CN115138333A - Calcium/iron-rich antibiotic bacterium residue harmless and resource utilization method - Google Patents
Calcium/iron-rich antibiotic bacterium residue harmless and resource utilization method Download PDFInfo
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- CN115138333A CN115138333A CN202210855956.4A CN202210855956A CN115138333A CN 115138333 A CN115138333 A CN 115138333A CN 202210855956 A CN202210855956 A CN 202210855956A CN 115138333 A CN115138333 A CN 115138333A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000011575 calcium Substances 0.000 title claims abstract description 57
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 55
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 53
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 20
- 241000894006 Bacteria Species 0.000 title abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 63
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- 239000001569 carbon dioxide Substances 0.000 claims abstract description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 241000209140 Triticum Species 0.000 claims description 2
- 235000021307 Triticum Nutrition 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052760 oxygen Inorganic materials 0.000 claims description 2
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- -1 urine Substances 0.000 claims description 2
- 210000002700 urine Anatomy 0.000 claims description 2
- 241000233866 Fungi Species 0.000 abstract description 35
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000003242 anti bacterial agent Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 229940088710 antibiotic agent Drugs 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 4
- 235000015493 Chenopodium quinoa Nutrition 0.000 description 3
- 239000002920 hazardous waste Substances 0.000 description 3
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000010828 animal waste Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002686 phosphate fertilizer Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
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- UCSJYZPVAKXKNQ-HZYVHMACSA-N streptomycin Chemical compound CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](NC(N)=N)[C@H](O)[C@@H](NC(N)=N)[C@H](O)[C@H]1O UCSJYZPVAKXKNQ-HZYVHMACSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- WNQQFQRHFNVNSP-UHFFFAOYSA-N [Ca].[Fe] Chemical compound [Ca].[Fe] WNQQFQRHFNVNSP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 229960005322 streptomycin Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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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
- B01J20/30—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
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/40—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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
Abstract
The invention discloses a harmless and resource utilization method of calcium/iron-rich antibiotic bacterium residues. The method comprises the steps of firstly, pyrolyzing and carbonizing calcium/iron-rich antibiotic fungi residues to obtain magnetic biochar; secondly, the magnetic biochar is used for recovering phosphorus in the wastewater; and finally, applying the magnetic biochar enriched with phosphorus as a phosphorus slow-release fertilizer into soil. The method provided by the invention can reduce the emission of carbon dioxide, truly realize harmless and resource utilization of antibiotic bacterium residues and high-efficiency recovery of phosphorus in the wastewater, and has remarkable environmental and social benefits.
Description
Technical Field
The invention relates to the field of solid waste resource utilization, in particular to a harmless and resource utilization method of calcium/iron-rich antibiotic bacterium residues.
Background
Antibiotic residues are residual solid waste produced during antibiotic fermentation. 10t antibiotic residues are produced every 1t antibiotic production. Antibiotic residues are rich in protein and have been used as feed or feed additives in the early days. However, the fungus dregs contain toxic and harmful substances such as residual antibiotics, resistance genes, heavy metals and the like, and the potential threats to the ecological environment and the human health cannot be ignored. As hazardous waste, the treatment and disposal cost of the antibiotic fungi residues reaches 2000 to 4000 yuan/t. How to realize the harmless and resource utilization of the antibiotic fungi residues is a troublesome problem for antibiotic production enterprises.
In order to improve the dehydration efficiency of the wet fungus residues and reduce the total amount of the fungus residues, an antibiotic production enterprise adds medicaments such as limestone, calcium sulfate, polyferric sulfate and the like into the wet fungus residues with the water content of 90-95%, then the wet fungus residues are treated by dehydration equipment such as a high-pressure plate-and-frame filter press and the like to form calcium/iron-rich antibiotic fungus residues with the water content of about 50%, and then the calcium/iron-rich antibiotic fungus residues are treated by a hazardous waste disposal company. At present, the antibiotic fungus sediment is handled mainly with burning mode to danger useless processing company, has shortcomings such as treatment cost is high, living beings and calcium iron metal resource waste, and the fungus sediment burns simultaneously and still can emit a large amount of greenhouse gas, violates the national "two carbon" target. In addition, the treatment mode of the bacterial residues also comprises composting, anaerobic digestion and the like, and although the resource utilization of the bacterial residues can be realized, the treatment of residual antibiotics in the bacterial residues is incomplete, so that the environmental risk is caused.
The high-temperature oxygen-limited pyrolysis is a fungi residue treatment technology with simple operation and good prospect. Chinese patent application number 201910587294.5 discloses a resourceful treatment system for antibiotic mushroom dregs and animal wastes in a farm, and the system produces biochar by co-pyrolysis of the mushroom dregs and the animal wastes, but does not provide specific application of the biochar. Chinese patent application No. 20211020635.8 discloses a resource utilization method of streptomycin mushroom dregs, which is used for pyrolyzing mushroom dregs into biochar. The biochar can be applied after being modified, and the specific application is unknown. The pyrolysis carbonization technology can convert the mushroom dregs into the biochar, but the obtained biochar has different properties and large functional difference, so that the specific application is not needed, and the recycling degree of the mushroom dregs is limited.
Disclosure of Invention
In order to solve the above-mentioned defects of the prior art, the invention aims to provide a harmless and recycling method of calcium/iron-rich antibiotic residues. The method comprises the steps of firstly, pyrolyzing and carbonizing calcium/iron-rich antibiotic fungi residues to obtain magnetic biochar; secondly, the magnetic biochar is used for recovering phosphorus in the wastewater; and finally applying the magnetic biochar enriched with phosphorus as a phosphorus slow-release fertilizer to soil. The method provided by the invention can reduce the emission of carbon dioxide, truly realize harmless and resource utilization of antibiotic bacterium residues and high-efficiency recovery of phosphorus in the wastewater, and has remarkable environmental and social benefits.
The technical scheme adopted by the invention is as follows:
a harmless and resource utilization method of calcium/iron-rich antibiotic residues comprises the following steps:
(1) Pyrolysis and carbonization: preheating and drying the calcium/iron-rich antibiotic residues at 60-105 ℃ for 3-12h, then carrying out pyrolysis carbonization at 300-700 ℃ for 1-3h, and finally grinding into powder to obtain magnetic biochar;
(2) Adsorbing phosphorus in the wastewater: putting the magnetic biochar obtained in the step (1) into phosphorus-containing wastewater according to the proportion of 1 g/L, stirring 24 h, and separating the magnetic biochar from the wastewater by using a magnetic field to obtain phosphorus-rich magnetic biochar;
(3) Applying to soil: the phosphorus-rich magnetic biochar is applied to soil according to the proportion of 2-10 wt%, and then crops are planted on the soil.
Further, in the step (1), the calcium/iron-rich antibiotic fungi residues are vancomycin fermentation residues, the calcium and iron contents are 7-20 wt% and the water content is 20-50% by weight.
Further, in the step (1), the carbonization temperature is preferably 600 ℃.
Further, in the step (1), the pyrolytic carbonization is performed under the condition of isolating air or oxygen, or performed in a nitrogen or carbon dioxide atmosphere.
Further, in the step (2), the phosphorus-containing wastewater comprises at least one of culture tail water, urine, sludge anaerobic fermentation liquor and effluent of an urban sewage treatment plant.
Further, in the step (2), the magnetic field is provided by an electromagnet or a permanent magnet.
Further, in the step (3), the crop is one of quinoa and wheat.
The invention has the beneficial effects that:
(1) Residual antibiotics and resistance genes in the antibiotic mushroom dregs can be eliminated, and the mushroom dregs are harmless;
(2) Calcium and iron which are rich in the mushroom dregs can be fully utilized, and the calcium and the iron provide active sites for adsorbing phosphorus for the magnetic biochar after the mushroom dregs are carbonized, so that the magnetic biochar can efficiently adsorb the phosphorus in the wastewater without modification, and thus, the dual resource utilization of biomass resources and calcium/iron metal resources in the mushroom dregs is realized;
(3) The bacteria residues are pyrolyzed and carbonized into magnetic biochar for adsorbing phosphorus in the wastewater, and the adsorbed magnetic biochar can be separated from water through a magnetic field, so that the high-efficiency recovery of the phosphorus in the wastewater is realized, and the current situation of phosphorus resource shortage is favorably alleviated.
(4) The magnetic biochar enriched with phosphorus in the wastewater is applied to the soil, so that the biochar can be used for improving the soil, slow-release phosphate fertilizer can be provided for plant growth, and carbon in the mushroom dregs is fixed in the soil, so that carbon sequestration and emission reduction are realized.
(5) The influence of the specific surface area, the iron content and the calcium content in the magnetic biochar on the phosphorus adsorption quantity is comprehensively considered, and the optimal fungus residue carbonization temperature is obtained.
In a word, compared with the prior art, the invention provides a complete and systematic scheme for harmless and resource utilization of the antibiotic bacterial residues, and the method is simple, has strong operability and has multiple and obvious environmental and social benefits.
Drawings
FIG. 1 is an XRD spectrum of magnetic biochar prepared at different carbonization temperatures (in the diagram, VFR represents vancomycin fungi residues, and VBC 300-VBC 700 represent magnetic biochar obtained by pyrolysis and carbonization of the vancomycin fungi residues at 300-700 ℃).
FIG. 2 is a graph showing the correlation between the adsorption capacity of magnetic biochar for phosphorus in wastewater and the calcium content, iron content and specific surface Area in the magnetic biochar prepared at different carbonization temperatures (in the graph, AC represents the adsorption amount, area represents the specific surface Area, fe represents the iron content, and Ca represents the calcium content).
FIG. 3 is an XRD spectrum of phosphorus adsorption by charcoal obtained by pyrolysis and carbonization of vancomycin fungi residue at 600 ℃.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. The examples of the present invention are for better understanding of the present invention by those skilled in the art, and do not limit the present invention in any way. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art, and the raw materials used are commercially available products.
The calcium/iron antibiotic-rich fungi residues used in examples 1-5 had a calcium content of 11.97 wt%, an iron content of 8.80 wt%, and a water content of 30wt%.
Example 1
Preheating and drying the calcium/iron-rich antibiotic fungi residues at 60 ℃ for 6h, then carrying out pyrolysis and carbonization at 300 ℃ in a nitrogen atmosphere for 2h, and finally grinding into powder to obtain the magnetic biochar.
Example 2
Preheating and drying the calcium/iron-rich antibiotic fungi residues at 90 ℃ for 6h, then pyrolyzing and carbonizing the calcium/iron-rich antibiotic fungi residues at 400 ℃ in a nitrogen atmosphere for 2h, and finally grinding the calcium/iron-rich antibiotic fungi residues into powder to obtain the magnetic biochar.
Example 3
Preheating and drying the calcium/iron-rich antibiotic fungi residues at 90 ℃ for 6h, then carrying out pyrolysis and carbonization at 500 ℃ in a nitrogen atmosphere for 2h, and finally grinding into powder to obtain the magnetic biochar.
Example 4
Preheating and drying the calcium/iron-rich antibiotic fungi residues at 105 ℃ for 6h, then pyrolyzing and carbonizing the calcium/iron-rich antibiotic fungi residues at 600 ℃ in a nitrogen atmosphere for 2h, and finally grinding the calcium/iron-rich antibiotic fungi residues into powder to obtain the magnetic biochar.
Example 5
Preheating and drying the calcium/iron-rich antibiotic fungi residues at 105 ℃ for 6h, then pyrolyzing and carbonizing the calcium/iron-rich antibiotic fungi residues at 700 ℃ in nitrogen atmosphere for 2h, and finally grinding the calcium/iron-rich antibiotic fungi residues into powder to obtain the magnetic biochar.
The determination results of the vancomycin content in the calcium/iron-rich antibiotic fungi residues and the magnetic biochar obtained in example 1~5 are shown in table 1. As can be seen from Table 1, the vancomycin content in the mushroom dregs reaches 560.7 +/-157.7 mg/kg, and the mushroom dregs obviously have serious environmental hazard. After pyrolysis and carbonization, vancomycin in the biochar is not detected, which shows that the pyrolysis and carbonization can eliminate residual antibiotics in the mushroom dregs, so that the mushroom dregs are harmless.
TABLE 1 vancomycin content in fungi residue and magnetic charcoal
X-ray diffraction (XRD) analysis was performed on the calcium/iron-rich antibiotic fungi residues and the magnetic biochar obtained in example 1~5, and the results are shown in FIG. 1. In FIG. 1, VFR represents mushroom dregs, and VBC300 to VBC700 represent magnetic biochar obtained in example 1~5, respectively. As can be seen from FIG. 1, calcium in the mushroom dregs is mainly CaSO 4 While iron exists in the form of mainly amorphous polyferric sulfate and cannot be detected from an XRD spectrum. After pyrolysis and carbonization, calcium in the biochar is mainly CaSO 4 And CaCO 3 Exists in a form, and the polymeric ferric sulfate is converted into Fe 3 O 4 And Fe 2 O 3 . Due to Fe 3 O 4 And Fe 2 O 3 All of which are magnetic.
Example 6
The magnetic biochar obtained in example 1~5 was added to phosphorus-containing wastewater having an initial phosphorus concentration of 100 mg/L at a ratio of 1 g/L, and after stirring 24 h, the magnetic biochar was separated from the wastewater by a magnetic field. And measuring the concentration of residual phosphorus in the water, and calculating the adsorption quantity of the magnetic biochar to the phosphorus. The phosphorus adsorption amounts of the magnetic biochar obtained in example 1~5 were 5.71, 20.7, 24.3, 33.9, and 29.1 mg/g, respectively. Therefore, the carbonization temperature influences the adsorption amount of the magnetic biochar to the phosphorus.
The contents of calcium and iron and the specific surface area of the magnetic biochar obtained in example 1~5 were measured, and the correlations between the amount of adsorption, the calcium content, the iron content and the specific surface area were analyzed, and the results are shown in table 2 and fig. 2. As can be seen from FIG. 2, the correlation between the phosphorus adsorption amount of the magnetic biochar and the iron and calcium contents in the biochar is strong, which indicates that the iron and calcium are active sites of the magnetic biochar for adsorbing phosphorus. In order to further reveal the mechanism of phosphorus adsorption of the magnetic biochar, XRD analysis was performed on the phosphorus-rich magnetic biochar obtained after the magnetic biochar of example 4 was used to adsorb phosphorus, and the results are shown in fig. 3. As can be seen from FIG. 3, fe is produced after the magnetic biochar adsorbs phosphorus 3 (PO 4 ) 2 And Ca 5 (PO 4 ) 3 And OH new matter phase, which shows that iron and calcium on the magnetic biochar can adsorb phosphorus through chemical actions such as chemical precipitation or inner layer complexation. Therefore, as the carbonization temperature was increased from 300 ℃ to 600 ℃, the content of calcium and iron in the magnetic biochar was increased (table 2), and the amount of phosphorus adsorbed by the magnetic biochar was also increased. When the carbonization temperature is further increased to 700 ℃, the contents of calcium and iron are increased, but the specific surface area is reduced to 4.911 m 2 The adsorption capacity is reduced to 29.1 mg/g. It is seen that the specific surface area of the magnetic biochar also affects the amount of phosphorus adsorbed, and it is presumed that the magnetic biochar may adsorb phosphorus by physical action such as electrostatic attraction.
In summary, the mechanism of phosphorus adsorption by magnetic biochar includes chemical precipitation, inner layer complexation, electrostatic attraction, and the like.
TABLE 2 calcium and iron contents and specific surface area of magnetic biochar from example 1~5
Example 7
The magnetic biochar obtained in example 4 is put into phosphorus-containing wastewater with the initial phosphorus concentration of 100 mg/L according to the proportion of 1 g/L, and after 24 h is stirred, the magnetic biochar is separated from the wastewater by a magnetic field to obtain the phosphorus-rich magnetic biochar. The phosphorus-rich magnetic biochar is applied to soil according to the proportion of 2wt%, and then chenopodium quinoa is planted on the soil. After 5 days, the height of the quinoa stalk is 43% higher than that of the control group without the application of the phosphorus-rich magnetic charcoal.
Example 8
The magnetic biochar obtained in example 4 is put into phosphorus-containing wastewater with the initial phosphorus concentration of 100 mg/L according to the proportion of 1 g/L, and after 24 h is stirred, the magnetic biochar is separated from the wastewater by a magnetic field to obtain the phosphorus-rich magnetic biochar. Applying the phosphorus-rich magnetic biochar into soil according to the proportion of 5wt%, and then planting quinoa on the soil. After 5 days, the height of the Chenopodium quinoa stems was 56% higher than that of the control group to which the phosphorus-rich magnetic charcoal was not applied.
Example 9
The magnetic biochar obtained in example 4 is added into phosphorus-containing wastewater with the initial phosphorus concentration of 100 mg/L according to the proportion of 1 g/L, and after 24 h is stirred, the magnetic biochar is separated from the wastewater by a magnetic field, so that phosphorus-rich magnetic biochar is obtained. The phosphorus-rich magnetic biochar is applied to soil according to the proportion of 10wt%, and then chenopodium quinoa is planted on the soil. After 5 days, the height of the quinoa stalk is 95% higher than that of the control group without the application of the phosphorus-rich magnetic charcoal.
From the results of example 7, example 8 and example 9, it can be seen that the phosphorus-rich magnetic biochar can be applied to soil as a phosphate fertilizer to promote the growth of quinoa. Therefore, the recovery of phosphorus in the wastewater is realized, and the biochar applied to the soil can also play a role in carbon fixation.
In conclusion, the method for recycling the calcium/iron-rich antibiotic fungi residues is simple to operate, harmless and obvious in recycling effect; the obtained magnetic biochar has strong phosphorus adsorption capacity, does not need further modification and has clear application. The scheme provided by the invention can realize harmless treatment and resource utilization of hazardous waste, promote the recovery and circulation of phosphorus in the wastewater, and has the environmental benefits of carbon fixation and emission reduction and wide application prospect.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, combinations, and sub-combinations which do not depart from the spirit and principle of the present invention are deemed to be equivalent substitutions and all included within the scope of the present invention.
Claims (7)
1. A harmless and resource utilization method of calcium/iron-rich antibiotic residues is characterized by comprising the following steps:
(1) Pyrolysis and carbonization: preheating and drying the calcium/iron-rich antibiotic residues at 60 to 105 ℃ for 3 to 12h, then carrying out pyrolysis and carbonization at 300 to 700 ℃ for 1 to 3h, and finally grinding into powder to obtain magnetic charcoal;
(2) Adsorbing phosphorus in the wastewater: putting the magnetic biochar obtained in the step (1) into phosphorus-containing wastewater according to the proportion of 1 g/L, stirring 24 h, and separating the magnetic biochar from the wastewater by using a magnetic field to obtain phosphorus-rich magnetic biochar;
(3) Applying to soil: the phosphorus-rich magnetic biochar is applied to soil according to the proportion of 2-10 wt% and is used for planting crops.
2. The harmless and resource utilization method of the calcium/iron-rich antibiotic residues according to claim 1, wherein in the step (1), the calcium/iron-rich antibiotic residues are vancomycin fermentation residues, the calcium and iron contents are 7wt% -20 wt%, and the water content is 20wt% -50 wt%.
3. The method for harmless and resource utilization of calcium/iron-rich antibiotic residues according to claim 1, wherein in the step (1), the carbonization temperature is 600 ℃.
4. The method for harmless and resource utilization of calcium/iron-rich antibiotic residues according to claim 1, wherein in the step (1), the pyrolysis carbonization is performed under the condition of isolating air or oxygen, or in the atmosphere of nitrogen or carbon dioxide.
5. The method for harmless and resource utilization of calcium/iron-rich antibiotic residues according to claim 1, wherein in the step (2), the phosphorus-containing wastewater comprises at least one of culture tail water, urine, sludge anaerobic fermentation liquor and effluent of municipal sewage treatment plants.
6. The method for the harmless and resource utilization of the calcium/iron-rich antibiotic residues according to claim 1, wherein in the step (2), the magnetic field is provided by an electromagnet or a permanent magnet.
7. The method for harmlessly recycling and resource-utilizing the calcium/iron-rich antibiotic residues according to claim 1, wherein in the step (3), the crop is one of quinoa and wheat.
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