CN1868911A - Polyepichlorohydrin-dimethylamine organic polymer coargulator and its preparation technology - Google Patents

Abstract

An organic high-molecular flocculant with high flocculating effect for decoloring the printing and dyeing sewage in textile industry is prepared from epoxy chloropropane, dimethylamine and 1,6-hexyldiamine as cross-linking agent. Its preparing process is also disclosed.

Description

Polyepichlorohydrin-dimethylamine organic polymer coargulator and preparation technology thereof

(1) technical field

The present invention relates to polyepichlorohydrin-dimethylamine organic polymer coargulator and preparation technology thereof, belong to technical field of chemistry.

(2) background technology

Along with China's rapid economy development, shortage of water resources will be one of distinct issues of facing of China from now on.Shortage of water resources will directly restrict improving constantly of Chinese society sustainable development of economy and human living standard etc.Shortage of water resources is because the scarcity of China's water yield causes on the one hand, on the other hand because a large amount of useless (dirt) water are not effectively administered arbitrarily discharging caused water to pollute causing.Therefore, strengthen water prevention and cure of pollution work and have crucial meaning with the bad utilization ratio of following that improves water.A large amount of trade effluent and the sanitary sewages of the annual discharging of China, wherein waste water from dyestuff and dyeing waste water occupy sizable ratio.The characteristics of these waste water are that complicated component, high density, high chroma, hard-degraded substance are many, and contain multiple have bio-toxicity or carcinogenic, teratogenesis, mutagenic water soluble organic substance, are difficult to adopt conventional bioremediation or physical chemistry method to be administered.In dyestuff and dyeing waste water decolouring processing, the chemical flocculation method is one of direction of current domestic and international primary study.The effect key of chemical flocculation decoloring method depends on the performance of flocculation agent.So development and efficient, the inexpensive high-molecular coagulant adopting of development of new become a urgent task in the water treatment field, are of great immediate significance.

Polyepichlorohydrin-dimethylamine is a Cationic Polymers Containing Quaternary Ammonium Salts, in the drilling well of oil and performance history as preventing shale hydration expansible clay stabilizer, flotation agent, flocculation agent and breakdown of emulsion de-oiling agent etc. during drilling well and oil extraction-generated waste water are handled.In recent years, polyepichlorohydrin-dimethylamine has been subjected to increasing attention as a kind of flocculation agent of dyeing waste water, but because the flocculating agent molecule amount lower (viscosity that shows as polymkeric substance is lower) that is synthesized, influence its adsorption bridging ability in water greatly, thereby influenced its flocculating property.So develop full-bodied polyepichlorohydrin-dimethylamine is its important factor that can apply.

About the research report of polyepichlorohydrin-dimethylamine, referring to Ma Xiping, Hu Xingqi etc.Synthesizing of epoxy chloropropane-dimethylamine cation polymkeric substance.Polymer material science and engineering, 1996,12 (4): 50-54. Ma Xiping, synthetic and the inhibition research of Shao Dingbo .PA cationic polymers. drilling technology, 1999,22 (1): the high precious jade of 47-48., Zhang Hua, the preparation of .2005. polyepichlorohydrin amines such as Zou Xinhua and decoloration performance [J] thereof. fine chemistry industry, 22 (8): the high precious jade of 611-615., Zhang Hua, the study on the synthesis [J] of .2005. novel flocculant polyepichlorohydrin amines such as Yue Qinyan. environmental chemistry, 24 (4): 446-449. but in the building-up process of polyepichlorohydrin-dimethylamine by changing experiment condition, add 1, the 6-hexanediamine improves as linking agent that the molecular weight of product is at present domestic does not see bibliographical information.In the bibliographic data base, do not see the pertinent literature report at present abroad.

(3) summary of the invention

It is low to the present invention is directed to existing polyepichlorohydrin-dimethylamine decolor flocculating agent molecular weight, the deficiency that dosage is big, provide a kind of production technique simple and direct, economical, be suitable for, can be widely used in that textile printing and dyeing handles, not only have good storage stability but also have the polyepichlorohydrin-dimethylamine organic polymer coargulator and the preparation technology thereof of good flocculating effect.

A kind of polyepichlorohydrin-dimethylamine organic polymer coargulator, its outward appearance are light yellow or colourless liquid, and cationic degree is at 5～6mmol/g, and solid content is 60%～70%, and viscosity is 2800～3200mpas.

The preparation technology of above-mentioned polyepichlorohydrin-dimethylamine organic polymer coargulator is:

(1) getting mass percentage concentration is dimethylamine solution 89～91g of 33%, places three mouthfuls of round-bottomed flasks of 150ml, flask is placed in the frozen water bath cools off, and dimethylamine solution is cooled to below 10 ℃;

(2) epoxy chloropropane with 73～75g adds separating funnel, opens the water coolant of reflux exchanger, under condition of stirring, with 1～2h epoxy chloropropane is added drop-wise in the cold dimethylamine solution, makes the temperature in the reactor be controlled at 10 ℃～20 ℃;

(3) dropwise after, restir 30min drops to below 10 ℃ the temperature in the reactor once more;

(4) add 1 of 4.3～4.5g at last, 6-hexanediamine linking agent, thermostatic control stops behind the reaction 5h at 60 ℃～75 ℃, prepares the polyepichlorohydrin-dimethylamine organic polymer coargulator finished product.

The polyepichlorohydrin-dimethylamine organic floculant that the present invention prepares is as a kind of new and effective decolorizing printing and dyeing waste water medicament.Polyepichlorohydrin-dimethylamine flocculation agent of the present invention compared with prior art has following excellent results:

Polyepichlorohydrin-dimethylamine flocculation agent of the present invention belongs to novel organic polymer coargulator in the water treatment field.This flocculation agent is the inorganic organic polymer coargulator of NEW TYPE OF COMPOSITE that grows up at the lower polyepichlorohydrin-dimethylamine of original molecular weight, be to be raw material with epoxy chloropropane and dimethylamine, adopt to introduce on a small quantity 1, the method for 6-hexanediamine linking agent is prepared from.Have characteristics such as production technique is simple and direct, economic, suitable.This flocculation agent can be widely used in textile printing and dyeing and handle, and good water treatment effect is arranged.

(4) embodiment

Embodiment 1:

A kind of polyepichlorohydrin-dimethylamine organic polymer coargulator, its outward appearance are light yellow or colourless liquid, and cationic degree is at 5～6mmol/g, and solid content is 60%～70%, and viscosity is 2800～3200mpas.

The preparation technology of above-mentioned polyepichlorohydrin-dimethylamine organic polymer coargulator is:

(1) getting mass percentage concentration is dimethylamine solution 89～91g of 33%, places three mouthfuls of round-bottomed flasks of 150ml, flask is placed in the frozen water bath cools off, and dimethylamine solution is cooled to below 10 ℃;

(2) epoxy chloropropane with 73～75g adds separating funnel, opens the water coolant of reflux exchanger, under condition of stirring, with 1～2h epoxy chloropropane is added drop-wise in the cold dimethylamine solution, makes the temperature in the reactor be controlled at 10 ℃～20 ℃;

(3) dropwise after, restir 30min drops to below 10 ℃ the temperature in the reactor once more;

(4) add 1 of 4.3～4.5g at last, 6-hexanediamine linking agent, thermostatic control stops behind the reaction 5h at 60 ℃～75 ℃, prepares the polyepichlorohydrin-dimethylamine organic polymer coargulator finished product.

To be used for the coagulating treatment of DISPERSE NAVY BLUE EXSF 300﹠ BLUE 56 100 waste water by above-mentioned steps synthetic polyepichlorohydrin-dimethylamine, and with polymerize aluminum chloride (PAC), Poly Dimethyl Diallyl Ammonium Chloride (PDMDAAC) contrasts.The raw water quality situation is as follows: pH value 6.56, dispersed deep blue dye content are 100mg/L, and absorbancy is 2.023.Result is listed in table 1.

Table 1 polyepichlorohydrin-dimethylamine flocculation agent is used for the DISPERSE NAVY BLUE EXSF 300﹠ BLUE 56 100 decolorizing effect

No.	Under the different dosages (in mg/L), the percent of decolourization of water sample (%)
							10	15	20	30	40	50
	Polyepichlorohydrin-dimethylamine	10.7	56.8	96	94.4	76.6							30
PDMDAAC							34.3	45.3	80.5	93.7	88.1	42.3
	PAC	1.2	11.9	32.6	40.9	55.7							69.2

From above result as seen, percent of decolourization reached the best when polyepichlorohydrin-dimethylamine was 20mg/L at dosage, and its percent of decolourization is three times of PAC, and percent of decolourization has improved 15% than PDMDAAC under equal throwing amount condition.

To be used for the coagulating treatment of active emerald green blue waste water by above-mentioned steps synthetic polyepichlorohydrin-dimethylamine, and and PAC, PDMDAAC contrasts.The raw water quality situation is as follows: pH value 6.56, dispersed deep blue dye content are 100mg/L, and absorbancy is 2.023.Result is listed in table 2.

Table 2 polyepichlorohydrin-dimethylamine flocculation agent is used for active emerald green blue decolorizing effect

The flocculation agent kind	Under the different dosages (in mg/L), the percent of decolourization of water sample (%)
							50	100	150	200	250	300
	Polyepichlorohydrin-dimethylamine	80.7	85.3	92.6	81.5	79.9							78
PDMDAAC							71.2	73.2	75.9	86.2	89.2	92.3
	PAC	54	56.9	58.8	61.5	65							68

From above result as seen, polyepichlorohydrin-dimethylamine flocculation agent and PDMDAAC flocculation agent all can reach the percent of decolourization more than 90% when handling active emerald green blue water sample, obviously be better than the PAC flocculation agent.But the consumption of polyepichlorohydrin-dimethylamine flocculation agent has significantly reduced the cost of the output and the flocculation treatment of mud only for PDMDAAC half when reaching best decolorizing effect.

To be used for the coagulating treatment of the undressed waste water of Binzhou, Shandong spring dyeing and weaving group's water collecting basin dawn by above-mentioned steps synthetic polyepichlorohydrin-dimethylamine, and and PAC, PDMDAAC contrasts, and result sees Table 3.The raw water quality situation is as follows: the waste water water sample is blue-greenish colour, and maximum absorption wavelength is at the 420nm place after measured, and the absorbancy under this wavelength is 2.30, and water temperature is 20.5 ℃, pH value 8.03, and COD is 1236mg/L.

Table 3 polyepichlorohydrin-dimethylamine flocculation agent is used for the treatment effect of actual dying

Flocculant dosage (mg/L)	Polyepichlorohydrin-dimethylamine		PDMDAAC		PAC
							Percent of decolourization	The COD clearance	Percent of decolourization	The COD clearance	Percent of decolourization	The COD clearance
	50	55.8	10.5	26.1	7.6	11.6							3.3
100							72.1	17.4	62.9	12.6	17.5	10.2
	150	80.7	28.9	76.2	23.3	58.8							18.7
200							87.4	42	77.1	40.6	69.8	28.6
	250	92.6	54	78.7	42.6	74.5							33.3
300							90.3	67.8	70.6	50.6	77.1	40.8

From above result as seen, the flocculating effect that the polyepichlorohydrin-dimethylamine flocculation agent is handled actual dying obviously is better than PAC flocculation agent and PDMDAAC flocculation agent, percent of decolourization improves 14% than PDMDAAC when best feed rate 250mg/L, improve 18% than PAC, and the COD clearance improves 12% than PDMDAAC, improves 21% than PAC.

Claims (2)

1, a kind of polyepichlorohydrin-dimethylamine organic polymer coargulator is characterized in that, outward appearance is light yellow or colourless liquid, and cationic degree is between 5～6mmol/g, and solid content is 60%～70%, and viscosity is 2800～3200mpas.

2, a kind of preparation method of polyepichlorohydrin-dimethylamine organic polymer coargulator is characterized in that, preparation technology is:

(1) getting mass percentage concentration is dimethylamine solution 89～91g of 33%, places three mouthfuls of round-bottomed flasks of 150ml, flask is placed in the frozen water bath cools off, and dimethylamine solution is cooled to below 10 ℃;

(2) epoxy chloropropane with 73～75g adds separating funnel, opens the water coolant of reflux exchanger, under condition of stirring, with 1～2h epoxy chloropropane is added drop-wise in the cold dimethylamine solution, makes the temperature in the reactor be controlled at 10 ℃～20 ℃;

(3) dropwise after, restir 30min drops to below 10 ℃ the temperature in the reactor once more;

(4) add 1 of 4.3～4.5g at last, 6-hexanediamine linking agent, thermostatic control stops behind the reaction 5h at 60 ℃～75 ℃, prepares the polyepichlorohydrin-dimethylamine organic polymer coargulator finished product.