CN111253945B - Acidified soil conditioner and preparation method thereof - Google Patents
Acidified soil conditioner and preparation method thereof Download PDFInfo
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- CN111253945B CN111253945B CN202010207068.2A CN202010207068A CN111253945B CN 111253945 B CN111253945 B CN 111253945B CN 202010207068 A CN202010207068 A CN 202010207068A CN 111253945 B CN111253945 B CN 111253945B
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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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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
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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
- C09K17/04—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only applied in a physical form other than a solution or a grout, e.g. as granules or gases
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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
- C09K2101/00—Agricultural use
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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
- C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation
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Abstract
The invention provides an acidified soil conditioner and a preparation method thereof, wherein the acidified soil conditioner comprises expanded graphite, alkaline fertilizer and limestone, and is mainly prepared by adsorbing the alkaline fertilizer on the expanded graphite and mixing the alkaline fertilizer with limestone powder, wherein the expanded graphite is prepared by adding concentrated nitric acid into graphite powder tailings for reaction and expanding at high temperature. The acidified soil conditioner provided by the invention has the advantages that the main component of the acidified soil conditioner is alkaline fertilizer, the alkaline fertilizer is adsorbed on the expanded graphite, the soil acidification improvement effect is good, the buffer capacity and the long-acting property of the conditioner are improved by utilizing the characteristics of the expanded graphite, in addition, the physical adsorption and chemical adsorption characteristics of the conditioner are further enhanced by adding limestone powder, and the acidified soil conditioner has an obvious improvement effect on acidified soil.
Description
Technical Field
The invention relates to the technical field of soil remediation, in particular to an acidified soil conditioner and a preparation method thereof.
Background
In agricultural production, in order to meet the increasing demand of society for grains, people unreasonably utilize cultivated land in large quantities and use chemical fertilizers and pesticides without control, which finally causes the deterioration of soil physicochemical properties, the decline of soil fertility, the low utilization rate of fertilizers, and particularly has the prominent problems of soil acidification, shallow plough layer, unbalance of cultivated land nutrients and the like. The soil acidification refers to the process of pH value reduction and base saturation reduction caused by hydrogen ions generated inside the soil and input from the outside.
The reasons for soil acidification are mainly: the precipitation is large and centralized, the leaching effect is strong, and the large loss of alkaline salts such as calcium, magnesium, potassium and the like is the root cause of soil acidification; in China, most farmers do not form a scientific fertilizing idea, a large amount of chemical fertilizers are blindly applied unilaterally for high yield of crops, and excessive use of pesticides causes soil acidification; atmospheric pollution and acid rain, the development of the industry in China in recent decades, the emission of a large amount of acid gas, and the influence of acid sediments on the environment are increased continuously, so that the frequency and the intensity of acid sedimentation in many areas are increased.
The soil acidification can destroy the physiological function of plant roots, cause the death of the root systems, reduce the effectiveness of phosphorus, calcium and magnesium in the soil, reduce the absorption rate of the elements, cause the deficiency of plant elements and bring Al in the soil along with the soil acidification3+The activity of ions and other heavy metal ions is improved, and the soil and overground plants are damaged. Therefore, finding a suitable method or way to improve acid soil is the research subject of many researchers, and improving acid soil is also an important content of sustainable agricultural development.
Chinese patent application No. 201711297781.5 discloses a soil conditioner for repairing acidified soil, which comprises a basic conditioner obtained by mixing biochar, plant ash, decomposed cow dung organic fertilizer, amino acid waste liquid adsorbate and calcium carbonate, and bacillus amyloliquefaciens L3, wherein the moisture content of the conditioner is lower than 35%, and the content of the bacillus amyloliquefaciens L3 is 0.2 hundred million CFU/g. The Chinese patent application No. 201810360650.5 discloses an acidified soil conditioner, which comprises the following raw materials in parts by weight: 10-20 parts of soybean meal, 15-30 parts of humic acid, 8-15 parts of manure, 5-17 parts of crop straws, 3-10 parts of corn flour, 3-5 parts of polyacrylamide, 3-8 parts of wheat bran, 5-25 parts of rapeseed cakes, 10-30 parts of bentonite, 8-25 parts of plant ash, 1.3-2.3 parts of biological agent, 3-9 parts of mushroom residue and 3-15 parts of tea-making waste. With the increasingly prominent soil acidification problem, the existing acidified soil conditioner can not meet the use requirement.
In order to improve the acidification of soil and effectively avoid the problem of the reduction of crop yield and quality caused by soil acidification, a novel acidified soil conditioner is needed to be provided, so as to achieve the purpose of improving acid soil.
Disclosure of Invention
Aiming at the problems of large soil acidification area and serious acidification problem in China at present, a proper method needs to be found for improving acidified soil urgently, the invention provides the acidified soil conditioner and the preparation method, so that the obtained acidified soil conditioner has obvious effect on acidified soil and has good buffering capacity and long-acting property.
In order to solve the problems, the invention adopts the following technical scheme:
the acidified soil conditioner is characterized in that the acidified soil conditioner is prepared by adsorbing an alkaline fertilizer on expanded graphite and mixing the adsorbed alkaline fertilizer with limestone powder, wherein the expanded graphite is prepared by adding concentrated nitric acid into graphite tailing powder for reaction and expanding at high temperature; the graphite powder is natural crystalline flake graphite tailing powder and the concentrated nitric acid in a mass ratio of 1: 2.
The alkaline fertilizer is a calcium magnesium phosphate fertilizer and plant ash, wherein the mass ratio of the calcium magnesium phosphate fertilizer to the plant ash is 100: 20-30. The alkaline fertilizer can provide deficient nutrient elements and salt-based ions for the acidified soil, and is a good choice for improving the acidified soil. Wherein the calcium magnesium phosphate fertilizer belongs to physiological alkaline fertilizer, and the main component comprises Ca3(PO4)2、CaSiO3、MgSiO3The fertilizer is a multi-element fertilizer, the water solution is alkaline, the acid soil can be improved, the effect of serving as a base fertilizer is good when large seedlings are cultivated, the plants can slowly absorb required nutrients, the phosphorus element in the soil can be supplemented by applying the phosphate fertilizer, OH < - > can be released in the process of absorbing phosphate radical by the soil, the conditioner can relieve the acidification of the soil and has long-acting property, and the fertilizer has the characteristics of insolubility in water, no toxicity, no corrosivity, no moisture absorption and no caking; the plant ash is an inorganic farmyard manure with wide source, low cost, complete nutrients and obvious fertilizer effect, the plant ash is mineral elements contained in plants because the plant ash is ash generated after the plants are burnt, the plant ash almost contains potassium element with the most content, the potassium element exists in the form of carbonate, phosphorus also contains calcium, magnesium, silicon, sulfur and trace nutrient elements such as iron, manganese, copper, zinc, boron, molybdenum and the like, and the plant ash is light and alkaline and can neutralize active acid and exchangeable acid in soilCan adjust the pH value of the acid soil.
The mass fraction of the concentrated nitric acid is 70-80%.
Further provides a preparation method of the acidified soil conditioner, which is characterized by comprising the following steps:
(1) adding concentrated nitric acid as an intercalation agent into natural flake graphite tailing powder, reacting for 60-80min at 50 ℃, then adding clear water to wash until the mixture is neutral, drying, and then expanding at the high temperature of 900-1000 ℃ to obtain expanded graphite;
(2) grinding an alkaline fertilizer into powdery particles with the particle size of less than 5 mu m, dispersing the powdery particles in water, and uniformly mixing and stirring to obtain a mixed solution;
(3) and adding the expanded graphite into the mixed solution, soaking for reaction, drying to obtain expanded graphite loaded with the alkaline fertilizer, and uniformly mixing with limestone powder to obtain the acidified soil conditioner.
In the step (2), the mass ratio of the water to the alkaline fertilizer is 100: 60-90.
The soaking reaction time in the step (3) is 30-40 min.
The scale graphite tailings are layered, are easy to expand, have low cost, can instantly expand 150-300 times in volume when meeting high temperature after being treated by nitric acid, and are changed into worm shapes from sheet shapes, so that the structure is loose, porous and bent, the surface area is enlarged, the surface energy is improved, the adsorption force is enhanced, and the scale graphite tailings have rich pore structures, thereby having excellent adsorption performance. The invention utilizes the expanded graphite to adsorptively load the alkaline fertilizer, thereby further adsorbing the hydrogen ions and complexing the aluminum ions and other saline ions causing soil acidification, and further enhancing the buffer capacity and the long-acting property of the modifier.
The mass ratio of the expanded graphite loaded with the alkaline fertilizer to the limestone powder in the step (3) is 3: 1. Furthermore, the alkaline fertilizer is loaded on the expanded graphite and mixed with a small amount of limestone powder, limestone is an alkaline substance with high chemical activity and large surface porosity, surface alkaline groups enable the limestone to have strong adsorption capacity, and after the alkaline fertilizer is mixed with the alkaline fertilizer loaded expanded graphite, the physical adsorption and chemical adsorption properties of the modifier are further enhanced, so that the modifier has obvious improvement effect on acidified soil.
In the step (3), the particle size of the limestone powder is less than 10 μm.
The soil acidification area in China is large, and a proper method needs to be found for improvement, but the existing soil acidification modifier has an unsatisfactory effect and limits the application of the soil acidification modifier. In view of the above, the invention provides an acidified soil conditioner and a preparation method thereof, wherein an alkaline fertilizer is loaded on expanded graphite, and then the expanded graphite is mixed with a small amount of limestone to be used as the acidified soil conditioner. The modifier comprises the main component of alkaline fertilizer loaded on the expanded graphite, has good soil acidification improvement effect, improves the buffer capacity and the long-acting property of the modifier by utilizing the characteristics of the expanded graphite, further enhances the physical adsorption and chemical adsorption characteristics of the modifier by adding limestone powder, and has obvious effect on acidified soil.
Compared with the prior art, the invention provides an acidified soil conditioner and a preparation method thereof, and the outstanding characteristics and excellent effects are as follows:
1. the main component of the acidified soil conditioner provided by the invention is alkaline fertilizer loaded on expanded graphite, calcium magnesium phosphate fertilizer in the alkaline fertilizer can enable the conditioner to relieve soil acidification and has long-acting property, plant ash can adjust the pH value of acid soil and provide a nutrient element of potassium; meanwhile, after the alkaline fertilizer is loaded by utilizing the adsorption structure of the expanded graphite, the buffering capacity and the long-acting property of the modifying agent are further enhanced.
2. The limestone added into the acidified soil conditioner provided by the invention has alkaline groups on the surface, so that the limestone has strong adsorption capacity, the physical adsorption and chemical adsorption characteristics of the conditioner are further enhanced, and the acidified soil conditioner has obvious effect on acidified soil.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Mixing natural crystalline flake graphite tailing powder and concentrated nitric acid with the mass concentration of 70% according to the mass ratio of 1:2, reacting for 80min at 50 ℃, then adding clear water to wash the mixture to be neutral, drying the mixture and then expanding the mixture at the high temperature of 900 ℃ to obtain expanded graphite;
(2) mixing the calcium magnesium phosphate fertilizer and the plant ash according to the mass ratio of 100:20, grinding the mixture by using a jet mill until the particle size is less than 5 mu m, dispersing the ground mixture into water, and uniformly mixing and stirring the mixture to obtain a mixed solution; wherein the mass ratio of the water to the alkaline fertilizer is 100: 90.
(3) Adding the expanded graphite into the mixed solution, soaking for 40min for reaction, drying to obtain expanded graphite loaded with the alkaline fertilizer, and uniformly mixing the expanded graphite with limestone powder with the particle size of less than 10 mu m to obtain the acidified soil conditioner; wherein the mass ratio of the expanded graphite to the mixed solution is 2: 1; the mass ratio of the expanded graphite loaded with the alkaline fertilizer to the limestone powder is 3: 1.
The test method comprises the following steps:
the acidified soil conditioner prepared in the embodiment is subjected to performance test, the test soil is a Sichuan Danling orange garden, 0-20cm of plough layer soil is collected before the test, the initial pH value of the soil is tested, the test soil is divided into a control group and a test group, the control group is habitually applied with a compound fertilizer (prepared by taking urea, ammonium phosphate and potassium chloride as main raw materials, and the content of effective nutrients such as nitrogen, phosphorus and potassium is more than or equal to 25%), and the test group is applied with the compound fertilizer (the same as above) and at the same time, the amount of the compound fertilizer is 25kg/667m2The pH values of the test soils after 3 months and 6 months were respectively measured by applying the acidified soil conditioner prepared by the present invention, and the results are shown in table 1.
Example 2
(1) Mixing natural crystalline flake graphite tailing powder and concentrated nitric acid with the mass concentration of 70% according to the mass ratio of 1:2, reacting for 80min at 50 ℃, then adding clear water to wash the mixture to be neutral, drying the mixture and then expanding the mixture at the high temperature of 900 ℃ to obtain expanded graphite;
(2) mixing the calcium magnesium phosphate fertilizer and the plant ash in a mass ratio of 100:30, grinding the mixture by using a jet mill until the particle size is less than 5 mu m, dispersing the ground mixture into water, and uniformly mixing and stirring the mixture to obtain a mixed solution; wherein the mass ratio of the water to the alkaline fertilizer is 100: 80.
(3) Adding the expanded graphite into the mixed solution, soaking for 40min for reaction, drying to obtain expanded graphite loaded with the alkaline fertilizer, and uniformly mixing the expanded graphite with limestone powder with the particle size of less than 10 mu m to obtain the acidified soil conditioner; wherein the mass ratio of the expanded graphite to the mixed solution is 2: 1; the mass ratio of the expanded graphite loaded with the alkaline fertilizer to the limestone powder is 3: 1.
Example 3
(1) Mixing natural crystalline flake graphite tailing powder and concentrated nitric acid with the mass concentration of 70% according to the mass ratio of 1:2, reacting for 80min at 50 ℃, then adding clear water to wash the mixture to be neutral, drying the mixture and then expanding the mixture at the high temperature of 1000 ℃ to obtain expanded graphite;
(2) mixing the calcium magnesium phosphate fertilizer and the plant ash in a mass ratio of 100:25, grinding the mixture by using a jet mill until the particle size is less than 5 mu m, dispersing the ground mixture into water, and uniformly mixing and stirring the mixture to obtain a mixed solution; wherein the mass ratio of the water to the alkaline fertilizer is 100: 60.
(3) Adding the expanded graphite into the mixed solution, soaking for 40min for reaction, drying to obtain expanded graphite loaded with the alkaline fertilizer, and uniformly mixing the expanded graphite with limestone powder with the particle size of less than 10 mu m to obtain the acidified soil conditioner; wherein the mass ratio of the expanded graphite to the mixed solution is 2: 1; the mass ratio of the expanded graphite loaded with the alkaline fertilizer to the limestone powder is 3: 1.
Comparative example 1
(1) Mixing natural crystalline flake graphite tailing powder and concentrated nitric acid with the mass concentration of 70% according to the mass ratio of 1:2, reacting for 80min at 50 ℃, then adding clear water to wash the mixture to be neutral, drying the mixture and then expanding the mixture at the high temperature of 900 ℃ to obtain expanded graphite;
(2) mixing the calcium magnesium phosphate fertilizer and the plant ash according to the mass ratio of 100:20, grinding the mixture by using a jet mill until the particle size is less than 5 mu m, dispersing the ground mixture into water, and uniformly mixing and stirring the mixture to obtain a mixed solution; wherein the mass ratio of the water to the alkaline fertilizer is 100: 90.
(3) And adding the expanded graphite into the mixed solution, soaking for 40min for reaction, and then drying to obtain the expanded graphite loaded with the alkaline fertilizer, namely the acidified soil conditioner.
Comparative example 1 does not have auxiliary limestone powder, affecting the improvement of acidified soil.
The test was carried out by the method of example 1, and the test results are shown in Table 1.
Comparative example 2
(1) Mixing the calcium magnesium phosphate fertilizer and the plant ash according to the mass ratio of 100:20, grinding the mixture by using a jet mill until the particle size is less than 5 mu m, dispersing the ground mixture into water, and uniformly mixing and stirring the mixture to obtain a mixed solution; wherein the mass ratio of the water to the alkaline fertilizer is 100: 90.
(3) Adding unexpanded graphite tailing powder into the mixed solution, soaking for 40min, drying to obtain alkaline fertilizer composite graphite, and uniformly mixing with limestone powder with the particle size of less than 10 μm to obtain an acidified soil conditioner; wherein the mass ratio of the graphite to the mixed solution is 2: 1; the matching mass ratio of the alkaline fertilizer composite graphite to the limestone powder is 3: 1.
Comparative example 2 no expanded graphite was used, but unexpanded graphite was used.
The test was carried out by the method of example 1, and the test results are shown in Table 1.
Table 1:
as can be seen from the table 1, the acidified soil conditioner prepared by the invention can obviously improve the soil acidification degree, increase the soil pH, meet the growth requirements of crops, and further reduce the occurrence of soil hardening and other conditions.
Claims (8)
1. The acidified soil conditioner is characterized in that the acidified soil conditioner is prepared by adsorbing an alkaline fertilizer on expanded graphite and mixing the adsorbed alkaline fertilizer with limestone powder, wherein the expanded graphite is prepared by adding concentrated nitric acid into natural crystalline flake graphite tailing powder for reaction and expanding at high temperature; the mass ratio of the natural crystalline flake graphite tailing powder to the concentrated nitric acid is 1: 2; grinding an alkaline fertilizer into powdery particles with the particle size of less than 5 mu m, dispersing the powdery particles in water, and uniformly mixing and stirring to obtain a mixed solution; and adding the expanded graphite into the mixed solution, soaking for reaction, drying to obtain expanded graphite loaded with the alkaline fertilizer, and uniformly mixing with limestone powder to obtain the acidified soil conditioner.
2. The acidified soil conditioner of claim 1, wherein the alkaline fertilizer is a calcium magnesium phosphate fertilizer and plant ash, and the mass ratio of the calcium magnesium phosphate fertilizer to the plant ash is 100: 20-30.
3. An acidified soil amendment according to claim 1, wherein the mass fraction of concentrated nitric acid is 70-80%.
4. A method of preparing an acidified soil amendment as claimed in any one of claims 1 to 3, the specific method of preparation being as follows:
(1) adding concentrated nitric acid as an intercalation agent into natural flake graphite tailing powder, reacting for 60-80min at 50 ℃, then adding clear water to wash until the mixture is neutral, drying, and then expanding at the high temperature of 900-1000 ℃ to obtain expanded graphite;
(2) grinding an alkaline fertilizer into powdery particles with the particle size of less than 5 mu m, dispersing the powdery particles in water, and uniformly mixing and stirring to obtain a mixed solution;
(3) and adding the expanded graphite into the mixed solution, soaking for reaction, drying to obtain expanded graphite loaded with the alkaline fertilizer, and uniformly mixing with limestone powder to obtain the acidified soil conditioner.
5. The preparation method of the acidified soil conditioner as claimed in claim 4, wherein in the step (2), the mass ratio of the water to the alkaline fertilizer is 100: 60-90.
6. The method for preparing an acidified soil conditioner as claimed in claim 4, wherein the soaking reaction time in step (3) is 30-40 min.
7. The preparation method of the acidified soil conditioner as claimed in claim 4, wherein the mixing mass ratio of the expanded graphite loaded with the alkaline fertilizer to the limestone powder in step (3) is 3: 1.
8. The method for preparing an acidified soil conditioner according to claim 4, wherein the particle size of the limestone powder in step (3) is less than 10 μm.
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| CN112322305A (en) * | 2020-11-02 | 2021-02-05 | 王庆乐 | Method for producing soil conditioner by using iron ore tailings |
| CN115124379A (en) * | 2021-03-24 | 2022-09-30 | 国家能源投资集团有限责任公司 | Granular citrate soluble silicon fertilizer and its preparation method |
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