CN106865682A - Ferrihydrite MF/UF dual-membrane process organics removal and phosphatic method - Google Patents
Ferrihydrite MF/UF dual-membrane process organics removal and phosphatic method Download PDFInfo
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- CN106865682A CN106865682A CN201710241908.5A CN201710241908A CN106865682A CN 106865682 A CN106865682 A CN 106865682A CN 201710241908 A CN201710241908 A CN 201710241908A CN 106865682 A CN106865682 A CN 106865682A
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- ferrihydrite
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- 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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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to a kind of ferrihydrite MF/UF dual-membrane process removal Organic substance in water and phosphatic method, by two kinds of processes of adsorbent ferrihydrite particle and UF membrane be combined with it is integrated, belong to water-treatment technology field.Comprise the following steps, prepare high-specific surface area adsorbent ferrihydrite, ferrihydrite adsorbent is added under agitation in flat board membrane filtration system, it is kept suspended state, the ON-LINE SEPARATION of adsorbent ferrihydrite is realized using membrane filtration system.The group technology reaches 60%, UV to DOC clearances254Clearance reaches 80%, and removal rate of phosphate is more than 90%.There is ligand exchange reaction with the carboxyl of organic matter and phenolic group using the hydroxyl on ferrihydrite surface in ferrihydrite MF/UF dual-membrane process of the present invention, simultaneously with the monatomic or diatomic O and ferrihydrite surface bond on phosphoric acid surface, improve to organic matter and phosphatic clearance, pre- adsorption process reduces the pollutant for reaching film surface simultaneously, the formation of fouling membrane is reduced, drinking water safety has been ensured.
Description
Technical field
The present invention relates to water-treatment technology field, more particularly to during a kind of absorption-dual-membrane process goes to remove water, solubility has
Machine thing and phosphatic method.
Background technology
Bacterial preoxidation can cause pathogenic microorganism to grow in water body, and water transfer pipe network corrosion and biomembrane are in film processing system
A series of problems, such as surface enrichment, user's water quality deterioration is caused, reduce the biological stability of water supply.Bacterium is again in causing water body
Raw several principal elements include organic matter, microorganism and inorganic nutrient salt.Wherein, life of the inorganic nutrient salt phosphorus in microorganism
Played an important role in metabolic process, phosphate as bacterial cell important component (adenosine triphosphate atp, many phosphorus
Hydrochlorate), it is the key component of bacteria live.Even if under conditions of concentration of carbon is higher, the phosphate of low concentration can also be limited
The growth of biomembrane.Meanwhile, the presence of organic matter also compromises water quality, during cholorination generate haloform and
Other halogenated by-products, produce a series of organic DBPs of chloro, are detrimental to health.Therefore organic matter in water body is controlled
With the growth that inorganic nutrient salt (such as phosphate) concentration can effectively suppress microorganism, and then control biomembrane in water supply line and
The regrowth on membranous system surface, reduces the generation of DBPs.
In recent years, application of the membrane technology in water process has obtained extensive attention, and it has processing unit small volume,
Accessory substance is not produced in processing procedure, the advantages such as chemical agent dosage are reduced.Membrane separation technique includes micro-filtration (MF), ultrafiltration
(UF), counter-infiltration (RO), positive infiltration (FO), electrodialysis (ED).Two kinds of low pressure membrane technologies of wherein MF and UF are small due to operating pressure,
Low cost, can effectively remove the material such as pathogen in algae, microorganism, water body and be widely used.But due to such film
Molecular cut off is big, and the clearance for being used alone MF and UF to dissolved organic matter in water body (DOM) and inorganic nutrient salt is not high,
And this kind of material is the main cause for causing Biological Stability in Drinking Water problem, be also cause DBPs produce it is main before
Drive thing.Accordingly, it is considered to membrane technology is combined with effective pretreating process, and then improve the removal effect to dissolved matter
It is the main path for extending application of membrane.Ferrihydrite has high-specific surface area and high reaction activity, and the hydroxyl on its surface can
Ligand exchange is carried out with the carboxyl and phenolic group of DOM, compound is formed.On the other hand, the monatomic or diatomic O on phosphoric acid surface
With ferrihydrite surface bond, bidentate double-core material is formed.Based on ferrihydrite to DOM and phosphatic effective absorption, by its with it is low
Film pressing system is combined, and can effectively remove dissolubility pollutant, suppresses microorganisms reproduction potentiality, and cut using follow-up membranous system
The adsorbent ferrihydrite particle of pre-treatment is stayed, separation of solid and liquid is realized, while microorganism and part soluble pollutants are removed, to protect
Barrier drinking water water supply security provides technical support.
The content of the invention
The purpose of the present invention is directed to dissolved organic matter and phosphate substances in water, in order to overcome low pressure membranous system pair
The Organic substance in water defect poor with inorganic matter removal efficiency, there is provided a kind of efficiently feasible, based on ferrihydrite absorption-UF membrane mistake
The minimizing technology of journey synergy.Meanwhile, the adsorbent ferrihydrite particle using membrane technology effectively catching, is granule adsorbent exists
Application in water process provides new technical support.
What the present invention was used removes dissolved organic matter and phosphoric acid based on ferrihydrite absorption-membrane separating process synergy is lower
The know-why of salt is, under certain pH conditions, ferrihydrite particle, the carboxyl and phenol of organic matter is added in flat board membranous system
There is ligand exchange reaction in base, key reaction process includes with ferrihydrite surface hydroxyl：The protonation of metal surface hydroxyl, makes
It is more easy to carry out ligand exchange；Organic matter carboxyl forms outer surface compound substance with the hydroxyl reaction of protonation；Ligand exchange shape
Into Internal Spherical Surface compound.The monatomic or diatomic O on phosphoric acid surface and ferrihydrite surface bond, form double in its inner surface simultaneously
Tooth double-core material.The effect of good separation of solid and liquid can be reached due to membrane technology, is mutually tied using low pressure membranous system and ferrihydrite
Close, it is possible to achieve the ON-LINE SEPARATION of ferrihydrite particle, and pre- suction-operated can be reduced to the pollutant up to film surface, improve out
Water water quality, and then the formation of fouling membrane and the reduction of membrane flux are controlled, it is significant for ensureing drinking water quality.
A kind of ferrihydrite absorption-low pressure MF/UF dual-membrane process organics removal and phosphatic side that the present invention is provided
Method, comprises the following steps：
1) regenerated cellulose UF films, polyether sulfone UF films, mixed cellulose ester MF films is selected to be placed in the flat of dead-end filtration respectively
In plate film ultrafiltration cup；
2) will containing organic matter and phosphatic water sample add ultrafiltration cup in, adjust pH to 7；
3) by particulate form ferrihydrite addition membranous system reactor, regulation stir speed (S.S.) is 600rpm, is in ferrihydrite
Suspended state；
4) membranous system runs under constant-pressure conditions, and UF films are 60kPa, and MF films are 30kPa；
5) physics backwash is carried out to filter caudacoria, investigates membrane flux recovery rate.
In described method, entering organic matter of water concentration is 3.0mg/L in step 2, and phosphate concn is 0.5mg/L.
In described method, the concentration of ferrihydrite is 50mg/L in step 3.
Water body DOC clearances of the present invention reach 60%, UV254Clearance reaches 80%, removal rate of phosphate more than 90%,
Ferrihydrite is respectively 250mg/g and 95mg/g to the maximum adsorption capacity of organic matter and phosphorus, and phosphate concn is less than in water outlet
0.03mg/L, can effectively suppress microbial re-growth, it is to avoid the secondary pollution problem in water supply, ensure water supply quality.
Specific embodiment
With reference to embodiment, the present invention is further described, but protection scope of the present invention is not limited to that：
Fh is adsorbed in advance in continuous experiment is combined with membrane filtration system, Fh adsorbents are directly added to membrane reactor
Interior, micro-filtration is Flat Membrane with hyperfiltration membrane assembly, selects regenerated cellulose, three kinds of materials of polyether sulfone and cellulose mixture fat.Investigate
In the low-pressure membrane of different materials, aperture, hydrophilic and hydrophobic and charge property and the operational effect of the pre- adsorption combined technologies of Fh and water outlet
Target pollutant concentration, optimizes membrane material and improves film near surface hydrodynamic conditions, improves the operation of Fh- film combined systems
Efficiency.
Embodiment 1
In film reaction system, organics removal and phosphoric acid are cooperateed with regenerated cellulose UF films using adsorbent ferrihydrite
Salt.Ferrihydrite concentration 50mg/L is added, enters organic concentration 3.0mg/L in the aqueous solution, phosphate concn 0.5mg/L, in 60kPa
Constant-pressure conditions under run, the change of running membrane flux is little.DOC clearances 60%, UV254Clearance 90%, phosphate goes
Except rate 95%, phosphate concn is less than 0.03mg/L in water outlet, can effectively suppress microbial re-growth.Under above-mentioned condition, no
Addition phosphate solution, DOC clearances bring up to 60%.
Embodiment 2
In film reaction system, adsorbent ferrihydrite is individually added without to organic matter and phosphorus using regenerated cellulose UF films
Hydrochlorate is removed.Enter addition organic concentration 3.0mg/L, phosphate concn 0.5mg/L in the aqueous solution, in the constant pressure of 60kPa
Under the conditions of run.DOC clearances 40%, act on phosphate without removal.It is organic without phosphate solution under above-mentioned condition
Thing clearance is reduced to 30%.
Embodiment 3
In film reaction system, organics removal and phosphate are cooperateed with polyether sulfone UF films using adsorbent ferrihydrite.Plus
Enter ferrihydrite concentration 50mg/L, enter organic concentration 2.5mg/L in the aqueous solution, phosphate concn 0.5mg/L, in the perseverance of 60kPa
Run under the conditions of pressure.Flux depression substantially, reduces 50%.DOC clearances 50%, UV254Clearance 90%, phosphate goes
Except rate 95%.
Embodiment 4
In film reaction system, ferrihydrite is individually added without using polyether sulfone UF films organic matter is removed.Enter water-soluble
Organic concentration 2.5mg/L in liquid, phosphate concn 0.5mg/L, run under the constant-pressure conditions of 60kPa.DOC clearances are only
10%, to phosphate without removal.
Embodiment 5
In film reaction system, organics removal is cooperateed with cellulose mixture fat MF films using adsorbent ferrihydrite.Add
Ferrihydrite concentration 50mg/L, enters organic concentration 2.7mg/L in the aqueous solution, is run under the constant-pressure conditions of 30kPa.DOC is removed
Rate 65%, UV254Clearance 90%, membrane flux change is not obvious.
Embodiment 6
In film reaction system, cellulose mixture fat MF film organics removals are individually used.Enter organic matter in the aqueous solution dense
Degree 2.7mg/L, runs under the constant-pressure conditions of 30kPa.DOC clearances are less than 5%.
Embodiment 7
Ferrihydrite after filtering-film combined system is backwashed, membrane flux recovery rate reaches 96%.Ferrihydrite is added
Afterwards, cake layer is formed on film surface, while improving pollutant adsorption efficiency, reduces the pollution for reaching fenestra and film surface
Thing, makes polluted membrane surface be easier to physical cleaning.
Claims (7)
1. a kind of ferrihydrite adsorbs-micro-filtration (MF)/ultrafiltration (UF) dual-membrane process removal Organic substance in water and phosphatic side in advance
Method, its technique composition includes pre- adsorbent ferrihydrite particle, and MF/UF low-pressure membranes.It is characterized in that in flat board membrane filtration system
Adsorbent ferrihydrite particle is added in system, ferrihydrite is in suspended state using stirring, enhanced to dissolved organic matter and phosphorus
Removal efficiency, while using membranous system retain pre-treatment adsorbent ferrihydrite particle, realize effective separation of solid and liquid.Water outlet
Middle DOC clearances reach 60%, UV254Clearance is 80%, and, more than 90%, phosphate concn is low in water outlet for removal rate of phosphate
In 0.03mg/L, can effectively suppress microbial re-growth.Ferrihydrite addition simultaneously is little on membrane flux change influence, and reaction
Membranous system is easy to physical cleaning afterwards.
2. a kind of ferrihydrite according to claim 1-MF/UF dual-membrane process removal Organic substance in water with it is phosphatic
Method, it is characterised in that comprise the following steps：By adsorbent ferrihydrite add flat board membranous system in, in stirring for rotating speed 600rpm
Mixing down makes it be in dispersion suspended state；Water sample containing organic matter and phosphorus is entered in above-mentioned membrane reactor, constant membranous system pressure,
Milipore filter is 60kPa, and microfiltration membranes are 30kPa.
3. a kind of ferrihydrite according to claim 1 and 2-dual-membrane process removes Organic substance in water and phosphatic side
Method, it is characterised in that described influent concentration is organic matter 3mg/L and phosphate 0.5mg/L.
4. the method according to right 1 and 2, it is characterised in that the membrane material is regenerated cellulose UF films or composite fibre
The MF films of plain fat.And polyether sulfone UF films elecrtonegativity is strong, ferrihydrite is easily enriched in film surface causes flux depression.
5. the method according to right 1 and 2, it is characterised in that the concentration of ferrihydrite is 50mg/L Fe.
6. the method according to right 1 and 2, it is characterised in that membrane filtration pattern is dead-end filtration, and pH value of solution is adjusted to 7.
7. the method according to right 1 and 2, it is characterised in that adsorbent ferrihydrite influences smaller to membrane flux, after filtering
Ferrihydrite-film combined system is backwashed, and membrane flux recovery rate reaches 96%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710241908.5A CN106865682A (en) | 2017-04-14 | 2017-04-14 | Ferrihydrite MF/UF dual-membrane process organics removal and phosphatic method |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710241908.5A CN106865682A (en) | 2017-04-14 | 2017-04-14 | Ferrihydrite MF/UF dual-membrane process organics removal and phosphatic method |
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| CN201710241908.5A Pending CN106865682A (en) | 2017-04-14 | 2017-04-14 | Ferrihydrite MF/UF dual-membrane process organics removal and phosphatic method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113546604A (en) * | 2020-04-23 | 2021-10-26 | 日商藤田股份有限公司 | Adsorbent material |
| CN114014438A (en) * | 2021-06-18 | 2022-02-08 | 天津大学 | Sewage phosphorus recovery method based on pipe network ferrocyanide catcher |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011112898A1 (en) * | 2011-09-08 | 2013-03-14 | Charité - Universitätsmedizin Berlin | Nanoparticulate phosphate adsorbent based on maghemite or maghemite / magnetite, its preparation and uses |
| CN105036453A (en) * | 2015-05-25 | 2015-11-11 | 厦门紫金矿冶技术有限公司 | Organic wastewater treatment and recycling method |
-
2017
- 2017-04-14 CN CN201710241908.5A patent/CN106865682A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011112898A1 (en) * | 2011-09-08 | 2013-03-14 | Charité - Universitätsmedizin Berlin | Nanoparticulate phosphate adsorbent based on maghemite or maghemite / magnetite, its preparation and uses |
| CN103906523A (en) * | 2011-09-08 | 2014-07-02 | 柏林夏洛蒂医科大学 | Nanoparticulate phosphate adsorbent on the basis of maghemite or maghemite/magnetite, production and uses thereof |
| CN105036453A (en) * | 2015-05-25 | 2015-11-11 | 厦门紫金矿冶技术有限公司 | Organic wastewater treatment and recycling method |
Non-Patent Citations (1)
| Title |
|---|
| 杨禹等: "水铁矿-MF/UF组合工艺去除水体中有机物与磷的研究", 《2014年第12届全国水处理化学大会暨学术研讨会论文摘要集》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113546604A (en) * | 2020-04-23 | 2021-10-26 | 日商藤田股份有限公司 | Adsorbent material |
| CN113546604B (en) * | 2020-04-23 | 2023-11-03 | 日商藤田股份有限公司 | Adsorption material |
| CN114014438A (en) * | 2021-06-18 | 2022-02-08 | 天津大学 | Sewage phosphorus recovery method based on pipe network ferrocyanide catcher |
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Application publication date: 20170620 |
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