CN1331770C - Flocculant of cation of millicron SiOx compound polyacrylamide and preparing method thereof - Google Patents
Flocculant of cation of millicron SiOx compound polyacrylamide and preparing method thereof Download PDFInfo
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- CN1331770C CN1331770C CNB021523207A CN02152320A CN1331770C CN 1331770 C CN1331770 C CN 1331770C CN B021523207 A CNB021523207 A CN B021523207A CN 02152320 A CN02152320 A CN 02152320A CN 1331770 C CN1331770 C CN 1331770C
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Abstract
The present invention relates to a nanometer SiOx composite polyacrylamide cation flocculant and a preparation method thereof. The flocculant is prepared by the way that surface modification is carried out to nanometer SiOx by a coupling agent; modified nanometer SiOx is dispersed in a water solution which comprises acrylamide; free radical solution polymerization is initiated by a compounded initiator to obtain nanometer SiOx composite polyacrylamide gel; and then, functionalization reaction is carried out to the obtained gel with HCHO, HN(CH3)2 and BrCH2CH3 by means of Mannich reaction to obtain the nanometer SiOx composite polyacrylamide cation flocculant. The flocculant has the characteristics of moderate molecular weight, high flocculating speed, good antiageing degradation performance, fewer residual monomers, etc.
Description
Technical field
The present invention relates to the cationic flocculant in a kind of water treatment, especially a kind of nanometer SiOx composite polyacrylamide cationic flocculant and preparation method thereof.
Background technology
Flocculation is the important technical links of sewage treatment process with coagulation, only just can finish wastewater treatment alone with flocculation and coagulation process under some situation.Therefore, flocculation agent and coagulating agent are the importances of new process for treating waste water and new material development exploitation, and corresponding product amount is huge, various in style.Compare with other flocculation agent, polyacrylamide and derivatives class flocculation agent thereof have advantages such as consumption is few, flocculation rate fast, the mud growing amount is few, and the application aspect water treatment, particularly wastewater treatment is very extensive, and still in fast development.Polyacrylamide is the free yl solution polymerization preparation by acrylamide, and also uses with aqueous solution state as the polyacrylamide of flocculation agent or coagulating agent, yet commercially available polyacrylamide generally is Powdered dry state product.This be because liquid polyacrylamide in transportation and storage, thereby the cause that the degraded sex change loses flocculation or coagulation effect easily takes place.Liquid polyacrylamide will dehydrate storage, and the dry state polyacrylamide is dissolved in water before using again, not only consumes energy but also waste water resource and form wastewater pollution source.The dissolution rate of dry state polyacrylamide and derivative thereof is slow, dissolving needs dozens of minutes even several hrs fully, change event because of some physicochemical property in its drying process again, always have a certain amount of screenings to exist in the dissolution process of dry state polyacrylamide and derivative thereof, bothersome effort is wasted resource again.Simultaneously, the polyacrylamide solution that dissolving prepares must use up as early as possible, otherwise can lose the flocculation effect because of its degradation with aging, and storage period generally can not be above 48 hours.Therefore, the development of novel form high-performance polypropylene acid amides and derivatives class flocculation agent thereof is significant.
Nanoparticle is widely used in polymer modification because of nano effects such as its quantum size effect, small-size effect, surface effects and macro quanta tunnel effects, and has formed the series of new techniques high performance material.The hydroxyl that there is different residual bonds in nanometer SiOx surface and is in different bonding states has very high surfactivity, and it helps strengthening the ageing resistance of macromolecular material to the strong absorption of UV-light and to the good reflection effect of infrared light.Yet the agglomeration of nanoparticle is affected its dispersion in macromolecular material, only depends on the physical mixed effect to be difficult in the Polymer Systems and is uniformly dispersed.
Disclose a kind of " nanometer ultra-high efficiency flocculating agent " among the Chinese patent application CN1303821A, this flocculation agent is with SiOx and Al
2O
3Be scattered in the various polyacrylamide flocculants in the mechanical stirring mode Deng metal oxide nanoparticles; Because SiOx and Al
2O
3Deng the agglomeration of metal oxide nanoparticles, make its dispersion effect in polymeric flocculant relatively poor.U.S. Pat 5176891 is disclosed to be the blend of poly-aluminosilicate slightly soluble glue of nano level and polyacrylamide cationic polymers; U.S. Pat 6361653 is disclosed to be that gluey borosilicate and polyacrylamide or other positively charged ions are as the application of flocculation agent in papermaking.
Summary of the invention
The objective of the invention is for a kind of nanometer SiOx composite polyacrylamide cationic flocculant is provided, this flocculation agent has the entanglement effect of electric neutrality positively charged ion, superpower adsorptivity nanometer SiOx and high-molecular weight polymer chain simultaneously, constitute effectively collaborative flocculation system and improved its flocculating property, in addition because the introducing of nanometer SiOx, effectively alleviated the absorption Degradation of polyacrylamide chain, made flocculation agent have good ageing resistance light.
Another object of the present invention is for a kind of preparation method of nanometer SiOx composite polyacrylamide cationic flocculant is provided, this method is that the SiOx after the modification is introduced polyacrylamide, SiOx can be scattered in the polyacrylamide well, and form the correlated performance that improves polyacrylamide than the dispersion system of homogeneous.
Purpose of the present invention can realize by following measure:
A kind of nanometer SiOx composite polyacrylamide cationic flocculant, this flocculation agent is to add modified Nano SiOx when preparing polyacrylamide technology with known method, x is 1.2-1.6 in the formula, and cause the free yl solution polymerization reaction with redox initiator and obtain nanometer SiOx composite polyacrylamide hydrogel, then nanometer SiOx composite polyacrylamide hydrogel is carried out reaction kinetic and obtain nanometer SiOx composite polyacrylamide cationic flocculant.
Described modified Nano SiOx carries out modification at nanometer SiOx with coupling agent; Described coupling agent is (γ-propylene oxide base) propyl group-triethoxyl silane.
Described redox initiator is oxygenant ammonium persulphate and reductive agent N, N, and N ', the N '-Tetramethyl Ethylene Diamine aqueous solution, its redox initiator of adding are oxygenant ammonium persulphate and reductive agent sodium sulfite aqueous solution; Oxygenant is identical with the equivalence ratio of reductive agent.
It is described that nanometer SiOx composite polyacrylamide hydrogel is carried out reaction kinetic is that nanometer SiOx composite polyacrylamide hydrogel is carried out Mannich cation modifying reaction with formaldehyde, dimethylamine and monobromethane.
Another object of the present invention also can realize by following measure:
A kind of preparation method of nanometer SiOx composite polyacrylamide cationic flocculant comprises the steps:
(1) carries out surface modification and the modification of nanometer SiOx earlier;
(2) Preparation of Polyacrylamide and compound with nanometer SiOx;
A, be 1 by mass ratio: after (6-10) in modified Nano SiOx, adding water white suspension liquid;
B, in the above-mentioned a white suspension liquid in step, add acrylamide react acrylamide and nanometer SiOx dispersion liquid; Wherein modified Nano SiOx and acrylamide mass ratio (2-6): 100.
0.3-0.5% by quality in the dispersion liquid in c, above-mentioned b step adds redox initiator, at room temperature reacts 1-3 after individual hour; Be warming up to 40-55 ℃, reaction got reaction solution in 1-3 hour; The 0.15-0.3% initiator of adding the acrylamide quality again in reaction solution continues reaction and promptly gets white nanometer SiOx composite polyacrylamide hydrogel after 0.5-2 hour;
(3) nanometer SiOx composite polyacrylamide hydrogel is carried out known cation modifying.
The preparation method of described nanometer SiOx composite polyacrylamide cationic flocculant is characterized in that in above-mentioned (2) a step also being included between the step with b and feeds nitrogen in acrylamide and the nanometer SiOx dispersion liquid with removal oxygen.
The surface modification of described nanometer SiOx and modification comprise the steps: by volume 1: (1-3) add the absolute alcohol kind solvent at nanometer SiOx and soak, be 1 then by volume in the alcoholic solution of above-mentioned SiOx: (1-3) add coupling agent, sonic oscillation reaction 1-4 hour gets the nanometer SiOx of modification again with ethanol-extracted; X among the SiOx is 1.2-1.6.
Coupling agent in above-mentioned (1) step is (γ-propylene oxide base) propyl group-triethoxyl silane.
SiOx also comprised the reaction of employing sonic oscillation after adding water during above-mentioned (2) a went on foot.
Nanometer SiOx composite polyacrylamide hydrogel described in above-mentioned (3) step carry out known cation modifying comprise the steps: with formaldehyde and dimethylamine by volume 0.4-1.0 mix, the pH that regulates mixture is 3-4, (0.5-0.8) by volume: 1.0 join said mixture in the nanometer SiOx composite polyacrylamide hydrogel, and re-adjustment reaction system pH is 8-9; Reacted 1-3 hour down at 30-45 ℃; When above-mentioned reacted colloidal sol is diluted to 4-5 times of original volume, press formaldehyde and monobromethane volume ratio 1: (0.5-2), add monobromethane in the thin liquid above-mentioned releasing, after at room temperature stirring reaction 12-30 hour, promptly get nanometer SiOx composite polyacrylamide cationic flocculant.
The redox initiator of described (2) c in the step is oxygenant ammonium persulphate and reductive agent N, N, and N ', the N '-Tetramethyl Ethylene Diamine aqueous solution, its redox initiator of adding are oxygenant ammonium persulphate and reductive agent sodium sulfite aqueous solution; Oxygenant is identical with the equivalence ratio of reductive agent.
The present invention has following advantage compared to existing technology:
1, flocculation agent of the present invention has the entanglement effect of electric neutrality positively charged ion, superpower adsorptivity nanometer SiOx and high-molecular weight polymer chain, nano effects such as the quantum size effect of nanoparticle, small-size effect, surface effects and macro quanta tunnel effect particularly, improved absorption and the bridge formation function of polyacrylamide exponentially, constituted effectively collaborative flocculation system and improved flocculating property suspended particles in the water body.
2, the present invention is owing to introduce nanometer SiOx, and there is the hydroxyl of different residual bonds and different bonding states in nanometer SiOx surface, so flocculation agent of the present invention has very high surfactivity, UV-light had strong sorption and also very big to the reflection potential of infrared light, alleviated the absorption Degradation of polyacrylamide chain to light effectively, the introducing of nanometer SiOx makes flocculation agent have good ageing resistance.
3, flocculation agent of the present invention, can there be room temperature environment in the good anti-ageing performance that has because of the introducing of nanometer SiOx and degrade with gel state; Both save the Drying of gels process, also save dry powder flocculating agent dissolution process before use, improved flocculating property, reduced the environmental pollution in product energy consumption and the production process.
4, flocculation agent of the present invention can be used for the mud flocculation dewatering process of sewage disposal, also can be used for the precipitation process of coagulation of sewage disposal, and can partly remove COD in the sewage, NH
4 +Pollutents such as-N.
5, preparation method of the present invention is by nanometer SiOx is carried out modification with coupling agent, according to the theory of chemical bonds of coupling agent, coupling agent can improve the consistency of organism and inorganics and then make that the two is compound well, forms than the dispersion system of homogeneous and improve correlated performance; The present invention utilizes coupling agent that nano material SiOx is carried out surface modification and makes it to have reactive group under the ultra-sonic dispersion effect; Reacting nano SiOx adds when preparation polyacrylamide colloidal sol, by the ultra-sonic dispersion and IPN and inclusion iris action that the dispersed with stirring effect and the acrylamide polymerization of polymerization process become the macromole process in early stage, nanometer SiOx is dispersed in constitutes stabilized nano composite high-molecular system in the synthetic polyacrylamide colloidal sol; Then, with HCHO, HN (CH
3)
2And BrCH
2CH
3And carry out cationization by Mannich reaction pair gained colloidal sol and react, promptly get nanometer SiOx composite polyacrylamide cationic flocculant.This is a kind of nanometer SiOx composite polyacrylamide class flocculation agent that exists with aqueous solution state, neither needs to dehydrate the stirring and dissolving process of also having saved when using, and can standing storage and degradation with aging not.
Concrete embodiment
Embodiment 1:
A kind of nanometer SiOx composite polyacrylamide cationic flocculant, this flocculation agent is to add through (γ-propylene oxide base) propyl group-triethoxyl silane to carry out the nanometer SiOx of modification when known preparation polyacrylamide technology, x is 1.2-1.6 in the formula, and with ammonium sulfate solution and N, N, N ', N '-Tetramethyl Ethylene Diamine initiator solution causes the free yl solution polymerization reaction and obtains nanometer SiOx composite polyacrylamide hydrogel, then with nanometer SiOx composite polyacrylamide hydrogel formaldehyde, dimethylamine and monobromethane carry out the reaction of Mannich cation modifying and obtain nanometer SiOx composite polyacrylamide cationic flocculant.
The preparation method of above-mentioned flocculation agent comprises the steps:
(1) surface modification of nanometer SiOx particle and modification
The nanometer SiOx that gets the trade mark and be DP1 is in container, in nanometer SiOx, added absolute soaked in absolute ethyl alcohol in 1: 1.5 by volume, be 1: 1 adding (γ-propylene oxide base) propyl group-triethoxyl silane more by volume, sonic oscillation reaction 2 hours, after drying in the infrared drying oven, extracting is after 4 hours continuously in Soxhlet extractor with a certain amount of dehydrated alcohol, and preserve in the exsiccant bottle dry back.
(2) Preparation of Polyacrylamide and compound with nanometer SiOx
A, take into account in the container of spherical condensating tube in that electronic stirring, nitrogen conduit, temperature are housed, add deionized water, press modified Nano SiOx and quality than 1/9 adding modified Nano SiOx, sonic oscillation must white suspension liquid after 30 minutes;
B, in above-mentioned white suspension liquid, press modified Nano SiOx and acrylamide mass ratio 3/97 and add acrylamide stirring at room reaction 30 minutes; And logical nitrogen 5 minutes to be driveing oxygen,
The 0.3-0.5% that presses the acrylamide quality in the dispersion liquid in c, above-mentioned b step adds redox initiator, at room temperature reacts 1-3 hour; After be warming up to 40-55 ℃, reaction 1-3 hour reaction solution; The 0.15-0.3% initiator of adding the acrylamide quality again in reaction solution continued reaction after 0.5-2 hour, promptly got nanometer SiOx composite polyacrylamide hydrogel;
(3) cation modifying of nanometer SiOx composite polyacrylamide hydrogel
With formaldehyde and dimethylamine by volume 0.6-1.0 mix, the pH that regulates mixture is 3-4, said mixture joined in the nanometer SiOx composite polyacrylamide hydrogel in 0.75: 1.0 by volume, be 8 with NaOH solution regulation system pH again; Reacted 2 hours down at 35 ℃; Above-mentioned reacted colloidal sol is diluted to 35% o'clock of original volume concentration, presses formaldehyde and monobromethane volume ratio and add monobromethane at 1: 1, stir insulation reaction down after 24 hours, promptly get nanometer SiOx composite polyacrylamide cationic flocculant at 30 ℃.
Embodiment 2:
The storage stability test of nanometer SiOx composite polyacrylamide cationic flocculant:
The nanometer SiOx composite polyacrylamide cationic flocculant of 2% concentration is measured its flocculating property to kaolin manual simulation sewage after room temperature is placed 4 months, its settling time is 11.5 seconds; The nano combined polyacrylamide cationic flocculant of the certain density SiOx aqueous solution is in-12 ℃ environment after freezing one week of placement, the initial settlement time that records flco is 11.3 seconds, water transparency is constant substantially, basic identical settling velocity (9.8 seconds) in the nanometer SiOx of instant configuration composite polyacrylamide cationic flocculant, its mode of appearance and viscosity thereof do not change substantially yet simultaneously, demonstrate good ageing resistance.
Embodiment 3:
The coagulation performance test of nanometer SiOx composite polyacrylamide cationic flocculant:
Gather city domestic sewage, oil refinery company's containing wastewater from catalyst and Metal smelting factory effluent, carried out coagulation experiment in the laboratory.It is fast that the result shows that the nano combined polyacrylamide cationic flocculant of this SiOx has a flocculation rate, better to the clearance of the SS in three kinds of waste water, and can partly remove COD and NH in the aforementioned waste water
4 +-N demonstrates good coagulation property.The results are shown in Table 1, table 2 and table 3 column data.
1) city domestic sewage outward appearance: faint yellow, there is the black suspension thing to have water temperature: 19 ℃.Pungent stench is arranged, and whole water body has certain viscosity, about pH:7.6.
Table 1 city domestic sewage result
| Index | Former water | Treating water | Clearance (%) |
| COD(mg/L) | 295.96 | 228.34 | 22.85 |
| SS(mg/L) | 1596 | 63.34 | 96.00 |
2) oil refinery company containing wastewater from catalyst outward appearance: white suspension liquid has a large amount of suspended substances to exist, for Catalyst Production is handled composite waste, mainly be support of the catalyst silicon-dioxide, and various catalyst metal ion, strong ammonia flavor is arranged, water temperature: 39 ℃, about pH:8.35.
Table 2 oil refinery company containing wastewater from catalyst result
| Index | COD(mg/L) | NH 4 +-N(mg/L) | SS(mg/L) |
| Former water | 1249.01 | 28096.5 | 3120 |
| Treating water | 464.01 | 25063.5 | 110 |
| Clearance | 62.87％ | 10.57％ | 96.47％ |
3) Metal smelting factory effluent outward appearance: no stink has the smell of light petroleum hydrocarbon.There is minimum white particulate material to exist.Main component is some rare earth oxides and metal ion match.About pH:1.32.Water temperature: 21 ℃.
Table 3 Metal smelting production wastewater treatment result
| Index | COD(mg/L) | NH 4 +-N(mg/L) | SS(mg/L) |
| Former water | 344.54 | 27169. | 2120 |
| Treating water | 344.1 | 23252.31 | 1525 |
| Clearance | 0％ | 14.42％ | 28.07％ |
Embodiment 4:
The mud flocculation dewatering performance test of nanometer SiOx composite polyacrylamide cationic flocculant:
The mud flocculation dewatering test of nanometer SiOx composite polyacrylamide cationic flocculant divides laboratory test and industrial experimentation two portions content, and all tests are all carried out at scene, municipal sewage plant, Lanzhou.
1) the SiOx composite polyacrylamide cationic flocculant of laboratory test 5% concentration is at indoor storage after 4 weeks, and to be mixed with concentration be 0.1%, 0.2% in dilution respectively, 0.3%, 0.4% dilute solution is found this type flocculation agent dissolving rapidly in the dilution, dissolving evenly.It is (not nitrated to get the residual active sludge of 50mL after concentrating, water ratio 96.7%) as test mud sample, join in the 250mL beaker, to add 50mL concentration then be 0.4% flocculant solution and add water to 100mL, evenly stir with glass stick, observed reaction result is: flocculation agglomerate moment forms, the agglomerate volume is big, flco is closely knit, muddy water layering boundary line is obvious, the sense organ no suspended substance only slightly is yellow in the water layer, but certain turbidity is arranged, the dosage of used flocculant solution when writing down best flocculating effect.Simultaneously, successively with 0.3%, 0.2%, the flocculant solution of 0.1% concentration adds in the same mud sample, the dosage of used flocculant solution when observing and writing down best flocculating effect.The amount of consumption of drugs that each concentration flocculant solution dosage calculates when testing best flocculating effect according to every group sees Table 4.
Table 4 different concns flocculant solution dosage and amount of consumption of drugs thereof
| Flocculant concentration (%) | Optimal addn (mL) | Amount of consumption of drugs ‰ (dried medicine/dried mud) |
| 0.6 | 1.5 | 2.7 |
| 0.5 | 2.0 | 3.0 |
| 0.4 | 2.0 | 2.4 |
| 0.3 | 3.0 | 2.7 |
| 0.2 | 5.0 | 3.0 |
| 0.1 | 12.0 | 3.6 |
2) productivity sludge dewatering test sludge dewatering equipment model is HD-2000, and rotating cylinder concentrates the dehydration of press filtration form, and Yixing, Jiangsu produces.Strainer is wide 2 meters, 4 meters/minute of tape running speeds, and last filter cloth pressure 0.3MPa, following filter cloth pressure 0.2Mpa concentrates stirring velocity 80%.The dehydration shale for the second pond excess sludge concentrate after nitrifying sludge not, its water ratio 96.5%-96.7%.The dissolving of flocculant solution, dosing process are finished by automatic medicament feeding machine, and working concentration is constantly adjusted with process of the test between 1-5 ‰.The observations of gained sludge dewatering test is as follows:
(1) used flocculation agent dissolves in molten medicine process rapidly evenly, and no cotton-shaped residue in the solution, other solid PAM flocculation agent then have cotton-shaped residue when dissolving.
(2) used flocculation agent is in last machine test, and medicament and mud flocculation are even, and flocculation group particle is big, and filter cake more easily peels off, and the mud cake volume is big, and is flexible, and filtrate is more clear, slightly displaing yellow.Nanometer SiOx composite polyacrylamide cationic flocculant can overcome other flocculant products when high loading sludge dewatering is turned round, flocculating property reduces maybe to be needed to improve the problem that its working concentration can normally move, the lower and stable distinguishing feature of working concentration when demonstrating high loading sludge dewatering running.Productivity sludge dewatering testing data is listed in table 5, and its flocculation agent consumption reflects excellent operation stability with basic identical when the coagulating agent.
Table 5 productivity sludge dewatering testing data
| Former mud water ratio (%) | Moisture content of the cake (%) | Hmc (mm) | Filtrate settling ratio (SV %) | In the dosing (L/h) | Flocculation agent consumption (dried medicine/dried mud, ‰) |
| 96.7 | 76.8 | 5 | 3 | 300-330 | 2.8-3.0 |
Claims (10)
1, a kind of nanometer SiOx composite polyacrylamide cationic flocculant, this flocculation agent is to add modified Nano SiOx when preparation polyacrylamide technology, x is 1.2-1.6 in the formula, and cause the free yl solution polymerization reaction with redox initiator and obtain nanometer SiOx composite polyacrylamide hydrogel, then nanometer SiOx composite polyacrylamide hydrogel is carried out reaction kinetic and obtain nanometer SiOx composite polyacrylamide cationic flocculant.
2, nanometer SiOx composite polyacrylamide cationic flocculant as claimed in claim 1 is characterized in that described modified Nano SiOx carries out modification at nanometer SiOx with coupling agent; Described coupling agent is (γ-propylene oxide base) propyl group-triethoxyl silane.
3, nanometer SiOx composite polyacrylamide cationic flocculant as claimed in claim 1, it is characterized in that described redox initiator is oxygenant ammonium persulphate and reductive agent N, N, N ', the N '-Tetramethyl Ethylene Diamine aqueous solution, its redox initiator of adding are oxygenant ammonium persulphate and reductive agent sodium sulfite aqueous solution; Oxygenant is identical with the equivalence ratio of reductive agent.
4, nanometer SiOx composite polyacrylamide cationic flocculant as claimed in claim 1 is characterized in that described nanometer SiOx composite polyacrylamide hydrogel is carried out reaction kinetic is that nanometer SiOx composite polyacrylamide hydrogel is carried out Mannich cation modifying reaction with formaldehyde, dimethylamine and monobromethane.
5, a kind of preparation method of nanometer SiOx composite polyacrylamide cationic flocculant comprises the steps:
(1) carries out surface modification and the modification of nanometer SiOx earlier;
(2) Preparation of Polyacrylamide and compound with nanometer SiOx;
A, be 1 by mass ratio: after (6-10) in modified Nano SiOx, adding water white suspension liquid;
B, in the above-mentioned a white suspension liquid in step, add acrylamide react acrylamide and nanometer SiOx dispersion liquid; Wherein modified Nano SiOx and acrylamide mass ratio (2-6): 100;
0.3-0.5% by quality in the dispersion liquid in c, above-mentioned b step adds redox initiator, at room temperature reacts 1-3 after individual hour; Be warming up to 40-55 ℃, reaction got reaction solution in 1-3 hour; The 0.15-0.3% initiator of adding the acrylamide quality again in reaction solution continues reaction and promptly gets white nanometer SiOx composite polyacrylamide hydrogel after 0.5-2 hour; Described redox initiator is oxygenant ammonium persulphate and reductive agent N, N, and N ', the N '-Tetramethyl Ethylene Diamine aqueous solution, its redox initiator of adding are oxygenant ammonium persulphate and reductive agent sodium sulfite aqueous solution; Oxygenant is identical with the equivalence ratio of reductive agent;
(3) nanometer SiOx composite polyacrylamide hydrogel is carried out cation modifying.
6, the preparation method of nanometer SiOx composite polyacrylamide cationic flocculant as claimed in claim 5 is characterized in that in above-mentioned (2) a step also being included between the step with b and feeds nitrogen in acrylamide and the nanometer SiOx dispersion liquid with removal oxygen.
7, the preparation method of nanometer SiOx composite polyacrylamide cationic flocculant as claimed in claim 5, it is characterized in that the surface modification of described nanometer SiOx and modification comprise the steps: by volume 1: (1-3) add the absolute alcohol kind solvent and soak at nanometer SiOx, be 1 then by volume in the alcoholic solution of above-mentioned SiOx: (1-3) add coupling agent, sonic oscillation reaction 1-4 hour gets the nanometer SiOx of modification again with ethanol-extracted; X among the SiOx is 1.2-1.6.
8, the preparation method of nanometer SiOx composite polyacrylamide cationic flocculant as claimed in claim 5 is characterized in that the coupling agent in above-mentioned (1) step is (γ-propylene oxide base) propyl group-triethoxyl silane.
9, the preparation method of nanometer SiOx composite polyacrylamide cationic flocculant as claimed in claim 5 is characterized in that in above-mentioned (2) a step that SiOx adds and also comprises behind the water and adopt the sonic oscillation reaction.
10, the preparation method of nanometer SiOx composite polyacrylamide cationic flocculant as claimed in claim 5, it is characterized in that the nanometer SiOx composite polyacrylamide hydrogel described in above-mentioned (3) step carry out cation modifying comprise the steps: with formaldehyde and dimethylamine by volume 0.4-1.0 mix, the pH that regulates mixture is 3-4, (0.5-0.8) by volume: 1.0 join said mixture in the nanometer SiOx composite polyacrylamide hydrogel, and re-adjustment reaction system pH is 8-9; Reacted 1-3 hour down at 30-45 ℃; Above-mentioned reacted colloidal sol is diluted to 35% o'clock of original volume concentration, press formaldehyde and monobromethane volume ratio 1: (0.5-2), add monobromethane in the thin liquid above-mentioned releasing, after at room temperature stirring reaction 12-30 hour, promptly get nanometer SiOx composite polyacrylamide cationic flocculant.
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| CN103265104A (en) * | 2013-03-14 | 2013-08-28 | 苏州旭达环保科技有限公司 | Nano powder-organic polymer composite flocculating agent |
| CN103739051A (en) * | 2014-01-29 | 2014-04-23 | 江声 | Rapid flocculant |
| CN105314724A (en) * | 2015-11-25 | 2016-02-10 | 苏州书瑞环保科技有限公司 | Composite water treatment material and preparing method thereof |
| AU2018220496B2 (en) | 2017-02-17 | 2022-07-14 | Lg Electronics Inc. | Refrigerating or warming apparatus, and vehicle |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4927498A (en) * | 1988-01-13 | 1990-05-22 | E. I. Du Pont De Nemours And Company | Retention and drainage aid for papermaking |
| US5176891A (en) * | 1988-01-13 | 1993-01-05 | Eka Chemicals, Inc. | Polyaluminosilicate process |
| CN1303821A (en) * | 2000-01-11 | 2001-07-18 | 曾智勇 | Nanometer ultra-high efficiency flocculating agent |
| US6361653B2 (en) * | 1997-09-30 | 2002-03-26 | Nalco Chemical Company | Method of increasing retention in papermaking using colloidal borosilicates |
-
2002
- 2002-11-12 CN CNB021523207A patent/CN1331770C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4927498A (en) * | 1988-01-13 | 1990-05-22 | E. I. Du Pont De Nemours And Company | Retention and drainage aid for papermaking |
| US5176891A (en) * | 1988-01-13 | 1993-01-05 | Eka Chemicals, Inc. | Polyaluminosilicate process |
| US6361653B2 (en) * | 1997-09-30 | 2002-03-26 | Nalco Chemical Company | Method of increasing retention in papermaking using colloidal borosilicates |
| CN1303821A (en) * | 2000-01-11 | 2001-07-18 | 曾智勇 | Nanometer ultra-high efficiency flocculating agent |
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