CN113149719B - Calcium-based biochar for improving acidified soil and preparation method thereof - Google Patents
Calcium-based biochar for improving acidified soil and preparation method thereof Download PDFInfo
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- CN113149719B CN113149719B CN202110375343.6A CN202110375343A CN113149719B CN 113149719 B CN113149719 B CN 113149719B CN 202110375343 A CN202110375343 A CN 202110375343A CN 113149719 B CN113149719 B CN 113149719B
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D3/00—Calcareous fertilisers
- C05D3/02—Calcareous fertilisers from limestone, calcium carbonate, calcium hydrate, slaked lime, calcium oxide, waste calcium products
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
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- 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
- 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
Abstract
The invention discloses a preparation method of calcium-based biochar, wherein the calcium-based biochar is prepared by uniformly mixing agricultural and forestry wastes and calcium hydroxide in proportion and then carrying out ball milling, utilizing the strong basicity of the calcium hydroxide to enable biomass to be ground by balls and simultaneously carry out hydrolysis reaction, wherein a hydrolysate and calcium ions carry out complex reaction to form a precursor with a three-dimensional structure, and then carbonizing at the high temperature of 600-1000 ℃ to obtain the calcium-based biochar. The calcium-based biochar is prepared by applying agricultural and forestry wastes, calcium hydroxide and a ball milling technology, can be practically used, is used for treating farmland acidized soil, and has a wide application prospect.
Description
Field of application
The invention relates to the technical field of soil improvement, in particular to calcium-based biochar for improving acidified soil and a preparation method thereof.
Background
The soil is one of the indispensable conditions for the growth of crops, and fertile soil can promote the sound growth of crops. With the increase of market demand, the excessive consumption of soil is caused by long-season cultivation and out-of-season cultivation, meanwhile, the loss of a large amount of alkaline bases such as calcium, magnesium and the like in the soil is caused by rain wash and irrigation mode of flood irrigation, and the excessive application of nitrogen fertilizer and the like are main reasons for soil acidification. After acidification of the cultivated land soil, the soil structure is destroyed, Ca2+、Mg2+When alkaline (basic) ions are leached seriously, physical properties are deteriorated, soil aggregates are reduced, and massive or columnar structures are formed, so that the soil is hardened and hardened; the absorption and utilization rate of most medium and trace element crops is reduced, the loss of nitrogen, phosphorus and other nutrient elements is accelerated, the root development of the plants is poor, the fertilizer absorption and utilization efficiency is low, and the yield and the quality of the crops are seriously influenced. In China, soil acidification, particularly farmland soil acidification, has become a very serious problem. From the 80 s of the last century to the new century, the pH value of the soil of the farmland in China is averagely reduced by 0.5 unit, wherein 70% of acidification is caused by excessive nitrogen application in the grain fields of wheat, corn and rice; the excessive nitrogen in the fruit and vegetable field contributes up to 90 percent to acidification. Therefore, prevention and improvement of soil acidification is a very realistic topic.
The most common method of improving acidified soil is by applying an acidified soil conditioner. Quicklime or limestone powder is usually applied to acidified farmlands as a modifier, and organic matters such as decomposed farmyard manure and biochar are supplemented. However, the addition of calcium lime can cause the calcium content in the soil to be too high, so that crops can hardly absorb other cations, the growth of the crops is inhibited, and the activity of microorganisms can be inhibited due to the too high calcium environment.
At present, methods for treating soil acidification by using biochar or quicklime are reported, and the purpose of regulating acid and supplementing calcium is achieved by mostly using alkaline groups on the surface of the biochar and the alkalinity of the quicklime to improve the pH value of the soil or combining the alkaline groups and the quicklime. However, the simple utilization of biochar for treating acidified soil has high cost, and a large amount of alkaline (base) ions leached from soil cannot be supplemented; soil hardening is easily caused by using quicklime for improvement, the organic matter content is reduced, more negative effects are brought, if the biochar and the quicklime are simply mixed, the potential negative effects of soil hardening, element balance imbalance and the like caused by the release of a large amount of calcium salt cannot be compensated, and the application of the biochar and the quicklime in the improvement of acidified soil is greatly limited.
Disclosure of Invention
The invention overcomes the defects of the prior art, provides the calcium-based biochar for improving the acidified soil, and adopts the technical scheme that:
a preparation method of calcium-based biochar comprises the following steps:
step 1: the method comprises the following steps of (1) physically crushing the agricultural, forestry and animal husbandry waste, mixing the agricultural, forestry and animal husbandry waste with calcium hydroxide according to a certain mass ratio, uniformly mixing the agricultural, forestry and animal husbandry waste with water, putting the mixture into an agate ball-milling tank, and simultaneously adding agate round beads into the agate tank;
step 2: placing the agate tank in a planetary ball mill, ball-milling for 1-20h at the rotating speed of 150-;
and step 3: and carrying out 600-1000 ℃ high-temperature pyrolysis treatment on the biochar precursor in an atmosphere furnace or a muffle furnace to obtain a calcium-based biochar sample.
In a preferred embodiment of the invention, the mass ratio of the agricultural, forestry and animal husbandry waste to the calcium hydroxide is 1:1-10: 1.
In a preferred embodiment of the invention, the weight ratio of the mixture of the agricultural, forestry and animal husbandry waste and the calcium hydroxide to the water is 1:2-1: 50.
In a preferred embodiment of the invention, the agricultural and forestry waste is selected from one or more of straw, residual branches and leaves, and wood leftovers.
In a preferred embodiment of the present invention, in the step 3, nitrogen is used as a protective gas, and the temperature is raised to a predetermined temperature in a muffle furnace or an atmosphere furnace at a heating rate of 1-10 ℃ and maintained at 600-1000 ℃ for 1-10 h.
The invention also aims to provide the calcium-based biochar prepared by the preparation method of the calcium-based biochar.
Another object of the present invention is to provide an application of the above calcium-based biochar, especially an application of the same in the improvement of acid soil, comprising the following steps: adding calcium-based biochar into acidified soil according to a certain proportion, and treating for at least 5 days.
In a preferred embodiment of the present invention, after adding calcium-based biochar to acidified soil, deionized water is added, wherein the ratio of soil: calcium-based biochar: the mass ratio of water is 100: (0.1-3): (30-300).
The key of the preparation method of the calcium-based biochar is that the agricultural and forestry waste is hydrolyzed by cellulose under the conditions of strong alkalinity generated by calcium hydroxide and ball milling, and the hydrolysis product is complexed with calcium ions, so that the material is reconstructed in the aspects of structure and dimension, and the improvement capability of the biochar on acidified soil is greatly improved.
The preparation method of the calcium-based biochar comprises the steps of mixing agricultural and forestry wastes and calcium hydroxide in proportion, carrying out ball milling, grinding biomass into powder while carrying out hydrolysis reaction by utilizing strong basicity of the calcium hydroxide, carrying out complexation reaction on a hydrolysate and calcium ions to form a precursor with a three-dimensional structure, and carbonizing at the high temperature of 600-1000 ℃ to obtain the calcium-based biochar, wherein the calcium-based biochar is rich in pore channels and organic matters and slowly releases hydroxide ions and calcium ions in a soil environment, the hydroxide ions can improve the pH of the soil, the calcium ions can supplement the alkaline ions in the soil, the organic matters of the soil are improved, meanwhile, potential negative effects of hardening of the calcium salt, imbalance of elements and the like of the soil are avoided, the purpose of regulating acid and supplementing calcium is achieved, and the calcium-based biochar can be used for treating acidified soil.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with the conventional physical crushing modes such as ultrasonic and grinding, the mechanical ball milling method ensures that the biomass has smaller and more uniform particle size; the method has simple and convenient steps, is easy to produce the fine particles and the micro-nano grade biochar raw materials in batch, and has economic and easy realization of required equipment and preparation process.
2. Compared with the conventional biochar modification mode, the ball milling and calcium hydroxide modification mode adopted by the invention simultaneously achieves the purposes of efficient biomass hydrolysis and complexation of hydrolysate and calcium ions, and is environment-friendly, economic and simple to operate.
3. Compared with biochar and calcium hydroxide, the calcium-based biochar based on the agricultural and forestry waste and the calcium hydroxide, which is obtained by the preparation method, can be used for treating the problem of acidified soil.
4. The modified biochar based on the alkali hydrolysis of the agricultural and forestry waste and the biomass is developed, is beneficial to solving the problems of agricultural and forestry waste disposal and acidified soil treatment, is the best mode for realizing the resource utilization and industrialized utilization of the agricultural and forestry waste, can improve the soil structure, improve the pH value of the soil, increase the content of organic matters in the soil, realize the effects of regulating acid, supplementing calcium, increasing the yield of crops and the like after being applied to farmlands, and has very good environmental and ecological benefits.
Drawings
FIG. 1 is an SEM photograph of the preparation of calcium-based biochar by pyrolysis at 900 ℃ in example 3
FIG. 2 is an SEM photograph of the preparation of unmodified biochar by pyrolysis at 900 ℃ in comparative example 3
Detailed Description
In order that the above objects, features and advantages of the present invention can be more clearly understood, the present invention will be further described in detail with reference to the accompanying drawings and the detailed description, wherein the drawings are simplified schematic drawings and only the basic structure of the present invention is illustrated schematically, so that only the structure related to the present invention is shown, and it is to be noted that the embodiments and features of the embodiments in the present application can be combined with each other without conflict. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
First, preparation example
1. Example 1
Step 1. preparation of calcium-based biochar
(1) Physically crushing corn straws, mixing the corn straws with calcium hydroxide according to the mass ratio of 2:1, uniformly mixing the corn straws with water according to the mass ratio of 1:10, putting the mixture into an agate ball milling tank, and simultaneously adding 200g of agate beads into the agate tank;
(2) and placing the agate tank in a planetary ball mill, carrying out ball milling for 5h at the rotating speed of 250 r/min, taking out, and airing to obtain the biochar precursor.
(3) Performing high-temperature pyrolysis treatment on the biochar precursor at 600 ℃ in an atmosphere furnace or a muffle furnace to obtain a calcium-based biochar sample;
comparative example 1: crushing the straws, and directly performing high-temperature pyrolysis treatment at 600 ℃ to obtain a biochar sample.
Step 2. application of acidified soil
0.5g of the calcium-based biochar synthesized in step 1 was added to 50g of acidic soil, 50mL of water was added, and a soil sample was collected after 7 days of treatment. According to the standard method for measuring the pH value of the soil in Chinese agricultural standards, the method comprises the following steps: NY/T1121.2-2006 measures the pH of the soil after 5, 15 and 30 days of culture; according to the national standard soil moisture determination method, namely: GB7172-1987 measures the soil water content after 30 days of culture; the standard method for measuring the organic matter of the soil according to the Chinese agricultural standard comprises the following steps: and NY/T1121.6-2006 measures the organic matter content of the soil after 30 days of culture. The same dosage of comparative example 1 and quicklime are used as a comparison 1.
2. Example 2
Step 1. preparation of calcium-based biochar
(1) Physically crushing the rice straws, mixing the crushed rice straws with calcium hydroxide according to the mass ratio of 5:1, uniformly mixing the crushed rice straws with water according to the mass ratio of 1:5, and putting the mixture into an agate ball-milling tank, wherein 150g of agate round beads are simultaneously added into the agate tank;
(2) and placing the agate tank in a planetary ball mill, performing ball milling for 8 hours at the rotating speed of 200 revolutions per minute, taking out and airing to obtain the biochar precursor.
(3) Performing high-temperature pyrolysis treatment on the biochar precursor at 700 ℃ in an atmosphere furnace or a muffle furnace to obtain a calcium-based biochar sample;
comparative example 2: crushing the straws, and directly carrying out high-temperature pyrolysis treatment at 700 ℃ to obtain a biochar sample.
Step 2. application of acidified soil
0.75g of the calcium-based biochar synthesized in step 1 was added to 50g of acidic soil, 75mL of water was added, and a soil sample was collected after 7 days of treatment. According to the standard method for measuring the pH value of the soil in Chinese agricultural standards, the method comprises the following steps: NY/T1121.2-2006 measures the pH of the soil after 5, 15 and 30 days of culture; according to the national standard soil moisture determination method, namely: GB7172-1987 measures the soil water content after 30 days of culture; the standard method for measuring the organic matter of the soil according to the Chinese agricultural standard comprises the following steps: and NY/T1121.6-2006 measures the organic matter content of the soil after 30 days of culture. The same amount of comparative example 2 and quicklime was used as control 2.
3. Example 3
Step 1. preparation of calcium-based biochar
(1) Physically crushing the wood leftovers, mixing the wood leftovers with calcium hydroxide according to the mass ratio of 10:1, uniformly mixing the wood leftovers with water according to the mass ratio of 1:8, putting the mixture into an agate ball milling tank, and simultaneously adding 200g of agate round beads into the agate tank;
(2) and placing the agate tank in a planetary ball mill, carrying out ball milling for 10h at the rotating speed of 250 r/min, taking out, and airing to obtain the biochar precursor.
(3) Performing high-temperature pyrolysis treatment on the biochar precursor at 900 ℃ in an atmosphere furnace or a muffle furnace to obtain a calcium-based biochar sample;
comparative example 3: crushing the straws, and directly carrying out high-temperature pyrolysis treatment at 900 ℃ to obtain a biochar sample.
Step 2. application of acidified soil
1g of the calcium-based biochar synthesized in step 1 was added to 50g of acidic soil, 50mL of water was added, and a soil sample was collected after 7 days of treatment. According to the standard method for measuring the pH value of the soil in Chinese agricultural standards, the method comprises the following steps: NY/T1121.2-2006 measures the pH of the soil; according to the national standard soil moisture determination method, namely: GB7172-1987 measures the soil water content after 30 days of culture; the standard method for measuring the organic matter of the soil according to the Chinese agricultural standard comprises the following steps: and NY/T1121.6-2006 is used for measuring the organic matter content of the soil. The same amount of comparative example 3 and quicklime was used as control 3.
Second, application example
1. The materials prepared in the examples and comparative examples were subjected to specific surface area analysis, and the test results are shown in table 1:
TABLE 1 specific surface area of the materials prepared
As can be seen from table 1, the results of the specific surface areas of the calcium-based biochar and the biochar in examples 1 to 3 show that compared with biochar, the calcium-based biochar has a higher specific surface area and a more developed pore structure, can further increase the voidage and water retention capacity of soil after being applied to the soil, reduces the volume weight of the soil, is beneficial to the growth of plant roots, and shows great soil application potential.
2. After the soil of the examples and the comparative examples is treated, the pH value, the water content and the organic matter content are detected, and the test results are shown in Table 2:
TABLE 2 test results of soil treated by different treatments
As can be seen from table 2, the pH of the acid soil in example 1 of the present invention is increased from 3.82 before application to 4.64 after 30 days of application, and the increase in pH is significant, and the water content of the soil and the content of organic matter are increased; the calcium-based biochar of examples 2 and 3 increased soil pH by 0.28-0.35 units over the biochar in comparative examples 2 and 3. The change results of the pH after the application for 5-30 days in examples 1-3 show that compared with biochar and quicklime, the calcium-based biochar has the characteristics of porosity, large specific surface area and rich calcium, gradually improves acidified soil, has good buffering capacity and long-acting property, and has the technical characteristics of high carbon content of the biochar and strong acidification inhibiting effect of the quicklime.
In examples 1-3, the biochar raw materials are corn stalks, rice stalks and wood leftovers, and the preparation temperature comprises 600-. In examples 1 to 3, the calcium-based biochar material greatly improves the pH of the soil, improves the water content and organic matter content of the soil, and shows great application potential, which provides technical support for recycling of agricultural, forestry and animal husbandry waste and improvement of farmland acidified soil.
The above examples only show some embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. The preparation method of the calcium-based biochar is characterized by comprising the following steps:
s101, physically crushing wood leftovers, mixing the wood leftovers with calcium hydroxide according to a certain mass ratio, uniformly mixing the wood leftovers with water, putting the mixture into an agate ball milling tank, and simultaneously adding agate round beads into the agate tank;
s201, placing an agate tank in a planetary ball mill, carrying out ball milling for 1-20h at the rotating speed of 150-;
s301, performing 600-1000 ℃ high-temperature pyrolysis treatment on the biochar precursor in an atmosphere furnace or a muffle furnace to obtain a calcium-based biochar sample;
wherein the mass ratio of the wood leftovers to the calcium hydroxide is 1:1-10: 1.
2. The method for preparing calcium-based biochar as claimed in claim 1, wherein the weight ratio of the mixture of wood leftovers and calcium hydroxide to water is 1:2-1: 50.
3. The method as claimed in claim 1, wherein the temperature of the muffle furnace or the atmosphere furnace is increased to 600-1000 ℃ at a temperature rate of 1-10 ℃ for 1-10h by using nitrogen as a protective gas in S301.
4. Calcium-based biochar prepared by the method for preparing calcium-based biochar according to any one of claims 1-3.
5. Use of the calcium-based biochar of claim 4 for acidizing soil improvement.
6. The application according to claim 5, characterized in that it comprises the following steps:
adding the calcium-based biochar of claim 4 to acidified soil in a proportion for at least 5 days.
7. The use of claim 6, wherein the calcium-based biochar is added to acidified soil, and then deionized water is added and mixed uniformly.
8. Use according to claim 7, characterized in that the soil: calcium-based biochar: the weight ratio of water is 100: (0.1-3): (30-300).
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| CN110064369A (en) * | 2019-05-28 | 2019-07-30 | 江西农业大学 | A kind of preparation method and applications of charcoal supported nano-gold metal particles |
| CN111847423A (en) * | 2020-08-20 | 2020-10-30 | 南开大学 | Preparation method and application of phosphorus modified biochar |
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| CN107794050A (en) * | 2017-10-25 | 2018-03-13 | 湖南鼎玖能源环境科技有限公司 | A kind of preparation method and application of charcoal base cadmium pollution soil conditioner |
| CN110064369A (en) * | 2019-05-28 | 2019-07-30 | 江西农业大学 | A kind of preparation method and applications of charcoal supported nano-gold metal particles |
| CN111847423A (en) * | 2020-08-20 | 2020-10-30 | 南开大学 | Preparation method and application of phosphorus modified biochar |
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