CN106830267A - A kind of method for mitigating nano zero valence iron passivation - Google Patents
A kind of method for mitigating nano zero valence iron passivation Download PDFInfo
- Publication number
- CN106830267A CN106830267A CN201710027801.0A CN201710027801A CN106830267A CN 106830267 A CN106830267 A CN 106830267A CN 201710027801 A CN201710027801 A CN 201710027801A CN 106830267 A CN106830267 A CN 106830267A
- Authority
- CN
- China
- Prior art keywords
- iron
- pathogenic microorganism
- nano zero
- zero valence
- microorganism
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C02F1/705—Reduction by metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
-
- 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
- C02F2101/36—Organic compounds containing halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
Abstract
The present invention relates to field of material technology, the invention discloses a kind of method for mitigating nano zero valence iron passivation, it comprises the following steps：By at least one iron also pathogenic microorganism, suitable culture medium is selected to be cultivated, the stationary phase for reaching microorganism terminates culture；In the reaction system of Zero-valent Iron reduction organic pollution, when the reducing activity of nano zero valence iron be it is initial≤50% when, at least one iron also pathogenic microorganism of screening in addition step (1).Compared with the method for existing mitigation Zero-valent Iron passivation, the present invention is environment-friendly, uses the iron also pathogenic microorganism of generally existing in environment, simple to operate；Additionally, present invention power consumption is low, it is not necessary to external energy, and the mitigation of nano zero valence iron passivation is realized simultaneously and promotes the degraded of pollutant.
Description
Technical field
It is to be related to a kind of method for mitigating nano zero valence iron passivation more specifically the present invention relates to field of material technology.
Background technology
Nano zero valence iron has the features such as size is small, and surface-active is high, therefore is widely used in contaminant degradation and ring
The numerous areas such as border reparation.Nano zero valence iron is used to removing the range of application of pollutant mainly to be included, heavy metals removal, such as chromium
Cr, cadmium Cd, mercury Hg, nickel etc.；Organic pollutant degradation, such as organic chloro thing, including carbon tetrachloride, trichloro ethylene, many chlorine
Biphenyl etc.；And the removal of the nutriment in water body, such as nitrate, phosphate etc..
But, nano zero valence iron generally existing in application process problem of passivation.Wherein common passivation phenomenon is exactly
Nano zero valence iron its surface after reacting can generate the oxide or hydroxide of inert iron, and be covered in nano zero-valence
The surface of iron, causes its activity to reduce or even lose activity.The passivation layer that nano zero valence iron is formed in water is mainly the hydrogen of iron
Oxide, such as ferrihydrite.The solution of problem of passivation depends primarily on going for the hydroxide passivating layer of the iron for being covered in outside
Remove, nano zero valence iron is recovered reducing activity.
Prior art is favourable to eliminate the ironing surface passivation layer of zeroth order with electrochemical process or the method for externally-applied magnetic field, all deposits
In problems and defect：(1) high energy consumption；(2) complex operation is, it is necessary to install special equipment；(3) it is relatively difficult to achieve extensive
Use.
In order to solve the above technical problems, the present invention comes therefrom.
The content of the invention
Shortcoming it is an object of the invention to be directed to the existing elimination ironing surface passivation layer of zeroth order, there is provided one kind mitigates nanometer
The method of Zero-valent Iron passivation.
In order to solve these problems in currently available technology, the technical scheme that first aspect present invention is provided is that one kind subtracts
The method of light nano zero valence iron passivation, it comprises the following steps：
(1) screening and culture of iron also pathogenic microorganism
By at least one iron also pathogenic microorganism, select suitable culture medium to be cultivated, reach the stationary phase knot of microorganism
Beam culture；
(2) addition iron also pathogenic microorganism is used to mitigate Zero-valent Iron passivation
In the reaction system of Zero-valent Iron reduction organic pollution, when the reducing activity of nano zero valence iron be it is initial≤
When 50%, at least one iron also pathogenic microorganism of screening in addition step (1).
Preferably, iron reduction microbe has tolerance in the step (1).
Preferably, the iron also pathogenic microorganism includes but is not limited to：Oneida lake Shewanella Shewanella
Oneidensis, Shewanella putrefaciens Shewanella putrefaciens and metal reduction ground bacillus Geobactor
Metallireducens etc..
Preferably, at least one iron also pathogenic microorganism for being screened in addition step (1) in the step (2), and periodically supervise
The biological amount of micrometer, makes the concentration of iron also pathogenic microorganism maintain OD values 1.0~1.2.
If microorganism concn reduction is, it is necessary to add in good time.Or can also be by Zero-valent Iron and iron also pathogenic microorganism simultaneously
It is added in reaction system, the addition of Zero-valent Iron determines that the total concentration of iron also pathogenic microorganism is maintained according to the amount of pollutant
Optimum range (OD values are approximately 1.0~1.2).
In the present invention, a kind of metal reducing miroorganisms that iron-reducing bacterium is can be obtained with the hydroxide of reducing iron oxides/iron
The iron-bearing mineral of ferrous iron and secondary, such as blue ocher (Fe3(PO4)2), ferrous sulfide (FeS) etc., these secondary iron minerals
Can further deoxidization, degradation pollutant, such as some chlorinatedorganics.Therefore, nano zero valence iron and iron reduction microbes
Close, it would be possible to mitigate the passivation of nano zero valence iron, still further aspect, micro-reduction ferriferous oxide/iron hydroxide
The secondary iron mineral of generation can also further realize the degraded of pollutant.In addition nano zero valence iron is mitigated using microbial method
Passivation also have it is environment-friendly, it is not necessary to many advantages, such as external energy.
In the present invention, iron also pathogenic microorganism can be cultivated manually, it is also possible to using naturally occurring microorganism in environment.Sieve
Choosing has the iron also pathogenic microorganism of tolerance to pollutant, selects suitable culture medium to be cultivated, and reaches the steady of microorganism
Periodically terminate culture.
Compared with the method for existing mitigation Zero-valent Iron passivation, the invention has the advantages that：
(1) it is environment-friendly, the iron also pathogenic microorganism of generally existing in environment is used, it is simple to operate；
(2) consume energy low, it is not necessary to external energy, such as power supply, magnetic field etc.；
(3) while realizing the mitigation of nano zero valence iron passivation and promoting the degraded of pollutant；
(4) microorganism can continuous flourish so that the effect for maintaining lasting mitigation Zero-valent Iron to be passivated, is conducive to whole
The operation steady in a long-term of reaction system.
Brief description of the drawings
Fig. 1 is the reduction dechlorination that nano zero valence iron is used for carbon tetrachloride.
Fig. 2 is ESEM (SEM) phenogram.Fig. 2 (a) is the SEM phenograms before nano zero valence iron dechlorination reaction, Fig. 2
B () is the SEM phenograms after nano zero valence iron dechlorination reaction.
Fig. 3 is X-ray diffraction (XRD) phenogram.Fig. 3 (a) is the XRD before nano zero valence iron reaction, and Fig. 3 (b) is to receive
XRD phenograms after rice Zero-valent Iron reaction response.
Fig. 4 is the dealuminated USY cataluyst that iron reduction micro-reduction ferrihydrite is used for carbon tetrachloride.
Specific embodiment
Such scheme is described further below in conjunction with specific embodiment.It should be understood that these embodiments are for illustrating
The present invention and be not limited to limit the scope of the present invention.The implementation condition used in embodiment can be done according to the condition of specific producer
Further adjustment, unreceipted implementation condition is usually the condition in normal experiment.
Introduce and summarize
The present invention by way of example rather than provides the mode of limitation and illustrates.It should be noted that in present disclosure
Described " one " or " one kind " implementation method is not necessarily referring to same specific embodiment, and refers at least a kind of.
Various aspects of the invention are described below.However, as will be readily apparent to one of skill in the art, can
Only some or all of aspects of the invention implement the present invention.For purposes of illustration, be given herein specific numbering, material and
Configuration, enables one to thoroughly understand the present invention.However, be evident that for those of skill in the art,
The present invention can be implemented without concrete details.In other examples, not make, the present invention is obscure to be omitted or simplified many institutes
Known feature.
Various operations are described successively as multiple discrete steps, and with most helpful in understanding side of the invention
Formula is illustrated；However, in-order description should not be construed as to imply that into these operations are necessarily dependent on order.
Various implementation methods will be illustrated according to the reactant of type species.To show for those of skill in the art and
It is clear to, the present invention can be used any number of different types of reactant to implement, and is more than those for the purpose of illustration
And the reactant for being given herein.Additionally, be also evident that, the invention is not limited in any specific mixing is shown
Example.
A kind of method for mitigating nano zero valence iron passivation of embodiment
Step one, the preparation of nano zero valence iron and the reduction dechlorination for chlorinatedorganic
Using trivalent iron salt and boron hydride, nano zero valence iron is prepared by chemical precipitation method, and the product that will be obtained is done
Preserved after dry.50mg nano zero valence irons are added toward the anaerobism bottle equipped with 100mL carbon tetrachloride (35 μM) solution, is placed into and is shaken
In bed, at 30 DEG C, dechlorination reaction is carried out under the conditions of 180rpm, be sampled in particular point in time, and with gas chromatograph to four
Chlorination carbon is detected；Treat that carbon tetrachloride degraded is complete, the drop that 35 μM of carbon tetrachloride proceed next cycle is added again
Solution reaction, continuously runs four cycles (see Fig. 1).Fig. 1 shows, by the dechlorination reaction in several cycles, nano zero valence iron it is anti-
Active should substantially reduce, the speed constant of reduction dechlorination is by 0.6h-1It is reduced to 0.3h-1。
Step 2, iron reduction microbe to screen and culture
The iron that the present embodiment is used also pathogenic microorganism is the Shewanella putrefaciens CN32 (Wu of artificial culture
Chao,Yuan-Yuan Cheng,Hao Yin,et al.Oxygen promotes biofilm formation of
Shewanella putrefaciens CN32through a diguanylate cyclase and an adhesion[J]
Scientific Reports 2013,3:1945).By Shewanella inoculations to LB culture mediums (yeast extract 5g/
L, peptone 10g/L NaCl 10g/L) in be positioned in shaking table and cultivated, condition of culture is aerobic, 30 DEG C, 180rpm.
The later stage in growth period of strain collects bacterium solution, using refrigerated centrifuge, at 4 DEG C, under conditions of 5000rpm, 6min is centrifuged, and outwells
Clear liquid, collects thalline.And the Shewanella bacterium concentrates of purifying are finally obtained to twice of thalline eccentric cleaning with buffer salt.
Step 3, iron reduce micro-reduction ferrihydrite and for the degraded of chlorinatedorganic.
The iron that will be collected in step 2 also pathogenic microorganism carries out ferrihydrite in being added to the system of the ferrihydrite containing 50mM
Reduction reaction, control microorganism initial concentration be OD=1.0.After question response is complete, the carbon tetrachloride of 35 μM of addition, 30
DEG C, dechlorination reaction is carried out under the conditions of 180rpm in shaking table, and determine the content of carbon tetrachloride.
The present embodiment has investigated the ferrihydrite reduction situation under various reaction conditions, and experimental group is：(1) 50mM ferrihydrites+
Iron also pathogenic microorganism+carbon tetrachloride；(2) 50mM ferrihydrites+iron also pathogenic microorganism+1mM phosphate+carbon tetrachloride, dechlorination effect
See Fig. 4, as a result show, under different environmental conditions, microorganism all reduces ferrihydrite, and the secondary iron mineral tool for obtaining
There is good reduction dechlorination effect.
Step 4, material is collected and sign is shown in Fig. 2 and Fig. 3.
Fig. 2 is ESEM (SEM) phenogram.Fig. 2 (a) is the SEM phenograms before nano zero valence iron dechlorination reaction, Fig. 2
B () is reacted SEM phenograms.Characterization result shows that nano zero valence iron is formd big through dechlorination reaction after a while
Amount iron mineral is covered in the surface of Zero-valent Iron.
Fig. 3 is X-ray diffraction (XRD) phenogram.Fig. 3 (a) is the XRD before nano zero valence iron reaction, and Fig. 3 (b) is anti-
XRD phenograms after answering.Characterization result shows that nano zero valence iron forms various iron ores through dechlorination reaction after a while
Thing, mainly ferrihydrite.
The above specific embodiment is only the preferred embodiment of the present invention, it is noted that for the art
For those of ordinary skill, under the premise without departing from the principles of the invention, some improvement or replacement can also be made, these improvement
Or replacement should also be as being considered as protection scope of the present invention.
Claims (4)
1. a kind of to mitigate the method that nano zero valence iron is passivated, it comprises the following steps：
(1) screening and culture of iron also pathogenic microorganism
By at least one iron also pathogenic microorganism, suitable culture medium is selected to be cultivated, the stationary phase for reaching microorganism terminates training
Support；
(2) addition iron also pathogenic microorganism is used to mitigate Zero-valent Iron passivation
In the reaction system of Zero-valent Iron reduction organic pollution, when the reducing activity of nano zero valence iron be it is initial≤50%
When, at least one iron also pathogenic microorganism of screening in addition step (1).
2. method according to claim 1, it is characterised in that iron reduction microbe tool in the step (1)
There is tolerance.
3. method according to claim 1, it is characterised in that the iron also pathogenic microorganism is selected from Shewanella
Oneidensis, Shewanella putrefaciens and Geobactor metallireducens.
4. method according to claim 1, it is characterised in that screening is at least in addition step (1) in the step (2)
A kind of iron also pathogenic microorganism, and periodic monitoring microorganism amount, the concentration of iron also pathogenic microorganism is maintained OD values 1.0~1.2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710027801.0A CN106830267A (en) | 2017-01-16 | 2017-01-16 | A kind of method for mitigating nano zero valence iron passivation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710027801.0A CN106830267A (en) | 2017-01-16 | 2017-01-16 | A kind of method for mitigating nano zero valence iron passivation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106830267A true CN106830267A (en) | 2017-06-13 |
Family
ID=59124729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710027801.0A Pending CN106830267A (en) | 2017-01-16 | 2017-01-16 | A kind of method for mitigating nano zero valence iron passivation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106830267A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108821446A (en) * | 2018-06-26 | 2018-11-16 | 绍兴文理学院 | A kind of preparation method of permeable coefficient tensor that alleviating Zero-valent Iron passivation |
| CN111115841A (en) * | 2019-12-17 | 2020-05-08 | 上海大学 | Method for reinforcing coupling and passivating nano zero-valent iron system by iron reducing bacteria |
| CN111410305A (en) * | 2020-04-07 | 2020-07-14 | 佛山科学技术学院 | Chromium-polluted water body remediation method and application |
| CN111777186A (en) * | 2020-07-10 | 2020-10-16 | 北京伦至环境科技有限公司 | Anti-blocking zero-valent iron coupling response type slow-release persulfate two-stage permeable reaction wall device and application |
| CN114195247A (en) * | 2020-08-28 | 2022-03-18 | 中南民族大学 | Method for efficiently removing Cr (VI) in water body by using nano zero-valent iron under mediation of dissimilatory iron reducing bacteria |
| CN114195247B (en) * | 2020-08-28 | 2024-05-31 | 中南民族大学 | Method for removing Cr (VI) in water body by using nano zero-valent iron mediated by iron dissimilatory reduction bacteria |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006314903A (en) * | 2005-05-11 | 2006-11-24 | National Institute Of Advanced Industrial & Technology | Method and apparatus for treating ammonia anaerobically |
| CN105417728A (en) * | 2015-12-22 | 2016-03-23 | 广东省微生物研究所 | Method of treating azo dye wastewater with activation on sponge iron system through composite microbiota |
-
2017
- 2017-01-16 CN CN201710027801.0A patent/CN106830267A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006314903A (en) * | 2005-05-11 | 2006-11-24 | National Institute Of Advanced Industrial & Technology | Method and apparatus for treating ammonia anaerobically |
| CN105417728A (en) * | 2015-12-22 | 2016-03-23 | 广东省微生物研究所 | Method of treating azo dye wastewater with activation on sponge iron system through composite microbiota |
Non-Patent Citations (1)
| Title |
|---|
| 林海龙等: "《厌氧环境微生物学》", 31 October 2014, 哈尔滨：哈尔滨工业大学出版社 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108821446A (en) * | 2018-06-26 | 2018-11-16 | 绍兴文理学院 | A kind of preparation method of permeable coefficient tensor that alleviating Zero-valent Iron passivation |
| CN108821446B (en) * | 2018-06-26 | 2021-03-05 | 绍兴文理学院 | Preparation method of permeable reaction wall for relieving zero-valent iron passivation |
| CN111115841A (en) * | 2019-12-17 | 2020-05-08 | 上海大学 | Method for reinforcing coupling and passivating nano zero-valent iron system by iron reducing bacteria |
| CN111115841B (en) * | 2019-12-17 | 2021-07-30 | 上海大学 | Method for reinforcing coupling and passivating nano zero-valent iron system by iron reducing bacteria |
| CN111410305A (en) * | 2020-04-07 | 2020-07-14 | 佛山科学技术学院 | Chromium-polluted water body remediation method and application |
| CN111777186A (en) * | 2020-07-10 | 2020-10-16 | 北京伦至环境科技有限公司 | Anti-blocking zero-valent iron coupling response type slow-release persulfate two-stage permeable reaction wall device and application |
| CN114195247A (en) * | 2020-08-28 | 2022-03-18 | 中南民族大学 | Method for efficiently removing Cr (VI) in water body by using nano zero-valent iron under mediation of dissimilatory iron reducing bacteria |
| CN114195247B (en) * | 2020-08-28 | 2024-05-31 | 中南民族大学 | Method for removing Cr (VI) in water body by using nano zero-valent iron mediated by iron dissimilatory reduction bacteria |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kumar et al. | A review on accessible techniques for removal of hexavalent Chromium and divalent Nickel from industrial wastewater: Recent research and future outlook | |
| Akhtar et al. | Remediation of heavy metals (Cr, Zn) using physical, chemical and biological methods: a novel approach | |
| Dhal et al. | Reduction of hexavalent chromium by Bacillus sp. isolated from chromite mine soils and characterization of reduced product | |
| CN106830267A (en) | A kind of method for mitigating nano zero valence iron passivation | |
| CN110340132A (en) | A kind of method that charcoal base Zero-valent Iron cooperates with reparation chromium-polluted soil with microorganism | |
| CN106277283B (en) | Strengthen the method for removing arsenic antimony ion in water removal using iron and manganese oxides biological in filter tank | |
| CN112342029B (en) | Biological heavy metal contaminated soil remediation agent and preparation method and application thereof | |
| Greene et al. | Microbial formation of manganese oxides | |
| CN109604329A (en) | A kind of chromium-polluted soil renovation agent and its restorative procedure | |
| CN109351767A (en) | A kind of method of superfine iron powder collaboration microorganism remediation chromium-polluted soil | |
| CN109290366A (en) | A kind of method of bioleaching-Biostatic Combined Treatment heavy-metal contaminated soil | |
| CN113368811B (en) | Biological type iron-manganese composite material, preparation method and application | |
| Li et al. | Soil indigenous microorganisms alleviate soluble vanadium release from industrial dusts | |
| Gao et al. | Accelerated reduction of nitrate by driving the manganese (Mn) cycle process with dissimilatory Mn reducing bacteria: Differential reduction pathways and cycling mechanisms | |
| Liu et al. | Pyrite and sulfur-coupled autotrophic denitrification system for efficient nitrate and phosphate removal | |
| Mao et al. | Removal of manganese in acidic solutions utilizing Achromobacter sp. strain QBM-4 isolated from mine drainage | |
| Zhang et al. | Remediation of lead and cadmium co-contaminated mining soil by phosphate-functionalized biochar: Performance, mechanism, and microbial response | |
| CN113980830B (en) | Pseudomonas stutzeri, culture thereof and application thereof | |
| CN112250197B (en) | Method for treating copper-containing chromium-containing industrial wastewater by using bacterial detoxification | |
| Wu et al. | The key role of biogenic manganese oxides in enhanced removal of highly recalcitrant 1, 2, 4-triazole from bio-treated chemical industrial wastewater | |
| CN110484276A (en) | A kind of method and reagent of nanometer iron-based composite material coupling hexavalent chrome reduction bacterial remediation chromium-polluted soil | |
| Choi et al. | Biosorption of heavy metals by biomass of seaweeds, Laminaria species, Ecklonia stolonifera, Gelidium amansii and Undaria pinnatifida | |
| CN101397544A (en) | Manganese oxidizing bacteria bacillus strain WH4 and use thereof | |
| WO2022188834A1 (en) | Method for strengthening biogenic manganese oxidation by using magnetic field, and application thereof | |
| Kim et al. | Development of recycled aggregate bio-carrier with sulfate reducing bacteria for the elimination of heavy metals from seawater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170613 |
|
| RJ01 | Rejection of invention patent application after publication |