CN105838381A - Soil improver and method for improving soil - Google Patents

Abstract

The invention relates to a soil improver and a method for improving soil. The soil improver comprises mineral powder A, improving powder B, improving powder C and an improving solvent, wherein the mineral powder A is selected from one or more of sulfide mineral powder, oxide mineral powder and clay mineral powder; the improving powder B is selected from one or more of bentonite, a persulfate compound and kaolin; the improving powder C is selected from one or more of red mud, a DTC-chelating agent and iron and manganese oxide powder; the improving solvent is selected from one or more of humic acid, an organic solvent and reactive colloid. According to the soil improving agent, ionic heavy metals in the soil are permanently immobilized in newly formed soil minerals through adjustment of the pH value of soil, chemical immobilization action of environment mineral material dissolution products and heavy metal ions and interaction of the environment mineral material dissolution products and soil microorganisms, so that absorption of crops on the heavy metal ions is inhibited, and the purpose of reducing the content of heavy metals of the crops can be achieved.

Description

A kind of soil conditioner and the method for improvement soil

Technical field

The invention belongs to technical field of land improvement, be specifically related to a kind of soil conditioner and improvement The method of soil, relates more specifically to a kind of soil administering heavy-metal contaminated soil based on mineral method Soil improver and method.

Background technology

The most domestic heavy metal pollution of soil problem becomes after atmospheric pollution, water pollute Causing the great environmental problem that society's highest attention, urgent need solve, wherein soil pollution is serious Area is especially relatively broad with heavy metal contaminants such as chromium, lead, cadmiums, and area, farmland especially with Cadmium pollution is the most serious.

Existing improvement heavy metal-polluted soil minerals method substantially can be divided into: soil moved in improve the original method, soil removal and replacement Method, the bioid skills such as method, Electroremediation method, elution method, biological restoration of digging of deep ploughing Art.But, what method therein was all difficult to avoid that also exist input cost is too high and easily makes The problem becoming secondary pollution, does not have feasibility.

Domestic oryctologist Lu Anhuai professor and team are devoted to utilize at natural minerals always The research of reason environmental contaminants new method, excavates inorganic minerals natural self-purification, this It it is the 4th class method for governing pollution--ore deposit after Physical and chemical method especially bioanalysis Thing method.The method is concentrated and is solved two most basic problems: 1) selected administer soil weight The mineral of metallic pollution are the by-product of mining production, mine tailings or waste minerals, greatly Save greatly treatment cost；2) mineral material is had unique physics, chemical attribute are determined Determine the reaction of its heavy metal mineral, absorbed and fix and will not bring secondary pollution.

Mineral material is of a great variety, rich reserves, and some kind has certain purification function, Mineral material has the effect of uniqueness, natural ore at Heavy Metal Pollution Control and environment remediation field The surface of thing is the most coarse, and specific surface area is relatively big, and surface free energy is higher, passes through Mechanical Crushing Or chemical treatment can reduce the particle diameter of mineral, and many stratiform, caged mineral are under the same volume Easily reach high-specific surface area, be conducive to being removed in soil and water body by surface adsorption effect Harmful substance；Mineral material has a pore passage structure, clay mineral, zeolite, cryptomelane, soft Manganese ore, apatite, tourmaline, serpentine, Vermiculitum, feldspathoid etc. are all to have duct The mineral of structure, internal surface area is considerable；Natural minerals has stronger surface activity Owing to mineral surfaces lattice plane is blocked suddenly, easily produce the polarity table of charge density excess Face, polar surfaces easily with the molecule in the medium such as empty gas and water or ionic reaction, formed stable Isolated surface, therefore, be modified changing mineral to the employing with certain purification function Character, beneficially soil remediation, the modification to mineral material mainly includes following aspects: 1) surface area of mineral material is modified；2) pore passage structure is modified；3) surface-active-modified.

Summary of the invention

It is an object of the invention to provide a kind of for administering heavy metal pollution of soil based on mineral method Soil conditioner and soil improvement method, the soil conditioner heavy metal using the present invention is dirty Dye soil is administered, it is possible to significantly reduce content of beary metal, respond well.

To achieve these goals, one of technical scheme is: a kind of soil conditioner, Including mineral dust A, improvement powder B, improvement powder C, improvement solvent, wherein,

Wherein, described mineral dust A is selected from sulfide mineral powder, oxide mineral powder, glues One or more in soil mineral dust；

Described improvement powder B is selected from bentonite, persulfate compound, Kaolin Plant or multiple；

Described improvement powder C is selected from red mud, DTC-chelating agen, iron and manganese oxides mineral dust In one or more；

Described improvement solvent one in humic acid, organic solvent, the response type colloid or Multiple.

Wherein, in described oxide mineral powder chosen from Fe, manganese, aluminum oxide mineral dust One or more.

Described persulfate compound is ferrous sulfate heptahydrate with sodium peroxydisulfate according to 1:1 weight Compound than mixing and obtain.

Described response type colloid is Fe (OH)₃Colloid, Al (OH)₃In colloid, siliceous colloid One or more, react the most commercially available acquisition of colloid, or use this area routine techniques means Prepare, such as Fe (OH)₃Colloid can be by saturated FeCl₃Solution adds the side of boiling water Method prepares；Al(OH)₃The method that colloid can be reacted by aluminum chloride and ammonia prepares；Silicic acid glue Body can be prepared with mixed in hydrochloric acid by sodium silicate solution.

Described organic solvent is one or more in polycarboxylic acids mother solution, sodium lauryl sulphate.

Wherein, the particle diameter of mineral dust A is 20-50 mesh (preferably 30 mesh)；Improvement powder B's Particle diameter is 70-100 (preferably 90 mesh)；The particle diameter of improvement powder C is 70-100 mesh (preferably 90 Mesh).

Described mineral dust A is by the by-product of mining production, mill tailings or waste gas mineral powder Obtaining after broken, the composition in this, as soil conditioner can be greatly saved soil remediation cost； Mineral dust A is modified processing to change by the present invention by improvement solvent, improvement powder B, C The character of kind mineral material, increases mineral material surface activity, improves its connecing with reaction medium Touch surface area, be more conducive to formation and protonation reaction or the surface of surface ionizing reaction can occur Position, thus with other inorganic ions generation complexation reaction or with organic complex ion generation complex reaction； The ion reaction of mineral surfaces can form proton charge, and complexation reaction can produce surface coordination electricity Lotus, the inequitable exchange of some mineral framing structure Atom also can produce has ion exchange merit The permanent electric charge of energy, these electric charges all can make mineral surfaces charged；Saline minerals and sulfide mineral Surface also has alkali, and they can dissociate or be polymerized in a solvent.There is the hydroxyl at mineral surfaces Base, charge all can cause the character of surface phase to be different from inside, make mineral have higher Surface activity.After having reacted, the equal green non-pollution of organic solvent of employing, the environment of mineral Attribute can be formed new resistant mineral phase, thus reach steady by stable for heavy metal inside mineral Determine the purpose of curing heavy metal, prevent its Transport And Transformation, except soil of effectively degrading, especially It is content of beary metal in farmland, also can absorb and the element of available to plant in Enriching soil, fall Low applying quantity of chemical fertilizer.

Preferably, by weight, described mineral dust A by 25-30 part sulfide mineral powder, 10-30 part iron and manganese oxides mineral dust forms；

It is further preferred that described mineral dust A is by 30 parts of sulphide ore powder, 10 or 30 parts of ferrum Manganites film powder constituent.

Preferably, by weight, described improvement powder B is by 10-15 part bentonite, 2-5 Part persulfate compound composition；

It is further preferred that described improvement powder B is by 10 parts of bentonite, 2 parts of persulfates Compound forms；Or, by 15 parts of bentonite, 5 parts of persulfate compound compositions.

Preferably, described improvement powder C is red mud powder, or by 8-12 part red mud and 1-3 Part DTC-chelating agen composition；

It is further preferred that described improvement powder C is by 10 parts of red muds, 2 parts of DTC-chelating agen Composition.

Preferably, described improvement solvent is by 1-3 part humic acid and 1-3 part organic solvent or reaction Type colloid forms；

It is further preferred that described improvement solvent is by 2 parts of humic acid and 2 parts of polycarboxylic acids mother solution groups Become；Or, it is made up of 2 parts of humic acid and 2 parts of siliceous colloids.

Most preferably, the soil conditioner of the present invention includes the ore deposit that weight ratio is 15:5:5:1 Thing powders A, improvement powder B, improvement powder C, improvement solvent；Wherein, by weight, Mineral dust A is by 30 parts of sulphide ore powder, 30 parts of iron and manganese oxides mineral dust compositions； Improvement powder B is made up of 15 parts of bentonite, 5 parts of persulfate compounds；Improvement powder C It is 20 parts of red mud powder；Improvement solvent is by 2 parts of humic acid and 2 parts of polycarboxylic acids mother solutions；

Or, including the mineral dust A that weight ratio is 10:3:3:1, improvement powder B, Improvement powder C, improvement solvent；Wherein, by weight, mineral dust A is by 30 parts of sulfurations Breeze end, 10 parts of iron and manganese oxides mineral dust compositions；Powder B is by 10 parts of swellings in improvement Soil, 2 parts of persulfate compound compositions；Improvement powder C be 10 parts of red mud powder, 2 parts DTC chelating agen forms；Improvement solvent is made up of 2 parts of humic acid and 2 parts of siliceous colloids.

Use above-mentioned modifying agent that the soil containing heavy metal is administered, it is possible to effectively to reduce a huge sum of money Belonging to content, regulation effect is notable.

The two of technical scheme are: a huge sum of money administered by any one soil conditioner above-mentioned Belong to the application in contaminated soil.

Preferably, soil conditioner of the present invention can effectively reduce Cadmium in Soil, chromium, Arsenic, lead, hydrargyrum, copper, zinc, beryllium, barium content of beary metal.

Preferably, soil conditioner of the present invention is to the field crop such as Oryza sativa L., Semen Tritici aestivi and melon The heavy metal pollution of soil of the various nonirrigated farmlands industrial crops such as fruit vegetable, Folium Camelliae sinensis, Semen Maydis has good Regulation effect.

The three of technical scheme are: utilize the soil conditioner described in any of the above-described item The method of improvement soil, particularly as follows: dilute with water mineral dust A and the mixing of improvement solvent Thing, imposes on diluent in soil；The most successively improvement powder B, improvement powder C are executed In soil；

Or, directly impose in soil after four kinds of component mixing；

Preferably, water with the weight ratio of described mineral dust A and the mixture of improvement solvent is (90-110): 1 (preferably 100:1).

Preferably, improvement powder B is 0-1h with the administration interval of diluent；Improvement powder C It is 1-2h with the administration interval of diluent.

Preferably, the consumption of described soil conditioner is 180-220kg/ mu, preferably 200kg/ Mu.

The present invention mainly by regulation soil pH value and environment mineral material lysate with The chemical fixation of heavy metal ion, and with the reciprocal action of soil microorganism, by soil Earth intermediate ion state heavy metal is permanent to be fixed in the soil mineral being newly formed, and suppresses crop The absorption of heavy metal ion, thus reduce the purpose of crop heavy metal content.Ore deposit Thing material is mainly: sulfide mineral, oxide mineral；Modifying agent is by red mud, DTC-chelating Agent, ferrimanganic aluminum oxide mineral etc. form, mainly by microorganism liquid and other powder reagent Complexing, sequestering, make heavy metal ion be chelated and complexation fixed, reduce heavy metal The biological effectiveness of ion, is reduced the absorbtivity of plant, then is made by the absorption of powder reagent By physics chemical action such as, ion exchange, oxidoreductions, the heavy metal in stable soil, Improvement ecological environment of soil, recovers soil vitality.

The raw material that the present invention relates to and reagent are common commercially available prod.

On the basis of meeting common sense in the field, above-mentioned each optimum condition, can be mutually combined, Obtain each preferred embodiment of the present invention.

Accompanying drawing explanation

Fig. 1 is improvement solvent schematic diagram；

Fig. 2 is mineral dust A schematic diagram；

Fig. 3 is improvement powder B schematic diagram；

Fig. 4 is improvement powder C schematic diagram；

Fig. 5 is embodiment 2 agricultural land Heavy Metal Pollution Control scene photo.

Detailed description of the invention

Following example are used for illustrating the present invention, but are not limited to the scope of the present invention.

Embodiment 1

A kind of soil conditioner, including the mineral dust A that weight ratio is 15:5:5:1, changes Good powder B, improvement powder C, improvement solvent, wherein,

The particle diameter of described mineral dust A is 30 mesh, by the sulphide ore of 30 parts of weight portions, 30 The Fe-Mn oxidation mineral dust of part weight portion mixes；

The particle diameter of described improvement powder B is 90 mesh, by the bentonite of 15 parts of weight portions, 5 The persulfate compound of part weight portion mixes；

The particle diameter of described improvement powder C is 90 mesh, by the red mud powder of 20 weight portions；

Described improvement solvent is mixed by the humic acids of 2 parts of weight portions and the organic solvent of 2 parts of weight portions Conjunction forms.

Described organic solvent is polycarboxylic acids mother solution.

Embodiment 2

A kind of soil conditioner, including the mineral dust A that weight ratio is 10:3:3:1, Improvement powder B, improvement powder C, improvement solvent, wherein,

The particle diameter of described mineral dust A is 30 mesh, by the sulphide ore of 30 weight portions, 10 weights The iron and manganese oxides mineral dust of amount part mixes；

The particle diameter of described improvement powder B is 90 mesh, by the bentonite of 10 weight portions, 2 weights The persulfate compound powder of amount part mixes；

The particle diameter of described improvement powder C is 90 mesh, by the red mud of 10 weight portions, 2 weight The DTC-chelating agen powder of part mixes；

The described improvement solvent humic acids by 2 parts of weight portions and the response type glue of 2 parts of weight portions Body mixes.

Wherein, described sulfate compound is that ferrous sulfate heptahydrate compounds with sodium peroxydisulfate 1:1, Described response type colloid is siliceous colloid.

Experimental example 1 Hunan mining soil pollution control case

1, being administered mining area, Hunan by the soil of heavy metal pollution, after testing, mining area is subject to The situation of contaminated soil is as shown in table 1 below:

Table 1: mining area, Hunan is by heavy-metal contaminated soil testing result

pH	Moisture content	Organic	CEC	Quality
					5.5	4%	1.82%	20mmol/100g	Opaque soil

2, use following flow process that above-mentioned soil is administered:

1st step: take improvement reagent by the weight ratio of 1:15 and mix homogeneously with mineral dust A, By the dilution proportion of mixture Yu water 1:100, dilution is uniformly sprayed at and has been mined pine In the opaque soil dissipated；

2nd step: after the 1st step within 1h, takes the improvement reagent B of improvement 5 times of weight of reagent Uniformly apply in farmland or nonirrigated farmland with base manure；

3rd step: after the 1st step within 1-2h, takes the improvement reagent of improvement 5 times of weight of reagent C uniformly applies in contaminated land with topdressing.

Wherein, this test example uses the soil conditioner described in embodiment 1.

3, after administering, heavy metal in soil content is as shown in table 2, from table 2 it can be seen that After the soil conditioner of the employing present invention is to soil treatment, soil root system meets " GB 18598-2001 hazard waste landfill Environmental capacity standard " requirement.

Table 2: heavy metal in soil content before and after process

Agricultural land, Kelan County, city, experimental example 2 Xinzhou Shanxi Heavy Metal Pollution Control

Adopt and with the following method this ground soil administered:

1st step: basal dressing the previous day, takes improvement reagent and mineral powder by the weight ratio of 1:10 End A mix homogeneously, by the dilution proportion of mixture Yu water 1:100, uniformly sprays dilution It is sprinkled upon in farmland；

2nd step: basal dressing same day, takes the improvement reagent B of improvement 3 times of weight of reagent with base Fertilizer the most uniformly applies in farmland；

3rd step: when second time is topdressed (interval basal dressing 3-4h), take improvement reagent 3 times The improvement reagent C of weight uniformly applies in farmland with topdressing.

Wherein, this test example uses the soil conditioner described in embodiment 2.

Through above-mentioned improvement, before and after improvement, heavy metal in soil content is shown in Table 3.

Table 3: administer forward and backward heavy metal in soil content

Experimental example 3: middle mountain refuse-burning plant fly-ash heavy metal is administered

Incineration of refuse flyash is because rich in the heavy metal of high concentration and two English, causing two to environment Secondary pollution, the dangerous solid waste being well recognized as, it is necessary to it is taken appropriate measures and is disposed. The sample of power plant, centering mountain difference carries out using analyzes detection, and result is as shown in table 4 below:

Table 4: content of beary metal in the refuse-burning plant flying dust of mountain in before administering

Sequence number	Project	Sample 1	Sample 2	Sample 3	Sample 4	Sample 5
							1	Ag	<0.005	<0.005	<0.005	<0.005	<0.005
2	Cu	125.05	3.54	14.02	100.673	34.8
							3	Zn	209.6	114.8	202.2	2.431	222.7
4	Pb	21.08	4.69	37.36	11.22	35.02
							5	Cd	7.003	10.907	21.003	7.647	18.878
6	Be	0.099	0.095	0.104	0.159	0.076
							7	Ba	12.8	7.2	6.3	1.5	8.9
8	Ni	1.686	1.179	1.196	0.869	2.171
							9	As (total arsenic)	<0.3	<0.3	<0.3	<0.3	<0.3
10	Se (total selenium)	<0.005	<0.005	<0.005	<0.005	<0.005
							11	Cr (total chromium)	<4.5	<4.5	<4.5	<4.5	<4.5
12	Cr (Cr VI)	<1.5	<1.5	<1.5	<1.5	<1.5

The modifying agent using the embodiment of the present invention 1 uses following steps to administer it:

1st step: take improvement reagent with mineral dust A by 1:15 weight ratio mix and blend, Seal standby after diluting by the ratios with water of 1:100.

2nd step: collect flying dust and focus in reaction tank, by standby for first step modifying agent After pouring reaction tank stirring 1h into, take required powder reagent B and add reaction tank, weight ratio B: A=3:1, stirs 1h.

3rd step: after second step within 1h, takes powder reagent C and adds reaction tank, weight ratio C:B=1:1, stirs 1h.After administering, in flying dust, content of beary metal is as shown in table 5:

Table 5: content of beary metal in flying dust after improvement

Middle mountain garbage incinerating power plant is an enterprise specializing in house refuse generating, and it flies Ash has multiple content of beary metal such as nickel, cadmium, lead exceed standard phenomenon, use Japan, Argentina Processing Deng chelating agen, not only flying dust processing cost is higher, and process after some heavy metal still The most up to standard, use the present invention modifying agent process after, not only use cost be substantially reduced and Original heavy metal that exceeds standard drops to extremely low value.

Although, used general explanation, detailed description of the invention and test, to this Bright make detailed description, but on the basis of the present invention, it can have been made some modifications or improvements, This will be apparent to those skilled in the art.Therefore, without departing from present invention spirit On the basis of these modifications or improvements, belong to the scope of protection of present invention.

Claims (10)

1. a soil conditioner, it is characterised in that: include that weight ratio is (10-15): (3-5): (3-5): the mineral dust A of 1, improvement powder B, improvement powder C, improvement solvent；

Wherein, described mineral dust A is selected from sulfide mineral powder, oxide mineral powder, glues One or more in soil mineral dust；

Described improvement powder B is selected from bentonite, persulfate compound, Kaolin Plant or multiple；

Described improvement powder C is selected from red mud, DTC-chelating agen, iron and manganese oxides mineral dust In one or more；

Described improvement solvent one in humic acid, organic solvent, the response type colloid or Multiple.

Soil conditioner the most according to claim 1, it is characterised in that: described oxidation One or more in thing mineral dust chosen from Fe, manganese, aluminum oxide mineral dust；And/or,

Described organic solvent one or two in polycarboxylic acids mother solution or 100,000 alkyl sulfates Kind；And/or,

Described response type colloid is selected from Fe (OH)₃Colloid, Al (OH)₃In colloid, siliceous colloid One or more.

Soil conditioner the most according to claim 1 and 2, it is characterised in that: by weight Part meter, described mineral dust A is by 25-30 part sulfide mineral powder, 10-30 part iron and manganese oxides Mineral dust forms；

Preferably, described mineral dust A is by 30 parts of sulphide ore powder, 10 or 30 parts of Fe-Mn oxidations Thing mineral dust forms.

4. according to the soil conditioner described in any one of claim 1-3, it is characterised in that: By weight, described improvement powder B is by 10-15 part bentonite, and 2-5 part persulfate is multiple Join thing composition；

Preferably, described improvement powder B is by 10 parts of bentonite, 2 parts of persulfate compounds Composition；Or, by 15 parts of bentonite, 5 parts of persulfate compound compositions.

5. according to the soil conditioner described in any one of claim 1-4, it is characterised in that: By weight, described improvement powder C is red mud powder, or by 8-12 part red mud and 1-3 Part DTC-chelating agen composition；

Preferably, described improvement powder C is by 10 parts of red muds, 2 parts of DTC-chelating agen compositions.

6. according to the soil conditioner described in any one of claim 1-5, it is characterised in that: By weight, described improvement solvent is by 1-3 part humic acid and 1-3 part organic solvent or reaction Type colloid forms；

Preferably, described improvement solvent is made up of 2 parts of humic acid and 2 parts of polycarboxylic acids mother solutions；Or Person, is made up of 2 parts of humic acid and 2 parts of siliceous colloids.

7. according to the soil conditioner described in any one of claim 1-6, it is characterised in that: Including the mineral dust A that weight ratio is 15:5:5:1, improvement powder B, improvement powder C, Improvement solvent；Wherein, by weight, mineral dust A by 30 parts of sulphide ore powder, 30 Part iron and manganese oxides mineral dust composition；Powder B is by 15 parts of bentonite, 5 parts of over cures in improvement Hydrochlorate compound forms；Improvement powder C is 20 parts of red mud powder；Improvement solvent is by 2 parts of corruption Grow acid and 2 parts of polycarboxylic acids mother solutions；

Or, including the mineral dust A that weight ratio is 10:3:3:1, improvement powder B, Improvement powder C, improvement solvent；Wherein, by weight, mineral dust A is by 30 parts of sulfurations Breeze end, 10 parts of iron and manganese oxides mineral dust compositions；Powder B is by 10 parts of swellings in improvement Soil, 2 parts of persulfate compound compositions；Improvement powder C be 10 parts of red mud powder, 2 parts DTC chelating agen forms；Improvement solvent is made up of 2 parts of humic acid and 2 parts of siliceous colloids.

8. heavy metal polluted soil administered by the soil conditioner described in any one of claim 1-7 Application in earth, it is preferable that described heavy metal include cadmium, chromium, arsenic, lead, hydrargyrum, copper, zinc, One or more in beryllium, barium.

9. utilize the method that soil improved by the soil conditioner described in any one of claim 1-6, It is characterized in that: dilute with water mineral dust A and the mixture of improvement solvent, by diluent Impose in soil；The most successively improvement powder B, improvement powder C are imposed in soil；Its In, water is (90-110) with the weight ratio of described mineral dust A and the mixture of improvement solvent: 1；

Or, directly impose in soil after four kinds of component mixing；

Preferably, improvement powder B is 0-1h with the administration interval of diluent；Improvement powder C It is 1-2h with the administration interval of diluent.

Method the most according to claim 9, it is characterised in that: described soil conditioner Consumption be 180-220kg/ mu, preferably 200kg/ mu.