CN110697889A - Method for promoting anaerobic mineralization of phenolic wastewater - Google Patents
Method for promoting anaerobic mineralization of phenolic wastewater Download PDFInfo
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- CN110697889A CN110697889A CN201911145921.6A CN201911145921A CN110697889A CN 110697889 A CN110697889 A CN 110697889A CN 201911145921 A CN201911145921 A CN 201911145921A CN 110697889 A CN110697889 A CN 110697889A
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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
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
- C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
- C12P5/023—Methane
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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Abstract
The invention discloses a method for promoting anaerobic mineralization of phenolic wastewater, which is characterized in that an iron-based complexing agent is added into an anaerobic biological treatment system, wherein the iron-based complexing agent mainly comprises ferroferric oxide and monovalent iron. The iron-based complexing agent disclosed by the invention can remove the toxic action of phenol and intermediate products thereof on microorganisms by strengthening the hydrolysis of phenol and intermediate products thereof in the anaerobic biological treatment process of the phenol-containing wastewater, and can improve the methane production efficiency and methane yield of an anaerobic fermentation system of the phenol-containing wastewater, so that the phenol-containing wastewater is finally and completely mineralized.
Description
Technical Field
The invention relates to a method for promoting anaerobic mineralization of phenol-containing wastewater, belonging to the field of biological treatment of industrial wastewater.
Background
Phenol is an important organic chemical raw material and is widely applied to industries such as plastics, synthetic rubber, medicines, pesticides, spices, dyes, coatings, oil refining and the like. Phenol-containing wastewater is industrial wastewater generated in the process of producing various products, and thousands of tons of phenol-containing wastewater are generated every year due to wide application of phenol. The phenol-containing wastewater belongs to the second class of pollutants and can be discharged after the standards are detected at the discharge port of a production enterprise.
At present, the conventional treatment method of the phenol-containing wastewater mainly comprises a physical and chemical method and a biological method. The physicochemical method comprises an extraction method, a steam stripping method and the like, the method for treating the phenol-containing wastewater has the advantage of recovering phenol, but the treatment cost is too high, and the method is generally only suitable for treating the high-concentration phenol-containing wastewater. Compared with a physical and chemical method, the cost of biologically treating the phenol-containing wastewater can be greatly reduced, and particularly, the anaerobic biological treatment method has the advantages of small occupied area, low energy consumption, no generation of residual sludge and capability of recovering biological energy (methane), thereby being an ideal process for treating the phenol-containing wastewater. However, anaerobic biological treatment of phenolic wastewater also presents short plates, i.e. phenol and its intermediates have a poisoning effect on the activity of anaerobic methanogens, thus limiting the application of phenolic anaerobic biological treatment.
Disclosure of Invention
The invention aims to provide a method for promoting anaerobic mineralization of phenolic wastewater, which can effectively improve the degradation rate of toxic and harmful substances such as phenol, benzoic acid and the like in the phenolic wastewater and promote the mineralization of phenol to generate methane so as to achieve the aim of recovering bioenergy.
The invention relates to a method for promoting anaerobic mineralization of phenolic wastewater, which is to add an iron-based complexing agent into an anaerobic biological treatment system.
The iron-based complexing agent comprises monovalent iron and ferroferric oxide, wherein the monovalent iron accounts for 20-80% of the iron-based complexing agent by mass, and the ferroferric oxide accounts for 20-80% of the iron-based complexing agent by mass.
The dosage of the iron-based complexing agent is related to the Chemical Oxygen Demand (COD) concentration of the phenolic wastewater to be treated and the sludge concentration in an anaerobic biological treatment system, and the mass dosage of the iron-based complexing agent is 0.1-10 times of the COD or 0.1-5 times of the volatile suspended matter concentration (MLVSS) of the complete mixed solution.
The adding mode of the iron-based complexing agent can be determined according to the concentration of iron ions in effluent, an online iron ion monitor is arranged at the effluent of the anaerobic biological treatment system, and when the concentration of the iron ions is lower than 1-20% of MLVSS (mass ratio), the automatic dosing system can be opened, and the iron-based complexing agent is added into the sludge circulating system.
The stability and methane yield of the anaerobic biological system can be improved by adding the conductive material into the anaerobic biological treatment system. The conductive materials such as monovalent iron and ferroferric oxide serve as electron shuttles in the anaerobic system, and the inter-species electron transfer effect between the fermentation bacteria and the methanogenic bacteria in the anaerobic system is promoted. The ferroferric oxide in the iron agent complexing agent can strengthen the hydrolysis of phenol and intermediate products thereof, and simultaneously monovalent iron in the iron-based complexing agent has a remarkable promoting effect on anaerobic methane production, and the monovalent iron are strongly combined, so that the hydrolysis efficiency of the phenol is improved, and the biological energy recovery of an anaerobic system is improved. Experiments prove that the action mechanism of the iron-based complexing agent disclosed by the invention is that ferroferric oxide in the iron-based complexing agent can improve the abundance of acetic acid oxidizing bacteria Clostridium, so that the transfer of an intermediate product acetic acid in a phenol anaerobic digestion system to hydrogen and carbon dioxide is accelerated, and the monovalent iron in the iron-based complexing agent greatly promotes the growth of methanogen hydrogenophilum, so that the efficiency of the terminal methanogenesis process of the anaerobic fermentation system of phenol-containing wastewater is greatly improved. Therefore, the complexing agent not only effectively improves the degradation rate of phenolic compounds and intermediate products thereof in the phenol-containing wastewater, but also can quickly promote the rate of mineralizing the phenol-containing wastewater to produce methane and the yield of methane.
The iron-based complexing agent added by the invention has the advantages of wide and easily available raw materials, low price and little increase of the treatment cost of an anaerobic system.
The method can improve the phenol degradation rate by 14.1-42.8% and the methane yield by 13.7-32.9%.
The iron-based complexing agent added by the method can be intelligently added on line, can realize full-automatic control and is convenient to manage.
Drawings
FIG. 1 is a graph comparing anaerobic degradation rates of phenol at different concentrations. As can be seen from figure 1, compared with an anaerobic biological treatment system without adding the iron complex agent, the phenol degradation rate of the iron complex agent is improved by 14.1-42.8% by adding different iron complex agents into the anaerobic biological system.
FIG. 2 is a comparison of the cumulative total yield of anaerobic methane for different concentrations of phenol. As can be seen from FIG. 2, the cumulative total yield of methane in the anaerobic biological treatment system added with the iron complexing agent is improved by 13.7% -32.9% compared with the anaerobic biological treatment system not added with the iron complexing agent.
FIG. 3 is a comparison of anaerobic methanogenesis rates for different concentrations of phenol. As can be seen from FIG. 3, the methane production rate of the anaerobic biological treatment system added with the iron complexing agent is improved by 1.1-1.4 times compared with the anaerobic biological treatment system not added with the iron complexing agent.
Detailed Description
The invention relates to a method for promoting anaerobic mineralization of phenolic wastewater, which is to add an iron-based complexing agent into an anaerobic biological treatment system.
The iron-based complexing agent comprises monovalent iron and ferroferric oxide, wherein the monovalent iron accounts for 20-80% of the iron-based complexing agent by mass, and the ferroferric oxide accounts for 20-80% of the iron-based complexing agent by mass.
The dosage of the iron-based complexing agent is related to the COD concentration of the phenolic wastewater to be treated and the concentration of the seed sludge in the anaerobic biological treatment system, and the dosage of the iron-based complexing agent is 10-10 COD (mass ratio) or 10-5 MLVSS (mass ratio).
The adding mode of the iron-based complexing agent can be determined according to the concentration of iron ions in effluent, an online iron ion monitor is arranged in a sludge bed of the anaerobic biological treatment system, and when the concentration of the iron ions is lower than 10% of MLVSS (mass ratio), the automatic dosing system can be opened, and the iron-based complexing agent is added into the sludge circulating system.
Taking phenol as an example, adding an iron-based complexing agent into an anaerobic biological system of the phenol and the phenol, wherein the dosage of the iron-based complexing agent is 5g/L, and the iron oxide: 50 percent of monovalent iron and 50 percent of monovalent iron (mass ratio), wherein the initial concentration of phenol in the treated phenol-containing wastewater is 200mg/L, the initial concentration of inoculated sludge is 3gMLVSS/L, and the degradation rate of the iron-based complexing agent on phenol, the methane production rate and the total methane amount are compared under the same environmental conditions. As shown in the graph in FIG. 1, in the anaerobic biological treatment system, the phenol concentration is increased from 200mg/L to 800mg/L (i.e. the COD concentration is increased from 500mg/L to 1900mg/L), the adding ratios of the iron-based complexing agent are respectively 10 times COD, 7 times COD, 4.2 times COD and 2.6 times COD, compared with the iron-based complexing agent of a blank control group, the phenol degradation rate of the anaerobic biological system added with various doses of the iron-based complexing agent is increased, wherein the phenol degradation rate of the iron-based complexing agent with the adding ratio of 4.2 times COD is increased by 42.8%. As shown in fig. 2 and fig. 3, compared to the blank control group, the total cumulative methane yield and the methane production rate of the anaerobic biological system added with various dosages of the iron-based complexing agent are both improved, wherein the total cumulative methane yield is improved, and the cumulative methane yield and the methane production rate of the iron-based complexing agent with the addition ratio of 2.6 times of COD are improved by 32.9% and 1.4 times respectively.
Claims (4)
1. A method for promoting anaerobic mineralization of phenolic wastewater is characterized in that:
adding an iron-based complexing agent into an anaerobic biological treatment system.
2. The method of claim 1, wherein:
the iron-based complexing agent comprises monovalent iron and ferroferric oxide, wherein the monovalent iron accounts for 20-80% of the iron-based complexing agent by mass, and the ferroferric oxide accounts for 20-80% of the iron-based complexing agent by mass.
3. The method according to claim 1 or 2, characterized in that:
the dosage of the iron-based complexing agent is related to the Chemical Oxygen Demand (COD) concentration of the phenolic wastewater to be treated and the sludge concentration in an anaerobic biological treatment system, and the mass dosage of the iron-based complexing agent is 0.1-10 times of the COD or 0.1-5 times of the volatile suspended matter concentration of the complete mixed solution.
4. The method according to claim 1 or 2, characterized in that:
the adding mode of the iron-based complexing agent can be determined according to the concentration of iron ions in effluent, an online iron ion monitor is arranged in a sludge bed of the anaerobic biological treatment system, when the concentration of the iron ions is lower than 1-20% of MLVSS (layered double hydroxides), the automatic medicine adding system can be opened, and the iron-based complexing agent is added into the sludge circulating system.
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| CN201911145921.6A CN110697889A (en) | 2019-11-21 | 2019-11-21 | Method for promoting anaerobic mineralization of phenolic wastewater |
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| CN201911145921.6A CN110697889A (en) | 2019-11-21 | 2019-11-21 | Method for promoting anaerobic mineralization of phenolic wastewater |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111500646A (en) * | 2020-05-06 | 2020-08-07 | 苏州科技大学 | Method for producing methane from phenol-containing waste water |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105800897A (en) * | 2016-05-11 | 2016-07-27 | 合肥工业大学 | Method for intensifying rapid solid anaerobic digestion of residual sludge and straw by using zero-valent iron |
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- 2019-11-21 CN CN201911145921.6A patent/CN110697889A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105800897A (en) * | 2016-05-11 | 2016-07-27 | 合肥工业大学 | Method for intensifying rapid solid anaerobic digestion of residual sludge and straw by using zero-valent iron |
Non-Patent Citations (1)
| Title |
|---|
| CHUNHUA HE等: "Synergistic effect of magnetite and zero-valent iron on anaerobic degradation and methanogenesis of phenol", 《BIORESOURCE TECHNOLOGY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111500646A (en) * | 2020-05-06 | 2020-08-07 | 苏州科技大学 | Method for producing methane from phenol-containing waste water |
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