CN112794588A - Method for efficiently stabilizing heavy metals in animal manure biochar - Google Patents
Method for efficiently stabilizing heavy metals in animal manure biochar Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/10—Treatment of sludge; Devices therefor by pyrolysis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/13—Treatment of sludge; Devices therefor by de-watering, drying or thickening by heating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/06—Sludge reduction, e.g. by lysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/40—Valorisation of by-products of wastewater, sewage or sludge processing
Abstract
The invention belongs to the technical field of comprehensive utilization of livestock and poultry manure, and discloses a method for efficiently stabilizing heavy metals in livestock and poultry manure biochar, which comprises the following steps: s1, mixing 20-30% alkali liquor with fly ash according to the mass ratio of 30-50% dry matter, heating and stirring at 80-90 ℃ for 1-2h to obtain alkali liquor treated fly ash; s2, fully mixing the acid liquor and the livestock and poultry manure for 0.5-3h, and adding the fly ash treated by the S1 into the mixture according to the proportion of 2-5%. Hydrochloric acid is added to promote the formation of soluble heavy metal ions in the livestock and poultry manure, then the soluble heavy metal ions react with the fly ash treated by sodium hydroxide to form silicate, and the catalytic microwave pyrolysis technology is combined to effectively promote the formation of mineral heavy metal of aluminum silicate salt, so that the effect of efficiently stabilizing the heavy metal in the livestock and poultry manure biochar is finally achieved. In addition, the method not only can obviously reduce the energy consumption in the preparation process of the livestock and poultry manure biochar, but also can obviously improve the characteristics of the livestock and poultry manure biochar.
Description
Technical Field
The invention relates to the technical field of comprehensive utilization of livestock and poultry manure, in particular to a method for efficiently stabilizing heavy metals in livestock and poultry manure biochar.
Background
With the change of the food consumption structure of residents, the Chinese livestock and poultry breeding has developed to scale and intensification, which brings huge economic and social benefits, and simultaneously generates a large amount of livestock and poultry excrement wastes. Estimated that the total livestock and poultry manure discharge amount currently exceeds 3x10 per year in China9t (fresh weight). However, the treatment and resource utilization of livestock and poultry breeding wastes are relatively lagged, and more than 90% of large-scale farms lack the necessary pollution treatment measures for comprehensive utilization. The breeding pollution becomes a main source of non-point source pollution in rural areas in China, the continuous and efficient development of livestock and poultry breeding industry is seriously restricted, and an advanced and applicable livestock and poultry excrement resource recycling technology is urgently needed to be developed.
Compared with compost and anaerobic fermentation treatment, the pyrolysis technology has obvious advantages: the method can not only realize the reduction, the harmlessness and the resource utilization of the livestock and poultry manure, but also reduce the effectiveness of heavy metals in the livestock and poultry manure. The current research shows that the effectiveness of the heavy metal in the livestock manure biochar is gradually reduced along with the increase of the pyrolysis temperature, however, the effectiveness of part of the heavy metal in the pyrolysis product livestock manure biochar is still higher. In addition, biochar prepared at higher temperatures has poor properties, which limits its applications. Meanwhile, the preparation of the livestock manure biochar at higher temperature means that more energy is consumed. Therefore, it is necessary to develop a more effective pyrolysis technology to achieve the purpose of low energy consumption and good heavy metal stabilization effect.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for efficiently stabilizing heavy metals in animal manure biochar, which comprises the steps of adding hydrochloric acid to promote the formation of soluble heavy metal ions in animal manure, then reacting the soluble heavy metal ions with fly ash treated by sodium hydroxide to form silicate, and combining a catalytic microwave pyrolysis technology to better and effectively promote the formation of mineral heavy metals of aluminum silicate salt, thereby finally achieving the effect of efficiently stabilizing the heavy metals in the animal manure biochar. In addition, the method not only can obviously reduce the energy consumption in the preparation process of the livestock and poultry manure biochar, but also can obviously improve the characteristics of the livestock and poultry manure biochar.
In order to solve the technical problems, the invention provides a method for efficiently stabilizing heavy metals in animal manure biochar, which comprises the following steps:
s1, mixing 20-30% alkali liquor with fly ash according to the mass ratio of 30-50% dry matter, heating and stirring at 80-90 ℃ for 1-2h to obtain alkali liquor treated fly ash;
s2, fully mixing the acid liquor and the livestock and poultry manure for 0.5-3h, adding the fly ash treated by the S1 into the mixture according to the proportion of 3-5%, carrying out ultrasonic treatment for 0.5-3h, and drying at 60-80 ℃ until the water content is below 5%;
s3, crushing the dried livestock and poultry manure obtained in the step S2 by using a crusher, and sieving the crushed livestock and poultry manure by using a 20-50-mesh sieve;
s4, fully mixing the crushed livestock and poultry manure obtained in the step S3 with a pyrolysis catalyst;
s5, performing microwave pyrolysis on the livestock and poultry manure mixture obtained in the step S4 under the protection of inert gas, wherein the pyrolysis temperature is 450 ℃ and 550 ℃, the pyrolysis time is 1-3h, and the heating rate is 10-20 ℃/min;
and S6, collecting the solid pyrolysis product to stabilize the heavy metal in the livestock and poultry manure biochar.
Preferably, the alkali liquor is one of sodium hydroxide or potassium hydroxide.
Further, the acid solution in the S2 is dilute hydrochloric acid, the concentration of the dilute hydrochloric acid solution is 2-5%, and the adding proportion is 50-60%.
Preferably, the pyrolysis catalyst in S3 consists of: 40-50% of steel slag, 20-30% of red mud and 20-30% of bentonite, and the concrete preparation method comprises the steps of respectively drying and crushing the three raw materials, and uniformly mixing the three raw materials according to the weight ratio.
Further, the adding proportion of the pyrolysis catalyst in the S3 is 5-10% of the dry matter weight of the livestock and poultry manure.
Preferably, the microwave pyrolysis in S4 is performed by using a microwave device manufactured by Nanjing Europe manufacturing company Limited, and the microwave device has an operating frequency of 2500MHz and an operating power of 500w-1500 w.
Compared with the prior art, the invention has the following obvious substantial characteristics and obvious advantages:
firstly, the invention utilizes common alkali liquor to treat the fly ash to form silicate, then the formed silicate is matched with hydrochloric acid to activate heavy metal in the livestock and poultry manure, and the activated heavy metal is pyrolyzed under the high-temperature condition to form acid salt lattice mineral. In addition, the reaction speed is accelerated by matching with a pyrolysis catalyst on one hand, on the other hand, the pyrolysis catalyst selected by the invention can be combined with some heavy metals in a system, and Fe and CaO in the steel slag can be combined with arsenic to form stable CaFeAsO; alumina and silicate in the red mud form aluminosilicate crystal lattices to hold heavy metals; the bentonite belongs to a lattice type mineral, can form a molten state under the high-temperature condition of the invention except for the adsorption effect, and can be recombined with metal ions in livestock and poultry manure to form a new lattice structure, thereby assisting in the fixation of heavy metals. From the detection result, the method can efficiently stabilize various heavy metals in the livestock and poultry manure biochar at the moderate pyrolysis temperature, and the obtained livestock and poultry manure biochar reaches the relevant quality standards at home and abroad;
the method adopts the pyrolysis catalyst as the main raw material, is environment-friendly, has simple preparation process, does not need separation after being added into the livestock and poultry manure, improves the efficiency and improves the characteristics of the biochar;
and thirdly, compared with the conventional pyrolysis, the method for preparing the biochar by adopting the microwave pyrolysis technology has the advantages that the temperature rises to the same value, and the microwave pyrolysis consumes much less time.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to be clearly understood, the invention is further described by combining the specific embodiments.
Example 1
In order to illustrate the functions of adding the fly ash treated by the sodium hydroxide, treating the fly ash by dilute hydrochloric acid, adding a pyrolysis catalyst and performing microwave pyrolysis, the method is based on a control treatment, and comprises the following specific steps:
s1, mixing 30% sodium hydroxide with fly ash according to the mass ratio of 30% dry matter, and mechanically stirring for 1h under the heating condition (80 ℃) to obtain sodium hydroxide treated fly ash;
s2, fully mixing a dilute hydrochloric acid solution with the concentration of 5% with the livestock and poultry manure for 1h by adopting a magnetic stirring mode, adding the alkali-treated fly ash obtained in the step S1 into the mixture according to the proportion of 5%, carrying out ultrasonic treatment for 1h, drying at 60 ℃ until the water content is below 5%, and simultaneously carrying out control treatment on the fly ash without adding sodium hydroxide and the fly ash without adding dilute hydrochloric acid;
s3, crushing the dried livestock and poultry manure obtained in the step S2 by using a crusher, and sieving the crushed livestock and poultry manure by using a 50-60-mesh sieve to obtain powdery livestock and poultry manure;
s4, mixing a pyrolysis catalyst (40% of steel slag, 30% of red mud and 30% of bentonite) with the crushed livestock and poultry manure obtained in the step S3 according to a proportion of 5%, treating for 1min by using a crusher to achieve full mixing, and simultaneously carrying out treatment without adding the pyrolysis catalyst;
s5, putting the pig manure obtained in the step S4 into a porcelain crucible in two parts, then respectively putting the crucibles into a microwave pyrolysis furnace and an electric pyrolysis furnace, carrying out pyrolysis for 2 hours under the nitrogen protection atmosphere (flow rate of 500 mL/min), wherein the pyrolysis temperature is 500 ℃, the heating rate is 10 ℃/min, and naturally cooling to room temperature to take out a pyrolysis product.
S6, adding 0.5g of pig manure biochar into a 50mL centrifuge tube, adding 10mL of TCLP extracting solution (0.1mol/L acetic acid solution, pH 2.88), carrying out rotary oscillation for 16h under the condition of 30rmp, carrying out centrifugal filtration, transferring the mixture into a reagent bottle, measuring the concentration of heavy metal ions in the extracting solution by using an inductively coupled plasma emission spectrometer (ICP-OES, OPTIMA2100DV, PerkinElmer), and measuring the results to be shown in Table 1:
TABLE 1 influence of different treatment combinations on the leaching amount of heavy metals in pig manure biochar (mg/L)
As can be seen from Table 1, compared with the conventional electrothermal pyrolysis technology, the leaching amount of six heavy metals can be significantly reduced by adding the fly ash treated by sodium hydroxide, treating the fly ash by dilute hydrochloric acid, adding the pyrolysis catalyst and performing microwave pyrolysis, and the lowest leaching amount of the heavy metals can be obtained under the combined action of the four treatments.
Example 2
In order to further illustrate the effect of the addition amount of the fly ash treated by the sodium hydroxide, a plurality of addition amount combinations are added on the basis of the method, and the method comprises the following specific steps:
s1, mixing 30% potassium hydroxide with fly ash according to the mass ratio of 30% dry matter, and mechanically stirring for 1h under the heating condition (80 ℃) to obtain sodium hydroxide treated fly ash;
s2, fully mixing a dilute hydrochloric acid solution with the concentration of 5% with livestock and poultry manure for 1h by adopting a magnetic stirring mode, adding the alkali-treated fly ash obtained in the step S1 into the mixture according to the proportion of 0.5, 1, 2, 3, 5, 10 and 20%, carrying out ultrasonic treatment for 1h, drying at 60 ℃ until the water content is below 5%, and simultaneously carrying out comparison treatment on the fly ash treated without adding sodium hydroxide and the fly ash treated without adding dilute hydrochloric acid;
s3, crushing the dried livestock and poultry manure obtained in the step S2 by using a crusher, and sieving the crushed livestock and poultry manure by using a 50-60-mesh sieve to obtain powdery livestock and poultry manure;
s4, mixing a pyrolysis catalyst (50% of steel slag, 30% of red mud and 20% of bentonite) with the crushed livestock and poultry manure obtained in the step S3 according to a proportion of 5%, treating for 1min by using a crusher to achieve full mixing, and simultaneously carrying out treatment without adding the pyrolysis catalyst;
s5, putting the pig manure obtained in the step S4 into a porcelain crucible in two parts, then respectively putting the crucibles into a microwave pyrolysis furnace and an electric pyrolysis furnace, carrying out pyrolysis for 2 hours under the nitrogen protection atmosphere (flow rate of 500 mL/min), wherein the pyrolysis temperature is 500 ℃, the heating rate is 10 ℃/min, and naturally cooling to room temperature to take out a pyrolysis product.
S6, taking 0.5g of pig manure biochar, adding 10mL of TCLP extracting solution into a 50mL centrifuge tube, carrying out rotary oscillation for 16h under the condition of 30rmp, carrying out centrifugal filtration and transfer to a reagent bottle, measuring the concentration of heavy metal ions in the extracting solution by using an inductively coupled plasma emission spectrometer, and obtaining the results shown in Table 2:
TABLE 2 influence (mg/L) of different sodium hydroxide treatment fly ash addition ratios on heavy metal leaching amount in pig manure biochar
As can be seen from Table 2, when 0.5-3% sodium hydroxide was added to the treated fly ash, the eluviation amounts of 6 heavy metals gradually decreased, but the addition amount continued to increase, and the eluviation amount did not decrease significantly. Therefore, the method selects 3-5% as the adding proportion of the fly ash treated by the sodium hydroxide.
Example 3
In order to further illustrate the effect of the addition amount of the pyrolysis catalyst, various addition amount combinations are added on the basis of the method, and the method comprises the following specific steps:
s1, mixing 30% sodium hydroxide with fly ash according to the mass ratio of 30% dry matter, and mechanically stirring for 1h under the heating condition (80 ℃) to obtain sodium hydroxide treated fly ash;
s2, fully mixing a dilute hydrochloric acid solution with the concentration of 5% with the livestock and poultry manure for 1h by adopting a magnetic stirring mode, adding the fly ash treated by the S1 into the mixture according to the proportion of 5%, carrying out ultrasonic treatment for 1h, drying at 60 ℃ until the water content is below 5%, and simultaneously carrying out control treatment on the fly ash treated without adding sodium hydroxide and the fly ash treated without adding dilute hydrochloric acid;
s3, crushing the dried livestock and poultry manure obtained in the step S2 by using a crusher, and sieving the crushed livestock and poultry manure by using a 50-60-mesh sieve to obtain powdery livestock and poultry manure;
s4, mixing a pyrolysis catalyst (steel slag 40%, red mud 30% and bentonite 30%) with the crushed livestock and poultry manure obtained in the step S3 according to the proportion of 1%, 2%, 5%, 10%, 15% and 20%, treating for 1min by using a crusher to achieve full mixing, and simultaneously carrying out treatment without adding the pyrolysis catalyst;
s5, putting the pig manure obtained in the step S4 into a porcelain crucible in two parts, then respectively putting the crucibles into a microwave pyrolysis furnace and an electric pyrolysis furnace, carrying out pyrolysis for 2 hours under the nitrogen protection atmosphere (flow rate of 500 mL/min), wherein the pyrolysis temperature is 500 ℃, the heating rate is 10 ℃/min, and naturally cooling to room temperature to take out a pyrolysis product;
s6, taking 0.5g of pig manure biochar, adding 10mL of TCLP extracting solution into a 50mL centrifuge tube, carrying out rotary oscillation for 16h under the condition of 30rmp, carrying out centrifugal filtration, transferring the mixture into a reagent bottle, and measuring the concentration of heavy metal ions in the extracting solution by using an inductively coupled plasma emission spectrometer, wherein the measured results are shown in Table 3:
TABLE 3 influence of different pyrolysis catalyst addition ratios on the leaching amount of heavy metals in pig manure biochar (mg/L)
As can be seen from Table 3, the leaching amounts of the 6 heavy metals gradually decreased with the addition of 1-5% of the pyrolysis catalyst, but the leaching amounts did not decrease significantly with the continued increase in the addition amount. Therefore, the method selects 5-10% as the adding proportion of the pyrolysis catalyst.
Example 4
In order to further illustrate the application range of the method, the chicken manure, the cow manure and the sheep manure are alternatively taken and respectively subjected to high-temperature aerobic composting, anaerobic fermentation, conventional electric pyrolysis and the method for preparing the biochar, and the method comprises the following specific steps:
s1, mixing 30% sodium hydroxide with fly ash according to the mass ratio of 30% dry matter, and mechanically stirring for 1h under the heating condition (80 ℃) to obtain sodium hydroxide treated fly ash;
s2, fully mixing a dilute hydrochloric acid solution with the concentration of 5% with the livestock and poultry manure for 1h by adopting a magnetic stirring mode, adding the fly ash obtained by processing S1 into the mixture according to the proportion of 5%, carrying out ultrasonic treatment for 1h, drying at 60 ℃ until the water content is below 5%, and simultaneously carrying out comparison treatment on the fly ash without adding sodium hydroxide and the fly ash without adding dilute hydrochloric acid;
s3, crushing the dried livestock and poultry manure obtained in the step S2 by using a crusher, and sieving the crushed livestock and poultry manure by using a 50-60-mesh sieve to obtain powdery livestock and poultry manure;
s4, mixing a pyrolysis catalyst (50% of steel slag, 30% of red mud and 20% of bentonite) with the crushed livestock and poultry manure obtained in the step S3 according to a proportion of 5%, treating for 1min by using a crusher to achieve full mixing, and simultaneously carrying out treatment without adding the pyrolysis catalyst;
s5, putting the pig manure obtained in the step S4 into a porcelain crucible in two parts, then respectively putting the crucibles into a microwave pyrolysis furnace and an electric pyrolysis furnace, carrying out pyrolysis for 2 hours under the nitrogen protection atmosphere (flow rate of 500 mL/min), wherein the pyrolysis temperature is 500 ℃, the heating rate is 10 ℃/min, and naturally cooling to room temperature to take out a pyrolysis product;
s6, taking 0.5g of pig manure biochar, adding 10mL of TCLP extracting solution into a 50mL centrifuge tube, carrying out rotary oscillation for 16h under the condition of 30rmp, carrying out centrifugal filtration and transfer to a reagent bottle, measuring the concentration of heavy metal ions in the extracting solution by using an inductively coupled plasma emission spectrometer, and obtaining the results shown in Table 4:
TABLE 4 influence of heavy metal leaching amount (mg/L) in charcoal of various animal and fowl excrements
As can be seen from Table 4, compared with the high-temperature aerobic composting, anaerobic fermentation and conventional pyrolysis methods, the method provided by the invention can obviously reduce the leaching amount of 6 heavy metals in 3 livestock and poultry manure biochar. Therefore, the method can efficiently stabilize heavy metals in various animal manure biochar.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (6)
1. A method for efficiently stabilizing heavy metals in animal manure biochar is characterized by comprising the following steps: the method comprises the following steps:
s1, mixing 20-30% alkali liquor with the fly ash according to the mass ratio of 30-50% dry matter, heating and stirring at 80-90 ℃ for 1-2h after mixing to obtain alkali liquor treated fly ash;
s2, fully mixing the acid liquor and the livestock and poultry manure for 0.5-3h, adding the fly ash treated by the S1 into the mixture according to the proportion of 2-5%, carrying out ultrasonic treatment for 0.5-3h, and drying at the temperature of 60-80 ℃ until the water content is below 5%;
s3, crushing the dried livestock and poultry manure obtained in the step S2 by using a crusher, and sieving the crushed livestock and poultry manure by using a 20-50-mesh sieve;
s4, fully mixing the crushed livestock and poultry manure obtained in the step S3 with a pyrolysis catalyst;
s5, performing microwave pyrolysis on the livestock and poultry manure mixture obtained in the step S4 under the protection of inert gas, wherein the pyrolysis temperature is 450 ℃ and 550 ℃, the pyrolysis time is 1-3h, and the temperature rise rate is 10-20 ℃/min;
and S6, collecting the solid pyrolysis product to stabilize the heavy metal in the livestock and poultry manure biochar.
2. The method for efficiently stabilizing heavy metals in the biochar from the livestock and poultry manure as claimed in claim 1, which is characterized in that: the alkali liquor is sodium hydroxide and potassium hydroxide.
3. The method for efficiently stabilizing heavy metals in the biochar from the livestock and poultry manure as claimed in claim 1, which is characterized in that: the acid solution in the S2 is dilute hydrochloric acid, the concentration of the dilute hydrochloric acid solution is 2-5%, and the adding proportion is 50-60%.
4. The method for efficiently stabilizing heavy metals in the biochar from the livestock and poultry manure as claimed in claim 1, which is characterized in that: the pyrolysis catalyst in S3 consists of the following components: 40-50% of steel slag, 20-30% of red mud and 20-30% of bentonite.
5. The method for efficiently stabilizing heavy metals in the biochar from the livestock and poultry manure as claimed in claim 4, which is characterized in that: the adding proportion of the pyrolysis catalyst in the S3 is 5-10% of the dry matter weight of the livestock and poultry manure.
6. The method for efficiently stabilizing heavy metals in the biochar from the livestock and poultry manure as claimed in claim 1, which is characterized in that: the microwave pyrolysis in the S4 adopts a microwave device processed by Nanjing Europe-first Instrument manufacturing Co., Ltd, the working frequency of the microwave device is 2500MHz, and the working power is 500w-1500 w.
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| CN115259962A (en) * | 2021-12-22 | 2022-11-01 | 淮阴师范学院 | Preparation method of livestock and poultry manure biochar-based slow-release phosphorus-potassium fertilizer |
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| CN109382073A (en) * | 2018-12-26 | 2019-02-26 | 嘉应学院 | A kind of preparation method and applications of the flyash modified pig manure charcoal of alkali fusion |
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| CN115259962A (en) * | 2021-12-22 | 2022-11-01 | 淮阴师范学院 | Preparation method of livestock and poultry manure biochar-based slow-release phosphorus-potassium fertilizer |
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