CN116328721A - Biochar prepared from alkaline residue and straw and application of biochar in dephosphorization and demanganization - Google Patents

Biochar prepared from alkaline residue and straw and application of biochar in dephosphorization and demanganization Download PDF

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Publication number
CN116328721A
CN116328721A CN202310087783.0A CN202310087783A CN116328721A CN 116328721 A CN116328721 A CN 116328721A CN 202310087783 A CN202310087783 A CN 202310087783A CN 116328721 A CN116328721 A CN 116328721A
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biochar
straw
alkaline residue
phosphate
dephosphorization
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刘乐乐
张明亮
董鹏
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University of Jinan
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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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/045—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing sulfur, e.g. sulfates, thiosulfates, gypsum
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B17/00—Other phosphatic fertilisers, e.g. soft rock phosphates, bone meal
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/80—Soil conditioners
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/105—Phosphorus compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/206—Manganese or manganese compounds
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Thermal Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Physics & Mathematics (AREA)
  • Soil Sciences (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention belongs to the technical field of biochar preparation and waste recovery, and particularly relates to biochar prepared from alkaline residues and straws and application of the biochar in dephosphorization and demanganization. The straw is sweet sorghum straw; drying and grinding alkaline residue and straw, and then, according to the dry weight mass ratio of 1-2:1-2, and then placing the mixture into a tube furnace into which nitrogen is introduced, and performing high-temperature pyrolysis at a heating rate of 10 ℃/min. Compared with the traditional chemical material modified biochar, the modified biochar prepared by co-pyrolysis at 800 ℃ has higher phosphate adsorption efficiency, simple operation and lower cost, and can also realize recycling of the alkaline residue and the sweet sorghum straw, thereby providing phosphorus for wheat growth. Meanwhile, the high-efficiency removal of heavy metal manganese in the water body can be realized.

Description

Biochar prepared from alkaline residue and straw and application of biochar in dephosphorization and demanganization
Technical Field
The invention belongs to the technical field of biochar preparation and waste recovery, and particularly relates to biochar prepared from alkaline residues and straws and application of the biochar in dephosphorization and demanganization.
Background
At present, a plurality of technologies and methods for removing phosphorus and heavy metal manganese in a degraded water body comprise electrodialysis, ion exchange, precipitation and bioconversion, but the methods have various defects in a specific operation process, such as low removal efficiency, potential secondary pollution, high operation and maintenance cost and the like, so that the method is prevented from being applied to a large scale in practice.
In contrast, the adsorption method is an efficient, economical and environment-friendly method for removing phosphorus and heavy metals in water, and in the aspect of adsorbing pollutants, the adsorption method has been widely focused in recent years due to the advantages of high efficiency, environment friendliness, easily available materials, economy, large-scale application and the like of biochar. In addition, the application of the biochar can improve the agricultural productivity, purify the wastewater, and is favorable for reducing the use of chemical fertilizers, thereby having good development prospect. However, since biochar has a low adsorption capacity for anionic contaminants such as phosphate, it is necessary to modify it to increase its adsorption capacity for phosphate.
Disclosure of Invention
Aiming at the problems of dephosphorization at the present stage and the comprehensive utilization of alkaline residues, the invention adopts the alkaline residue modified biochar to adsorb phosphate in water, and adds the modified biochar after adsorbing the phosphate into soil, thereby improving the environment of acid soil, increasing the organic carbon content of the soil and mineral nutrients such as phosphorus, calcium, magnesium and the like, and effectively promoting the growth of wheat. Meanwhile, heavy metal manganese in the water body is removed by utilizing the alkaline residue modified biochar.
The technical scheme of the invention is as follows:
the biochar is prepared from alkaline residue and straw, wherein the straw is sweet sorghum straw; mixing the alkaline residue and the straw according to the dry weight mass ratio of 0:1, 1:1, 2:1, 1:2 and 1:0, drying, grinding, and performing high-temperature pyrolysis in a nitrogen atmosphere.
Preferably, the dry weight mass ratio of the alkaline residue to the straw is 2:1.
preferably, the grinding is performed by passing through a screen of less than 0.15 mm.
Preferably, the high-temperature pyrolysis is 700-900 ℃ and the pyrolysis time is 1-3h.
The invention also aims to protect the application of the biochar in dephosphorization.
Further, the dephosphorization is dephosphorization in the water body.
Further, the using method comprises the following steps: and (3) placing the biochar into phosphorus-containing wastewater to obtain the biochar after adsorbing phosphate.
Another object of the present invention is to protect a material loaded with phosphate, which is the biochar after adsorbing phosphate as described above.
The invention also aims at protecting the application of the material loaded with phosphate as a slow-release phosphate fertilizer.
Preferably for wheat planting.
The invention also aims to protect the application of the biochar in demanganization.
By adopting the method, the alkaline residue modified sweet sorghum straw biochar is prepared, the grain size is uniform, and the maximum adsorption capacity of phosphate can reach 114.96 mg/g; the maximum adsorption capacity for removing manganese reaches 125.97 mg/g.
Compared with the prior art, the invention has the following beneficial effects:
(1) The environmental protection benefit is high. The invention realizes the recycling of the industrial waste alkaline residue and the agricultural waste sweet sorghum straw, and avoids the excessive waste of resources. Meanwhile, compared with the dephosphorization and demanganization of chemical reagent modified biochar at the present stage, the alkaline residue modified biochar has no secondary pollution, does not generate new environmental problems, and accords with the environmental protection concept of treating waste with waste.
(2) The effect of removing pollutants is good. By optimizing the material proportion, the pyrolysis parameters and the like, the maximum adsorption capacity of the alkaline residue modified biochar for phosphate can reach 114.96mg/g, and the maximum adsorption capacity of the alkaline residue modified biochar for manganese can reach 125.97 mg/g, which are 100 times and 7 times that of the alkaline residue modified biochar respectively.
(3) The regeneration and utilization capability is strong. The modified biochar after adsorbing phosphate can be used as a slow-release phosphate fertilizer to effectively promote the growth of crops such as wheat and the like.
(4) The application range is wide. The invention not only has good removing effect on anion pollutants (phosphate), but also has good removing capability on heavy metal manganese, and provides possibility for removing more pollutants in future.
(5) The practicability is strong. The invention has the advantages of easily obtained raw materials, low preparation cost, simple process flow, good decontamination effect, small limitation and high practical application value.
Drawings
FIG. 1 is a process flow diagram of the invention for preparing modified biochar from alkaline residue;
the left isotherm model for adsorbing phosphate and the right isotherm model for adsorbing heavy metal Mn in FIG. 2 (BC is pure straw biochar, SRB is biochar prepared by mixing alkaline residue with straw according to a certain proportion, and SR is soda residue biochar).
Detailed Description
Example 1
The preparation method of the biochar prepared from the alkaline residue and the straw comprises the following steps:
(1) drying the alkaline residue at 105 ℃ for 24 hours, crushing the dried alkaline residue by a crusher, and sieving the crushed alkaline residue with a 0.1mm sieve. Drying sweet sorghum straw at 75 ℃ for 24 hours, crushing the dried sweet sorghum by a crusher, and sieving the crushed sweet sorghum by a 0.1mm screen.
(2) Uniformly mixing the sieved alkaline residue and sweet sorghum straw powder in a mass ratio of 2:1, and then carrying out pyrolysis for 2 hours at 800 ℃ by using a tube furnace under an N2 atmosphere. During the temperature rising process, the speed of 10 ℃/min is kept unchanged. And (5) grinding the modified biochar after naturally cooling the modified biochar, and sieving the modified biochar with a 0.1mm sieve.
Example 2
The preparation method of the biochar prepared from the alkaline residue and the straw comprises the following steps:
(1) drying the alkaline residue at 105 ℃ for 24 hours, crushing the dried alkaline residue by a crusher, and sieving the crushed alkaline residue with a 0.1mm sieve. Drying sweet sorghum straw at 75 ℃ for 24 hours, crushing the dried sweet sorghum by a crusher, and sieving the crushed sweet sorghum by a 0.1mm screen.
(2) Uniformly mixing the sieved alkaline residue and sweet sorghum straw powder in a mass ratio of 2:1, and then carrying out pyrolysis for 1h at 900 ℃ by using a tube furnace under an N2 atmosphere. During the temperature rising process, the speed of 10 ℃/min is kept unchanged. And (5) grinding the modified biochar after naturally cooling the modified biochar, and sieving the modified biochar with a 0.1mm sieve.
Example 3
The preparation method of the biochar prepared from the alkaline residue and the straw comprises the following steps:
(1) drying the alkaline residue at 105 ℃ for 24 hours, crushing the dried alkaline residue by a crusher, and sieving the crushed alkaline residue with a 0.1mm sieve. Drying sweet sorghum straw at 75 ℃ for 24 hours, crushing the dried sweet sorghum by a crusher, and sieving the crushed sweet sorghum by a 0.1mm screen.
(2) Uniformly mixing the sieved alkaline residue and sweet sorghum straw powder in a mass ratio of 2:1, and then carrying out pyrolysis for 3 hours at 700 ℃ by using a tube furnace under an N2 atmosphere. During the temperature rising process, the speed of 10 ℃/min is kept unchanged. And (5) grinding the modified biochar after naturally cooling the modified biochar, and sieving the modified biochar with a 0.1mm sieve.
Example 4
Compared with the example 1, the mass ratio of the alkaline residue to the sweet sorghum straw is 1:1.
Example 5
Compared with the example 1, the mass ratio of the alkaline residue to the sweet sorghum straw is 1:2.
Comparative example 1
Compared with the example 1, the single caustic sludge is thermally hydrolyzed according to the method of the step (2) of the example 1 to obtain the calcined soda sludge biochar.
Comparative example 2
Compared with the embodiment 1, the independent sweet sorghum straw is subjected to pyrolysis according to the method of the embodiment 1 step (2) to obtain the straw biochar.
Examples of the effects
Experimental example 1
The adsorbents obtained in examples 1 to 5 and comparative examples 1 and 2 were added in an amount of 0.05g to 30ml of phosphate solution (concentrations of 50, 100, 150, 200, 250, 300, 350, 400 mg/L, ph=5), respectively, and when the adsorption reaction reached equilibrium, the concentration of phosphate remaining in the solution was measured and the maximum adsorption capacity of the material obtained in each example was calculated, and as a result, the left graph of fig. 2 was shown, and biochar adsorbing phosphate was obtained. The maximum adsorption capacity for phosphate for the different examples is shown in table 1.
Table 1 maximum adsorption capacity of the resulting adsorbents for phosphorus at different mass ratios.
Figure SMS_1
As can be seen from Table 1, in all materials, the phosphate removal effect of the modified biochar mixed in a mass ratio of 2:1 is inferior to that of the soda ash biochar, and 114.96mg P/g is about 100 times that of the adsorbent prepared from the pure straw.
Experimental example 2
The adsorbents obtained in examples 1 to 5 and comparative examples 1 and 2 were added in an amount of 0.05g to 100 mg/L phosphate solutions (pH 2, 3, 5, 7, 9, 11), respectively, and when the adsorption reaction reached equilibrium, the remaining phosphate concentrations in the solutions were measured. The results are shown in Table 2.
Table 2 removal rates of phosphorus at different pH for each example
Figure SMS_2
As can be seen from Table 2, the effect of the adsorbent of the present invention on phosphorus removal at different pH values is different, wherein the adsorbents doped with caustic sludge according to different proportions have better phosphorus removal effect at different pH values.
Experimental example 3
The material obtained by adsorbing phosphate in example 1 was uniformly mixed with soil obtained from a farm in the city of coastal state at a ratio of 1:100, and wheat was planted in the mixed soil. Compared with the original soil, the plant height of the wheat is improved by 36 percent, and the fresh weight and the dry weight of the wheat are respectively improved by 19.3 percent and 23.2 percent.
Experimental example 4 manganese removal Effect
0.1g of the adsorbents obtained in examples 1 to 5 and comparative examples 1 and 2 were added to each of the above materials40ml of manganese sulfate (Mn) 2+ ) In the solution ( concentration 50, 100, 150, 200, 250, 350, 500 mg/L, pH=5), when the adsorption reaction reaches equilibrium, the remaining Mn in the solution was measured 2+ Concentration and calculation of the respective examples the maximum adsorption capacity of the material was obtained, see in particular the right-hand graph of fig. 2.
By fitting an isotherm data model, the maximum adsorption capacity of the pure straw biochar is 17.96 mg/g, the manganese removal effect of the alkaline residue to straw mass ratio is optimal and is 1:2, the maximum adsorption capacity of the removed manganese reaches 125.97 mg/g, the maximum adsorption capacity is about 7 times that of the unmodified pure straw biochar, and the maximum adsorption capacities of the rest of the alkaline residue to straw mass ratio are 89.52 mg/g and 79.80 mg/g respectively.

Claims (10)

1. The biochar prepared from the alkaline residue and the straw is characterized in that the straw is sweet sorghum straw; drying and grinding alkaline residue and straw, and then, according to the dry weight mass ratio of 1-2:1-2, and placing the mixture in a tube furnace into which nitrogen is introduced for high-temperature pyrolysis.
2. The biochar according to claim 1, wherein the dry weight mass ratio of the alkaline residue to the straw is 2:1.
3. the biochar according to claim 1, wherein the grinding is performed with a screen of less than 0.15 mm.
4. The biochar according to claim 1, wherein the pyrolysis is performed at 700-900 ℃ for 1-3 hours.
5. Use of the biochar according to any one of claims 1 to 4 for dephosphorization.
6. The use of claim 5, wherein the dephosphorization is in a body of water.
7. A phosphate-supporting material, which is the biochar after adsorbing phosphate according to claim 6.
8. The use of the phosphate-loaded material according to claim 7 as a slow-release phosphate fertilizer.
9. The use according to claim 8, for the cultivation of wheat.
10. Use of the biochar according to any one of claims 1-4 for demanganization.
CN202310087783.0A 2023-02-02 2023-02-02 Biochar prepared from alkaline residue and straw and application of biochar in dephosphorization and demanganization Pending CN116328721A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110223088A1 (en) * 2010-03-11 2011-09-15 Ramsay Chang Method and Apparatus for On-Site Production of Lime and Sorbents for Use in Removal of Gaseous Pollutants
CN108676564A (en) * 2018-08-20 2018-10-19 沂南县迎辉农业开发有限公司 A kind of acidic soil conditioner and preparation method being suitable for by heavy metal pollution
CN110354804A (en) * 2019-07-29 2019-10-22 江西省科学院 A kind of its application of the preparation method of wetland plant and pig manure compound bio charcoal
CN110423160A (en) * 2019-09-02 2019-11-08 南开大学 It is a kind of using cornstalk biological charcoal as the slow-release phosphate fertilizer preparation method of carrier
CN111303900A (en) * 2020-03-25 2020-06-19 广东省农业科学院农业资源与环境研究所 Modified charcoal-based soil conditioner for repairing Cd pollution and preparation method and application thereof
CN111921498A (en) * 2020-08-14 2020-11-13 生态环境部南京环境科学研究所 Method for recycling caustic sludge, product and application
CN113000025A (en) * 2021-03-08 2021-06-22 济南大学 Phosphorus removal adsorbent and preparation method and application thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110223088A1 (en) * 2010-03-11 2011-09-15 Ramsay Chang Method and Apparatus for On-Site Production of Lime and Sorbents for Use in Removal of Gaseous Pollutants
CN108676564A (en) * 2018-08-20 2018-10-19 沂南县迎辉农业开发有限公司 A kind of acidic soil conditioner and preparation method being suitable for by heavy metal pollution
CN110354804A (en) * 2019-07-29 2019-10-22 江西省科学院 A kind of its application of the preparation method of wetland plant and pig manure compound bio charcoal
CN110423160A (en) * 2019-09-02 2019-11-08 南开大学 It is a kind of using cornstalk biological charcoal as the slow-release phosphate fertilizer preparation method of carrier
CN111303900A (en) * 2020-03-25 2020-06-19 广东省农业科学院农业资源与环境研究所 Modified charcoal-based soil conditioner for repairing Cd pollution and preparation method and application thereof
CN111921498A (en) * 2020-08-14 2020-11-13 生态环境部南京环境科学研究所 Method for recycling caustic sludge, product and application
CN113000025A (en) * 2021-03-08 2021-06-22 济南大学 Phosphorus removal adsorbent and preparation method and application thereof

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