CN103351047B - Organic-inorganic hybrid flocculant and preparation method thereof - Google Patents
Organic-inorganic hybrid flocculant and preparation method thereof Download PDFInfo
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- CN103351047B CN103351047B CN201310326604.0A CN201310326604A CN103351047B CN 103351047 B CN103351047 B CN 103351047B CN 201310326604 A CN201310326604 A CN 201310326604A CN 103351047 B CN103351047 B CN 103351047B
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Abstract
The invention discloses an organic-inorganic hybrid ionic bond efficient flocculant which is characterized in that an initiator, namely ammonium persulfate is added in a DMDAAC (dimethyl diallyl ammonium chloride) polymerization process to allow a molecular chain end of a composited polymer, namely PDMDAAC (poly dimethyl diallyl ammonium chloride) to be provided with sulfate radicals, the sulfate radicals are bonded with hydroxy aluminium ions with positive charge in an ionic bond form, and the PAC (poly aluminium chloride)-PDMDAAC organic-hybrid ionic bond efficient flocculant is obtained, and fully exerts excellent charge neutralizing capacity of PAC and an adsorption bridging action of PDMDAAC. In a water treatment process, the PAC-PDMDAAC hybrid flocculant is less in dosing quantity, and a formed flocculating body is quick in sedimentation, large and compact, so that the water treatment efficiency is improved significantly.
Description
Technical field
The present invention relates to water treatment field, particularly relate to a kind of Organic-inorganic hybrid flocculant and preparation method thereof.
Background technology
Flocculation technique is a kind of economy of processing efficiency, the easy water conditioning method of increasing water quality that be generally used for both at home and abroad at present, and flocculation process is also one of key link of whole water treatment.Thus efficient, safe flocculation agent has irreplaceable effect in whole water treatment procedure.The flocculation agent used both at home and abroad at present comprises inorganic flocculating agent and organic floculant.
Inorganic flocculating agent is aluminium system and Polyferric Sulfate class flocculation agent mainly.Inorganic flocculating agent has good coagulation effect, applied widely, and charge neutrality ability is strong, the series of advantages such as cost is low.But also there is a series of problem, as the toxicity problem of residual aluminum, low-temperature and low turbidity processing power is poor, the corrodibility that iron class flocculation agent is stronger to equipment simultaneously, colored problem of process water etc.Organic polymer coargulator consumption is few, and it is fast that flco forms speed, has excellent adsorption bridging ability simultaneously.But it is lower for organic removal ability, hydrolysis reaction is unstable and price is higher.
Patent documentation CN103011359A discloses a kind of inorganic organic composite coagulator, its inorganic part is polymerize aluminum chloride and poly-ferric chloride, the problem of a synthetic ratio is certainly existed in preparation process, simultaneously aluminium salt and molysite add simultaneously and there is basicity and be polymerized on the two the impact formed, and it is not purified, be difficult to reach desirable flocculating effect.In addition, in drinking water treatment process, adding of molysite has certain corrodibility to water treating equipment, and water outlet simultaneously has colourity.
Summary of the invention
The object of this invention is to provide a kind of hybrid inorganic-organic efficient flocculant, by the reasonable selection of raw material, obtain a kind of ionic linkage hybrid flocculant, is namely a kind of new hybrid material, improve flocculating effect, and preparation method is easy, practical.
The invention provides a kind of flocculation agent preparation method, it comprises the following steps:
The first step, take by the mass ratio 2:1 ~ 10:1 of polymerize aluminum chloride (PAC) with monomer diallyldimethylammonChloride Chloride, i.e. polymerize aluminum chloride: 67-91%, monomer diallyldimethylammonChloride Chloride: 9-33%, adds distilled water and makes it dissolve completely;
Second step, auxiliary agent tetrasodium ethylenediamine tetraacetate is added by monomer mass mark 0.004% in the aqueous solution of above-mentioned configuration, pass into high pure nitrogen protection simultaneously, slowly drip the initiator being equivalent to monomer total mass 0.1% ~ 0.9% after 30min, and continue to pass into high pure nitrogen to reacting end in water bath with thermostatic control;
3rd step, the solution after reaction being terminated is dried to constant weight in thermostatic drying chamber, obtains the yellow flocculation agent powder of hybrid inorganic-organic after grinding.
Initiator used in the present invention is redox initiator, comprises persulphate and sodium bisulfite.
Water bath with thermostatic control temperature of the present invention is 40 DEG C ~ 70 DEG C.
The water bath with thermostatic control reaction times of the present invention is 2 ~ 6h.
Its optimum feed stock composition weight percent is: polymerize aluminum chloride (PAC) 76%; Dimethyl diallyl ammonium chloride (DMDAAC): 24%.
The present invention forms ionic linkage hybrid structure by between positively charged hydroxy aluminum particle and organic polymer chain.Initiator ammonium persulfate is added in the process that dimethyl diallyl ammonium chloride (DMDAAC) is polymerized, make polymer poly dimethyl diallyl ammonium chloride (PDMDAAC) molecular chain-end synthesized with sulfate radical, itself and positively charged oxyaluminum ion are with the form bonding of ionic linkage, obtain PAC-PDMDAAC organic inorganic hybridization ionic linkage efficient flocculant, make it give full play to the charge neutrality ability of PAC excellence and the adsorption bridging effect of PDMDAAC.The inorganic part of flocculation agent is PAC, shows as excellent charge neutrality ability, applied widely; Organic moiety is PDMDAAC, and by the adsorption bridging ability that organic polymer is good, the flco that water treatment is formed is large and closely knit, and settling velocity is fast.Thus in water treatment procedure, PAC-PDMDAAC hybrid flocculant dosage is few, and the flco of formation is large and closely knit, and settling of floccus is fast, and water treatment efficiency is significantly improved.
Compared with prior art, difference of the present invention is that flocculation agent of the present invention is a kind of ionic linkage hybrid flocculant, namely be a kind of hybrid material, hybrid flocculant of the present invention is that PAC(is adopted finished product PAC) be linked to be an entirety with PDMDAAC, obtaining macromolecular substance, is namely that hydroxy aluminum and PDMDAAC form polymer substance, by infrared spectra, thermogravimetric analysis, and scanning electron microscope characterizes, what prove to obtain is kind of a novel material, is not simple composite mixing material.In addition, this hybrid flocculant only use only bi-material, and it more saves on raw material, prepares convenient.
The present invention has following characteristics:
1, hydroxy aluminum particle and the Poly Dimethyl Diallyl Ammonium Chloride end of the chain are by ionic linkage bonding.
2, the hybrid flocculant formed has more bigger serface, and it is more superior that its adsorption bridging ability also shows.
3, flco is large, and sedimentation is fast, and flocculating effect is good.
Embodiment
Below in conjunction with embodiment, flocculation agent of the present invention and preparation method thereof is described:
Embodiment 1:
The first step, takes polymerize aluminum chloride 2g, is dissolved in 100ml distilled water, is placed in four-hole boiling flask, adds the monomer dimethyl diallyl aqueous solution 1.02ml of massfraction 40%, adds the tetrasodium ethylenediamine tetraacetate 2.4ml of massfraction 10mg/L simultaneously.
Second step, above-mentioned four-hole boiling flask being placed in temperature is 60 DEG C of thermostat water baths, after logical high pure nitrogen 30min, slowly drips the ammonium persulfate solution 2.8ml that concentration is 1g/L, and maintaining nitrogen purge, terminate after reaction 5h.
3rd step, by the solution of gained in drying in oven to constant weight, obtains the Organic-inorganic hybrid flocculant that PAC content is 77%.
Embodiment 2:
The first step, takes polymerize aluminum chloride 2g, is dissolved in 100ml distilled water, is placed in four-hole boiling flask, adds the monomer dimethyl diallyl aqueous solution 1.33ml of massfraction 40%, adds the tetrasodium ethylenediamine tetraacetate 3.2ml of massfraction 10mg/L simultaneously.
Second step, above-mentioned four-hole boiling flask being placed in temperature is 70 DEG C of thermostat water baths, after logical high pure nitrogen 30min, slowly drips the ammonium persulfate solution 2.8ml that concentration is 1g/L, and maintaining nitrogen purge, terminate after reaction 3h.
3rd step, by the solution of gained in drying in oven to constant weight, obtains the Organic-inorganic hybrid flocculant that PAC content is 71%.
Embodiment 3:
The first step, takes polymerize aluminum chloride 2g, is dissolved in 100ml distilled water, is placed in four-hole boiling flask, adds the monomer dimethyl diallyl aqueous solution 1.67ml of massfraction 40%, adds the tetrasodium ethylenediamine tetraacetate 2.4ml of massfraction 10mg/L simultaneously.
Second step, above-mentioned four-hole boiling flask being placed in temperature is 50 DEG C of thermostat water baths, after logical high pure nitrogen 30min, slowly drips the ammonium persulfate solution 2ml that concentration is 1g/L, and maintaining nitrogen purge, terminate after reaction 4h.
3rd step, by the solution of gained in drying in oven to constant weight, obtains the Organic-inorganic hybrid flocculant that PAC content is 67%.
Embodiment 4:
The water-soluble aqueous solution being made into 1g/L of hybrid inorganic-organic type flocculation agent that above-described embodiment 1 is obtained, for the process of the high and low muddy water in Jia Lingjiang River, for low-cloudy water (turbidity is 12.2NTU), dispensing 12ml, can make the clearance of turbidity and UV reach 97% and 55%.For high muddy water (turbidity is 682NTU), dispensing 12ml, can make the clearance of turbidity and UV reach 99% and 54%.
Embodiment 5:
The water-soluble aqueous solution being made into 1g/L of hybrid inorganic-organic type flocculation agent obtained by above-described embodiment 1, for the process of the high and low muddy water in the Changjiang river, for low-cloudy water (turbidity is 20.9NTU), dispensing 12ml, can make the clearance of turbidity and UV reach 98% and 50%.For high muddy water (turbidity is 756NTU), dispensing 12ml, can make the clearance of turbidity and UV reach 99% and 53%.
Embodiment 6:
The water-soluble aqueous solution being made into 10g/L of hybrid inorganic-organic type flocculation agent that above-described embodiment 1 is obtained, for the process of direct tan and disperse purple dye waste water, wherein direct tan and disperse purple dye waste strength are as 30mg/L, dispensing 10ml, can make the clearance of the two colourity all reach 95%.
Comparative example:
By the present invention be used alone PAC, and the composite use of PAC and PDMDAAC contrasts, and processing the Changjiang river and Jiangling river experiment effect shows, hydridization effect is better than the latter two.It is at UV
254with the removal of turbidity is good.Simultaneously on desolventing technology, treatment of dyeing and printing effect is significantly good a lot.
1, desolventing technology: process dye dispersion is purple, dye strength 100mg/L, hydridization type PAC-PDMDAAC(are namely
The flocculation agent obtained of the present invention) and Compositional type PAC+1%PDMDAAC dosage be 450mg/L, under different pH, effect comparison is as follows:
| pH | 2 | 4 | 6 | 8 | 10 | 12 |
| Initial absorbance | 1.178 | 1.179 | 1.181 | 1.126 | 1.332 | 1.505 |
| Compositional type clearance (%) | 91.35 | 95.67 | 98.56 | 86.41 | 97.82 | 98.47 |
| Hydridization type clearance (%) | 89.05 | 96.10 | 99.49 | 97.87 | 99.25 | 99.07 |
Process direct yellow dye, dye strength 100mg/L, hydridization type PAC-PDMDAAC and Compositional type PAC+1%PDMDAAC dosage are 450mg/L, and under different pH, effect comparison is as follows:
| pH | 2 | 4 | 6 | 8 | 10 | 12 |
| Initial absorbance | 2.162 | 2.366 | 2.350 | 2.301 | 2.506 | 2.420 |
| Compositional type clearance (%) | 83.95 | 89.69 | 94.64 | 86.41 | 97.96 | 97.52 |
| Hydridization type clearance (%) | 83.02 | 91.76 | 98.00 | 92.13 | 99.20 | 98.84 |
2, process low turbid the Changjiang river water sample, water sample initial haze is 20.9NTU, UV
254=0.024.pH=7.33, compared for respectively and adds PAC separately, and the treatment effect of Compositional type PAC+1%PDMDAAC and hydridization type PAC-PDMDAAC is as follows:
3, process low turbid Jia Lingjiang River water sample, water sample initial haze is 12.2NTU, UV
254=0.052.pH=7.35, compared for respectively and adds PAC separately, and the treatment effect of Compositional type PAC+1%PDMDAAC and hydridization type PAC-PDMDAAC is as follows:
Claims (6)
1. an Organic-inorganic hybrid flocculant, it forms weight percent by the raw material of following proportioning:
Finished product polymerize aluminum chloride: 67-91%
Monomer diallyldimethylammonChloride Chloride: 9-33%
Wherein initiator is the 0.1-0.9% of the quality of monomer diallyldimethylammonChloride Chloride, and auxiliary agent tetrasodium ethylenediamine tetraacetate massfraction is 0.004% of monomer diallyldimethylammonChloride Chloride;
Described flocculation agent is a kind of ionic linkage hybrid flocculant, is prepared by following method:
The first step, takes finished product polymerize aluminum chloride and monomer diallyldimethylammonChloride Chloride in above ratio, adds distilled water and makes it dissolve completely;
Second step, adds auxiliary agent tetrasodium ethylenediamine tetraacetate in proportion in the aqueous solution of above-mentioned configuration, passes into high pure nitrogen protection simultaneously, slowly drips initiator in proportion, and continue to pass into high pure nitrogen to reacting end in water bath with thermostatic control after 30min;
3rd step, the solution after reaction being terminated is dried to constant weight in thermostatic drying chamber, obtains the yellow flocculation agent powder of hybrid inorganic-organic after grinding.
2. Organic-inorganic hybrid flocculant according to claim 1, is characterized in that: described raw material composition optimum weight per-cent is: finished product polymerize aluminum chloride (PAC): 76%; Monomer diallyldimethylammonChloride Chloride (DMDAAC): 24%; Auxiliary agent tetrasodium ethylenediamine tetraacetate quality is 0.004% of monomer diallyldimethylammonChloride Chloride quality; Initiator quality is 0.7% of monomer diallyldimethylammonChloride Chloride.
3. Organic-inorganic hybrid flocculant according to claim 1 and 2, is characterized in that, described initiator is redox initiator, and wherein oxygenant is persulphate, and reductive agent is sodium bisulfite.
4. Organic-inorganic hybrid flocculant preparation method according to claim 3, is characterized in that, persulphate is Potassium Persulphate or ammonium persulphate.
5. Organic-inorganic hybrid flocculant according to claim 1 and 2, is characterized in that, water bath with thermostatic control temperature is 40 DEG C ~ 70 DEG C.
6. Organic-inorganic hybrid flocculant according to claim 1 and 2, is characterized in that, the water bath with thermostatic control reaction times is 2 ~ 6h.
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| CN103739051A (en) * | 2014-01-29 | 2014-04-23 | 江声 | Rapid flocculant |
| CN103833117B (en) * | 2014-03-07 | 2015-07-15 | 重庆大学 | Organic-inorganic composite coagulant for processing printing and dyeing wastewater and preparation method thereof |
| CN104891620A (en) * | 2015-04-16 | 2015-09-09 | 广西福斯特再生资源环保科技有限公司 | Compound polyaluminum chloride and preparation method thereof |
| CN105217757A (en) * | 2015-10-22 | 2016-01-06 | 石家庄蓝江生物环保科技有限公司 | Inorganic whisker coagulating agent and its production and use |
| CN107056985A (en) * | 2017-01-13 | 2017-08-18 | 重庆工商大学 | A kind of preparation method of cationic microbial flocculant |
| CN106745624B (en) * | 2017-01-17 | 2020-07-10 | 中国科学院过程工程研究所 | Inorganic-organic hybrid flocculation material and preparation method thereof |
| CN108529836B (en) * | 2018-04-23 | 2021-03-26 | 杜瑞 | Efficient settling agent special for sludge expansion |
| CN110759451A (en) * | 2019-10-18 | 2020-02-07 | 东北石油大学 | Rare earth cationic-composite aluminum organic heteropolymeric flocculant |
| CN110606534B (en) * | 2019-10-30 | 2021-09-28 | 常州市振邦化工制造有限公司 | Preparation method of flocculating agent for treating oil-containing sewage of petroleum refining delayed coking |
| CN114684900A (en) * | 2020-12-31 | 2022-07-01 | 中国石油化工股份有限公司 | Hybrid coagulant and preparation method thereof |
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| CN1266051C (en) * | 2004-06-30 | 2006-07-26 | 山东大学 | PDMDAAC homopolymer inorganic and organic composite flocculant and preparation process thereof |
| CN101885528B (en) * | 2010-07-27 | 2012-03-21 | 长沙理工大学 | Powdery high-whiteness polyaluminium chloride complex and preparation method thereof |
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