CN110467271A - A kind of bio-electrochemical process for synchronizing removing sulfate and recycling elemental sulfur - Google Patents
A kind of bio-electrochemical process for synchronizing removing sulfate and recycling elemental sulfur Download PDFInfo
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- CN110467271A CN110467271A CN201910520654.XA CN201910520654A CN110467271A CN 110467271 A CN110467271 A CN 110467271A CN 201910520654 A CN201910520654 A CN 201910520654A CN 110467271 A CN110467271 A CN 110467271A
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- sulfate
- anode
- cathode
- elemental sulfur
- wastewater
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/0253—Preparation of sulfur; Purification from non-gaseous sulfur compounds other than sulfides or materials containing such sulfides
- C01B17/0259—Preparation of sulfur; Purification from non-gaseous sulfur compounds other than sulfides or materials containing such sulfides by reduction of sulfates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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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
- C02F3/005—Combined electrochemical biological processes
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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
- 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
- C02F3/345—Biological treatment of water, waste water, or sewage characterised by the microorganisms used for biological oxidation or reduction of sulfur compounds
Abstract
The present invention relates to a kind of bio-electrochemical process for synchronizing removing sulfate and recycling elemental sulfur, belong to bioelectrochemistry field, the system is characterized on the Research foundation of existing bipolar chamber structure-biological electro-chemical systems, anode electrode is modified to semiconductor titanium dioxide, apply certain external voltage simultaneously, anode utilizes ultraviolet catalytic electrolysis water, the biomembrane that cathode passes through the certain microbial biomass of culture, add the sulfate wastewater of a certain concentration sodium sulphate mixed liquor simulation, reasonable anode and cathode spacing is determined, to realize sulfate reduction and simple substance sulfur recovery.
Description
Technical field
The invention belongs to bioelectrochemistry field, which is characterized in existing bipolar chamber structure-biological electrochemistry system
On the Research foundation of system, anode electrode is modified to semiconductor titanium dioxide, while applying certain external voltage, anode utilizes purple
Outer light carrys out catalytic electrolysis water, by cultivating the cathode biomembrane of certain microbial biomass, adds a certain concentration sodium sulphate mixed liquor mould
Quasi- sulfate wastewater determines reasonable anode and cathode spacing, to realize sulfate reduction and simple substance sulfur recovery simultaneously.
Background technique
Many can be generated during paper pulp, papermaking, food processing, animal husbandry, production of dyestuff etc. is rich in sulfate wastewater,
The discharge of these waste water is one of main source of water pollution, and will cause great harm to human body and ecological environment.Sulfuric acid
Although salt itself is harmless, high concentration sulfate wastewater, which is discharged into water body, can make water acidification, and pH value reduces, and endanger aquatic life
Object；Soil texture can be destroyed by being discharged into farmland, make soil hardening, reduced crop yield and reduced quality of agricultural product；Sulfate exists
Hydrogen sulfide can be generated in anaerobic environment under the action of sulfate reducing bacteria, vulcanizes Hydrogen Energy heavy corrosion treatment facility and drainpipe
Road can also cause people's neurotoxic when concentration reaches certain restrictions.The solubility of sulfate in water is very big, and
Chemical property is highly stable, self catharsis for relying solely on environment is difficult to eliminate the pollution of sulfate wastewater.Europe and beauty
Sulfate wastewater is included in the pollutant inventory for needing to establish discharge threshold by Environmental Protection Department, state, find not only efficient stable but also
The processing method of economical and practical sulfate wastewater has become the urgent need of various countries.
CN104140155A discloses a kind of method that elemental sulfur is generated in sulfate wastewater biological treatment process.The side
Method includes: using the anaerobic reactor of at least three series connection compartments, and wherein the one before compartment is that sulfide generates compartment, intermediate compartment
It is that elemental sulfur generates compartment, last compartment is methane phase compartment.
CN103523909A disclose it is a kind of from high-concentration sulfuric acid salt organic waste water recycle elemental sulfur process and
Its reactor is made biological desulphurization process generate elemental sulfur, is realized using stripping technology single by optimizing the aerating system of reactor
Matter sulphur is separated with waste water, is captured using a protruded ripple plate filler to elemental sulfur, and recycle elemental sulfur.
Bioelectrochemical system is a kind of biocatalyst, i.e., microorganism on the electrode carries out oxidation or reduction reaction
Electro-chemical systems.Photoelectricity drive bioelectrochemical system using photocatalysis come electrolysis water by electron transmission to the two poles of the earth, generate simultaneously
Energy and gas sulphate reducing and sulfur oxide compound come by cathode microbial utilization, and then reach processing sulfate wastewater
Purpose.
Currently, traditional processing method for sulfate wastewater includes physical method, chemical method and biological method.
Although physico-chemical process quickly and effectively, is easy to produce secondary pollution, and treatment process generally requires to be separated by solid-liquid separation, Gu
Mutually disposition etc., this considerably increases cost for wastewater treatment and energy consumption, limit the application of these methods.Using Biochemical method sulphur
Hydrochlorate waste water, by sulfate reducing bacteria by intractable SO4 2-It is changed into more tractable S2-, then pass through sulfide oxidation
Bacterium is by S2-Selective oxidation carries out resource utilization or contacts to form heavy metal vulcanization with heavy metal waste liquid by it at elemental sulfur
The precipitating of object realizes heavy metal ion and S2-Synchronization process.Not only cost is lower for biological treatment, while not generating secondary pollution,
It is considered as the ideal processing method of sulfate wastewater.
Summary of the invention
The present invention is using sulfate wastewater as research object, in the research of existing bipolar chamber structure-biological electro-chemical systems
On the basis of anode electrode is improved as semiconductor titanium dioxide, using its to the absorption of sunlight come electrolysis water, to be cathode
The growth of microorganism and processing sulfate wastewater provide suitable condition, and study the system core operating parameter, lead to
Cross the method that the research of these service conditions finds efficient sulphate reducing and recycles elemental sulfur.
It is respectively 6*6*2cm that the device of bioelectrochemical system processing sulfate wastewater, which is by anode chamber and cathode chamber,3With
6*6*4cm3Organic glass cuboid be connected in series, with cation-exchange membrane interval, anode electrode is for anode chamber and cathode chamber
Electro-conductive glass coated with titanium dioxide, cathode are the carbon brush of carbon fiber establishment, the resistance for 10 Ω that wherein connect outside cathode, in yin
The DC power supply of the additional 1.2V in anode both ends.Reactor anode utilizes photocatalysis electrolysis water, and the energy of generation is respectively by cathode sulphur
Sulfate reduction is divalent sulfur using reduction and oxidation reaction is carried out by hydrochlorate reducing bacteria and sulfur bacteria, goes forward side by side one
Step is oxidized to elemental sulfur, and therefore, reactor constitutes a circuit formed by optical drive electron transmission in anode to cathode.
Anode and cathode is located at anode chamber and cathode chamber, and the anode of reaction system is by the conduction coated with titanium dioxide
Glass composition, cathode are made of the carbon brush for being attached with microorganism, and anode and cathode spacing is between 2-6cm.
In 500mg/L NaSO4 2-、1000mg/L NaHCO3、300mg/L NH4The sulfate wastewater item of Cl mixed liquor simulation
Under part, suitable catholyte is selected, so that cathode microbial is in higher activity, while not influencing the electricity production of the system again
Energy.Using 36h as a cycle, SO at the end of periodic duty4 2-Up to 61%, wherein the production quantity of elemental sulfur accounts for is removed removal rate
The 49% of sulfate.
In 500mg/L NaSO4 2-、1000mg/L NaHCO3、300mg/L NH4The sulfate wastewater item of Cl mixed liquor simulation
Under part, suitable catholyte is selected, density peak value is up to 70A/m3。
Use the 50mM phosphate buffer solution of pH=7 as catholyte, cathode intakes dissolved oxygen control to 0mg/L, is somebody's turn to do
System maximum current density is up to 70A/m3, SO at the end of periodic duty4 2-Reduction rate is up to 61%, the wherein production quantity of elemental sulfur
Account for the 49% of gone removing sulfate.
A kind of photoelectricity driving microorganism electrochemical sulphate reducing provided by the present invention and the method for recycling elemental sulfur
Advantage is: anode electrode being changed to semiconductor dioxy on the Research foundation of existing bipolar chamber structure-biological electro-chemical systems
Change titanium, using its to the absorption of sunlight come electrolysis water, thus for cathode microbial growth and handle sulfate wastewater provide
Suitable condition, and the system core operating parameter is studied, efficient reduction is found by the research of these service conditions
Sulfate and the method for generating elemental sulfur realize the sulfate reduction rate up to 61%, and wherein the production quantity of elemental sulfur, which accounts for, is removed
The 49% of sulfate thereby realizes energy saving and recycling elemental sulfur double effects.
Detailed description of the invention
Attached drawing 1 is the schematic illustration of bioelectrochemical system processing sulfate wastewater.Wherein each digital generation respectively in figure
Table: 1- ultraviolet lamp；2- ultraviolet light；3-TiO2Electro-conductive glass；The anode chamber 4-；5- cation-exchange membrane；6- cathode chamber；7- sulfate
Reducing bacteria, sulfur-oxidizing bacteria；8- carbon brush；9-10 Ω resistance；10-1.2V DC power supply.
Attached drawing 2 is bio-electrochemical reactor current density plot schematic diagram.
Attached drawing 3 is the sulfate concentration variation schematic diagram in bio-electrochemical reactor entire reaction time.
Attached drawing 4 is the production concentration variation schematic diagram in bio-electrochemical reactor entire reaction time.
Attached drawing 5 is each sulfur speciation substance accounting schematic diagram in solution at the end of bio-electrochemical reactor periodic duty.
Attached drawing 6 is each form substance distribution schematic diagram of bioelectrochemical system cathode surface sulphur, wherein each number in figure
Respectively represent: each number respectively represents in figure: 1-S2-, 2-S0, 3-SO4 2-, SO3 2-。
Specific embodiment
The device of photoelectricity microorganism electrochemical system processing sulfate wastewater is a two-compartment reactor, yin-yang two-stage it is positive from
Proton exchange separates, and for anode by photocatalytic semiconductor material come electrolysis water, cathode realizes going back for sulfate using microorganism
Former and elemental sulfur recycling.Got up by the applied voltage system stable operation for applying certain.Wherein anode substrate is (molten in 1L
Liquid) are as follows: 2.0g NaHCO3、3.782g K2HPO4.2H2O、2.152g KH2PO4, cathode is sulfuric acid base status, and main component is
(in 1L solution): 0.74g Na2SO4、6.84g NaH2PO4、2.20g Na2HPO4、0.1g KCl、0.04g MgCl2、0.3g
NH4Cl、1.0g NaHCO3, 1mL trace element solution and 10mL vitamin solution.
Utilize a kind of intensifying method of photoelectricity microorganism electrochemical system processing sulfate wastewater of the invention, sulfate
The more traditional two-compartment reactor of rate of reduction can be improved 126%, and elemental sulfur generating rate can be improved 55%, be that one kind more optimizes
Bioelectrochemical system.
The concentration that photoelectricity microorganism electrochemical system handles sulfate wastewater is 500mg/L, is produced under this service condition
Raw maximum current density is 70A/m3。
Photoelectricity microorganism electrochemical system import photocatalysis technology is the growth of cathode microbial and the place of sulfate wastewater
Reason provides advantageous condition, and with this condition, sulfate reduction is now sulfide by sulfate reducing bacteria, and sulfide then exists
It is further oxidized to elemental sulfur under the action of sulfur bacteria, since system pH value can rise during this, keeps away
The generation of intermediate product hydrogen sulfide is exempted from.
Claims (6)
1. a kind of bio-electrochemical process for synchronizing removing sulfate and recycling elemental sulfur, which is characterized in existing double
On the Research foundation of pole room structure-biological electro-chemical systems, anode electrode is modified to semiconductor titanium dioxide, while applying one
Fixed external voltage, anode utilize ultraviolet catalytic electrolysis water, and cathode is added certain by the biomembrane of the certain microbial biomass of culture
The sulfate wastewater of concentration sodium sulphate mixed liquor simulation, determines reasonable anode and cathode spacing, to realize sulfate reduction simultaneously
With simple substance sulfur recovery.
2. the method according to claim 1, wherein reaction system is respectively 6*6* by anode chamber and cathode chamber
2cm3、6*6*4cm3Organic cuboid glass is connected in series, and anode chamber and cathode chamber are with cation-exchange membrane interval, outside reactor
Resistance is 10 Ω, and anode material is semiconductor titanium dioxide, and cathode material is graphite fibre carbon brush, sanitary sewage inoculation, yin-yang
Interpolar is away from 2-6cm.
3. selecting suitable anode electricity the method according to claim 1, wherein applying the applied voltage of 1.2V
Liquid is solved, so that system has good electricity generation performance, density peak value is up to 70A/m3。
4. the method according to claim 1, wherein adding a certain concentration sodium sulphate, sodium bicarbonate and ammonium chloride
The sulfate wastewater of equal mixed liquors simulation, using 36h as a cycle, SO at the end of periodic duty4 2-Removal rate up to 61%, wherein
The production quantity of elemental sulfur accounts for the 49% of gone removing sulfate.
5. according to method described in claim 1, which is characterized in that in a certain concentration sodium sulphate, sodium bicarbonate and ammonium chloride etc.
Mixed liquor simulation sulfate wastewater under the conditions of, select suitable catholyte, enable system realize simultaneously sulfate reduction and
Simple substance sulfur recovery.
6. according to claim 5, when using the 50mM phosphate buffer solution of pH=7 as catholyte, cathode chamber 500mg/L
NaSO4 2-、1000mg/LNaHCO3、300mg/LNH4The sulfate wastewater of Cl mixed liquor simulation, cathode water inlet dissolved oxygen control are
0mg/L, the system maximum current density are up to 70A/m3, SO at the end of periodic duty4 2-Removal rate is up to 61%, wherein elemental sulfur
Production quantity account for the 49% of gone removing sulfate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910520654.XA CN110467271A (en) | 2019-06-06 | 2019-06-06 | A kind of bio-electrochemical process for synchronizing removing sulfate and recycling elemental sulfur |
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| CN201910520654.XA CN110467271A (en) | 2019-06-06 | 2019-06-06 | A kind of bio-electrochemical process for synchronizing removing sulfate and recycling elemental sulfur |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111115847A (en) * | 2019-12-30 | 2020-05-08 | 浙江大学 | Denitrification method and device based on electrochemical sulfate circulation |
| CN112390459A (en) * | 2020-10-20 | 2021-02-23 | 衡阳师范学院 | Electrode for treating wastewater, wastewater treatment apparatus including the same, and wastewater treatment method |
| CN113845217A (en) * | 2021-11-02 | 2021-12-28 | 中山大学 | Method and device for removing refractory organic pollutants through sulfur-mediated bioelectrochemistry enhancement |
| CN114634241A (en) * | 2022-04-07 | 2022-06-17 | 中山大学 | Method for simultaneously removing sulfate and florfenicol in water |
| CN114671513A (en) * | 2022-04-09 | 2022-06-28 | 中山大学 | Photoelectrocatalysis method for degrading sulfamethoxazole by utilizing synergistic effect of microorganisms |
| CN115947446A (en) * | 2023-01-03 | 2023-04-11 | 四川轻化工大学 | Nitrogen-containing strong salt wastewater treatment device |
-
2019
- 2019-06-06 CN CN201910520654.XA patent/CN110467271A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111115847A (en) * | 2019-12-30 | 2020-05-08 | 浙江大学 | Denitrification method and device based on electrochemical sulfate circulation |
| CN112390459A (en) * | 2020-10-20 | 2021-02-23 | 衡阳师范学院 | Electrode for treating wastewater, wastewater treatment apparatus including the same, and wastewater treatment method |
| CN112390459B (en) * | 2020-10-20 | 2024-02-02 | 衡阳师范学院 | Electrode for treating wastewater, wastewater treatment apparatus including the same, and wastewater treatment method |
| CN113845217A (en) * | 2021-11-02 | 2021-12-28 | 中山大学 | Method and device for removing refractory organic pollutants through sulfur-mediated bioelectrochemistry enhancement |
| CN114634241A (en) * | 2022-04-07 | 2022-06-17 | 中山大学 | Method for simultaneously removing sulfate and florfenicol in water |
| CN114634241B (en) * | 2022-04-07 | 2023-10-17 | 中山大学 | Method for simultaneously removing sulfate and florfenicol in water |
| CN114671513A (en) * | 2022-04-09 | 2022-06-28 | 中山大学 | Photoelectrocatalysis method for degrading sulfamethoxazole by utilizing synergistic effect of microorganisms |
| CN114671513B (en) * | 2022-04-09 | 2023-12-22 | 中山大学 | Photoelectrocatalysis method for degrading sulfamethoxazole by utilizing synergistic effect of microorganisms |
| CN115947446A (en) * | 2023-01-03 | 2023-04-11 | 四川轻化工大学 | Nitrogen-containing strong salt wastewater treatment device |
| CN115947446B (en) * | 2023-01-03 | 2024-04-16 | 四川轻化工大学 | Nitrogen-containing concentrated salt wastewater treatment device |
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