CN114455703A - Method for treating heavy metal-containing organic wastewater by biochar-loaded zero-valent iron coupling sulfate reduction - Google Patents
Method for treating heavy metal-containing organic wastewater by biochar-loaded zero-valent iron coupling sulfate reduction Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000002351 wastewater Substances 0.000 title claims abstract description 51
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 39
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 32
- 230000009467 reduction Effects 0.000 title claims abstract description 32
- 230000008878 coupling Effects 0.000 title claims abstract description 18
- 238000010168 coupling process Methods 0.000 title claims abstract description 18
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 14
- 230000000694 effects Effects 0.000 claims abstract description 13
- 238000000197 pyrolysis Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 230000002195 synergetic effect Effects 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 238000005303 weighing Methods 0.000 claims abstract description 5
- 239000010802 sludge Substances 0.000 claims description 41
- 238000002360 preparation method Methods 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 16
- 229910001868 water Inorganic materials 0.000 claims description 11
- 239000011573 trace mineral Substances 0.000 claims description 9
- 235000013619 trace mineral Nutrition 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 4
- 239000007836 KH2PO4 Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 229910052927 chalcanthite Inorganic materials 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 4
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 244000005700 microbiome Species 0.000 abstract description 12
- 230000004060 metabolic process Effects 0.000 abstract description 5
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 5
- 238000003763 carbonization Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 15
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 13
- 229910001431 copper ion Inorganic materials 0.000 description 13
- 230000008859 change Effects 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000005515 coenzyme Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- C02F3/28—Anaerobic digestion 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
-
- 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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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Microbiology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention discloses a method for treating organic wastewater containing heavy metals by biochar-loaded zero-valent iron coupling sulfate reduction. Weighing 15g of biochar and FeCl prepared by high-temperature carbonization3·6H2Dissolving O40 g in 60mL deionized water, drying in a drying oven at constant temperature of 80 ℃, and filling N2And (4) protecting, heating to 500 ℃ in a tubular furnace at the heating rate of 10 ℃/min, carrying out constant-temperature pyrolysis for 3h, and naturally cooling to room temperature to obtain the biochar loaded zero-valent iron material. The composite carrier is added into an anaerobic system for treating the organic wastewater containing the heavy metals according to 0.6g/L, SO4 2‑The concentration was 2000 mg/L. The invention has the advantages that the biochar-loaded zero-valent iron coupling sulfate reduction system has synergistic effect, promotes the growth and metabolism of microorganisms and electron transfer, improves the anaerobic treatment effect and improves the heavy goldThe method has the advantages of improving the removal efficiency, optimizing the effluent quality, enhancing the running performance of the reactor and prolonging the running time of the reactor.
Description
Technical Field
The invention belongs to the technical field of environmental engineering wastewater treatment, and relates to a method for treating heavy metal-containing organic wastewater by biochar-loaded zero-valent iron coupling sulfate reduction.
Background
With the progress and development of the industry, agriculture and animal husbandry, the existence of organic wastewater containing heavy metals is more and more common. At present, anaerobic biological treatment technology is considered to be the most common and promising method for treating heavy metal organic wastewater, but anaerobic biological method has long reactor starting time, anaerobic microbial flora is sensitive to surrounding environment, and the effluent quality of the system is easily affected. In addition, heavy metals in the wastewater can generate a large toxic effect on anaerobic microorganisms, further influence the operation performance of the reactor, and finally lead to the consequences that the reactor is difficult to operate for a long time, the effluent quality is difficult to reach the standard and the like. Therefore, there is an urgent need to develop a new method for improving the treatment effect of heavy metal organic wastewater.
In recent years, zero-valent iron is widely applied to the research of anaerobic biological treatment technology, and the zero-valent iron is one of essential trace elements of microorganisms and is also an important coenzyme component and plays a key role in the growth and the propagation of the microorganisms. Oxidation product of zero-valent iron Fe2+Can provide electrons for the anaerobic microorganisms, promote the electron transfer and accelerate the degradation process of the anaerobic microorganisms. The larger specific surface area enables the zero-valent iron to have stronger adsorption performance, so the reaction activity is higher, and the rate of degrading organic pollutants is faster. However, zero-valent iron is easily agglomerated and easily settles to the bottom in the reactor, and its promoting effect is greatly reduced. The biochar has larger specific surface area and functional groups, if the biochar is compounded with zero-valent iron, the defects of the zero-valent iron can be overcome, the advantages of the zero-valent iron are further better exerted, and the biochar can also promote the electron transfer among microorganisms, and has a certain promotion effect on the growth and metabolism of the microorganisms. Furthermore, in recent years by adding SO to anaerobic biological treatment systems4 2-The improvement of the removal rate of the heavy metals in the organic wastewater has become a research focus, and the heavy metals in the organic wastewater can react with S2-The corresponding precipitate is generated by the reaction, and the sulfate reduction product H can be relieved while the heavy metal is removed2S toxic effect on microorganisms.
The inventionAiming at overcoming the defects of the prior art according to biochar, zero-valent iron and SO4 2-The respective advantages in an anaerobic system and the promotion effect of the anaerobic system on the treatment of heavy metals by anaerobic organisms provide a method for treating heavy metal organic wastewater by coupling zero-valent iron-loaded biochar with sulfate reduction. Coupling zero-valent iron/biochar complex with SO4 2-The reduction system is applied to an anaerobic biochemical system for treating heavy metal organic wastewater, promotes the growth and metabolism of microorganisms, improves the wastewater treatment efficiency, optimizes the effluent quality, improves the running performance of a reactor, and provides an economic and effective technology for solving the problem of treating the heavy metal organic wastewater by anaerobic organisms at present.
Disclosure of Invention
The invention aims to provide an economic and efficient method for biochar-loaded zero-valent iron coupling sulfate reduction treatment of heavy metal-containing organic wastewater, aiming at the defects that the effluent quality of an anaerobic system for treating heavy metal organic wastewater is difficult to reach the standard, a reactor cannot stably run for a long time, and the heavy metal removal efficiency is low.
The technical scheme of the invention is that the excess activated sludge of the sewage treatment plant is utilized, a simple high-temperature carbonization method is adopted to prepare the biochar/zero-valent iron complex, and the biochar/zero-valent iron complex and SO are mixed4 2-Adding into anaerobic activated sludge system for treating organic wastewater containing heavy metals, improving wastewater treatment effect by utilizing strong adsorption property of biochar/zero-valent iron complex and promoting microorganism growth metabolism and electron transfer, and adding appropriate amount of SO4 2-The efficiency of removing heavy metal in the organic wastewater is improved.
The technical scheme of the invention is as follows:
a method for treating organic wastewater containing heavy metals by biochar-loaded zero-valent iron coupling sulfate reduction comprises the following steps:
step 1: preparation of biochar loaded zero-valent iron
(1) Sludge pretreatment
Naturally drying the sludge, grinding, and sieving the ground sludge with a 100-mesh sieve to obtain sludge powder.
(2) Preparation of biochar
And (3) putting the sludge powder into a crucible, putting the crucible into a tubular furnace, heating the crucible to 500 ℃ at the heating rate of 10 ℃/min, pyrolyzing the sludge for 3h at constant temperature (introducing nitrogen to maintain oxygen-free in the whole pyrolysis process), and naturally cooling the sludge powder to room temperature to obtain the biochar.
(3) Preparation of biochar loaded zero-valent iron
Weighing 40g of FeCl3 & 6H2O, dissolving in 60mL of deionized water, adding 15g of sludge powder, uniformly mixing by using a stirrer, carrying out suction filtration, drying filter residues in a constant-temperature drying oven at 80 ℃, grinding the dried sample again, putting the ground sample into a crucible, putting the crucible into a tubular furnace (the pyrolysis condition is the same as that of the preparation of the biochar), and carrying out pyrolysis cooling to obtain the biochar loaded zero-valent iron material.
Step 2: operation of anaerobic sludge System
Adopting heavy metal-containing organic wastewater and feeding water into CODCrThe concentration is about 5000mg/L according to CODCr: n: adding (NH) 500:5:14)2SO4And KH2PO4And adding MgSO4·7H2O100 mg/L and CaCl2·2H2O10 mg/L, adding 1mL of trace element solution into each liter of wastewater, wherein the trace element solution comprises the following components: FeCl3·6H2O 1.5g·L-1，H3BO3 0.15g·L-1，CuSO4·5H2O 0.03g·L-1，KI 0.03g·L-1，MnSO4·H2O 0.10g·L-1，(NH4)6Mo7O24·4H2O 0.065g·L-1，ZnCl2 0.057g·L-1，CoCl2·6H2O 0.15g·L-1，Ni(NO3)2 0.15g·L-1. The pH is controlled to be 6.7-7.5, the dissolved oxygen concentration is controlled to be below 0.2mg/L, the temperature is controlled to be 37 ℃, the MLSS is 6-10g/L, and the hydraulic retention time is 12 hours.
And step 3: reduction treatment of heavy metal-containing organic wastewater by biochar-loaded zero-valent iron coupled with sulfate
The biochar loaded zero-valent iron material prepared in the step 1 is prepared according to the proportion of 06g/L of the mixture is added into an anaerobic system for treating the organic wastewater containing the heavy metals in the step 2, and sodium sulfate is added to ensure that influent SO is4 2-The concentration was 2000 mg/L.
The invention has the beneficial effects that:
(1) biochar loaded zero-valent iron coupled SO4 2-The reduction system can promote the growth and metabolism of microorganisms and electron transfer, accelerate the degradation of organic matters, improve the treatment effect of an anaerobic system, improve the removal efficiency of heavy metals and overcome the defects of the conventional anaerobic treatment of heavy metal organic wastewater.
(2) Zero-valent iron/biochar coupled SO4 2-The reduction system can make up the respective defects to play a synergistic effect while exerting the advantages of the three, and eliminates the inhibition effect of the three on the system when being used independently.
(3) The adopted biochar/zero-valent iron complex has simple preparation method, low cost and no pollution.
Drawings
FIG. 1 shows that the biochar loaded zero-valent iron provided by the invention is coupled with sulfate reduction to treat heavy metal-containing organic wastewater CODCrGraph of the change of removal rate. In the figure: ordinate represents CODCrRemoval rate, unit is%; the abscissa is time in units of d.
The figure shows that 0.6g/L biochar/zero-valent iron composite carrier and SO are added into an anaerobic sludge system for treating simulated heavy metal organic wastewater4 2-The concentration is controlled to be 2000mg/L, and after a period of treatment, the COD is obtainedCrThe removal rate can finally reach 97.0 percent, and is increased by 11.0 percent compared with a blank control group; COD in zero-valent iron coupled sulfate reduction systemCrThe removal rate is 93.5 percent, which is improved by 7.0 percent compared with a blank control group; in the biochar coupled sulfate reduction system, CODCrThe removal rate is 89.7 percent, which is improved by 2.6 percent compared with a blank control group; COD in sulfate-alone reduction SystemCrThe removal rate is 89.2%, which is improved by 2.1% compared with the blank control group. Biochar-loaded zero-valent iron coupled sulfate reduction system CODCrThe removal rate is higher than that of other coupling systems, and the heavy metal organic waste is generatedWater CODCrThe improvement of the removal rate has a synergistic effect and can improve the anaerobic treatment effect.
FIG. 2 is a graph showing the change of the removal rate of zinc ions in the organic wastewater containing zinc ions in the reduction treatment of zero-valent iron-loaded biochar coupled sulfate, wherein the concentration of the zinc ions is 60 mg/L. In the figure, the ordinate represents the zinc ion removal rate in%; the abscissa is time in units of d.
The figure shows SO control in an anaerobic sludge system for treating organic wastewater containing zinc ions4 2-The concentration is 2000mg/L, and after a period of treatment, the removal rate of zinc ions of the four coupling systems can finally reach more than 99.7 percent, which is improved by about 25.6 percent compared with a blank control group; the addition of the sulfate is favorable for improving the removal rate of zinc ions and improving the effluent quality.
FIG. 3 is a graph showing the change of the copper ion removal rate of the organic wastewater containing copper ions in the reduction treatment of zero-valent iron-loaded biochar coupled sulfate, wherein the concentration of the copper ions is 30 mg/L. In the figure, the ordinate represents the copper ion removal rate in%; the abscissa is time in units of d.
The figure shows SO control in an anaerobic sludge system for treating organic wastewater containing copper ions4 2-The concentration is 2000mg/L, and after a period of treatment, the copper ion removal rate of the four coupling systems can finally reach more than 99.5 percent, and is improved by nearly 16.8 percent compared with a blank control group; the addition of the sulfate is favorable for improving the removal rate of copper ions and improving the quality of the effluent.
Detailed Description
The present invention will be described in detail below with reference to the drawings, but the present invention is not limited to the following examples.
Example 1
1. Preparation of biochar loaded zero-valent iron
(1) Sludge pretreatment
Naturally drying the sludge, grinding, and sieving the ground sludge with a 100-mesh sieve to obtain sludge powder.
(2) Preparation of biochar
And (3) putting the sludge powder into a crucible, putting the crucible into a tubular furnace, heating the crucible to 500 ℃ at the heating rate of 10 ℃/min, pyrolyzing the sludge for 3h at constant temperature (introducing nitrogen to maintain oxygen-free in the whole pyrolysis process), and naturally cooling the sludge powder to room temperature to obtain the biochar.
(3) Preparation of biochar loaded zero-valent iron
Weighing 40g of FeCl3 & 6H2O, dissolving in 60mL of deionized water, adding 15g of sludge powder, uniformly mixing by using a stirrer, carrying out suction filtration, drying filter residues in a constant-temperature drying oven at 80 ℃, grinding the dried sample again, putting the ground sample into a crucible, putting the crucible into a tubular furnace (the pyrolysis condition is the same as that of the preparation of the biochar), and carrying out pyrolysis cooling to obtain the biochar loaded zero-valent iron material.
2. Operation of anaerobic sludge System
In the organic wastewater with the zinc ion concentration of 60mg/L, the COD of the inlet waterCrThe concentration is 5000mg/L according to CODCr: n: adding (NH) 500:5:14)2SO4And KH2PO4And adding MgSO4·7H2O100 mg/L and CaCl2·2H2O10 mg/L, adding 1mL of trace element solution into each liter of wastewater, wherein the trace element solution comprises the following components: FeCl3·6H2O 1.5g·L-1，H3BO30.15g·L-1，CuSO4·5H2O 0.03g·L-1，KI 0.03g·L-1，MnSO4·H2O 0.10g·L-1，(NH4)6Mo7O24·4H2O 0.065g·L-1，ZnCl2 0.057g·L-1，CoCl2·6H2O 0.15g·L-1，Ni(NO3)20.15g·L-1. The pH is controlled to be 6.7-7.5, the dissolved oxygen concentration is controlled to be below 0.2mg/L, the temperature is controlled to be 37 ℃, the MLSS is 6-10g/L, and the hydraulic retention time is 12 hours.
3. Biochar-loaded zero-valent iron coupling sulfate reduction treatment of zinc ion-containing organic wastewater
Adding the biochar loaded zero-valent iron material prepared in the step 1 into the anaerobic reactor for treating the zinc ion-containing organic wastewater in the step 2 according to 0.6g/LIn an oxygen system, the water inlet SO is controlled by adding sodium sulfate4 2-The concentration was 2000 mg/L.
The results of the experiment are shown in FIGS. 1 and 2. FIG. 1 shows that biological carbon loaded zero-valent iron is coupled with sulfate to reduce COD in zinc ion-containing organic wastewaterCrA removal rate change curve chart, and fig. 2 is a graph showing the change of the removal rate of zinc ions in the organic wastewater containing zinc ions in the biological carbon load zero-valent iron coupling sulfate reduction treatment. In the water inlet CODCrThe concentration is 5000mg/L, SO4 2-When the concentration is 2000mg/L and the zinc ion content is 60mg/L, the biological carbon loads zero-valent iron and couples COD of the sulfate reduction systemCrThe removal rate can reach 97.0%, the removal rate of zinc ions reaches more than 99.7%, and the removal rate is obviously higher than that of a blank control system, so that the biochar loaded zero-valent iron coupled sulfate reduction system has a synergistic effect on accelerating the degradation of organic matters, can obviously improve the anaerobic treatment effect, and simultaneously improves the removal efficiency of heavy metals.
Example 2
1. Preparation of biochar loaded zero-valent iron
(1) Sludge pretreatment
Naturally drying the sludge, grinding, and sieving the ground sludge with a 100-mesh sieve to obtain sludge powder.
(2) Preparation of biochar
And (3) putting the sludge powder into a crucible, putting the crucible into a tubular furnace, heating the crucible to 500 ℃ at the heating rate of 10 ℃/min, pyrolyzing the sludge for 3h at constant temperature (introducing nitrogen to maintain oxygen-free in the whole pyrolysis process), and naturally cooling the sludge powder to room temperature to obtain the biochar.
(3) Preparation of biochar loaded zero-valent iron
Weighing 40g FeCl3And 6H2O, dissolving in 60mL of deionized water, adding 15g of sludge powder, uniformly mixing by using a stirrer, performing suction filtration, drying filter residues in a drying oven at the constant temperature of 80 ℃, grinding the dried sample again, putting the ground sample into a crucible, putting the crucible into a tubular furnace (the pyrolysis condition is the same as that of the preparation of the biochar), and performing pyrolysis cooling to obtain the biochar loaded zero-valent iron material.
2. Operation of anaerobic sludge System
In the organic wastewater with the copper ion concentration of 30mg/L, the COD of the inlet waterCrThe concentration is 5000mg/L according to CODCr: n: adding (NH) 500:5:14)2SO4And KH2PO4And adding MgSO4·7H2O100 mg/L and CaCl2·2H2O10 mg/L, adding 1mL of trace element solution into each liter of wastewater, wherein the trace element solution comprises the following components: FeCl3·6H2O 1.5g·L-1，H3BO30.15g·L-1，CuSO4·5H2O 0.03g·L-1，KI 0.03g·L-1，MnSO4·H2O 0.10g·L-1，(NH4)6Mo7O24·4H2O 0.065g·L-1，ZnCl2 0.057g·L-1，CoCl2·6H2O 0.15g·L-1，Ni(NO3)20.15g·L-1. The pH is controlled to be 6.7-7.5, the dissolved oxygen concentration is controlled to be below 0.2mg/L, the temperature is controlled to be 37 ℃, the MLSS is 6-10g/L, and the hydraulic retention time is 12 hours.
3. Reduction treatment of copper ion-containing organic wastewater by biochar-loaded zero-valent iron coupled sulfate
Adding the biochar loaded zero-valent iron material prepared in the step 1 into an anaerobic system for treating the copper ion-containing organic wastewater in the step 2 according to 0.6g/L, and adding sodium sulfate to control water inlet SO4 2-The concentration was 2000 mg/L.
The results of the experiment are shown in FIGS. 1 and 3. FIG. 1 shows that biological carbon loaded zero-valent iron is coupled with sulfate to reduce COD in zinc ion-containing organic wastewaterCrA removal rate change curve chart, and fig. 3 is a curve chart of the removal rate change of copper ions in organic wastewater containing copper ions by biochar loaded zero-valent iron coupling sulfate reduction treatment. In the water inlet CODCrThe concentration is 5000mg/L, SO4 2-When the concentration is 2000mg/L and the copper ion content is 30mg/L, the biological carbon loads zero-valent iron and couples COD of the sulfate reduction systemCrThe removal rate can reach 97.0 percent, the removal rate of copper ions reaches more than 99.4 percent and is obviously higher than that of a blank control system, which shows that the biochar loads the zero-valent iron coupled sulfate reduction system pairHas synergistic effect in accelerating the degradation of organic matters, can obviously improve the anaerobic treatment effect, and simultaneously improves the heavy metal removal efficiency.
Claims (3)
1. A method for treating organic wastewater containing heavy metals by biochar-loaded zero-valent iron coupling sulfate reduction is characterized by comprising the following steps:
step 1: preparation of biochar loaded zero-valent iron
(1) Sludge pretreatment
Naturally drying the sludge, grinding, and sieving the ground sludge with a 100-mesh sieve to obtain sludge powder.
(2) Preparation of biochar
And (3) putting the sludge powder into a crucible, putting the crucible into a tubular furnace, heating the crucible to 500 ℃ at the heating rate of 10 ℃/min, pyrolyzing the sludge for 3h at constant temperature (introducing nitrogen to maintain oxygen-free in the whole pyrolysis process), and naturally cooling the sludge powder to room temperature to obtain the biochar.
(3) Preparation of biochar loaded zero-valent iron
Weighing 40g of FeCl3 & 6H2O, dissolving in 60mL of deionized water, adding 15g of sludge powder, uniformly mixing by using a stirrer, carrying out suction filtration, drying filter residues in a constant-temperature drying oven at 80 ℃, grinding the dried sample again, putting the ground sample into a crucible, putting the crucible into a tubular furnace (the pyrolysis condition is the same as that of the preparation of the biochar), and carrying out pyrolysis cooling to obtain the biochar loaded zero-valent iron material.
Step 2: operation of anaerobic sludge System
Adopting heavy metal-containing organic wastewater and feeding water with CODCrThe concentration is about 5000mg/L according to CODCr: n: adding (NH) 500:5:14)2SO4And KH2PO4And adding MgSO4·7H2O100 mg/L and CaCl2·2H2O10 mg/L, adding 1mL of trace element solution into each liter of wastewater, wherein the trace element solution comprises the following components: FeCl3·6H2O 1.5g·L-1，H3BO3 0.15g·L-1，CuSO4·5H2O 0.03g·L-1，KI 0.03g·L-1，MnSO4·H2O 0.10g·L-1，(NH4)6Mo7O24·4H2O 0.065g·L-1，ZnCl2 0.057g·L-1，CoCl2·6H2O 0.15g·L-1，Ni(NO3)2 0.15g·L-1. The pH is controlled to be 6.7-7.5, the dissolved oxygen concentration is controlled to be below 0.2mg/L, the temperature is controlled to be 35-40 ℃, the MLSS is 6-10g/L, and the hydraulic retention time is 8-12 hours.
And step 3: treatment of heavy metal organic wastewater by biochar loaded zero-valent iron coupled sulfate reduction
Adding the biochar loaded zero-valent iron material prepared in the step 1 into an anaerobic system for treating heavy metal organic wastewater in the step 2 according to 0.6g/L, and adding sodium sulfate to enable inlet water SO4 2-The concentration was 2000 mg/L.
2. The method for treating heavy metal organic wastewater by coupling zero-valent iron-loaded biochar with sulfate reduction according to claim 1, wherein 0.6g/L of zero-valent iron-loaded biochar material, SO, is added in step 34 2-2000mg/L, has synergistic effect on the treatment effect of heavy metal organic wastewater, and can improve the treatment effect of wastewater.
3. The method for treating heavy metal organic wastewater by coupling biochar-loaded zero-valent iron with sulfate reduction according to claim 1, wherein the biochar-loaded zero-valent iron material prepared in the step 1 is prepared by mixing biochar and zero-valent iron according to a mass ratio of 1: 1 are compounded.
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| CN115611437A (en) * | 2022-10-28 | 2023-01-17 | 上海城市水资源开发利用国家工程中心有限公司 | Bioremediation material for underground water metal antimony pollution and preparation method thereof |
| CN116332343A (en) * | 2023-05-22 | 2023-06-27 | 江苏省环境工程技术有限公司 | Sulfur autotrophic denitrification sulfur-based magnetic filler and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115611437A (en) * | 2022-10-28 | 2023-01-17 | 上海城市水资源开发利用国家工程中心有限公司 | Bioremediation material for underground water metal antimony pollution and preparation method thereof |
| CN116332343A (en) * | 2023-05-22 | 2023-06-27 | 江苏省环境工程技术有限公司 | Sulfur autotrophic denitrification sulfur-based magnetic filler and preparation method and application thereof |
| CN116332343B (en) * | 2023-05-22 | 2023-08-18 | 江苏省环境工程技术有限公司 | Sulfur autotrophic denitrification sulfur-based magnetic filler and preparation method and application thereof |
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