CN109370596A - A kind of in-situ passivation the reparation medicament, preparation method and application of cadmium arsenic combined pollution agricultural land soil - Google Patents
A kind of in-situ passivation the reparation medicament, preparation method and application of cadmium arsenic combined pollution agricultural land soil Download PDFInfo
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- CN109370596A CN109370596A CN201811379503.9A CN201811379503A CN109370596A CN 109370596 A CN109370596 A CN 109370596A CN 201811379503 A CN201811379503 A CN 201811379503A CN 109370596 A CN109370596 A CN 109370596A
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- steel slag
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/08—Aluminium compounds, e.g. aluminium hydroxide
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01B—SOIL WORKING IN AGRICULTURE OR FORESTRY; PARTS, DETAILS, OR ACCESSORIES OF AGRICULTURAL MACHINES OR IMPLEMENTS, IN GENERAL
- A01B79/00—Methods for working soil
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2101/00—Agricultural use
Abstract
A kind of in-situ passivation the reparation medicament, preparation method and application of cadmium arsenic combined pollution agricultural land soil, belong to farmland soil heavy metals pollution remediation technology field.The ratio of ground phosphate rock and steel slag is 1:4~1:1, reduces exchangeable species Cd content by 26.76%-29.54%, and residual form Cd content improves 90.52%-113.75%；Exchangeable species As content maximum is set to reduce by 29.41%, residual form As content improves 16.82%.The raw material ground phosphate rock and steel slag of medicament are cheap and easy to get, and modification processing method is simple, and environmental-friendly, also there is the nutrient situation that can also improve agricultural land soil while doing renovation agent as phosphate fertilizer and complex mineral fertilizer in agricultural production.Individually addition steel slag and ground phosphate rock are compared, ground phosphate rock enhances the ability that steel slag reduces exchange state cadmium, and steel slag compensates for ground phosphate rock to the defect of the passivation ability difference of arsenic, improves repairing effect, more reduce the risk of field-crop.
Description
Technical field
The invention belongs to farmland soil heavy metals pollution remediation technology field, specially a kind of cadmium arsenic combined pollution farmland soil
Earth in-situ passivation repairs medicament, preparation method and application.
Background technique
It is influenced by mankind's activity such as metal mining smelting, sewage irrigation, agricultural production etc., farmland soil heavy metals pollution is asked
Topic becomes increasingly conspicuous, and cadmium and arsenic are common farmland soil heavy metals pollution elements." national Soil Pollution Investigation is public within 2014
Report " it shows, cadmium, arsenic exceeding standard rate account for the 7.0% of total point, 2.7% respectively in " five poisonous creatures: scorpion, viper, centipede, house lizard, toad " element.Cadmium in Soil, arsenic pollution make soil
Functional deterioration, causing crop failure also makes the safety of the agricultural product such as wheat, rice at great problems, has very to human health
Big potential hazard.In addition, geobiont, surrounding water is also seriously threatened.
Cd in soil mainly exists with the effect of physical absorption.The mobility of Cd in the soil is stronger, and with soil
The reduction of earth pH, exchangeable species Cd ratio significantly increase.As mainly exists with inorganic arsenous anion and arsenic acid root morphology in soil,
Organic arsenic content is lower and toxicity is lower than inorganic arsenic.Inorganic arsenic has certain migration in the soil, is influenced by soil pH
Larger, as the raising migration of system pH reduces, acidic environment is conducive to the migration of As, and alkaline environment is conducive to consolidating for As
It is fixed.Cadmium and arsenic pollution agricultural land soil are repaired, soil ecology function is restored, ensures that agricultural product security is important class urgently to be resolved
Topic.
Currently, the repair mode of heavy metal pollution agricultural land soil mainly has agriculture project reparation, bioremediation technology, chemistry
With physical-chemical process etc..Chemical passivation method is since expense is low, repair time is short, can handle a variety of Compound Heavy Metals, easy behaviour
The advantages that making has preferable superiority to the reparation of soil pollution low in large area, is widely used in heavy metals in farmland
In contaminated soil remediation.In nature and the difference of occurrence patterns due to Cd and As, for the agricultural land soil of cadmium arsenic pollution, generally
Passivation renovation agent be difficult to combine the effect of two heavy metal species.There is literature research to add ferric sulfate, the TCLP of Pb and Cd are mentioned
State is taken to reduce 65.7%-81.9% and 12.5%-15.3% respectively；The TCLP of Pb and Cd extracts state reduces 23.7%- respectively
81.8% and 0.1%-3.9%；But ferric sulfate and calcium carbonate make the TCLP of As that state content be taken to improve 0.5-1.0 and 1.0-respectively
1.2 times (Tian Tao thunders, and Zhou Hang waits two kinds of passivator of to vegetable plot repairing effect [J] ring of P in soil b, Cd, As combined pollution
Border science, 2017, (6): 2553-2560).Separately there is research to add bamboo charcoal and rice hull carbon, available state respectively in water paddy soil
The content of Cd reduces 4.79%, 9.46% compared to control respectively, and the content of available state As rises respectively compared to control
18.33% 42.64%, (Li Yuanxing dew, leaf Great Wall, Liu Yuling wait the coupling water management of charcoal raw to paddy soil As-Cd
Object validity and influence [J] agro-environment science journal of rice accumulation, 2018, (4): 696-704.).Currently, rarely having to agriculture
Cadmium and arsenic are passivated the pertinent literature and patent of reparation simultaneously in the soil of field.Therefore it is necessary to design a kind of while being passivated Cd
With the medicament of As, to improve soil remediation effect.
Some phosphorus containg substances such as ground phosphate rock, apatite etc. because have the characteristics that it is from a wealth of sources, cheap, environmental-friendly by
It is paid close attention to soil remediation researcher.Ground phosphate rock phosphate radical rich in and calcium ion can discharge phosphoric acid through peracid treatment for a long time
Root can reduce rapidly the heavy metals such as Pb, Cd, Cu, Zn available state concentration in soil, have preferable repairing effect.Chinese patent
CN 102559198A is by P2O5% content is that the rock phosphate powder of 20-30% is broken into 100 mesh powder, and is activated with oxalic acid treatment, is applied
In Cu, Pb, Cd contaminated soil, hence it is evident that reduce the exchange state and lettuce uptake of heavy metal in soil.There is literature research to exist
In soil after 0.1 μm of ground phosphate rock of addition 0.4%, Cd and Pb content is significantly reduced and is significantly reduced respectively in Shanghai leafiness and root
(46.9% and 61.9% are reduced in leaf respectively, reduces by 47.9% and 35.3%) in root respectively, soil exchange state Cd and Pb content
Respectively reduce by 44.8% and 44.9% (Hu Qinhuai, Zhang Qing, Wang Huangping, wait different-grain diameter ground phosphate rock passivation heavy metal-polluted soil Cd,
Mechanism Study [J] the agricultural resource and environment journal of Pb, 2014,31 (2): 164-168.).Yin Fei etc. is added in the soil
5%, Cd biological effectiveness reduces by 22.5%, 40.2% respectively after 20% ground phosphate rock；As biologically effective state content reduces respectively
12.7%, 29.2% (Yin Fei, Wang Haijuan, Li Yanyan wait the recovery dynatron effect of difference passivator counterweight metal combined contamination soil
Study [J] agro-environment science journal, 2015,34 (3): 438-448.).
Steel slag is the solid waste generated in steelmaking process, mainly contains CaO, SiO2、FeO、Al2O3, MgO etc., have
Certain alkalinity.Steel slag has preferable repairing effect to heavy metals such as Cd, Zn, Pb, As.There is literature research in water sample pH 1.5-
9.0, As (III) content 10-20mg/L, by As/ steel slag mass ratio be 1/2000 add steel slag when, As removal rate is up to 98% or more
([1] Zheng Lisheng, Wang Shilong, Zhang Hong, Wu Xiao east slag processing waste water containing As [J] chemical industry environmental protection, 1996 (06): 342-
345.).Also have literature research, be added in the soil Cd biological effectiveness after 5%, 20% steel slag reduce by 27.5% respectively,
41.9%；As biologically effective state content reduces by 22.4%, 32.99% respectively, and (Yin Fei, Wang Haijuan, Li Yanyan wait difference to be passivated
The recovery dynatron effect of agent counterweight metal combined contamination soil studies [J] agro-environment science journal, 2015,34 (3): 438-
448.).Rice can be effectively reduced, in pakchoi plant in soil plus the steel slag of 0.5%-1% in Chinese patent CN106281330A
Cd content.China is Chan Gang big country, and the burden of annual steel slag is huge but utilization rate is low, and steel slag is used for heavy metal polluted soil
The reparation of earth can have the function that " treatment of wastes with processes of wastes against one another ".
In view of ground phosphate rock to Cd and steel slag to the good result of As, the present invention combines ground phosphate rock with steel slag, with exploitation
A kind of pair of Cd and As contaminated soil has the renovation agent of good result.
Summary of the invention
The present invention is intended to provide a kind of cadmium arsenic combined pollution agricultural land soil in-situ passivation repairs medicament.
Technical solution of the present invention:
A kind of cadmium arsenic combined pollution agricultural land soil in-situ passivation reparation medicament, preparation step are as follows:
(1) material is ground, and ground phosphate rock and steel slag are ground respectively, crosses 100-400 mesh；
(2) material acid is modified, takes ground phosphate rock and steel slag powder, is added in 10ml liquid solution by every g solid powder
Ground phosphate rock and steel slag powder are added separately in the oxalic acid solution of 0.1-0.5mol/L, are modified respectively by ratio；It stirs and evenly mixs
Afterwards, 2-3 days are stood at room temperature, then temperature is dried under the conditions of being 50-70 DEG C, and grinding sieves with 100 mesh sieve, and dry sealing is spare；
(3) modified material mixes, and modified ground phosphate rock and steel slag powder 1:4~1:1 in mass ratio are mixed with vibrating sieving machine
Uniformly to get passivation renovation agent.
Above-mentioned ground phosphate rock used, P2O5The range of % is in 10%-35%；Steel slag used, the content of main component
Range: CaO 30-50%, SiO2For 10-40%, Al2O3For 2-15%, MgO 5-15%, Fe2O3For 0-40%, MnO 0-
10%.
It repairs the use of medicament: renovation agent is added in contaminated soil by the 0.5%-5% of soil quality, and mix equal
Even, maintaining soil moisture content is the 50%-70% of maxmun field capacity.
The beneficial effects of the invention are as follows a kind of cadmium arsenic combined pollution agricultural land soil in-situ passivation reparation medicament is provided, effectively
Reduce the activity of cadmium and arsenic in soil.Ground phosphate rock mainly reduces the activity of cadmium in renovation agent, and steel slag, which has both, reduces arsenic and cadmium
Activity.Ground phosphate rock and two kinds of raw materials of steel slag are cheap and easy to get, and modification processing method is simple, and environmental-friendly, in agricultural production
In also have the nutrient situation that can also improve agricultural land soil while doing renovation agent as phosphate fertilizer and complex mineral fertilizer.Compare list
Solely addition steel slag and ground phosphate rock, ground phosphate rock enhance the ability that steel slag reduces exchange state cadmium, and steel slag compensates for ground phosphate rock to arsenic
The defect of passivation ability difference more reduces the risk of field-crop.
Detailed description of the invention
Fig. 1 is ground phosphate rock: steel slag=1:4 compares steel slag and ground phosphate rock to the repairing effect figure of Cd and As.
Fig. 2 is ground phosphate rock: steel slag=1:2 compares steel slag and ground phosphate rock to the repairing effect figure of Cd and As.
Fig. 3 is ground phosphate rock: steel slag=1:1 compares steel slag and ground phosphate rock to the repairing effect figure of Cd and As.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, the present embodiment be premised on technical solution of the present invention under
Implement.
Embodiment 1
Ground phosphate rock P used in embodiment2O5% is 25%, and steel slag mainly forms: CaO 42.4%, SiO2For 33%, Al2O3
For 12%, MgO 5.86%, Fe2O3For 0.57%, MnO 0.39%, other 5.78%.
Ground phosphate rock and steel slag are ground respectively, and cross 400 mesh, measures ground phosphate rock partial size D50It is 17.23 μm, steel slag partial size
D50Be 21.22 μm, and press powder quality: the oxalic acid solution of 0.5mol/L is added in liquor capacity=1:10.After stirring and evenly mixing,
2 days are stood at room temperature, is then dried at 60 DEG C, grinding sieves with 100 mesh sieve.By modified ground phosphate rock and the steel slag ratio of 1:4 in mass ratio
Example is mixed with vibrating sieving machine, obtains renovation agent 1.
Renovation agent 1 is uniformly mixed with 100g for examination soil with the 1% of soil quality.Add water daily, maintains soil water-containing
Amount be maxmun field capacity 60%, 20 DEG C constant temperature aerlbic culture 20 days.After culture, natural air drying is taken out, and survey
The available state concentration of soil Cd and As and Tessier continuously extract form concentration after fixed processing.
After adding composite drug, compared with the control group, Cd exchangeable species and carbonate combine state content are reduced in soil, point
26.76% and 0.85% are not reduced；Organically combine state, iron and manganese oxides reference state content and residual form content increase, respectively
Increase 22.13%, 12.50% and 103.72%.As exchangeable species content reduces 14.71% in soil, and carbonate combines
State, iron and manganese oxides reference state, organically combine state and residual form content increase, respectively content increase 6.52%, 7.55%,
1.82% and 16.53%.
Embodiment 2
Ground phosphate rock P used in embodiment2O5% is 25%, and steel slag mainly forms: CaO 42.4%, SiO2For 33%, Al2O3
For 12%, MgO 5.86%, Fe2O3For 0.57%, MnO 0.39%, other 5.78%.
Ground phosphate rock and steel slag are ground respectively, and cross 400 mesh, measures ground phosphate rock partial size D50It is 17.23 μm, steel slag partial size
D50Be 21.22 μm, and press powder quality: the oxalic acid solution of 0.5mol/L is added in liquor capacity=1:10.After stirring and evenly mixing, in room
Temperature is lower to stand 2 days, then dries at 60 DEG C, grinding sieves with 100 mesh sieve.By modified ground phosphate rock and steel slag 1:2 ratio in mass ratio
It is mixed with vibrating sieving machine, obtains renovation agent 2.
Renovation agent 2 is uniformly mixed with 100g for examination soil with the 1% of soil quality.Add water daily, maintains soil water-containing
Amount be maxmun field capacity 60%, 20 DEG C constant temperature aerlbic culture 20 days.After culture, natural air drying is taken out, and survey
The available state concentration of soil Cd and As and Tessier continuously extract form concentration after fixed processing.
After adding composite drug, compared with the control group, Cd exchangeable species, carbonate combine state and organically combine state in soil
Content reduces, and reduces 29.54%, 9.57% and 44.23% respectively；Iron and manganese oxides reference state content and residual form content liter
Height increases 18.53% and 90.52% respectively.As exchangeable species, iron and manganese oxides reference state and organically combine state contain in soil
Amount reduces 29.41%, 21.74% and 12.87% respectively, and carbonate combine state and residual form content increase, respectively content liter
It is high by 23.91% and 16.82%.
Embodiment 3
Ground phosphate rock P used in embodiment2O5% is 25%, and steel slag mainly forms: CaO 42.4%, SiO2For 33%, Al2O3
For 12%, MgO 5.86%, Fe2O3For 0.57%, MnO 0.39%, other 5.78%.
Ground phosphate rock and steel slag are ground respectively, and cross 400 mesh, measures ground phosphate rock partial size D50It is 17.23 μm, steel slag partial size
D50Be 21.22 μm, and press powder quality: the oxalic acid solution of 0.5mol/L is added in liquor capacity=1:10.After stirring and evenly mixing, in room
Temperature is lower to stand 2 days, then dries at 60 DEG C, grinding sieves with 100 mesh sieve.By modified ground phosphate rock and steel slag 1:1 ratio in mass ratio
It is mixed with vibrating sieving machine, obtains renovation agent 3.
Renovation agent 3 is uniformly mixed with 100g for examination soil with the 1% of soil quality.Add water daily, maintains soil water-containing
Amount be maxmun field capacity 60%, 20 DEG C constant temperature aerlbic culture 20 days.After culture, natural air drying is taken out, and survey
The available state concentration of soil Cd and As and Tessier continuously extract form concentration after fixed processing.
After adding composite drug, compared with the control group, Cd exchangeable species, carbonate combine state and organically combine state in soil
Content reduces, and reduces 27.65%, 15.52% and 8.65% respectively；Iron and manganese oxides reference state content and residual form content liter
Height increases 16.15% and 113.75% respectively.As iron and manganese oxides reference state reduces 18.09% in soil, commutative
State, carbonate combine state, organically combine state and residual form content increase, respectively content increase 2.94%, 30.43%,
19.77% and 13.21%.
Claims (4)
1. a kind of cadmium arsenic combined pollution agricultural land soil in-situ passivation repairs medicament, which is characterized in that the cadmium arsenic combined pollution
It includes the modified ground phosphate rock of acid and sour modified steel slag powder that agricultural land soil in-situ passivation, which repairs medicament, and the mass ratio of the two is 1:
4~1:1；The partial size for the steel slag powder that the modified ground phosphate rock of acid and acid are modified is 100-400 mesh.
2. cadmium arsenic combined pollution agricultural land soil in-situ passivation according to claim 1 repairs medicament, which is characterized in that described
Ground phosphate rock, P2O5The range of % is in 10%-35%；The steel slag, the content range of main component: CaO 30-
50%, SiO2For 10-40%, Al2O3For 2-15%, MgO 5-15%, Fe2O3For 0-40%, MnO 0-10%.
3. the preparation method that a kind of cadmium arsenic combined pollution agricultural land soil in-situ passivation repairs medicament, which is characterized in that steps are as follows:
(1) material is ground, and ground phosphate rock and steel slag are ground respectively, crosses 100-400 mesh；
(2) material acid is modified, takes ground phosphate rock and steel slag powder, is added to the ratio in 10ml liquid solution in every g solid powder,
Ground phosphate rock and steel slag powder are added separately in the oxalic acid solution of 0.1-0.5mol/L, are modified respectively；After stirring and evenly mixing, in room
Temperature is lower to stand 2-3 days, and then temperature is dried under the conditions of being 50-70 DEG C, and grinding sieves with 100 mesh sieve, and dry sealing is spare；
(3) modified material mixes, and modified ground phosphate rock and steel slag powder 1:4~1:1 in mass ratio are uniformly mixed with vibrating sieving machine,
Up to passivation renovation agent.
4. the application that a kind of cadmium arsenic combined pollution agricultural land soil in-situ passivation repairs medicament, which is characterized in that answer a kind of cadmium arsenic
It closes polluted farmland soil in-situ passivation reparation medicament to be added in contaminated soil by the 0.5%-5% of soil quality, and mixes equal
Even, maintaining soil moisture content is the 50%-70% of maxmun field capacity.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112251235A (en) * | 2020-10-23 | 2021-01-22 | 安徽理工大学环境友好材料与职业健康研究院(芜湖) | Preparation method of steel slag-based curing agent and treatment system and method of Cd-polluted soil |
| CN113877954A (en) * | 2021-09-26 | 2022-01-04 | 中国地质大学（北京） | Passivation restoration agent for cadmium-polluted soil and preparation method and application thereof |
| CN114752388A (en) * | 2022-05-13 | 2022-07-15 | 哈尔滨工业大学 | Stabilizer for copper, chromium and lead compound contaminated soil and preparation method and application thereof |
| CN115466621A (en) * | 2022-06-02 | 2022-12-13 | 中南民族大学 | Application of double-effect repairing agent taking electrolytic manganese residues as base material in repairing heavy metal contaminated soil |
| CN115466622A (en) * | 2022-06-02 | 2022-12-13 | 中南民族大学 | Soil remediation agent using phosphogypsum as base material and preparation method and application thereof |
| CN115537205A (en) * | 2022-09-30 | 2022-12-30 | 云南天朗节能环保集团有限公司 | Soil remediation agent for heavy metal contaminated farmland |
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| CN112251235A (en) * | 2020-10-23 | 2021-01-22 | 安徽理工大学环境友好材料与职业健康研究院(芜湖) | Preparation method of steel slag-based curing agent and treatment system and method of Cd-polluted soil |
| CN112251235B (en) * | 2020-10-23 | 2021-11-26 | 安徽理工大学环境友好材料与职业健康研究院(芜湖) | Preparation method of steel slag-based curing agent and treatment system and method of Cd-polluted soil |
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| CN114752388A (en) * | 2022-05-13 | 2022-07-15 | 哈尔滨工业大学 | Stabilizer for copper, chromium and lead compound contaminated soil and preparation method and application thereof |
| CN114752388B (en) * | 2022-05-13 | 2024-03-29 | 哈尔滨工业大学 | Stabilizing agent for copper, chromium and lead composite polluted soil and preparation method and application thereof |
| CN115466621A (en) * | 2022-06-02 | 2022-12-13 | 中南民族大学 | Application of double-effect repairing agent taking electrolytic manganese residues as base material in repairing heavy metal contaminated soil |
| CN115466622A (en) * | 2022-06-02 | 2022-12-13 | 中南民族大学 | Soil remediation agent using phosphogypsum as base material and preparation method and application thereof |
| CN115537205A (en) * | 2022-09-30 | 2022-12-30 | 云南天朗节能环保集团有限公司 | Soil remediation agent for heavy metal contaminated farmland |
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Application publication date: 20190222 |