CN116282577A - Method for repairing copper-containing wastewater by biomineralization based on pH value regulation and control - Google Patents
Method for repairing copper-containing wastewater by biomineralization based on pH value regulation and control Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 136
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 113
- 239000002351 wastewater Substances 0.000 title claims abstract description 99
- 230000033558 biomineral tissue development Effects 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 49
- 230000033228 biological regulation Effects 0.000 title claims abstract description 24
- 230000008439 repair process Effects 0.000 claims abstract description 78
- 239000007788 liquid Substances 0.000 claims abstract description 44
- 150000002500 ions Chemical class 0.000 claims abstract description 43
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 32
- 230000007613 environmental effect Effects 0.000 claims abstract description 29
- 230000008859 change Effects 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 17
- 229910001779 copper mineral Inorganic materials 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 10
- 230000001105 regulatory effect Effects 0.000 claims abstract description 9
- 239000013049 sediment Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 230000001276 controlling effect Effects 0.000 claims abstract description 3
- 241000192023 Sarcina Species 0.000 claims description 46
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 30
- 238000001556 precipitation Methods 0.000 claims description 25
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 22
- 239000004202 carbamide Substances 0.000 claims description 22
- 239000001963 growth medium Substances 0.000 claims description 18
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 15
- 235000019270 ammonium chloride Nutrition 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- -1 nitrate ions Chemical class 0.000 claims description 14
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 11
- 229940041514 candida albicans extract Drugs 0.000 claims description 10
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims description 10
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 10
- 239000012138 yeast extract Substances 0.000 claims description 10
- 241000907663 Siproeta stelenes Species 0.000 claims description 9
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000005067 remediation Methods 0.000 claims description 9
- 238000012258 culturing Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 229910052951 chalcopyrite Inorganic materials 0.000 claims description 7
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 6
- 239000005750 Copper hydroxide Substances 0.000 claims description 6
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 6
- DDBREPKUVSBGFI-UHFFFAOYSA-N phenobarbital Chemical compound C=1C=CC=CC=1C1(CC)C(=O)NC(=O)NC1=O DDBREPKUVSBGFI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 241000193388 Bacillus thuringiensis Species 0.000 claims description 5
- YCBYDPWDCYAAPQ-UHFFFAOYSA-N [N+](=O)(OO)[O-].[Cu] Chemical compound [N+](=O)(OO)[O-].[Cu] YCBYDPWDCYAAPQ-UHFFFAOYSA-N 0.000 claims description 5
- 229940097012 bacillus thuringiensis Drugs 0.000 claims description 5
- 230000001089 mineralizing effect Effects 0.000 claims description 4
- 241001057978 Balanococcus Species 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 238000002835 absorbance Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 241001467552 Mycobacterium bovis BCG Species 0.000 claims 1
- 229960000190 bacillus calmette–guérin vaccine Drugs 0.000 claims 1
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 claims 1
- 230000029219 regulation of pH Effects 0.000 claims 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 239000011707 mineral Substances 0.000 description 7
- 235000010755 mineral Nutrition 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000004088 simulation Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000031700 light absorption Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 241000193830 Bacillus <bacterium> Species 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 241000606860 Pasteurella Species 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- BESJRHHIPGWPTC-UHFFFAOYSA-N azane;copper Chemical class N.[Cu] BESJRHHIPGWPTC-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 241000530268 Lycaena heteronea Species 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 108010046334 Urease Proteins 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- XAEGGWBYHVPCKP-UHFFFAOYSA-M copper;hydroxide;nitrate Chemical compound [OH-].[Cu+2].[O-][N+]([O-])=O XAEGGWBYHVPCKP-UHFFFAOYSA-M 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
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- 238000005065 mining Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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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- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Biodiversity & Conservation Biology (AREA)
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Abstract
The invention discloses a method for remedying copper-containing wastewater by biomineralization based on pH value regulation, which comprises the following steps: determining a copper mineral sediment composition and a change rule of Cu ion restoration efficiency in the restoration process by using environmental water chemical balance software, adding the Bazier restoration liquid into copper-containing wastewater to carry out biomineralization restoration and regulating and controlling an environmental pH value to a high-efficiency restoration area according to the change rule of the restoration efficiency; the high-efficiency repair area is the pH with the highest Cu ion repair efficiency shown by the change rule of the repair efficiency. The method can effectively avoid repairing copper-containing wastewater under the condition of non-efficient repair, avoid generating free copper ions and copper ammonia complex, and improve the repair efficiency.
Description
Technical Field
The invention belongs to the technical field of environmental engineering, and particularly relates to a method for repairing copper-containing wastewater by biomineralization based on pH value regulation.
Background
In industrial society, the copper mining and smelting, metal working, electroplating and electronics industries emit excessive amounts of copper into the surrounding environment, forming copper pollution that is transmitted and accumulated through air, water, soil and other media, severely threatening human health.
In recent years, various physical and chemical restoration methods have been proposed for copper-containing wastewater pollution, and these methods have the common defects of long time consumption, low economic benefit and easiness in causing secondary environmental pollution. Therefore, environmental friendly bioremediation methods are attracting attention, and bioremediation of copper-containing wastewater pollution is mainly based on urea hydrolysis by urease secreted by microorganisms, and heavy metal ion conversion carbonate precipitation is induced. In theory, carbonate ions are generated in the bioremediation process, the surrounding environment of the remediation system tends to be alkaline, the heavy metal ions are combined with the carbonate ions to generate carbonate precipitates, and the remediation efficiency is increased along with the increase of the carbonate amount generated by urea decomposition. However, in this process, copper ions are easily left in a free state and cannot be solidified, or copper ions and NH 3 And carrying out coordination complexing to obtain a free copper ammonia complex, wherein the copper ammonia complex is converted into copper ions again when the environment changes, and the environment and the human health are continuously damaged.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for remedying copper-containing wastewater by biomineralization based on pH value regulation. According to the method for repairing copper-containing wastewater by biomineralization based on pH value regulation, disclosed by the invention, the biological repair efficiency rule of the Balanococcus barbites is obtained through simulation of environmental water chemistry balance software, so that the efficient repair parameters conforming to a repair system are obtained, the copper-containing wastewater can be effectively prevented from being repaired under the condition of non-efficient repair, free copper ions and copper ammonia complexes are prevented from being generated, and the repair efficiency is improved.
In order to solve the technical problems, the invention adopts the following technical scheme: the method for remedying the copper-containing wastewater by biomineralization based on pH value regulation is characterized by comprising the following steps: determining a copper mineral sediment composition and a change rule of Cu ion restoration efficiency in the restoration process of the copper-containing wastewater by mineralizing and restoring the copper-containing wastewater by using environmental water chemical balance software, adding the Bazier restoration liquid into the copper-containing wastewater according to the change rule of the restoration efficiency, and regulating and controlling the pH value of the environment to a high-efficiency restoration area at the same time of biomineralization restoration; the high-efficiency repair area is the pH with the highest Cu ion repair efficiency shown by the change rule of the repair efficiency.
The method for remedying copper-containing wastewater by biomineralization based on pH value regulation is characterized in that the copper mineral precipitate comprises copper blue, copper hydroxide, copper hydroxy nitrate, malachite and/or copper black.
The method for remedying the copper-containing wastewater by biomineralization based on pH value regulation is characterized in that the method for remedying the copper-containing wastewater by mineralizing the bacillus thuringiensis by using environmental water chemistry balance software is characterized in that the change rule of copper mineral sediment composition and Cu ion restoration efficiency in the restoration process of the copper-containing wastewater by mineralizing the bacillus thuringiensis specifically comprises the following steps: inputting the concentration of each ion in the restoration system into environmental water chemical balance software, setting the environmental temperature and possible precipitation types, and determining the copper mineral precipitation constitution and the change rule of Cu ion restoration efficiency by taking pH as an independent variable; the ions in the repair system include copper ions, nitrate ions, carbonate ions and ammonium ions.
The method for remedying copper-containing wastewater by biomineralization based on pH value regulation is characterized in that the 600nm wavelength absorbance value of the spore sarcina bardana restoration liquid is 1.5-2.5.
The method for remedying copper-containing wastewater by biomineralization based on pH value regulation is characterized in that the preparation method of the bacillus thuringiensis sarcina restoration liquid comprises the following steps: culturing the sarcina bardana in a culture medium to obtain sarcina bardana repair liquid; the culture medium comprises 16-20 g/L of yeast extract, 16-20 g/L of urea, 6-10 g/L of ammonium chloride, 6-10 mg/L of manganese sulfate monohydrate and 16-24 mg/L of nickel chloride hexahydrate.
The method for remedying the copper-containing wastewater by biomineralization based on pH value regulation is characterized in that the copper-containing wastewater is an aqueous solution of copper nitrate.
The method for remedying the copper-containing wastewater by biomineralization based on pH value regulation is characterized in that the concentration of copper ions in the copper-containing wastewater is 20-60 mM.
The method for remedying copper-containing wastewater by biomineralization based on pH value regulation is characterized in that the volume ratio of the copper-containing wastewater to the sarcina barbita repair liquid is 1:1.
The method for remedying the copper-containing wastewater by biomineralization based on pH value regulation is characterized by comprising the steps of adding the sarcina barbita restoration liquid into the copper-containing wastewater and standing.
Compared with the prior art, the invention has the following advantages:
1. the method for remedying the copper-containing wastewater by biomineralization based on pH value regulation creatively obtains the rule of the biological restoration efficiency of the Balanococcus barbites through the simulation of environmental water chemical balance software, obtains the efficient restoration parameters conforming to a restoration system, can effectively avoid restoring the copper-containing wastewater under the condition of non-efficient restoration, avoids the generation of free copper ions and copper ammonia complexes, and improves the restoration efficiency.
2. The method for remedying the copper-containing wastewater based on the pH value regulation and control of the biomineralization is based on the optimal restoration condition of the product reverse thrust obtained through simulation, and is used for guiding the bioremediation technology of the copper-containing wastewater, and the bioremediation efficiency of the copper-containing wastewater is close to 100% under the same condition.
3. According to the method for remedying the copper-containing wastewater by biomineralization based on pH value regulation, disclosed by the invention, a method for verifying through simulation and experiment is used for establishing a remedying model for remedying the copper-containing wastewater by biomineralization, so that a theoretical basis is provided for definitely remedying system influence factors and evaluating the remedying efficiency, and popularization and application are facilitated.
The technical scheme of the invention is further described in detail below with reference to the accompanying drawings and the examples.
Drawings
FIG. 1 is the output of the environmental water chemistry balance software of example 1;
FIG. 2 shows the results of an X-ray diffraction analysis of mineral precipitation according to example 1;
FIG. 3 shows the results of Raman spectroscopy of the mineral precipitation of example 1;
FIG. 4 is the output of the environmental water chemistry balance software of example 2;
FIG. 5 shows the results of the environmental water chemistry balance software output in step 3 of example.
Detailed Description
Example 1
The embodiment provides a method for remedying copper-containing wastewater by biomineralization based on pH value regulation, which comprises the following steps:
inputting the concentration of each ion in a repairing system into environmental water chemical balance software, setting the environmental temperature and possible precipitation types, and determining the copper mineral precipitation constitution and the change rule of Cu ion repairing efficiency by taking pH as an independent variable; the concentration of each ion in the repair system comprises 20mM of copper ion, 40mM of nitrate ion, 166.5mM of carbonate ion and 426.5mM of ammonium ion; the concentration of the carbonate ions is obtained by fully decomposing urea, and the concentration of the ammonium ions is the sum of the concentration of the ammonium ions in the ammonium chloride and the concentration of the urea after fully decomposing; the pH range is 2-13; the ambient temperature may be 30 ℃;
the ion concentration in the restoration system changes along with the pH value, the environmental water chemical balance software can determine the ion product IP under different pH values according to the ion concentration in the system, and determine the saturation index A according to the ion product IP, so as to determine the change rule of the saturation index A under different pH values, and when the saturation index A is maximum, the precipitation amount is maximum, and the restoration efficiency is highest; the possible precipitation species include copper blue, copper hydroxide, copper hydroxy nitrate, malachite and/or chalcopyrite; the saturation index A=log IP-log Ks, wherein the Ks are solubility constants of different precipitation types, are built in software, and can automatically search and calculate various chemical morphology distributions in a system; the repair efficiency = precipitated copper ion concentration/copper ion initial concentration x 100%, the precipitated copper ion concentration being automatically calculated based on software;
the repairing system is obtained by mixing copper-containing wastewater and sarcina bardana repairing liquid, and the preparation method of the sarcina bardana repairing liquid comprises the following steps: culturing the sarcina bardana in a culture medium for 30 hours to obtain sarcina bardana repair liquid; the culture temperature is 30 ℃, the rotation speed of a shaking table is 180rpm, and the culture medium comprises 20g/L of yeast extract, 20g/L of urea, 10g/L of ammonium chloride, 10mg/L of manganese sulfate monohydrate and 24mg/L of nickel chloride hexahydrate; the 600nm wavelength light absorption value of the spore sarcina bardana repair liquid is 1.5-2.5; the concentration of copper ions in the copper-containing wastewater is 20mM, and the copper-containing wastewater is a copper nitrate solution; the volume ratio of the spore sarcina bardana repair liquid to the copper-containing wastewater is 1:1;
preparing copper-containing wastewater with copper ion concentration of 20mM, adding the repairing liquid of the Bazier pasteurella to carry out biomineralization repairing and regulating the pH value to a high-efficiency repairing area according to the repairing efficiency rule obtained by simulation, and repairing for 48 hours to realize the high-efficiency repairing of the copper-containing wastewater; the pH of the efficient repairing area is the pH with the highest Cu ion repairing efficiency shown according to the change rule of the Cu ion repairing efficiency in the step one, in the embodiment, the pH of the efficient repairing area is 7.08-7.09, the temperature in the repairing process is 30 ℃, the copper-containing wastewater is copper nitrate solution, the volume ratio of the spore sarcina bardanensis repairing solution to the copper-containing wastewater is 1:1, and the pH value is regulated and controlled to the efficient repairing area through sodium hydroxide or hydrochloric acid.
In the implementation, after the repair is completed, the repair efficiency is close to 100%, the output result of the environmental water chemistry balance software in the step one is shown in fig. 1, and according to fig. 1, copper exists in a free copper ion form all at the pH of < 4; in the process of gradually increasing the pH to 7.08, copper ions are gradually converted into copper blue ore precipitate, and the repair efficiency is close to 100%; at ph=7.08 to 7.09, both the chalcopyrite and malachite-like precipitates are present; the malachite precipitate gradually converts to a cuprammonium complex and the repair efficiency decreases during the further pH rise to 9; at ph=9 to 10, copper exists as a copper ammine complex throughout, with a repair efficiency of 0.
The repaired system is stable mineral sediment, and X-ray diffraction and Raman spectrum analysis are carried out on the mineral sediment, as shown in figures 2-3, according to figures 2-3, the mineral sediment is mainly malachite and blue copper ore sediment, and also comprises the mineral types such as hydroxy copper nitrate, chalcopyrite, copper hydroxide, chalcopyrite and the like, so that the invention can enable copper in copper-containing wastewater to generate stable mineral types.
Comparative example 1
The comparative example provides a method for remedying copper-containing wastewater by biomineralization based on pH value regulation, which comprises the following steps:
step one, repairing copper-containing wastewater for 48 hours according to a biomineralization repairing technology, which specifically comprises the following steps: adding the sarcina barbita repairing liquid into the copper-containing wastewater to obtain a repairing system, and standing the repairing system for 48 hours to finish biomineralization repairing; the preparation method of the bacillus bardanus repairing liquid comprises the following steps: culturing the sarcina bardana in a culture medium for 30 hours to obtain sarcina bardana repair liquid; the culture temperature is 30 ℃, the rotation speed of a shaking table is 180rpm, and the culture medium comprises 20g/L of yeast extract, 20g/L of urea, 10g/L of ammonium chloride, 10mg/L of manganese sulfate monohydrate and 24mg/L of nickel chloride hexahydrate; the 600nm wavelength light absorption value of the spore sarcina bardana repair liquid is 1.5-2.5; the concentration of copper ions in the copper-containing wastewater is 20mM; the volume ratio of the spore sarcina bardana repair liquid to the copper-containing wastewater is 1:1, and the copper-containing wastewater is a copper nitrate solution.
The repair efficiency of this comparative example was 3.81% after completion of biomineralization repair.
Example 2
The embodiment provides a method for remedying copper-containing wastewater by biomineralization based on pH value regulation, which comprises the following steps:
inputting the concentration of each ion in a repairing system into environmental water chemical balance software, setting the environmental temperature and possible precipitation types, and determining the copper mineral precipitation constitution and the change rule of Cu ion repairing efficiency by taking pH as an independent variable; the concentration of each ion in the repair system comprises 40mM of copper ion, 80mM of nitrate ion, 166.5mM of carbonate ion and 426.5mM of ammonium ion; the concentration of the carbonate ions is obtained by fully decomposing urea, and the concentration of the ammonium ions is the sum of the concentration of the ammonium ions in the ammonium chloride and the concentration of the urea after fully decomposing; the pH range is 2-13; the ambient temperature may be 30 ℃;
the ion concentration in the restoration system changes along with the pH value, the environmental water chemical balance software can determine the ion product IP under different pH values according to the ion concentration in the system, and determine the saturation index A according to the ion product IP, so as to determine the change rule of the saturation index A under different pH values, and when the saturation index A is maximum, the precipitation amount is maximum, and the restoration efficiency is highest; the possible precipitation species include copper blue, copper hydroxide, copper hydroxy nitrate, malachite and/or chalcopyrite; the saturation index A=log IP-log Ks, wherein the Ks are solubility constants of different precipitation types, are built in software, and can automatically search and calculate various chemical morphology distributions in a system; the repair efficiency = precipitated copper ion concentration/copper ion initial concentration x 100%, the precipitated copper ion concentration being automatically calculated based on software;
the repairing system is obtained by mixing copper-containing wastewater and sarcina bardana repairing liquid, and the preparation method of the sarcina bardana repairing liquid comprises the following steps: culturing the sarcina bardana in a culture medium for 30 hours to obtain sarcina bardana repair liquid; the culture temperature is 30 ℃, the rotation speed of a shaking table is 180rpm, and the culture medium comprises 20g/L of yeast extract, 20g/L of urea, 10g/L of ammonium chloride, 10mg/L of manganese sulfate monohydrate and 24mg/L of nickel chloride hexahydrate; the 600nm wavelength light absorption value of the spore sarcina bardana repair liquid is 1.5-2.5; the concentration of copper ions in the copper-containing wastewater is 40mM, and the copper-containing wastewater is a copper nitrate solution; the volume ratio of the spore sarcina bardana repair liquid to the copper-containing wastewater is 1:1;
preparing copper-containing wastewater with copper ion concentration of 40mM, adding the repairing liquid of the Bazier pasteurella to carry out biomineralization repairing and regulating the pH value to a high-efficiency repairing area according to the repairing efficiency rule obtained by simulation, and repairing for 48 hours to realize the high-efficiency repairing of the copper-containing wastewater; the pH of the efficient repair area is the pH with the highest Cu ion repair efficiency shown according to the change rule of the Cu ion repair efficiency in the step one, in this embodiment, the pH of the efficient repair area is 7.03-7.04, the temperature in the repair process is 30 ℃, the copper-containing wastewater is a copper nitrate solution, the volume ratio of the spore sarcina bardanensis repair solution to the copper-containing wastewater is 1:1, and the pH is regulated and controlled to the efficient repair area through sodium hydroxide or hydrochloric acid.
In this embodiment, the repair efficiency after repair is close to 100%. The law of Cu repair efficiency with pH is similar to that of example 1, and the output result of the environmental water chemistry balance software in step one is shown in fig. 4, and it can be seen from fig. 4 that at ph=9.38 to 9.39, precipitation of malachite and chalcopyrite forms simultaneously exist, and the repair efficiency is about 20%.
Comparative example 2
This comparative example provides a method for biomineralization remediation of copper-containing wastewater, comprising:
step one, repairing copper-containing wastewater for 48 hours according to a biomineralization repairing technology, which specifically comprises the following steps: adding the sarcina barbita repairing liquid into the copper-containing wastewater to obtain a repairing system, and standing the repairing system for 48 hours to finish biomineralization repairing; the preparation method of the bacillus bardanus repairing liquid comprises the following steps: culturing the sarcina bardana in a culture medium for 30 hours to obtain sarcina bardana repair liquid; the culture temperature is 30 ℃, the rotation speed of a shaking table is 180rpm, and the culture medium comprises 20g/L of yeast extract, 20g/L of urea, 10g/L of ammonium chloride, 10mg/L of manganese sulfate monohydrate and 24mg/L of nickel chloride hexahydrate; the 600nm wavelength light absorption value of the spore sarcina bardana repair liquid is 1.5-2.5; the concentration of copper ions in the copper-containing wastewater is 40mM; the volume ratio of the spore sarcina bardana repair liquid to the copper-containing wastewater is 1:1, and the copper-containing wastewater is a copper nitrate solution.
The repair efficiency of this comparative example was 3.59% after completion of biomineralization repair.
Example 3
The embodiment provides a method for remedying copper-containing wastewater by biomineralization based on pH value regulation, which comprises the following steps:
inputting the concentration of each ion in a repairing system into environmental water chemical balance software, setting the environmental temperature and possible precipitation types, and determining the copper mineral precipitation constitution and the change rule of Cu ion repairing efficiency by taking pH as an independent variable; the concentration of each ion in the repair system comprises 60mM of copper ion, 120mM of nitrate ion, 166.5mM of carbonate ion and 426.5mM of ammonium ion; the concentration of the carbonate ions is obtained by fully decomposing urea, and the concentration of the ammonium ions is the sum of the concentration of the ammonium ions in the ammonium chloride and the concentration of the urea after fully decomposing; the pH range is 2-13; the ambient temperature may be 30 ℃;
the ion concentration in the restoration system changes along with the pH value, the environmental water chemical balance software can determine the ion product IP under different pH values according to the ion concentration in the system, and determine the saturation index A according to the ion product IP, so as to determine the change rule of the saturation index A under different pH values, and when the saturation index A is maximum, the precipitation amount is maximum, and the restoration efficiency is highest; the possible precipitation species include copper blue, copper hydroxide, copper hydroxy nitrate, malachite and/or chalcopyrite; the saturation index A=log IP-log Ks, wherein the Ks are solubility constants of different precipitation types, are built in software, and can automatically search and calculate various chemical morphology distributions in a system; the repair efficiency = precipitated copper ion concentration/copper ion initial concentration x 100%, the precipitated copper ion concentration being automatically calculated based on software;
the repairing system is obtained by mixing copper-containing wastewater and sarcina bardana repairing liquid, and the preparation method of the sarcina bardana repairing liquid comprises the following steps: culturing the sarcina bardana in a culture medium for 30 hours to obtain sarcina bardana repair liquid; the culture temperature is 30 ℃, the rotation speed of a shaking table is 180rpm, and the culture medium comprises 20g/L of yeast extract, 20g/L of urea, 10g/L of ammonium chloride, 10mg/L of manganese sulfate monohydrate and 24mg/L of nickel chloride hexahydrate; the 600nm wavelength light absorption value of the spore sarcina bardana repair liquid is 1.5-2.5; the concentration of copper ions in the copper-containing wastewater is 60mM, and the copper-containing wastewater is a copper nitrate solution; the volume ratio of the spore sarcina bardana repair liquid to the copper-containing wastewater is 1:1;
preparing copper-containing wastewater with copper ion concentration of 60mM, adding the repairing liquid of the Bazier pasteurella to carry out biomineralization repairing and regulating the pH value to a high-efficiency repairing area according to the repairing efficiency rule obtained by simulation, and repairing for 48 hours to realize the high-efficiency repairing of the copper-containing wastewater; the pH of the efficient repairing area is the pH with the highest Cu ion repairing efficiency shown according to the change rule of the Cu ion repairing efficiency in the step one, in the embodiment, the pH of the efficient repairing area is 6.98-7.01, the temperature in the repairing process is 30 ℃, the copper-containing wastewater is copper nitrate solution, the volume ratio of the spore sarcina bardanensis repairing solution to the copper-containing wastewater is 1:1, and the pH value is regulated and controlled to the efficient repairing area through sodium hydroxide or hydrochloric acid.
In this embodiment, the repair efficiency after repair is close to 100%. The output result of the environmental water chemistry balance software in the step one is shown in fig. 5, and according to fig. 5, it can be seen that the law of Cu repair efficiency with pH change is similar to that of example 1, and at ph=9.37 to 9.39, precipitation of malachite and chalcopyrite forms simultaneously exist, and the repair efficiency is about 45%.
Comparative example 3
This comparative example provides a method for biomineralization remediation of copper-containing wastewater, comprising:
step one, repairing copper-containing wastewater for 48 hours according to a biomineralization repairing technology, which specifically comprises the following steps: adding the sarcina barbita repairing liquid into the copper-containing wastewater to obtain a repairing system, and standing the repairing system for 48 hours to finish biomineralization repairing; the preparation method of the bacillus bardanus repairing liquid comprises the following steps: culturing the sarcina bardana in a culture medium for 30 hours to obtain sarcina bardana repair liquid; the culture temperature is 30 ℃, the rotation speed of a shaking table is 180rpm, and the culture medium comprises 20g/L of yeast extract, 20g/L of urea, 10g/L of ammonium chloride, 10mg/L of manganese sulfate monohydrate and 24mg/L of nickel chloride hexahydrate; the 600nm wavelength light absorption value of the spore sarcina bardana repair liquid is 1.5-2.5; the concentration of copper ions in the copper-containing wastewater is 60mM; the volume ratio of the spore sarcina bardana repair liquid to the copper-containing wastewater is 1:1; the copper-containing wastewater is a copper nitrate solution.
The repair efficiency of the comparative example after completion of biomineralization repair was 4.52%.
Example 4
This example is the same as example 1, except that in step one, the culture temperature is 20℃and the shaking table rotation speed is 160rpm, and the culture medium comprises 16g/L of yeast extract, 16g/L of urea, 6g/L of ammonium chloride, 6mg/L of manganese sulfate monohydrate and 16mg/L of nickel chloride hexahydrate; the concentration of carbonate ions is obtained by fully decomposing urea, and the concentration of ammonium ions is the sum of the concentration of ammonium ions in ammonium chloride and the fully decomposed urea.
In this example, the law of the Cu repair efficiency with pH change is similar to that of example 1, and the repair efficiency of the high-efficiency repair zone is substantially the same as that of example 1.
Example 5
This example is the same as example 1, except that in step one, the culture temperature is 25℃and the shaking table rotation speed is 170rpm, and the culture medium comprises 18g/L of yeast extract, 18g/L of urea, 8g/L of ammonium chloride, 8mg/L of manganese sulfate monohydrate and 20mg/L of nickel chloride hexahydrate; the concentration of carbonate ions is obtained by fully decomposing urea, and the concentration of ammonium ions is the sum of the concentration of ammonium ions in ammonium chloride and the fully decomposed urea.
In this example, the law of the Cu repair efficiency with pH change is similar to that of example 1, and the repair efficiency of the high-efficiency repair zone is substantially the same as that of example 1.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent structural changes of the above embodiment according to the technical matter of the present invention still fall within the scope of the technical solution of the present invention.
Claims (9)
1. The method for remedying the copper-containing wastewater by biomineralization based on pH value regulation is characterized by comprising the following steps: determining a copper mineral sediment composition and a change rule of Cu ion restoration efficiency in the restoration process of the copper-containing wastewater by mineralizing and restoring the copper-containing wastewater by using environmental water chemical balance software, adding the Bazier restoration liquid into the copper-containing wastewater according to the change rule of the restoration efficiency, and regulating and controlling the pH value of the environment to a high-efficiency restoration area at the same time of biomineralization restoration; the high-efficiency repair area is the pH with the highest Cu ion repair efficiency shown by the change rule of the repair efficiency.
2. The method for biomineralization remediation of copper-containing wastewater based on ph control of claim 1, wherein the copper mineral precipitate comprises copper blue, copper hydroxide, copper hydroxy nitrate, malachite, and/or chalcopyrite.
3. The method for remedying the copper-containing wastewater by biomineralization based on pH value regulation and control according to claim 1, wherein the determination of the copper mineral precipitation constitution and the change rule of the Cu ion restoration efficiency in the restoration process of the copper-containing wastewater by mineralization restoration of the Balanococcus barbituric by environmental water chemical balance software specifically comprises: inputting the concentration of each ion in the restoration system into environmental water chemical balance software, setting the environmental temperature and possible precipitation types, and determining the copper mineral precipitation constitution and the change rule of Cu ion restoration efficiency by taking pH as an independent variable; the ions in the repair system include copper ions, nitrate ions, carbonate ions and ammonium ions.
4. The method for remedying copper-containing wastewater by biomineralization based on pH regulation according to claim 1, wherein the absorbance at 600nm wavelength of the liquid for remedying the bacillus thuringiensis is 1.5-2.5.
5. The method for remedying copper-containing wastewater by biomineralization based on pH control according to claim 4, wherein the preparation method of the bacillus thuringiensis sarcina restoration solution comprises the following steps: culturing the sarcina bardana in a culture medium to obtain sarcina bardana repair liquid; the culture medium comprises 16-20 g/L of yeast extract, 16-20 g/L of urea, 6-10 g/L of ammonium chloride, 6-10 mg/L of manganese sulfate monohydrate and 16-24 mg/L of nickel chloride hexahydrate.
6. The method for biomineralization remediation of copper-containing wastewater based on ph control of claim 1, wherein the copper-containing wastewater is an aqueous solution of copper nitrate.
7. The method for remedying copper-containing wastewater by biomineralization based on pH control according to claim 1, wherein the concentration of copper ions in the copper-containing wastewater is 20-60 mM.
8. The method for remedying copper-containing wastewater by biomineralization based on pH control according to claim 1, wherein the volume ratio of the copper-containing wastewater to the sarcina barbita repair liquid is 1:1.
9. The method for biomineralization remediation of copper-containing wastewater based on ph control of claim 1, wherein the biomineralization remediation comprises adding a bacillus calmette guerin remediation solution to the copper-containing wastewater and allowing the mixture to stand.
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