CN105199036A - Ammonium acrylate/acrylamide copolymerized emulsion flocculant and preparation method thereof - Google Patents
Ammonium acrylate/acrylamide copolymerized emulsion flocculant and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an ammonium acrylate/acrylamide copolymerized emulsion flocculant and a preparation method thereof, in particular to an emulsion flocculant capable of efficiently treating red mud slurry in the aluminum oxide production process and a preparation method of the flocculant. Acrylic acid, ammonia water and acrylamide are taken as raw materials, a monomer solution is dispersed in an oil phase by the aid of an emulsifier, a water-in-oil (W/O) type emulsion is formed and polymerized, and the anionic emulsion flocculant is prepared. A reverse emulsion polymerization method is adopted, the high polymerization rate and the high molecular weight can be realized simultaneously, and the prepared emulsion is good in stability, high in effective content, easy to reverse, water-soluble, very high in dissolution rate and convenient to use; compared with a flocculant containing a single functional group, the prepared copolymerized flocculant contains multiple functional groups such as carboxylate radicals, amide groups and the like and has various and large action forces with red mud, the settling speed is greatly increased, the flocculating performance is improved, the dosage of the flocculant is decreased, the cost is reduced, and the economic benefit is improved.
Description
Technical field
The invention belongs to Polymer Synthesizing, mineral extract and environmental technology field, relate to a kind of can the anionic emulsion flocculant effectively realizing red-mud settlement in aluminum oxide industry and preparation method thereof.
Background technology
Red mud is the waste material generated in aluminum oxide production process, and its texture is soft, poor fluidity, and particle diameter is little, easily scabs, and between liquid-solid particle, density difference is also little.Along with the development of domestic aluminum oxide industry, the detached job of red mud becomes " bottleneck " in process for making alumina gradually, greatly limit China's alumina producing industrial expansion.Flocculation sedimentation is the method extensively adopted in the external aluminum oxide industry red-mud separation of Present Domestic.Synthetic polymeric flocculant is than early stage natural macromolecule flocculating agent, and the advantage such as, good economy performance few, simple to operate with its good flocculating result, materials, serves irreplaceable effect in alumina producing industry.
In recent years, research both at home and abroad about flocculation agent increases gradually, but mostly adopt water solution polymerization process synthetic product, as Chinese invention patent CN101942052A, CN101831030A, the flocculation agent obtained by water solution polymerization process is mostly powdery or granular, and its water absorbability is strong, causes effective constituent to decline, and dissolution rate is extremely slow, substantially increases use cost.Although scholars is also improving the research enthusiasm of emulsion flocculant at present, but that studies is mostly acrylamide flocculating agent, as Chinese invention patent CN101845105A, or single carboxylate salt flocculation agent, as patent of invention CN101544454A, because contained functional group is single, more weak with red mud reactive force, flocculating settling effect is poor, and acrylamide exists monomer residue toxicity problem, be unfavorable for the health of people, also can pollute environment.Along with the reinforcement of environmental requirement, the development of the flocculation agent that more suitabilities are strong, environmental pollution is little, also will contribute to the development of aluminum oxide industry.
Summary of the invention
In order to solve the problem, the invention provides a kind of anionic acrylic ammonium/acrylamide copoly type emulsion flocculant and preparation method thereof, thus solve powdery that traditional aqueous polymerization obtains or the problem such as granular flocculation agent dissolution rate is slow, consumption is large, and improve the shortcomings such as poor containing single functional group flocculation agent settling property, environmental pollution is serious.
The invention discloses a kind of ammonium acrylate/acrylamide copoly type emulsion flocculant, the molecular formula of described multipolymer is: (CH
2cHCOONH
4)
m(CH
2cHCONH
2)
n.
The invention also discloses a kind of ammonium acrylate/acrylamide copoly type emulsion flocculant and preparation method thereof, preparation process is as follows:
(1) a certain amount of vinylformic acid is mixed with ammoniacal liquor, under condition of ice bath, carry out neutralization reaction, obtained ammonium acrylate solution;
(2) a certain amount of acrylamide is dissolved in water, is made into acrylamide soln;
(3) by ammonium acrylate solution and acrylamide soln mix and blend, add the reaction promoter that quality is 0.005% ~ 0.4% of system total mass wherein, be stirred to and dissolve completely, obtained aqueous phase;
(4) in external phase, add the emulsifying agent that quality is system total mass 2% ~ 12%, stir, obtained oil phase;
(5) oil phase is transferred in reaction flask, the rotating speed of control about 400r/min stirs, pass into nitrogen and drain air in system, under 30 DEG C of water bath condition, adjustment mixing speed is that 800 ~ 1200r/min instills aqueous phase obtained in step (3), after aqueous phase drips off, continue to stir, make it fully emulsified;
(6) control 100 ~ 300r/min rotating speed to stir and bath temperature 40 DEG C ~ 90 DEG C, after reaction 6 ~ 12h, obtain ammonium acrylate/acrylamide copoly type emulsion flocculant;
In above-mentioned steps, wherein, in (3), (4), (5) arbitrary steps, add initiator, described initiator quality is 0.005% ~ 0.4% of system total mass.
The feed postition of described initiator is: added by water soluble starter in described aqueous phase; Or oil-soluble initiator is added in described oil phase; Or the water soluble starter of arbitrary proportion and oil-soluble initiator are added in described aqueous phase and described oil phase respectively.
Described initiator is oil-soluble initiator dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroxide, di-isopropyl peroxydicarbonate, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), nitrogen, one or more in nitrogen-xylidine; Or be water soluble starter hydrogen peroxide, Potassium Persulphate, ammonium persulphate, 2, two (the 2-amidine azoles quinoline propane) hydrochloride, 2 of 2 '-azo, two (2-amidine propane) dihydrochloride, 4 of 2 '-azo, one or more in 4 '-azo two (4-cyanopentanoic acid), S-WAT, sodium bisulfite; Or be oil-soluble initiator, water soluble starter compound use.
Step (1) and (2) middle ammonium acrylate are 1:1 ~ 4:1 with the molar mass ratio of acrylamide.
Reaction promoter described in step (3) is one or more in ethylenediamine tetraacetic acid (EDTA), disodium ethylene diamine tetraacetate, urea.
In step (4), the mass ratio of external phase and the middle aqueous phase of step (3) is 0.6:1 ~ 1.4:1, and described external phase is any one in hexanaphthene, octane-iso, dodecane, the tetradecane, isoparaffin, white oil, aviation kerosene, whiteruss.
Emulsifying agent described in step (4) comprise sorbitan oleate, sorbitol anhydride laurate, polyoxyethylenesorbitan sorbitan monooleate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitol acid anhydride laurate, alkylphenol polyoxyethylene-10 one or more, the HLB value of described emulsifying agent is 5 ~ 9.
The total time passing into nitrogen in step (5) is about 30min, and emulsification total time is 0.5 ~ 2h.Polyreaction described in step (6) reacts 6 ~ 12h between 40 DEG C ~ 90 DEG C, is that a step-up temperature or substep heat up in process.
Principle of the present invention is: with ammonium acrylate and acrylamide for reaction monomers, formed by antiphase emulsifiable method copolymerization, the molecular formula of multipolymer is (CH
2cHCOONH
4)
m-(CH
2cHCONH
2)
n, containing carboxylate radical, ammonium root and amide group, in Bayer digestion of bauxite process in leaching, usually add unslaked lime and promote stripping, make in red mud ore pulp containing more Ca
2+carboxylate radical in multipolymer is by " calcium bridge " ionic linkage and red mud effect, polyacrylic acid calcium deposit is formed at mineral particle surface, this absorption not only selectivity is strong, and chemical bond energy is larger, reactive force is comparatively strong, and carboxyl can also lead to O ... H-O hydrogen bond is combined with red mud surface hydroxyl, thus enhances settlement action; Amide group is high reactivity hydrophilic radical, not charged, by N ... H-O hydrogen bond action is adsorbed on suspended solids surface, bridge company between adsorbed particle is connect, integrated for small-particle large floc sedimentation, thus accelerates red-mud settlement.
Monomer solution for raw material monomer, is dispersed in oil phase by emulsifying agent with vinylformic acid, ammoniacal liquor, acrylamide by the present invention, forms water-in-oil (W/O) type emulsion and is polymerized, preparing anionic emulsion flocculant.Compared with the water solution polymerization process extensively adopted at present, the present invention adopts reversed emulsion polymerization, and polymerization velocity is fast, preparation efficiency is high, prepared emulsion flocculant solid content and molecular weight all higher, good stability, and it is water-soluble to be easy to reversion, dissolution rate is fast, easy to use; In addition, compared with the flocculation agent containing single functional group, the copoly type flocculation agent prepared by the present invention is containing the multiple functional group such as carboxylate radical, amide group, various with the intermolecular forces of red mud, substantially increases flocculating settling characteristics, decreases flocculant usage.
The preparation method of ammonium acrylate of the present invention/acrylamide copoly type emulsion flocculant, successfully can prepare the emulsion flocculant that solid content is high, molecular weight is higher, good stability, dissolution rate fast, toxicity is lower, preparation process is simpler, efficiency is higher, greatly reduce cost, improve benefit.
Accompanying drawing explanation
Fig. 1 is the FT-IR collection of illustrative plates of ammonium acrylate/acrylamide copolymer prepared by antiphase emulsifiable method;
Fig. 2 is the SEM figure of ammonium acrylate/acrylamide copoly type emulsion flocculant;
Fig. 3 is the TEM figure of ammonium acrylate/acrylamide copoly type emulsion flocculant;
Fig. 4 is ammonium acrylate from acrylamide molar mass than the different impact on inverse emulsion copolymer molecular weight (wherein 1 is ammonium acrylate, and 2 is acrylamide);
Fig. 5 is ammonium acrylate from acrylamide molar mass than the impact (wherein 1 be ammonium acrylate, 2 be acrylamide) of copoly type emulsion flocculant time different on red-mud settlement speed;
Fig. 6 be ammonium acrylate from acrylamide molar mass than the impact of copoly type emulsion flocculant time different on supernatant liquor transmittance after red-mud settlement
Fig. 7 is the supernatant liquor transmittance that dissimilar reversed-phase emulsion flocculation agent is corresponding
Embodiment
Preparation method and the character thereof of ammonium acrylate of the present invention/acrylamide copoly type emulsion flocculant is introduced further below by way of specific embodiment.
Embodiment 1: the preparation embodiment 1 of ammonium acrylate/acrylamide copoly type emulsion flocculant
1. prepare aqueous phase:
(1) neutralization reaction: take vinylformic acid 7.2g and ammoniacal liquor 6.8g respectively, dropwise being added drop-wise to by ammoniacal liquor under continuous stirring state in ice-water bath in vinylformic acid (keeps system temperature to be no more than 40 DEG C), after treating that ammoniacal liquor dropwises, continue to stir 10min in ice-water bath, be prepared into ammonium acrylate solution, stand-by;
(2) 7.1g acrylamide is taken, complete by 9.8g water dissolution, be made into acrylamide soln;
(3) ammonium acrylate solution and acrylamide soln are mixed, take ethylenediamine tetraacetic acid (EDTA) 0.04g, add in mixing solutions, magnetic stirring apparatus stirs 30min;
(4) claim Potassium Persulphate 0.035g, with being added to solution in (3) after 3g water dissolution, stirring, obtaining aqueous phase.
2. prepare oil phase: claim 26g white oil, add sorbitan oleate 2.5g wherein, polyoxyethylene sorbitol acid anhydride stearate 1.3g, be placed in stirring on magnetic stirring apparatus and make it fully mix.
3. mixing and emulsifying:
(1) be transferred in four-hole boiling flask by the oil phase mixed, connect reaction unit, arranging rotating speed is 400r/min, while stirring logical nitrogen about 10min;
(2) agitator speed is adjusted to 800r/min, bath temperature is set to 30 DEG C, is transferred in dropping funnel by the aqueous phase prepared, insert nitrogen tube, while lead to nitrogen limit to drip aqueous phase, after dripping off aqueous phase simultaneously, after continuing logical nitrogen 10min, airtight emulsification about 1h under 800r/min rotating speed.
4. polyreaction: after emulsification terminates, arranging temperature of reaction is 60 DEG C, and rotating speed reduces to 200r/min, reaction 6h, then temperature is upgraded to 70 DEG C and continues reaction 2h, finally obtain faint yellow translucent latex.
Embodiment 2: the preparation embodiment 2 of ammonium acrylate/acrylamide copoly type emulsion flocculant
1. prepare aqueous phase:
(1) neutralization reaction: take vinylformic acid 11.5g and ammoniacal liquor 10.9g respectively, dropwise being added drop-wise to by ammoniacal liquor under continuous stirring state in ice-water bath in vinylformic acid (keeps system temperature to be no more than 40 DEG C), after treating that ammoniacal liquor dropwises, continue to stir 10min in ice-water bath, be prepared into ammonium acrylate solution, stand-by;
(2) 2.8g acrylamide is taken, complete by 7.0g water dissolution, be made into acrylamide soln;
(3) ammonium acrylate solution and acrylamide soln are mixed, take ethylenediamine tetraacetic acid (EDTA) 0.04g, add in mixing solutions, magnetic stirring apparatus stirs 30min;
(4) claim ammonium persulphate 0.051g, with being added to solution in (3) after 3g water dissolution, stirring, obtaining aqueous phase.
2. prepare oil phase: claim 28g whiteruss, add sorbitol anhydride laurate 3.9g wherein, be placed in stirring on magnetic stirring apparatus and make it fully mix.
3. mixing and emulsifying:
(1) be transferred in four-hole boiling flask by the oil phase mixed, connect reaction unit, arranging rotating speed is 400r/min, while stirring logical nitrogen about 10min;
(2) agitator speed is adjusted to 900r/min, bath temperature is set to 30 DEG C, is transferred in dropping funnel by the aqueous phase prepared, insert nitrogen tube, while lead to nitrogen limit to drip aqueous phase, after dripping off aqueous phase simultaneously, after continuing logical nitrogen 10min, airtight emulsification about 1h under 900r/min rotating speed.
4. polyreaction: after emulsification terminates, arranging temperature of reaction is 65 DEG C, and rotating speed reduces to 300r/min, reaction 7h, then temperature is upgraded to 75 DEG C and continues reaction 2h, finally obtain faint yellow translucent latex.
Embodiment 3: the preparation embodiment 3 of ammonium acrylate/acrylamide copoly type emulsion flocculant
1. prepare aqueous phase:
(1) neutralization reaction: take vinylformic acid 10.8g and ammoniacal liquor 10.2g respectively, dropwise being added drop-wise to by ammoniacal liquor under continuous stirring state in ice-water bath in vinylformic acid (keeps system temperature to be no more than 40 DEG C), after treating that ammoniacal liquor dropwises, continue to stir 10min in ice-water bath, be prepared into ammonium acrylate solution, stand-by;
(2) 3.55g acrylamide is taken, complete by 4.2g water dissolution, be made into acrylamide soln;
(3) ammonium acrylate solution and acrylamide soln are mixed, take ethylenediamine tetraacetic acid (EDTA) 0.03g, add in mixing solutions, magnetic stirring apparatus stirs 30min;
(4) take initiator 2, two (2-amidine propane) the dihydrochloride 0.051g of 2 '-azo, with being added to solution in (3) after 3g water dissolution, stirring, obtaining aqueous phase.
2. prepare oil phase: claim 24.6g white oil, add sorbitan oleate 3.0g wherein, alkylphenol polyoxyethylene-101.2g, be placed in stirring on magnetic stirring apparatus and make it fully mix.
3. mixing and emulsifying:
(1) be transferred in four-hole boiling flask by the oil phase mixed, connect reaction unit, arranging rotating speed is 400r/min, while stirring logical nitrogen about 10min;
(2) agitator speed is adjusted to 1000r/min, bath temperature is set to 30 DEG C, is transferred in dropping funnel by the aqueous phase prepared, insert nitrogen tube, while lead to nitrogen limit to drip aqueous phase, after dripping off aqueous phase simultaneously, after continuing logical nitrogen 10min, airtight emulsification about 1h under 1000r/min rotating speed.
4. polyreaction: after emulsification terminates, arranging temperature of reaction is 55 DEG C, and rotating speed reduces to 200r/min, reaction 8h, then temperature is upgraded to 75 DEG C and continues reaction 2h, finally obtain faint yellow translucent latex.
Embodiment 4: the preparation embodiment 4 of ammonium acrylate/acrylamide copoly type emulsion flocculant
1. prepare aqueous phase:
(1) neutralization reaction: take vinylformic acid 10.8g and ammoniacal liquor 10.2g respectively, dropwise being added drop-wise to by ammoniacal liquor under continuous stirring state in ice-water bath in vinylformic acid (keeps system temperature to be no more than 40 DEG C), after treating that ammoniacal liquor dropwises, continue to stir 10min in ice-water bath, be prepared into ammonium acrylate solution, stand-by;
(2) 3.55g acrylamide is taken, complete by 14.7g water dissolution, be made into acrylamide soln;
(3) ammonium acrylate solution and acrylamide soln are mixed, take disodium ethylene diamine tetraacetate 0.03g, sodium bisulfite 0.03g, add in mixing solutions, magnetic stirring apparatus stirs 30min;
(4) take Potassium Persulphate 0.03g, with being added to solution in (3) after 2g water dissolution, stirring, obtaining aqueous phase.
2. prepare oil phase: claim 33.8g isoparaffin, add sorbitol anhydride list hard acid ester 3.3g wherein, polyoxyethylene sorbitol acid anhydride stearate 1.6g, be placed in stirring on magnetic stirring apparatus and make it fully mix.
3. mixing and emulsifying:
(1) be transferred in four-hole boiling flask by the oil phase mixed, connect reaction unit, arranging rotating speed is 400r/min, while stirring logical nitrogen about 10min;
(2) agitator speed is adjusted to 800r/min, bath temperature is set to 30 DEG C, is transferred in dropping funnel by the aqueous phase prepared, insert nitrogen tube, while lead to nitrogen limit to drip aqueous phase, after dripping off aqueous phase simultaneously, after continuing logical nitrogen 10min, airtight emulsification about 1h under 800r/min rotating speed.
4. polyreaction: after emulsification terminates, arranging temperature of reaction is 50 DEG C, and rotating speed reduces to 200r/min, and reaction 4h, rises to 60 DEG C by temperature, reaction 4h, rises to 70 DEG C afterwards and continues reaction 2h, finally obtain faint yellow translucent latex.
Embodiment 5: the preparation embodiment 5 of ammonium acrylate/acrylamide copoly type emulsion flocculant
1. prepare aqueous phase:
(1) neutralization reaction: take vinylformic acid 7.2g and ammoniacal liquor 6.8g respectively, dropwise being added drop-wise to by ammoniacal liquor under continuous stirring state in ice-water bath in vinylformic acid (keeps system temperature to be no more than 40 DEG C), after treating that ammoniacal liquor dropwises, continue to stir 10min in ice-water bath, be prepared into ammonium acrylate solution, stand-by;
(2) 7.1g acrylamide is taken, complete by 9.8g water dissolution, be made into acrylamide soln;
(3) ammonium acrylate solution and acrylamide soln are mixed, take ethylenediamine tetraacetic acid (EDTA) 0.04g, urea 0.03g, add in monomer solution, magnetic stirring apparatus stirs 30min, solution left standstill is for subsequent use;
2. prepare oil phase: claim 26g white oil, add dilauroyl peroxide 0.0445g wherein, be stirred to after dissolving completely, add sorbitan oleate 2.5g, polyoxyethylenesorbitan sorbitan monooleate 1.3g, is placed in stirring on magnetic stirring apparatus and makes it fully mix.
3. mixing and emulsifying:
(1) be transferred in four-hole boiling flask by the oil phase mixed, connect reaction unit, arranging rotating speed is 400r/min, while stirring logical nitrogen about 10min;
(2) agitator speed is adjusted to 900r/min, bath temperature is set to 30 DEG C, is transferred in dropping funnel by the aqueous phase prepared, insert nitrogen tube, while lead to nitrogen limit to drip aqueous phase, after dripping off aqueous phase simultaneously, after continuing logical nitrogen 10min, airtight emulsification about 1h under 900r/min rotating speed.
4. polyreaction: after emulsification terminates, arranging temperature of reaction is 65 DEG C, and rotating speed reduces to 300r/min, reaction 8h, then temperature is upgraded to 80 DEG C and continues reaction 3h, finally obtain faint yellow translucent latex.
Embodiment 6: the preparation embodiment 6 of ammonium acrylate/acrylamide copoly type emulsion flocculant
1. prepare aqueous phase:
(1) neutralization reaction: take vinylformic acid 10.8g and ammoniacal liquor 10.2g respectively, dropwise being added drop-wise to by ammoniacal liquor under continuous stirring state in ice-water bath in vinylformic acid (keeps system temperature to be no more than 40 DEG C), after treating that ammoniacal liquor dropwises, continue to stir 10min in ice-water bath, be prepared into ammonium acrylate solution, stand-by;
(2) 3.55g acrylamide is taken, complete by 7.25g water dissolution, be made into acrylamide soln;
(3) ammonium acrylate solution and acrylamide soln are mixed, take ethylenediamine tetraacetic acid (EDTA) 0.03g, join in monomer solution, after magnetic stirring apparatus stirs 30min, stand for standby use;
(4) take initiator ammonium persulfate 0.0306g, with being added to solution in (3) after 2g water dissolution, stirring, obtaining aqueous phase.
2. prepare oil phase: claim 27.04g octane-iso, add 2,2'-Azobis(2,4-dimethylvaleronitrile) 0.037g wherein, after stirring and dissolving is complete, add 2.58g, polyoxyethylenesorbitan sorbitan monooleate 1.36g, is placed in stirring on magnetic stirring apparatus and makes it fully mix.
3. mixing and emulsifying:
(1) be transferred in four-hole boiling flask by the oil phase mixed, connect reaction unit, arranging rotating speed is 400r/min, while stirring logical nitrogen about 10min;
(2) agitator speed is adjusted to 1000r/min, bath temperature is set to 30 DEG C, is transferred in dropping funnel by the aqueous phase prepared, insert nitrogen tube, while lead to nitrogen limit to drip aqueous phase, after dripping off aqueous phase simultaneously, after continuing logical nitrogen 10min, airtight emulsification about 1h under 1000r/min rotating speed.
4. polyreaction: after emulsification terminates, arranging temperature of reaction is 55 DEG C, and rotating speed reduces to 200r/min, reaction 8h, then temperature is upgraded to 75 DEG C and continues reaction 2h, finally obtain faint yellow translucent latex.
Embodiment 7: the relevant characterization of ammonium acrylate/acrylamide copoly type emulsion flocculant and performance test:
1.FT-IR collection of illustrative plates: emulsion acetone breakdown of emulsion is washed, the solid obtained is placed in vacuum drying oven and is dried to constant weight, dried sample is mixed with KBr, grinds, compressing tablet, adopt model to be that Tensor27 type Fourier infrared spectrograph (FT-IR) characterizes sample, its result as shown in Figure 1.3143cm as can be seen from Figure 1
-1neighbouring is NH
4 +the stretching band of upper N-H and CONH
2the stretching band acting in conjunction result of upper N-H, 1671cm
-1neighbouring is CONH
2the stretching vibration peak of upper C=O, 1569cm
-1and 1402cm
-1respectively there is a peak at place, and be respectively the C=O symmetrical stretching vibration peak on carboxylate salt and asymmetrical stretching vibration peak, can infer thus, polymerisate is the multipolymer of ammonium acrylate and acrylamide.
2.SEM schemes: get appropriate flocculation agent emulsion, post-drying is diluted with sherwood oil, in metal ion sputtering instrument after metal spraying, observe pattern and the size of latex particle under being placed in S-4800 II field emission scanning electron microscope (SEM), its result as shown in Figure 2.As can be seen from Figure 2, it is spherical that latex particle is rule substantially, and particle diameter is mostly in 200 ~ 500nm scope.
3.TEM schemes: get appropriate flocculation agent emulsion, and drop in sample preparation on copper mesh with after sherwood oil dilution, under Tecnai12 type transmission electron microscope (TEM), observe pattern and the size of latex particle, its result as shown in Figure 3.As can be seen from Figure 3, latex particle be substantially rule spherical, particle diameter mostly at about 300nm, this result and SEM result basically identical.
4. according to the relative molecular mass of GB12005.1-89 and G/T12005.10-92 with determination of ubbelohde viscometer polymkeric substance.The X-coordinate of Fig. 4 is that ammonium acrylate (wherein 1 represents ammonium acrylate with the molar mass ratio of acrylamide, 2 represent acrylamide), ordinate zou is the molecular weight of reversed-phase emulsion copolymerization product, as can be seen from Figure 4, when ammonium acrylate and acrylamide molar mass are than when being 3:1, the molecular weight of reversed-phase emulsion copolymerization product is maximum, is 2.25 × 10
6.
5. red-mud settlement performance test:
Take a certain amount of known flocculation agent emulsion admittedly contained, add anti-phase dose of Tween-80 on a small quantity, make polymkeric substance depart from the parcel of oil phase, enter into the aqueous solution, the NaOH solution of preparation 20g/L, dissolve with it flocculant solution that emulsion is mixed with mass concentration 0.2%.Be added in a certain amount of sodium aluminate solution by dry for 8.0g red mud, stir and be diluted to 110mL, being mixed with Nk is 100g/L, the solid dilution ore pulp containing being 80g/L.Above-mentioned dilution ore pulp is heated to boil, then adds 0.5mL flocculant solution, to pour into rapidly after stirring in 100mL graduated cylinder and to be placed in 95 DEG C of waters bath with thermostatic control.Start timing when red mud slurry liquid/solid interface drops to l00mL scale, record red mud slurry liquid/solid interface drops to 80mL required time t (s), and is converted into red-mud settlement speed v, Unit/mL/s.After sedimentation 10min, under 400 ~ 800nm wavelength, survey supernatant liquor transmittance with ultraviolet-visible pectrophotometer, in order to judge supernatant liquor clarity.
1) ammonium acrylate and acrylamide molar mass than copoly type emulsion flocculant time different on the impact of red-mud settlement speed, as shown in Figure 5.As can be seen from Figure 5, when ammonium acrylate and acrylamide molar mass are than when being 3:1, flocculation settling velocity is the fastest.
2) ammonium acrylate and acrylamide molar mass are than the impact of copoly type emulsion flocculant time different on supernatant liquor transmittance after red-mud settlement, as shown in Figure 6,1 to 5 ammonium acrylate is respectively with acrylamide molar mass than the supernatant liquor transmittance recorded when being 3:1,4:1,2:1,1:1 and 0 (wherein 0 curve is do not add flocculation agent).As can be seen from Figure 6, when ammonium acrylate and acrylamide molar mass are than during for 3:1, supernatant liquor transmittance is the strongest, and namely flocculating settling characteristics is best.
3) under identical condition, ammonium polyacrylate emulsion flocculant 7, sodium polyacrylate emulsion flocculant 8, polyacrylamide emulsion flocculation agent 9, sodium acrylate/acrylamide copoly type emulsion flocculant 10 has been prepared again by antiphase emulsifiable method, compare with ammonium acrylate/acrylamide copoly type emulsion flocculant 6, as shown in Figure 7, the settling time is as shown in table 1 below for supernatant liquor transmittance.As can be seen from Figure 7, after adopting ammonium acrylate/acrylamide copoly type emulsion flocculant to carry out red-mud settlement, supernatant liquor transmittance is the strongest.As seen from Table 1, ammonium acrylate/acrylamide copoly type emulsion flocculant red-mud settlement is fastest, and shortest time, only needs 3s.No matter synthesizing map 7 and table 1 are supernatant liquor transmittance or settling velocity, all prove that ammonium acrylate/acrylamide copoly type emulsion flocculant red-mud settlement performance is best.
The red-mud settlement time that the dissimilar emulsion flocculant of table 1 is corresponding
The above; it is only preferred embodiment of the present invention; not any pro forma restriction is done to the present invention; any those skilled in the art; do not departing within the scope of technical solution of the present invention; according to technical spirit of the present invention, any simple amendment that above embodiment is done, equivalently replace and improve, within the protection domain all still belonging to technical solution of the present invention.
Claims (10)
1. ammonium acrylate/acrylamide copoly type emulsion flocculant, is characterized in that: the molecular formula of described multipolymer is:
(CH
2CHCOONH
4)
m(CH
2CHCONH
2)
n。
2. ammonium acrylate/acrylamide copoly type emulsion flocculant and preparation method thereof, is characterized in that:
Preparation process is as follows:
(1) a certain amount of vinylformic acid is mixed with ammoniacal liquor, under condition of ice bath, carry out neutralization reaction, obtained ammonium acrylate solution;
(2) a certain amount of acrylamide is dissolved in water, is made into acrylamide soln;
(3) by ammonium acrylate solution and acrylamide soln mix and blend, add the reaction promoter that quality is 0.005% ~ 0.4% of system total mass wherein, be stirred to and dissolve completely, obtained aqueous phase;
(4) in external phase, add the emulsifying agent that quality is system total mass 2% ~ 12%, stir, obtained oil phase;
(5) oil phase is transferred in reaction flask, the rotating speed of control about 400r/min stirs, pass into nitrogen and drain air in system, under 30 DEG C of water bath condition, adjustment mixing speed is that 800 ~ 1200r/min instills aqueous phase obtained in step (3), after aqueous phase drips off, continue to stir, make it fully emulsified;
(6) control 100 ~ 300r/min rotating speed to stir and bath temperature 40 DEG C ~ 90 DEG C, after reaction 6 ~ 12h, obtain ammonium acrylate/acrylamide copoly type emulsion flocculant;
In above-mentioned steps, wherein, in (3), (4), (5) arbitrary steps, add initiator, described initiator quality is 0.005% ~ 0.4% of system total mass.
3. ammonium acrylate/acrylamide copoly type emulsion flocculant as claimed in claim 2 and preparation method thereof, is characterized in that: the feed postition of described initiator is: added by water soluble starter in described aqueous phase; Or oil-soluble initiator is added in described oil phase; Or the water soluble starter of arbitrary proportion and oil-soluble initiator are added in described aqueous phase and described oil phase respectively.
4. ammonium acrylate/acrylamide copoly type emulsion flocculant as claimed in claim 2 and preparation method thereof, it is characterized in that: described initiator is oil-soluble initiator dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroxide, di-isopropyl peroxydicarbonate, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), nitrogen, one or more in nitrogen-xylidine; Or be water soluble starter hydrogen peroxide, Potassium Persulphate, ammonium persulphate, 2, two (the 2-amidine azoles quinoline propane) hydrochloride, 2 of 2 '-azo, two (2-amidine propane) dihydrochloride, 4 of 2 '-azo, one or more in 4 '-azo two (4-cyanopentanoic acid), S-WAT, sodium bisulfite; Or be oil-soluble initiator, water soluble starter compound use.
5. ammonium acrylate/acrylamide copoly type emulsion flocculant as claimed in claim 2 and preparation method thereof, is characterized in that: step (1) and (2) middle ammonium acrylate are 1:1 ~ 4:1 with the molar mass ratio of acrylamide.
6. ammonium acrylate/acrylamide copoly type emulsion flocculant as claimed in claim 2 and preparation method thereof, is characterized in that: the reaction promoter described in step (3) is one or more in ethylenediamine tetraacetic acid (EDTA), disodium ethylene diamine tetraacetate, urea.
7. ammonium acrylate/acrylamide copoly type emulsion flocculant as claimed in claim 2 and preparation method thereof, it is characterized in that: in step (4), the mass ratio of external phase and the middle aqueous phase of step (3) is 0.6:1 ~ 1.4:1, and described external phase is any one in hexanaphthene, octane-iso, dodecane, the tetradecane, isoparaffin, white oil, aviation kerosene, whiteruss.
8. ammonium acrylate/acrylamide copoly type emulsion flocculant as claimed in claim 2 and preparation method thereof, it is characterized in that: emulsifying agent described in step (4) comprise sorbitan oleate, sorbitol anhydride laurate, polyoxyethylenesorbitan sorbitan monooleate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitol acid anhydride laurate, alkylphenol polyoxyethylene-10 one or more, the HLB value of described emulsifying agent is 5 ~ 9.
9. ammonium acrylate/acrylamide copoly type emulsion flocculant as claimed in claim 2 and preparation method thereof, is characterized in that: the total time passing into nitrogen in step (5) is about 30min, and emulsification total time is 0.5 ~ 2h.
10. ammonium acrylate/acrylamide copoly type emulsion flocculant as claimed in claim 2 and preparation method thereof, it is characterized in that: polyreaction described in step (6) reacts 6 ~ 12h between 40 DEG C ~ 90 DEG C, is that a step-up temperature or substep heat up in process.
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| CN117050229A (en) * | 2023-10-11 | 2023-11-14 | 矿冶科技集团有限公司 | Emulsion type alumina red mud sedimentation flocculant and preparation method thereof |
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