CN111069267A - Alkali-chelate modified palygorskite-based heavy metal passivation material and preparation method thereof - Google Patents
Alkali-chelate modified palygorskite-based heavy metal passivation material and preparation method thereof Download PDFInfo
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- CN111069267A CN111069267A CN201911365428.5A CN201911365428A CN111069267A CN 111069267 A CN111069267 A CN 111069267A CN 201911365428 A CN201911365428 A CN 201911365428A CN 111069267 A CN111069267 A CN 111069267A
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- palygorskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/06—Calcium compounds, e.g. lime
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
Abstract
The invention discloses an alkali chelate modified palygorskite-based heavy metal passivation material and a preparation method thereof, and is characterized by comprising the following steps: the heavy metal passivation material comprises the following components in parts by weight: 60-80 parts of palygorskite and 20-40 parts of quicklime; firstly, palygorskite is prepared into 160-sand 200-mesh powder after being crushed, crushed and ground; weighing and mixing the powdery palygorskite and the quicklime according to the weight part ratio, adding water for mixing, stirring for 12-108 hours under the conditions that the solid-liquid ratio is 1:10 and the stirring speed is 500r/min, uniformly mixing, standing, precipitating and drying to obtain a solid product; and then mechanically crushing and screening the solid product to prepare particles with the particle size of 1.7mm, thus obtaining the finished product. The invention greatly improves the passivation and adsorption performance of the palygorskite and has obvious effect on the passivation of heavy metals in soil.
Description
Technical Field
The invention belongs to the technical field of soil improvement, and particularly relates to an alkali chelating Gansu palygorskite heavy metal passivation material and a preparation method thereof.
Background
With the rapid growth of industry and agriculture, the problem of heavy metal pollution of soil is more and more serious, and the problem of heavy metal pollution of soil in China is more and more prominent; according to the reports of the State general administration of environmental protection and the Ministry of national soil resources, the soil environment conditions in China are not optimisticThe soil pollution in some areas is serious, the environment quality of cultivated land soil is great, the problem of the soil environment of industrial and mining waste land is prominent, the total exceeding rate of the national soil is 16.1 percent, the inorganic type is mainly used, and the number of the inorganic pollutant exceeding standard points accounts for 82.8 percent of the total exceeding standard points; the area of the sewage irrigation area in China is about 140 kilohm2The land area polluted by heavy metals such As Cd, As, Cr, Pb, Hg, Cu, Ni and Zn accounts for 64.8 percent of the total area polluted, wherein the area polluted by Hg and Cd is the largest.
Palygorskite is an inorganic mineral material which is cheap and easy to obtain and is a hydrated layer chain magnesium silicate mineral; the theoretical chemical components are as follows: SiO 2256.96％；(Mg,Al,Fe)O 23.83％；H219.21 percent of O; the components are often mixed with Al and Fe, and Al2O3Replacing part of MgO; the basic structural unit is 2:1 layer type, namely 2 layers of silicon-oxygen tetrahedrons sandwich 1 layer of magnesium-oxygen octahedron to form a unit layer; si due to tetrahedron4+Is covered with Al3+Instead of substitution, a residual negative charge appears; the palygorskite crystal is hair-shaped or fibrous, is in long column shape or needle shape under an electron microscope, is white, gray, light green or light brown, and is in fibrous shape under an atomic mechanics microscope; the palygorskite is internally provided with a plurality of pore channels, and the cross section of each pore channel is about 0.38nm multiplied by 0.63 nm; the palygorskite has larger specific surface area and stronger adsorption and passivation capability, and draws more and more attention in the utilization of soil heavy metal passivation, and the modified palygorskite can be better used as a soil heavy metal passivation material to improve soil.
Disclosure of Invention
The invention aims to: the heavy metal passivation material prepared from the alkali-chelated modified Gansu palygorskite and the preparation method thereof are provided, and the heavy metal passivation material contains palygorskite and quicklime and can better passivate heavy metals in soil.
The technical scheme adopted by the invention is as follows: the alkali-chelated modified palygorskite-based heavy metal passivation material consists of palygorskite and quicklime, and the heavy metal passivation material consists of the following components in parts by weight: 60-80 parts of palygorskite and 20-40 parts of quicklime.
The reaction mechanism of the invention is as follows:
1. drying palygorskite ore in the board bridge town of Linze county in Gansu province for 3-7 days in the sun without adopting a heating and drying mode and preventing rainwater from soaking palygorskite; the attapulgite clay ore crushing and sieving are carried out after sun drying, so that the stability of chemical substances in the attapulgite clay ore is effectively ensured, and the surface humidity of the ore is controlled by sun drying so as to facilitate subsequent crushing.
2. The palygorskite and the quicklime are mixed according to the weight ratio of 3-4: 1, the passivation effect of the passivation material can be increased along with the increase of the content of the quicklime in the range, if the content of the quicklime is too high, the pH value of soil can be increased, the normal growth of plants is influenced, and researches show that the effective state content of heavy metals can be increased when the weight fraction of the quicklime exceeds 40%, the application amount of the quicklime is too large, the soil can be hardened and alkalized, the heavy metals in the soil can be activated, and in addition, the acid-soluble state content is the minimum when the palygorskite and the quicklime are mixed according to the weight ratio of 4: 1.
3. And drying the precipitate at 20-50 ℃, opening an internal channel of the palygorskite, exposing more internal surfaces and active groups, avoiding high-temperature drying, effectively controlling the performance of a finished product, and controlling the quality of batch production more easily.
Further, the heavy metal passivation material comprises the following components in parts by weight: 80 parts of palygorskite and 20 parts of quicklime.
Further, the heavy metal passivation material comprises the following components in parts by weight: 66 parts of palygorskite and 34 parts of quicklime.
A preparation method of an alkali chelate modified palygorskite-based heavy metal passivation material is characterized by comprising the following steps:
s1, crushing and grinding the palygorskite to prepare 160-sand 200-mesh powder;
s2, weighing and mixing the powdery palygorskite and the quicklime according to the weight part ratio, adding water for mixing, and stirring for 12-108 hours under the conditions that the solid-liquid ratio is 1:10 and the stirring speed is 500r/min to uniformly mix the palygorskite and the quicklime;
s3, standing, precipitating and drying the substance obtained in the step S2 to obtain a solid product;
s4, mechanically crushing and screening the solid product to prepare particles with the particle size of 1.7mm, and obtaining the finished product.
Further, in step S1, the palygorskite is made into 200-mesh powder.
Further, in step S2, the stirring time is 72 hours.
Further, the step S3 is to dry the standing precipitate naturally or in a drying oven at 20-50 ℃.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
the alkali-chelating modified Gansu palygorskite heavy metal passivation material prepared by the preparation method greatly improves the passivation property and the adsorption property of palygorskite, can passivate organic pollutants and toxic and harmful heavy metals, reduces the biotoxicity and the mobility of soil pollutants, and reduces the bioavailability of heavy metals; part of heavy metals in the soil exist in a cation form, the heavy metals have high mobility and high bioavailability and are most harmful, the pH value of the soil can be increased by applying quicklime, negative charges on the surface of soil particles are increased, hydroxide precipitates of the heavy metals in the soil are promoted to form, the stability of the heavy metals is facilitated, and the adsorbability of palygorskite to the heavy metals is enhanced.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A preparation method of an alkali chelate modified palygorskite-based heavy metal passivation material is characterized by comprising the following steps: the heavy metal passivation material comprises the following components in parts by weight: 60-80 parts of palygorskite and 20-40 parts of quicklime;
s1, crushing and grinding the palygorskite to prepare 160-sand 200-mesh powder;
s2, weighing and mixing the powdery palygorskite and the quicklime according to the weight part ratio, adding water for mixing, and stirring for 12-108 hours under the conditions that the solid-liquid ratio is 1:10 and the stirring speed is 500r/min to uniformly mix the palygorskite and the quicklime;
s3, standing, precipitating and drying the substance obtained in the step S2, wherein the standing, precipitating and drying is natural drying or drying in a drying furnace at the temperature of 20-50 ℃ to obtain a solid product;
s4, mechanically crushing and screening the solid product to prepare particles with the particle size of 1.7mm, and obtaining the finished product.
Example 1
A preparation method of an alkali chelate modified palygorskite-based heavy metal passivation material is characterized by comprising the following steps: the heavy metal passivation material comprises the following components in parts by weight: 80 parts of palygorskite and 20 parts of quicklime.
S1, crushing and grinding the palygorskite into 200-mesh powder;
s2, weighing and mixing the powdery palygorskite and the quicklime according to the weight part ratio, adding water for mixing until the solid-liquid ratio is 1:10, and stirring for 72 hours at the stirring speed of 500r/min to uniformly mix the palygorskite and the quicklime;
s3, standing, precipitating and drying the substance obtained in the step S2 at the drying temperature of 40 ℃ to obtain a solid product;
s4, mechanically crushing and screening the solid product to prepare particles with the particle size of 1.7mm, and obtaining the finished product.
Example 2:
a preparation method of an alkali chelate modified palygorskite-based heavy metal passivation material is characterized by comprising the following steps: the heavy metal passivation material comprises the following components in parts by weight: 75 parts of palygorskite and 25 parts of quicklime.
S1, crushing and grinding the palygorskite into 190-mesh powder;
s2, weighing and mixing the powdery palygorskite and the quicklime according to the weight part ratio, adding water for mixing until the solid-liquid ratio is 1:10, and stirring for 72 hours at the stirring speed of 500r/min to uniformly mix the palygorskite and the quicklime;
s3, standing, precipitating and drying the substance obtained in the step S2 at the drying temperature of 50 ℃ to obtain a solid product;
s4, mechanically crushing and screening the solid product to prepare particles with the particle size of 1.7mm, and obtaining the finished product.
Example 3:
a preparation method of an alkali chelate modified palygorskite-based heavy metal passivation material is characterized by comprising the following steps: the heavy metal passivation material comprises the following components in parts by weight: 66.6 parts of palygorskite and 33.4 parts of quicklime.
S1, crushing and grinding the palygorskite into 180-mesh powder;
s2, weighing and mixing the powdery palygorskite and the quicklime according to the weight part ratio, adding water for mixing until the solid-liquid ratio is 1:10, and stirring for 48 hours at the stirring speed of 500r/min to uniformly mix the palygorskite and the quicklime;
s3, standing, precipitating and drying the substance obtained in the step S2 at the drying temperature of 45 ℃ to obtain a solid product;
s4, mechanically crushing and screening the solid product to prepare particles with the particle size of 1.7mm, and obtaining the finished product.
Comparative experiment
And carrying out a manual simulation passivation experiment on the soil passivation material obtained by the method for preparing the heavy metal passivation material by alkali chelating modified Gansu palygorskite.
Exogenous heavy metals such as zinc (Zn), copper (Cu), chromium (Cr), nickel (Ni) and cadmium (Cd) are added manually and respectively to simulate heavy metal contaminated soil, and palygorskite and quicklime are added according to the proportion of 1: 1. 2: 1. 3: 1. 4: 1. 5: 1. 6: 1. 7: 1, adding water for alkali chelation modification, standing and precipitating after 12h, 24h, 36h, 48h, 72h, 96h and 108h respectively to obtain 49 passivation materials, and performing passivation experiments according to the addition of 32g/kg of the passivation materials.
The results of the experiments are analyzed in tables 1-5 using the acetic acid extraction as a reference standard;
table 1: zinc (Zn)
Acid soluble content (mg/kg) of artificial contaminated soil
| Zn | 12h | 24h | 36h | 48h | 72h | 96h | 108h |
| 1:1 | 406.72 | 377.68 | 371.28 | 339.04 | 352.64 | 376.16 | 369.44 |
| 2:1 | 403.84 | 391.32 | 375.32 | 333.68 | 311.40 | 382.76 | 390.88 |
| 3:1 | 386.04 | 376.80 | 328.52 | 303.80 | 318.96 | 351.76 | 377.56 |
| 4:1 | 328.48 | 316.60 | 302.28 | 249.40 | 241.84 | 353.52 | 358.96 |
| 5:1 | 405.48 | 394.68 | 379.00 | 341.40 | 319.60 | 362.80 | 365.08 |
| 6:1 | 408.60 | 394.76 | 382.76 | 347.68 | 348.04 | 353.48 | 381.24 |
| 7:1 | 452.20 | 451.40 | 437.12 | 432.52 | 402.96 | 445.00 | 426.48 |
In table 1, as the ratio of palygorskite to quicklime increases, the acid-soluble content in the soil gradually decreases, and when the ratio of palygorskite to quicklime is 4:1, the acid-soluble content reaches the minimum value; the stirring time has little influence on the acid soluble content, and the acid soluble content is the lowest when the stirring time is 72 hours; table 1 shows the passivation effect of alkali-chelated modified palygorskite and purified palygorskite and quicklime on heavy metal Zn, and when the ratio of palygorskite to quicklime is 4:1, the passivation effect on the acetic acid extraction state content of Zn in soil is the best.
Table 2: copper (Cu)
Acid soluble content (mg/kg) of artificial contaminated soil
Table 2 shows the passivation effect of alkali-chelated modified palygorskite and purified palygorskite and quicklime on heavy metal copper (Cu), and when the ratio of palygorskite to quicklime is 3:1, the effect on the acetic acid extraction state content of Cu in soil is the best when the stirring time is 72 h.
Table 3: chromium (Cr)
Acid soluble content (mg/kg) of artificial contaminated soil
| Cr | 12h | 24h | 36h | 48h | 72h | 96h | 108h |
| 1:1 | 152.32 | 149.92 | 159.72 | 122.64 | 149.64 | 150.12 | 153.16 |
| 2:1 | 117.72 | 115.84 | 106.68 | 92.76 | 109.56 | 113.16 | 116.24 |
| 3:1 | 109.96 | 98.44 | 89.96 | 77.96 | 97.00 | 103.32 | 107.32 |
| 4:1 | 116.40 | 94.96 | 99.84 | 81.16 | 100.56 | 107.16 | 100.16 |
| 5:1 | 116.84 | 115.04 | 105.76 | 89.36 | 108.92 | 105.92 | 101.44 |
| 6:1 | 156.88 | 157.04 | 151.04 | 154.40 | 129.44 | 148.68 | 149.16 |
| 7:1 | 159.20 | 164.80 | 166.92 | 146.40 | 168.08 | 174.84 | 178.24 |
Table 3 shows the passivation effect of alkali-chelated modified palygorskite and purified palygorskite and quicklime on heavy metal chromium (Cr), and when the ratio of palygorskite to quicklime is 3:1, the effect on the acetic acid extraction state content of Cr in soil is the best when the stirring time is 48 h.
Table 4: nickel (Ni)
Acid soluble content (mg/kg) of artificial contaminated soil
| Ni | 12h | 24h | 36h | 48h | 72h | 96h | 108h |
| 1:1 | 157.28 | 146.32 | 130.92 | 123.72 | 114.16 | 120.88 | 134.40 |
| 2:1 | 143.64 | 120.36 | 115.48 | 103.76 | 95.68 | 110.96 | 122.60 |
| 3:1 | 156.76 | 141.84 | 128.44 | 111.56 | 112.16 | 125.88 | 146.68 |
| 4:1 | 162.60 | 152.44 | 138.76 | 136.40 | 135.28 | 140.24 | 160.88 |
| 5:1 | 165.72 | 164.48 | 147.56 | 142.12 | 142.96 | 142.56 | 161.96 |
| 6:1 | 168.20 | 165.80 | 156.80 | 144.40 | 147.88 | 149.80 | 166.44 |
| 7:1 | 172.92 | 172.48 | 168.64 | 153.60 | 150.00 | 154.68 | 167.64 |
Table 4 shows the passivation effect of alkali-chelated modified palygorskite and purified palygorskite and quicklime on heavy metal nickel (Ni), and when the ratio of palygorskite to quicklime is 2:1, the effect on the acetic acid extraction state content of Ni in soil is the best when the stirring time is 72 h.
Table 5: cadmium (Cd)
Acid soluble content (mg/kg) of artificial contaminated soil
Table 5 shows the passivation effect of alkali-chelated modified palygorskite and purified palygorskite and quicklime on heavy metal cadmium (Cd), and when the ratio of palygorskite to quicklime is 2:1 and the stirring time is 48h, the effect on the acetic acid extraction state content of Cd in soil is the best.
The experiment shows that when the ratio of the palygorskite to the quicklime is 2-4:1 and the stirring time is 48-72 hours, the effect on the acetic acid extraction state content of heavy metals in the soil is the best.
The above description is only a preferred embodiment of the present invention, and not intended to limit the present invention, and the scope of the present invention is defined by the appended claims, and all changes that come within the meaning and range of equivalency of the specification are therefore intended to be embraced therein.
Claims (7)
1. The alkali-chelated modified palygorskite-based heavy metal passivation material is composed of palygorskite and quicklime, and is characterized in that the heavy metal passivation material is composed of the following components in parts by weight: 60-80 parts of palygorskite and 20-40 parts of quicklime.
2. The base-chelated modified palygorskite-based heavy metal passivation material according to claim 1, characterized in that: the heavy metal passivation material comprises the following components in parts by weight: 80 parts of palygorskite and 20 parts of quicklime.
3. The base-chelated modified palygorskite-based heavy metal passivation material according to claim 1, characterized in that: the heavy metal passivation material comprises the following components in parts by weight: 66 parts of palygorskite and 34 parts of quicklime.
4. The method for preparing the alkali chelate modified palygorskite-based heavy metal passivation material according to any one of claims 1-3, characterized by comprising the following steps:
s1, crushing and grinding the palygorskite to prepare 160-sand 200-mesh powder;
s2, weighing and mixing the powdery palygorskite and the quicklime according to the weight part ratio, adding water for mixing, and stirring for 12-108 hours under the conditions that the solid-liquid ratio is 1:10 and the stirring speed is 500r/min to uniformly mix the palygorskite and the quicklime;
s3, standing, precipitating and drying the substance obtained in the step S2 to obtain a solid product;
s4, mechanically crushing and screening the solid product to prepare particles with the particle size of 1.7mm, and obtaining the finished product.
5. The method for preparing the alkali-chelate modified palygorskite-based heavy metal passivation material according to the claim 4, wherein the palygorskite prepared in the step S1 is 200-mesh powder.
6. The method for preparing the alkali-chelate modified palygorskite-based heavy metal passivation material according to claim 4, wherein the stirring time of step S2 is 72 h.
7. The method for preparing the alkali-chelate modified palygorskite-based heavy metal passivation material according to claim 4, wherein the standing, precipitating and drying step S3 is natural drying or drying in a drying furnace at 20-50 ℃.
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| CN106890720A (en) * | 2017-03-30 | 2017-06-27 | 兰州坤仑环保科技有限公司 | A kind of alkali chelates the preparation method of palygorskite base heavy metal passivating material |
| CN108329921A (en) * | 2017-12-27 | 2018-07-27 | 环境保护部南京环境科学研究所 | A kind of preparation method of modified attapulgite and its application in soil remediation |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1631561A (en) * | 2005-01-14 | 2005-06-29 | 中国矿业大学（北京校区） | In situ restoring agent for heavy metal polluted soil |
| CN102343357A (en) * | 2011-08-25 | 2012-02-08 | 上海市环境科学研究院 | Stabilizer suitable for heavy metal contaminated soil and application method thereof |
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