CN102174326A - Heavy metal composite passivating agent used for paddy soil and preparation method thereof - Google Patents
Heavy metal composite passivating agent used for paddy soil and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a heavy metal composite passivating agent used for paddy soil and a preparation method thereof. The heavy metal composite passivating agent is prepared from three raw materials, namely meerschaum mineral powder, iron and manganese oxides and quicklime, in proportion by the following steps of: A, preparing the meerschaum mineral powder; B preparing the iron and manganese oxides; and C, uniformly mixing the raw materials prepared in the steps A and B with the quicklime to obtain the composite passivating agent. The heavy metal composite passivating agent has a reasonable formula, the method is easy and simple to operate; and the heavy metal composite passivating agent can reduce 70.5 to 95.0 percent of the content of the effective components of meerschaum with heavy metal activity, the iron and manganese oxides (Fe2O3+MnO2), calcium oxide (CaO) and the like in the soil, and also has multiple functions of passivating soil heavy metals, restoring acidified soil and the like, can reduce the contents of active cadmium and lead in the soil of a polluted paddy field by 39.7 to 53.8 percent and 49.9 to 59.1 percent respectively, lower the contents of the cadmium and the lead in agriculture products by 35.1 to 46.9 percent and 35.3 to 53.1 percent respectively, and simultaneously improve the pH value of the soil by 0.22 and 0.43. The heavy metal composite passivating agent is mainly used for paddy production of extensive heavy metal pollution zones, and can also be used for the productions of corns, vegetables and the like planted in paddy fields.
Description
Technical field
The invention belongs to agricultural environment child care and recovery technique field, what more specifically relate to is a kind of heavy metal composite passivant that is used for paddy soil, also relate to a kind of preparation method who is used for the heavy metal composite passivant of paddy soil simultaneously, mainly be applicable to the Rice Production in vast heavy metal contamination district, also can be used for the production of rice field corn, vegetables etc.
Background technology
Along with the continuous propelling of industrialization and urbanization, China's heavy metal pollution of soil problem more and more is subjected to people's great attention.According to related data, phase at beginning of the eighties in last century China cultivated area 2,670,000 hm only of being subjected to heavy metal contaminations such as cadmium, lead, mercury, arsenic, chromium, nickel
2, just be increased to 6,670,000 hm in the time of 1988
2, surpassed 1,000 ten thousand hm to last century end
2, broken through 2,000 ten thousand hm at present
2, account for 20% of whole cultivated areas.Even more serious is that the heavy metal contamination of China's basic farmland is also quite serious.According to national environmental protection portion in recent years to 300,000 hm
2The sampling monitoring result of basic farmland protection district soil harmful heavy metal has been found 3.6 ten thousand hm
2Heavy metal content in soil exceed standard, exceeding standard rate is up to 12.1%.The pollution of heavy metal-polluted soil has directly caused exceeding standard of agricultural-food heavy metal content.According to existing disclosed documents and materials report, the exceeding standard rate of the suburbs, Hangzhou vegetables cadmium, copper, mercury, zinc is respectively 28%, 15%, 59% and 4%; The exceeding standard rate of Changsha vegetables heavy metal is 50%; The suburbs, Shenyang Chinese cabbage exceeding standard rate plumbous and cadmium is respectively 100% and 58%, and cucumber cadmium, mercury, plumbous exceeding standard rate are respectively 73%, 27% and 18%; The exceeding standard rate of suburbs, Tianjin vegetables cadmium is 40%; The exceeding standard rate of Nanning City's vegetables cadmium and mercury is respectively 92% and 50%; The exceeding standard rate of Baoshan District, Shanghai vegetables lead and cadmium is respectively up to 82% and 54%; The content of Wenzhou City's vegetables cadmium surpasses 1.7 times of national standards, and fruit is 1.6 times; The 9 kinds of vegetables in Chengdu exceeding standard rate plumbous and cadmium is respectively 22% and 29%; Chongqing City's paddy rice cadmium, plumbous exceeding standard rate are 25-50%, and corn lead content exceeding standard rate is that the exceeding standard rate of 22-66%, cadmium and mercury is 11%; Bulk vegetable cadmium, the plumbous exceeding standard rate in domestic Xiang River basin, Hunan have all surpassed 10%, and the exceeding standard rate that the Pearl River Delta beach is enclosed and cultivated farming district rice nickel, lead, chromium, cadmium reaches 48.3%, 28.9%, 12.3% and 2.6% respectively.According to another the measurement result of units such as the tealeaves institute of the Chinese Academy of Agricultural Sciences and the Ministry of Agriculture, the plumbous exceeding standard rate of tealeaves of mainly producing the tea district in recent years is increase trend.The plumbous exceeding standard rate of tealeaves sample was 12.5% in 1999, and calendar year 2001 then rises to 25%.At present, the pollution situation of China's heavy metal-polluted soil has badly influenced the healthy of farmland quality, food safety and even the mankind.In the annual meetings in 2010 that China Council for International Cooperation on Environment and Development's (being called for short " state credit union ") holds; the special numerous common people of prompting of the specialist paper that project team of state credit union " research of Chinese soil Environment Protection Policy " submits to and relevant departments: heavy metal pollution of soil has reached one by the serious key point of paying close attention to of country, need take urgent and secular improvement action immediately.
The restorative procedure research of the physical/chemical of heavy metal pollution of soil etc. is all attached great importance in countries in the world, has successively explored deep ploughing, casting method, soil moved in to improve the original method, thermal desorption method, heat treating process, electrochemical process and chemical irrigation, chemical original position deactivation method etc.In view of aforesaid method all has certain limitation, fail to become the ideal reclamation activities, also not large scale application.As casting method and soil moved in to improve the original method, because of every mu of soil up to 150,000 kg, traffic capacity is huge, cost is too high, and mishandlingly can cause secondary pollution, considers from economy and method angle, can not become the main flow recovery technique.The most frequently used physical/chemical restorative procedure is the in-situ passivation method of heavy metal-polluted soil now, and has begun to take shape the soil heavy metal passivant of eight big classifications such as alkaline species material, organic materials and composite passivant such as clay mineral, phosphate fertilizer class material, iron and manganese oxides, the plain class material of silicon, trace element fertilizer, iron and manganese oxides.Its principle is by changing the existence of heavy metal in soil, making it change stable state into by activated state, thereby reduce its toxic action.
Sepiolite is a kind of fibrous hydrous magnesium silicate mineral, and its standard crystal chemical formula is Mg8 (H
2O)
4[Si
6O
16]
2(OH)
48H
2O, its SiO
2Generally between the 54-60%, in the many scopes at 21-25% of MgO content, hardness is 2-2.5 ° to content, and density is 1-2.2g/cm
3, having performances such as extremely strong absorption and dispersion, its heat impedance, formative nature, anti-salinity etc. are all very good, and the purposes on agricultural is very extensive.The present patent application person is since 2006 bear relevant items such as central rings guarantor special fund, national supporting plan, system has carried out the research of sepiolite to the adsorption-desorption feature of cadmium and influence factor thereof etc., with adsorption-desorption characteristics and the form transformation thereof of interpolation sepiolite to reddish yellow mud, yellow mud field and three kinds of typical rice soil cadmiums of red husky mud, and sepiolite is used for the original position recovery dynatron effect of cadmium pollution rice soil.Result of study shows: (1) sepiolite is a process fast to the absorption of cadmium, and its maximal absorptive capacity can reach 2290mg/kg, and adsorption process is based on physical adsorption and ion-exchange absorption.When pH value of solution＜4, the pH value reduces can obviously reduce the adsorptive capacity of sepiolite to cadmium; PH＞4 o'clock, the pH value is less to the influence of sepiolite adsorptive capacity.Accompany ionic strength (Na
+And NO
3-) increase can suppress the absorption of sepiolite to cadmium.(2) add sepiolite and can effectively strengthen loading capacity and the intensity of rice soil cadmium.When the solution cadmium concentration is identical, adding sepiolite can make reddish yellow mud, yellow mud field and three kinds of rice soil of red husky mud that the adsorptive capacity of cadmium is increased 17%-60%, and making the desorption efficiency of absorption cadmium reduce (being up to 25%), its effect strengthens with the increase of sepiolite addition.(3) the isothermal adsorption process (coefficient of determination R of three kinds of rice soil to cadmium added behind the sepiolite in the match preferably of Freundlich equation
2＞0.95).Under the lower condition of pH value of solution value (pH＜4), the pH value reduces can reduce the adsorptive capacity of three kinds of rice soil to cadmium; When pH value of solution value higher (pH＞4), the pH value changes the adsorptive capacity influence of three kinds of rice soil less.(4) add the effectively activated state cadmium in the passivation rice soil of sepiolite, its effect strengthens with the increase of sepiolite addition, and is subjected to the influence of Soil Moisture bigger.The experiment starting stage (2d), under 45%WHC and 110%WHC (waterflooding) moisture condition, add sepiolite and make reddish yellow mud, yellow mud field and three kinds of rice soil DTPA extractions of red husky mud cadmium content reduce 8%-54% and 7%-59% respectively; Along with the prolongation of incubation time, this effect weakens gradually under the 45%WHC moisture condition, and under the waterflooding condition, it reduces effect and changes little.Under two kinds of moisture conditions, add sepiolite and make that the exchange state cadmium content significantly reduces in three kinds of rice soil (the maximum range of decrease 55%), carbonate combined and iron and manganese oxides combined cadmium content significantly increase (maximum amplification reaches 232% and 329% respectively), and all with the variable quantity maximum under the waterflooding condition.(5) adding sepiolite and can significantly improve pH in soil, reduce its Eh value, is the major reason that causes cadmium metamorphosis in the soil.(6) use the content that sepiolite can significantly reduce cadmium in the validity of cadmium in the cadmium pollution rice soil and the agricultural-food.Field test results shows, uses sepiolite and lime and makes soil pH value improve 0.3-2.0, and the ratio of acid extraction attitude cadmium reduces 3%-15%, the corresponding raising of ratio of reducible attitude cadmium and residual form.The variation of soil cadmium form has effectively suppressed the absorption of crop to cadmium: the paddy rice on the ground content of each several part cadmium significantly reduces, and brown rice has reduced that 28.7-51.7%, rice husk have reduced 25%-60%, straw has reduced 19%-53%.The effect of different passivator is followed successively by sepiolite+iron and manganese oxides＞sepiolite＞iron and manganese oxides, and its effect all strengthens with the increase of consumption.Executing sepiolite and iron and manganese oxides has no significant effect in the intravital regularity of distribution of paddy rice output, biomass and the cadmium of paddy rice.
The essential mineral of soil is formed except that clay mineral, also exist natural mineral such as a certain amount of iron and manganese oxides, toxic heavy metal elements such as cadmium, lead, copper, zinc, chromium, nickel had stronger confinement capabilities, have nature and reduce the toxic function of (gently) soil toxic heavy metal element, but the iron and manganese oxides content in the soil also is not enough to remove fully the toxicity of soil toxic heavy metal element.The result of study of Chlopecka and Adriano (1997) shows, adds ferriferous oxide and can significantly reduce exchange state cadmium, lead content, significantly increases carbonate combined and iron and manganese oxides combined cadmium, lead content, significantly reduces the absorption of crop to cadmium, lead.Santana etc. (2006) find by the adsorption-desorption experimental study, red soil (Fe
2O
3Content 〉=27%) heavy metals such as cadmium is had very strong confinement capabilities, in heavy-metal contaminated soil, can play the effect that reduces heavy metal content and bioavailability of heavy metals in the solution.Discovering of Yi etc. (2006), use red soil and can make that free cadmium ion content significantly reduces in the heavy-metal contaminated soil, and point out after by the ECOSTA model contribution of the heavy metal adsorbate in the soil (organic matter, hydrated state ferriferous oxide, clay etc.) being analyzed, use red soil and strengthened the confinement capabilities of hydrated state ferriferous oxide heavy metal.Brown etc. (2005) find, add red soil and can significantly reduce the soil solution and NH
4NO
3Extract the content of attitude cadmium.The result of study of Chen etc. (2000) shows, adds the content that manganese oxide can reduce EDTA in the soil, HAc and Hal extraction attitude cadmium, reduces the absorption of crop field top to cadmium; Add ferric oxide and also can reduce the content that HAc extracts the attitude cadmium, crop field top is absorbed cadmium also bigger restraining effect, but a little less than its effect all wants than manganese oxide.Discovering of Yuan Shikai's Tomb (2010), ferro manganese composite oxides has stronger confinement capabilities to cadmium ion, lead ion, and its maximal absorptive capacity (25 ℃) is respectively 5880mg/kg and 1640mg/kg.
Summary of the invention
The objective of the invention is to be to provide a kind of heavy metal composite passivant that is used for paddy soil.It is made by a certain percentage by sepiolite, iron and manganese oxides and three kinds of raw materials of unslaked lime, and it reduces the active sepiolite of heavy metal-polluted soil, iron and manganese oxides (Fe
2O
3+ MnO
2) and calcium oxide content of effective such as (CaO) reach 70.5-95.0%, have the function of in-situ passivation heavy metal-polluted soil and reparation acidified soil etc. concurrently, prescription rationally, be applicable to the rice soil that various soil parent materials are grown, be a kind of broad spectrum type, multi-functional environmentfriendly products, it is characterized in that to reduce the active sepiolite of heavy metal-polluted soil, iron and manganese oxides (Fe
2O
3+ MnO
2), calcium oxide content of effective such as (CaO) reaches 70.5-95.0%, make the soil activation attitude cadmium, the lead content that pollute in the rice field descended respectively 39.7-53.8% and 49.9-59.1%, agricultural-food cadmium, lead content descended 35.1-46.9% and 35.3-53.1%, also make soil pH value improve 0.22-0.43 simultaneously, have huge application value in vast heavy metal contamination area.The reduced rate of soil activation attitude cadmium lead content of the present invention and agricultural-food cadmium lead content is calculated by formula " (1-uses soil activation attitude cadmium lead (or the agricultural-food cadmium lead) content that soil activation attitude cadmium lead (or agricultural-food cadmium lead) content ÷ behind the product of the present invention does not use product of the present invention) * 100% ".
Another object of the present invention has been to provide a kind of preparation method who is used for the heavy metal composite passivant of paddy soil, and is simple to operate, easy to implement the method.
In order to realize above-mentioned target and task, the present invention has adopted following technical measures:
A kind of heavy metal composite passivant that is used for paddy soil, it is made by the massfraction of following three kinds of raw materials:
Raw materials quality mark %
Sepiolite breeze 75.0-90.0
Iron and manganese oxides 1.0-24.0
Unslaked lime 1.0-9.0.
A kind of preferred version (scope) that is used for the heavy metal composite passivant of paddy soil of the present invention is:
Raw materials quality mark %
Sepiolite breeze 82.0-88.0
Iron and manganese oxides 4.0-13.5
Unslaked lime 4.5-8.0.
A kind of preferred plan that is used for the heavy metal composite passivant of paddy soil of the present invention is:
Raw materials quality mark %
Sepiolite breeze 83.0
Iron and manganese oxides 12.0
Unslaked lime 5.0.
Described sepiolite breeze, being sieved through ball milling by its raw ore makes, and it is the sizable hydrous magnesium silicate mineral of a kind of specific surface area, and chemical formula is Mg8 (H
2O)
4[Si
6O
16]
2(OH)
48H
2O, its SiO
2Being respectively 54-60% and 21-25% with the content of MgO, having extremely strong adsorptive power and cation exchange property, is the most frequently used a kind of soil heavy metal passivant.
Described iron and manganese oxides, cleaning red soil by 69% and 31% ferric manganese ore raw ore sieve through ball milling and make its Fe
2O
3+ MnO
2Total amount reaches 40.0-55.0%, and heavy metal elements such as cadmium, lead, copper, zinc, chromium, nickel are had stronger confinement capabilities.Wherein: described cleaning red soil is a kind of laterite of being grown by soil parent materials such as pyrrhosiderite or rhombohedral iron ore, its Fe
2O
3, MnO
2Content etc. iron and manganese oxides is many between 25-35%, has nature and reduces the toxic function of (gently) soil toxic heavy metal element, often is used as the solid support material of passivation heavy metal-polluted soil; Described ferric manganese ore, contain abundant iron and manganese oxides, its manganese (in Mn) content is generally 18-25%, iron (in Fe) content is many between 30-40%, its major function in the present invention provides the iron and manganese oxides of more (greatly) quantity, consolidates and strengthen the effect of passivation heavy metal-polluted soil.
Described unslaked lime, it is a kind of strong alkaline substance of producing through operations such as acidolysis, adding reaction of sodium bicarbonate and calcinings by lime carbonate, main component is a calcium oxide, chemical formula is CaO, its major function in the present invention is can improve soil pH value quickly in the short period of time, consolidates and strengthen the effect of passivation heavy metal-polluted soil.
A kind of preparation method who is used for the heavy metal composite passivant of paddy soil the steps include:
A. sepiolite breeze preparation: select the sepiolite raw ore for use, cross the 100-140 mesh sieve through ball milling, standby.Described sepiolite raw ore, its sepiolite content reaches 80-95%, heavy metal cadmium and plumbous content (in Cd, Pb) 5mg/kg, moisture content is (with H
2The O meter)≤1.5%.
B. iron and manganese oxides preparation: select cleaning red soil and two kinds of materials of ferric manganese ore raw ore for use, by cleaning red soil 69%: the mixed of ferric manganese ore raw ore 31% is even, crosses the 100-140 mesh sieve through ball milling, and is standby.Described cleaning red soil, its Fe
2O
3+ MnO
2Sum reaches 25-35%, heavy metal cadmium and plumbous content (in Cd, Pb)≤0.2mg/kg, and moisture content is (with H
2The O meter)≤2.5%; Described ferric manganese ore raw ore, its manganese content (in Mn) is 18-25%, iron level (in Fe) is 30-40%, heavy metal cadmium and plumbous content (in Cd, Pb)≤10mg/kg, moisture content is (with H
2The O meter)≤2.5%.By the iron and manganese oxides of the prepared raw material of present method (with Fe
2O
3+ MnO
2The sum meter) content is 40.0-55.0%.
C. raw material and the unslaked lime with steps A, B preparation mixes in proportion, and is a kind of composite passivant of paddy soil heavy metal.Described unslaked lime, its CaO content reaches 90-99%, heavy metal cadmium and plumbous content (in Cd, Pb) 5mg/kg, moisture content is (with H
2The O meter)≤1.5%.
Product after making, it reduces the active sepiolite of heavy metal-polluted soil, iron and manganese oxides (Fe
2O
3+ MnO
2) and calcium oxide content of effective such as (CaO) reach 70.5-95.0%, wherein: the content of sepiolite is 60.0-85.5%, iron and manganese oxides is (with Fe
2O
3+ MnO
2The sum meter) content is 0.4-13.2%, and the content of calcium oxide (in CaO) is 0.9-8.9%, can be widely used in the geographic Rice Production of vast heavy metal contamination, also can be used for the production of rice field corn, vegetables etc.
The present invention compared with prior art has the following advantages and effect:
A. with directly sepiolite is compared as the prior art of soil heavy metal passivant, the an amount of iron and manganese oxides that heavy metal elements such as cadmium, lead, copper, zinc, chromium, nickel is had strong confinement capabilities that principal character of the present invention is a reasonable disposition, with the unslaked lime of rapid raising soil pH, make and reduce the active sepiolite of heavy metal-polluted soil, iron and manganese oxides (Fe in the product
2O
3+ MnO
2) and calcium oxide content of effective such as (CaO) reach 70.5-95.0%, not only increased the kind of soil heavy metal passivant, and significantly strengthened the ability of product passivation heavy metal-polluted soil.Pilot plant test is promoted the result with demonstration and is shown: use product of the present invention, the reduced rate of soil activation attitude cadmium, lead content is respectively 39.7-53.8% and 49.9-59.1%, use comparing of sepiolite with equivalent, its reduced rate has improved 6.2-11.1 percentage point and 6.7-12.2 percentage point respectively; Cadmium, plumbous reduced rate in the agricultural-food such as paddy rice, corn, vegetables are respectively 35.1-46.9% and 35.3-53.1%, than equivalent use sepiolite improved respectively 4.9-10.9 percentage point with the 10.1-14.3 percentage point.
B. the present invention not only has the function of in-situ passivation heavy metal-polluted soil, and can also improve soil pH value greatly, has the function of repairing acidified soil concurrently, is applicable to the rice soil that various soil parent materials are grown, and is a kind of broad spectrum type, multi-functional environmentfriendly products.Use comparing of sepiolite with equivalent, use product of the present invention, pH in soil has improved 0.22-0.43.
C. raw material sources of the present invention are extensive, simple, the easy row of preparation method, and easy to use, popularizing application prospect is wide.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail, but is not to be limitation of the present invention, all any this areas of doing according to the disclosure of invention be equal to replacement, all belong to protection scope of the present invention.
Embodiment 1:
A kind of heavy metal composite passivant that is used for paddy soil, it is made by the massfraction of following three kinds of raw materials:
Raw materials quality mark %
Sepiolite breeze 83.0
Iron and manganese oxides 12.0
Unslaked lime 5.0.
A kind of preparation method who is used for the heavy metal composite passivant of paddy soil the steps include:
A. select the sepiolite raw ore for use, cross 100 orders through ball milling, or 110 orders, or 120 orders, or 130 orders, 140 mesh sieves, standby.Described sepiolite raw ore, its sepiolite content reaches 80-95%, heavy metal cadmium and plumbous content (in Cd, Pb)≤5mg/kg, moisture content is (with H
2The O meter)≤1.5%.
B. select cleaning red soil and two kinds of materials of ferric manganese ore raw ore for use, by cleaning red soil 69%: the mixed of ferric manganese ore raw ore 31% is even, crosses 100 orders through ball milling, or 110 orders, or 120 orders, or 130 orders, and 140 mesh sieves are standby.Described cleaning red soil, its Fe
2O
3+ MnO
2Sum reaches 25-35%, heavy metal cadmium and plumbous content (in Cd, Pb)≤0.2mg/kg, and moisture content is (with H
2The O meter)≤2.5%.Described ferric manganese ore raw ore, its manganese content (in Mn) is 18-25%, iron level (in Fe) is 30-40%, heavy metal cadmium and plumbous content (in Cd, Pb)≤10mg/kg, moisture content is (with H
2The O meter)≤2.5%.By the iron and manganese oxides of the prepared raw material of present method (with Fe
2O
3+ MnO
2The sum meter) content is 40.0-55.0%.
C. raw material and the unslaked lime with step (A, B) preparation mixes in proportion, and is a kind of composite passivant of paddy soil heavy metal.Described unslaked lime, its CaO content reaches 90-99%, and the content of heavy metal cadmium and lead is in Cd, Pb≤5mg/kg, and moisture content is with H
2O meter≤1.5%.
Product after making, it reduces the active sepiolite of heavy metal-polluted soil, iron and manganese oxides (Fe
2O
3+ MnO
2) and calcium oxide content of effective such as (CaO) reach 75.7-90.4%, wherein: the content of sepiolite is 66.4-78.9%, iron and manganese oxides is (with Fe
2O
3+ MnO
2The sum meter) content is 4.8-6.6%, and the content of calcium oxide (in CaO) is 4.5-5.0%, can be widely used in the geographic Rice Production of vast heavy metal contamination, also can be used for the rice field corn, the production of vegetables etc.
Embodiment 2-example 16:
A kind of heavy metal composite passivant that is used for paddy soil, it is made by the massfraction of following raw material:
Its preparation process is identical with embodiment 1.
Product after making, it reduces the active sepiolite of heavy metal-polluted soil, iron and manganese oxides (Fe
2O
3+ MnO
2) and calcium oxide content of effective scopes such as (CaO) (with sepiolite+Fe
2O
3+ MnO
2+ CaO sum meter) as shown in the table:
| 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 | 16 | |
| Minimum value | 70.5 | 71.2 | 71.8 | 72.5 | 73.1 | 73.8 | 74.4 | 75.1 | 76.4 | 77.0 | 77.7 | 78.3 | 79.2 | 79.9 | 80.5 |
| Maximum value | 85.4 | 86.1 | 86.7 | 87.3 | 87.9 | 88.5 | 89.2 | 89.8 | 91.0 | 91.6 | 92.3 | 92.9 | 93.7 | 94.3 | 95.0 |
Product after making can be widely used in the geographic Rice Production of vast heavy metal contamination, also can be used for the production of rice field corn, vegetables etc.
A kind of pilot plant test that is used for the heavy metal composite passivant of paddy soil is promoted as described below with demonstration:
During the 2009-2010, (soil belongs to cadmium-nickel combined pollution type), (soil belongs to the cadmium pollution type) and Tao Jiahe heavy metal contamination district, Jiahe (soil belongs to lead-cadmium combined pollution type) three ground, 715 ore deposits, Anhua farming district have carried out the field pilot plant test, and have carried out (30hm on a fairly large scale in 2010 in Ma Jiahe heavy metal contamination district, Zhuzhou
2/ district) demonstration is promoted.Above-mentioned three ground all belong to " the agriculture safe utilization technical research demonstration area of heavy metals exceeding standard soil " that " heavy metal pollution of soil is promptly administered comprehensive demonstration area " that national environmental protection portion and Hunan Province government hang out one's shingle supervise and direct and unit consolidations such as Hunan Province Department of Agriculture and the present patent application people-The Institute of Subtropical Agriculture, The Chinese Academy of Sciences are set up.
A. test is handled: be provided with and do not execute any passivator (being CK1), every mu and use 75.0kg sepiolite (being CK2) and every mu and use three processing of 75.0kg product of the present invention (being FM), and three repetitions, the sub-district area of rice cultivation is 55.0m
2(the sub-district area of 5.5m * 10.0m), maize planting and vegetables is 15.0m
2(3.0m * 5.0m), the ridge (buried depth 0.3m) that wraps up with the wide thick plastic film of 0.2m separates.Fertilization Level and other field management measures, it is in full accord that each is handled.
B. for studying the article kind: various places are all unified select for use Y two excellent 19 (semilate rice), middle list 808 (corn) and April slow Plantula Brassicae chinensis crop varieties such as (vegetables).
C. use usage: according to the test design scheme, the passivator application in two dressings of rice cultivation, corn, the then disposable of planting vegetable used with base manure.Paddy rice: using for the first time is at the ear differentiation initial stage, and its consumption is 30% of a total amount; For the second time be to use behind neat fringe, its consumption is 70% of a total amount at once.Corn: using for the first time is that its consumption is 25% of a total amount fringe initial stage (being panicle primordium dif ferentiation stage); Use for the second time is that its consumption is 75% of a total amount in the flower grain phase.
D. see (inspection) survey project: soil activation attitude cadmium, lead content, the cadmium in the agricultural-food, lead content, soil pH value.
E. main result: the result shows (1-7 sees attached list), use product of the present invention, make the soil activation attitude cadmium, the lead content that pollute in the rice field descended respectively 39.7-53.8% and 49.9-59.1%, also make simultaneously cadmium, lead content in the agricultural-food such as paddy rice, corn, vegetables descended respectively 35.1-46.9% and 35.3-53.1%, pH in soil has improved 0.22-0.43.
Subordinate list-1 product is used on paddy rice falls the cadmium effect
Annotate:, be the reduced rate of FM processing and the reduced rate difference that CK2 handles, down together than the variable value of CK2.
Subordinate list-2 product is used on vegetables falls the cadmium effect
Subordinate list-3 product is used on corn falls the cadmium effect
Subordinate list-4 product is used on paddy rice falls plumbous effect
Subordinate list-5 product is used on vegetables falls plumbous effect
Subordinate list-6 product is used on corn falls plumbous effect
Subordinate list-7 product increases the effect of soil pH value
Claims (10)
1. heavy metal composite passivant that is used for paddy soil, it is made by the massfraction of following raw material:
Raw materials quality mark %
Sepiolite breeze 75.0-90.0
Iron and manganese oxides 1.0-24.0
Unslaked lime 1.0-9.0
Described sepiolite breeze, being sieved through ball milling by raw ore makes, and it is the sizable hydrous magnesium silicate mineral of a kind of specific surface area, and chemical formula is Mg8 (H
2O)
4[Si
6O
16]
2(OH)
48H
2O, its SiO
2Be respectively 54-60% and 21-25% with MgO content;
Described iron and manganese oxides, cleaning red soil by 69% and 31% ferric manganese ore raw ore sieve through ball milling and make its Fe
2O
3+ MnO
2Total amount reaches 40.0-55.0%, and cadmium, lead, copper, zinc, chromium, nickel heavy metal element are had stronger confinement capabilities;
Described unslaked lime is a kind of strong alkaline substance of being produced through acidolysis, adding reaction of sodium bicarbonate and calcination process by lime carbonate, and its composition is a calcium oxide, and chemical formula is CaO.
2. a kind of heavy metal composite passivant that is used for paddy soil according to claim 1 is characterized in that:
Raw materials quality mark %
Sepiolite breeze 82.0-88.0
Iron and manganese oxides 4.0-13.5
Unslaked lime 4.5-8.0.
3. a kind of heavy metal composite passivant that is used for paddy soil according to claim 1 is characterized in that:
Raw materials quality mark %
Sepiolite breeze 83.0
Iron and manganese oxides 12.0
Unslaked lime 5.0.
4. a kind of heavy metal composite passivant that is used for paddy soil according to claim 1 is characterized in that:
Raw materials quality mark %
Sepiolite breeze 75.0
Iron and manganese oxides 24.0
Unslaked lime 1.0.
5. a kind of heavy metal composite passivant that is used for paddy soil according to claim 1 is characterized in that:
Raw materials quality mark %
Sepiolite breeze 77.0
Iron and manganese oxides 21.0
Unslaked lime 2.0.
6. a kind of heavy metal composite passivant that is used for paddy soil according to claim 1 is characterized in that:
Raw materials quality mark %
Sepiolite breeze 80.0
Iron and manganese oxides 16.5
Unslaked lime 3.5.
7. a kind of heavy metal composite passivant that is used for paddy soil according to claim 1 is characterized in that:
Raw materials quality mark %
Sepiolite breeze 85.0
Iron and manganese oxides 9.0
Unslaked lime 6.0.
8. a kind of heavy metal composite passivant that is used for paddy soil according to claim 1 is characterized in that:
Raw materials quality mark %
Sepiolite breeze 87.0
Iron and manganese oxides 6.0
Unslaked lime 7.0.
9. a kind of heavy metal composite passivant that is used for paddy soil according to claim 1 is characterized in that:
Raw materials quality mark %
Sepiolite breeze 90.0
Iron and manganese oxides 1.0
Unslaked lime 9.0.
10. the described a kind of preparation method who is used for the heavy metal composite passivant of paddy soil of claim 1 the steps include:
A. sepiolite breeze preparation: it is standby to select for use the sepiolite raw ore to cross the 100-140 mesh sieve through ball milling; Described sepiolite raw ore, its sepiolite content reaches 80-95%, and the content of heavy metal cadmium and lead is in Cd, Pb≤5mg/kg, and moisture content is with H
2O meter≤1.5%;
B. iron and manganese oxides preparation: will clean red soil and ferric manganese ore raw ore by cleaning red soil 69%: the mixed of ferric manganese ore raw ore 31% is even, and it is standby to cross the 100-140 mesh sieve through ball milling; Described cleaning red soil, its Fe
2O
3+ MnO
2Sum reaches 25-35%, and the content of heavy metal cadmium and lead is in Cd, Pb≤0.2mg/kg, and moisture content is with H
2O meter≤2.5%; Described ferric manganese ore raw ore, its manganese content is counted 18-25% with Mn, and iron level is counted 30-40% with Fe, and the content of heavy metal cadmium and lead is in Cd, Pb≤10mg/kg, and moisture content is with H
2O meter≤2.5%;
C. raw material and the unslaked lime with step (A, B) preparation mixes in proportion, and is a kind of composite passivant of paddy soil heavy metal; Described unslaked lime, its CaO content reaches 90-99%, and the content of heavy metal cadmium and lead is in Cd, Pb≤5mg/kg, and moisture content is with H
2O meter≤1.5%.
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