agent for inhibiting tobacco from absorbing cadmium and lead elements in soil and application thereof |
| CN107699249A (en) * | 2017-10-25 | 2018-02-16 | 中国矿业大学(北京) | A kind of passivator of farmland soil heavy metals pollution and its preparation method and application |
| CN107699249B (en) * | 2017-10-25 | 2020-03-17 | 中国矿业大学(北京) | Passivator for farmland soil heavy metal pollution and preparation method and application thereof |
| CN108034426A (en) * | 2017-12-20 | 2018-05-15 | 袁阔 | A kind of agent for preserving soil moisture and its preparation method and application |
| CN109622594A (en) * | 2018-12-07 | 2019-04-16 | 重庆玖正环境科技有限公司 | A method of improving heavy metal pollution of soil using polymer absorption process |
| CN109622594B (en) * | 2018-12-07 | 2021-04-30 | 重庆玖正环境科技有限公司 | Method for improving heavy metal pollution of soil by using polymer adsorption method |
| CN109604319A (en) * | 2018-12-27 | 2019-04-12 | 广西博世科环保科技股份有限公司 | The combined governance packet of fortification of plants extraction repairing heavy metal pollution farming land |
| CN110467924A (en) * | 2019-09-09 | 2019-11-19 | 山东胜伟盐碱地科技有限公司 | A kind of alkaline land soil mercury, cadmium ion remover and preparation method thereof |
| CN112934942A (en) * | 2021-01-15 | 2021-06-11 | 华北地质勘查局五一四地质大队 | Heavy metal contaminated soil remediation agent, preparation method and use method |
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