CN115672965B - A kind of environmental rock-based mineral material and its preparation method and application - Google Patents
A kind of environmental rock-based mineral material and its preparation method and application Download PDFInfo
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- 239000011707 mineral Substances 0.000 title claims abstract description 118
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 117
- 239000011435 rock Substances 0.000 title claims abstract description 100
- 239000000463 material Substances 0.000 title claims abstract description 95
- 230000007613 environmental effect Effects 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- 239000002689 soil Substances 0.000 claims abstract description 76
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 19
- 235000010755 mineral Nutrition 0.000 claims description 112
- 238000000034 method Methods 0.000 claims description 39
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- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000010433 feldspar Substances 0.000 claims description 4
- 238000005067 remediation Methods 0.000 claims description 4
- 229910052656 albite Inorganic materials 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 229910052661 anorthite Inorganic materials 0.000 claims description 2
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 claims description 2
- 238000009837 dry grinding Methods 0.000 claims description 2
- 229910052655 plagioclase feldspar Inorganic materials 0.000 claims description 2
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- 229910052651 microcline Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
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- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
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Landscapes
- Processing Of Solid Wastes (AREA)
Abstract
本发明属于土壤改良与修复技术领域，具体涉及一种环境岩基矿物材料及其制备方法和应用。本发明提供了一种环境岩基矿物材料的制备方法，包括以下步骤，将岩石矿物进行初步粉碎后置于密闭容器中，然后向所述密闭容器中通入饱和水蒸气进行反应，反应结束后再进行二次粉碎，得到所述环境岩基矿物材料；其中，反应过程中，所述密闭容器的压力为1‑3MPa，温度为200‑350℃。本发明通过将水溶液加热至临界温度进行材料制备，制备的粉体具有晶粒发育完整、粒度小、分布均匀、分散性好等优点，避免了硬团聚体的形成。精细的岩基矿物具有粒径小、比表面积大的特点，有利于对重金属Cd的吸附和固持。
The present invention belongs to the technical field of soil improvement and restoration, and specifically relates to an environmental rock-based mineral material and a preparation method and application thereof. The present invention provides a preparation method for an environmental rock-based mineral material, comprising the following steps: the rock mineral is initially crushed and placed in a closed container, saturated water vapor is then introduced into the closed container for reaction, and secondary crushing is performed after the reaction is completed to obtain the environmental rock-based mineral material; wherein, during the reaction, the pressure of the closed container is 1-3MPa and the temperature is 200-350°C. The present invention prepares the material by heating the aqueous solution to a critical temperature, and the prepared powder has the advantages of complete grain development, small particle size, uniform distribution, good dispersibility, etc., and avoids the formation of hard agglomerates. Fine rock-based minerals have the characteristics of small particle size and large specific surface area, which are conducive to the adsorption and fixation of heavy metal Cd.
Description
Technical Field
The invention belongs to the technical field of soil improvement and restoration, and particularly relates to an environmental rock-based mineral material, a preparation method and application thereof.
Background
A rock-based mineral is a natural mineral that is widely found in subterranean formations. Soil minerals, including primary minerals and secondary minerals, are the primary material source of soil mineral nutrients. The primary minerals in the soil are mainly inherited and evolved by the earth-forming parent rock, mainly comprise feldspar, mica, quartz and the like, and exist in the soil sand grains and the powder particle components, the primary minerals in the soil comprise secondary minerals such as hydrated mica, chlorite, kaolinite, montmorillonite, vermiculite, diaspore and the like gradually under the action of physics, chemistry and biology, and the particles are finer and mainly exist in the clay particle components of the soil, which are also called clay minerals.
The environmental rock-based mineral material is generally prepared from natural minerals or rock and other raw materials through purification, processing, modification and other processes, and is a mineral material with good coordination with ecological environment or direct functions of preventing and treating pollution and restoring environment. The rock-based mineral material has the characteristics of wide sources, abundant reserves, low price, unique surface adsorptivity, ion exchange property, spontaneous polarization and the like, and is considered as a green, efficient and environment-friendly heavy metal passivation material. The preparation of rock-based mineral materials at present mainly comprises a mechanical method, a physical method and a chemical method. The mechanical force method is to purposefully activate the mineral surface by utilizing superfine grinding and other strong mechanical force actions, so that the crystal structure, the dissolution property, the reactivity and the like of the mineral surface are changed to a certain extent, and the mechanical force method mainly comprises ball milling superfine grinding and mechanical extrusion. Physical heating is divided into a conventional drying method and a microwave heating method according to a heat conduction mode, and the mineral can lose crystal water and structural water through high temperature, so that the specific surface area and pore volume of the mineral are changed. The common chemical method is to add inorganic acid to increase the specific surface area of mineral and obtain solid material with many empty and active sites. At present, the bottleneck of research and application of rock-based mineral materials at home and abroad is still how to prepare the rock-based mineral materials in a large scale, low cost and controllable manner.
Currently, with rapid economic development and highly intensive agricultural production, soil is constantly contaminated with various "harmful" substances. Heavy metals polluting farmland soil mainly comprise elements with obvious biological toxicity such as mercury, cadmium, lead, chromium, metal-like arsenic and the like, and elements with certain toxicity such as zinc, copper, nickel and the like, mainly come from mining waste residues, pesticides, wastewater, sludge, atmospheric sedimentation and the like, and excessive heavy metals can cause physiological dysfunction and malnutrition of plants, have higher enrichment coefficient in crop seeds, and threaten human health after entering human bodies through food chains. The in-situ passivation repair technology is widely promoted in the repair of heavy metal contaminated farmland soil in China because of the characteristics of low cost, convenient operation, short repair time, capability of remarkably relieving the phytotoxicity of the heavy metal in the soil and the like, and capability of meeting the treatment requirements of large-area medium-light heavy metal contaminated farmland in China. Currently, there are many researches on materials for in-situ passivation (stabilization) of heavy metals, and common materials include different phosphorus-containing materials, biochar, clay minerals, oxides, agricultural byproducts (compost, organic fertilizer, etc.), and the like. In recent 20 years, more researches are carried out on farmland soil remediation of heavy metal pollution by utilizing an in-situ passivation technology in China, the research field is currently in the world leading position, but the existing research results and the existing patent technology are seen to face certain technical limitations, such as poor single technical performance of the polluted soil remediation, few combination modes and poor synergy of the integrated technology, unstable effect of the existing farmland remediation inhibitor and passivating agent product (material), lack of stabilizing material with high cost performance and lasting effect, waste compatibilization problem due to the fact that the passivating agent material contains other harmful elements, high cost of the passivating material and the like. Based on the above, development of a stabilizing material with high cost performance and long-acting and environment-friendly performance is still one of important development directions of stabilizing and repairing technologies for farmland heavy metals in the future.
Disclosure of Invention
The invention provides an environmental rock-based mineral material, a preparation method and application thereof, and aims to solve the problems that in the prior art, the raw material cost of a soil passivating agent is high and secondary pollution is caused to the soil environment.
In view of the above technical drawbacks, one of the purposes of the present invention is to provide a method for preparing an environmental rock-based mineral material, another purpose of the present invention is to provide an environmental rock-based mineral material obtained by the method, and another purpose of the present invention is to provide an application of the environmental rock-based mineral material.
In a first aspect, the invention provides a method of preparing an environmental rock-based mineral material, comprising the steps of,
Placing rock minerals in a closed container after preliminary crushing, then introducing saturated steam into the closed container for reaction, and performing secondary crushing after the reaction is finished to obtain the environmental rock-based mineral material;
wherein, in the reaction process, the pressure of the closed container is 1-3MPa (such as 2 MPa), and the temperature is 200-350 ℃ (such as 210 ℃, 220 ℃, 230 ℃, 240 ℃, 310 ℃ and 330 ℃).
The preparation process can ensure that the particle size of the obtained rock-based mineral material reaches the micron level, the specific surface area is large, the cation exchange capacity is large, and the adsorption performance on heavy metals can be further improved.
In the above preparation method, as a preferred embodiment, the pressure and temperature are maintained for 60-180min (e.g., 80min, 100min, 120min, 140min, 160 min) during the reaction.
In the above preparation method, as a preferred embodiment, the pressure of the closed vessel is 1.2-2.4MPa (e.g., 1.6MPa, 1.8MPa, 2.0MPa, 2.2 MPa), and the temperature is 250-300 ℃ (e.g., 260 ℃, 270 ℃, 280 ℃ and 290 ℃).
In the above preparation method, as a preferable embodiment, the particle size of the rock mineral after the preliminary pulverization is not less than 30mm, more preferably 30 to 60mm (e.g., 40mm, 50 mm).
The method can process the large-size rock mineral with low energy consumption to obtain the nano-scale rock-based mineral material powder, namely the method adopts critical state water to process the large-size rock mineral, and then obtains the micro-scale rock-based mineral material powder through simple grinding, so that a great amount of energy sources are not required to be consumed as the method of directly crushing the rock mineral with mechanical force.
In the above preparation method, as a preferred embodiment, the secondary pulverization time is 10s-1min (e.g., 20s, 40s, 50 s);
the secondary crushing mode is dry grinding, and the stable power of the crusher is preferably 1.1kW.
The apparatus for carrying out the secondary pulverization in the present invention may be a dry mill, a crusher or a pulverizer.
In the above preparation method, as a preferred embodiment, the rock mineral includes one or more of albite, potash feldspar, anorthite, plagioclase, petalite.
In a second aspect, the invention also provides an environmental rock-based mineral material obtained by the preparation method.
In the above-mentioned environmental rock-based mineral material, as a preferred embodiment, the particle size of the environmental rock-based mineral material is less than 1mm, preferably the particle size of the environmental rock-based mineral material is 10-40 μm, such as 14.59-28.43 μm.
In the above-mentioned environmental rock-based mineral material, as a preferred embodiment, the specific surface area of the environmental rock-based mineral material is 35m 2/g or more, preferably 35-80m 2/g, such as 42.36-58.70m 2/g.
In the above-mentioned environmental rock-based mineral material, as a preferred embodiment, the cation exchange amount of the soil is 80cmol/kg or more, preferably 80 to 140cmol/kg, such as 96.43 to 126.4cmol/kg.
In a third aspect, the invention also provides application of the environmental rock-based mineral material in treating heavy metal pollution of soil.
In the application, as a preferred embodiment, the application is that the environmental rock-based mineral material is mixed with heavy metal contaminated soil, more preferably, the mass ratio of the environmental rock-based mineral material to the heavy metal contaminated soil is (1-3): 100, and the Cd content in the heavy metal contaminated soil is 0.8-2.2mg/kg.
Compared with the prior art, the invention has the following beneficial effects:
1. The invention provides a preparation method of an environmental rock-based mineral material, which comprises the following steps of primarily crushing rock minerals, placing the crushed rock minerals in a closed container, then introducing saturated steam into the closed container for reaction, and secondarily crushing the crushed rock minerals after the reaction is finished, wherein the pressure of the closed container is 1-3MPa and the temperature is 200-350 ℃ in the reaction process. The material has the advantages of low cost of raw materials, simple and easy operation of a preparation method, low equipment requirement, low energy consumption, short reaction time, suitability for industrial production, natural formation of rock minerals, non-chemical synthesis, no secondary pollution to the environment, suitability for repairing large-area heavy metal polluted soil, capability of preparing the material by heating an aqueous solution to a critical temperature, complete grain development, small granularity, uniform distribution, good dispersibility and the like, and capability of avoiding the formation of hard agglomerates. The fine rock-based mineral has the characteristics of small particle size and large specific surface area, and is favorable for adsorbing and holding heavy metal Cd.
2. The environmental rock-based mineral material provided by the invention has the characteristics of large specific surface area and strong adsorptivity, and can be subjected to complexation, precipitation and other reactions with heavy metal ions, so that the bioavailability of heavy metals in soil is reduced. Specifically, the specific surface area of the environmental rock-based mineral material may be 42.36-58.70m 2/g. The environmental rock-based mineral material is a simple, economical and efficient passivating agent for heavy metal contaminated soil.
Drawings
FIG. 1 is an XRD pattern of an environmental rock-based mineral material prepared in example 1 of the present invention;
FIG. 2 is a graph showing the measurement result of a laser particle sizer for the average particle size of the environmental rock-based mineral material prepared in example 6 of the present invention;
FIG. 3 shows the results of measuring the specific surface area of the environmental rock-based mineral material prepared in example 6 of the present invention.
Detailed Description
Technical solutions in the embodiments of the present invention will be clearly and completely described below to enable one skilled in the art to practice and reproduce the present invention. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the invention, fall within the scope of protection of the invention.
Example 1
The embodiment provides a preparation method of an environmental rock-based mineral material, which comprises the following steps:
(1) Crushing potassium feldspar in a crusher to obtain minerals with average particle size of 50 mm;
(2) Placing the crushed potassium feldspar in a high-pressure reaction kettle, introducing saturated steam into the reaction kettle for reaction, controlling the temperature in the reaction kettle to be 250 ℃ in the reaction process, controlling the pressure in the reaction kettle to be 1.2MPa, and keeping the temperature and the pressure for 120min;
(3) After the reaction is finished, cooling, opening the reaction kettle, collecting the mixture obtained in the reaction kettle, crushing and grinding the mixture for 30s by using a crusher, wherein the stable power of the crusher is 1.1kW, and obtaining the environment rock-based mineral material after crushing, wherein the analysis result according to fig. 1 shows that the main composition of the mineral is SiO2、KAlSi3O8、Na(Si2Al)O6·H2O、(K0.94Na0.06)(AlSi3O8)、NaAlSi3O8 and the like.
Example 2
The embodiment provides a preparation method of an environmental rock-based mineral material, which comprises the following steps,
Steps (1) and (3) of this example are the same as example 1, step (2) being as follows:
placing the crushed potassium feldspar in a high-pressure reaction kettle, introducing saturated steam into the reaction kettle for reaction, controlling the temperature in the reaction kettle to be 250 ℃ in the reaction process, controlling the pressure in the reaction kettle to be 2.4MPa, and keeping the temperature and the pressure for 120min.
Example 3
The embodiment provides a preparation method of an environmental rock-based mineral material, which comprises the following steps,
Steps (1) and (3) of this example are the same as example 1, step (2) being as follows:
Placing the crushed potassium feldspar in a high-pressure reaction kettle, introducing saturated steam into the reaction kettle for reaction, controlling the temperature in the reaction kettle to be 300 ℃ in the reaction process, controlling the pressure in the reaction kettle to be 1.2MPa, and keeping the temperature and the pressure for 120min.
Example 4
The embodiment provides a preparation method of an environmental rock-based mineral material, which comprises the following steps,
Steps (1) and (3) of this example are the same as example 1, step (2) being as follows:
Placing the crushed potassium feldspar in a high-pressure reaction kettle, introducing saturated steam into the reaction kettle for reaction, controlling the temperature in the reaction kettle to be 300 ℃ in the reaction process, controlling the pressure in the reaction kettle to be 2.4MPa, and keeping the temperature and the pressure for 120min.
Example 5
The embodiment provides a preparation method of an environmental rock-based mineral material, which comprises the following steps:
(1) Crushing the amphibole in a crusher to obtain minerals with average particle size of 50 mm;
(2) Placing crushed amphibole into a high-pressure reaction kettle, introducing saturated steam into the reaction kettle for reaction, controlling the temperature in the reaction kettle to be 250 ℃ in the reaction process, controlling the pressure in the reaction kettle to be 1.2MPa, and keeping the temperature and the pressure for 120min;
(3) And after the reaction is finished, cooling, opening the reaction kettle, collecting a mixture obtained in the reaction kettle, crushing and grinding the mixture for 30s by adopting a crusher, wherein the stable power of the crusher is 1.1kW, and crushing to obtain the environment rock-based mineral material.
Example 6
The embodiment provides a preparation method of an environmental rock-based mineral material, which comprises the following steps,
Steps (1) and (3) of this example are the same as example 5, step (2) being as follows:
placing the crushed amphibole into a high-pressure reaction kettle, introducing saturated steam into the reaction kettle for reaction, controlling the temperature in the reaction kettle to be 250 ℃ in the reaction process, controlling the pressure in the reaction kettle to be 2.4MPa, and keeping the temperature and the pressure for 120min.
Example 7
The embodiment provides a preparation method of an environmental rock-based mineral material, which comprises the following steps,
Steps (1) and (3) of this example are the same as example 5, step (2) being as follows:
Placing the crushed amphibole into a high-pressure reaction kettle, introducing saturated steam into the reaction kettle for reaction, controlling the temperature in the reaction kettle to be 300 ℃ in the reaction process, controlling the pressure in the reaction kettle to be 1.2MPa, and keeping the temperature and the pressure for 120min.
Example 8
The embodiment provides a preparation method of an environmental rock-based mineral material, which comprises the following steps,
Steps (1) and (3) of this example are the same as example 5, step (2) being as follows:
Placing the crushed amphibole into a high-pressure reaction kettle, introducing saturated steam into the reaction kettle for reaction, controlling the temperature in the reaction kettle to be 300 ℃ in the reaction process, controlling the pressure in the reaction kettle to be 2.4MPa, and keeping the temperature and the pressure for 120min.
Example 9
(1) Crushing potassium feldspar in a crusher to obtain minerals with average particle size of 80 mm;
(2) Placing the crushed potassium feldspar in a high-pressure reaction kettle, introducing saturated steam into the reaction kettle for reaction, controlling the temperature in the reaction kettle to be 250 ℃ in the reaction process, controlling the pressure in the reaction kettle to be 1.2MPa, and keeping the temperature and the pressure for 120min;
(3) And after the reaction is finished, cooling, opening the reaction kettle, collecting a mixture obtained in the reaction kettle, crushing and grinding the mixture for 30s by adopting a crusher, wherein the stable power of the crusher is 1.1kW, and crushing to obtain the environment rock-based mineral material.
Test example 1
The mineral materials obtained from the environmental rock-based mineral materials obtained in examples 1 to 9 were subjected to performance tests, and the indexes of the tests include pH, specific surface area, average particle diameter, soil cation exchange capacity, quick-acting potassium content, volume weight and Cd content.
The pH test method refers to a soil detection series standard, namely NY/T1121.1-2006;
The specific surface area was measured by a low-temperature nitrogen adsorption method using a specific surface area analyzer (BET-N2:
quantachrome Instruments, u.s.);
the test method of the cation exchange capacity of the soil refers to a soil detection series standard, namely NY/T1121.5-2006;
The test method of the quick-acting potassium content refers to the quick-acting potassium and slow-acting potassium of soil, NY/T889-2004;
the volume weight test method refers to a soil detection series standard, namely NY/T1121.4-2006;
The method for testing the Cd content refers to a graphite furnace atomic absorption spectrophotometry for measuring the quality of lead and cadmium in soil, namely GB/T17141-1997.
The specific test results are shown in Table 1.
TABLE 1
Test example 2
The test example adopts a method of simulating field test, and the soil used in the test is taken from surface soil of 0-20cm of two different types of Hunan province (main production area of rice) and Henan province (main production area of wheat). The average value of cadmium content in two kinds of soil exceeds the soil pollution risk screening value specified in national soil environmental quality standard GB 15618-2018 by more than 3 times (paddy field 0.4 mg.kg -1, pH is less than or equal to 6.5 and other pH is less than or equal to 0.3 mg.kg -1, pH is less than or equal to 7.5). The basic physicochemical properties of the two soils are shown in Table 2.
TABLE 2
The rice variety is indica type rice XS09, and the wheat variety is Liaochun No. 18.
The test is arranged in a greenhouse of China national academy of agricultural science, and the greenhouse environment adopts rain shielding treatment of a top transparent film. Two kinds of soil were respectively put into PVC culture vessels (0.8 x 1.2 x 0.4 m), filled up to 0.25m, urea (0.429 g·kg -1 soil), KH2PO4 (0.263 g·kg -1 soil), KCl (0.420 g·kg -1 soil) were added to the soil as base fertilizers, each treatment was repeated three times, the test including the treatment of the rock-based mineral material of examples 1 to 9 with no rock-based mineral material (CK) added thereto at a concentration of 2% (meaning that 2g of rock-based mineral material was added to 100g of soil), followed by irrigation to 70% of the maximum water holding capacity of the soil, and equilibration was carried out for two weeks.
Soaking rice and wheat seeds in 5% H 2O2 for 20min, washing with deionized water, placing on a culture dish covered with wet filter paper, and culturing at 28deg.C in a plant climatic incubator until germination. Finally, the rice is transferred into a PVC culture container for containing S1 soil, the wheat is transferred into a PVC culture container for containing S2 soil, and seedlings are thinned after the seedlings grow out, and the spacing between the seedlings is kept to be 5cm.
TABLE 3 Table 3
The letters a, b, c, d, e, f, g, h in table 3 are used to indicate the significance of the differences between different treatment conditions in the same soil, the differences in letters represent significant differences in properties or content (P < 0.01) compared to the two treatment regimes, and if one letter is the same, the differences are not significant.
Table 3 shows the effect of the rock-based mineral materials prepared by the treatment methods of examples 1-9 on the physicochemical properties and the content of Cd in the effective state of two kinds of soil, and the detection of the two kinds of soil-related data in Table 3 was performed by sampling 40 days after mixing the rock-based mineral materials in the corresponding soil and completing the detection. Specifically, after the rock-based mineral material is applied, the pH, CEC and quick-acting K contents of the soil are improved. In contrast to the control group (without addition of the rock-based mineral material), the use of the rock-based mineral materials of examples 1-9 significantly reduced the effective Cd content in the soil. Specifically, for S1, the Cd deactivation rate is 37.2-50.7%, and for S2, the Cd deactivation rate is 34.5-47.9%. For the different treatments, the Cd effective state content at 2 soils was expressed overall as example 6+.example 3< example 2< example 7< example 5< example 8+.example 4< example 1< example 9< control group.
TABLE 4 Table 4
Letter a, b, c, d, e, f, g in table 4 is used to indicate the significance of the difference in Cd content between different treatment conditions in the same soil, at the same location of the rice or wheat plant, and the difference in Cd content at the later letters represents a significant difference (P < 0.01) compared to the two treatment modes, and if one letter is the same, the difference is not significant.
Table 4 shows the Cd content (mg/kg) of each part of rice (S1) and wheat (S2) plants corresponding to the two kinds of soil respectively by the rock-based mineral materials prepared by the treatment methods of examples 1-9, and as can be seen from Table 4, the accumulated amounts of Cd at different parts of rice and wheat plants are root > stem and leaf > seed in sequence. For the two different treatments of the soil, the Cd accumulation was expressed overall as example 6< example 3< example 8< example 4< example 2 ≡example 7< example 5< example 1< example 9< control group.
As can be seen from Table 4, compared with the control group (without adding rock-based mineral material), the method for restoring heavy metal in soil of example 1 was adopted to reduce the Cd content of rice grains by 36.4%, the method for restoring heavy metal in soil of example 2 was adopted to reduce the Cd content of wheat grains by 29.1%, the method for restoring heavy metal in soil of example 2 was adopted to reduce the Cd content of rice grains by 45.5%, the method for restoring heavy metal in soil of example 3 was adopted to reduce the Cd content of rice grains by 59.1%, the method for restoring heavy metal in soil of wheat grains by 49.1%, the method for restoring heavy metal in soil of example 4 was adopted to reduce the Cd content of rice grains by 63.6%, the method for restoring heavy metal in soil of wheat grains by 47.3%, the method for restoring heavy metal in soil of example 5 was adopted to reduce the Cd content of rice grains by 27.3%, the Cd content of wheat grains by 36.4%, the method for restoring heavy metal in soil of example 6 was adopted to reduce the Cd content of rice grains by 65.9%, the Cd content of wheat grains by 54.5%, the method for restoring heavy metal in soil of example 7 was adopted to reduce the Cd content of rice grains by 40.9%, the Cd content of wheat grains by 43%, and the method for restoring heavy metal in soil of rice grains by 8.8%. By adopting the soil heavy metal restoration method of the embodiment 9, the Cd content of rice grains is reduced by 20.5 percent, and the Cd content of wheat grains is reduced by 23.6 percent.
TABLE 5
Letter a, b, c, d, e, f, g, h, v in table 5 is used to indicate the significance of the difference in yield of corresponding rice, wheat in the same soil between different treatment conditions, the difference in yield after yield represents a significant difference in yield (P < 0.01) compared to the two treatment modes, and if one letter is the same, the difference is not significant.
Table 5 shows the respective rice and wheat yields (expressed in thousand grain weight (g)) of the rock-based mineral materials prepared by the treatment methods of examples 1-9 for the two soils, and it can be seen from Table 5 that the rice and wheat yields are generally expressed as example 6> example 3 ≡example 8> example 7> example 4 ≡example 5> example 2> example 1> example 9> for the different treatment methods. Specifically, compared with a control group (without adding rock-based mineral materials), the yield of the paddy rice is increased by 8.95-31.3% by adopting different soil heavy metal passivation restoration methods, and the yield of wheat seeds is increased by 13.4-42.2%.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the particular embodiments disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
Claims (11)
1. A preparation method of an environmental rock-based mineral material is characterized by comprising the following steps,
Placing rock minerals in a closed container after preliminary crushing, then introducing saturated steam into the closed container for reaction, and performing secondary crushing after the reaction is finished to obtain the environmental rock-based mineral material;
Wherein, in the reaction process, the pressure of the closed container is 1-3MPa, and the temperature is 200-350 ℃;
the rock mineral comprises one or more of albite, potash feldspar, middle feldspar, aragonite, amphibole, plagioclase and anorthite;
The particle size of the environmental rock-based mineral material is 10-40 mu m;
the specific surface area of the environmental rock-based mineral material is 35-80m 2/g.
2. The method for preparing an environmental rock-based mineral material according to claim 1, wherein the pressure and temperature are maintained for 60 to 180 minutes during the reaction.
3. The method for preparing an environmental rock-based mineral material according to claim 1, wherein the pressure of the closed container is 1.2-2.4MPa and the temperature is 250-300 ℃.
4. The method for producing an environmental rock-based mineral material according to claim 1, wherein the rock mineral has a particle diameter of 30mm or more after the preliminary pulverization.
5. The method for producing an environmental rock-based mineral material according to claim 4, wherein the rock mineral has a particle size of 30 to 60mm after the preliminary pulverization.
6. The method for preparing an environmental rock-based mineral material according to claim 1, wherein the time of the secondary pulverization is 10s to 1min;
The secondary crushing mode is dry grinding, and the stable power of the crusher is 1.1kW.
7. An environmental rock-based mineral material obtained by the method of any one of claims 1 to 6.
8. The environmental rock-based mineral material according to claim 7, wherein,
The cation exchange capacity of soil of the environmental rock-based mineral material is more than 80 cmol/kg.
9. The environmental rock-based mineral material of claim 7, wherein the environmental rock-based mineral material has a soil cation exchange capacity of 80-140cmol/kg.
10. Use of an environmental rock-based mineral material obtained by the method of any one of claims 1 to 6 or the environmental rock-based mineral material of any one of claims 7 to 9 for the remediation of heavy metal pollution of soil.
11. The use according to claim 10, wherein the use is to mix the environmental rock-based mineral material obtained by the production method according to any one of claims 1 to 6 or the environmental rock-based mineral material according to any one of claims 7 to 9 with heavy metal contaminated soil, the mass ratio of the environmental rock-based mineral material to the heavy metal contaminated soil is (1 to 3): 100, and the Cd content in the heavy metal contaminated soil is 0.8 to 2.2mg/kg.
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