CN112619615A - Preparation method of biochar-microorganism composite material and method for treating tailing wastewater - Google Patents
Preparation method of biochar-microorganism composite material and method for treating tailing wastewater Download PDFInfo
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- C02F1/28—Treatment of water, waste water, or sewage by sorption
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Abstract
The embodiment of the invention discloses a preparation method of a biochar-microorganism composite material and a method for treating tailing wastewater. The preparation method comprises the following steps: step (1): pyrolyzing biomass to obtain biochar, the biochar having a porous structure; step (2): preparing xanthate function degradation flora, including inoculation flora, culture flora, domestication flora and construction flora; and (3): mixing the biochar with xanthate function degrading flora to obtain a biochar-microorganism composite material. The biochar-microorganism composite material can effectively remove xanthate and heavy metal ions in the tailing wastewater.
Description
Technical Field
The invention relates to the technical field of tailing wastewater treatment, in particular to a preparation method of a biochar-microorganism composite material and a method for treating tailing wastewater.
Background
In the process of mining and selecting metal ores such as gold ores and the like, a large amount of flotation reagents are usually required to be added for the mining, separation and enrichment of mineral resources such as various metals and the like; meanwhile, a large amount of tailing wastewater is generated along with the processes of crushing, grinding, flotation and concentration. The beneficiation reagent used in large amount in the metal mining area remains in the waste water and waste residue in the tailing area along with the discharge of the tailings. The beneficiation reagent can be subjected to leaching, oxidation and the like due to long-term existence in the environment, so that harmful ingredients in the beneficiation reagent can flow into water, soil and the like along with surface runoff or subsurface infiltration. This pollutes the ecological environment and poses a potential threat to the living body. The flotation reagents are various in types and large in dosage, so that the beneficiation wastewater is complex in components, high in pollutant concentration and high in toxicity. Because the mineral processing wastewater contains a flotation reagent and a foaming agent, the direct recycling of the mineral processing wastewater has strong foamability, so that the flotation is difficult to control and pipelines are blocked, and meanwhile, the flotation effect is influenced by heavy metal ions in the tailing wastewater. Therefore, the advanced treatment of the beneficiation wastewater effectively controls the discharge of the wastewater of the beneficiation plants, improves the utilization rate of the beneficiation water, and is an effective way for controlling the pollution and harm of the wastewater.
Disclosure of Invention
In order to solve at least one aspect of the above technical problems, the present invention provides a method for preparing a biochar-microorganism composite and a method for treating tailing wastewater.
According to an aspect of the present invention, there is provided a method for preparing a biochar-microorganism composite, comprising: step (1): pyrolyzing biomass to obtain biochar, the biochar having a porous structure; step (2): preparing xanthate function degradation flora; and (3): mixing the biochar with xanthate function degrading flora to obtain a biochar-microorganism composite, wherein the step (2) comprises the following steps: inoculating a pollution source into a culture solution according to the volume ratio of 10-30%, maintaining the temperature at 15-37 ℃, controlling the dissolved oxygen to be 3-7 mg/L, and detecting the removal rate of xanthate in the culture solution according to a preset time period; after the removal rate of the xanthate reaches more than 80 percent, continuously supplementing the xanthate and the induction substrate so as to ensure that the concentration of the xanthate in the culture solution reaches 300-500mg/L and the concentration of the induction substrate reaches 120-240 mg/L; continuously culturing the bacteria until the removal rate of the xanthate reaches over 90 percent, thereby obtaining a culture solution after the induction and domestication are finished; standing the culture solution after the induction domestication is finished, discarding 30-60% of supernatant, supplementing fresh culture solution to the expected total volume, supplementing xanthate to 900-1500 mg/L, and continuously culturing bacteria; and then when the removal rate of each xanthate reaches more than 90%, discarding 30-60% of supernatant, continuously supplementing fresh culture solution, and continuously culturing for 5-10 periods to construct xanthate function degradation flora.
According to an embodiment of the invention, the culture solution comprises: 0.2-5 g/L of yeast extract; the co-matrix composed of one or more of glucose, starch, ethanol and hydroximic acid is 0.1-5 g/L; 0.01-5 g/L of nitrogen source; 0.2-2 g/L of phosphorus source; CaCl2 0.001～1.02g/L；MgSO4 0.05～1.5g/L；FeSO40.03-0.2 g/L; 0.02-0.2 g/L of surfactant; 50-300 mg/L of xanthate; inducing substrate 60-200 mg/L, and adjusting the pH value of the culture solution to 5-8.
According to an embodiment of the present invention, the nitrogen source comprises one of peptone, urea, ammonium chloride, ammonium sulfate, ammonium nitrate or any combination thereof; and/or the phosphorus source comprises one or any combination of dipotassium hydrogen phosphate, potassium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, sodium tripolyphosphate and potassium tripolyphosphate; and/or the surfactant comprises sophorolipid, algal glycolipid, or a combination thereof; and/or the inducing substrate comprises one or any combination of ethidium, radix Polygoni Ciliinerve and pinitol oil; and/or the predetermined period of time is 12 hours, 24 hours, 48 hours, or 72 hours.
According to an embodiment of the present invention, the step (3) includes: sterilizing the biochar; mixing and oscillating the sterilized biological carbon and the bacteria liquid of the xanthate function degradation flora, adding sodium alginate and polyvinyl alcohol as composite carriers, adding one or any combination of 3-6% of calcium chloride boric acid saturated solution, 3-6% of calcium carbonate boric acid saturated solution and 3-6% of calcium lactate boric acid saturated solution to carry out hardening reaction, and wrapping with gauze after hardening to obtain the biological carbon-microorganism composite material.
According to the embodiment of the invention, the bacterial liquid of the sterilized biochar and xanthate function degradation flora is prepared by mixing 0.5-3 g: mixing at a ratio of 25 mL; and/or culturing the sterilized bacterial liquid of the biochar and xanthate function degradation flora for 12-36 h at the temperature of 20-30 ℃ and the oscillation speed of 120-240 r/min, wherein the number of the active xanthate function degradation bacteria is not less than 1 multiplied by 107cfu/mL; and/or adding 0.5-2 g: 25mL of Sodium Alginate (SA) and polyvinyl alcohol (PVA).
According to an embodiment of the present invention, the step (1) comprises: drying the biomass, washing to be neutral, drying, and crushing the dried biomass to 50-100 meshes; pyrolyzing the crushed biomass for 6-8 h at 300-700 ℃ in a protective atmosphere; adding an acidic solution or an alkaline solution into the pyrolyzed biomass to remove ash in the pyrolyzed biomass, oscillating for 10-12 h at room temperature, and then performing centrifugal separation; and repeatedly cleaning the filtrate by using deionized water until the pH value of the filtrate is 7, and drying for 6-18 h at the temperature of 60-80 ℃.
According to an embodiment of the invention, the biomass comprises one or any combination of straw, grain hulls, trees and their waste, livestock and poultry manure; and/or the source of pollution is from leachate from tailings waste water contaminated with xanthate or activated sludge in tailings ponds.
According to another aspect of the present invention, there is provided a process for treating tailings waste water comprising xanthate and heavy metal ions, the process comprising: step (1): standing the tailing wastewater for 1-2 d (days), pretreating the tailing wastewater by using a filter, and then adjusting the pH value of the tailing wastewater to be less than 10; step (2): adding the biochar in claim 1 into the pretreated tailing wastewater to remove xanthate and heavy metal ions in the tailing wastewater, oscillating for 10-120 min, and filtering to retain upper-layer wastewater; and (3): and (3) carrying out suction filtration on the retained wastewater, adding the biochar-microorganism composite material as defined in claim 1 into the filtrate to further remove xanthate and heavy metal ions in the tailing wastewater, oscillating for 10-120 min (min), and filtering to obtain a supernatant, wherein the supernatant is the treated tailing wastewater.
According to the embodiment of the invention, in the step (1), a quartz sand filter is used, the obtained filter material comprises natural quartz sand and manganese sand, the grain size of the sand is 0.5-2 mm, and the thickness of the filter layer is 5-15 cm; adjusting the pH value of the tailing wastewater to 6-8; in the step (2), the ratio of the biochar to the tailing wastewater is 20-50 g:1L, and/or the temperature is set to be 20-30 ℃ in the removal process, and the oscillation time is 10-60 min.
According to the embodiment of the invention, the diameter of the quartz sand filter is 7cm, and the filtering area is 38.47cm2The water flow is 14L/h; in the step (3), the ratio of the biochar-microorganism composite material to the tailing wastewater is 5-10 g: 1L; and/or setting the temperature to be 20-30 ℃ in the removing process, and the oscillation time to be 10-60 min.
Drawings
Fig. 1 illustrates a method of preparing a biochar-microorganism composite according to an embodiment of the present invention;
FIG. 2 illustrates a process for preparing xanthate function degrading flora according to an embodiment of the present invention;
figure 3 illustrates a method of treating tailings wastewater according to an embodiment of the invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described herein, and it will be apparent to those of ordinary skill in the art that the present invention may be practiced without departing from the spirit and scope of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
In the embodiment of the invention, the treatment method of the tailing wastewater comprises a chemical oxidation method, an advanced oxidation technology, a coagulation sedimentation method, an adsorption method and a biological method. Chemical oxidation and advanced oxidation techniques oxidize organic chemicals into small molecular substances by means of strongly oxidizing substances. The coagulation sedimentation method is to coagulate organic macromolecules into large-particle floc precipitates by adding a coagulant. The adsorption method is to adsorb organic pollutants by adding an adsorbent. The biological method is to carry out biodegradation on heavy metal ions or organic medicaments by special functional flora.
However, a single treatment method is often only capable of treating a certain type of contaminant. For example, the chemical oxidation method is only suitable for treating mineral processing wastewater containing organic chemicals, the treatment effect on the wastewater containing metal ions is limited, and the dosage of the chemical oxidant is difficult to be clear; although the biological method has good removal effect on metal ions and organic agents in the wastewater, biological strains are difficult to survive and play a role due to poor biodegradability of the beneficiation wastewater, so that the biological treatment method is difficult to be applied to beneficiation wastewater treatment in the actual production process; the flocculation sedimentation method is generally only applicable to mineral processing wastewater containing metal ions, and has a very limited effect of removing organic chemicals in the wastewater and chemical oxygen demand (CODCr) calculated by using potassium dichromate as an oxidizing agent. Therefore, the method has no ideal effect on the industrial treatment of beneficiation wastewater.
In another embodiment of the present invention, as shown in fig. 1-2, there is provided a method for preparing a biochar-microorganism composite, including: step (1): pyrolyzing biomass to obtain biochar, the biochar having a porous structure; step (2): preparing xanthate Degrading flora XDB (xanthate Degrading Bacteria); and (3): mixing the biochar with xanthate function degrading flora to obtain a biochar-microorganism composite, wherein the step (2) comprises the following steps: inoculating a pollution source into a culture solution according to the volume ratio of 10-30%, maintaining the temperature at 15-37 ℃, controlling the Dissolved Oxygen (DO) to be 3-7 mg/L, and detecting the removal rate of xanthate in the culture solution according to a preset time period; after the removal rate of the xanthate reaches more than 80 percent, continuously supplementing the xanthate and the induction substrate so as to ensure that the concentration of the xanthate in the culture solution reaches 300-500mg/L and the concentration of the induction substrate reaches 120-240 mg/L; continuously culturing the bacteria until the removal rate of the xanthate reaches over 90 percent, thereby obtaining a culture solution after the induction and domestication are finished; standing the culture solution after the induction domestication is finished, discarding 30-60% of supernatant, supplementing fresh culture solution to the expected total volume, supplementing xanthate to 900-1500 mg/L, and continuously culturing bacteria; and then when the removal rate of each xanthate reaches more than 90%, discarding 30-60% of supernatant, continuously supplementing fresh culture solution, and continuously culturing for 5-10 periods to construct xanthate function degradation flora. In the embodiment, the bacteria can take the biochar as a carrier and enhance the activity of the biochar because the biochar has large specific surface area, developed pore structure and rich nutrient elements; moreover, the domesticated flora can effectively remove xanthate in the wastewater.
In an embodiment, the biomass comprises one of straw, grain hulls, trees and their waste, livestock and poultry manure, or any combination thereof. For example, the straw includes corn stover, wheat straw, rice straw, sugar cane straw, and the like; the grain shell comprises peanut shells, rice shells, soybean shells and the like; the trees and their waste materials comprise bamboo, bark, etc.; the livestock and poultry manure comprises chicken manure, duck manure, pig manure and the like. In an embodiment, the source of pollution is from groundwater of tailings waste water or leachate of tailings pond activated sludge. For example, the tailings waste water is waste water of gold tailings.
In an embodiment, the culture solution of bacteria comprises: 0.2-5 g/L of yeast extract; the co-matrix composed of one or any combination of glucose, starch, ethanol and hydroximic acid is 0.1-5 g/L; 0.01-5 g/L of nitrogen source, preferably, the nitrogen source comprises one or any combination of peptone, urea, ammonium sulfate and ammonium nitrate; 0.2-2 g/L of a phosphorus source, preferably, the phosphorus source comprises one or any combination of dipotassium hydrogen phosphate, potassium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, sodium tripolyphosphate and potassium tripolyphosphate; CaCl20.001～1.02g/L；NaCl 0.5～5g/L；MgSO4 0.05～1.5g/L；FeSO40.03-0.2 g/L; 0.02-0.2 g/L of surfactant, preferably, the surfactant comprises sophorolipid, algal glycolipid or a combination thereof; 50-300 mg/L of xanthate; the induction substrate is 60-200 mg/L, and preferably comprises one or any combination of ethidium, radix linderae and pine oil. In an embodiment, the pH of the culture solution is adjusted to 5 to 8, preferably 6 to 7.
In an embodiment, the step (1) comprises: drying the biomass, washing to neutrality, drying, crushing the dried biomass to 50-100 meshes, and crushing by using a plant crusher for example; pyrolyzing the crushed biomass in a protective atmosphere at 300-700 ℃, preferably at 300-600 ℃, and more preferably at 400-600 ℃ for 6-8 h; adding an acidic solution or an alkaline solution into the pyrolyzed biomass to remove ash in the biochar, oscillating at room temperature for 10-20 hours, such as 12-18 hours, then performing centrifugal separation, preferably standing for 24 hours, and then filtering; repeatedly washing the filtrate by using deionized water until the pH value of the filtrate is 7, and then drying for 6-18 h, preferably 9-15 h, more preferably 12h at the temperature of 60-80 ℃.
In the examples, for removing ash in the biochar, an acidic solution such as hydrochloric acid (e.g., 1mol/L), sulfuric acid (e.g., 0.1mol/L), nitric acid (e.g., 0.5mol/L), hydrofluoric acid (e.g., 0.1mol/L), or an alkaline solution such as a sodium hydroxide solution (e.g., 0.1mol/L) may be added.
In the embodiment, the biomass is put into a crucible, covered and then placed in a muffle furnace, nitrogen is introduced as a protective atmosphere, for example, the nitrogen flow is 100-200 mL/min, the temperature rise speed is set to be 5-20 ℃/min, the temperature is controlled to be 300-700 ℃, and the temperature is kept for 6-8 hours.
In the examples, in the step (2), the removal rate of xanthate from the culture solution is measured every 12 hours, 24 hours, 48 hours, or 72 hours after the contamination source is inoculated into the culture solution.
In an embodiment, the step (3) comprises: sterilizing the biochar; and mixing the sterilized biochar with the bacterial liquid of the xanthate function degradation flora and oscillating. Preferably, the mixing ratio of the biochar to the xanthate function degradation flora is 0.5-3 g: 25 mL. In the embodiment, the sterilized bacterial liquid of the biochar and xanthate function degradation flora is cultured for 12-36 h (preferably 20-30 h, more preferably 22-28 h) at the temperature of 20-30 ℃ and the oscillation speed of 120-240 r/min (preferably 160-200 r/min), wherein the number of the active xanthate function degradation bacteria is not less than 1 x 107cfu/mL. Adding sodium alginate and polyvinyl alcohol into the uniformly mixed bacterial liquid to serve as composite carriers, wherein the mixing ratio of the sodium alginate to the polyvinyl alcohol to the xanthate function degradation flora is 0.5-2 g: 25mL, preferably 0.8-1.5 g: 25mL, more preferably 1-1.2 g: 25 mL. In an embodiment, one or any combination of 3-6% (preferably 4-5%) saturated calcium chloride-boric acid solution, 3-6% (preferably 4-5%) saturated calcium carbonate-boric acid solution, and 3-6% (preferably 4-5%) saturated calcium lactate-boric acid solution is added to the mixture to perform a hardening reaction. Calcium chloride, calcium carbonate or calcium lactate is reacted with sodium alginate, while the boric acid solution is reacted with polyvinyl alcohol. Thus, the domesticated xanthate function degrading bacteria can be fixed. And (3) wrapping the cured product by using gauze to obtain the biochar-microorganism composite material.
In yet another embodiment of the present invention, as shown in fig. 3, there is provided a method of treating tailings wastewater comprising xanthate and heavy metal ions, the method comprising: step (1): standing the tailing wastewater for 1-2 d, pretreating the tailing wastewater by using a filter, and then adjusting the pH value of the tailing wastewater to be less than 10; step (2): adding the biochar in the embodiment into the pretreated tailing wastewater to remove xanthate and heavy metal ions in the tailing wastewater, oscillating for 10-120 min, and filtering to retain the upper-layer wastewater; and (3): and (3) carrying out suction filtration on the retained wastewater, adding the biochar-microorganism composite material in the previous embodiment into the filtrate to further remove xanthate and heavy metal ions in the tailing wastewater, oscillating for 10-120 min, and filtering to obtain a supernatant, wherein the supernatant is the treated tailing wastewater. The biochar in the biochar-microorganism composite material can adsorb xanthate and heavy metal ions in tailing wastewater, and the microporous structure of the biochar-microorganism composite material is richer than that of an immobilized matrix in a traditional composite carrier and has larger adsorption capacity; moreover, after the biochar is compounded with the xanthate degrading bacteria, the activity of the xanthate degrading bacteria is enhanced, and the degrading efficiency is obvious. Therefore, this treatment method uses both biochar and biochar-composite, enabling the combined use of chemical and biological processes, which enables efficient removal of both xanthates and heavy metal ions in wastewater. This will allow the waste water to be reused for beneficiation operations, thereby achieving full resource utilization of the tailing waste water. Moreover, the treatment method is low in cost, the biochar is prepared by roasting cheap and easily-obtained biomass, the biochar is used as a carrier, the xanthate function degradation flora is used as an immobilized strain, and a biochar-microorganism composite material is prepared. In addition, the treatment method is easy to operate and control, has little environmental pollution, has good treatment effect on the tailing wastewater, and has excellent industrial application prospect.
In embodiments, the heavy metal ion includes, but is not limited to, Pb2+And Zn2+Including but not limited to etihuang and buthuang.
In the examples, the tailings were wasted using a quartz sand filterThe water is pretreated. Preferably, the quartz sand filter has a diameter of 7cm and a filter area of 38.47cm2The water flow is 14L/h. In an embodiment, the obtained filter material comprises natural quartz sand and manganese sand; the grain size of the sand grains is 0.5-2 mm, preferably 0.8-1.5 mm, more preferably 1-1.2 mm; the thickness of the filtering layer is 5-15 cm, preferably 8-12 cm, and more preferably 10-11 cm. In an embodiment, the pH value of the tailing wastewater can be adjusted to 6-8.
In an embodiment, when biochar is used for treating tailing wastewater, the ratio of biochar to tailing wastewater is 5-30 g:1L, and preferably 15-25 g: 1L. In the embodiment, when the biochar is used for treating the tailing wastewater, the tailing wastewater is subjected to constant-temperature oscillation, the temperature is set to be 20-30 ℃, and the oscillation time is set to be 10-60 min, preferably 20-50 min, and more preferably 30 min.
In an embodiment, when the biochar-microorganism composite material is used for treating the tailing wastewater, the proportion of the biochar-microorganism composite material to the tailing wastewater is 5-10 g:1L, preferably 6-8 g: 1L. In the embodiment, when the biochar-microorganism composite material is used for treating the tailing wastewater, the tailing wastewater is subjected to constant-temperature oscillation, the temperature is set to be 20-30 ℃, and the oscillation time is set to be 10-60 min, preferably 20-50 min, and more preferably 30 min.
In the embodiment, before treating the tailing wastewater, the tailing wastewater is subjected to water quality analysis. The wastewater can be filtered, for example, by using a 0.45 micron filter membrane, and then the pH, COD, suspended matter, heavy metal ion content of the sample can be measured by using a portable pH meter, a COD rapid digestion instrument, an ultraviolet spectrophotometer, an inductively coupled plasma emission spectrometer (ICP-OES), and the like. The analysis can provide a reference basis for subsequent removal effect analysis.
The following will describe in detail the use of corn stover as a specific example. It will be appreciated by persons skilled in the art that the present invention is not limited to the specific embodiments described, but that reasonable modifications are possible in light of the teaching of the present invention.
Water quality analysis
The inventor takes 10Kg of wastewater sample from gold tailings wastewater in Hunan province, filters the wastewater sample by using a 0.45 micron filter membrane, determines the pH value of the sample to be 10.1-11.7 by adopting a portable pH meter, and determines the pH, COD, suspended matters and heavy metal ion content of the sample by adopting a COD rapid digestion instrument, an ultraviolet spectrophotometer inductively coupled plasma emission spectrometer (ICP-OES) and other equipment. The specific results of the measurement are shown in the following table.
To compare the removal rates of xanthate and heavy metal ions for various treatment methods, the example of the present invention employed simulated xanthate wastewater. In the embodiment, according to the adding amount of the xanthate in the factory flotation process and the detection result of the tailing wastewater, the pH value, COD (chemical oxygen demand), xanthate content and heavy metal ion content of the xanthate wastewater are simulated.
Example 1: xanthate wastewater simulated by charcoal adsorption
(1) Preparing the biochar: placing the screened corn straw powder into a crucible, covering the crucible, placing the crucible in a muffle furnace for pyrolysis, raising the temperature to 600 ℃ at the heating rate of 20 ℃/min, keeping the temperature for 8 hours, cooling to room temperature, and taking out; in order to remove ash in the corn straw biochar obtained by initial preparation, adding the corn straw biochar into HCl with the concentration of 1mol/L, oscillating for 12 hours at room temperature, and then performing centrifugal separation (standing for 24 hours and then filtering); repeatedly cleaning the filtrate with deionized water until the pH value of the filtrate is 7, and drying at 80 ℃ for 12h to obtain the biochar.
(2) Preparing simulated xanthate wastewater: preparing simulated xanthate wastewater, wherein the xanthate wastewater comprises 200mg/L of ethidium, 100mg/L of butyl xanthate, 80mg/L of zinc nitrate, 80mg/L of lead nitrate and 80mg/L of copper sulfate, and adjusting the pH value of the xanthate wastewater to 6-8.
(3) Adsorption: adding 5-30 g of corn straw biochar into xanthate wastewater, wherein the proportion of the biochar to the wastewater is 5-30 g 1L, oscillating at a constant temperature of 25 ℃ for 30min, filtering the wastewater, and then using an ultraviolet spectrophotometerThe removal rate of the etihuang and the butyl xanthate is measured to be more than 60 percent, and Pb is measured2+、Zn2+The removal rate of the catalyst reaches 70-80%.
Example 2: biological degradation simulated xanthate wastewater
(1) Constructing xanthate function degrading flora XDB: sampling gold tailing wastewater from a certain gold tailing in Hunan province, inoculating the sample into a culture solution according to the volume ratio of 10%, maintaining the temperature at 30 ℃, controlling the dissolved oxygen to be 5mg/L, and detecting the removal rate of xanthate in the culture solution every 24 hours; after the removal rate of the xanthate reaches more than 80%, continuously supplementing the xanthate and the induction substrate to ensure that the concentration of the xanthate in the culture solution reaches 500mg/L and the concentration of the induction substrate reaches 80 mg/L; continuously culturing the bacteria until the removal rate of the xanthate reaches over 90 percent, thereby obtaining a culture solution after the induction and domestication are finished; standing the culture solution after the induction domestication is finished, discarding 50% of supernatant, supplementing fresh culture solution to the expected total volume, supplementing xanthate to the concentration of 900mg/L, and continuing to culture bacteria; and after that, when the removal rate of each xanthate reaches more than 90%, discarding 50% of supernatant, continuously supplementing fresh culture solution, and continuously culturing for 5 cycles to construct xanthate function degradation flora. Wherein the culture solution comprises: 0.15g/L of yeast extract; glucose 0.2 g/L; 1g/L of ammonium sulfate; dipotassium phosphate 1.6g/L and potassium dihydrogen phosphate 0.5 g/L; CaCl20.001g/L；MgSO4 0.2g/L；FeSO40.002 g/L; 300mg/L of xanthate; ethidium chloride 60mg/L, and the pH of the culture broth was adjusted to 8.
(2) And (3) degradation: inoculating the bacterial liquid of the constructed xanthate function degrading flora XDB into a culture medium, wherein the culture medium comprises 200mg/L of ethidium, 100mg/L of butylated xanthate, 0.15g/L of yeast extract, 0.2g/L of glucose, 0.5g/L of monopotassium phosphate, 1.6g/L of dipotassium phosphate, 1g/L of ammonium sulfate, 0.2g/L of MgSO40.002g/L of FeSO41mg/L of CaCl2The inoculation amount (volume ratio) of the thalli is 2-6%, shaking culture is carried out for 24 hours at 30 ℃ under 120r/min, and then ultraviolet spectrophotometer is used for measuring the removal rate of the etihuang and the buthuang to reach about 85%.
Example 3: xanthate wastewater simulated by adsorption and degradation of biochar-microorganism composite material
(1) Preparing the biochar: biochar was prepared according to the method in example 1.
(2) Constructing xanthate function degrading flora XDB: xanthate function-degrading flora was constructed according to the method in example 2.
(3) Preparing a biochar-microorganism composite material: mixing the biochar with the bacterial liquid of the xanthate function degradation flora XDB obtained by construction according to the proportion of 0.5-3 g: 25mL, and adding 0.5-2 g: 25mL of sodium alginate and polyvinyl alcohol are used as composite carriers, the mixed liquid is subjected to oscillation culture at the temperature of 20-30 ℃ and the oscillation speed of 100-240 r/min to obtain a biochar degrading bacteria suspension, 4% calcium chloride boric acid saturated solution is added into the mixed liquid to be hardened, and gauze is used for wrapping after the hardening to obtain the biochar of the corn stalks attached with xanthate degrading bacteria.
(4) Preparing simulated xanthate wastewater: preparing simulated xanthate wastewater, wherein the xanthate wastewater comprises 200mg/L of ethidium, 100mg/L of butyl xanthate, 80mg/L of zinc nitrate, 80mg/L of lead nitrate and 80mg/L of copper sulfate, and adjusting the pH value of the xanthate wastewater to 6-8.
(5) And (3) adsorption degradation: respectively weighing biochar-microorganism composite material powder with different amounts (5-10 g), adding the biochar-microorganism composite material into simulated xanthate wastewater, wherein the proportion of the biochar-microorganism composite material to the simulated xanthate wastewater is 5-10 g:1L, oscillating at the constant temperature of 25 ℃ for 10-60 min, filtering the wastewater, and measuring that the xanthate degradation in filtrate reaches about 95% and Pb is measured by an ultraviolet spectrophotometer2+、Zn2+The removal rate reaches 55 percent.
The removal rate of the corn stalk biochar-microorganism composite material to the etihuang and the butyl xanthate is obviously higher than the removal rate of the corn stalk biochar and xanthate functional degradation bacteria XRD to the xanthate alone. The reason is that the corn stalk biochar contains a large number of microporous structures, not only can adsorb xanthate and heavy metal ions, but also can be used as a carrier of xanthate degrading bacteria, so that the functional flora is improvedActivity, thereby improving the biodegradation rate of functional flora to xanthate. But the single corn stalk biochar microbial composite material is used for treating Pb2+、Zn2+The removal efficiency of heavy metal ions is not good than the removal effect of corn stalk biochar, so the two methods are combined to be capable of treating ethidium xanthate, butyl xanthate and Pb in xanthate wastewater2+、Zn2+The heavy metal ions have better removal effect.
Example 4: corn stalk biochar and biochar-microorganism composite material for adsorbing and degrading actual beneficiation xanthate wastewater
(1) Treating tailing wastewater: sampling is carried out in xanthate flotation wastewater of certain gold tailings in Hunan province, and preliminary treatment such as standing, sedimentation, sand filtration and the like is carried out on the obtained sample to remove large-particle impurities of sand and stone, oil stains and the like.
(2) And (3) biochar adsorption: weighing 5-30 g of the corn straw biochar prepared according to the embodiment 1, adding the biochar into xanthate wastewater, wherein the ratio of the biochar to the wastewater is 20g:1L, oscillating at a constant temperature of 25 ℃ for 30min, filtering the wastewater, and reserving supernatant for subsequent treatment.
(3) Adsorbing and degrading the biochar-microorganism composite material: adding 5-10 g/1L of the corn straw biochar-microorganism composite material prepared according to the embodiment 3 into the supernatant, oscillating at a constant temperature of 25 ℃ for 10-60 min, filtering the wastewater, and measuring the degradation rate of xanthate in the filtrate by using an ultraviolet spectrophotometer to be 90-95% and Pb by using an ultraviolet spectrophotometer2+、Zn2+The removal rate of heavy metal ions is 70-80%.
Parts of the invention not described in detail are well known in the art.
Although illustrative embodiments of the present invention have been described above to facilitate the understanding of the present invention by those skilled in the art, it should be understood that the present invention is not limited to the scope of the embodiments, and various changes may be made apparent to those skilled in the art as long as they are within the spirit and scope of the present invention as defined and defined by the appended claims, and all matters of the invention which utilize the inventive concepts are protected.
Claims (10)
1. A preparation method of a biochar-microorganism composite material comprises the following steps:
step (1): pyrolyzing biomass to obtain biochar, the biochar having a porous structure;
step (2): preparing xanthate function degradation flora;
and (3): mixing the biochar with xanthate function degrading flora to obtain a biochar-microorganism composite material,
wherein the step (2) comprises the steps of:
inoculating a pollution source into a culture solution according to the volume ratio of 10-30%, maintaining the temperature at 15-37 ℃, controlling the dissolved oxygen to be 3-7 mg/L, and detecting the removal rate of xanthate in the culture solution according to a preset time period; after the removal rate of xanthate reaches more than 80%, continuously supplementing xanthate and an induction substrate to ensure that the concentration of the xanthate in the culture solution reaches 300-500mg/L and the concentration of the induction substrate reaches 120-240 mg/L; continuously culturing the bacteria until the removal rate of the xanthate reaches over 90 percent, thereby obtaining a culture solution after the induction and domestication are finished;
standing the culture solution after the induction domestication is finished, discarding 30-60% of supernatant, supplementing fresh culture solution to the expected total volume, supplementing xanthate to 900-1500 mg/L, and continuously culturing bacteria; and then when the removal rate of each xanthate reaches more than 90%, discarding 30-60% of supernatant, continuously supplementing fresh culture solution, and continuously culturing for 5-10 periods to construct xanthate function degradation flora.
2. The method for preparing biochar-microorganism composite according to claim 1,
the culture solution comprises: 0.2-5 g/L of yeast extract; the co-matrix composed of one or more of glucose, starch, ethanol and hydroximic acid is 0.1-5 g/L; 0.01-5 g/L of nitrogen source; 0.2-2 g/L of phosphorus source; CaCl20.001～1.02g/L；MgSO4 0.05～1.5g/L；FeSO40.03-0.2 g/L; 0.02-0.2 g/L of surfactant; yellow colour50-300 mg/L of medicine; an induction substrate 60-200 mg/L, and
the pH value of the culture solution is adjusted to 5-8.
3. The method for preparing biochar-microorganism composite according to claim 2,
the nitrogen source comprises one or any combination of peptone, urea, ammonium chloride, ammonium sulfate and ammonium nitrate; and/or
The phosphorus source comprises one or any combination of dipotassium hydrogen phosphate, potassium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, sodium tripolyphosphate and potassium tripolyphosphate; and/or
The surfactant comprises sophorolipid, algal glycolipid, or a combination thereof; and/or
The inducing substrate comprises one or any combination of ethidium, radix Polygoni Ciliinerve and pinitol oil; and/or
The predetermined period of time is 12 hours, 24 hours, 48 hours, or 72 hours.
4. The biochar-microorganism composite production method according to any one of claims 1 to 3, wherein,
the step (3) comprises the following steps:
sterilizing the biochar;
mixing and oscillating the sterilized biological carbon and the bacteria liquid of the xanthate function degradation flora, adding sodium alginate and polyvinyl alcohol as composite carriers, adding one or any combination of 3-6% of calcium chloride boric acid saturated solution, 3-6% of calcium carbonate boric acid saturated solution and 3-6% of calcium lactate boric acid saturated solution to carry out hardening reaction, and wrapping with gauze after hardening to obtain the biological carbon-microorganism composite material.
5. The biochar-microorganism composite preparation method according to claim 4,
and (3) sterilizing the bacterial liquid of the biochar and xanthate function degradation flora according to the ratio of 0.5-3 g: mixing at a ratio of 25 mL; and/or
Culturing the sterilized bacterial liquid of the biochar and xanthate function degradation flora at the temperature of 20-30 ℃ and the oscillation speed of 120-240 r/min for 12-36 hours, wherein the number of the active xanthate function degradation bacteria is not less than 1 multiplied by 107cfu/mL; and/or
Adding 0.5-2 g: 25mL of Sodium Alginate (SA) and polyvinyl alcohol (PVA).
6. The biochar-microorganism composite production method according to any one of claims 1 to 5, wherein,
the step (1) comprises the following steps:
drying the biomass, washing to be neutral, drying, and crushing the dried biomass to 50-100 meshes;
pyrolyzing the crushed biomass for 6-8 hours at 300-700 ℃ in a protective atmosphere;
adding an acidic solution or an alkaline solution into the pyrolyzed biomass to remove ash in the pyrolyzed biomass, oscillating for 10-12 hours at room temperature, and then performing centrifugal separation;
and repeatedly cleaning the filtrate by using deionized water until the pH value of the filtrate is 7, and drying for 6-18 h at the temperature of 60-80 ℃.
7. The biochar-microorganism composite production method according to any one of claims 1 to 6, wherein,
the biomass comprises one or any combination of straw, grain shells, trees and waste materials thereof, and livestock and poultry manure; and/or
The source of the pollution is from tailings waste water polluted by xanthate or leachate of activated sludge in tailings ponds.
8. A process for treating tailings wastewater comprising xanthate and heavy metal ions, the process comprising:
step (1): standing the tailing wastewater for 1-2 days, pretreating the tailing wastewater by using a filter, and then adjusting the pH value of the tailing wastewater to be less than 10;
step (2): adding the biochar in claim 1 into the pretreated tailing wastewater to remove xanthate and heavy metal ions in the tailing wastewater, oscillating for 10-120 minutes, and filtering to retain upper-layer wastewater;
and (3): and (3) carrying out suction filtration on the retained wastewater, adding the biochar-microorganism composite material as defined in claim 1 into the filtrate to further remove xanthate and heavy metal ions in the tailing wastewater, oscillating for 10-120 minutes, and filtering to obtain a supernatant, wherein the supernatant is the treated tailing wastewater.
9. A process for treating tailings wastewater as set forth in claim 8 wherein,
in the step (1), a quartz sand filter is used, the obtained filter material comprises natural quartz sand and manganese sand, the grain size of the sand is 0.5-2 mm, and the thickness of the filter layer is 5-15 cm; adjusting the pH value of the tailing wastewater to 6-8;
in the step (2), the ratio of the biochar to the tailing wastewater is 20-50 g:1L, and/or the temperature is set to be 20-30 ℃ in the removal process, and the oscillation time is 10-60 minutes.
10. A process for treating tailings wastewater as set forth in claim 9 wherein,
the diameter of the quartz sand filter is 7cm, and the filtering area is 38.47cm2The water flow is 14L/h;
in the step (3), the ratio of the biochar-microorganism composite material to the tailing wastewater is 5-10 g: 1L; and/or the temperature is set to be 20-30 ℃ in the removing process, and the oscillation time is 10-60 minutes.
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