CN104174645A - Method for remedying heavy metal pollution of soil by using calcium silicate hydrate generated by treating silicon tetrachloride - Google Patents
Method for remedying heavy metal pollution of soil by using calcium silicate hydrate generated by treating silicon tetrachloride Download PDFInfo
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Abstract
The invention discloses a method for remedying the heavy metal pollution of soil by using calcium silicate hydrate generated by treating silicon tetrachloride. The method comprises the following steps: putting silicon tetrachloride into a hydrolytic tank, adding water according to a weight ratio of silicon tetrachloride to the water of 1 to 20, simultaneously an adding nano-titanium dioxide immobilized catalytic piece and catalyzing for 1-3 hours to prepare a mixed solution of silicic acid and hydrochloric acid; adding quick lime and water into a container according to a weight ratio of the quick lime to the water of 1 to 10 to prepare a lime emulsion; mixing the mixed solution of silicic acid and hydrochloric acid with the lime emulsion, reacting, controlling a pH value to 7-9, uniformly stirring, reacting to prepare calcium silicate hydrate precipitation and a calcium chloride solution, and separating the calcium silicate hydrate precipitation from the calcium chloride solution to obtain the calcium silicate hydrate; washing the calcium silicate hydrate for twice by using clear water, adding the clear water and uniformly shaking to obtain a calcium silicate hydrate emulsion; finally diluting the calcium silicate hydrate emulsion by using the water and spraying the diluted calcium silicate hydrate emulsion on the surface of the soil with heavy metals. According to the method for remedying the heavy metal pollution of the soil by using calcium silicate hydrate generated by treating silicon tetrachloride, the heavy metals are absorbed by virtue of the porosity of the calcium silicate hydrate, so that the migration of the heavy metals in the soil is limited; the absorption of the heavy metals in crops is reduced; the pollution is effectively reduced.
Description
Technical field
The present invention relates to soil environment engineering technical field, relate in particular to a kind of method of utilizing afwillite repairing heavy metal in soil that processing silicon chloride obtains to pollute.
Background technology
Heavy metal pollution of soil refers to because mankind's activity joins metal in soil, causes heavy metal in soil apparently higher than primary content the phenomenon that causes eco-environmental quality to worsen.The heavy metal of contaminated soil mainly comprises the significant elements of bio-toxicity such as mercury, cadmium, lead, chromium and metalloid arsenic, and has the elements such as the zinc, copper, nickel of certain toxicity.And these heavy metals are mainly from agricultural chemicals, waste water, mud and atmospheric sedimentation etc., if mercury is mainly from mercury-containing waste water; Cadmium, lead contamination are mainly from smelting discharge and automobile exhaust gas sedimentation; Arsenic is mainly from pesticide, bactericide, rat poison and herbicide.Excessive heavy metal can cause physiological function of plants disorder, trophic disturbance, the element such as cadmium, mercury concentration coefficient in crop grain is higher, even if exceed food hygienic standard, do not affect plant growth, growth and output yet, in addition mercury, arsenic can weaken and suppress nitrated in soil, amonifying bacteria is movable, affects nitrogen supply.Heavy metal contaminants mobility in soil is very little, is difficult for water leaching,, for microbial degradation, does not enter after human body by food chain, and potential hazard is very big.Stone grand style and Tailings Dam are not yet set up in some mines in exploitation, barren rock and mine tailing are arbitrarily stacked, cause the heavy metal that is rich in difficult degradation in mine tailing to enter soil, after ore processing, remaining metal waste residue enters ground water regime with rainwater in addition, causes serious heavy metal pollution of soil; And generally can only there is transformation and the migration of form in these heavy metals in soil, hard degradation.
Be that original position is administered and dystopy is administered to the control measures of heavy metal pollution of soil at present.Dystopy improvement environmental risk is lower, and it is higher that instant effect and system are processed predictability, but cost is high, large to environmental perturbation.Comparatively speaking, original position is administered more economical and practical, simple to operate.According to the difference of administering technique and principle, can be divided into again: engineering control measure and physical chemistry are repaired two large classes.Engineering control measure mainly comprises: soil moved in to improve the original, soil removal and replacement, go to show soil and the deep ploughing measure such as dig; Physical chemistry reparation mainly comprises: solidify, electronic reparation, complexing drip washing, steam lixiviate, redox etc.
Publication number is CN 103302092A, within open day, be that the Chinese patent literature of on 09 18th, 2013 discloses a kind of heavy metal-polluted soil Cr, Cu, Pb, Zn and pollutes quick passivation restorative procedure, by being nine hydrated sodium silicates by composition, be that sodium metasilicate renovation agent spray solution is in soil, its soil moisture content 20-25%, temperature is 15-22 DEG C, and the passivation time is 15 days.
The disclosed heavy metal-polluted soil restorative procedure of this patent documentation, its service condition is quite harsh, must ensure that soil moisture content is at 20-25% simultaneously, and temperature is at 15-22 DEG C, and engineering application is difficult to meet this two conditions simultaneously, implements difficulty large.
Summary of the invention
For solving the problems of the technologies described above, the present invention proposes a kind of method of utilizing afwillite repairing heavy metal in soil that processing silicon chloride obtains to pollute, the present invention is by being sprayed at the soil surface containing heavy metal by the afwillite emulsion after dilution, can evenly infiltrate soil layer, afwillite reacts with heavy metal and generates water-fast salt, sedimentation rapidly, utilize porous Adsorption of Heavy Metals, thereby the migration of restriction heavy metal in soil, reduce the absorption of crops, reduce and pollute, have and implement easily, repair fast feature.
The technical solution used in the present invention is:
A method of utilizing afwillite repairing heavy metal in soil that processing silicon chloride obtains to pollute, is characterized in that: comprise following processing step:
A, silicon tetrachloride is put into hydrolytic tank, in hydrolytic tank, add water, the weight ratio of silicon tetrachloride and water is 1:20, adds the immobilized catalysis sheet of nano titanium oxide to carry out catalytic reaction simultaneously, and catalysis 1-3 hour makes the mixed liquor of silicic acid and hydrochloric acid;
B, in container, add quick lime and water, the weight ratio of quick lime and water is 1:10, makes lime slurry;
C, by the lime slurry hybrid reaction in the silicic acid in steps A and hydrochloric acid mixed solution and step B, pH value is controlled at 7-9, stirs, reaction makes silicate hydrate calcium precipitate and calcium chloride solution;
D, the silicate hydrate calcium precipitate making in step C is separated with calcium chloride solution, obtain afwillite;
E, by the afwillite making in step D clear water washed twice, add clear water and shake up, obtain milky afwillite emulsion;
F, the afwillite emulsion dilute with water making in step e is sprayed to the surface containing heavy metal soil.
The immobilized catalysis sheet of nano titanium oxide in described steps A is made up of ceramic body, glazed layer and nano titanium dioxide film surface layer from top to bottom successively, and glazed layer is attached on ceramic body surface, and nano titanium dioxide film surface layer bakes on glazed layer.
The concentration of the afwillite emulsion making in described step e is 950 grams per liters.
In described step F, afwillite emulsion is diluted with water 5 times, and the afwillite emulsion concentration after dilution is 190 grams per liters, and sprinkling amount is 65 kgs/acre.
The immobilized catalysis sheet of nano titanium oxide of the present invention makes by following method: the glazed layer on a, clean ceramic body surface; B, by weight by 1 part of Ti0
2, 0.02 part of NaHC0
3, 3 parts of H
2o and 0.05 part of CuS0
4.5H
20 weighing is put into container and is fully stirred and make film liquid; C, the film liquid of preparation is evenly coated on the ceramic glaze surface layer of clean decontamination and forms nano titanium dioxide film surface layer; D, the pottery that forms nano titanium dioxide film surface layer is sent in kiln and baked face, firing temperature is 600-900 DEG C, and the firing time is 20-40 minute; E, the cooling immobilized catalysis sheet of nano titanium oxide that obtains of kiln discharge.
Titanium dioxide of the present invention is a kind of white solid or pulverous amphoteric oxide, can be decomposed and extracts or decomposed and obtained by titanium tetrachloride, titanium dioxide stable in properties with acid by rutile.
Beneficial effect of the present invention is mainly manifested in the following aspects:
One, silicon tetrachloride is put into hydrolytic tank, in hydrolytic tank, add water, the weight ratio of silicon tetrachloride and water is 1:20, adds the immobilized catalysis sheet of nano titanium oxide to carry out catalytic reaction simultaneously, and catalysis 1-3 hour makes the mixed liquor of silicic acid and hydrochloric acid; The silicic acid chemistry increased activity making after catalysis;
In container, add quick lime and water, the weight ratio of quick lime and water is 1:10, makes lime slurry, and its chemical equation is CaO+ 2H
2o=Ca (OH)
2; By the lime slurry hybrid reaction in the silicic acid in steps A and hydrochloric acid mixed solution and step B, pH value is controlled at 7-9, stirs, and reaction makes silicate hydrate calcium precipitate and calcium chloride solution; Because hydrochloric acid is strong acid, when reaction, hydrochloric acid and calcium hydroxide preferential reaction generate calcium chloride, silicic acid be weak acid than the acidity of carbonic acid also a little less than, although calcium hydroxide is highly basic but solubility is very low, in water, can not react, and after catalysis, silicic acid just can close calcium silicates with calcium hydroxide aqueous solution water generation reaction under normal conditions; The silicate hydrate calcium precipitate making in step C is separated with calcium chloride solution, obtain afwillite; Calcium chloride is dissolved in water, and afwillite is precipitation, is convenient to separate; By the afwillite making in step D clear water washed twice, add clear water and shake up, obtain milky afwillite emulsion; Silicate hydrate calcium concentration after separation is high, and adding water to be formulated to needs concentration to shake up, can use, find sedimentation a little shaking emulsion; The afwillite emulsion dilute with water making in step e is sprayed to the surface containing heavy metal soil, afwillite particle in afwillite emulsion is trickle, easily infiltrate soil, large with heavy metal in soil ion contact probability, because afwillite particle is the easy Adsorption of Heavy Metal Ions of porous mass, the migration of restriction heavy metal ion is absorbed by plants, in addition, in afwillite particle, there is siloxy and silanol base, can promote heavy metal to generate related salts sedimentation, further reduce the quantity of transportable heavy metal ion in soil; The method forms a complete technical scheme, make afwillite emulsion by series of process step, afwillite emulsion after dilution is sprayed to the soil surface containing heavy metal, can evenly infiltrates soil layer, afwillite reacts with heavy metal and generates water-fast salt, sedimentation rapidly, utilize porous Adsorption of Heavy Metals, thereby the migration of restriction heavy metal in soil reduces the absorption of crops, reduce and pollute, have and implement easily, repair fast feature.
Two, the immobilized catalysis sheet of the nano titanium oxide in steps A is made up of ceramic body, glazed layer and nano titanium dioxide film surface layer from top to bottom successively, glazed layer is attached on ceramic body surface, nano titanium dioxide film surface layer bakes on glazed layer, by preventing the reunion of catalyst in catalytic reaction after titanium dioxide is immobilized, also can prevent the fluid loss that it generates with silicon tetrachloride reaction, be convenient to Reusability, improve catalytic effect.
The concentration of the afwillite emulsion three, making in step e is 950 grams per liters, and afwillite density is little, lighter than water, make the afwillite emulsion of certain concentration, be beneficial to the abundant haptoreaction of afwillite particle and heavy metal ion, generate the rapid sedimentation of salt, and then rehabilitating soil.
Four, in step F, afwillite emulsion is diluted with water to 5 times, afwillite emulsion concentration after dilution is 190 grams per liters, sprinkling amount is 65 kgs/acre, adopt specific extension rate to make near 190 grams per liters of afwillite emulsion concentration, every mu is sprayed 65 kilograms, without controlling soil moisture content, just can make at normal temperatures afwillite uniform particles infiltrate upper soll layer, utilize its porous Adsorption of Heavy Metal Ions, thereby the migration of restriction heavy metal ion in soil, reduce the absorption of crops, reduce and pollute, engineering construction is quite convenient.
Detailed description of the invention
Embodiment 1
A method of utilizing afwillite repairing heavy metal in soil that processing silicon chloride obtains to pollute, comprises following processing step:
A, silicon tetrachloride is put into hydrolytic tank, in hydrolytic tank, add water, the weight ratio of silicon tetrachloride and water is 1:20, adds the immobilized catalysis sheet of nano titanium oxide to carry out catalytic reaction simultaneously, and catalysis 1 hour makes the mixed liquor of silicic acid and hydrochloric acid;
B, in container, add quick lime and water, the weight ratio of quick lime and water is 1:10, makes lime slurry;
C, by the lime slurry hybrid reaction in the silicic acid in steps A and hydrochloric acid mixed solution and step B, pH value is controlled at 7, stirs, reaction makes silicate hydrate calcium precipitate and calcium chloride solution;
D, the silicate hydrate calcium precipitate making in step C is separated with calcium chloride solution, obtain afwillite;
E, by the afwillite making in step D clear water washed twice, add clear water and shake up, obtain milky afwillite emulsion;
F, the afwillite emulsion dilute with water making in step e is sprayed to the surface containing heavy metal soil.
The immobilized catalysis sheet of nano titanium oxide of the present invention makes by following method: the glazed layer on a, clean ceramic body surface; B, by weight by 1 part of Ti0
2, 0.02 part of NaHC0
3, 3 parts of H
2o and 0.05 part of CuS0
4.5H
20 weighing is put into container and is fully stirred and make film liquid; C, the film liquid of preparation is evenly coated on the ceramic glaze surface layer of clean decontamination and forms nano titanium dioxide film surface layer; D, the pottery that forms nano titanium dioxide film surface layer is sent in kiln and baked face, firing temperature is 600-900 DEG C, and the firing time is 20-40 minute; E, the cooling immobilized catalysis sheet of nano titanium oxide that obtains of kiln discharge.
Titanium dioxide of the present invention is a kind of white solid or pulverous amphoteric oxide, can be decomposed and extracts or decomposed and obtained by titanium tetrachloride, titanium dioxide stable in properties with acid by rutile.
The present embodiment is the most basic embodiment, make afwillite emulsion by series of process step, afwillite emulsion after dilution is sprayed to the soil surface containing heavy metal, can evenly infiltrates soil layer, afwillite reacts with heavy metal and generates water-fast salt, sedimentation rapidly, utilize porous Adsorption of Heavy Metals, thereby the migration of restriction heavy metal in soil reduces the absorption of crops, reduce and pollute, have and implement easily, repair fast feature.
Embodiment 2
A method of utilizing afwillite repairing heavy metal in soil that processing silicon chloride obtains to pollute, comprises following processing step:
A, silicon tetrachloride is put into hydrolytic tank, in hydrolytic tank, add water, the weight ratio of silicon tetrachloride and water is 1:20, adds the immobilized catalysis sheet of nano titanium oxide to carry out catalytic reaction simultaneously, and catalysis 2 hours makes the mixed liquor of silicic acid and hydrochloric acid;
B, in container, add quick lime and water, the weight ratio of quick lime and water is 1:10, makes lime slurry;
C, by the lime slurry hybrid reaction in the silicic acid in steps A and hydrochloric acid mixed solution and step B, pH value is controlled at 8, stirs, reaction makes silicate hydrate calcium precipitate and calcium chloride solution;
D, the silicate hydrate calcium precipitate making in step C is separated with calcium chloride solution, obtain afwillite;
E, by the afwillite making in step D clear water washed twice, add clear water and shake up, obtain milky afwillite emulsion;
F, the afwillite emulsion dilute with water making in step e is sprayed to the surface containing heavy metal soil.
The immobilized catalysis sheet of nano titanium oxide in described steps A is made up of ceramic body, glazed layer and nano titanium dioxide film surface layer from top to bottom successively, and glazed layer is attached on ceramic body surface, and nano titanium dioxide film surface layer bakes on glazed layer.
The present embodiment is a preferred embodiments, the immobilized catalysis sheet of nano titanium oxide in steps A is made up of ceramic body, glazed layer and nano titanium dioxide film surface layer from top to bottom successively, glazed layer is attached on ceramic body surface, nano titanium dioxide film surface layer bakes on glazed layer, by preventing the reunion of catalyst in catalytic reaction after titanium dioxide is immobilized, also can prevent the fluid loss that it generates with silicon tetrachloride reaction, be convenient to Reusability, improve catalytic effect.
Embodiment 3
A method of utilizing afwillite repairing heavy metal in soil that processing silicon chloride obtains to pollute, comprises following processing step:
A, silicon tetrachloride is put into hydrolytic tank, in hydrolytic tank, add water, the weight ratio of silicon tetrachloride and water is 1:20, adds the immobilized catalysis sheet of nano titanium oxide to carry out catalytic reaction simultaneously, and catalysis 2.5 hours makes the mixed liquor of silicic acid and hydrochloric acid;
B, in container, add quick lime and water, the weight ratio of quick lime and water is 1:10, makes lime slurry;
C, by the lime slurry hybrid reaction in the silicic acid in steps A and hydrochloric acid mixed solution and step B, pH value is controlled at 8.5, stirs, reaction makes silicate hydrate calcium precipitate and calcium chloride solution;
D, the silicate hydrate calcium precipitate making in step C is separated with calcium chloride solution, obtain afwillite;
E, by the afwillite making in step D clear water washed twice, add clear water and shake up, obtain milky afwillite emulsion;
F, the afwillite emulsion dilute with water making in step e is sprayed to the surface containing heavy metal soil.
The immobilized catalysis sheet of nano titanium oxide in described steps A is made up of ceramic body, glazed layer and nano titanium dioxide film surface layer from top to bottom successively, and glazed layer is attached on ceramic body surface, and nano titanium dioxide film surface layer bakes on glazed layer.
The concentration of the afwillite emulsion making in described step e is 950 grams per liters.
The present embodiment is another preferred embodiments, the concentration of the afwillite emulsion making in step e is 950 grams per liters, afwillite density is little, lighter than water, make the afwillite emulsion of certain concentration, be beneficial to the abundant haptoreaction of afwillite particle and heavy metal ion, generate the rapid sedimentation of salt, and then rehabilitating soil.
Embodiment 4
A method of utilizing afwillite repairing heavy metal in soil that processing silicon chloride obtains to pollute, comprises following processing step:
A, silicon tetrachloride is put into hydrolytic tank, in hydrolytic tank, add water, the weight ratio of silicon tetrachloride and water is 1:20, adds the immobilized catalysis sheet of nano titanium oxide to carry out catalytic reaction simultaneously, and catalysis 3 hours makes the mixed liquor of silicic acid and hydrochloric acid;
B, in container, add quick lime and water, the weight ratio of quick lime and water is 1:10, makes lime slurry;
C, by the lime slurry hybrid reaction in the silicic acid in steps A and hydrochloric acid mixed solution and step B, pH value is controlled at 9, stirs, reaction makes silicate hydrate calcium precipitate and calcium chloride solution;
D, the silicate hydrate calcium precipitate making in step C is separated with calcium chloride solution, obtain afwillite;
E, by the afwillite making in step D clear water washed twice, add clear water and shake up, obtain milky afwillite emulsion;
F, the afwillite emulsion dilute with water making in step e is sprayed to the surface containing heavy metal soil.
The immobilized catalysis sheet of nano titanium oxide in described steps A is made up of ceramic body, glazed layer and nano titanium dioxide film surface layer from top to bottom successively, and glazed layer is attached on ceramic body surface, and nano titanium dioxide film surface layer bakes on glazed layer.
The concentration of the afwillite emulsion making in described step e is 950 grams per liters.
In described step F, afwillite emulsion is diluted with water 5 times, and the afwillite emulsion concentration after dilution is 190 grams per liters, and sprinkling amount is 65 kgs/acre.
The present embodiment is preferred forms, in step F, afwillite emulsion is diluted with water to 5 times, afwillite emulsion concentration after dilution is 190 grams per liters, sprinkling amount is 65 kgs/acre, adopt specific extension rate to make near 190 grams per liters of afwillite emulsion concentration, every mu is sprayed 65 kilograms, without controlling soil moisture content, just can make at normal temperatures afwillite uniform particles infiltrate upper soll layer, utilize its porous Adsorption of Heavy Metal Ions, thereby the migration of restriction heavy metal ion in soil, reduce the absorption of crops, reduce and pollute, engineering construction is quite convenient.
The invention is not restricted to above-described embodiment, according to the description of above-described embodiment, those of ordinary skill in the art also can make some apparent changes to the present invention, but within these changes all should fall into the protection domain of the claims in the present invention.
Claims (4)
1. a method of utilizing afwillite repairing heavy metal in soil that processing silicon chloride obtains to pollute, is characterized in that: comprise following processing step:
A, silicon tetrachloride is put into hydrolytic tank, in hydrolytic tank, add water, the weight ratio of silicon tetrachloride and water is 1:20, adds the immobilized catalysis sheet of nano titanium oxide to carry out catalytic reaction simultaneously, and catalysis 1-3 hour makes the mixed liquor of silicic acid and hydrochloric acid;
B, in container, add quick lime and water, the weight ratio of quick lime and water is 1:10, makes lime slurry;
C, by the lime slurry hybrid reaction in the silicic acid in steps A and hydrochloric acid mixed solution and step B, pH value is controlled at 7-9, stirs, reaction makes silicate hydrate calcium precipitate and calcium chloride solution;
D, the silicate hydrate calcium precipitate making in step C is separated with calcium chloride solution, obtain afwillite;
E, by the afwillite making in step D clear water washed twice, add clear water and shake up, obtain milky afwillite emulsion;
F, the afwillite emulsion dilute with water making in step e is sprayed to the surface containing heavy metal soil.
2. a kind of method of utilizing afwillite repairing heavy metal in soil that processing silicon chloride obtains to pollute according to claim 1, it is characterized in that: the immobilized catalysis sheet of nano titanium oxide in described steps A is made up of ceramic body, glazed layer and nano titanium dioxide film surface layer from top to bottom successively, glazed layer is attached on ceramic body surface, and nano titanium dioxide film surface layer bakes on glazed layer.
3. a kind of method of utilizing afwillite repairing heavy metal in soil that processing silicon chloride obtains to pollute according to claim 1, is characterized in that: the concentration of the afwillite emulsion making in described step e is 950 grams per liters.
4. according to a kind of method of utilizing afwillite repairing heavy metal in soil that processing silicon chloride obtains to pollute described in claim 1 or 3, it is characterized in that: in described step F, afwillite emulsion is diluted with water 5 times, afwillite emulsion concentration after dilution is 190 grams per liters, and sprinkling amount is 65 kgs/acre.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105540594A (en) * | 2016-01-05 | 2016-05-04 | 四川大学 | Comprehensive utilizing method for fluorine-containing silicon dioxide |
| CN114350376A (en) * | 2022-01-21 | 2022-04-15 | 乐山师范学院 | Heavy metal contaminated soil remediation agent and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105540594A (en) * | 2016-01-05 | 2016-05-04 | 四川大学 | Comprehensive utilizing method for fluorine-containing silicon dioxide |
| CN114350376A (en) * | 2022-01-21 | 2022-04-15 | 乐山师范学院 | Heavy metal contaminated soil remediation agent and preparation method and application thereof |
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Application publication date: 20141203 |