CN109107529B - Method for improving cadmium adsorption and fixation capacity of corn straw biochar through abdominal transformation - Google Patents
Method for improving cadmium adsorption and fixation capacity of corn straw biochar through abdominal transformation Download PDFInfo
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Abstract
The invention discloses a method for improving cadmium adsorption fixing capacity of corn straw biochar through over-abdominal conversion, which comprises the steps of mixing fresh corn straws with 0.1% of salt, feeding cattle with only feed, collecting cattle manure excreted by the cattle through the over-abdominal conversion of the cattle, drying, putting into a muffle furnace, controlling the heating rate to be 20 ℃/min under the nitrogen atmosphere, and pyrolyzing for 3 hours at 600-700 ℃ to prepare biochar. The properties of the biochar are obviously changed through the bovine transabdominal transformation, the maximum adsorption quantity of the biochar to cadmium is 161.2-175.4mg/g, and the fixing capacity of the biochar prepared through the bovine transabdominal transformation to soil cadmium is improved by 45.1-47.2%. The method has the remarkable characteristics of low energy consumption, good quality and the like, realizes the multi-stage cyclic utilization of the corn straw resource, and provides a good repairing material for the passivation and repair of the cadmium-polluted soil.
Description
Technical Field
The invention relates to the field of agricultural waste recycling and soil heavy metal passivation and restoration, in particular to a method for improving cadmium adsorption and fixation capacity of corn straw biochar through abdominal transformation.
Background
The pollution situation of heavy metals and the like in soil in China is severe, the safety of agricultural products and the health of human bodies are seriously threatened, and the remediation of the heavy metal polluted soil is very urgent. The in-situ passivation restoration technology for the heavy metal pollution of the soil has the advantages of low cost, simple and convenient operation, quick response, suitability for large-area pollution treatment and the like, and is concerned in the application of soil restoration. The key point of the in-situ passivation and restoration of the heavy metal lies in the development of a passivating agent, and the raw materials of the passivating agent mainly comprise calcareous substances, clay minerals, phosphorus-containing materials, organic fertilizers and the like. Due to the shortage of raw material sources, different passivation effects, secondary pollution and the like, the popularization of the in-situ passivation repair technology is limited. Therefore, the development of cheap, efficient and environment-friendly in-situ passivators becomes a hotspot in the field. Researches in recent years show that the biochar produced by using the agricultural and forestry waste has unique structures and physicochemical properties of rich microporous structures, large specific surface area, strong adsorption force, high pH value, strong decomposition resistance and the like, and has wide application prospects in the aspects of soil improvement, pollution treatment, carbon sequestration and emission reduction, environmental treatment and the like. The biochar serving as an in-situ passivator for repairing heavy metal contaminated soil has strong adsorption capacity on heavy metals, can effectively reduce the effectiveness of the heavy metals in the soil, reduces the toxicity of the biochar on plants and the content of the heavy metals in the plants, and has great repairing potential.
On the other hand, the annual yield of the straws in China currently breaks through 8 multiplied by 108And t, for a long time, the utilization mode of the straw resources in China is single, the industrial chain is short, the economic benefit is poor, the industrialization degree is low, and the improvement of the comprehensive utilization level of the straw is severely restricted. In recent years, a biochar resource utilization technology, namely, the preparation of biochar by using straws, has become the leading edge of the research of straw resource utilization technology. However, the technology can not treat the nutrients such as protein, amino acid, sugar and the like in the strawsThe materials are fully utilized, and simultaneously, due to the characteristics of large biomass of the straws, high water content and the like, a large amount of energy is consumed in the preparation process of the biochar. Therefore, according to the concept of recycling agriculture, straw recycling agriculture characterized by multi-stage recycling of straws is developed, so that the added value of straw resources is increased, the utilization rate of the straw resources is improved, and meanwhile, the biochar prepared from multi-stage utilization products is used for passivating and repairing heavy metal polluted soil by combining with a biochar resource utilization technology, so that the maximization of the economic benefit and the environmental benefit of straw resource utilization is facilitated.
In order to improve the resource utilization efficiency of the corn straws, the research tries to improve the adsorption and fixation capacity of the corn straws to cadmium by feeding the corn straws to cattle, performing abdominal transformation and preparing the biochar by a slow pyrolysis method. The method not only realizes the multi-stage utilization of the corn straw resource, but also provides a good repairing material for the passivation and repair of the cadmium-polluted soil.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a method for improving the cadmium adsorption and fixation capacity of corn straw biochar. In order to achieve the purpose, corn straws are fed to cattle for abdominal transformation, excrement and cow dung are collected, a slow pyrolysis method is used for preparing biochar, and the biochar is used for adsorbing and fixing cadmium in soil. The method not only realizes the multi-stage utilization of the corn straw resource, but also provides a good passivator material for the passivation and restoration of the cadmium-polluted soil.
The method for improving the cadmium adsorption and fixation capacity of the corn straw biochar through abdominal transformation specifically comprises the following steps:
(1) and (3) corn straw abdominal transformation: taking fresh corn straws, cutting into small sections with the size of 2-3cm, mixing with 0.1% of salt, feeding cattle as the only feed, and continuously feeding for more than 4 days;
(2) collecting and treating cow dung: collecting cow dung from the second day of feeding, continuously collecting for more than 3 days, and air-drying the collected cow dung at room temperature, wherein the water content is controlled to be 15-20%;
(3) preparing biochar: putting the dried cow dung into a crucible, putting the crucible into an oven, and drying the cow dung for 22 to 24 hours at the temperature of between 65 and 70 ℃ to control the water content to be between 4 and 8 percent; then, putting the dried cow dung into a muffle furnace, and preparing the biochar by adopting a one-step method for slow pyrolysis; the pyrolysis condition is that the temperature is raised to 600-700 ℃ at the speed of 20 ℃/min in the nitrogen atmosphere, the temperature is kept for 3 hours, the biochar obtained after cooling is ground and sieved by a 40-mesh sieve.
Adsorption and fixation of cadmium: carrying out isothermal adsorption test of cadmium on the cow dung biochar prepared by cracking, wherein the concentration gradient of cadmium is 1-300mg/L, the solid-liquid ratio is 0.002, and the maximum adsorption quantity of cadmium is simulated and calculated by adopting a Langmuir equation; in a fixation test of the biochar to the cadmium in the soil, the adding proportion of the biochar is 0.5%, the field water holding capacity is kept at 60%, the content of the cadmium in the soil in an effective state is measured after balanced culture for one week, and the fixation efficiency of the cadmium in the soil is calculated.
By means of the scheme, the invention has the following advantages: (1) according to the invention, the corn straws are subjected to abdominal transformation, so that nutrients such as protein, amino acid and sugar in the straws are fully utilized, the biomass of the corn straws is greatly reduced, and the reduction is realized; (2) according to the invention, the biochar is prepared by one-step slow pyrolysis by using the abdominal conversion product (cow dung), so that the energy consumption for preparing the corn straw biochar is greatly reduced. (3) According to the invention, the multi-stage utilization of the corn straws is organically combined with the utilization technology of the biochar resources, so that the cow dung is changed into valuable, and the adsorption and fixation capacity of the biochar on cadmium is improved.
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FIG. 1A is a scanning electron microscope image of corn stalk charcoal at 600 deg.C in comparison example;
FIG. 1B is a scanning electron microscope image of corn stalk charcoal at 700 ℃ in a comparative example;
FIG. 1C is a scanning electron microscope image of biochar obtained by the laparotomy conversion of corn stalks in example 1 at 600 ℃;
FIG. 1D is the scanning electron microscope image of biochar obtained by the laparotomy conversion of corn stalks in example 1 at 700 ℃.
FIG. 2 is a comparison of cadmium isothermal adsorption curves for example 2 and comparative biochar;
FIG. 3A is a comparison of the change in available cadmium content in the soil of example 3 and a comparative example of biochar;
FIG. 3B is a comparison of the cadmium fixation efficiency of the biochar soil of example 3 and a comparative example.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Comparative example
Meanwhile, taking fresh corn straws, cutting the fresh corn straws into small sections with the size of 2-3cm, air-drying for 1 week, drying for 22 hours at 70 ℃, then putting the corn straws into a muffle furnace, and preparing the biochar by adopting a one-step method for slow pyrolysis. The pyrolysis condition is that the temperature is raised to 600 ℃ or 700 ℃ at the speed of 20 ℃/min in the nitrogen atmosphere, and the temperature is naturally reduced to the room temperature after 3 hours of pyrolysis. Taking out the product, grinding and sieving the product with a 40-mesh sieve, and storing the product for later use.
Example 1
(1) And (3) corn straw abdominal transformation: taking fresh corn straws, cutting into small sections with the size of 2-3cm, mixing with 0.1% of salt, feeding cattle as the only feed, and continuously feeding for more than 4 days.
(2) Collecting and treating cow dung: collecting cow dung from the second day of feeding, continuously collecting for more than 3 days, air drying the collected cow dung at room temperature, and controlling the water content at 15-20%.
(3) Preparing biochar: and (3) putting the dried cow dung into a crucible, putting the crucible into an oven, and drying the cow dung for 22 to 24 hours at the temperature of between 65 and 70 ℃ while controlling the water content to be between 4 and 8 percent. And then putting the dried cow dung into a muffle furnace, and preparing the biochar by adopting one-step slow pyrolysis. The pyrolysis condition is that the temperature is raised to 600 ℃ or 700 ℃ at the speed of 20 ℃/min in the nitrogen atmosphere, and the temperature is naturally reduced to the room temperature after 3 hours of pyrolysis. Taking out the product, grinding and sieving the product with a 40-mesh sieve, and storing the product for later use.
The pH, ash content, elemental composition and BET specific surface area of the biochar product were determined and the data are shown in Table 1. Meanwhile, the morphology characteristics of the biochar are analyzed by adopting a scanning electron microscope, and the results are shown in fig. 1A to 1D.
As can be seen from the table 1, under the conditions of 600-700 ℃, the ash content and the specific surface area of the biological carbon of the over-abdominal conversion corn straws are obviously increased, wherein the ash content is increased by 58.3-83.4%, and the specific surface area is increased by 4.0-4.8 times. Meanwhile, as can be seen from fig. 1, the corn straw biochar has smooth surface and less porous structures in comparison example, and the surface porous structures of the belly-converted corn straw biochar are obviously increased and are arranged in order, so that the specific surface area is obviously increased.
TABLE 1 basic physicochemical properties of comparative examples corn stalk biochar and laparotomy transformed corn stalk biochar
Example 2
(1) And (3) corn straw abdominal transformation: taking fresh corn straws, cutting into small sections with the size of 2-3cm, mixing with 0.1% of salt, feeding cattle as the only feed, and continuously feeding for more than 4 days.
(2) Collecting and treating cow dung: collecting cow dung from the second day of feeding, continuously collecting for more than 3 days, air drying the collected cow dung at room temperature, and controlling the water content at 15-20%.
(3) Preparing biochar: and (3) putting the dried cow dung into a crucible, putting the crucible into an oven, and drying the cow dung for 22 to 24 hours at the temperature of between 65 and 70 ℃ while controlling the water content to be between 4 and 8 percent. And then putting the dried cow dung into a muffle furnace, and preparing the biochar by adopting one-step slow pyrolysis. The pyrolysis condition is that the temperature is raised to 600 ℃ or 700 ℃ at the speed of 20 ℃/min in the nitrogen atmosphere, and the temperature is naturally reduced to the room temperature after 3 hours of pyrolysis. Taking out the product, grinding and sieving the product with a 40-mesh sieve, and storing the product for later use.
(4) Adsorption of cadmium: and (3) carrying out isothermal adsorption test of cadmium on the cow dung biochar prepared by cracking, and comparing the adsorption capacity of the comparative corn straw biochar to cadmium with that of the laparotomy conversion corn straw biochar, wherein the specific result is shown in figure 2. Wherein the cadmium concentration gradient is 1-300mg/L, the solid-liquid ratio is 0.002, and the maximum adsorption quantity of cadmium is simulated and calculated by adopting a Langmuir equation.
Fig. 2 is a cadmium adsorption curve of the biochar product in the embodiment, and it can be seen from fig. 2 that the adsorption amount of cadmium by the laparotomy conversion corn stalk biochar is far higher than that of the comparative example corn stalk biochar. The maximum adsorption amounts of cadmium of the laparotomy conversion corn stalk biochar prepared at 600 ℃ and 700 ℃ are 161.2mg/g and 175.4mg/g respectively, and compared with the corn stalk biochar of the comparative example, the adsorption amount of cadmium is increased by 1.6-2.1 times.
Example 3
(1) And (3) corn straw abdominal transformation: taking fresh corn straws, cutting into small sections with the size of 2-3cm, mixing with 0.1% of salt, feeding cattle as the only feed, and continuously feeding for more than 4 days.
(2) Collecting and treating cow dung: collecting cow dung from the second day of feeding, continuously collecting for more than 3 days, air drying the collected cow dung at room temperature, and controlling the water content at 15-20%.
(3) Preparing biochar: and (3) putting the dried cow dung into a crucible, putting the crucible into an oven, and drying the cow dung for 22 to 24 hours at the temperature of between 65 and 70 ℃ while controlling the water content to be between 4 and 8 percent. And then putting the dried cow dung into a muffle furnace, and preparing the biochar by adopting one-step slow pyrolysis. The pyrolysis condition is that the temperature is raised to 600 ℃ or 700 ℃ at the speed of 20 ℃/min in the nitrogen atmosphere, and the temperature is naturally reduced to the room temperature after 3 hours of pyrolysis. Taking out the product, grinding and sieving the product with a 40-mesh sieve, and storing the product for later use.
(4) Fixation of cadmium: and (3) carrying out a cadmium fixing test on the cow dung biochar prepared by cracking, and comparing the fixing capacity of the corn straw biochar to cadmium of the over-abdomen converted corn straw biochar, wherein the specific result is shown in figure 3. In a fixation test, 100g of cadmium-contaminated soil is taken, the adding proportion of biochar is 0.5%, the biochar is fully and uniformly mixed, the field water holding capacity is kept at 60%, the effective cadmium content of the soil is measured after balanced culture for one week, and the fixation efficiency of the cadmium in the soil is calculated.
Fig. 3A and 3B show the cadmium fixing effect of the biochar product in this example, and it can be seen from fig. 3A that the cadmium fixing ability of the laparotomy transformed corn stalk biochar is much higher than that of the comparative example corn stalk biochar. The soil has a concentration of 600 mug/L, 0.5 percent of biochar is used, and the content of the effective cadmium is obviously reduced. As can be seen from fig. 3B, the immobilization efficiency of cadmium of the overdriven corn stalk biochar prepared under the conditions of 600 ℃ and 700 ℃ was 80.9% and 86.2%, respectively, and the immobilization efficiency of cadmium was improved by 45.1-47.2% as compared to the comparative corn stalk biochar.
Claims (6)
1. The method for improving the cadmium adsorption and fixation capacity of the corn straw biochar through abdominal transformation is characterized by comprising the following steps: fresh corn straws are converted through cattle belly crossing, and then biochar is prepared by a slow pyrolysis method, so that the adsorption and fixation capacity of the biochar on cadmium is improved; the method comprises the following steps:
(1) and (3) corn straw abdominal transformation: taking fresh corn straws, cutting the fresh corn straws into small sections with uniform sizes, mixing with a proper amount of salt, feeding the cattle as a unique feed, and continuously feeding for more than 4 days;
(2) collecting and treating cow dung: collecting cow dung from the next day of feeding, and air-drying the obtained cow dung at room temperature;
(3) preparing biochar: and (3) putting the cow dung subjected to air drying treatment into a crucible, putting the crucible into an oven for drying, putting the cow dung subjected to preheating treatment into a muffle furnace, preparing biochar by slow pyrolysis under the anoxic condition by adopting a one-step method, and grinding and sieving the biochar prepared by pyrolysis.
2. The method for improving cadmium adsorption and fixation capacity of corn stalk biochar by means of over-abdominal transformation according to claim 1, wherein the method comprises the following steps: cutting the corn straws in the step (1) into small sections of 2-3cm, and mixing with 0.1% of salt.
3. The method for improving cadmium adsorption and fixation capacity of corn straw biochar through laparotomy transformation according to claim 1, which is characterized in that: and (3) air-drying the cow dung in the step (2), wherein the water content is controlled to be 15-20%.
4. The method for improving cadmium adsorption and fixation capacity of corn straw biochar through laparotomy transformation according to claim 1, which is characterized in that: the drying temperature in the step (3) is 65-70 ℃, the drying time is 22-24 hours, and the water content is 4-8%.
5. The method for improving cadmium adsorption and fixation capacity of corn straw biochar through laparotomy transformation according to claim 1, which is characterized in that: the one-step pyrolysis condition in the step (3) is that the temperature is raised to 600-700 ℃ at a speed of 20 ℃/min in the nitrogen atmosphere, the temperature is kept for 3 hours, and the biochar is obtained after cooling.
6. The method for improving cadmium adsorption and fixation capacity of corn straw biochar through laparotomy transformation according to claim 1, which is characterized in that: and (4) grinding the biochar in the step (3) and sieving the biochar with a 40-mesh sieve.
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| CN102113623A (en) * | 2011-03-25 | 2011-07-06 | 曹孟 | Method for producing biological particle grain-saving straw feed |
| CN105921110A (en) * | 2016-06-02 | 2016-09-07 | 环境保护部华南环境科学研究所 | Preparation method and application of cow dung biological carbon |
| KR20180029125A (en) * | 2016-09-09 | 2018-03-20 | 대한민국(농촌진흥청장) | Method for manufacturing pellet type of slow releasing fertilizer using biochar and manure compost |
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| CN102113623A (en) * | 2011-03-25 | 2011-07-06 | 曹孟 | Method for producing biological particle grain-saving straw feed |
| CN105921110A (en) * | 2016-06-02 | 2016-09-07 | 环境保护部华南环境科学研究所 | Preparation method and application of cow dung biological carbon |
| KR20180029125A (en) * | 2016-09-09 | 2018-03-20 | 대한민국(농촌진흥청장) | Method for manufacturing pellet type of slow releasing fertilizer using biochar and manure compost |
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