CN108160037B - Modified biochar and preparation method thereof - Google Patents
Modified biochar and preparation method thereof Download PDFInfo
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- CN108160037B CN108160037B CN201810101721.XA CN201810101721A CN108160037B CN 108160037 B CN108160037 B CN 108160037B CN 201810101721 A CN201810101721 A CN 201810101721A CN 108160037 B CN108160037 B CN 108160037B
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Abstract
The invention discloses a preparation method of modified biochar, which utilizes bagasse as a raw material, not only carries out resource utilization on the bagasse, but also utilizes the bagasse to prepare the modified biochar with small particle size, larger specific surface area and more prominent micropore structure, not only can adsorb more nutrient ions such as iron, nitrogen, phosphorus, potassium, silicon and the like in micropores of the modified biochar, but also can replace the nutrient ions in the micropores with cadmium and arsenic ions, and simultaneously reduces the content of cadmium and arsenic in soil. In addition, the modified biochar disclosed by the invention is simple in component and low in cost, contains nutrient elements required by plants, and also contains components for solidifying cadmium and arsenic, so that the absorption of the plants on the cadmium and arsenic can be reduced, and the yield of the plants can be improved.
Description
Technical Field
The invention relates to the technical field of environmental protection engineering, in particular to modified biochar and a preparation method thereof.
Background
In heavy metal contaminated soil, the arsenic and cadmium combined pollution problem is prominent, about one sixth of rice fields are subjected to arsenic and cadmium combined pollution of different degrees, and the pollution area is increased year by year. Mining and smelting are main approaches for arsenic-cadmium combined pollution of soil, waste slag and tailing sand usually contain high-concentration arsenic and cadmium waste ore or tailing sand, and after natural weathering and rain erosion, arsenic and cadmium are released into the soil, so that the soil suffers from serious arsenic-cadmium combined pollution. Too high cadmium and arsenic may cause gradual variation in soil biological properties, resulting in degradation of soil quality. And the arsenic and cadmium in the soil have strong biological mobility and toxicity, are easily absorbed and accumulated by crops, and directly influence the quality and yield of the crops. And poses serious health risks to humans through the food chain. Therefore, how to repair the arsenic-cadmium composite polluted soil becomes a great problem to be solved urgently.
In recent years, the application of the biochar material in the aspect of heavy metal pollution remediation is gradually paid attention. The biochar raw material has wide source, a large amount of microporous structures, a large specific surface area and strong adsorption capacity, and the adsorption behavior of the biochar raw material can influence the processes of migration, transformation, biological ecological effect of heavy metals in the environment, control and restoration of polluted environment media and the like. The surface of the biochar contains a large number of functional groups such as carboxyl, hydroxyl, acid anhydride and the like and negative charges, and the specific surface area is large. After the biological carbon is applied to soil, the biological carbon can adsorb heavy metals and fix the heavy metals on the surface, so that the biological effectiveness of most heavy metals is obviously reduced, and the physical, chemical and biological characteristics of the soil can be improved, so that the soil fertility and the crop yield are improved to a certain extent.
However, the biochar material can obviously improve the flowability and effectiveness of arsenic in soil. Research reports that the biochar can reduce the concentration of cadmium and zinc in soil filtrate (by 300 times and 45 times respectively), but the concentration of arsenic in the filtrate obviously improves the quotient, and the biochar improves the mobility of arsenic. In addition, research reports that the addition of biochar can improve the microenvironment of rice rhizosphere and promote the formation of iron films on the root surface, the concentrations of Cd, Zn and Pb in rice roots can be respectively reduced by 98%, 83% and 72%, but the concentration of arsenic is increased by 327%. Therefore, how to improve the composition and the property of the biochar, improve the arsenic adsorption and fixation capacity of the biochar, and reduce the effectiveness of arsenic and cadmium in soil at the same time is a highly challenging task and also a work with great environmental significance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a modified biochar and a preparation method and a using method thereof, and by modifying the biochar, the flowability and effectiveness of arsenic in soil can be reduced, the content of cadmium and arsenic in plants can be reduced, and the yield of the plants can be improved.
In order to solve the technical problem, the invention provides a preparation method of modified biochar, which is characterized by comprising the following steps:
s1: drying bagasse and crushing to obtain bagasse powder with particle size less than 0.2 mm;
s2: adding the sugarcane powder in the step S1 into an iron solution, and stirring by using a stirrer to obtain a sugarcane mixture A;
s3: adding the sugarcane mixture A in the step S2 into a nitrogen-phosphorus-potassium-silicon mixed solution, and oscillating for 1-3 hours to obtain a sugarcane mixture B;
s4: drying the sugarcane mixture B in the step S3, and putting the dried sugarcane mixture B into an atmosphere furnace for carbonization, wherein protective gas is introduced into the atmosphere furnace, the temperature is raised to 300-500 ℃ at every minute by 15-30 ℃, and the temperature is kept for 1-3 hours, so as to obtain a biochar primary product;
s5: and (4) adding chitosan and biological starch into the primary biological carbon product obtained in the step S4, uniformly stirring, and drying to obtain the modified biological carbon.
As an improvement of the scheme, the mass ratio of the iron to the sugarcane powder in the step S2 is 1:1.25-1: 40.
As a modification of the above, the iron solution in step S2 includes ferric chloride and a catalyst.
As a modification of the above, the catalyst is platinum or palladium.
As an improvement of the proposal, the nitrogen-phosphorus-potassium-silicon mixed solution in the step S3 comprises KNO of 50-70mg/L3Solution, 50-70mg/L KH2PO4Solution and 50-70mg/L silicate solution.
As a modification of the above, the silicate solution is at least one of a sodium silicate solution, a potassium silicate solution, a sodium peroxydisilicate solution, and a sodium metasilicate solution.
As a modification of the above, the protective gas in step S4 is nitrogen and oxygen.
As a modification of the above, the volume ratio of the nitrogen gas to the oxygen gas in step S4 is 30:1 to 5: 1.
As an improvement of the scheme, the biological starch in the step S5 is corn flour, sweet potato flour, potato flour or tapioca flour.
S4: correspondingly, the invention also provides modified biochar by drying the sugarcane mixture B in the step S3, wherein the modified biochar is prepared by adopting the method.
The implementation of the invention has the following beneficial effects:
1. according to the preparation method of the modified biochar provided by the invention, bagasse is used as a raw material, so that the bagasse is recycled, the modified biochar prepared from the bagasse is small in particle size, larger in specific surface area and more prominent in micropore structure, more nutrient ions such as iron, nitrogen, phosphorus, potassium and silicon can be adsorbed in micropores of the modified biochar, the nutrient ions in the micropores can be replaced by cadmium and arsenic ions, and the content of cadmium and arsenic in soil is reduced. In addition, the modified biochar disclosed by the invention is simple in component and low in cost, contains nutrient elements required by plants, and also contains components for solidifying cadmium and arsenic, so that the absorption of the plants on the cadmium and arsenic can be reduced, and the yield of the plants can be improved.
2. According to the preparation method of the modified biochar, provided by the invention, the biochar primary product in the step S3 is added into the nitrogen-phosphorus-potassium-silicon mixed solution, so that the obtained modified biochar not only can improve the plant product, but also can improve the arsenic adsorption and fixation capacity of the biochar, and the effectiveness of arsenic and cadmium in soil is reduced at the same time.
3. According to the preparation method of the modified biochar, provided by the invention, the protective gas is introduced into the atmosphere furnace, so that the carbonization time of bagasse can be reduced, and iron ions adsorbed in sugarcane powder can be prevented from undergoing a carbonization reaction. In addition, the biochar primary product is added into the nitrogen-phosphorus-potassium-silicon mixed solution, so that nitrogen, phosphorus, potassium and silicon ions can be adsorbed into the biochar primary product, then chitosan and biological starch are added into the biochar primary product, and nutrient ions such as iron, nitrogen, phosphorus, potassium and silicon can be wrapped in biochar, so that the nutrient ions such as iron, nitrogen, phosphorus, potassium and silicon can be slowly released into soil, the using amount of fertilizer and biochar is reduced, and the problem that the nitrogen, phosphorus and potassium ions are quickly released into the soil to cause the loss of a large amount of nutrient nitrogen, phosphorus and potassium ions and the eutrophication of a water body is caused is avoided.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below.
The invention provides a preparation method of modified biochar, which is characterized by comprising the following steps:
s1: drying bagasse and crushing to obtain bagasse powder with particle size less than 0.2 mm;
s2: adding the sugarcane powder in the step S1 into an iron solution, and stirring by using a stirrer to obtain a sugarcane mixture A;
s3: adding the sugarcane mixture A in the step S2 into a nitrogen-phosphorus-potassium-silicon mixed solution, and oscillating for 1-3 hours to obtain a sugarcane mixture B;
s4: drying the sugarcane mixture B in the step S3, and putting the dried sugarcane mixture B into an atmosphere furnace for carbonization, wherein protective gas is introduced into the atmosphere furnace, the temperature is raised to 300-500 ℃ at every minute by 15-30 ℃, and the temperature is kept for 1-3 hours, so as to obtain a biochar primary product;
s5: and (4) adding chitosan and biological starch into the primary biological carbon product obtained in the step S4, uniformly stirring, and drying to obtain the modified biological carbon.
S4: drying the sugarcane mixture B in the step S3
The bagasse, which remains after sugar extraction, contains a large amount of cellulose, hemicellulose and lignin. Wherein the bagasse fiber has a length of about 0.65-2.17 mm and a width of 21-28 μm. Although the fiber form is inferior to wood and bamboo, the fiber form is better than rice and wheat straw fiber. The modified biochar provided by the invention utilizes bagasse as a raw material, so that the bagasse is recycled, the modified biochar prepared from the bagasse is small in particle size, larger in specific surface area and more prominent in microporous structure, more nutrient ions such as iron, nitrogen, phosphorus, potassium, silicon and the like can be adsorbed in micropores of the modified biochar, the nutrient ions in the micropores can be replaced by cadmium and arsenic ions, and the content of cadmium and arsenic in soil is reduced. In addition, the modified biochar disclosed by the invention is simple in component and low in cost, contains nutrient elements required by plants, and also contains components for solidifying cadmium and arsenic, so that the absorption of the plants on the cadmium and arsenic can be reduced, and the yield of the plants can be improved.
The modified charcoal provided by the invention adsorbs a large amount of silicon, wherein the silicon can improve the product of plants, can also improve the arsenic adsorption and fixation capacity of the charcoal, and reduces the effectiveness of arsenic and cadmium in soil.
The preparation method of the modified biochar is simple, wherein the protective gas is introduced into the atmosphere furnace, so that the carbonization time of bagasse can be shortened, and iron ions adsorbed in sugarcane powder can be prevented from undergoing carbonization reaction. In addition, the biochar primary product is added into the nitrogen-phosphorus-potassium-silicon mixed solution, so that nitrogen, phosphorus, potassium and silicon ions can be adsorbed into the biochar primary product, then chitosan and biological starch are added into the biochar primary product, and nutrient ions such as iron, nitrogen, phosphorus, potassium and silicon can be wrapped in biochar, so that the nutrient ions such as iron, nitrogen, phosphorus, potassium and silicon can be slowly released into soil, the using amount of fertilizer and biochar is reduced, and the problem that the nitrogen, phosphorus and potassium ions are quickly released into the soil to cause the loss of a large amount of nutrient nitrogen, phosphorus and potassium ions and the eutrophication of a water body is caused is avoided.
It should be noted that the mass ratio of the iron to the sugarcane powder in step S2 is 1:1.25-1: 40. When the mass ratio of the iron to the sugarcane powder is less than 1:1.25, excessive iron is adsorbed to the sugarcane powder, so that the modification of the biochar is not facilitated; when the mass ratio of the iron to the sugarcane powder is more than 1:40, the content of the iron adsorbed into the modified biochar is too low, the modifying capability of the modified biochar on soil is weakened, and the capability of the modified biochar for curing cadmium and arsenic is reduced.
In order to reduce the carbonization time of the sugar cane powder, the iron solution in step S2 includes ferric chloride and a catalyst. Wherein the catalyst is platinum and palladium. Specifically, in the process of carbonizing the sugarcane powder, the catalyst plays a catalytic role, the carbonization of the sugarcane powder is accelerated, and the carbonization time is shortened.
Specifically, the catalyst can promote iron ions to be rapidly adsorbed into the bagasse powder, and can accelerate the carbonization time of the sugarcane mixture, so that the sugarcane mixture is more fully carbonized, the particle size of the modified biochar is small, the specific surface area is larger, and the microporous structure is more prominent.
The nitrogen, phosphorus, potassium and silicon mixed solution in the step S3 comprises KNO of 50-70mg/L3Solution, 50-70mg/L KH2PO4Solution and 50-70mg/L silicate solution. Preferably, the silicate solution is at least one of a sodium silicate solution, a potassium silicate solution, a sodium peroxydisilicate solution, and a sodium metasilicate solution. When KNO3When the concentration of the solution is less than 50mg/L, the concentration is too low, and nitrogen and potassium ions cannot be fully adsorbed to the biochar primary product; when KNO3When the concentration of the solution is more than 70mg/L, excessive nitrogen and potassium ions are adsorbed to the biochar primary product, so that the adsorption of other ions is inhibited. When KH2PO4When the concentration of the solution is less than 50mg/L, the concentration is too low, and potassium and phosphorus ions cannot be fully adsorbed to the biochar primary product; when KH2PO4When the concentration of the solution is more than 70mg/L, excessive potassium and phosphorus ions are adsorbed to the biochar primary product, so that the adsorption of other ions is inhibited. When the concentration of the silicate solution is less than 50mg/L, the concentration is too low, and silicon ions cannot be fully adsorbed to the biochar primary product; when the concentration of the silicate solution is more than 70mg/L, excessive silicon ions are adsorbed to the charcoal primary product, thereby inhibiting the adsorption of other ions. Preferably, the silicate solution is at least one of a sodium silicate solution, a potassium silicate solution, a sodium peroxydisilicate solution, and a sodium sheet silicate solution. The sodium silicate, the potassium silicate, the sodium peroxydisilicate and the sodium metasilicate belong to water-soluble silicon fertilizers and can be effectively dissolved in soil, so that arsenic in the soil can be effectively solidified and can be quickly replaced, and the modified charcoal can conveniently absorb the arsenic in the soil.
In order to reduce the carbonization time of the sugarcane powder while preventing the iron ions adsorbed in the sugarcane powder from undergoing a carbonization reaction, the protective gas in step S4 is nitrogen and oxygen. Preferably, the volume ratio of nitrogen to oxygen is 30:1 to 5: 1. When the volume ratio of the nitrogen to the oxygen is less than 5:1, the content of the oxygen is too much, so that the carbonization time is increased; when the volume ratio of nitrogen to oxygen is more than 30:1, the content of oxygen is too low, so that the sugarcane powder is too carbonized, modified biochar is not favorably formed, and iron adsorbed in the sugarcane powder is also easily carbonized.
Wherein the biological starch in step S5 is corn flour, sweet potato flour, potato flour or tapioca flour.
Correspondingly, the invention also provides modified biochar which is prepared by the method.
The invention is further illustrated by the following specific examples
Example 1
A preparation method of modified biochar comprises the following steps:
s1: drying bagasse and crushing to obtain bagasse powder with particle size less than 0.2 mm;
s2: adding 100g of the sugarcane powder obtained in the step S1 into 1L of iron solution, and stirring by using a stirrer to obtain a sugarcane mixture A, wherein the iron solution contains 12.08 g of FeCl3·H2O；
S3: adding the sugarcane mixture A obtained in the step S2 into 5 liters of nitrogen-phosphorus-potassium-silicon mixed solution, and oscillating for 1 hour to obtain a sugarcane mixture B, wherein the nitrogen-phosphorus-potassium-silicon mixed solution comprises 50mg/L KNO3Solution, 50mg/L KH2PO4Solution and 50mg/L sodium silicate solution;
s4: drying the sugarcane mixture B in the step S3, and putting the dried sugarcane mixture into an atmosphere furnace for carbonization, wherein protective nitrogen and oxygen are introduced into the atmosphere furnace, the volume ratio of the nitrogen to the oxygen is 30:1, the temperature is raised by 15 ℃ per minute, the temperature is raised to 300 ℃ and kept for 3 hours, and a biochar primary product is obtained;
s5: and (4) adding the chitosan and the corn flour into the primary biochar product obtained in the step S4, uniformly stirring, and drying to obtain the modified biochar.
Example 2
A preparation method of modified biochar comprises the following steps:
s1: drying bagasse and crushing to obtain bagasse powder with particle size less than 0.2 mm;
s2: adding 100g of the sugarcane powder obtained in the step S1 into 1L of iron solution, and stirring with a stirrer to obtain sugarcaneMixture A, in which the iron solution contained 24.15 g FeCl3·H2O；
S3: adding the sugarcane mixture A obtained in the step S2 into 5 liters of nitrogen-phosphorus-potassium-silicon mixed solution, and oscillating for 1 hour to obtain a sugarcane mixture B, wherein the nitrogen-phosphorus-potassium-silicon mixed solution comprises 50mg/L KNO3Solution, 50mg/L KH2PO4Solution and 50mg/L potassium silicate solution;
s4: drying the sugarcane mixture B in the step S3, and putting the dried sugarcane mixture into an atmosphere furnace for carbonization, wherein protective nitrogen and oxygen are introduced into the atmosphere furnace, the volume ratio of the nitrogen to the oxygen is 25:1, the temperature is raised by 15 ℃ per minute, the temperature is raised to 300 ℃ and kept for 2.7 hours, and a biochar primary product is obtained;
s5: and (4) adding the chitosan and the corn flour into the primary biochar product obtained in the step S4, uniformly stirring, and drying to obtain the modified biochar.
Example 3
A preparation method of modified biochar comprises the following steps:
s1: drying bagasse and crushing to obtain bagasse powder with particle size less than 0.2 mm;
s2: adding 100g of the sugarcane powder obtained in the step S1 into 1L of iron solution, and stirring by using a stirrer to obtain a sugarcane mixture A, wherein the iron solution contains 48.31 g of FeCl3·H2O；
S3: adding the sugarcane mixture A obtained in the step S2 into 5 liters of nitrogen-phosphorus-potassium-silicon mixed solution, and oscillating for 1 hour to obtain a sugarcane mixture B, wherein the nitrogen-phosphorus-potassium-silicon mixed solution comprises 60mg/L KNO3Solution, 60mg/L KH2PO4Solution and 60mg/L sodium metasilicate solution;
s4: drying the sugarcane mixture B in the step S3, and putting the dried sugarcane mixture into an atmosphere furnace for carbonization, wherein protective nitrogen and oxygen are introduced into the atmosphere furnace, the volume ratio of the nitrogen to the oxygen is 20:1, the temperature is raised by 15 ℃ per minute, the temperature is raised to 300 ℃ and kept for 2.3 hours, and a biochar primary product is obtained;
s5: and (4) adding the chitosan and the corn flour into the primary biochar product obtained in the step S4, uniformly stirring, and drying to obtain the modified biochar.
Example 4
A preparation method of modified biochar comprises the following steps:
s1: drying bagasse and crushing to obtain bagasse powder with particle size less than 0.2 mm;
s2: adding 100g of the sugarcane powder obtained in the step S1 into 1L of iron solution, and stirring by using a stirrer to obtain a sugarcane mixture A, wherein 96.61 g of FeCl is contained in the iron solution3·H2O；
S3: adding the sugarcane mixture A obtained in the step S2 into 5 liters of nitrogen-phosphorus-potassium-silicon mixed solution, and oscillating for 1 hour to obtain a sugarcane mixture B, wherein the nitrogen-phosphorus-potassium-silicon mixed solution comprises 60mg/L KNO3Solution, 60mg/L KH2PO4Solution and 60mg/L sodium peroxydisilicate solution;
s4: drying the sugarcane mixture B in the step S3, and putting the dried sugarcane mixture into an atmosphere furnace for carbonization, wherein protective nitrogen and oxygen are introduced into the atmosphere furnace, the volume ratio of the nitrogen to the oxygen is 15:1, the temperature is raised by 15 ℃ per minute, the temperature is raised to 300 ℃ and kept for 2 hours, and a biochar primary product is obtained;
s5: and (4) adding the chitosan and the corn flour into the primary biochar product obtained in the step S4, uniformly stirring, and drying to obtain the modified biochar.
Example 5
A preparation method of modified biochar comprises the following steps:
s1: drying bagasse and crushing to obtain bagasse powder with particle size less than 0.2 mm;
s2: adding 100g of the sugarcane powder obtained in the step S1 into 1L of iron solution, and stirring by using a stirrer to obtain a sugarcane mixture A, wherein the iron solution contains 193.22 g of FeCl3·H2O；
S3: adding the sugarcane mixture A obtained in the step S2 into 5 liters of nitrogen, phosphorus, potassium and silicon mixtureMixing the solution, shaking for 1 hr to obtain sugarcane mixture B, wherein the mixed solution of nitrogen, phosphorus, potassium and silicon comprises 70mg/L KNO3Solution, 70mg/L KH2PO4The solution and 70mg/L of mixed solution of sodium silicate and potassium silicate;
s4: drying the sugarcane mixture B in the step S3, and putting the dried sugarcane mixture into an atmosphere furnace for carbonization, wherein protective nitrogen and oxygen are introduced into the atmosphere furnace, the volume ratio of the nitrogen to the oxygen is 10:1, the temperature is raised by 15 ℃ per minute, the temperature is raised to 300 ℃ and kept for 1.8 hours, and a biochar primary product is obtained;
s5: and (4) adding the chitosan and the corn flour into the primary biochar product obtained in the step S4, uniformly stirring, and drying to obtain the modified biochar.
Example 6
A preparation method of modified biochar comprises the following steps:
s1: drying bagasse and crushing to obtain bagasse powder with particle size less than 0.2 mm;
s2: adding 100g of the sugarcane powder obtained in the step S1 into 1L of iron solution, and stirring by using a stirrer to obtain a sugarcane mixture A, wherein the iron solution contains 386.44 g of FeCl3·H2O；
S3: adding the sugarcane mixture A obtained in the step S2 into 5 liters of nitrogen-phosphorus-potassium-silicon mixed solution, and oscillating for 1 hour to obtain a sugarcane mixture B, wherein the nitrogen-phosphorus-potassium-silicon mixed solution comprises 70mg/L KNO3Solution, 70mg/L KH2PO4The solution and 70mg/L of a mixed solution of sodium silicate, potassium silicate and sodium peroxydisilicate;
s4: drying the sugarcane mixture B in the step S3, and putting the dried sugarcane mixture into an atmosphere furnace for carbonization, wherein protective nitrogen and oxygen are introduced into the atmosphere furnace, the volume ratio of the nitrogen to the oxygen is 5:1, the temperature is raised by 15 ℃ per minute, the temperature is raised to 300 ℃ and kept for 1.2 hours, and a biochar primary product is obtained;
s5: and (4) adding the chitosan and the corn flour into the primary biochar product obtained in the step S4, uniformly stirring, and drying to obtain the modified biochar.
Example 7
A preparation method of modified biochar comprises the following steps:
s1: drying bagasse and crushing to obtain bagasse powder with particle size less than 0.2 mm;
s2: adding 100g of the sugarcane powder obtained in the step S1 into 1L of iron solution, and stirring by using a stirrer to obtain a sugarcane mixture A, wherein the iron solution contains 12.08 g of FeCl3·H2O；
S3: adding the sugarcane mixture A obtained in the step S2 into 5 liters of nitrogen-phosphorus-potassium-silicon mixed solution, and oscillating for 1 hour to obtain a sugarcane mixture B, wherein the nitrogen-phosphorus-potassium-silicon mixed solution comprises 55mg/L KNO3Solution, 55mg/L KH2PO4The solution and 55mg/L of a mixed solution of sodium silicate, potassium silicate, sodium peroxydisilicate and sodium metasilicate;
s4: drying the sugarcane mixture B in the step S3, and putting the dried sugarcane mixture into an atmosphere furnace for carbonization, wherein protective nitrogen and oxygen are introduced into the atmosphere furnace, the volume ratio of the nitrogen to the oxygen is 30:1, the temperature is raised to 20 ℃ per minute, the temperature is raised to 400 ℃ and kept for 3 hours, and a biochar primary product is obtained;
s5: and (4) adding chitosan and sweet potato powder into the primary biochar product obtained in the step S4, uniformly stirring, and drying to obtain the modified biochar.
Example 8
A preparation method of modified biochar comprises the following steps:
s1: drying bagasse and crushing to obtain bagasse powder with particle size less than 0.2 mm;
s2: adding 100g of the sugarcane powder obtained in the step S1 into 1L of iron solution, and stirring by using a stirrer to obtain a sugarcane mixture A, wherein the iron solution contains 24.15 g of FeCl3·H2O；
S3: adding the sugarcane mixture A obtained in the step S2 into 5 liters of nitrogen-phosphorus-potassium-silicon mixed solution, and oscillating for 1 hour to obtain a sugarcane mixture B, wherein the nitrogen-phosphorus-potassium-silicon mixed solution comprises60mg/L KNO3Solution, 60mg/L KH2PO4The solution and 60mg/L of a mixed solution of sodium silicate, sodium peroxydisilicate and sodium metasilicate;
s4: drying the sugarcane mixture B in the step S3, and putting the dried sugarcane mixture into an atmosphere furnace for carbonization, wherein protective nitrogen and oxygen are introduced into the atmosphere furnace, the volume ratio of the nitrogen to the oxygen is 25:1, the temperature is raised to 20 ℃ per minute, the temperature is raised to 400 ℃ and kept for 2.7 hours, and a biochar primary product is obtained;
s5: and (4) adding chitosan and potato powder into the primary biochar product obtained in the step S4, uniformly stirring, and drying to obtain the modified biochar.
Example 9
A preparation method of modified biochar comprises the following steps:
s1: drying bagasse and crushing to obtain bagasse powder with particle size less than 0.2 mm;
s2: adding 100g of the sugarcane powder obtained in the step S1 into 1L of iron solution, and stirring by using a stirrer to obtain a sugarcane mixture A, wherein the iron solution contains 48.31 g of FeCl3·H2O；
S3: adding the sugarcane mixture A obtained in the step S2 into 5 liters of nitrogen-phosphorus-potassium-silicon mixed solution, and oscillating for 1 hour to obtain a sugarcane mixture B, wherein the nitrogen-phosphorus-potassium-silicon mixed solution comprises 65mg/L KNO3Solution, 65mg/L KH2PO4The solution and 65mg/L sodium metasilicate solution;
s4: drying the sugarcane mixture B in the step S3, and putting the dried sugarcane mixture into an atmosphere furnace for carbonization, wherein protective nitrogen and oxygen are introduced into the atmosphere furnace, the volume ratio of the nitrogen to the oxygen is 20:1, the temperature is raised to 25 ℃ per minute, the temperature is raised to 400 ℃ and kept for 2.3 hours, and a biochar primary product is obtained;
s5: and (4) adding chitosan and cassava powder into the primary biochar product obtained in the step S4, uniformly stirring, and drying to obtain the modified biochar.
Example 10
A preparation method of modified biochar comprises the following steps:
s1: drying bagasse and crushing to obtain bagasse powder with particle size less than 0.2 mm;
s2: adding 100g of the sugarcane powder obtained in the step S1 into 1L of iron solution, and stirring by using a stirrer to obtain a sugarcane mixture A, wherein 96.61 g of FeCl is contained in the iron solution3·H2O；
S3: adding the sugarcane mixture A obtained in the step S2 into 5 liters of nitrogen-phosphorus-potassium-silicon mixed solution, and oscillating for 1 hour to obtain a sugarcane mixture B, wherein the nitrogen-phosphorus-potassium-silicon mixed solution comprises 55mg/L KNO3Solution, 50mg/L KH2PO4The solution and a mixed solution of 65mg/L of sodium silicate and potassium silicate;
s4: drying the sugarcane mixture B in the step S3, and putting the dried sugarcane mixture into an atmosphere furnace for carbonization, wherein protective nitrogen and oxygen are introduced into the atmosphere furnace, the volume ratio of the nitrogen to the oxygen is 15:1, the temperature is raised to 25 ℃ per minute, the temperature is raised to 450 ℃ and kept for 2 hours, and a biochar primary product is obtained;
s5: and (4) adding the chitosan and the corn flour into the primary biochar product obtained in the step S4, uniformly stirring, and drying to obtain the modified biochar.
Example 11
A preparation method of modified biochar comprises the following steps:
s1: drying bagasse and crushing to obtain bagasse powder with particle size less than 0.2 mm;
s2: adding 100g of the sugarcane powder obtained in the step S1 into 1L of iron solution, and stirring by using a stirrer to obtain a sugarcane mixture A, wherein the iron solution contains 193.22 g of FeCl3·H2O；
S3: adding the sugarcane mixture A obtained in the step S2 into 5 liters of nitrogen-phosphorus-potassium-silicon mixed solution, and oscillating for 1 hour to obtain a sugarcane mixture B, wherein the nitrogen-phosphorus-potassium-silicon mixed solution comprises 60mg/L KNO3Solution, 50mg/L KH2PO4The solution and a mixed solution of 65mg/L of sodium silicate and sodium peroxydisilicate;
s4: drying the sugarcane mixture B in the step S3, and putting the dried sugarcane mixture into an atmosphere furnace for carbonization, wherein protective nitrogen and oxygen are introduced into the atmosphere furnace, the volume ratio of the nitrogen to the oxygen is 10:1, the temperature is raised to 30 ℃ per minute, the temperature is raised to 450 ℃ and kept for 1.1h, and a biochar primary product is obtained;
s5: and (4) adding the chitosan and the corn flour into the primary biochar product obtained in the step S4, uniformly stirring, and drying to obtain the modified biochar.
Example 12
A preparation method of modified biochar comprises the following steps:
s1: drying bagasse and crushing to obtain bagasse powder with particle size less than 0.2 mm;
s2: adding 100g of the sugarcane powder obtained in the step S1 into 1L of iron solution, and stirring by using a stirrer to obtain a sugarcane mixture A, wherein the iron solution contains 386.44 g of FeCl3·H2O；
S3: adding the sugarcane mixture A obtained in the step S2 into 5 liters of nitrogen-phosphorus-potassium-silicon mixed solution, and oscillating for 1 hour to obtain a sugarcane mixture B, wherein the nitrogen-phosphorus-potassium-silicon mixed solution comprises 60mg/L KNO3Solution, 40mg/L KH2PO4The solution and 60mg/L potassium silicate, sodium peroxydisilicate and sodium metasilicate mixed solution;
s4: drying the sugarcane mixture B in the step S3, and putting the dried sugarcane mixture into an atmosphere furnace for carbonization, wherein protective nitrogen and oxygen are introduced into the atmosphere furnace, the volume ratio of the nitrogen to the oxygen is 5:1, the temperature is raised to 30 ℃ per minute, the temperature is raised to 500 ℃ and kept for 1h, and a biochar primary product is obtained;
s5: and (4) adding the chitosan and the corn flour into the primary biochar product obtained in the step S4, uniformly stirring, and drying to obtain the modified biochar.
Comparative example 1
A preparation method of modified biochar comprises the following steps:
s1: drying bagasse and crushing to obtain bagasse powder with particle size less than 0.2 mm;
s2: adding 100g of the sugarcane powder obtained in the step S1 into 1L of iron solution, and stirring by using a stirrer to obtain a sugarcane mixture, wherein the iron solution contains 50 g of FeCl3·H2O；
S3: and (5) drying the sugarcane mixture in the step S2, and putting the dried sugarcane mixture into an atmosphere furnace for carbonization, wherein nitrogen is introduced into the atmosphere furnace, the temperature is increased by 15 ℃ per minute, so that the temperature is increased to 300 ℃ and is kept for 8 hours, and the biochar is obtained.
Comparative example 2
A preparation method of modified biochar comprises the following steps:
s1: drying bagasse and crushing to obtain bagasse powder with particle size less than 0.2 mm;
s2: adding 100g of the sugarcane powder obtained in the step S1 into 1L of iron solution, and stirring by using a stirrer to obtain a sugarcane mixture A, wherein the iron solution contains 200 g of FeCl3·H2O；
S3: adding the sugarcane mixture A obtained in the step S2 into 5 liters of nitrogen-phosphorus-potassium mixed solution, and oscillating for 1 hour to obtain a sugarcane mixture B, wherein the nitrogen-phosphorus-potassium-silicon mixed solution comprises 60mg/L KNO3Solution and 70mg/L KH2PO4A solution;
s4: and (5) drying the sugarcane mixture B in the step S3, and putting the dried sugarcane mixture B into an atmosphere furnace for carbonization, wherein protective nitrogen is introduced into the atmosphere furnace, the temperature is raised to 30 ℃ per minute, the temperature is raised to 450 ℃ and is kept for 6 hours, and the biochar is obtained.
The modified biochar prepared in examples 1-12 and the biochar prepared in comparative examples 1 and 2 were subjected to a remediation test of heavy metal contaminated soil.
Soil is collected from the surface layer of a farmland polluted by mining at the vital county of Tanzhou, Hunan province by 0-20 cm; the soil was naturally air dried and sieved through a 2mm sieve, and the basic physicochemical properties of the soil are shown in table 1. After 10kg of soil was weighed into each pot and placed in a plastic bucket (diameter 35cm, height 40cm), the following treatments were carried out:
t1: 10kg of soil +100g of the modified biochar prepared in example 1;
t2: 10kg of soil +100g of the modified biochar prepared in example 2;
t3: 10kg of soil +100g of the modified biochar prepared in example 3;
t4: 10kg of soil +100g of the modified biochar prepared in example 4;
t5: 10kg of soil +100g of the modified biochar prepared in example 5;
t6: 10kg of soil +100g of the modified biochar prepared in example 6;
t7: 10kg of soil +100g of the modified biochar prepared in example 7;
t8: 10kg of soil +100g of the modified biochar prepared in example 8;
t9: 10kg of soil +100g of the modified biochar prepared in example 9;
t10: 10kg of soil +100g of the modified biochar prepared in example 10;
t11: 10kg of soil +100g of the modified biochar prepared in example 11;
t12: 10kg of soil +100g of the modified biochar prepared in example 12;
t13: 10kg of soil +100g of the biochar prepared in comparative example 1;
t14: 10kg of soil +100g of the biochar prepared in comparative example 2;
t15: 10kg of soil and 5g of potassium metasilicate;
t16: 10kg of soil, 15g of potassium metasilicate and 5g of iron powder;
control (CK) was made without any conditioning agent added.
Each treatment was performed in 3 replicates and placed in a glass greenhouse. Planting rice 5 days after applying various modified biochar; collecting soil samples after the rice grows for 30 days, and analyzing the contents of the heavy metals Cd and As in the effective state; collecting rice samples during rice harvesting, and analyzing the Cd and As contents of grains.
TABLE 1 basic physicochemical Properties of the soil for testing potted plants
| Test index | Content (wt.) |
| pH | 6.82 |
| Total As (mg. kg)-1) | 328.9 |
| Total Cd (mg kg)-1) | 3.54 |
| Cation exchange capacity (cmol. kg)-1) | 19.1 |
| TOC(g·kg-1) | 38.2 |
As shown in Table 2, the effective states of Cd and As of the potted rice soil after the treatment of different modified biochar are reduced to different degrees. The reduction range of the effective As and Cd of the soil is maximum by the modified biochar prepared in example 11, and the reduction range reaches 76.98% and 75.38% respectively. Moreover, the 12 kinds of modified biochar prepared by the method can effectively passivate heavy metals As and Cd in soil at the same time (the effective As and Cd after treatment by T1, T2, T3, T4, T5, T6, T7, T8, T9, T10, T11 and T12 are all obviously lower than those of a control); while the biochar prepared in comparative example 1 and comparative example 2 can only passivate a small amount of Cd, the potassium metasilicate treatment (T15) alone has no ideal effect on passivating 2 heavy metals, and the potassium metasilicate and iron powder treatment (T16) can only passivate a small amount of Cd. Correspondingly, the inorganic As and total Cd of the potted rice brown rice can be greatly reduced at the same time only after the modified biochar of the invention is applied (see Table 3); wherein the modified biochar prepared in example 11 is the best to reduce inorganic As and total Cd of rice, which respectively reach 78.91% and 82.04%. Compared with the common biochar, the modified biochar prepared by the technology can simultaneously passivate the As and Cd combined pollution of soil with high efficiency, and reduce the absorption and accumulation of rice on the 2 heavy metals. Correspondingly, the dry weight of the potted rice was also increased substantially after application of the modified biochar of the invention (see table 4); the modified biochar prepared in examples 11 and 12 had the best effect on increasing the dry weight of rice, reaching 20.51%. Compared with the common biochar, the modified biochar prepared by the technology disclosed by the invention can efficiently passivate the As and Cd combined pollution of soil, reduce the absorption and accumulation of rice on the 2 heavy metals, and increase the yield of rice.
TABLE 2 influence of different modified charcoal treatments on the content of As and Cd in the pot soil
TABLE 3 influence of different modified charcoal treatments on the content of heavy metals As and Cd in brown rice of potted rice
TABLE 4 Effect of different modified charcoal treatments on potted Rice yield
| Group of | Dry weight of Rice (g) | Increase ratio (%) |
| CK | 356 | 0 |
| T1 | 411 | 15.45 |
| T2 | 404 | 13.48 |
| T3 | 505 | 41.85 |
| T4 | 415 | 16.57 |
| T5 | 416 | 16.85 |
| T6 | 419 | 17.70 |
| T7 | 414 | 16.29 |
| T8 | 420 | 17.98 |
| T9 | 427 | 19.94 |
| T10 | 425 | 19.38 |
| T11 | 429 | 20.51 |
| T12 | 427 | 19.94 |
| T13 | 389 | 9.27 |
| T14 | 396 | 11.24 |
| T15 | 366 | 2.81 |
| T16 | 368 | 3.37 |
While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
Claims (8)
1. The preparation method of the modified biochar is characterized by comprising the following steps:
s1: drying bagasse and crushing to obtain bagasse powder with particle size less than 0.2 mm;
s2: adding the sugarcane powder in the step S1 into an iron solution, and stirring by using a stirrer to obtain a sugarcane mixture A, wherein the mass ratio of iron to the sugarcane powder is 1 (1.25-40);
s3: adding the sugarcane mixture A in the step S2 into a nitrogen-phosphorus-potassium-silicon mixed solution, and oscillating for 1-3 hours to obtain a sugarcane mixture B, wherein the nitrogen-phosphorus-potassium-silicon mixed solution comprises 50-70mg/L KNO3Solution, 50-70mg/L KH2PO4Solution and silicate solution of 50-70 mg/L;
s4: drying the sugarcane mixture B in the step S3, and putting the dried sugarcane mixture B into an atmosphere furnace for carbonization, wherein protective gas is introduced into the atmosphere furnace, the temperature is raised to 300-500 ℃ at every minute by 15-30 ℃, and the temperature is kept for 1-3 hours, so as to obtain a biochar primary product;
s5: and (4) adding chitosan and biological starch into the primary biological carbon product obtained in the step S4, uniformly stirring, and drying to obtain the modified biological carbon.
2. The method of claim 1, wherein the iron solution in step S2 includes ferric chloride and a catalyst.
3. The method of claim 2, wherein the catalyst is platinum or palladium.
4. The method of claim 1, wherein the silicate solution is at least one of a sodium silicate solution, a potassium silicate solution, a sodium peroxydisilicate solution, and a sodium metasilicate solution.
5. The method of claim 1, wherein the protective gas in step S4 is nitrogen or oxygen.
6. The method for preparing modified biochar according to claim 5, wherein the volume ratio of nitrogen to oxygen in step S4 is 30:1-5: 1.
7. The method of claim 1, wherein the bio-starch of step S5 is corn flour, sweet potato flour, or tapioca flour.
8. A modified biochar produced by the method of any one of claims 1 to 7.
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| CN109225133A (en) * | 2018-09-28 | 2019-01-18 | 中国地质大学（武汉） | FeCl3Modification biological charcoal and preparation method thereof, the method for repairing pollution of chromium underground water |
| CN110294536B (en) * | 2019-07-30 | 2021-09-28 | 山西大学 | Preparation method of biomass carbon nitrifying bacteria carrier |
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| CN110724013A (en) * | 2019-08-30 | 2020-01-24 | 广州草木蕃环境科技有限公司 | Conditioner for repairing medium and light cadmium polluted soil and preparation method and use method thereof |
| CN115956416A (en) * | 2022-12-14 | 2023-04-14 | 贵州师范学院 | Method for reducing enrichment of cadmium in asparagus lettuce by using modified charcoal |
| CN115806825B (en) * | 2023-02-03 | 2023-04-25 | 中国建设基础设施有限公司 | Soil conditioner for increasing yield and improving quality of astragalus membranaceus, preparation method and application |
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