CN110373199B - Composite soil repairing agent and preparation method and repairing method thereof - Google Patents
Composite soil repairing agent and preparation method and repairing method thereof Download PDFInfo
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- CN110373199B CN110373199B CN201910542004.5A CN201910542004A CN110373199B CN 110373199 B CN110373199 B CN 110373199B CN 201910542004 A CN201910542004 A CN 201910542004A CN 110373199 B CN110373199 B CN 110373199B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
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Images
Classifications
-
- 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
-
- 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
- C09K17/08—Aluminium compounds, e.g. aluminium hydroxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
-
- 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
- C09K2101/00—Agricultural use
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Abstract
The invention discloses a composite soil repairing agent and a preparation method and a repairing method thereof, wherein the repairing agent consists of a hydroxyapatite-calcium silicate composite material and biochar, the mass ratio of the hydroxyapatite-calcium silicate composite material to the biochar is 4:6-9:1, and the biochar is poplar-based biochar. The preparation method comprises the following steps: respectively preparing a calcium chloride dispersion liquid and a sodium silicate dispersion liquid, then dropwise adding a calcium chloride solution into the sodium silicate solution under ultrasonic waves, reacting, washing with deionized water after the reaction is finished, filtering to obtain a calcium silicate hydrate precipitate, then adding the calcium silicate hydrate precipitate into a phosphate solution, reacting, filtering to obtain a hydroxyapatite-calcium silicate composite material, and mixing biochar with the composite material according to a mass ratio to obtain the soil remediation agent. When the ratio of the two is 4:6, the materials are mutually promoted to generate a synergistic effect, the composite repairing agent can achieve long-term and high-efficiency repairing effect on severe and composite metal polluted soil, and has the advantages of low cost, small usage amount and environmental protection.
Description
Technical Field
The invention belongs to the technical field of soil remediation, and particularly relates to a composite soil remediation agent using a hydroxyapatite-calcium silicate composite material in cooperation with biochar, a preparation method of the composite soil remediation agent, and a method for remedying heavy metal contaminated soil and vegetable land.
Background
Soil is the material basis for human survival and development and is the basic production data of agricultural production. However, with continuous and deep urbanization and industrialization, human activities such as mineral resource development, metal smelting, sewage irrigation, large-scale use of chemical fertilizers and the like cause pollutants containing various heavy metals to enter soil through various ways, and soil heavy metal pollution is caused. Soil heavy metal pollution has the characteristics of concealment, long-term property and irreversibility, the detention time in soil is long, the soil heavy metal pollution cannot be degraded by microorganisms, and heavy metals can enter organisms through a geochemical chain and a food chain to endanger human health. Investigation shows that the farmland soil in China suffers from heavy metal pollution up to 19.4%, wherein the standard exceeding rates of Cu, Zn, Pb and Cd respectively reach 2.1%, 0.9%, 1.5% and 7.0%. Generally, a single heavy metal contaminated soil system is relatively simple and easy to treat, and a composite heavy metal contaminated soil system is more complex and more difficult.
The soil is used as an ecological system and has buffering performance and self-cleaning capacity. Within a certain pollution limit, under the action of microorganisms, organic matters and mineral substances, the soil can convert heavy metals into low-toxicity or non-toxic substances, so that the heavy metals do not present harm to the outside. However, the self-cleaning capacity of the soil is limited and needs to be managed and repaired in combination with artificial measures. At present, the treatment approaches to the heavy metal contaminated soil mainly comprise 2 types according to the mechanism: (1) changing the existing form of heavy metal in soil, fixing the heavy metal so as to reduce the mobility and bioavailability of the heavy metal in the environment; (2) heavy metals are removed from the soil so that the residual concentration approaches or reaches a background value. Many researches on heavy metal contaminated soil remediation technologies, including bioremediation, physical remediation and chemical remediation, have been carried out at home and abroad. The bioremediation method generally has the problems of low remediation efficiency, high treatment cost and the like. The traditional physical repair methods such as landfill, physical leaching, soil turning repair and the like have large engineering quantity and high cost, and often cause the damage of the soil structure and the loss of certain nutrient elements. The chemical fixation method is emphasized due to the characteristics of simple operation, low investment and the like, but the conventional soil remediation agents such as lime, biochar, compost and the like have the problems of large dosage, unobvious reduction efficiency, adverse effect on the physical and chemical properties of soil, easy decomposition of compost when being applied into soil and the like. In addition, the existing remediation agent is usually applied to soil polluted by single heavy metal, and is rarely applied to soil polluted by compound heavy metal.
Disclosure of Invention
The invention provides a composite soil remediation agent and a preparation method and a remediation method thereof, aiming at solving the problems of large dosage and poor remediation effect of the existing single soil remediation agent.
The invention adopts the following technical scheme:
the composite soil remediation agent is characterized by consisting of a hydroxyapatite-calcium silicate composite material and biological carbon, wherein the mass ratio of the hydroxyapatite-calcium silicate composite material to the biological carbon is 4:6-9: 1.
The biological carbon is poplar-based biological carbon.
The mass ratio of the hydroxyapatite-calcium silicate composite material to the poplar-based biochar is 4: 6.
The Zeta potential of the hydroxyapatite-calcium silicate composite material is-15.1 to-10.4 mV, the cation exchange capacity is 19.4 to 14.5cmol/kg, the Zeta potential of the biological carbon is-28.1 to-34.47 mV, and the cation exchange capacity is 5.3 to 8.6 cmol/kg.
The preparation method of the composite soil remediation agent comprises the following steps:
ultrasonically dispersing calcium chloride into water to obtain a calcium chloride dispersion liquid;
ultrasonically dispersing sodium silicate into water to obtain a dispersion liquid of the sodium silicate;
dropwise adding the calcium chloride solution into the sodium silicate solution under ultrasonic wave for reaction, washing with deionized water after the reaction is finished, and filtering to obtain a precipitate product, namely calcium silicate hydrate;
adding the calcium silicate hydrate into a phosphate solution, continuously reacting for 24 hours, adding acid liquor or alkali liquor to enable the pH of the mixed liquor to be 5.0 +/-0.2, filtering to obtain the hydroxyapatite-calcium silicate composite material,
and mixing the hydroxyapatite-calcium silicate composite material and biological carbon according to the mass ratio of 1:9-9:1 to obtain the soil remediation agent.
The liquid-solid ratio of the calcium chloride solution and the liquid-solid ratio of the sodium silicate solution are both 9-11, the mass ratio of the calcium chloride to the sodium silicate is 1.0-1.4, and the reaction time of the calcium chloride to the sodium silicate is 20-30 h.
The concentration of phosphorus in the phosphate solution is 50-70mg/L, the mass ratio of the calcium silicate hydrate to the phosphorus in the phosphate is 8: 1-12: 1, the reaction is carried out at room temperature for 20-30h, and the rotating speed is 120-240 rpm.
The concentration of H & lt + & gt in the acid liquor is 0.01-0.05M, and the concentration of OH & lt- & gt in the alkali liquor is 0.01-0.05M.
By using the repairing method of the composite soil repairing agent, the repairing agent is fully mixed with the heavy metal contaminated soil, the water content of the soil is maintained to be 50% -80%, the repairing time is 7-90 days, and the adding amount of the repairing agent is 3 wt%.
The soil polluted by the composite heavy metal is described, and the total metal comprises lead, cadmium and/or copper.
The invention has the technical effects that:
according to the soil remediation agent, the hydroxyapatite-calcium silicate composite material is prepared by firstly preparing calcium silicate hydrate by adopting an ultrasonic-assisted sol-gel reaction, then reacting the calcium silicate hydrate with a phosphate solution to generate hydroxyapatite, recovering phosphorus in the solution through the calcium silicate hydrate to obtain the hydroxyapatite-calcium silicate composite material, finally separating the hydroxyapatite-calcium silicate composite material from the solution, and then mixing and compounding the synthesized composite material and biochar according to a certain proportion.
The calcium silicate hydrate is a loose laminated structure, has uniform shape and a large amount of gaps, is easier to recover phosphate from a solution to form hydroxyapatite through a single crystallization process, is easy to build on the basis of a calcium silicate framework to form a fine and uniform fiber structure, finally forms a hydroxyapatite-calcium silicate composite material, and has the main component of hydroxyapatite and a small amount of calcium silicate, wherein the calcium silicate not only serves as the framework, but also can effectively adsorb heavy metal ions. Compared with single hydroxyapatite, the composite material has larger and more pore structures, the Zeta potential is-12.1 mV, and no isoelectric point exists, which indicates that the composite material has high affinity to heavy metal ions, and heavy metals in soil can form fixed ions which are difficult to desorb in the environment through electrostatic attraction, ion exchange, precipitation and chelation of the heavy metals; in addition, the phosphate carried by the composite material can promote the fixation of heavy metals. Therefore, the cadmium adsorbed on the activated carbon can be prevented from being released into the soil again by being compounded with the biochar, the problem that the cadmium-polluted soil repaired by the single biochar is easy to mineralize is solved, and the long-term repairing effect is achieved.
Meanwhile, the surface of the biochar is rich in carboxyl, hydroxyl, acid anhydride and a series of functional groups, and has more negative charges, so that heavy metal ions (Cu, Cd, Pb and Zn) can be effectively fixed, the biochar has unique surface properties, morphological structures and abundant and discrete pore systems, and can be used together with hydroxyapatite-calcium silicate to better improve the physical and chemical properties of soil, improve the pH value of the soil, increase the negative charges on the soil surface, enhance adsorption and reduce the bioavailability of metal ions.
The optimal ratio of the two is 4:6, a better synergistic promotion effect can be generated, the physical and chemical properties of soil can be improved by the early stage biochar, the soil PH, the soil water-soluble carbon, the urease and the dehydrogenase can reach a more appropriate condition, the reduction of the bioavailability of heavy metals is facilitated, a proper amount of the hydroxyapatite-calcium silicate composite material can play a longer role, the soil can be continuously and stably repaired in the middle and later stages, the problem that the pH of the soil is reduced due to the early degradation of the biochar is solved, the defect that the biochar is unstable in the later stage is overcome, the synergistic effect is generated, the conversion rate of heavy metals is better than the case of single application and the case of less than 4:6 ratio, the long-term and high-efficiency repairing effect on the heavily and composite metal contaminated soil can be achieved, the cost is greatly reduced, and the use amount is small.
The soil remediation agent can greatly reduce the accumulation concentration of heavy metals in vegetables planted in the heavy metal contaminated vegetable field while remedying the heavy metal soil, effectively regulate and control the heavy metal transmission of a food chain, and reduce the threat of the heavy metals to the human health.
The repairing agent of the invention also has the following advantages:
the main components of the composite soil repairing agent are biological carbon and hydroxyapatite, the source of the biological carbon is wide, and compared with a hydroxyapatite-calcium silicate composite material, the composite soil repairing agent has low synthesis and transportation cost and greatly reduces the cost; and the soil conditioner is a nontoxic, green and environment-friendly material, and does not bring toxic action to the soil environment after being applied to the soil.
In addition, the hydroxyapatite-calcium silicate composite material has rich phosphorus and releases PO after being applied to soil4 3-Part of PO4 3-The phosphate compounds can be converted, and the other part of free phosphate ions can improve the effective phosphorus content in the soil and promote the growth of plants; the biochar has rich carbon, and can improve the content of water-soluble carbon in soil after being applied to the soil, thereby further improving the physical and chemical properties of the soil.
Drawings
FIG. 1 is a scanning electron micrograph of calcium silicate hydrate prepared according to example 1 of the present invention;
fig. 2 is a scanning electron microscope image of the hydroxyapatite-calcium silicate composite material prepared in example 1 of the present invention.
Detailed Description
Example 1
Raw materials: poplar-based biochar: wuhan Guanggu blue research New energy Co Ltd, specific surface area is 28.9317m2785.8g/kg of total carbon and 34.85g/kg of total nitrogen.
A preparation method of a composite soil remediation agent comprises the following steps:
(a) preparing a hydroxyapatite-calcium silicate composite material:
dissolving 6g of calcium chloride in 60ml of water to obtain a calcium chloride solution;
dissolving 5g of sodium silicate in 50ml of water to obtain a sodium silicate solution;
the resulting calcium chloride solution was slowly added dropwise to the sodium silicate solution under sonication conditions to produce a white sol and gradually hardened and sampled, taken out and incubated in a plastic container for 24 hours at room temperature. Washing and filtering the calcium hydroxide solution by using deionized water after the reaction is finished, and finally drying the calcium hydroxide solution for 24 hours at the temperature of 80 ℃ to obtain calcium silicate hydrate;
0.26gKH2PO4Dissolving in 1L deionized water to prepare phosphate solution;
adding 0.6g of calcium silicate hydrate into the 1L of phosphate solution, continuously reacting for 24 hours in a constant temperature shaking table at the speed of 25 ℃ and 180rpm, adding 0.01mol/L HCl or 0.01mol/L NaOH to enable the pH of a mixed solution to be 5, filtering after the reaction is finished, washing with water, and finally drying for 12 hours at the temperature of 60 ℃ to obtain the hydroxyapatite-calcium silicate composite material.
(b) The hydroxyapatite-calcium silicate composite material and poplar-based biochar are mixed to prepare the composite soil remediation agent.
The calcium silicate prepared by the method is in a loose laminated structure from the microstructure, as can be seen from figure 1, the hydroxyapatite-calcium silicate composite material is an excellent uniform fiber structure, the surface pore structure is more, the fiber structure is possibly corresponding to the calcium silicate, as can be seen from figure 2, the Zeta potential of the hydroxyapatite-calcium silicate composite material is-12.1 mV, the cation exchange capacity is 16.5cmol/kg, the Zeta potential of the poplar-based biochar is-31.47 mV, and the cation exchange capacity is 7.2 cmol/kg.
Example 2
A method for repairing composite heavy metal contaminated soil by using a composite soil repairing agent comprises the following steps:
(1) collecting the composite heavy metal contaminated soil:
the test soil is collected from Hunan agriculture university, the composite heavy metal contaminated soil is prepared by artificially adding cadmium solution, copper solution, lead solution and zinc solution, and the composite heavy metal contaminated soil is cultured at the constant temperature of 25 ℃ for two months, so that the forms of copper, cadmium, lead and zinc tend to be stable. The total copper content in the soil is 293.5mg/kg, the total cadmium content is 3.05mg/kg, the total lead content is 1195.6mg/kg, and the total zinc content is 724mg/kg through a graphite furnace digestion method;
(2) repairing the composite heavy metal contaminated soil:
preparing five groups of stable composite heavy metal contaminated soil with the same weight, wherein the first group is not added with any repairing agent and is used as a blank control group; adding hydroxyapatite-calcium silicate composite material (HAP10.S) accounting for 3% of the cadmium-polluted soil in the second group, and uniformly mixing; adding biochar (Bio10.S) accounting for 3% of the weight of the cadmium-polluted soil into the third group, and uniformly mixing; adding hydroxyapatite-calcium silicate composite material and biochar which are 3 percent of the weight of the composite heavy metal contaminated soil in the fourth group, wherein the adding ratio of the hydroxyapatite-calcium silicate composite material to the biochar is 2:8(H2B8.M), and uniformly mixing; and adding hydroxyapatite-calcium silicate composite material and biological carbon which are 3 percent of the weight of the composite heavy metal contaminated soil in the fifth group, wherein the adding ratio of the hydroxyapatite-calcium silicate composite material to the biological carbon is 4:6(H4B6.M), and uniformly mixing. And (3) respectively supplementing water to the five groups of composite heavy metal contaminated soil by using deionized water, so that the water content of the cadmium contaminated soil is kept to be about 60% of the maximum field water capacity.
After 42 days of stabilization, five groups of heavy metals in the cadmium-contaminated soil were extracted with glacial acetic acid having a PH of 2.88 ± 0.05 as an extractant, and measured with an inductively coupled plasma emission spectrometer (ICP-OES). The immobilization rates of the respective heavy metals are shown in tables 1 to 4. And simultaneously, the form and the proportion of the heavy metal elements in the soil are known by a BCR four-step extraction method, and different forms and proportions of copper, cadmium, lead and zinc elements are measured by an inductively coupled plasma emission spectrometer (ICP-OES), wherein various metal forms are shown in tables 1-4.
The BCR continuous extraction method can better reflect the biological effectiveness of heavy metals Cu, Cd, Pb and Zn in soil. The weak acid state of the heavy metal is weakly combined with soil, is most easily released, has the maximum mobility and biological effectiveness, and is easily released under an acidic condition.
TABLE 1 morphological changes of remediation Agents at different ratios to copper in soil
| Treatment method | Weak acid state of F1 | F2 reducible state | F3 oxidizable state | F4 residual state | Fixation Rate (%) |
| CK.M | 34.65％ | 41.81％ | 6.27％ | 17.27％ | — |
| HAP10.M | 18.83％ | 43.45％ | 17.35％ | 20.37％ | 34 |
| Bio10.M | 28.50％ | 45.69％ | 8.65％ | 17.16％ | 13.7 |
| H2B8.M | 30.74％ | 39.12％ | 10.47％ | 19.67％ | 30.4 |
| H4B6.M | 16.32％ | 44.70％ | 14.36％ | 24.62％ | 35.5 |
TABLE 2 morphological changes of cadmium in soil with remediation agents in different ratios
| Treatment method | Weak acid state of F1 | F2 reducible state | F3 oxidizable state | F4 residual state | Fixation Rate (%) |
| CK.M | 55.51％ | 17.84％ | 9.71％ | 16.94％ | — |
| HAP10.M | 44.92％ | 21.24％ | 11.58％ | 22.26％ | 33.3 |
| Bio10.M | 51.20％ | 22.09％ | 8.06％ | 18.65％ | 9.8 |
| H2B8.M | 47.25％ | 17.32％ | 12.58％ | 22.85％ | 23.5 |
| H4B6.M | 40.26％ | 14.39％ | 20.04％ | 25.31％ | 32.7 |
TABLE 3 morphological changes of lead in soils with remediation agents in different proportions
TABLE 4 morphological changes of remediation Agents at different ratios to Zinc in soil
| Treatment method | Weak acid state of F1 | F2 reducible state | F3 oxidizable state | F4 residual state | Fixation Rate (%) |
| CK.M | 55.61％ | 16.43％ | 7.95％ | 20.01％ | — |
| HAP10.M | 55.04％ | 12.17％ | 11.70％ | 21.09％ | 14.8 |
| Bio10.M | 60.80％ | 15.62％ | 10.16％ | 13.42％ | 1.4 |
| H2B8.M | 56.31％ | 16.90％ | 9.53％ | 17.26％ | 8.3 |
| H4B6.M | 46.81％ | 18.02％ | 12.13％ | 23.04％ | 10 |
As shown in tables 1-4, after 42 days of repair, when the addition ratio of the hydroxyapatite-calcium silicate composite material to the biochar is 4:6, F1 weak acid states of copper, cadmium, lead and zinc are all reduced, F4 residue states are increased, particularly the amplitudes of lead, cadmium and copper are large, and most preferably lead is reduced by 34% in the weak acid states and increased by 33% in the residue states.
Meanwhile, the contents of heavy metals of lead, copper and cadmium in a glacial acetic acid extraction state are all obviously reduced, particularly, the lead repairing effect of H4B6.M is over 80 percent, compared with a single hydroxyapatite-calcium silicate composite material, the fixation rates of lead, cadmium and zinc are not greatly different, but the fixation rate of copper is improved, and the repairing agent in the proportion can realize good soil repairing and reduce the using amount of hydroxyapatite-calcium silicate. When the hydroxyapatite-calcium silicate composite material is put into the field for independent use, the demand is high, the synthesis is complex, the difficult problem is well solved if the hydroxyapatite-calcium silicate composite material is applied together with biological carbon, and the biological carbon is low in price, so that the repair cost can be greatly reduced.
Example 3
Since the water spinach is a common edible vegetable in south China and an annual plant, the adaptability is strong, and the planting cost is low, the water spinach is selected as a researched object in the embodiment. The soil remediation agent can also be used for improving other vegetables in heavy metal polluted vegetable fields.
A method for repairing water spinach polluted by composite heavy metals in soil by using a composite soil repairing agent comprises the following steps:
(1) collecting the composite heavy metal contaminated soil:
the test soil is collected from Hunan agriculture university, the composite heavy metal contaminated soil is prepared by artificially adding cadmium solution, copper solution, lead solution and zinc solution, and the composite heavy metal contaminated soil is cultured at the constant temperature of 25 ℃ for two months, so that the forms of copper, cadmium, lead and zinc tend to be stable. The total copper content in the soil is 210.5mg/kg, the total cadmium content is 1.6mg/kg, the total lead content is 1195.6mg/kg, and the total zinc content is 597.7mg/kg through a graphite furnace digestion method;
(2) repairing the composite heavy metal contaminated soil of the water spinach field:
accelerating germination: soaking water spinach seed (seed of Thailand water spinach of Wuhan Wuchang Shen cattle seedling business) in warm water for about 30 min at about 60 deg.C, soaking in clear water for 24 hr, taking out, and performing germination acceleration at room temperature. During the pregermination, certain temperature and humidity must be kept, and the seeds can be sown after being washed with water for 1-2 times every day until large-area white spots are exposed on the surfaces of the seeds.
Sowing: preparing five groups of stabilized composite heavy metal contaminated soil, wherein each group is 800g, and the five groups are respectively filled in pots, and the first group is not added with any repairing agent and is used as a blank control group; adding hydroxyapatite-calcium silicate composite material (HAP10.S) accounting for 3% of the cadmium-polluted soil in the second group, and uniformly mixing; adding biochar (Bio10.S) accounting for 3% of the weight of the cadmium-polluted soil into the third group, and uniformly mixing; adding hydroxyapatite-calcium silicate composite material and biochar which are 3 percent of the weight of the composite heavy metal contaminated soil in the fourth group, wherein the adding ratio of the hydroxyapatite-calcium silicate composite material to the biochar is 2:8(H2B8.M), and uniformly mixing; adding hydroxyapatite-calcium silicate composite material and biochar which are 3 percent of the weight of the composite heavy metal contaminated soil in the fifth group, wherein the adding ratio of the hydroxyapatite-calcium silicate composite material to the biochar is 4:6(H4B6.M), uniformly mixing, then uniformly sowing 6 seeds for accelerating germination in each pot, covering a layer of fine soil after sowing, and watering to keep the soil humidity;
and (3) potting management: watering every day during the growth period to keep the soil moist, keeping the water content of the soil to be about 60% of the maximum field water capacity, and moving the flowerpots randomly during the growth period to ensure the sunshine.
(3) Testing the content of heavy metal in the water spinach:
harvesting the water spinach after growing for 42 days, washing the water spinach with distilled water for 3 times after washing with tap water, measuring the fresh weight after naturally drying the water spinach, deactivating enzymes of a sample at 105 ℃ for 20 minutes, then drying the sample at 70 ℃ to constant, dividing the plant into three parts, namely roots, stems and leaves, weighing the dry mass, calculating the water content of the sample, and digesting the plant after grinding the sample through a 0.25mm sieve. The digested solution was filtered at 0.45 μm, and the contents of copper, cadmium, lead and zinc were measured by inductively coupled plasma emission spectrometry (ICP-OES), and the results are shown in tables 5 to 8.
TABLE 5 Effect of remediation Agents on the content of copper in the roots, stems, leaves of swamp cabbage growing in composite contaminated soil
| Cu adsorption amount (mg/kg) | CK.M | HAP10.M | Bio10.M | H2B8.M | H4B6.M |
| Root of herbaceous plant | 7.77 | 4.85 | 9.48 | 7.15 | 3.03 |
| Stem of a tree | 7.39 | 3.18 | 6.47 | 5.15 | 2.91 |
| Leaf of Chinese character | 5.73 | 4.12 | 4.52 | 4.92 | 2.61 |
TABLE 6 Effect of remediation Agents on cadmium content of Roots, stems, leaves of swamp cabbage growing in composite contaminated soil
| Cd adsorption capacity (mg/kg) | CK.M | HAP10.M | Bio10.M | H2B8.M | H4B6.M |
| Root of herbaceous plant | 3.22 | 2.66 | 2.10 | 2.48 | 1.24 |
| Stem of a tree | 3.01 | 2.34 | 1.98 | 1.84 | 1.21 |
| Leaf of Chinese character | 2.92 | 1.94 | 2.01 | 1.56 | 1.15 |
TABLE 7 Effect of remediation Agents on the content of lead in the root, Stem, leaf of swamp cabbage growing in Complex contaminated soil
| Pb adsorption amount (mg/kg) | CK.M | HAP10.M | Bio10.M | H2B8.M | H4B6.M |
| Root of herbaceous plant | 7.78 | 2.82 | 6.68 | 5.45 | 2.12 |
| Stem of a tree | 7.38 | 3.01 | 6.56 | 5.53 | 3.23 |
| Leaf of Chinese character | 2.32 | 2.47 | 6.51 | 2.27 | 1.67 |
TABLE 8 Effect of remediation Agents on Zinc content in roots, stems, leaves of swamp cabbage growing in Complex contaminated soil
| Zn adsorption amount (mg/kg) | CK.M | HAP10.M | Bio10.M | H2B8.M | H4B6.M |
| Root of herbaceous plant | 45.87 | 35.16 | 41.24 | 34.05 | 26.35 |
| Stem of a tree | 40.11 | 29.21 | 37.77 | 28.54 | 25.12 |
| Leaf of Chinese character | 28.16 | 26.76 | 28.44 | 26.05 | 21.64 |
TABLE 9 removal rate of different heavy metals from the root, diameter and leaves of water spinach by H4B6.M
| Removal rate | Copper (Cu) | Cadmium (Cd) | Lead (II) | Zinc |
| Root of herbaceous plant | 61.0％ | 61.5％ | 72.8％ | 42.6％ |
| Stem of a tree | 60.6％ | 60.0％ | 56.2％ | 37.4％ |
| Leaf of Chinese character | 54.4％ | 60.6％ | 28％ | 23.2％ |
As can be seen from tables 4-8, the hydroxyapatite-calcium silicate composite material and the biochar are added in a ratio of 4:6 to the composite soil remediation agent H4B6.M, which is the most effective agent for removing heavy metals in cabbage, compared with the blank group, the hydroxyapatite-calcium silicate composite material alone, the biochar alone and the composite soil remediation agent in a ratio of 2: 8. From table 9, it can be seen that after H4B6 is added to the composite contaminated soil, the accumulation amounts of copper, cadmium, lead and zinc in the roots, stems and leaves of the water spinach are greatly reduced, especially the concentration of lead in the roots of the water spinach is reduced by 72.8%, the concentration of cadmium and copper in the roots, stems and leaves of the water spinach is reduced by about 60%, and the concentration of zinc in the roots of the water spinach is reduced by 42.6%. Therefore, the water spinach can effectively fix a plurality of heavy metals at the same time and effectively reduce the content of various heavy metals in the water spinach.
In conclusion, the H4B6.M effect in the composite soil remediation agent of the hydroxyapatite-calcium silicate composite material and the biological carbon is the best, the synergistic effect is greater than that of a single component, and the fixation effect on the composite heavy metal contaminated soil is the best.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (6)
1. A composite soil repairing agent is characterized by consisting of a hydroxyapatite-calcium silicate composite material and biological carbon, wherein the mass ratio of the hydroxyapatite-calcium silicate composite material to the biological carbon is 4: 6;
the Zeta potential of the hydroxyapatite-calcium silicate composite material is-15.1 to-10.4 mV, and the cation exchange capacity is 19.4 to 14.5 cmol/kg;
the preparation method of the hydroxyapatite-calcium silicate composite material comprises the following steps:
ultrasonically dispersing calcium chloride into water to obtain a calcium chloride dispersion liquid;
ultrasonically dispersing sodium silicate into water to obtain a dispersion liquid of the sodium silicate;
dropwise adding the calcium chloride solution into the sodium silicate solution under ultrasonic wave for reaction, washing with deionized water after the reaction is finished, and filtering to obtain a precipitate product, namely calcium silicate hydrate;
adding the calcium silicate hydrate into a phosphate solution, continuously reacting for 24 hours, adding an acid solution or an alkali solution to enable the pH of the mixed solution to be =5.0 +/-0.2, and filtering to obtain a hydroxyapatite-calcium silicate composite material;
the biochar is poplar-based biochar;
the concentration of phosphorus in the phosphate solution is 50-70mg/L, the mass ratio of the calcium silicate hydrate to the phosphorus in the phosphate is 8: 1-12: 1, the reaction is carried out at room temperature for 20-30h, and the rotating speed is 120-240 rpm.
2. The soil remediation agent of claim 1, wherein said biochar has a Zeta potential of-28.1 to-34.47 mV and a cation exchange capacity of 5.3 to 8.6 cmol/kg.
3. The compound soil remediation agent of claim 1, wherein the liquid-solid ratio of the calcium chloride solution and the liquid-solid ratio of the sodium silicate solution are both 9-11, the mass ratio of the calcium chloride to the sodium silicate is 1.0-1.4, and the reaction time of the calcium chloride to the sodium silicate is 20-30 hours.
4. The composite soil remediation agent of claim 1, wherein said acid solution contains H+The concentration of (A) is 0.01-0.05M, OH in the alkali liquor-The concentration of (A) is 0.01-0.05M.
5. The method for remedying the composite soil remediation agent as claimed in any one of claims 1 to 4, wherein the remediation agent is fully mixed with the heavy metal contaminated soil, the water content of the soil is maintained to be 50-80%, the remediation time is 7-90 days, and the addition amount of the remediation agent is 3 wt%.
6. The remediation method of claim 5, wherein the heavy metal contaminated soil is a complex heavy metal contaminated soil comprising lead, cadmium and/or copper.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007296463A (en) * | 2006-04-28 | 2007-11-15 | Onoda Chemical Industry Co Ltd | Hydroxyapatite silica composite porous adsorbent and its manufacturing method |
| CN101700415A (en) * | 2009-11-13 | 2010-05-05 | 中国科学院上海硅酸盐研究所 | Calcium silicate/hydroxylapatite composite biological ceramic material and preparation method and application thereof |
| CN101700414A (en) * | 2009-11-13 | 2010-05-05 | 中国科学院上海硅酸盐研究所 | Calcium silicate nanowire/hydroxylapatite nanoparticle composite powder and preparation method thereof |
| CN102336400A (en) * | 2010-07-21 | 2012-02-01 | 中国地质大学（北京） | Technology for recovering phosphorus from sewage through calcium silicate hydrate seed method |
| CN102616762A (en) * | 2011-02-01 | 2012-08-01 | 中国科学院上海硅酸盐研究所 | Method for hydro-thermal preparation of hydroxyapatite powder by calcium silicate precursor |
| CN103406093A (en) * | 2013-07-22 | 2013-11-27 | 陕西科技大学 | Tobermorite/ HAP composite sewage heavy-metal treating material and preparation method thereof |
| CN103449460A (en) * | 2012-06-05 | 2013-12-18 | 中央民族大学 | Preparation method of calcium silicate hydrate nano material |
| CN105419805A (en) * | 2015-11-27 | 2016-03-23 | 同济大学 | Preparing method for complex function repairing agent for treatment of heavy metal contaminated soil |
-
2019
- 2019-06-21 CN CN201910542004.5A patent/CN110373199B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007296463A (en) * | 2006-04-28 | 2007-11-15 | Onoda Chemical Industry Co Ltd | Hydroxyapatite silica composite porous adsorbent and its manufacturing method |
| CN101700415A (en) * | 2009-11-13 | 2010-05-05 | 中国科学院上海硅酸盐研究所 | Calcium silicate/hydroxylapatite composite biological ceramic material and preparation method and application thereof |
| CN101700414A (en) * | 2009-11-13 | 2010-05-05 | 中国科学院上海硅酸盐研究所 | Calcium silicate nanowire/hydroxylapatite nanoparticle composite powder and preparation method thereof |
| CN102336400A (en) * | 2010-07-21 | 2012-02-01 | 中国地质大学（北京） | Technology for recovering phosphorus from sewage through calcium silicate hydrate seed method |
| CN102616762A (en) * | 2011-02-01 | 2012-08-01 | 中国科学院上海硅酸盐研究所 | Method for hydro-thermal preparation of hydroxyapatite powder by calcium silicate precursor |
| CN103449460A (en) * | 2012-06-05 | 2013-12-18 | 中央民族大学 | Preparation method of calcium silicate hydrate nano material |
| CN103406093A (en) * | 2013-07-22 | 2013-11-27 | 陕西科技大学 | Tobermorite/ HAP composite sewage heavy-metal treating material and preparation method thereof |
| CN105419805A (en) * | 2015-11-27 | 2016-03-23 | 同济大学 | Preparing method for complex function repairing agent for treatment of heavy metal contaminated soil |
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