CN110143658A - A kind of nano-magnetic cationic flocculant and preparation method thereof - Google Patents
A kind of nano-magnetic cationic flocculant and preparation method thereof Download PDFInfo
- Publication number
- CN110143658A CN110143658A CN201910402117.5A CN201910402117A CN110143658A CN 110143658 A CN110143658 A CN 110143658A CN 201910402117 A CN201910402117 A CN 201910402117A CN 110143658 A CN110143658 A CN 110143658A
- Authority
- CN
- China
- Prior art keywords
- nano
- magnetic
- flocculant
- cationic flocculant
- preparation
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
Abstract
The present invention relates to a kind of nano-magnetic cationic flocculant and preparation methods, are applied to sewage sludge process field.The nano-magnetic cationic flocculant has gelatinized starch via graft copolymerization and cationization, builds electrolytic cell by coprecipitation reaction and generates nanometer Fe3O4Starch graft copolymer coal-water finally is prepared in conjunction with magnetic fluid in particle.Nano-magnetic cationic flocculant prepared by the present invention has preferable absorption and flocculation to the suspended matter in sewage sludge, is acted on by externally-applied magnetic field, can accelerate flocculation settling velocity, is also beneficial to the recycling and reusing of later period flocculant.This nano-magnetic flocculant is suitably applied the processing of the sewage sludge of the enterprises such as paper industry, petrochemical industry.
Description
Technical field
The present invention relates to Sewage Sludge Treatment Techniques fields, and in particular to a kind of nano-magnetic cationic flocculant and its system
Preparation Method.
Background technique
China generates the sludge of enormous amount every year, and the excess sludge moisture content not being dehydrated is up to 99%~99.5%,
Its density is small, is not easy to be dehydrated, and poor chemical stability is bulky, makes troubles to transport, storage, it is also possible to cause to environment
Secondary pollution will cause environment direct or potentially hazardous if not dealt carefully with and being disposed.Therefore, how properly
These sludge are disposed, are the realistic problems put in urban development process.
Flocculation is common mud dewatering method, is mainly carried out at dehydration decrement by launching chemical agent to sludge
It sets, common flocculant has polyacrylamide (PAM), aluminium polychloride (PAC) etc..Flocculant adds, and makes between mud granule
Structure enhancing is convenient for mechanical dehydration operation.Flocculant unite in actual use to pollutants such as suspended particulates in water
Removal rate it is limited, and it is subsequent needed for mud-water separation process it is longer so that needing biggish precipitating pool volume, cause initial investment
The raising of cost and the increase of occupied area need the method for improving sludge to flocculant to improve.
Organic polymer coargulator is that one kind that chemical monomer is generated by polymerization reaction or chemical copolymerization reaction is organic
High-molecular compound.Its flocculant mechanism is so that macromolecular chain is passed through chemical bond and multiple colloidal solid phases by charge neutrality
In conjunction with formation bridging.Macromolecule has stronger suction-operated because of its biggish molecular weight, can make colloidal solid formed compared with
Big floc sedimentation settles down by gravity.On the other hand, also there is net laying in the flocculation process of organic polymer coargulator
The effect of sweeping is rolled up, to keep floc sedimentation sedimentation rapider.The graft copolymerization of vinyl monomer and starch is that starch conversion system is each
One of the important channel of biodegradable high molecular material.
Magnetic separation technique belongs to physical method for sewage treatment, i.e., obtains the substance of different magnetism by the effect of magnetic field force
With separation.Magnetic separation technique has easy to operate, removal pollutant kind mostly and removal rate is high, there is no the apertures in membrane process
Obstructing problem, processing equipment do not take up space and the low advantage that consumes energy, and is the sewage disposal technology for having very much development potentiality.
Summary of the invention
The object of the present invention is to provide a kind of nano-magnetic cationic flocculant and preparation methods.
In order to achieve the above object, the present invention provides a kind of nano-magnetic cationic flocculants, which is characterized in that it is tied
Structure is load Fe3O4The graft copolymer of nano particle, the graft copolymer is by gelatinized starch and grafted monomers graft copolymerization shape
At.
The present invention also provides a kind of preparation methods of nano-magnetic cationic flocculant, which is characterized in that is formed sediment by gelatinization
Powder and graft copolymerization monomer tap into capable branch and are copolymerized and load Fe simultaneously3O4Nano particle, then through cation modifying prepare and
At.
Preferably, the paste starch is gelatinized method, super-pressure gelatinization method, extruding paste by Heat Gelatinization method, microwave heating
Any one in change method and chemical gelatinization method is prepared.
Preferably, the medium comonomer is acrylamide, acrylic acid, styrene, acrylonitrile, two allyl of dimethyl
Any one in ammonium chloride, butadiene and methyl methacrylate.
Preferably, the preparation method of the nano-magnetic cationic flocculant, specifically includes the following steps:
Step 1: graft copolymerization and load Fe3O4Nano particle:
It is cathode by anode, carbon-point of iron plate, connection DC power supply builds electrolytic cell, and gelatinized starch is added to electrolytic cell
In, temperature of reaction system is adjusted to 60 DEG C, initiation system is added and stirs evenly, power supply is opened and is slowly added to grafting simultaneously altogether
Polycondensation monomer solution adjusts reaction system to 30 DEG C, and NaOH solution is added dropwise and adjusts pH to 11~12, then by temperature of reaction system tune
Whole is 70~80 DEG C, generates Fe by electrochemistry coprecipitation reaction3O4Nano particle, under constant temperature stirring condition, paste starch with
Acrylic amide graft copolymerization simultaneously coats Fe3O4Nano particle；
Step 2: cation modifying:
70~80 DEG C of constant temperature stirrings are kept, etherifying agent is added, carries out priming reaction, obtains product；
Step 3: washing and drying:
By step 2 products therefrom, using water and acetone, alternately washing can be obtained nano-magnetic after dry, pulverize to neutrality
Cationic flocculant.
Preferably, the preparation method of gelatinized starch includes: to weigh corn by the solid-to-liquid ratio of 0.1g/mL to form sediment in the step 1
Powder and deionized water, under sealing state, 70 DEG C of constant temperature are gelatinized 1h, obtain gelatinized starch.
Preferably, graft copolymerization monomer is acrylamide, acrylic acid, styrene, acrylonitrile, dimethyl in the step 1
Any one in diallyl ammonium chloride, butadiene and methyl methacrylate.
Preferably, graft copolymerization monomer solution is acrylamide aqueous solution in the step 1, and concentration is
The mass ratio of 0.5~1g/mL, starch and acrylamide is 1:2~3.
Preferably, causing system in the step 1 is that ammonium ceric nitrate-potassium peroxydisulfate causes system, sodium thiosulfate-over cure
Sour potassium causes system, sodium thiosulfate-ammonium persulfate and causes any one in system or sodium thiosulfate-hydrogen peroxide.
It is highly preferred that causing system in the step 1 is that ammonium ceric nitrate-potassium peroxydisulfate causes system, the throwing of ammonium ceric nitrate
It is high-volume the 1~2% of acrylamide quality, the injected volume of potassium peroxydisulfate is the 3~5% of acrylamide quality.
It preferably, the use of NaOH solution concentration is 2mol/L in the step 1.
Preferably, iron plate quality is at least the 10~15% of starch and acrylamide gross mass in the step 1, and power supply is applied
Making alive is 5~7V.Anode iron plate can gradually lose the electrolytically generated Fe of electronics2+Into reaction system, while Fe2+It can be in system
Oxidation generates Fe under the action of middle dissolved oxygen3+, most 30 DEG C of reaction system adjustment, dropwise addition NaOH solution adjustment pH to 11~12,
Reaction system is adjusted most 70~80 DEG C again, Fe2+And Fe3+Coprecipitation reaction will occur and generate nanoscale Fe3O4Particle, it is coprecipitated
Shallow lake reaction equation: Fe2++2Fe3++8OH-→Fe3O4+4H2O。
Preferably, the etherifying agent in the step 2 be 2,3- epoxypropyltrimethylchloride chloride (GTA), tertiary amine alkyl ether,
It is any one in father-in-law's kind of starch ether (including quaternary ammonium, phosphine, sulfonium derivative), alkyl primary amine ether, secondary amine alkyl ether and imines starch ether
Kind.
It is highly preferred that the molar ratio of 2, the 3- epoxypropyltrimethylchloride chloride and acrylamide is 0.5~0.6:1.
Preferably, the priming reaction time is 2.5h in the step 2.
Preferably, dry for 48h dry in 40 DEG C of thermostatic drying chambers in the step 3.
The principle of the present invention:
The present invention prepares nanometer Fe using the method for electrochemistry3O4Particle is accelerated using the cathode protection method of additional power source
Electrolytic anode iron, electrolytically generated Fe2+Into reaction system, due to containing a large amount of dissolved oxygens, Fe in system2+It can aoxidize and generate Fe3 +, under the alkaline environment of pH=11~12, Fe2+And Fe3+Coprecipitation reaction will occur to generate nanoscale Fe3O4Particle.?
Under stirring action, Starch Modified Flocculant will coat nanometer Fe3O4Particle, and keep its diffusion uniform.
Magnetic flocculant is by by Fe3O4Particle passes through a series of chemical reaction preparation from different flocculation monomers
A kind of novel flocculant.Fe3O4Particle is flocculated agent and coats to form magnetic core, this kind of flocculant have typical core-shell structure and compared with
Good magnetic responsiveness.Compared with aluminium system, iron-based flocculating agent, under the action of externally-applied magnetic field, the wadding body that magnetic flocculant generates is more
Encryption is real, and faster, and the sludge quantity and moisture percentage in sewage sludge that generate are greatly reduced sinking speed.The magnetic core of magnetic flocculant is big
Part can obtain Magneto separate recycling by magnetic separation technique.
Cationic organic polymer coargulator is that have by what the monomer of acrylamide monomer and ammonium salt-containing was copolymerized
Machine high-molecular copolymer, the monomer of typical ammonium salt-containing have methyl-propyl acyloxyethyl trimethyl ammonium chloride (DMC), dimethyl two
Allyl ammonium chloride (DMDAAC) etc..Group on strand containing ammonium salt shows cationic characteristic, for being suspended in band in water body
The colloidal solid of negative electrical charge can play its charge neutrality effect, compress the electric double layer of colloidal grain surface, make particle surface zeta
Current potential reduces, and surely settles to achieve the purpose that take off.
Compared with prior art, the beneficial effects of the present invention are:
(1) present invention is compared with original flocculation technique, in starch and acrylic amide graft copolymerization and cation modifying
In reaction process, nanometer Fe has been loaded by electrochemical method3O4Particle makes it under magnetic fields, accelerates sinking speed, produces
Raw wadding body is more closely knit, and then substantially reduces the sludge quantity and moisture percentage in sewage sludge of generation.
(2) present invention not only meets the requirement of sludge flocculation processing and moisture content, has allowed also for prepared wadding
Solidifying agent is easy to the performance degraded, since plant amylum is easy to be biodegradable in the environment, this flocculation in the natural environment
Agent has that the time is very short and residual quantity is very low in the environment.
(3) present invention has also carried out graft copolymerization and cation-modified to starch, and macromolecular chain is made to pass through chemical bond and more
A colloidal solid combines, and forms bridging.Colloidal solid forms biggish floc sedimentation and settles down by gravity, organic high score
Also there is sub- flocculant net laying volume to sweep effect, to keep floc sedimentation sedimentation rapider.
(4) primary raw material of the present invention is plant amylum, and raw material are simple and easy to get and cheap, reduces production cost.
Detailed description of the invention
Fig. 1 is the nano-magnetic cationic flocculant FTIR spectrum figure of embodiment 6；
Fig. 2 is the nano-magnetic cationic flocculant transmission electron microscope picture of embodiment 6.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Reagent used in the embodiment of the present invention is as follows:
Embodiment 1
A kind of nano-magnetic cationic flocculant is present embodiments provided, specific preparation process is as follows:
Step 1: graft copolymerization and load Fe3O4Nano particle:
Weighing 5g cornstarch and 50mL deionized water, under sealing state, 70 DEG C of constant temperature are gelatinized 1h, gelatinized starch is obtained,
It is cathode by anode, carbon-point of iron plate, connection DC power supply builds electrolytic cell, and gelatinized starch is added in electrolytic cell, will be anti-
System temperature is answered to adjust to 60 DEG C, as drawing after taking 0.15g ammonium ceric nitrate and 0.3g potassium peroxydisulfate to use 10mL deionized water dissolving
Hair system is added in reaction system, and 300r/min stirs 10min, is opened power supply and is slowly added to 20mL 0.5g/mL propylene simultaneously
Amide aqueous solution (starch is 1:2 with the proportion of acylamide), reaction system is adjusted to 30 DEG C, NaOH solution is added dropwise and adjusts pH
Value is adjusted to 70 DEG C to 11, then by temperature of reaction system, and under constant temperature stirring condition, paste starch and acrylamide graft are total
It is poly-, Fe is generated by coprecipitation reaction3O4Nano particle is simultaneously grafted copolymer cladding；
The direct current power source voltage is 6V, and iron plate quality is the 10% of cornstarch and acrylamide gross mass；NaOH is molten
Liquid concentration is 2mol/L；
Step 2: cation modifying:
Kept for 70 DEG C, the stirring of 300r/min constant temperature weighs 2, the 3- epoxy third that mole is 0.5 times of acrylamide mole
Base trimethyl ammonium chloride is added in reaction system, carries out priming reaction 2.5h, obtains product；
Step 3: washing and drying:
By step 2 products therefrom, using water and acetone, alternately washing is to neutrality, the dry 48h in 40 DEG C of thermostatic drying chambers,
It can be obtained nano-magnetic cationic flocculant after crushing.
Embodiment 2
A kind of nano-magnetic cationic flocculant is present embodiments provided, specific preparation process is as follows:
Step 1: graft copolymerization and load Fe3O4Nano particle:
Weighing 5g cornstarch and 50mL deionized water, under sealing state, 70 DEG C of constant temperature are gelatinized 1h, gelatinized starch is obtained,
It is cathode by anode, carbon-point of iron plate, connection DC power supply builds electrolytic cell, and gelatinized starch is added in electrolytic cell, will be anti-
System temperature is answered to adjust to 60 DEG C, as drawing after taking 0.15g ammonium ceric nitrate and 0.3g potassium peroxydisulfate to use 10mL deionized water dissolving
Hair system is added in reaction system, stirs 10min, it is water-soluble that unlatching power supply is slowly added to 20mL 0.5g/mL acrylamide simultaneously
Liquid (starch is 1:2 with the proportion of acylamide), reaction system is adjusted to 30 DEG C, dropwise addition NaOH solution adjustment pH value to 12,
Temperature of reaction system is adjusted to 70 DEG C again, under constant temperature stirring condition, paste starch and acrylic amide graft copolymerization, by altogether
Precipitation reaction generates Fe3O4Nano particle is simultaneously grafted copolymer cladding；
The direct current power source voltage is 6V, and iron plate quality is the 15% of cornstarch and acrylamide gross mass；NaOH is molten
Liquid concentration is 2mol/L；
Step 2: cation modifying:
Kept for 70 DEG C, the stirring of 300r/min constant temperature weighs 2, the 3- epoxy third that mole is 0.5 times of acrylamide mole
Base trimethyl ammonium chloride is added in reaction system, carries out priming reaction 2.5h, obtains product；
Step 3: washing and drying:
By step 2 products therefrom, using water and acetone, alternately washing is to neutrality, the dry 48h in 40 DEG C of thermostatic drying chambers,
It can be obtained nano-magnetic cationic flocculant after crushing.
Embodiment 3
A kind of nano-magnetic cationic flocculant is present embodiments provided, specific preparation process is as follows:
Step 1: graft copolymerization and load Fe3O4Nano particle:
Weighing 5g cornstarch and 50mL deionized water, under sealing state, 70 DEG C of constant temperature are gelatinized 1h, gelatinized starch is obtained,
It is cathode by anode, carbon-point of iron plate, connection DC power supply builds electrolytic cell, and gelatinized starch is added in electrolytic cell, will be anti-
System temperature is answered to adjust to 60 DEG C, as drawing after taking 0.15g ammonium ceric nitrate and 0.3g potassium peroxydisulfate to use 10mL deionized water dissolving
Hair system is added in reaction system, and 300r/min stirs 10min, is opened power supply and is slowly added to 20mL 0.75g/mL third simultaneously
Acrylamide aqueous solution (starch is 1:3 with the proportion of acylamide), reaction system is adjusted to 30 DEG C, NaOH solution adjustment is added dropwise
PH to 11, then temperature of reaction system is adjusted to 70 DEG C, under constant temperature stirring condition, paste starch and acrylamide graft are total
It is poly-, Fe is generated by coprecipitation reaction3O4Nano particle is simultaneously grafted copolymer cladding；
The direct current power source voltage is 6V, and iron plate quality is the 10% of cornstarch and acrylamide gross mass；NaOH is molten
Liquid concentration is 2mol/L；
Step 2: cation modifying:
Being kept for 70 DEG C, 300r/min constant temperature stirs, weigh 2, the 3- epoxy that mole is 0.6 times of acrylamide mole
Hydroxypropyltrimonium chloride is added in reaction system, carries out priming reaction 2.5h, obtains product；
Step 3: washing and drying:
By step 2 products therefrom, using water and acetone, alternately washing is to neutrality, the dry 48h in 40 DEG C of thermostatic drying chambers,
It can be obtained nano-magnetic cationic flocculant after crushing.
Embodiment 4
A kind of nano-magnetic cationic flocculant is present embodiments provided, specific preparation process is as follows:
Step 1: graft copolymerization and load Fe3O4Nano particle:
Weighing 5g cornstarch and 50mL deionized water, under sealing state, 70 DEG C of constant temperature are gelatinized 1h, gelatinized starch is obtained,
It is cathode by anode, carbon-point of iron plate, connection DC power supply builds electrolytic cell, and gelatinized starch is added in electrolytic cell, will be anti-
System temperature is answered to adjust to 60 DEG C, as drawing after taking 0.15g ammonium ceric nitrate and 0.3g potassium peroxydisulfate to use 10mL deionized water dissolving
Hair system is added in reaction system, and 300r/min stirs 10min, is opened power supply and is slowly added to 20mL 0.75g/mL third simultaneously
Acrylamide aqueous solution (starch is 1:3 with the proportion of acylamide), reaction system is adjusted to 30 DEG C, NaOH solution adjustment is added dropwise
PH to 12, then temperature of reaction system is adjusted to 70 DEG C, under constant temperature stirring condition, paste starch and acrylamide graft are total
It is poly-, Fe is generated by coprecipitation reaction3O4Nano particle is simultaneously grafted copolymer cladding；
The direct current power source voltage is 6V, and iron plate quality is the 15% of cornstarch and acrylamide gross mass；NaOH is molten
Liquid concentration is 2mol/L；
Step 2: cation modifying:
Kept for 70 DEG C, the stirring of 300r/min constant temperature weighs 2, the 3- epoxy third that mole is 0.6 times of acrylamide mole
Base trimethyl ammonium chloride is added in reaction system, carries out priming reaction 2.5h, obtains product；
Step 3: washing and drying:
By step 2 products therefrom, using water and acetone, alternately washing is to neutrality, the dry 48h in 40 DEG C of thermostatic drying chambers,
It can be obtained nano-magnetic cationic flocculant after crushing.
Embodiment 5
2,3- epoxypropyltrimethylchloride chloride mole used is 0.6 times of acrylamide mole, other and embodiment 1
It is identical.
Embodiment 6
2,3- epoxypropyltrimethylchloride chloride mole used is acrylamide mole 0.6, other and 2 phase of embodiment
Together.
Embodiment 7
2,3- epoxypropyltrimethylchloride chloride mole used is acrylamide mole 0.5, other and 3 phase of embodiment
Together.
Embodiment 8
2,3- epoxypropyltrimethylchloride chloride mole used is acrylamide mole 0.5, other and 4 phase of embodiment
Together.
Embodiment 9
It is 80 DEG C that temperature of reaction system is adjusted in step 2 middle-jiao yang, function of the spleen and stomach ion modification process, other are same as Example 1.
Embodiment 10
It is 80 DEG C that temperature of reaction system is adjusted in step 2 middle-jiao yang, function of the spleen and stomach ion modification process, other are same as Example 2.
Embodiment 11
It is 80 DEG C that temperature of reaction system is adjusted in step 2 middle-jiao yang, function of the spleen and stomach ion modification process, other are same as Example 3.
Embodiment 12
It is 80 DEG C that temperature of reaction system is adjusted in step 2 middle-jiao yang, function of the spleen and stomach ion modification process, other are same as Example 4.
Embodiment 13
It is 80 DEG C that temperature of reaction system is adjusted in step 2 middle-jiao yang, function of the spleen and stomach ion modification process, other are same as Example 5.
Embodiment 14
It is 80 DEG C that temperature of reaction system is adjusted in step 2 middle-jiao yang, function of the spleen and stomach ion modification process, other are same as Example 6.
Embodiment 15
It is 80 DEG C that temperature of reaction system is adjusted in step 2 middle-jiao yang, function of the spleen and stomach ion modification process, other are same as Example 7.
Embodiment 16
It is 80 DEG C that temperature of reaction system is adjusted in step 2 middle-jiao yang, function of the spleen and stomach ion modification process, other are same as Example 8.
The sample for preparing of embodiment 1-16 is uniformly tested, test item includes COD removal rate, sludge specific resistance and
Sludge capillary dewatering time, the results are shown in Table 1:
Table 1 is sewage sludge indices and removal rate after processing
According to the experimental results, the nano-magnetic cationic flocculant of this experiment, it is good for the flocculating effect of sewage sludge
Good, sludge specific resistance and sludge capillary water absorbing time are greatly lowered, and illustrating that treated, dewatering performance of sludge is excellent.It is comprehensive
Consider, the nano-magnetic cationic flocculant treatment effect of embodiment 6 is better than other embodiments, it can be deduced that of the invention is best
Preparation method is, in acrylic amide graft copolymerization step, acrylamide quality is 2 times of starch, in load Fe3O4Particle
In step, 15% that iron plate quality is cornstarch and acrylamide gross mass is chosen, pH value of solution is adjusted to 12, changes in cationization
Property step in, temperature of reaction system is adjusted to 70 DEG C, and GTA mole is 0.5 times of acrylamide mole.
Embodiment 17
This experiment chooses four groups of samples and compares experiment, handles the anaerobism of 1000mL sewage treatment plant A2O technique respectively
Sludge, primary sludge resistivity are 15.6 × 1011cm·g-1, the nano-magnetic cationic flocculant additive amount difference of each group.Respectively
The nano-magnetic cationic flocculant of the preparation of 200mg, 300mg, 400mg and 500mg embodiment 6 is weighed, then by four groups of flocculants
It launches among sewage sludge respectively.
The sludge specific resistance of sludge, it is as shown in table 2 to obtain experimental result after measurement processing.
Table 2 is treated sludge specific resistance
According to the experimental results, if flocculant usage is very few, to the suspended particulate substance and colloid coagulation effect in sludge
Fruit is unobvious, and effect is poor, but if flocculant usage is excessive, then bridge linking effect can occur between flocculant, cannot be well
Coagulation is contacted with suspended matter, excess or deficiency amount all can cause flocculant effect unobvious.It is obtained by laboratory, of the invention receives
Optimum quantum of utilization of the rice magnetic cation flocculant in sludge is about 400mg/L, and treated, and sludge specific resistance is substantially reduced.
Embodiment 18
This Experimental comparison commodity flocculant includes organic polymer coargulator polyacrylamide PAM, inorganic polymer flocculation
Agent PB1 gene, the nano-magnetic cationic flocculant with the embodiment of the present invention 6 compare.1000mL is handled respectively
The anaerobic sludge of sewage treatment plant's A2O technique, primary sludge resistivity are 15.6 × 1011cm·g-1, flocculant dosage is using this
The optimum quantum of utilization 400mg/L of invention.
The sludge specific resistance of sludge, it is as shown in table 3 to obtain experimental result after measurement processing.
Table 3 is treated sludge specific resistance
According to the experimental results, nano-magnetic cationic flocculant of the invention manages the flocculation treatment effect of sewage sludge
Think, better than common traditional flocculant, commercial value is high.
Material property characterization
The fourier infrared analysis spectrum of the nano-magnetic cationic flocculant of embodiment 6 is as shown in Figure 1.The modified starch
Sludge flocculant is in 580cm-1There is Fe in left and right3O4Characteristic peak, this is mainly derived from Fe3O4The stretching vibration of middle Fe-O,
In 1022cm-1Locate appearance-CH2Rocking vibration peak, in 1405cm-1There is alkanes C-H in-plane bending vibration characteristic absorption peak in place,
In 2920cm-1There is unsaturation C-H stretching vibration absworption peak in place, in 3405cm-1The strong wide absorption peak in place is in magnetic flocculant
The absorption peak that-OH group stretching vibration in the-OH group and adsorbed constitution water being connected with iron ion generates；Graft copolymerization
Object is respectively in 1528,1645cm-1There is carbonyl and amido characteristic absorption peak in place, in 1022cm-1、1405cm-1、1528cm-1、
1645cm-1、2920cm-1There is the characteristic absorption peak of cornstarch in place, shows that grafting has occurred altogether in cornstarch and acrylamide
Poly- reaction.The product for illustrating synthesis is to contain Fe3O4The cornstarch graft copolymer of nano particle.
Morphological analysis
Embodiment 6 is scanned by microscopic appearance of the transmission electron microscope to above-mentioned nano-magnetic cationic flocculant, institute
It obtains shown in transmission electron microscope TEM Fig. 2.It can be seen that being in gained flocculant rough surface, internal black dough within sweep of the eye
Fe3O4Nano particle shows that the flocculant has successfully loaded nanoscale Fe3O4Particle.
The present invention is prepared for a kind of magnetic cation flocculant using electrochemical method, combines starch graft copolymer and sun
Ionization Modification technique overcomes traditional flocculant by gravitational settling and realizes separation of solid and liquid, the slow disadvantage of the rate of departure.Outside
Under the action of adding magnetic field, wadding body is formed by after magnetic cation flocculant process to be realized fast along magnetic direction displacement
Speed is separated by solid-liquid separation, and provides new idea and method for the preparation and application of flocculant.
Claims (10)
1. a kind of nano-magnetic cationic flocculant, which is characterized in that its structure is load Fe3O4The graft copolymerization of nano particle
Object, the graft copolymer are formed by gelatinized starch and grafted monomers graft copolymerization.
2. the preparation method of nano-magnetic cationic flocculant described in claim 1, which is characterized in that by gelatinized starch and grafting
Comonomer taps into capable branch and is copolymerized and loads Fe simultaneously3O4Then nano particle is prepared through cation modifying.
3. the preparation method of nano-magnetic cationic flocculant as claimed in claim 2, which is characterized in that specifically include following step
It is rapid:
Step 1: graft copolymerization and load Fe3O4Nano particle:
It is cathode by anode, carbon-point of iron plate, connection DC power supply builds electrolytic cell, gelatinized starch is added in electrolytic cell,
Temperature of reaction system is adjusted to 60 DEG C, initiation system is added and is stirred evenly, power supply is opened and is slowly added to graft copolymerization simultaneously
Monomer solution adjusts reaction system to 30 DEG C, and NaOH solution is added dropwise and adjusts pH to 11~12, then reaction system is adjusted to 70
~80 DEG C, Fe is generated by electrochemistry coprecipitation reaction3O4Nano particle, under constant temperature stirring condition, paste starch and acryloyl
Amine graft copolymerization simultaneously coats Fe3O4Nano particle；
Step 2: cation modifying:
70~80 DEG C of constant temperature stirrings are kept, etherifying agent is added, carries out priming reaction, obtains product；
Step 3: washing and drying:
By step 2 products therefrom using water and acetone alternately washing to neutrality, can be obtained after dry, pulverize nano-magnetic sun from
Sub- flocculant.
4. the preparation method of nano-magnetic cationic flocculant as claimed in claim 3, which is characterized in that pasted in the step 1
The preparation method for changing starch includes: to weigh cornstarch and deionized water by the solid-to-liquid ratio of 0.1g/ml, under sealing state, 70 DEG C
Constant temperature is gelatinized 1h, obtains gelatinized starch.
5. the preparation method of nano-magnetic cationic flocculant as claimed in claim 3, which is characterized in that connect in the step 1
Branch comonomer is acrylamide, acrylic acid, styrene, acrylonitrile, dimethyl diallyl ammonium chloride, butadiene and methyl-prop
Any one in e pioic acid methyl ester；Initiation system is that ammonium ceric nitrate-potassium peroxydisulfate causes system, sodium thiosulfate-potassium peroxydisulfate
Initiation system, sodium thiosulfate-ammonium persulfate cause any one in system or sodium thiosulfate-hydrogen peroxide.
6. the preparation method of nano-magnetic cationic flocculant as claimed in claim 3, which is characterized in that connect in the step 1
Branch comonomer solution is acrylamide aqueous solution, and concentration is 0.5~1g/mL, the mass ratio of starch and acrylamide be 1:2~
3。
7. the preparation method of nano-magnetic cationic flocculant as claimed in claim 3, which is characterized in that draw in the step 1
Hair system is that ammonium ceric nitrate-potassium peroxydisulfate causes system, and the injected volume of ammonium ceric nitrate is the 1~2% of acrylamide quality, over cure
The injected volume of sour potassium is the 3~5% of acrylamide quality.
8. the preparation method of nano-magnetic cationic flocculant as claimed in claim 3, which is characterized in that iron in the step 1
Tablet quality is at least the 10~15% of starch and acrylamide gross mass, and it is 5~7V that power supply, which applies voltage,.
9. the preparation method of nano-magnetic cationic flocculant as claimed in claim 3, which is characterized in that in the step 2
Etherifying agent is 2,3- epoxypropyltrimethylchloride chloride, tertiary amine alkyl ether, father-in-law's kind of starch ether, alkyl primary amine ether, secondary amine alkyl ether
With any one in imines starch ether.
10. the preparation method of nano-magnetic cationic flocculant as claimed in claim 3, which is characterized in that in the step 2
Etherifying agent is 2,3- epoxypropyltrimethylchloride chloride；The molar ratio of 2,3- epoxypropyltrimethylchloride chloride and acrylamide is
0.5~0.6:1；The priming reaction time is 2.5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910402117.5A CN110143658A (en) | 2019-05-15 | 2019-05-15 | A kind of nano-magnetic cationic flocculant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910402117.5A CN110143658A (en) | 2019-05-15 | 2019-05-15 | A kind of nano-magnetic cationic flocculant and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110143658A true CN110143658A (en) | 2019-08-20 |
Family
ID=67595310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910402117.5A Pending CN110143658A (en) | 2019-05-15 | 2019-05-15 | A kind of nano-magnetic cationic flocculant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110143658A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111908514A (en) * | 2020-08-12 | 2020-11-10 | 重庆邮电大学 | Preparation method and product of bowl-shaped C-doped magnetic hollow mesoporous nano material |
| CN112939175A (en) * | 2019-12-10 | 2021-06-11 | 河北省科学院能源研究所 | Modified starch flocculant with function of removing heavy metal ions and preparation method and application thereof |
| CN113336959A (en) * | 2021-06-11 | 2021-09-03 | 中国科学院青岛生物能源与过程研究所 | Preparation method of magnetic graft polymer carrier, prepared carrier and application thereof |
| CN113789320A (en) * | 2021-09-29 | 2021-12-14 | 淮阴工学院 | Preparation method of immobilized enzyme with magnetic starch as carrier |
| CN115594265A (en) * | 2021-07-09 | 2023-01-13 | 中国石油化工股份有限公司（Cn） | Flocculation polymer based on magnetic nanoparticles, preparation method and application thereof, and method for treating oily sewage |
| CN117228783A (en) * | 2023-09-07 | 2023-12-15 | 河海大学 | Magnetic ecological flocculation material, micro-polluted water treatment device and micro-polluted water treatment method thereof |
| CN117228783B (en) * | 2023-09-07 | 2024-05-17 | 河海大学 | Magnetic ecological flocculation material, micro-polluted water treatment device and micro-polluted water treatment method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2460064A (en) * | 2008-05-15 | 2009-11-18 | Maria Catherine Tabiner | A method of forming a permanently magnetic absorbent composite material |
| CN108658199A (en) * | 2018-05-03 | 2018-10-16 | 西北民族大学 | Polyferric Sulfate-cornstarch graft composite flocculant and its preparation method and application |
-
2019
- 2019-05-15 CN CN201910402117.5A patent/CN110143658A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2460064A (en) * | 2008-05-15 | 2009-11-18 | Maria Catherine Tabiner | A method of forming a permanently magnetic absorbent composite material |
| CN108658199A (en) * | 2018-05-03 | 2018-10-16 | 西北民族大学 | Polyferric Sulfate-cornstarch graft composite flocculant and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| 孙明东: ""阳离子化淀粉接枝聚丙烯酰胺及其包覆纳米Fe3O4的研究"", 《中国优秀硕士论文全文库 工程科技1辑》 * |
| 林松竹等: "磁性Fe3O4纳米晶的电化学制备及在线混凝过程研究", 《高等学校化学学报》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112939175A (en) * | 2019-12-10 | 2021-06-11 | 河北省科学院能源研究所 | Modified starch flocculant with function of removing heavy metal ions and preparation method and application thereof |
| CN111908514A (en) * | 2020-08-12 | 2020-11-10 | 重庆邮电大学 | Preparation method and product of bowl-shaped C-doped magnetic hollow mesoporous nano material |
| CN111908514B (en) * | 2020-08-12 | 2022-07-08 | 重庆邮电大学 | Preparation method and product of bowl-shaped C-doped magnetic hollow mesoporous nano material |
| CN113336959A (en) * | 2021-06-11 | 2021-09-03 | 中国科学院青岛生物能源与过程研究所 | Preparation method of magnetic graft polymer carrier, prepared carrier and application thereof |
| CN113336959B (en) * | 2021-06-11 | 2022-08-02 | 中国科学院青岛生物能源与过程研究所 | Preparation method of magnetic graft polymer carrier, prepared carrier and application thereof |
| CN115594265A (en) * | 2021-07-09 | 2023-01-13 | 中国石油化工股份有限公司（Cn） | Flocculation polymer based on magnetic nanoparticles, preparation method and application thereof, and method for treating oily sewage |
| CN113789320A (en) * | 2021-09-29 | 2021-12-14 | 淮阴工学院 | Preparation method of immobilized enzyme with magnetic starch as carrier |
| CN117228783A (en) * | 2023-09-07 | 2023-12-15 | 河海大学 | Magnetic ecological flocculation material, micro-polluted water treatment device and micro-polluted water treatment method thereof |
| CN117228783B (en) * | 2023-09-07 | 2024-05-17 | 河海大学 | Magnetic ecological flocculation material, micro-polluted water treatment device and micro-polluted water treatment method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110143658A (en) | A kind of nano-magnetic cationic flocculant and preparation method thereof | |
| Wang et al. | Synthesis and characterization of a novel cationic chitosan-based flocculant with a high water-solubility for pulp mill wastewater treatment | |
| Rabiee et al. | A survey on cationic polyelectrolytes and their applications: acrylamide derivatives | |
| Pal et al. | Synthesis, characterization and flocculation characteristics of cationic glycogen: a novel polymeric flocculant | |
| Banerjee et al. | Study of algal biomass harvesting through cationic cassia gum, a natural plant based biopolymer | |
| Guan et al. | Effect of template on structure and properties of cationic polyacrylamide: characterization and mechanism | |
| Mittal et al. | Preparation of poly (acrylamide-co-acrylic acid)-grafted gum and its flocculation and biodegradation studies | |
| Noor et al. | Synthesis and application of polyacrylamide grafted magnetic cellulose flocculant for palm oil wastewater treatment | |
| Zhang et al. | Impact of molecular structure and charge property of chitosan based polymers on flocculation conditioning of advanced anaerobically digested sludge for dewaterability improvement | |
| Anthony et al. | Cationic starch for microalgae and total phosphorus removal from wastewater | |
| Feng et al. | Better understanding the polymerization kinetics of ultrasonic-template method and new insight on sludge floc characteristics research | |
| Chen et al. | Cationic starch-grafted-cationic polyacrylamide based graphene oxide ternary composite flocculant for the enhanced flocculation of oil sludge suspension | |
| CN107176661A (en) | A kind of preparation method and applications of poly- titanium aluminium chloride PAMC composite flocculation agent | |
| Klein et al. | Preparation of cashew gum-based flocculants by microwave-and ultrasound-assisted methods | |
| Xu et al. | Cu2+ tunable temperature-responsive Pickering foams stabilized by poly (N-isopropylacrylamide-co-vinyl imidazole) microgel: Significance for Cu2+ recovery via flotation | |
| Wang et al. | Kinetics of dispersion polymerization of dimethyl diallyl ammonium chloride and acrylamide | |
| Toh et al. | The role of cationic coagulant-to-cell interaction in dictating the flocculation-aided sedimentation of freshwater microalgae | |
| CN105712494B (en) | A kind of method of microbial flocculant and surfactant coagulating treatment mining industry waste water | |
| CN108299607B (en) | A kind of preparation method and applications of lignin modified object | |
| He et al. | Carbon dioxide and nitrogen-modulated shape transformation of chitosan-based composite nanogels | |
| Liang et al. | Preparation of cationic aggregates derived from sewage sludge for efficient capture of organic matter | |
| CN105753125B (en) | A kind of excellent flocculant of flco sediment dehydration property | |
| CN110669171B (en) | Anionic polyacrylamide and application thereof | |
| CN100558808C (en) | Nano calcium carbonate/polystyrene composite material and preparation method thereof | |
| CN113980295A (en) | Chitosan/sodium alginate hydrogel and preparation method and use method thereof |
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: 20190820 |
|
| RJ01 | Rejection of invention patent application after publication |