CN109160596A - A kind of quick start method of the bioelectrochemistry technique for oil field waste deoxygenation - Google Patents
A kind of quick start method of the bioelectrochemistry technique for oil field waste deoxygenation Download PDFInfo
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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
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
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Abstract
The invention discloses a kind of quick start methods of bioelectrochemistry technique for oil field waste deoxygenation, by the culture medium ratio for controlling starting period, it is inoculated with source, connection, the efficient electricity-producing microorganism of effective fast enriching may be implemented in the conditions such as DO control, and the quick start of bio-electrochemical reactor may be implemented.Control condition adjustment starting substrate is the most suitably used substrate of common advantage anode microorganism, the bio-diversity of inoculum is improved using activated sludge simultaneously, control connection forms the high pressure screening to functional microorganism, the control of DO has then cooperated demand of the aerobic-anaerobic microbe in objective function microorganism to oxygen well, while balancing demand of the cathode to oxygen.
Description
Technical field
The invention belongs to the technical fields of microbial control oxygen electrochemical corrosion, are related to a kind of bioelectrochemistry deoxygenation work
The quick start method of skill.
Background technique
Heavy corrosion will cause to filling pipe equipment and casing containing dissolved oxygen in injection water, based on for oil field injection
The necessity of water deoxygenation, therefore novel bioelectrochemistry is designed and developed out except oxygen reactor, and for the reactor, it is main
Working centre is the electricity-producing microorganism that can be enriched on anode, from 1910 earliest discovery microorganism (Escherichia coli,
E.coli. yeast) can be aoxidized on the electrode and obtains electric current output and is started, since electron transmission efficiency is very low, later
Quite a long time in do not cause people to the interest of microbial cell exoelectron transfer study, until 60 years
It is just mentioned and reports again for microorganisms ability.In the 1980s, researcher begins trying to add someization
Class conduction mediator is learned, on the one hand helps and raising microorganism is extracellular by electronics export, on the other hand promote microorganism and electrode
Between connection and electron transmission, promote electron transmission between microorganism and electrode by adding electron medium, by 2000
Left and right electron transmission ability obtains considerable degree of raising, and energy output is from reporting less than 0.01mWm-2It is increased to
100mW·m-2More than.At the same time, it is also suggested simultaneously about a kind of mode of electron mechanism-mediator auxiliary electron transmitting
Constantly approve and perfect.Mediator adds adjoint problem then and be the chemical characteristic of mediator itself, and there is stability deficiencies and certain
The disadvantages of toxicity, and the increase to development cost, these limit decisions hair of additional amboceptor microbial fuel cell (MFC)
Exhibition limitation.
It is not especially low electricity production that 1999, which can equally be run and be obtained by MFC of the discovery such as Kim without mediator first,
Ability.Thus start, the development of MFC is increasingly turned to the research and development to specific function microorganism, finds efficient electronics and passes
It passs bacterium and is increasingly becoming Developing mainstream.Rabaey etc. has found not adding in the MFC system of mediator in its research, pyo
(pyocyanin) play the role of mediator and help microorganism transmitting electronics.And this substance is then by a kind of Pseudomonas
What aeruginosa was generated, secretion can not only help the electron transmission between oneself cell of the bacterium, can also be micro- by other
It is utilized between biology and improves electron transmission ability.In fact, Pseudomonas aeruginosa is with cell exoelectron
The function bacterium of the ability of transmitting, but the ability of MFC operation electricity production is but very low.Then has the function of direct electron transfer function
Bacterium finds and develops successively, and it is some of there is very high electron transmission ability, including Shiva Pseudomonas (Shewanella),
Native Bacillus (Geobacter), fusobacterium (Clostridium), pseudomonas (pseudomonas), desulfovibrio class
(Desulfovibrio) etc..In the research to these bacterium, the electron transmission research of the direct contact-type of microorganism is then proposed
Mechanism, including Geobacter and Shewanella oneidensis MR-1 be representative nm-class conducting wire electron transmission model and
Cell membrane direct electron transfer mechanism based on cromoci.For cell membrane direct electron transfer mechanism research
Through very deep, at present using Shewanella and Geobacter as type strain, more clearly explain including cell color
Multiple functions structure including element is in the cell to the effect in extracellular electron transfer process.Electronics be can see from cell
It is interior by the way that there are four types of epicyte transferring structures, other than the cytochromes linked with cytoplasm, there are also β relevant to film to be tied
Structure albumen, this albumen can directly with cell outer contacting and realize electron transmission, Geobacter belongs to this kind.It ties herein
It is general on structure that there are also other functional proteins (such as ferritin, iron-sulfur protein) or extracellular cytochromes structure mutually to assist realizing
The direct transmitting of electronics.
Therefore, a kind of simple and quick Starting mode is researched and developed, bio-electrochemical reactor not only can be effectively accelerated
Start-up course, and the raising of later period bio-electrochemical reactor oxygen scavenging ability is had practical significance.
Summary of the invention
In order to solve the problems, such as the quick start of current bioelectrochemistry deaerating plant, the present invention provides one kind to be used for oil field
The quick start method of the bioelectrochemistry technique of waste water deoxygenation, can effectively be enriched to bioelectrochemistry in a short time
The functional microorganism of reactor anode, the start-up course of accelerating reactor.
A kind of quick start method of the bioelectrochemistry technique for oil field waste deoxygenation, includes the following steps:
(1) oil field influent waste water solution is deployed, the oil field waste is by oil field ground sewage and biochemical wastewater treatment bottom of pond
Sludge is (10-100) according to weight ratio: 1 proportions form, and the oil field waste is additionally added consisting of and is deployed into water
Solution:
Acetate concentration is 0.8-1.5g/L, and the concentration of vitamin liquid is 0.8-1.2ml/L, and the concentration of liquid microelement is
0.8-1.8ml/L uses the pH of 45-65mM phosphate buffer solution adjustment water inlet solution for 7.0；
(2) connection and voltage setting
Power supply is connect with two anodes and a cathode respectively, and controls the voltage stabilization between positive electrode and negative electrode and exists
0.9-1.1V；
(3) service condition is controlled
By the 0th day as run starting point, water inlet dissolved oxygen control between 1.5-3.2mg/L, the 1-3 days daily into
Water dissolved oxygen controls between 3.8-5.3mg/L, and water inlet dissolved oxygen control daily is between 5.5-7.5mg/L within the 4-5 days；
The control of water conservancy residence time: started control at 2-3 days, then since the 5th day in the 0th day to 4 day residence time
The control residence time is 6-8h.
Further, the main component concentration of the vitamin liquid are as follows: the biotin of 0.15-0.35g/L, 0.15-
The folic acid of 0.35g/L, the vitamin B6 of 1-1.3g/L, the riboflavin of 0.45-0.65g/L, the vitamin B1 of 0.45-0.65g/L,
The niacin of 0.45-0.65g/L, the pantothenic acid of 0.45-0.65g/L, the P- amino of the B-12 of 0.01-0.04g/L, 0.45-0.65g/L
Benzoic acid, the lipoic acid of 0.45-0.65g/L.
Further, the main component concentration of liquid microelement are as follows: MgSO42.5-4g/L, MnSO4·H2O0.45-
0.65g/L, NaCl 0.8-1.5g/L, FeSO4·7H2O 0.1-0.3g/L, CaCl2·2H2O0.1-0.3g/L, CoCl2·
6H2O 0.1-0.3g/L, ZnCl20.1-0.3g/L, CuSO4·5H2O0.01-0.028g/L, AlK (SO4)2·12H2O
0.01-0.03g/L, H3BO30.01-0.03g/L, Na2MoO40.02-0.038g/L, NiCl2·6H2O 0.02-0.035g/
L, Na2WO4·2H2O0.02-0.035g/L。
Further, phosphate buffer solution composition is as follows: the disodium hydrogen phosphate dodecahydrate of 11-12.5g/L, 2.5-
The sodium dihydrogen phosphate dihydrate of 3.0g/L, the ammonium chloride of 0.3-0.55g/L, the potassium chloride of 0.1-0.3g/L.
Further, the effective volume of used reactor is 1.8L, ratio of height to diameter 15:1.
Further, temperature is 30 DEG C during operation.
The present invention is inoculated with source, connection, service condition etc. is comprehensive to be adjusted by the culture medium ratio in control starting period
Match, the efficient electricity-producing microorganism of effective fast enriching may be implemented, the quick start of bio-electrochemical reactor may be implemented.
Control condition adjustment starting substrate is the most suitably used substrate of common advantage anode microorganism, while being improved using activated sludge
The bio-diversity of inoculum, control connection are formed to the screening of the high pressure of functional microorganism, and the control of service condition is then very
Good has cooperated demand of the aerobic-anaerobic microbe in objective function microorganism to oxygen, while balancing cathode to the need of oxygen
It asks.
Main substrate uses acetate, while using the pH value of the phosphate buffer solution of 50mM concentration control water inlet, adding
The microorganism added and microelement guarantee that the growth of microorganism synthesizes demand.The mixed solution that inoculation source uses includes that sewage is raw
Change processing pool bottom sludge and the diversity of inoculum can be improved in oil field ground sewage, biochemical wastewater treatment pool bottom sludge, and it is micro-
The water outlet of biological electrolytic cell then ensure that the presence of a large amount of anode function flora in inoculation source.Two are used on connection
A anode corresponds to single cathode, while voltage is higher than working voltage, reaches 1.0V or more, improves the choosing for functional microorganism
Select pressure.Service condition control process uses the strategy stepped up, and the lower 2mg/L dissolved oxygen concentration of beginning can guarantee
Demand of the cathode to electron acceptor, anode at this time are substantially at anaerobic condition, are conducive to the growth of anaerobe and facultative
The culture of microorganism, with the enrichment of anode microorganism, cathode improves the demand of electron acceptor, therefore properly increases at this time
DO concentration, the demand of further satisfaction cathode, and DO concentration at this time has been increased to 4mg/L, not only meets the need of cathode
It asks, while carrying out the environment of micro- oxygen in anode strap, be conducive to the growth of aerobic-anaerobic microbe, at the 4th, 5 day, electric current started to occur bright
Water inlet dissolved oxygen concentration can be increased to 5.5mg/L at this time by aobvious raising, and the electron acceptor for capableing of further satisfaction cathode needs
It asks.
The present invention can be enriched to the functional microorganism of bio-electrochemical reactor anode, accelerating reactor in a short time
Start-up course, remove dissolved oxygen, reduce oxygen corrosion, improve water quality.
Detailed description of the invention
Fig. 1 is connection schematic diagram of the present invention.
Fig. 2 is the curent change figure during the present invention starts.
Fig. 3 is the potential change figure during the present invention starts.
Fig. 4 is that starting period water-in and water-out COD changes schematic diagram.
Fig. 5 is that the dissolved oxygen in starting period changes schematic diagram.
Fig. 6 is the dissolved oxygen removal rate schematic diagram in starting period.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawings and examples, but implementation of the invention is not limited only to this.
Embodiment 1
(1) reactor effective volume 1.8L, ratio of height to diameter 15:1.
(2) water inlet formula is as follows:
Acetate concentration 1.0g/L；The vitamin liquid of 1ml/L and the liquid microelement of 1ml/L, 50mM phosphate buffer solution
(pH 7.0): phosphate buffer solution main component concentration: 11.55g/L disodium hydrogen phosphate dodecahydrate, 2.77g/L bis- are hydrated phosphorus
Acid dihydride sodium, 0.31g/L ammonium chloride, 0.13g/L potassium chloride；Vitamin liquid main component concentration: biotin, 0.2g/L, leaf
Acid, 0.2g/L, vitamin B6,1g/L, riboflavin, 0.5g/L, vitamin B1,0.5g/L, niacin, 0.5g/L, pantothenic acid, 0.5g/
L, B-12,0.01g/L, P- aminobenzoic acid, 0.5g/L, lipoic acid, 0.5g/L.
Liquid microelement main component concentration are as follows: MgSO43g/L, MnSO4·H2O 0.5g/L, NaCl 1g/L,
FeSO4·7H2O 0.1g/L, CaCl2·2H2O 0.1g/L, CoCl2·6H2O 0.1g/L, ZnCl2
0.13g/L, CuSO4·5H2O 0.01g/L, AlK (SO4)2·12H2O 0.01g/L, H3BO30.01g/L,
Na2MoO40.025g/L, NiCl2·6H2O 0.024g/L, Na2WO4·2H2O 0.025g/L。
(3) connection and voltage setting
Connection as shown in Figure 1, control cathode 1 and anode 2, anode 3 between voltage stabilization in 1.0V.
(4) service condition controls
DO control: in 2mg/L, the 1st, 2,3 day water inlet dissolved oxygen controls 4mg/L for the dissolved oxygen control that starts for the 0th day to intake, the
4,5 days control dissolved oxygens are 5.5mg/L.
Hydraulic detention time control: started control at 2 days in the 0th day to 4 day residence time, then controlled since the 5th day
Residence time 6h processed.
Wherein, hydraulic detention time refers to mean residence time of the treatment sewage in reactor, that is, sewage and life
The average reaction time of microbial action in object reactor, hydraulic detention time are equal to the ratio between reactor volume and flow of inlet water.
Temperature control: 30 degrees Celsius of temperature during control starting.
PH control: pH=7 during control starting.
Embodiment 2
(1) reactor effective volume 1.8L, ratio of height to diameter 15:1.
(2) water inlet formula is as follows:
Acetate concentration 1.2g/L；The vitamin liquid of 1ml/L and the liquid microelement of 1.5ml/L, 60mM phosphoric acid buffer are molten
Liquid (pH 7.0): phosphate buffer solution main component concentration: 12.3g/L disodium hydrogen phosphate dodecahydrate, 2.95g/L bis- are hydrated phosphorus
Acid dihydride sodium, 0.5g/L ammonium chloride, 0.25g/L potassium chloride；Vitamin liquid main component concentrations of vitamin H, 0.3g/L, folic acid,
0.3g/L, vitamin B6,1.2g/L, riboflavin, 0.6g/L, vitamin B1,0.6g/L, niacin, 0.6g/L, pantothenic acid, 0.6g/L,
B-12,0.03g/L, P- aminobenzoic acid, 0.6g/L, lipoic acid, 0.6g/L.
The main component concentration of liquid microelement includes MgSO43.5g/L, MnSO4·H2O 0.6g/L, NaCl
1.2g/L, FeSO4·7H2O 0.2g/L, CaCl2·2H2O 0.2g/L, CoCl2·6H2O 0.2g/L, ZnCl2
0.25g/L, CuSO4·5H2O 0.02g/L, AlK (SO4)2·12H2O 0.02g/L, H3BO30.02g/L, Na2MoO4
0.035g/L, NiCl2·6H2O 0.03g/L, Na2WO4·2H2O0.032g/L。
(3) connection and voltage setting
Connection as shown in Figure 1, control cathode 1 and anode 2, anode 3 between voltage stabilization in 1.1V.
(4) service condition controls
DO control: in 3mg/L, the 1st, 2,3 day water inlet dissolved oxygen controls 5mg/L for the dissolved oxygen control that starts for the 0th day to intake, the
4,5 days control dissolved oxygens are 7mg/L.
The control of water conservancy residence time: started control at 3 days in the 0th day to 4 day residence time, then controlled since the 5th day
Residence time 7h processed.
Temperature control: 30 degrees Celsius of temperature during control starting.
PH control: pH=7 during control starting.
Embodiment 3
For the starting measure of merit of embodiment 2:
(1) then steady as shown in Fig. 2, electric current has fluctuation when just starting water inlet, second day water inlet dissolved oxygen from
Electric current fluctuates when 2mg/L is increased to 4mg/L, then steady, and stablizes and improve, and raising is more slow, opens from second day
Begin to improve rapidly, at the 6th day, reaches maximum, 6.4mA then begins to tend to be steady, and after the 5th day, electric current is maintained essentially in
The level of 6mA.
(2) from the figure 3, it may be seen that two anode potentials the phase declines rapidly on startup, the phase declines respectively from 0mV on startup
For -0.5mV (vs Ag/AgCl).
(3) as can be seen from FIG. 4, after starting is stablized, the COD concentration of water inlet is discharged in 1000mg/L in 600mg/L or so,
Removal rate is 40%.After tested, anode coulombic efficiency is 4% after stable operation.
(4) start the domestication stage referring to Fig. 5-6, anode potential persistently maintains <-400mV, hydraulic detention time 6h, realizes
Dissolved oxygen removal 80%, underlying metallic cathode can remove 50% dissolved oxygen by reduction reaction first, and subsequent anode passes through micro-
Biology breathing can further consume dissolved oxygen.
The preferred embodiment of the present invention has been described in detail above, but the invention be not limited to it is described
Embodiment, those skilled in the art can also make various equivalent on the premise of not violating the inventive spirit of the present invention
Variation or replacement, these equivalent variation or replacement are all included in the scope defined by the claims of the present application.
Claims (6)
1. a kind of quick start method of the bioelectrochemistry technique for oil field waste deoxygenation, which is characterized in that including as follows
Step:
(1) oil field influent waste water solution is deployed, the oil field waste is by oil field ground sewage and biochemical wastewater treatment pool bottom sludge
According to weight ratio be (10-100): 1 proportions form, the oil field waste be additionally added consisting of be deployed into it is molten into water
Liquid:
Acetate concentration is 0.8-1.5g/L, and the concentration of vitamin liquid is 0.8-1.2ml/L, and the concentration of liquid microelement is 0.8-
1.8ml/L uses the pH of 45-65mM phosphate buffer solution adjustment water inlet solution for 7.0.
(2) connection and voltage setting
Power supply is connect with two anodes and a cathode respectively, and controls the voltage stabilization between positive electrode and negative electrode in 0.9-
1.1V。
(3) service condition is controlled
By the 0th day as starting point is run, water inlet dissolved oxygen control is intake molten for the 1-3 days daily between 1.5-3.2mg/L
Oxygen control is solved between 3.8-5.3mg/L, water inlet dissolved oxygen control daily is between 5.5-7.5mg/L within the 4-5 days；
The control of water conservancy residence time: started control at 2-3 days in the 0th day to 4 day residence time, then controlled since the 5th day
Residence time is 6-8h.
2. quick start method according to claim 1, which is characterized in that the main component concentration of the vitamin liquid
Are as follows: the biotin of 0.15-0.35g/L, the folic acid of 0.15-0.35g/L, the vitamin B6 of 1-1.3g/L, 0.45-0.65g/L's
Riboflavin, the vitamin B1 of 0.45-0.65g/L, the niacin of 0.45-0.65g/L, the pantothenic acid of 0.45-0.65g/L, 0.01-
The P- aminobenzoic acid of the B-12 of 0.04g/L, 0.45-0.65g/L, the lipoic acid of 0.45-0.65g/L.
3. quick start method according to claim 1, which is characterized in that the main component concentration of liquid microelement are as follows:
MgSO42.5-4g/L, MnSO4·H2O 0.45-0.65g/L, NaCl 0.8-1.5g/L, FeSO4·7H2O 0.1-0.3g/L,
CaCl2·2H2O 0.1-0.3g/L, CoCl2·6H2O 0.1-0.3g/L, ZnCl20.1-0.3g/L, CuSO4·5H2O
0.01-0.028g/L, AlK (SO4)2·12H2O 0.01-0.03g/L, H3BO30.01-0.03g/L, Na2MoO4 0.02-
0.038g/L, NiCl2·6H2O 0.02-0.035g/L, Na2WO4·2H2O 0.02-0.035g/L。
4. quick start method according to claim 1 to 3, which is characterized in that phosphate buffer solution composition is as follows: 11-
The disodium hydrogen phosphate dodecahydrate of 12.5g/L, the sodium dihydrogen phosphate dihydrate of 2.5-3.0g/L, the ammonium chloride of 0.3-0.55g/L,
The potassium chloride of 0.1-0.3g/L.
5. quick start method according to claim 1, which is characterized in that the effective volume of used reactor is
1.8L, ratio of height to diameter 15:1.
6. quick start method according to claim 1, which is characterized in that temperature is 30 DEG C during operation.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2292974Y (en) * | 1997-02-04 | 1998-09-30 | 冶金工业部钢铁研究总院 | Boiler water deaerating device |
| CN103613206A (en) * | 2013-12-04 | 2014-03-05 | 江南大学 | Microorganism electrochemical denitrification method for enhancing bio-hydrogen production |
| CN103956510A (en) * | 2014-04-21 | 2014-07-30 | 华南理工大学 | Microbial fuel cell with double chambers for simultaneous phosphorus and nitrogen removal |
| JP6327718B2 (en) * | 2016-01-07 | 2018-05-23 | 国立研究開発法人農業・食品産業技術総合研究機構 | Microbial electrolysis cell |
-
2018
- 2018-10-16 CN CN201811202428.9A patent/CN109160596B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2292974Y (en) * | 1997-02-04 | 1998-09-30 | 冶金工业部钢铁研究总院 | Boiler water deaerating device |
| CN103613206A (en) * | 2013-12-04 | 2014-03-05 | 江南大学 | Microorganism electrochemical denitrification method for enhancing bio-hydrogen production |
| CN103956510A (en) * | 2014-04-21 | 2014-07-30 | 华南理工大学 | Microbial fuel cell with double chambers for simultaneous phosphorus and nitrogen removal |
| JP6327718B2 (en) * | 2016-01-07 | 2018-05-23 | 国立研究開発法人農業・食品産業技術総合研究機構 | Microbial electrolysis cell |
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