CN102616901A - Preparation of magnetic cucurbituril and application of magnetic cucurbituril in removing HA (humic acid) pollutants from drinking source water - Google Patents
Preparation of magnetic cucurbituril and application of magnetic cucurbituril in removing HA (humic acid) pollutants from drinking source water Download PDFInfo
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- CN102616901A CN102616901A CN201110442417XA CN201110442417A CN102616901A CN 102616901 A CN102616901 A CN 102616901A CN 201110442417X A CN201110442417X A CN 201110442417XA CN 201110442417 A CN201110442417 A CN 201110442417A CN 102616901 A CN102616901 A CN 102616901A
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Abstract
The invention discloses preparation of a magnetic cucurbituril and application of the magnetic cucurbituril in removing HA (humic acid) pollutants from drinking source water. The invention realizes synchronization of flocculation material preparation and a magnetism covering process. The preparation process is simple, and the magnetic cucurbituril has good dispersibility. Due to great relative gravity of a magnetic flocculating agent, the flocculation and precipitation time is greatly shortened. After flocculation balance, an external magnetic field can realize rapid magnetic separation, and the flocculating agent can be recovered effectively. When applying the flocculating agent in HA pollutants in drinking source water, the removal rate of the HA pollutants can reach over 98.2%, which is far higher than the removal rates of HA by products of the same kind. At the same time, the preparation method of the magnetic cucurbituril in the invention is characterized by simplicity and convenient operation, and the treatment effect is obvious. The flocculating agent can realize good magnetic separation and can be recycled.
Description
Technical field
The invention belongs to organic/inorganic composite material and water technology scope, particularly utilize magnetic melon ring particulate to handle the application of humic acid pollutants aspect in micro-polluted water and the drinking water sources water.
Technical background
Humic acid (HA) extensively is present in the natural water environment, and the high more water quality condition of its content is poor more.Organic substance in the natural drink water is mainly HA, and the 30mg/L of its concentration range from phreatic 20 μ g/L to surface water, content are higher, and water quality condition is poorer.The content of humic acid is about 10mg/L in the general water source; Account for 50%~90% of total organic matter in the water; The existence of humic acid has brought a series of influence for the mankind and plant-animal in the natural drink water source: humic acid is one of environmental factors that causes liver cancer and Kaschin-Beck disease in the drinking water source; Also be to drink malodorous important source in the water body, and HA also can produce and various human body is had the haloform class by product of carcinogenic, teratogenesis, mutagenesis with tap water chlorhexidine-containing disinfectant reaction, to human health potential threaten greatly; Therefore, the removal of HA is become the key object of the little pollution control in drinking water source.
The method of removing at present humic acid in the water body mainly contains absorption method, membrane filtration, flocculence, oxidation style and photoelectrochemical method etc., and is wherein more with membrane filtration, absorption method, flocculence Application Research.Though adopt the membrane filtration technology can remove most of humic acid material in the water, the metals ion in the natural water body can with humic acid molecule generation complexing action, cause film to pollute, reduce the clearance of humic acid; Absorption method be used for removing the sorbent material of water body HA commonly used mainly contain gac, chitosan resin, polyacrylonitrile fibre membrane and polypyrrole etc., but the sorbent material separation difficulty after the absorption, it is low to recycle efficient, has had a strong impact on the further application of sorbent material.
Common flocculation agent is not only low to hydrophilic component clearance in the humic acid, and the safety performance of the flocculation agent that uses also is under suspicion, so development of new high effect nontoxic flocculation agent is significant.The present invention is compound with inorganic flocculating agent and synthetic organic molecule flocculation agent, has explored a kind of compound method of novel inorganic composite floculant.
The melon ring is the novel cage shape macrocylc compound that is formed by methylene-bridged glycosides urea unit, and this cage structure has hydrophobicity, can hold the hydrophobic parts or the organic molecule of various molecules; The two ends of melon ring are distributing respectively and are constituting the identical carbonylic oxygen atom of melon ring number of monomers; This carbonylic oxygen atom possess hydrophilic property; Can interact with functional groups such as dissociated carboxyl of HA and phenolic hydroxyl groups and form mixture; But the HA in the efficient flocculating water, and the melon ring has flocculation capacity height, easy for desorption and regeneration, does not produce advantages such as secondary pollution.The melon ring as flocculation agent flocculation balance after, separation difficulty, and the recovery is low.
Summary of the invention
The defective that exists to prior art or not enough, the present invention carries out melon ring and Z 250 compound, has obtained magnetic melon ring; Magnetic ferroferric oxide composition absorption impurity and suspended particulates; Make to form particle and increase gradually, and organic molecule melon ring composition utilizes the reactive group that is adsorbed on the organic molecule to produce net and catches effect through the bridge linking effect of self; Net is caught other impurity particle and is together sunk; Magnetic melon ring after compound does not influence the flocculating effect of melon ring, and is convenient to reclaim, and can be recycled.
In order to realize above-mentioned technical assignment, the present invention adopts following technical scheme to be achieved:
A kind of preparation method of magnetic melon ring flocculation agent, this method comprises the steps:
(1) preparation of melon ring midbody glycosides urea:
In urea, add entry and concentrated hydrochloric acid successively, treat after urea dissolves fully oxalic dialdehyde dropwise to be joined in the mixing solutions, react 2h down at 75 ℃, with the throw out of deionized water wash generation; Dry 6h obtains melon ring midbody glycosides urea under 75 ℃.Urea in the reaction process wherein: water: concentrated hydrochloric acid: oxalic dialdehyde mol ratio be 2.5: 1.0: 1.0: 1.0, the concentration of described concentrated hydrochloric acid is 12mol/L.
(2) preparation of melon ring
Glycosides urea and polyformaldehyde reaction that step (1) is obtained prepare the melon ring.According to glycosides urea and Paraformaldehyde 96 mol ratio is to carry out uniform mixing at 1: 2, with 8molL
-1Hydrochloric acid is solvent, and under 95 ℃ of conditions, reacts 3h, and mixing solutions naturally cooling behind the stopped reaction utilizes the methanol extraction method will react the throw out that generates and separates out, and the throw out of separating out is used washing with acetone, and dry 8h obtains the melon ring under 80 ℃.
(3) preparation of magnetic melon ring
The melon ring that step (2) is prepared carries out purifying, and takes by weighing an amount of melon ring and be dissolved in and be mixed with the melon ring solution that mass concentration is 0.0075-0.0125g/mL in the deionized water, in melon ring solution, adds (NH then
4)
2Fe (SO
4)
26H
2O and NH
4Fe (SO
4)
212H
2O carries out supersound process 10~30min with the melon ring mixing solutions that obtains, wherein the melon ring: (NH
4)
2Fe (SO
4)
26H
2O: NH
4Fe (SO
4)
212H
2The mol ratio of O is 1: 5: 10~5: 5: 10.
(4) mixing solutions after the supersound process is inserted in the reaction unit of sealing, at 300rmin
-1Constant speed stirs under the condition, and temperature rises to 50 ℃ gradually, and constant temperature stirs 5min, and in solution, dropwise adding ammoniacal liquor to pH value of solution value is 11~12, stopped reaction behind the reaction 30min.
(5) reacted mixing solutions is left standstill; Waste liquid inclines; With deionized water and absolute ethyl alcohol difference cleaning reaction product several, be neutral to reacted mixing solutions, adopt magnet that the magnetic melon ring of generation is separated with mixing solutions; Separate the magnetic melon ring flocculation agent that obtains, subsequent use behind dry 5h under 70 ℃.
The present invention also has following other technologies characteristics:
The ammonia soln mass percent concentration that wherein dropwise adds in the step (4) is 25%~28%.
The magnetic melon ring flocculation agent that the present invention prepares can be used for removing humic acid pollutants in the drinking water resource.Utilize magnetic melon ring flocculation agent to remove that the concrete treating processes of HA pollutant comprises the steps: in the drinking water resource
(1) in containing the water body that the humic acid mass concentration is 5-30mg/L, and to contain mass concentration in the water quality be 10-100mg/L Ca
2+Or Mg
2+Then according to water: magnetic melon ring flocculation agent mass percent is to add magnetic melon ring flocculation agent in 400: 1~1600: 1; With its thorough mixing, be to leave standstill several minutes under the 15-45 ℃ of condition in temperature, there is flocculent precipitate to generate in the mixing solutions; Mixing solutions pH value is 6.0-6.5, and time of repose is 30-80min.
(2) will leave standstill the mixing solutions that obtains and place the external magnetic field; Flocculation equilibrated magnetic melon ring flocculation agent gathers the magnetic field medium surface under the effect in magnetic field; Adopt 2mol/L NaOH solution that flocculation equilibrated magnetic melon ring flocculation agent is washed then; And extremely neutral with the washing of deionized water magnetic melon ring flocculation agent, the dry realization reclaimed magnetic melon ring flocculation agent.
Preparing magnetic melon ring flocculation agent according to the method described in the present invention compares with existing flocculation agent and have following technological merit: the present invention has realized the flocculation material preparation and has covered the timing of magnetic process; Preparation flow is simple; Magnetic melon ring good dispersivity; Because the relative gravity of magnetic flocculant is bigger, can increase substantially the flocculation sediment time, can be applied in the three grades of water treatments and eutrophication water of sewage work.After the flocculation balance, externally-applied magnetic field can separate by rapid magnetic, ability efficient recovery flocculation agent; This flocculation agent is applied to the removal of the humic acid pollutants in the drinking water resource, and the clearance of humic acid pollutants can reach more than 98.2%, and flocculation process of the present invention need not concussion; Only rock evenly behind the need input flocculation agent and get final product; The solution colour that can see humic acid after leaving standstill obviously shoals, and in solution, has flocculent precipitate to generate magnetic resolution after leaving standstill certain hour; Let the solution after flocculating directly flow out, reach the purpose of sharp separation.
It is simple to operate that magnetic melon ring is applied to the removal of humic acid pollutants in the drinking water sources water, and the reaction times is short, can not cause secondary pollution; Renewable recycling, and need not concussion, be water cellar water; Pond water, three grades of water treatment water of sewage work and the desirable flocculation agent of eutrophic water.Therefore, magnetic melon ring flocculation agent is applied to that the removal of humic acid pollutants has good benefits in environment and economic worth in the sewage.
Description of drawings
The X-ray powder diffraction pattern of Fig. 1 magnetic melon ring
The sem of Fig. 2 Z 250 (SEM) photo
Sem (SEM) photo of Fig. 3 magnetic melon ring flocculation agent.
Fig. 4 equal conditions magnetic melon ring flocculation agent and other flocculation agent are to the clearance of humic acid.
Fig. 5 recycles the clearance of magnetic melon ring to humic acid.
Below in conjunction with accompanying drawing particular content of the present invention is done further explain.
Embodiment
Because this magnetic melon ring surface has a large amount of carbonyls, amidine functional group has good flocculation removal effect to humic acid pollutants in the water.Humic acid pollutants mainly comprises: the heavy metal ion that exceeds standard, nitro compound, aminated compounds, organic pesticide degraded midbody, polycyclic aromatic hydrocarbons , dioxin.
Flocculation agent of the present invention has higher saturation magnetization, and under the condition of externally-applied magnetic field, the flocculation agent after the flocculation balance can separate from solution fast, and the magnetic melon ring that therefore can utilize the present invention to generate is removed the humic acid pollutants in the water body.The present invention is coated to the surface of magnetic iron oxide with the melon ring, has formed magnetic melon ring particle.With magnetic melon ring is flocculation agent, can guarantee the flocculating effect of melon ring, can carry out magnetic resolution to the material after the flocculation again, can effectively solve the problem of flocculation back separation difficulty.
The preparation of melon ring midbody glycosides urea.Take by weighing 30g urea, add 3.6mL water, 6.1mL hydrochloric acid is heated to 75 ℃, treats dropwise to drip the 10.16mL oxalic dialdehyde after urea dissolves fully, and at 75 ℃ of refluxed reaction 2h, the adularescent deposition generates.Behind the solution naturally cooling with a large amount of deionized water lotion throw out for several times, decompress filter, subsequent use behind 70 ℃ of dry 6h.
The preparation of melon ring.In beaker, add glycosides urea 15.5g (0.109mol), 8molL
-1Hydrochloric acid 80ml treats that glycosides urea dissolving back adds Paraformaldehyde 96 7.0g (2.33mol), stirs down in 95 ℃ of reaction 3h; Behind the solution naturally cooling; Utilize the methanol extraction method will react the throw out that generates and separate out, adopt acetone to carry out lotion the throw out of separating out, and obtain the melon ring at the dry 8h of 80 ℃ of conditions.
The preparation of magnetic melon ring.Behind the melon ring purifying for preparing, take by weighing 1.5g melon ring and be dissolved in the 200ml deionized water, add (NH
4)
2Fe (SO
4)
26H
2O (1.7g, 4.33mmol) and NH
4Fe (SO
4)
212H
2O (2.51g, 8.66mmol) and ultrasonic 20min.Melon ring wherein: (NH
4)
2Fe (SO
4)
26H
2O: NH
4Fe (SO
4)
212H
2The mol ratio of O is: 0.348: 1: 2.After the reaction unit sealing, 300rmin
-1Following constant speed stirs, and temperature rises to 50 ℃ gradually, behind the stirring 5min, dropwise adds ammoniacal liquor pH value of solution is controlled between 11~12.Solution colour becomes shiny black look by sorrel rapidly after adding ammoniacal liquor, shows Fe
2+, Fe
3+Reaction has generated magnetic Fe
3O
4, stopping behind the 30min stirring, waste liquid is removed in the hypsokinesis of solution left standstill certain hour, with deionized water and absolute ethyl alcohol wash products 4 times respectively, shows neutral to solution, with magnet the magnetic flocculant that generates is separated, and is subsequent use after 70 ℃ of down dry 8h grindings.
The preparation of melon ring, takes by weighing 2.5g melon ring and is dissolved in the 200ml deionized water behind the melon ring purifying for preparing with embodiment 1, adds (NH
4)
2Fe (SO
4)
26H
2O (1.7g, 4.33mmol) and NH
4Fe (SO
4)
212H
2O (2.51g, 8.66mmol) and ultrasonic 20min.Melon ring wherein: (NH
4)
2Fe (SO
4)
26H
2O: NH4Fe (SO
4)
212H
2The mol ratio of O is: 0.58: 1: 2.After the reaction unit sealing, 300rmin
-1Following constant speed stirs, and temperature rises to 50 ℃ gradually, behind the stirring 5min, dropwise adds ammoniacal liquor pH value of solution is controlled between 11~12.Solution colour becomes shiny black look by sorrel rapidly after adding ammoniacal liquor, shows Fe
2+, Fe
3+Reaction has generated magnetic Fe
3O
4, stopping behind the 30min stirring, waste liquid is removed in the hypsokinesis of solution left standstill certain hour, with deionized water and absolute ethyl alcohol wash products 4 times respectively, shows neutral to solution, and is with the magnetic flocculant separation that generates, subsequent use behind dry 8h under 70 ℃ with magnet.
Fig. 1 is the XRD figure of magnetic melon ring, can know in 2 θ=30.1,35.5 that from figure 43.2,53.6,57.0 and 62.7 places have the obvious characteristics peak, respectively corresponding inverse spinel structure F.C.C. phase Fe
3O
4(220), (311), (400), (421), (510) and (440) crystal plane, with standard Fe
3O
4Characteristic diffraction peak match, show that magnetic particle is Fe in the magnetic melon ring
3O
4, explain that this flocculation agent has magnetic.
Fig. 2 is Fe
3O
4The SEM photo, Fig. 3 is the SEM photo of magnetic melon ring, Fig. 2 and Fig. 3 contrast can be known Fe
3O
4Surface particles is relatively disperseed, and magnetic melon ring surface group has formed the sheet aggregate, and this irregular aggregate is to be nuclear with the Z 250, and the melon ring attached to the Z 250 surface, forms assembly or inclusion complex with Intermolecular Forces.
Application implementation example 1
With embodiment 1 synthetic magnetic melon ring particulate is flocculation agent; Processing contains the micro-polluted water of humic acid, in the brown volumetric flask of 50ml, carries out flocculating experiment, and the starting point concentration of humic acid is 5mg/L; Magnetic melon ring dosage is 0.06g; PH=6.0-6.5, temperature is 27 ℃, according to water: magnetic melon ring flocculation agent mass percent is 833: 1.Add flocculation agent, solution stirring leaves standstill after evenly, the magnetic resolution flocculation agent agent of flocculation back, and the flocculation starting time is 90min, the clearance of humic acid can reach 99.85% and (see Fig. 4-A).
Application implementation example 2
Condition is with application implementation example 1, and the starting point concentration of humic acid is 10mg/L, water: magnetic melon ring flocculation agent mass percent is 833: 1, and the clearance of humic acid is 99.22% and (sees Fig. 4-B).
Condition is with application implementation example 1, and the starting point concentration of humic acid is 20mg/L, water: magnetic melon ring flocculation agent mass percent is 833: 1, and the clearance of humic acid is 98.16% and (sees Fig. 4-C).
Condition is with application implementation example 1, and the starting point concentration of humic acid is 30mg/L, water: magnetic melon ring flocculation agent mass percent is 833: 1, and the clearance of humic acid is 94.62% and (sees Fig. 4-D).
Application implementation example 3
Condition is with application implementation example 1, and the starting point concentration of humic acid is 10mg/L, water: magnetic melon ring flocculation agent mass percent is 1600: 1, and the clearance of humic acid can reach 93.48% and (see Fig. 4-E).
Application implementation example 4
Condition is with application implementation example 1, and the starting point concentration of humic acid is 20mg/L, wherein water: magnetic melon ring flocculation agent mass percent is 400: 1, and the clearance of humic acid can reach 98.79% and (see Fig. 4-F).
Application implementation example 5
Condition adds Mg respectively with application implementation example 3 in the solution
2+, Ca
2+, concentration range is 10~100mg/L, and the adsorptive capacity of humic acid is along with the continuous increase of being increased in of concentration of metal ions, and the also corresponding raising of clearance brings up to 98.25% by 93.48%.It is that the metals ion of 10~100mg/L does not influence magnetic melon ring humic acid is removed that this explanation contains the mass concentration scope in water body, promotes the clearance of magnetic melon ring to humic acid on the contrary.
Application implementation example 6
Because martial ethiops also has certain removal effect to humic acid, the humic acid solution that this experiment is handled same concentrations with simple red stone and magnetic melon ring has carried out simultaneous test.Select for use the starting point concentration of humic acid to be respectively 20mg/L, the dosage of magnetic melon ring and red stone is 0.06g, and humic acid solution is 50ml; Water wherein: magnetic melon ring flocculation agent mass percent is 400: 1; Temperature is 25 ℃, and pH is 6.5, and the flocculation starting time is 65min.Magnetic melon ring and Z 250 are respectively 98.16% to the clearance of humic acid, and (see Fig. 4-C), 37.67% (sees Fig. 4-G).
Application implementation example 7
Condition is with application implementation example 1, and the starting point concentration of humic acid is 20mg/L, wherein water: Poly aluminum Chloride (PAC) (PAC) mass percent is 833: 1, and the clearance of humic acid is 55.35% and (sees Fig. 4-H).
Application implementation example 8
Condition is with application implementation example 1, and the starting point concentration of humic acid is 20mg/L, wherein water: Poly aluminum Chloride (PAC) (PAC) mass percent is 200: 1, and the clearance of humic acid is 70.64% and (sees Fig. 4-J).
Application implementation example 9
Condition is with application implementation example 1, and the starting point concentration of humic acid is 20mg/L, wherein water: poly-ferric chloride (PFC) mass percent is 833: 1, and the clearance of humic acid is 59.78% and (sees Fig. 4-K).
Application implementation example 10
Method is with application implementation example 2, and magnetic melon ring has descended about 30% to the adsorptive capacity of HA after the reciprocation cycle 4 times, and the clearance of HA is dropped to 88.54% (see figure 5) by 98.79%.This explanation magnetic melon ring flocculation agent desorption and regeneration that can circulate preferably can recycle the removal of humic acid pollutants.In addition, with the humic acid flocculation in the magnetic melon ring of the present invention flocculation water saturated after, with magnet flocculation agent is carried out magnetic resolution, adopt NaOH that flocculation agent is carried out desorption and regeneration.Extremely neutral with deionized water lotion magnetic melon ring behind the desorption, dry recycle is used.The present invention has overcome the common flocculation agent problem low to the clearance of humic acid pollutants; Need not after this magnetic melon ring flocculation agent adds in the entry to stir, solved flocculation stirring technique complicated problems, saved the flocculation cost; And flocculation back magnetic resolution is rapid, can be recycled.
Claims (5)
1. the preparation method of a magnetic melon ring flocculation agent, it is characterized in that: this method comprises the steps:
(1) preparation of melon ring midbody glycosides urea:
In urea, add entry and concentrated hydrochloric acid successively; Treat dropwise to join oxalic dialdehyde in the mixing solutions after urea dissolves fully; Under 75 ℃ of conditions, react 2h, with the throw out that deionized water wash generates, dry 6h obtains melon ring midbody glycosides urea under 75 ℃ of conditions; Urea in the reaction process wherein: water: concentrated hydrochloric acid: oxalic dialdehyde mol ratio be 2.5: 1.0: 1.0: 1.0, the concentration of described concentrated hydrochloric acid is 12mol/L;
(2) preparation of melon ring
Glycosides urea and polyformaldehyde reaction that step (1) is obtained prepare the melon ring.According to glycosides urea and Paraformaldehyde 96 mol ratio is to carry out uniform mixing at 1: 2; With 8mo1L-1 hydrochloric acid is solvent; And under 95 ℃ of conditions, reacting 3h, mixing solutions naturally cooling behind the stopped reaction utilizes the methanol extraction method will react the throw out that generates and separates out; The throw out of separating out is used washing with acetone, and dry 8h obtains the melon ring under 80 ℃;
(3) preparation of magnetic melon ring
The melon ring that step (2) is prepared carries out purifying, and takes by weighing an amount of melon ring and be dissolved in and be mixed with the melon ring solution that mass concentration is 0.0075-0.0125g/mL in the deionized water, in melon ring solution, adds (NH then
4)
2Fe (SO
4)
26H
2O and NH
4Fe (SO
4)
212H
2O carries out supersound process 10~30min with the melon ring mixing solutions that obtains, wherein the melon ring: (NH
4)
2Fe (SO
4)
26H
2O: NH
4Fe (SO
4)
212H
2The mol ratio of O is 1: 5: 10~5: 5: 10;
(4) mixing solutions after the supersound process is inserted in the reaction unit of sealing, at 300rmin
-1Constant speed stirs under the condition, and temperature rises to 50 ℃ gradually, and constant temperature stirs 5min, and in solution, dropwise adding ammoniacal liquor to pH value of solution value is 11~12, stopped reaction behind the reaction 30min;
(5) reacted mixing solutions is left standstill; Waste liquid inclines; With deionized water and absolute ethyl alcohol difference cleaning reaction product several, be neutral to reacted mixing solutions, adopt magnet that the magnetic melon ring of generation is separated with mixing solutions; Separate the magnetic melon ring flocculation agent that obtains, subsequent use behind dry 5h under 70 ℃.
2. the preparation method of magnetic melon ring flocculation agent as claimed in claim 1 is characterized in that: the ammonia soln mass percent concentration that dropwise adds in the described step (4) is 25%~28%.
3. the application of humic acid pollutants in claim 1, the 2 described magnetic melon ring flocculation agents removal drinking water resources.
4. magnetic melon ring flocculation agent as claimed in claim 3 is removed the application of humic acid pollutants in the drinking water resource, it is characterized in that: the concrete treating processes of HA pollutant comprises the steps: in the described magnetic melon ring flocculation agent removal drinking water resource
(1) magnetic melon ring flocculation agent is applied in the water body that the humic acid mass concentration is 5-30mg/L; According to water: magnetic melon ring flocculation agent mass percent is to add flocculation agent in 400: 1~1600: 1; Adding flocculation agent mixing solutions afterwards fully shakes up; In temperature is to leave standstill several minutes under the 15-45 ℃ of condition, has flocculent precipitate to generate in the mixing solutions; The pH scope of mixing solutions is 6.0-6.5, and leaving standstill starting time is 30-80min;
The solution that (2) will flocculate after the balance utilizes magnet to separate with flocculation agent; Magnetic melon ring flocculation agent after the separation adopts 2mol/L NaOH solution that it is washed; And extremely neutral with deionized water wash magnetic melon ring, the dry realization reclaimed magnetic melon ring flocculation agent.
5. magnetic melon ring flocculation agent as claimed in claim 3 is removed the application of humic acid pollutants in the drinking water resource, it is characterized in that:
(1) in containing the water body that the humic acid mass concentration is 5-30mg/L, and to contain mass concentration in the water body be 10-100mg/L Ca
2+Or Mg
2+Then according to water: magnetic melon ring flocculation agent mass percent is to add magnetic melon ring flocculation agent in 400: 1~1600: 1; With its thorough mixing, be to leave standstill several minutes under the 15-45 ℃ of condition in temperature, there is flocculent precipitate to generate in the mixing solutions; Mixing solutions pH value is 6.0-6.5, and time of repose is 30-80min;
(2) will leave standstill the mixing solutions that obtains and place the external magnetic field; Flocculation equilibrated magnetic melon ring flocculation agent gathers the magnetic field medium surface under the effect in magnetic field; Adopt 2mol/L NaOH solution that flocculation equilibrated magnetic melon ring flocculation agent is washed then; And extremely neutral with the washing of deionized water magnetic melon ring flocculation agent, the dry realization reclaimed magnetic melon ring flocculation agent.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104722276A (en) * | 2015-04-14 | 2015-06-24 | 中国工程物理研究院材料研究所 | Magnetic cucurbit urils/grapheme oxide composite material and preparation method thereof |
CN110642343A (en) * | 2019-11-08 | 2020-01-03 | 北京林业大学 | Preparation and application of magnetic flocculant for removing suspended particles in water |
CN111921497A (en) * | 2020-07-15 | 2020-11-13 | 西安建筑科技大学 | Method for preparing magnetic biochar by pyrolyzing apple pomace |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101085688A (en) * | 2006-06-08 | 2007-12-12 | 广州格隆环保技术开发有限公司 | Decolorization flocculating agent for printing and dyeing waste water |
CN101108851A (en) * | 2007-07-11 | 2008-01-23 | 贵州大学 | Melon ring and method of synthesizing substituted melon ring |
CN101723503A (en) * | 2009-12-16 | 2010-06-09 | 暨南大学 | Organic-inorganic compound high-efficient decolorizing flocculant and preparation method and application thereof |
-
2011
- 2011-12-19 CN CN 201110442417 patent/CN102616901B/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101085688A (en) * | 2006-06-08 | 2007-12-12 | 广州格隆环保技术开发有限公司 | Decolorization flocculating agent for printing and dyeing waste water |
CN101108851A (en) * | 2007-07-11 | 2008-01-23 | 贵州大学 | Melon ring and method of synthesizing substituted melon ring |
CN101723503A (en) * | 2009-12-16 | 2010-06-09 | 暨南大学 | Organic-inorganic compound high-efficient decolorizing flocculant and preparation method and application thereof |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104722276A (en) * | 2015-04-14 | 2015-06-24 | 中国工程物理研究院材料研究所 | Magnetic cucurbit urils/grapheme oxide composite material and preparation method thereof |
CN104722276B (en) * | 2015-04-14 | 2016-09-28 | 中国工程物理研究院材料研究所 | A kind of melon ring/graphene oxide magnetic composite and preparation method thereof |
CN110642343A (en) * | 2019-11-08 | 2020-01-03 | 北京林业大学 | Preparation and application of magnetic flocculant for removing suspended particles in water |
CN111921497A (en) * | 2020-07-15 | 2020-11-13 | 西安建筑科技大学 | Method for preparing magnetic biochar by pyrolyzing apple pomace |
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