CN105085102A - Compound fertilizer for arsenic contaminated soil and preparation method therefor and application thereof - Google Patents
Compound fertilizer for arsenic contaminated soil and preparation method therefor and application thereof Download PDFInfo
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Abstract
The invention provides a compound fertilizer for arsenic contaminated soil. The compound fertilizer contains nutritional components, i.e., N, P and K and a proper proportioning ratio of components, i.e., agricultural rare earth nitrate, catalyst waste, iron ore powder, humic acid mineral powder, sepiolite, plant ash, kaolin clay and zeolite; and after the compound fertilizer is applied to arsenic contaminated soil, under the synergistic action of all the components, the contaminated soil can be effectively remedied while arsenic in the soil is effectively passivated and immobilized, so that the activity of the arsenic in the soil is remarkably lowered, the lowering of arsenic absorption of crops is facilitated, and then, the content of arsenic in the crops is remarkably lowered. The compound improver provided by the invention has relatively good stability and environment-friendliness, does not generate secondary pollution and is low in cost and easy in large-area popularization, and the amount of application is only 10-200kg/hm<2> when the compound improver is applied to the arsenic contaminated soil, so that the content of arsenic in the crops can be remarkably lowered, and the crops can reach national edible safety standards.
Description
Technical field
The present invention relates to a kind of composite fertilizer for As polluted soil and its preparation method and application, belong to the technical field of contaminated soil remediation.
Background technology
Arsenic (As) is a kind of metalloid element human health to material impact.In recent years, along with the fast development of mining industry and the many reasons such as the unreasonable exploitation in indivedual small-sized mining area and discharge, China's some areas arsenic contamination phenomenon is appeared in the newspapers repeatly.And in some Rural areass, owing to using containing the higher fertilizer of arsenic or using containing many-sided reasons such as arsenic sterilant, veterinary drugs, in arable land, arsenic content overproof problem also happens occasionally, and brings potential threat to crop production safety.Arsenic in soil, especially available state arsenic absorb by the farm crop such as paddy rice, wheat and finally enter in agricultural-food, agricultural product security is reduced, all there is great threat to HUMAN HEALTH and ecological safety.
Arsenic exists with variform in soil, but generally exists mainly with the form of mineral compound, as with the form such as pentavalent arsenic, trivalent arsenic; Sometimes also can exist with the form of organic compound, as monomethyl arsenic (MMA), dimethyl arsenic (DMA), arsenous methide (TMA) etc.Studies have found that, the content of organic arsenic is very low in its natural state usually, and the content of inorganic states arsenic and toxicity are all greater than organic arsenic, and arsenious toxicity is 60 times of pentavalent arsenic, is 70 times of methyl arsenic (MMA, DMA) toxicity.Therefore, inorganic states arsenic is classified as No.1 environmental pollutant by Environmental Defense, and has formulated the limit value of arsenic content in a series of soil, water body and agricultural-food.Therefore, in a sense, reduce the activity of Arsenic in Soil, in fact mainly reduce the toxicity of inorganic states arsenic, reduce the possibility that it is absorbed by crops.
Chinese patent literature CN102974601A discloses a kind of method of As polluted soil stablizer and repairing polluted soil, this stablizer comprises following component: montmorillonite, calcium oxide, magnesiumcarbonate, iron filings, with stablizer finished product butt for 100kg, component is by weight as follows: montmorillonite 30-40kg, calcium oxide 20-30kg, magnesiumcarbonate 20-30kg, iron filings 10-20kg.Aforementioned stable agent is administered in As polluted soil, montmorillonite wherein can adsorb the arsenic in soil, generate unformed ferric arsenate with As effect after iron filings are oxidized and form weak crystallization ironic hydroxide in soil or generate the lower secondary mineral of the solubleness such as scorodite, and then reduce the movability of As, the calcium oxide added and magnesiumcarbonate component can promote the generation of precipitated metal thing and be conducive to sedimentary stable existence, but, after aforementioned stable agent is applied to As polluted soil, repairing effect is unsatisfactory, in farm crop, arsenic content is still higher, and need disposablely to use in a large number, transportation cost and to use cost all higher, peasant not easily accepts, be difficult to spread.
Summary of the invention
After technical problem to be solved by this invention is that soil improvement agent of the prior art is applied to As polluted soil, repairing effect is unsatisfactory, in farm crop, arsenic content is still higher, thus proposes a kind of effective and effectively can reduce the composite fertilizer for As polluted soil of arsenic content in farm crop to soil remediation.
For solving the problems of the technologies described above, technical scheme of the present invention is:
For a composite fertilizer for As polluted soil, its raw material composition comprises:
Nitrogenous fertilizer, 10-60 weight part;
Phosphate fertilizer, 10-60 weight part;
Potash fertilizer, 10-60 weight part;
Arsenic determination, 0.5-2 weight part;
Catalyzer gives up agent, 2-10 weight part;
Powdered iron ore, 10-40 weight part;
Humic acid breeze, 25-55 weight part;
Sepiolite, 15-25 weight part;
Plant ash, 3-11 weight part;
Kaolin, 0.5-1.1 weight part;
Zeolite, 0.3-1.2 weight part.
Described adopting is prepared with the following method:
The agent of giving up of described catalyzer is be that the catalst for synthesis of methanol of carrier gives up agent with aluminum oxide.
The give up active ingredient of agent of described catalyzer is cupric oxide and zinc oxide.
Described powdered iron ore is the mixture of one or more in ferrihydrite powder, pyrrhosiderite powder, lepidocrocite powder.
Described nitrogenous fertilizer is the mixture of one or more in urea, volatile salt, ammonium sulfate, ammonium chloride, nitrocalcite and ammonium nitrate, described phosphate fertilizer is the mixture of one or more in monoammonium phosphate, diammonium phosphate, calcium superphosphate, double superhosphate and fused(calcium magnesium)phosphate, and described potash fertilizer is the mixture of one or more in Repone K, potassium sulfate, potassium silicate and saltpetre.
The give up particle diameter of agent of described catalyzer is less than or equal to 10nm, the particle diameter of described powdered iron ore is less than or equal to 10nm, the particle diameter of described humic acid breeze is 110-140 order, the particle diameter of described sepiolite is 110-140 order, the particle diameter of described plant ash is 110-140 order, described kaolinic particle diameter is 110-140 order, and the particle diameter of described zeolite is 110-140 order.
Also be added with at least one in unslaked lime, wilkinite, hydroxyapatite and fertilizer;
In described fertilizer, to dry quality of organic matter mark >=40% of base; To dry massfraction >=4.0% of the nitrogen of base, Vanadium Pentoxide in FLAKES and potassium oxide total nutrient; Massfraction≤30% of the moisture of fresh sample, potential of hydrogen pH value is 5.5-8.5.
The preparation method of the described composite fertilizer for As polluted soil, its step is as follows:
Get various feed composition according to above-mentioned weight part and mix, namely obtaining described composite modifying agent through extruder grain.
The described application of composite fertilizer in As polluted soil is repaired for As polluted soil.
The application process of the described composite fertilizer for As polluted soil, its step is as follows:
In arsenic contaminated soil, add the described composite fertilizer for As polluted soil, addition is 10-200kg/hm
2, the balance improvement soil time is 7-14 days.
Technique scheme of the present invention has the following advantages compared to existing technology:
(1) composite fertilizer for As polluted soil of the present invention, comprise the arsenic determination of n p k nutrition component and applicable proportioning, catalyzer gives up agent, powdered iron ore, humic acid breeze, sepiolite, plant ash, kaolin and zeolite component, after being applied to As polluted soil, under the synergy of above-mentioned each component, realize Arsenic in Soil being carried out effective passivation and effectively repairing polluted soil while fixing, thus make the active significantly reduction of the arsenic in soil on the one hand, be conducive to reducing farm crop to the absorption of arsenic, and then arsenic content in farm crop is significantly reduced, the n p k nutrition component contained on the other hand and plant ash etc. can provide nutrition to improve soil fertility for soil again, continue the repairing effect of strengthening to polluted soil, in addition, rare earth component in arsenic determination itself has antagonistic action to arsenic, be conducive to further reducing farm crop to the absorption of arsenic, composite modifying agent of the present invention has good stability and environment friendly, secondary pollution can not be produced, with low cost, be easy to spread, when being applied to As polluted soil, amount of application is only 10-200kg/hm
2, just significantly can reduce arsenic content in farm crop, make it reach national edible safety standard, reach management goal.
(2) composite fertilizer for As polluted soil of the present invention, also be added with unslaked lime, wilkinite, hydroxyapatite and fertilizer, by the arsenic in the inorganic component fixed-contamination soil in unslaked lime, wilkinite, hydroxyapatite, and improve the fertility of soil in conjunction with fertilizer, thus the repair of strengthening to polluted soil while improving Arsenic in Soil fixed action.
Embodiment
1g is represented with 1 weight part in following examples.
Embodiment 1
The present embodiment provides a kind of composite fertilizer for As polluted soil, and its raw material composition comprises:
Urea, 10 weight parts;
Monoammonium phosphate, 60 weight parts;
Repone K, 10 weight parts;
Arsenic determination, 2 weight parts;
Catalst for synthesis of methanol gives up agent, 2 weight parts;
Ferrihydrite powder, 40 weight parts;
Humic acid breeze, 55 weight parts;
Sepiolite, 15 weight parts;
Plant ash, 11 weight parts;
Kaolin, 0.5 weight part;
Zeolite, 1.2 weight parts.
The particle diameter of described arsenic determination is 10 orders, and the give up particle diameter of agent of described catalst for synthesis of methanol is 10nm, and the particle diameter of described ferrihydrite powder is 10nm; The particle diameter of described humic acid breeze, sepiolite, plant ash, kaolin and zeolite is 110 orders.
Further, the preparation method of the described composite fertilizer for As polluted soil is provided, is specially:
Get various feed composition according to above-mentioned weight part and mix, namely obtaining described composite modifying agent through extruder grain.
Embodiment 2
The present embodiment provides a kind of composite fertilizer for As polluted soil, and its raw material composition comprises:
Volatile salt, 60 weight parts;
Diammonium phosphate, 10 weight parts;
Potassium sulfate, 60 weight parts;
Arsenic determination, 0.5 weight part;
Catalst for synthesis of methanol gives up agent, 10 weight parts;
Pyrrhosiderite powder, 10 weight parts;
Humic acid breeze, 25 weight parts;
Sepiolite, 25 weight parts;
Plant ash, 3 weight parts;
Kaolin, 1.1 weight parts;
Zeolite, 0.3 weight part;
Unslaked lime, 10 weight parts;
Wilkinite, 15 weight parts;
Hydroxyapatite, 10 weight parts;
Fertilizer, 20 weight parts.
The particle diameter of described arsenic determination is 10 orders, and the give up particle diameter of agent of described catalst for synthesis of methanol is 9nm, and the particle diameter of described pyrrhosiderite powder is 9nm, and the particle diameter of described humic acid breeze, sepiolite, plant ash, kaolin and zeolite is 140 orders.
The particle diameter of described unslaked lime, wilkinite, hydroxyapatite is 10 orders.
In described fertilizer, to dry the quality of organic matter mark of base for 40%; To dry the massfraction of the nitrogen of base, Vanadium Pentoxide in FLAKES and potassium oxide total nutrient for 4.0%; The massfraction of the moisture of fresh sample is 30%, and potential of hydrogen pH value is 5.5.
Further, the preparation method of the described composite fertilizer for As polluted soil is provided, is specially:
Get various feed composition according to above-mentioned weight part and mix, namely obtaining described composite modifying agent through extruder grain.
Embodiment 3
The present embodiment provides a kind of composite fertilizer for As polluted soil, and its raw material composition comprises:
Ammonium sulfate, 40 weight parts;
Calcium superphosphate, 35 weight parts;
Potassium silicate, 50 weight parts;
Arsenic determination, 1.5 weight parts;
Catalst for synthesis of methanol gives up agent, 5 weight parts;
Lepidocrocite powder, 30 weight parts;
Humic acid breeze, 40 weight parts;
Sepiolite, 17 weight parts;
Plant ash, 8 weight parts;
Kaolin, 0.9 weight part;
Zeolite, 0.8 weight part;
Wilkinite, 10 weight parts;
Fertilizer, 20 weight parts.
The particle diameter of described arsenic determination is 10 orders, and the give up particle diameter of agent of described catalst for synthesis of methanol is 8nm, and the particle diameter of described lepidocrocite powder is 8nm, and described humic acid breeze, sepiolite, plant ash, kaolin, zeolite and bentonitic particle diameter are 140 orders.
In described fertilizer, to dry the quality of organic matter mark of base for 55%; To dry the massfraction of the nitrogen of base, Vanadium Pentoxide in FLAKES and potassium oxide total nutrient for 8.0%; The massfraction of the moisture of fresh sample is 18%, and potential of hydrogen pH value is 7.5.
Further, the preparation method of the described composite fertilizer for As polluted soil is provided, is specially:
Get various feed composition according to above-mentioned weight part and mix, namely obtaining described composite modifying agent through extruder grain.
Embodiment 4
The present embodiment provides a kind of composite fertilizer for As polluted soil, and its raw material composition comprises:
The mixture that ammonium chloride, nitrocalcite and ammonium nitrate form according to mass ratio 1:1:1,45 weight parts;
The mixture that double superhosphate and fused(calcium magnesium)phosphate form according to mass ratio 1:1,45 weight parts;
The mixture that potassium silicate and saltpetre form according to mass ratio 1:1,45 weight parts;
Arsenic determination, 1.2 weight parts;
Catalyzer gives up agent, 6 weight parts;
Pyrrhosiderite powder, 20 weight parts;
Humic acid breeze, 38 weight parts;
Sepiolite, 21 weight parts;
Plant ash, 10 weight parts;
Kaolin, 0.8 weight part;
Zeolite, 0.9 weight part;
Hydroxyapatite, 20 weight parts;
Fertilizer, 20 weight parts.
The particle diameter of described arsenic determination is 10 orders, and the give up particle diameter of agent of described catalyzer is 8nm, and the particle diameter of described pyrrhosiderite powder is 8nm, and described humic acid breeze, sepiolite, plant ash, kaolin, zeolite and bentonitic particle diameter are 140 orders.
Described catalyzer give up agent be take aluminum oxide as carrier, agent of giving up with cupric oxide and the zinc oxide catalyzer that is active ingredient.
In described fertilizer, to dry the quality of organic matter mark of base for 45%; To dry the massfraction of the nitrogen of base, Vanadium Pentoxide in FLAKES and potassium oxide total nutrient for 5.0%; The massfraction of the moisture of fresh sample is 20%, and potential of hydrogen pH value is 7.
Further, the preparation method of the described composite fertilizer for As polluted soil is provided, is specially:
Get various feed composition according to above-mentioned weight part and mix, namely obtaining described composite modifying agent through extruder grain.
The extruder grain technique that above-described embodiment and comparative example adopt can adopt extruder grain production technique general in prior art, and special compound fertilizer process flow process also can be adopted to carry out producing (see " agricultural modernization research " the 18th volume the 2nd phase the 108th page).
Comparative example 1
This comparative example provides a kind of composite modifying agent for As polluted soil, and its raw material composition comprises:
Montmorillonite, 30 weight parts;
Calcium oxide, 20 weight parts;
Magnesiumcarbonate, 20 weight parts;
Iron filings, 10 weight parts.
Further, the preparation method of the described composite modifying agent for As polluted soil is provided, is specially:
Get various feed composition according to above-mentioned weight part and mix, namely obtaining described composite modifying agent through extruder grain.
Experimental example
The composite fertilizer being used for As polluted soil described in embodiment 1-4 and comparative example 1 and modifying agent are numbered as A-D, E successively, select heavy metal As contaminated soil as subject, the described composite fertilizer for As polluted soil and modifying agent is added respectively in above-mentioned As contaminated soil, and arsenic content effective in soil after reparation is measured, concrete grammar is: claim 5.0g to cross the pedotheque of 100 mesh sieves in 100ml centrifuge tube, add the NH that 25ml concentration is 1mol/L
4cl solution, centrifugation after vibration 2h, filters and obtains extracting solution, adopts the soluble state metal A s content in aas determination extracting solution, is effective arsenic content.
What table 1 showed is the measurement result adopting sample A-E to carry out repairing rear effectively arsenic content to the soil being initially 5.23mg/kg containing As amount, and wherein, the addition of composite modifying agent is 10kg/hm
2, balance improvement soil 7 days;
Table 2 show for adopting sample A to being initially followed successively by 5.23 containing effective As amount, 5.56,6.05,4.53, the measurement result of the soil of 5.86mg/kg effective arsenic content after carrying out repairing;
The measurement result for adopting sample A soil (the initial As of containing amount is 5.23mg/kg) to be carried out to effective arsenic content after repairing under Different adding amount that table 3 shows;
What table 4 showed is adopt sample A at same addition 10kg/hm
2under, soil (initial be 5.23mg/kg containing As amount) is not carried out under homostasis improvement time to the measurement result of effectively arsenic content after repairing.
Table 1-initially containing As amount for the soil of 5.23mg/kg carry out repairing after the measurement result of effective arsenic content
Table 2-sample A is to the measurement result of arsenic content effective after As contaminated soil remediation
| Initial effectively As content/(mg/kg) | 5.23 | 5.56 | 6.05 | 4.53 | 5.86 |
| Addition/(the kg/hm of composite modifying agent 2) | 10 | 10 | 10 | 10 | 10 |
| Balance improvement soil time/(my god) | 15 | 15 | 15 | 15 | 15 |
| Effective As content/(mg/kg) after repairing | 0.76 | 0.90 | 1.16 | 0.68 | 0.93 |
| Effective As reduced rate in soil | 85.48％ | 83.86％ | 80.87％ | 84.99％ | 84.10％ |
Table 3-sample A under Different adding amount to soil remediation after the measurement result of effective arsenic content
Table 4-sample A under not homostasis improvement time to soil remediation after the measurement result of effective arsenic content
As can be seen from the test result of above-mentioned table 1-4, after adopting the composite fertilizer for As polluted soil of the present invention to repair As contaminated soil, in soil, effective As reduced rate is all positioned at more than 80%, thus illustrate that composite modifying agent of the present invention can realize effective passivation of heavy metal in soil As and fixing and adopt modifying agent described in comparative example (see table 1) to repair effective As reduced rate in rear soil to soil to be only 55.04%, to illustrate that the repairing effect of modifying agent of the prior art to As polluted soil is unsatisfactory.
Further, in order to study in soil As content to the impact of crop growth, in blank soil, add heavy metal As makes As content in soil be respectively 0, 1, 5, 10, 20mg/kg, for often organizing As content, control group and experimental group are set respectively, wherein, do not add the soil of composite modifying agent of the present invention (sample A) as a control group, soil after adopting sample A to repair is as experimental group, respectively in the culturing on soil Plantula Brassicae chinensis of above-mentioned experimental group and control group, adopt the biomass of weighting method after dried difference experiment with computing group and control group, calculate biomass increment rate further, adopt atomic absorption spectrophotometer to measure As content in Plantula Brassicae chinensis, result is as shown in table 5.
The table 5 – impact that soil absorbs Growth of Cabbage and As after composite modifying agent is repaired
Test result as can be seen from above-mentioned table 5, in Plantula Brassicae chinensis, the detected result of As content shows, compared with control group, when the initial addition of soil As is respectively 1mg/kg, 5mg/kg, during 10mg/kg and 20mg/kg, after composite modifying agent of the present invention is repaired, biomass increment rate is respectively 53.4%, 61.6%, 10.3% and 10.5%, illustrate that described composite modifying agent effectively can promote the growth of Plantula Brassicae chinensis, in Plantula Brassicae chinensis, As content reduces by 47.4% respectively, 53.1%, 40.9% and 31.4%, illustrate that composite fertilizer of the present invention can make the active significantly reduction of the arsenic in soil, reduce farm crop to the absorption of arsenic, arsenic content in farm crop is significantly reduced.Even if for not by arsenic contaminated soil (initial As content is 0mg/kg), use after composite modifying agent of the present invention repairs, biomass increment rate is up to 69.1%, illustrate that described composite modifying agent effectively can promote the growth of Plantula Brassicae chinensis, also make As content in Plantula Brassicae chinensis reduce by 14.3% simultaneously.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (10)
1. for a composite fertilizer for As polluted soil, it is characterized in that, raw material composition comprises:
Nitrogenous fertilizer, 10-60 weight part;
Phosphate fertilizer, 10-60 weight part;
Potash fertilizer, 10-60 weight part;
Arsenic determination, 0.5-2 weight part;
Catalyzer gives up agent, 2-10 weight part;
Powdered iron ore, 10-40 weight part;
Humic acid breeze, 25-55 weight part;
Sepiolite, 15-25 weight part;
Plant ash, 3-11 weight part;
Kaolin, 0.5-1.1 weight part;
Zeolite, 0.3-1.2 weight part.
2. the composite fertilizer for As polluted soil according to claim 1, is characterized in that, the agent of giving up of described catalyzer is be that the catalst for synthesis of methanol of carrier gives up agent with aluminum oxide.
3. the composite fertilizer for As polluted soil according to claim 1 and 2, is characterized in that, the give up active ingredient of agent of described catalyzer is cupric oxide and zinc oxide.
4. the composite fertilizer for As polluted soil according to any one of claim 1-3, is characterized in that, described powdered iron ore is the mixture of one or more in ferrihydrite powder, pyrrhosiderite powder, lepidocrocite powder.
5. the composite fertilizer for As polluted soil according to any one of claim 1-4, it is characterized in that, described nitrogenous fertilizer is the mixture of one or more in urea, volatile salt, ammonium sulfate, ammonium chloride, nitrocalcite and ammonium nitrate, described phosphate fertilizer is the mixture of one or more in monoammonium phosphate, diammonium phosphate, calcium superphosphate, double superhosphate and fused(calcium magnesium)phosphate, and described potash fertilizer is the mixture of one or more in Repone K, potassium sulfate, potassium silicate and saltpetre.
6. the composite fertilizer for As polluted soil according to any one of claim 1-5 is characterized in that, the give up particle diameter of agent of described catalyzer is less than or equal to 10nm, the particle diameter of described powdered iron ore is less than or equal to 10nm, the particle diameter of described humic acid breeze is 110-140 order, the particle diameter of described sepiolite is 110-140 order, the particle diameter of described plant ash is 110-140 order, and described kaolinic particle diameter is 110-140 order, and the particle diameter of described zeolite is 110-140 order.
7. the composite fertilizer for As polluted soil according to any one of claim 1-6, is also added with at least one in unslaked lime, wilkinite, hydroxyapatite and fertilizer;
In described fertilizer, to dry quality of organic matter mark >=40% of base; To dry massfraction >=4.0% of the nitrogen of base, Vanadium Pentoxide in FLAKES and potassium oxide total nutrient; Massfraction≤30% of the moisture of fresh sample, potential of hydrogen pH value is 5.5-8.5.
8. the preparation method of the composite fertilizer for As polluted soil according to any one of claim 1-7, its step is as follows:
Get various feed composition according to above-mentioned weight part and mix, namely obtaining described composite modifying agent through extruder grain.
9. the application of composite fertilizer in As polluted soil is repaired for As polluted soil described in any one of claim 1-7.
10. the application process of the composite fertilizer for As polluted soil described in any one of claim 1-7, its step is as follows:
In arsenic contaminated soil, add the described composite fertilizer for As polluted soil, addition is 10-200kg/hm
2, the balance improvement soil time is 7-14 days.
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| CN108865152A (en) * | 2018-04-04 | 2018-11-23 | 史国民 | A kind of preparation method of contaminated soil remediation material |
| CN108559515A (en) * | 2018-04-05 | 2018-09-21 | 谢永琴 | A kind of iron tailings base weight metallic pollution soil stabilizer and preparation method thereof |
| CN108559515B (en) * | 2018-04-05 | 2021-08-27 | 海峡绿色(福建)建筑科技发展有限公司 | Iron tailing based heavy metal contaminated soil stabilizer and preparation method thereof |
| CN108906877A (en) * | 2018-08-07 | 2018-11-30 | 湖南艾布鲁环保科技股份有限公司 | For repairing the soil activating agent, preparation method and its application of As polluted soil |
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