CN114031222A - Method for purifying pig-raising wastewater by using manganese metal self-loaded biochar - Google Patents
Method for purifying pig-raising wastewater by using manganese metal self-loaded biochar Download PDFInfo
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 61
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- 241001057636 Dracaena deremensis Species 0.000 claims description 2
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- QFGIVKNKFPCKAW-UHFFFAOYSA-N [Mn].[C] Chemical compound [Mn].[C] QFGIVKNKFPCKAW-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
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- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
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- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
-
- 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
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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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
- C02F2101/20—Heavy metals or heavy metal compounds
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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
- C02F2101/30—Organic compounds
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/20—Nature of the water, waste water, sewage or sludge to be treated from animal husbandry
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Abstract
The invention discloses a method for purifying pig raising wastewater by using manganese metal self-loading biochar, which comprises the following steps: preparing the manganese metal self-loading biochar; pretreating pig raising excrement, and carrying out solid-liquid separation; blending pig raising wastewater; and (5) purifying. The preparation of the manganese metal self-loading biochar comprises the steps of crushing maize straws harvested from manganese-rich soil, drying, pyrolyzing at high temperature, cooling,Grinding to obtain the manganese metal self-loading biochar. Blending the pig raising wastewater, namely adding the pig raising wastewater after solid matter separation into the manganese metal self-loading biochar according to the weight ratio of 1: 500-1: 300; and (3) purifying, namely keeping the water depth of the blended pig raising wastewater not more than 1.2m, keeping the water temperature at 10-55 ℃, keeping the water temperature at 100r/min, and treating for 6-10 h. The invention can realize the effect of antibiotics and Cu in the pig-raising wastewater2+Has high efficiency, low cost and synergistic removal of antibiotics and Cu2+The removal rate is more than or equal to 90 percent.
Description
Technical Field
The invention relates to a method for purifying pig raising wastewater, belongs to the technical field of environmental protection, and particularly relates to the technical field of wastewater treatment.
Background
Through the rapid development of nearly 20 years, China becomes the first producing and consuming country for meat, poultry and eggs, and the annual livestock and poultry excrement production amount is about 38 hundred million tons. In order to accelerate the growth of livestock and poultry and reduce the occurrence of diseases, a large amount of feed additives and antibiotics are used in the livestock and poultry breeding process. In 2019, a Chinese veterinary antibacterial drug use condition report issued by the Ministry of rural agriculture suggests that in 2019, veterinary antibiotics used in China are 30903.66 tons, and because the livestock and poultry have limited absorption to the antibiotics, the antibiotics usually enter breeding excrement through excretion, so that a large amount of antibiotics exist in the breeding excrement. Antibiotics generally have mobility, stability and accumulation, after entering the environment, part of microbial populations and ecological functions of the microbial populations disappear in a polluted environment medium due to the sterilization and bacteriostasis effects of the antibiotics in a short time, and antibiotic resistance genes, drug-resistant bacteria and even super bacteria can be caused by long-term pollution. The addition of copper in the feed can promote the growth of piglets, maintain the production performance and improve the hematopoietic function and immunity of organisms, so that the pig raising feces contain excessive copper, which is easy to cause environmental pollution and damage to the ecological environment. Therefore, how to effectively remove the antibiotic residues and the copper residues in the culture manure is one of the important challenges facing water quality safety, environmental safety and ecological safety. Due to the microbial toxicity of antibiotics, the biological water treatment process with obvious economic benefits is difficult to efficiently and stably operate in the pig-raising wastewater treatment, so that the effluent quality is difficult to reach the standard. Therefore, the physical method and the chemical method are widely applied to the treatment of the pig-raising wastewater, and the chemical method needs a large amount of actual consumption, so that the economy is poor, and secondary pollution is caused by the large amount of chemical reagents. The adsorption method is one of the widely used physical treatment methods at present, and adsorbs and fixes antibiotics and heavy metals in the wastewater through an adsorbent with rich specific surface area, but the method only realizes the transfer of pollutants, does not completely eliminate and convert the pollutants, and has the possibility of secondary environmental pollution caused by the use of a large amount of the adsorbent and the adsorbent after saturated adsorption.
In the invention, manganese metal ions contained in the manganese metal self-loading biochar come from manganese-rich soil (such as iron and manganese tailing reservoirs, slag, plant and mine surrounding soil and the like), manganese is enriched in plant bodies by utilizing developed root systems of corns and manganese enrichment capacity, on one hand, the remediation of soil pollution is realized, on the other hand, non-exogenous added manganese metal is realized, and further, the biochar loaded with manganese contains rich specific surface area and can be used for treating Cu in wastewater2+Has excellent adsorption effect, and simultaneously forms manganese-carbon and manganese-copper microelectrode pairs in the biochar body, can form rich electron-hole pairs, the electron-hole pairs oxidize OH absorbed on the biochar surface into hydroxyl free radicals (HO.), and O excited by the electrons is dissolved in water2Combined to form superoxide anion radical (. O)2-) dissolved organic pollutants and antibiotics in the pig raising wastewater are degraded into carbon dioxide, water and other small molecular substances by hydroxyl radicals and superoxide anion radicals, and the antibiotics and Cu in the pig raising wastewater2+The removal rate is more than or equal to 90 percent. The invention relates to antibiotics and Cu in pig raising wastewater2+The efficient synergistic removal of (a) provides a new technical approach and method.
Disclosure of Invention
The invention aims to provide a method for purifying pig raising wastewater by using manganese metal self-loading biochar, which can realize low-cost and high-efficiency synergistic removal of antibiotics and Cu in pig raising wastewater2+Provides a new idea for resource utilization of the metal-rich plant bodies and provides a new technical approach and method for deep purification of the pig-raising wastewater.
The invention is realized by the following technical scheme:
a method for purifying pig raising wastewater by using manganese metal self-loading biochar sequentially comprises the following steps: A. preparing the manganese metal self-loading biochar; b. Pretreating pig raising excrement, and carrying out solid-liquid separation; C. blending pig raising wastewater; D. and (5) purifying.
Preferably, in the step A, the manganese metal self-loading biochar is prepared by crushing, drying, pyrolyzing at high temperature, cooling and grinding corn straws.
Preferably, in the step B, the pig raising manure is pretreated and solid-liquid separation is carried out; the method comprises the steps of filtering with a 20-270-mesh screen and performing plate-frame filter pressing to realize solid-liquid separation of suspended solids, and adding 0.01-0.05% of polyacrylamide flocculant into filtrate to realize solid-liquid separation of insoluble impurities, so as to finally obtain the swine wastewater after solid matters are separated.
Preferably, in the step C, the pig raising wastewater is prepared by adding the manganese metal self-supported biochar into the pig raising wastewater after the solid matter is separated according to the weight ratio of 1: 500-1: 300.
Preferably, in the step D, the purification treatment is to keep the water depth of the blended pig raising wastewater not more than 1.2m, the water temperature is 10-55 ℃, 100r/min and the treatment time is 6-10 h.
Preferably, in the step A, the corn stalks are corn plants which grow in manganese-rich soil for 30 to 50 days.
Preferably, in the step A, the drying is carried out in an oven at 80 ℃ for 12 hours.
Preferably, in the step A, the high-temperature pyrolysis is high-temperature heat treatment at 400-600 ℃ in a tubular furnace in a nitrogen atmosphere, the high-temperature pyrolysis time is 1-2 h, and the temperature rise speed is 5-10 ℃/min.
The invention utilizes developed root system of corn and enrichment capacity of manganese to enrich manganese in plant body, and manganese-rich organism is obtained by high-temperature pyrolysis in nitrogen atmosphereCarbon with abundant specific surface area for Cu in waste water2+Realizing high-efficiency adsorption, forming manganese-carbon and manganese-copper microelectrode pairs, forming abundant electron-hole pairs, oxidizing OH absorbed on the surface of the biochar into hydroxyl free radical (HO), and dissolving the excited electrons in water2Combined to form superoxide anion radical (. O)2-) dissolved organic pollutants and antibiotics in the pig raising wastewater are degraded into carbon dioxide, water and other small molecular substances by hydroxyl radicals and superoxide anion radicals. Antibiotics and Cu in pig raising wastewater2+The removal rate is more than or equal to 90 percent.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
FIG. 1 is an SEM image of the manganese metal self-supporting biochar prepared in example 1 of the present invention.
FIG. 2 is an XPS graph of a self-supporting biochar of manganese metal prepared in example 1 of the present invention.
FIG. 3 is a FT-IR chart of the manganese metal self-supporting biochar prepared in example 1 of the present invention.
Fig. 4 is an XRD pattern of the manganese metal self-supporting biochar prepared in example 1 of the present invention.
FIG. 5 is a graph showing the effect of metal manganese self-supporting biochar on tetracycline removal in examples 1, 2, and 3 of the present invention.
FIG. 6 shows the results of examples 1, 2 and 3 of the present invention in which manganese metal is self-supported on charcoal and Cu is added2+The removal effect map of (1).
As can be seen from figure 1, the prepared manganese metal self-loading biochar has a rich and complete cavity-hole structure, and the pore channel of the biochar is not seriously damaged by high-temperature pyrolysis. The Mn peak, except C, N, O, appears in the self-supported biochar shown in fig. 2, indicating that Mn achieves successful loading. As can be seen from FIG. 3, the prepared manganese metal self-loading biochar contains rich and various oxygen-containing functional groups, and simultaneously forms unique metal-O functional groups, which may be the prepared manganese metal self-loading biocharThe important reason for the excellent performance. The XRD characterization result shown in figure 4 shows that the manganese in the prepared manganese metal self-loading biochar is mainly Mn2O3，MnO2And oxides of manganese such as MnO, which are in communication with the metal oxide catalyst. As can be seen from FIG. 5, when the initial concentration of the antibiotics in the pig raising wastewater is 68.6-83.1 mg/kg, the removal rate of the antibiotics can reach more than 90% after 5 hours of treatment, and can reach more than 97% after 8 hours of treatment. As can be seen from FIG. 6, for Cu in the wastewater from pig farming2+The initial concentration is 4.75-6.64 mg/kg, and Cu is obtained after 4 hours of treatment2+The removal rate can reach more than 98 percent, the antibiotic removal rate can reach more than 99 percent after the treatment for 8 hours.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1: A. preparing the metal manganese self-loading biochar: harvesting corn straws collected from manganese-rich soil and growing for 30 days, crushing the corn straws to 2cm, drying the corn straws in an oven at 80 ℃ for 12 hours, putting the corn straws into a nitrogen atmosphere tube furnace, setting the temperature rise speed to be 5 ℃/min, and treating the corn straws at 400 ℃ for 2 hours; cooling to room temperature, and grinding to 60 meshes to obtain the manganese metal self-loading biochar; B. pretreating pig raising manure, and performing solid-liquid separation: filtering with a 140-mesh screen and performing plate-and-frame filter pressing to realize solid-liquid separation of suspended solids, and adding 0.01% polyacrylamide flocculant into the filtrate to realize solid-liquid separation of insoluble impurities, thereby finally obtaining the swine wastewater after solid matters are separated; C. blending pig raising wastewater: adding the pig raising wastewater after the solid matter separation into the manganese metal self-loading biochar according to the weight ratio of 1: 500; D. and (3) purification treatment: keeping the water depth of the blended pig raising wastewater to be not more than 1.0m, keeping the water temperature at 25 ℃, and treating for 8 hours at 100 r/min. Can realize the antibiotics and Cu in the pig raising wastewater2+Efficient, inexpensive, synergistic removal.
Example 2: A. preparing the metal manganese self-loading biochar: harvesting corn stalks collected from manganese-rich soil and growing for 30 days, pulverizing to 2cm, drying in an oven at 80 deg.C for 12 hr, and placing in nitrogen atmosphereA tubular furnace, wherein the temperature rise speed is set to be 5 ℃/min, and the treatment is carried out for 2h at the temperature of 400 ℃; cooling to room temperature, and grinding to 60 meshes to obtain the manganese metal self-loading biochar; B. pretreating pig raising manure, and performing solid-liquid separation: filtering with a 140-mesh screen and performing plate-and-frame filter pressing to realize solid-liquid separation of suspended solids, and adding 0.01% polyacrylamide flocculant into the filtrate to realize solid-liquid separation of insoluble impurities, thereby finally obtaining the swine wastewater after solid matters are separated; C. blending pig raising wastewater: adding the pig raising wastewater after the solid matter separation into the manganese metal self-loading biochar according to the weight ratio of 1: 400; D. and (3) purification treatment: keeping the water depth of the blended pig raising wastewater to be not more than 1.0m, keeping the water temperature at 25 ℃, and treating for 8 hours at 100 r/min. Can realize the antibiotics and Cu in the pig raising wastewater2+Efficient, inexpensive, synergistic removal.
Example 3: A. preparing the metal manganese self-loading biochar: harvesting corn straws collected from manganese-rich soil and growing for 30 days, crushing the corn straws to 2cm, drying the corn straws in an oven at 80 ℃ for 12 hours, putting the corn straws into a nitrogen atmosphere tube furnace, setting the temperature rise speed to be 5 ℃/min, and treating the corn straws at 400 ℃ for 2 hours; cooling to room temperature, and grinding to 60 meshes to obtain the manganese metal self-loading biochar; B. pretreating pig raising manure, and performing solid-liquid separation: filtering with a 140-mesh screen and performing plate-and-frame filter pressing to realize solid-liquid separation of suspended solids, and adding 0.01% polyacrylamide flocculant into the filtrate to realize solid-liquid separation of insoluble impurities, thereby finally obtaining the swine wastewater after solid matters are separated; C. blending pig raising wastewater: adding the pig raising wastewater after the solid matter separation into the manganese metal self-loading biochar according to the weight ratio of 1: 300; D. and (3) purification treatment: keeping the water depth of the blended pig raising wastewater to be not more than 1.0m, keeping the water temperature at 25 ℃, and treating for 8 hours at 100 r/min. Can realize the antibiotics and Cu in the pig raising wastewater2+Efficient, inexpensive, synergistic removal.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes, modifications, additions or substitutions that can be easily made by those skilled in the art within the technical scope of the present invention are within the spirit of the present invention and are also covered by the scope of the present invention.
Claims (8)
1. A method for purifying pig-raising wastewater by using manganese metal self-loading biochar is characterized by comprising the following steps: the method sequentially comprises the following steps: A. preparing the manganese metal self-loading biochar; b. Pretreating pig raising excrement, and carrying out solid-liquid separation; C. blending pig raising wastewater; D. and (5) purifying.
2. The method for purifying the pig wastewater by using the manganese metal self-loading biochar as claimed in claim 1, is characterized in that: in the step A, the manganese metal self-loading biochar is prepared by crushing, drying, pyrolyzing at high temperature, cooling and grinding corn straws.
3. The method for purifying the pig wastewater by using the manganese metal self-loading biochar as claimed in claim 1, is characterized in that: b, pretreating the pig raising excrement and separating solid from liquid; the method comprises the steps of filtering with a 20-270-mesh screen and performing plate-frame filter pressing to realize solid-liquid separation of suspended solids, and adding 0.01-0.05% of polyacrylamide flocculant into filtrate to realize solid-liquid separation of insoluble impurities, so as to finally obtain the swine wastewater after solid matters are separated.
4. The method for purifying the pig wastewater by using the manganese metal self-loading biochar as claimed in claim 1, is characterized in that: and C, blending the pig raising wastewater after the solid matter is separated into the pig raising wastewater according to the weight ratio of 1: 500-1: 300, and adding the manganese metal self-loading biochar.
5. The method for purifying the pig wastewater by using the manganese metal self-loading biochar as claimed in claim 1, is characterized in that: in the step D, the purification treatment is to keep the water depth of the blended pig raising wastewater not more than 1.2m, the water temperature is 10-55 ℃, 100r/min and the treatment time is 6-10 h.
6. The method for purifying the pig-raising wastewater by using the manganese metal self-loading biochar according to the claims 1 and 2, is characterized in that: in the step A, the corn straws are corn plants which grow in the manganese-rich soil for 30-50 days.
7. The method for purifying the pig-raising wastewater by using the manganese metal self-loading biochar according to the claims 1 and 2, is characterized in that: in the step A, the drying is carried out in an oven at 80 ℃ for 12 h.
8. The method for purifying the pig-raising wastewater by using the manganese metal self-loading biochar according to the claims 1 and 2, is characterized in that: in the step A, the high-temperature pyrolysis is high-temperature heat treatment at 400-600 ℃ in a nitrogen atmosphere tube furnace, the high-temperature pyrolysis time is 1-2 h, and the temperature rise speed is 5-10 ℃/min.
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