CN103408120B - Polyaluminum ferric chloride-polyepichlorohydrin-ethylene diamine preparation method - Google Patents
Polyaluminum ferric chloride-polyepichlorohydrin-ethylene diamine preparation method Download PDFInfo
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- CN103408120B CN103408120B CN201310352916.9A CN201310352916A CN103408120B CN 103408120 B CN103408120 B CN 103408120B CN 201310352916 A CN201310352916 A CN 201310352916A CN 103408120 B CN103408120 B CN 103408120B
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Abstract
The invention relates to a polyaluminum ferric chloride-polyepichlorohydrin-ethylene diamine preparation method comprising the steps that: (1) a polyepichlorohydrin-ethylene diamine solution is prepared; (2) a polyaluminum ferric chloride solution is prepared; and (3) the prepared polyepichlorohydrin-ethylene diamine solution and the polyaluminum ferric chloride solution with a weight ratio of 1:20-1:50 are subjected to ultrasonic oscillation in an ultrasonic wave generator, such that polyaluminum ferric chloride-polyepichlorohydrin-ethylene diamine flocculant is prepared. According to the invention, epichlorohydrin, ethylene diamine, aluminum chloride and iron chloride are adopted as raw materials, and the polyaluminum ferric chloride-polyepichlorohydrin-ethylene diamine is prepared. The flocculant is a novel inorganic-organic high-molecular flocculant. As a high-efficiency water-processing agent, the flocculant can be widely applied in dye wastewater processing, and has advantages such as high molecular weight, good stability, good decolorizing effect, and the like.
Description
Technical field
The present invention relates to a kind of preparation method of aluminium iron polychloride-Hydrin-quadrol composite flocculation agent, belong to flocculation agent preparation field.
Background technology
Textile and dyeing industry is one of water resource pollution person and consumer maximum in the world.China have every day ton up to a million unprocessed or process dyeing waste water not up to standard enter rivers and lakes, the environmental destruction caused thus and financial loss are immeasurable.Therefore, to the purification treatment of dyeing waste water, oneself becomes the key issue of the current dyeing existence of restriction and Sustainable development.
Dyeing waste water has the features such as complicated component, concentration is high, colourity is dark, and has bio-toxicity or carcinogenic, teratogenesis, mutagenic water soluble organic substance containing multiple, is difficult to adopt conventional biological method or physical chemistry method to administer.How to decolour is the key issue of waste water from dyestuff purification treatment.At present, chemical flocculation is with its strong adaptability, and operational administrative is simple, advantages such as initial cost is low and being widely used in dye wastewater treatment.And the key factor of decolorizing effect is the performance of flocculation agent.
Aluminium iron polychloride (PFAC) be a kind of by aluminium salt and molysite under certain condition through the ferro-aluminum copoly type Composite Inorganic Polymer Flocculants of hydrolytic polymerization, have the feature of poly-aluminium and Polyferric Sulfate concurrently, both overcome that the alumen ustum that aluminium salt generates is light, the shortcoming of low-temperature and low turbidity purifying water effect difference, overcome again that molysite colourity is high, the shortcoming of equipment and pipeline corrosion.Have nontoxic, speed of response fast, formed flco large and closely, the advantage such as settling velocity is fast, applicable pH range is wide, dosage is few and coagulation effect is good, become the focus that water conditioner is in recent years studied.But compared with organic floculant, molecular weight, globule size and flocculation bridge formation ability are all mutually far short of what is expected.
Hydrin-quadrol is a kind of high effect nontoxic, good water solubility, the quaternary ammonium salt organic polymer coargulator that molecular weight is higher, research about Hydrin-quadrol is reported see Niyazi Bipk, Bahire Filiz Senkal. Removal of nitrite ions from aqueous solutions by cross-linked polymer of ethylenediamine with epichlorohydrin. Reactive & Functional Polymers, 1998, 36:7 l-77(Niyazi Bipk, Bahire Filiz Senkal. Hydrin-quadrol is studied the removal of nitrite nitrogen. Reactive & Functional Polymers, 1998, 36:7 l-77).
In order to overcome respective shortcoming, synergy is utilized to prepare the direction that composite flocculation agent is flocculation development.Disclosed in CN1654348 " composite flocculation agent for treatment of dyeing wastewater ", it consists of natural polymer water-soluble chitosan (CTS) and polymerize aluminum chloride (PAC).CN1868910 disclosed " polymerized aluminium-polyepichlorohydrin amine inorganic organic composite coagulator and preparation technology thereof ", with AlCl
36H
2o, polyepichlorohydrin amine are raw material, adopt the method be incorporated in PAC solution by polyepichlorohydrin amine to be prepared from.
But be not seen in bibliographical information about the novel composite flocculating agent prepared for raw material compound with aluminium iron polychloride and Hydrin-quadrol.
Summary of the invention
In order to overcome the deficiency that existing flocculation agent technology exists, the invention provides a kind of preparation method of aluminium iron polychloride-Hydrin-quadrol, the composite flocculation agent good decolorizing effect of preparation, stable performance.
The preparation method of aluminium iron polychloride-Hydrin-quadrol of the present invention, comprises the following steps:
(1) get whiteruss and be placed in four-hole boiling flask with agitator and reflux exchanger, flask is placed in frozen water bath, makes temperature control at 0 ~ 8 DEG C;
(2) in whiteruss, passing into flow is 0.5m
3/ hour nitrogen 15 ~ 20 minutes, then adds in the four-hole boiling flask of frozen water bath by quadrol, quadrol and whiteruss mass ratio are 1:3, open the water coolant of reflux exchanger, is 150 ~ 250 S in stirring G value
-1lower warming while stirring, makes the temperature in water-bath control at 20 ~ 25 DEG C, is the ratio of 2:1 in the mol ratio of epoxy chloropropane and quadrol, and slowly drip epoxy chloropropane and carry out addition reaction, time for adding is 2 ~ 3 hours;
(3) epoxy chloropropane dropwises rear continuation and stirs insulation reaction 60 ~ 90 minutes, then makes temperature drop to 15 DEG C;
(4) ratio being 1:1.5 in Trimethylamine 99 and epoxy chloropropane mol ratio gets the trimethylamine aqueous solution that mass percentage concentration is 33%, add above-mentioned solution as linking agent, thermostatic control, at 85 ~ 90 DEG C, is reacted 5 hours, naturally cool to room temperature, obtained Hydrin-ethylenediamine solution;
(5) ratio being 5:2 in aluminium and iron mol ratio gets AlCl
36H
2o and FeCl
36H
2o solid, is placed in beaker, and adding distil water makes both dissolve, and is 100 ~ 300 S in stirring G value
-1under to be heated to temperature be 70-80 DEG C, maintain after 1.0 hours-1.5 hours, utilize and slowly drip alkaline process, slowly add Na
2cO
3basicity (equivalence ratio of hydroxyl equivalent and aluminium and iron) is adjusted to 1.0 by solution; After lather collapse, add Na according to phosphorus mole number and aluminium and iron total moles than the ratio being 0.08
2hPO
412H
2o powder, as stablizer, continues to stir 3-4 hour, naturally cools to room temperature, obtained polymerize aluminum chloride ferrous solution;
(6) Hydrin-ethylenediamine solution of preparation is got with the ratio of weight ratio 1:20 ~ 1:50 and polymerize aluminum chloride ferrous solution is placed in ultrasonic generator, power be 220-350W, frequency be the Ultrasonic Conditions of 60Hz under ultrasonic vibration 60-90 minute, prepare aluminium iron polychloride-Hydrin-quadrol flocculation agent.
The present invention with epoxy chloropropane, quadrol, aluminum chloride and iron(ic) chloride for raw material, prepare aluminium iron polychloride-Hydrin-quadrol, this flocculation agent belongs to a kind of novel inorganic organic polymer flocculation agent, as the efficient water treatment agent of one, the process of waste water from dyestuff can be widely used in, there is the advantages such as molecular weight is high, good stability, good decolorizing effect.Aluminium iron polychloride-Hydrin-quadrol flocculation agent prepared by the present invention has following characteristics:
(1) in preparation process, pass into nitrogen, oxygen in air can be reduced on the impact of Hydrin-quadrol preparation process, improve the transformation efficiency of monomeric substance;
(2) Hydrin-quadrol is owing to being adopt the method introducing a small amount of Trimethylamine 99 linking agent to be prepared from, and its molecular weight improves, and the adsorption bridging ability in water strengthens;
(3) the aluminium iron polychloride coagulating agent prepared of the present invention is conventional as compared with polymerize aluminum chloride, iron(ic) chloride, poly-ferric chloride etc. with other, has speed of response fast, the advantages such as alumen ustum is closely knit, flocculating effect is good;
(4) in Hydrin-quadrol, introduce that aluminium iron polychloride can make that the dosage of flocculation agent reduces, charge neutrality ability strengthens, alumen ustum sedimentation speed is accelerated, water treatment capacity in the unit time improve, have that molecular weight is large, adsorption bridging ability and the advantage such as stronger.
Embodiment
Embodiment 1
(1) get 24mL whiteruss in 250mL with in four mouthfuls of round-bottomed flasks of agitator and reflux exchanger, be placed on by flask in frozen water bath, temperature controls at 8 DEG C
,and to pass into nitrogen 20 min(flow in flask be 0.5m
3/ h), then weighing 6.02 g quadrols and add (quadrol and whiteruss mass ratio are 1:3) in round-bottomed flask, open the water coolant of reflux exchanger, is 150 S in stirring G value
-1under be warming up to 25 DEG C while stirring, slowly drip 18.56 g epoxy chloropropane (mol ratio of epoxy chloropropane and quadrol is 2:1) with separating funnel and carry out addition reaction, time for adding is 2.5 hours, dropwises and continues stirring 60 minutes; Then make temperature drop to less than 15 DEG C, the ratio being 1:1.5 according to the mol ratio of Trimethylamine 99 and epoxy chloropropane adds the trimethylamine aqueous solution linking agent of 33%; Make temperature again be increased to 87 DEG C, isothermal reaction 5 hours, naturally cools to room temperature, obtained Hydrin-ethylenediamine solution;
(2) 12.22gAlCl is taken
36H
2o solid and 5.47gFeCl
36H
2o solid (aluminium and iron mol ratio are 5:2), is placed in beaker, adds distilled water and dissolves; Be 200 S in stirring G value
-1under to be heated to temperature be 70-80 DEG C, maintain after 1.2 hours, slowly add 3.75gNa
2cO
3basicity is adjusted to 1.0 by liquid; After lather collapse, add 2g stablizer Na
2hPO
412H
2o powder (phosphorus mole number is 0.08 with aluminium and iron total moles ratio); Continue stirring 3 hours, obtain polymerize aluminum chloride ferrous solution;
(3) get with the ratio of weight ratio 1:35 Hydrin-ethylenediamine solution that aforesaid method prepares and polymerize aluminum chloride ferrous solution is placed in beaker, and beaker is placed in ultrasonic generator, power be 350W, frequency be the Ultrasonic Conditions of 60Hz under ultrasonic vibration 60 minutes, prepare aluminium iron polychloride-Hydrin-quadrol composite flocculation agent finished product, represent with No.1.
Aluminium iron polychloride-Hydrin-quadrol composite flocculation agent that the present embodiment obtains, outward appearance is light yellow liquid, containing Fe
2o
3, Al
2o
3content be respectively 6.15 g/L, 9.81 g/L, the content of Hydrin-quadrol is 18.78 g/L.
Embodiment 2
(1) get 24mL whiteruss in 250mL with in four mouthfuls of round-bottomed flasks of agitator and reflux exchanger, be placed on by flask in frozen water bath, temperature controls at 5 DEG C
,and to pass into nitrogen 15 min(flow in flask be 0.5m
3/ h), then weighing 6.02 g quadrols and add in round-bottomed flask, open the water coolant of reflux exchanger, is 250 S in stirring G value
-1under be warming up to 20 DEG C while stirring, slowly drip 18.56 g epoxy chloropropane (mol ratio of epoxy chloropropane and quadrol is 2:1) with separating funnel and carry out addition reaction, time for adding is 2 hours, dropwises and continues stirring 60 minutes; Then make temperature drop to less than 15 DEG C, the ratio being 1:1.5 according to the mol ratio of Trimethylamine 99 and epoxy chloropropane adds the trimethylamine aqueous solution linking agent of 33%; Make temperature again be increased to 90 DEG C, isothermal reaction 5 hours, naturally cools to room temperature, obtained Hydrin-ethylenediamine solution;
(2) 12.22gAlCl is taken
36H
2o solid and 5.47gFeCl
36H
2o solid (aluminium and iron mol ratio are 5:2), is placed in beaker, adds distilled water and dissolves; Be 100 S in stirring G value
-1under to be heated to temperature be 70-80 DEG C; Maintain after 1.5 hours, slowly add 3.75gNa
2cO
3basicity is adjusted to 1.0 by liquid; After lather collapse, add 2g stablizer Na
2hPO
412H
2o powder (phosphorus mole number is 0.08 with aluminium and iron total moles ratio); Continue stirring 4 hours, obtain polymerize aluminum chloride ferrous solution;
(3) get with the ratio of weight ratio 1:20 Hydrin-ethylenediamine solution that aforesaid method prepares respectively and polymerize aluminum chloride ferrous solution is placed in beaker, and beaker is placed in ultrasonic generator, power be 220W, frequency be the Ultrasonic Conditions of 60Hz under ultrasonic vibration 90 minutes, prepare aluminium iron polychloride-Hydrin-quadrol composite flocculation agent finished product, represent with No.1.
Aluminium iron polychloride-Hydrin-quadrol composite flocculation agent prepared by the present embodiment, outward appearance is light yellow liquid, containing Fe
2o
3, Al
2o
3content be respectively 6.45 g/L, 9.71 g/L, the content of Hydrin-quadrol is 23.26 g/L.
Embodiment 3
(1) get 24mL whiteruss in 250mL with in four mouthfuls of round-bottomed flasks of agitator and reflux exchanger, be placed on by flask in frozen water bath, temperature controls at 0 DEG C
,and to pass into nitrogen 17 min(flow in flask be 0.5m
3/ h), then weighing 6.02 g quadrols and add in round-bottomed flask, open the water coolant of reflux exchanger, is 200 S in stirring G value
-1under be warming up to 23 DEG C while stirring, slowly drip 18.56 g epoxy chloropropane (mol ratio of epoxy chloropropane and quadrol is 2:1) with separating funnel and carry out addition reaction, time for adding is the aqueous solution 3 hours, dropwises and continues stirring 60 minutes; Then make temperature drop to 15 DEG C, the ratio being 1:1.5 according to the mol ratio of Trimethylamine 99 and epoxy chloropropane adds the trimethylamine aqueous solution linking agent of 33%; Make temperature again be increased to 85 DEG C, isothermal reaction 5 hours, naturally cools to room temperature, obtained Hydrin-ethylenediamine solution;
(2) 12.22gAlCl is taken
36H
2o solid and 5.47gFeCl
36H
2o solid (aluminium and iron mol ratio are 5:2), is placed in beaker, adds distilled water and dissolves; Be 300 S in stirring G value
-1under to be heated to temperature be 70-80 DEG C; Maintain after 1 hour, slowly add 3.75gNa
2cO
3basicity is adjusted to 1.0 by liquid; After lather collapse, add 2g stablizer Na
2hPO
412H
2o powder (phosphorus mole number is 0.08 with aluminium and iron total moles ratio); Continue stirring 3.5 hours, obtain polymerize aluminum chloride ferrous solution;
(3) get with the ratio of weight ratio 1:50 Hydrin-ethylenediamine solution that aforesaid method prepares respectively and polymerize aluminum chloride ferrous solution is placed in beaker, and beaker is placed in ultrasonic generator, power be 300W, frequency be the Ultrasonic Conditions of 60Hz under ultrasonic vibration 80 minutes, prepare aluminium iron polychloride-Hydrin-quadrol composite flocculation agent finished product, represent with No.1.
Aluminium iron polychloride-Hydrin-quadrol composite flocculation agent prepared by the present embodiment, outward appearance is light yellow liquid, containing Fe
2o
3, Al
2o
3content be respectively 6.27 g/L, 10.04 g/L, the content of Hydrin-quadrol is 9.63 g/L.
Aluminium iron polychloride-Hydrin-quadrol organic polymer coargulator prepared by the present invention is applicable to dye wastewater treatment field, is below embody rule example:
Aluminium iron polychloride-Hydrin-quadrol the product each embodiment prepared is used for the coagulating treatment containing dispersed deep blue dye waste water, compares with aluminium iron polychloride (PFAC) and Poly Dimethyl Diallyl Ammonium Chloride (PDMDAAC) simultaneously.Former water pH value 6.58, dispersed deep blue dye content is 100 mg/L, pH value 6.56, and absorbancy is 2.021 ± 0.003, and percent of decolourization is water sample absorbancy reduced value and the ratio processing front water sample absorbancy after process, and result is listed in the table below.
Aluminium iron polychloride-Hydrin-quadrol is to the decolorizing effect of dispersed deep blue dye waste water
From above result, under identical dosage condition, aluminium iron polychloride-Hydrin-quadrol composite flocculation agent is to the percent of decolourization containing DISPERSE NAVY BLUE EXSF 300& BLUE 56 100 waste water apparently higher than PFAC and PDMDAAC, and the percent of decolourization when dosage is 20 mg/L reaches best.
Claims (1)
1. a preparation method for aluminium iron polychloride-Hydrin-quadrol, is characterized in that, comprise the following steps:
(1) get whiteruss and be placed in four-hole boiling flask with agitator and reflux exchanger, flask is placed in frozen water bath, makes temperature control at 0 ~ 8 DEG C;
(2) in whiteruss, passing into flow is 0.5m
3/ hour nitrogen 15 ~ 20 minutes, then adds in the four-hole boiling flask of frozen water bath by quadrol, quadrol and whiteruss mass ratio are 1:3, open the water coolant of reflux exchanger, is 150 ~ 250 S in stirring G value
-1lower warming while stirring, makes the temperature in water-bath control at 20 ~ 25 DEG C, is the ratio of 2:1 in the mol ratio of epoxy chloropropane and quadrol, and slowly drip epoxy chloropropane and carry out addition reaction, time for adding is 2 ~ 3 hours;
(3) epoxy chloropropane dropwises rear continuation and stirs insulation reaction 60 ~ 90 minutes, then makes temperature drop to 15 DEG C;
(4) ratio being 1:1.5 in Trimethylamine 99 and epoxy chloropropane mol ratio gets the trimethylamine aqueous solution that mass percentage concentration is 33%, add above-mentioned solution as linking agent, thermostatic control, at 85 ~ 90 DEG C, is reacted 5 hours, naturally cool to room temperature, obtained Hydrin-ethylenediamine solution;
(5) ratio being 5:2 in aluminium and iron mol ratio gets AlCl
36H
2o and FeCl
36H
2o solid, is placed in beaker, and adding distil water makes both dissolve, and is 100 ~ 300 S in stirring G value
-1under to be heated to temperature be 70-80 DEG C, maintain after 1.0 hours-1.5 hours, utilize and slowly drip alkaline process, slowly add Na
2cO
3basicity is adjusted to 1.0 by solution; After lather collapse, add Na according to phosphorus mole number and aluminium and iron total moles than the ratio being 0.08
2hPO
412H
2o powder, as stablizer, continues stirring 3 hours-4 hours, naturally cools to room temperature, obtained polymerize aluminum chloride ferrous solution;
(6) Hydrin-ethylenediamine solution of preparation is got with the ratio of weight ratio 1:20 ~ 1:50 and polymerize aluminum chloride ferrous solution is placed in ultrasonic generator, power be 220-350W, frequency be the Ultrasonic Conditions of 60Hz under ultrasonic vibration 60-90 minute, prepare aluminium iron polychloride-Hydrin-quadrol flocculation agent.
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| CN105347454A (en) * | 2015-11-25 | 2016-02-24 | 苏州书瑞环保科技有限公司 | Flocculating material for water treatment and preparation method thereof |
| CN105601771B (en) * | 2015-12-19 | 2017-09-26 | 湖南科技大学 | Microwave radiation technology prepares polyacrylamide glutathione aluminium chloride method and application |
| CN108622988A (en) * | 2017-08-29 | 2018-10-09 | 乌鲁木齐市科发展精细化工有限公司 | High synergistic non-molten composite dephosphorization flocculant and its application process altogether |
| CN112624283A (en) * | 2020-11-27 | 2021-04-09 | 飞潮(上海)环境技术有限公司 | Method for preparing water purifying agent by using dust-collecting slag |
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Non-Patent Citations (3)
| Title |
|---|
| Functional Polymers》.1998,第72页2.1 交联聚合物的制备. * |
| Niyazi Bicak et al.Removal of nitrite ions from aqueous solutions by cross-linked polymer of ethylenediamine with epichlorohydrin.《Reactive & * |
| 环氧氯丙烷-二甲胺聚合物和聚合氯化铝用于印染废水的处理;孙逊等;《环境化学》;20070131;第26卷(第1期);第51页1.1 PAC-EPI-DMA的制备 * |
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