CN103450393B - A kind of direct process is containing the nano-compound adsorbent preparation method of chrome tanning waste water - Google Patents

A kind of direct process is containing the nano-compound adsorbent preparation method of chrome tanning waste water Download PDF

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CN103450393B
CN103450393B CN201310447811.1A CN201310447811A CN103450393B CN 103450393 B CN103450393 B CN 103450393B CN 201310447811 A CN201310447811 A CN 201310447811A CN 103450393 B CN103450393 B CN 103450393B
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waste water
chrome tanning
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CN103450393A (en
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马宏瑞
鄂涛
畅浩
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Shaanxi University of Science and Technology
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Abstract

A kind of direct process is containing the nano-compound adsorbent preparation method of chrome tanning waste water.At present, for low concentration heavy metal water, conventional treatment process has absorption method, ion exchange method etc., and these class methods cannot carry out selective adsorption to chromium.The present invention for raw material, adopts aqueous free radical polymerization to prepare vinylic polymers/nano titanium oxide P(DMDAAC-MAA-AM-HEA with diallyldimethylammonium chloride, methacrylic acid, acrylamide, Hydroxyethyl acrylate and nano titanium oxide)/TiO 2nano-compound adsorbent, adopt sorbent material of the present invention processing under acidic conditions, directly process lower concentration Chrome Tanning Wastewater, chromium clearance can reach 98.6%.Sorbent material of the present invention has pH value adaptability widely, high Selective adsorption to Cr, and be not subject to the interference of other pollutents in waste water, loading capacity is large, and processing efficiency is high, is particularly suitable for directly processing acid lower concentration Chrome Tanning Wastewater.

Description

A kind of direct process is containing the nano-compound adsorbent preparation method of chrome tanning waste water
Technical field
The present invention relates to the preparation method of a kind of leather chrome tanning Sewage advanced treatment nano-compound adsorbent used, be specifically related to the nano-compound adsorbent preparation method of a kind of direct process containing chrome tanning waste water.
Background technology
Chromic tanning is the most ripe in current tanning industry, that quality product is the most reliable, cost is minimum process for tanning [RaoJ.R., NairB.U.; Integrationofchrometanningandwetfinishingprocessformakin ggarmentleathers.JournaloftheAmericanLeatherChemistsAsso ciation100:225-232,2005.].The annual working ability of whole world leather industry is 1,500 ten thousand t hides, the finished leather of about 90% produces [Fundamentalsofleathermanufacture.EduardRoetherKG by chromic tanning, pp.270,1993.], its Cr of the chromate waste water produced after chrome tanning 2o 3content generally at 500 ~ 2000mg/L, secondly, in tanning dyeing section, due to high temperature action under acidic conditions can make tanning after originally combine that unstable chromium is de-from skin surely to be entered in waste water.If these chromium enter environment, can deposit in large quantities in soil and water, trivalent Cr can be oxidized to sexavalence Cr and can directly cause damage to human body skin simultaneously, brings out various disease or even cancer [V.J.Sundar, J.RaghavaRao, C.Muralidharan; Cleanerchrometanning-emergingoptions [J] .JournalofCleanerProduction, 2002, (10): 69-74.].
The sewage quantity that tannery gives off is more than 600,000,000 m 3/ year [SalmaA.A.S., Gurashi.A.G., A.EMusa; ExtractionofChromiumSixfromChromeShavings.JournalofFores tProducts & Industries2,21-26,2013.], the chromate waste water wherein discharged accounts for more than 1/10th.For high density high concentration chrome wastewater, tannery adopts the process of alkaline chemical precipitation method usually, this method treatment effect is better, in tanning sewage after process, the clearance of total chromium can reach more than 98%, but the total chromium concn in processed waste water is generally within 2.0 ~ 10mg/L, particularly the master that reuse number of times is more is tanned water and retanning dyeing section waste water, due to adding of various chemical assistant, pH value changes, the generation of water-disintegrable Collagen material in metal ion and leather making process, chromium and these materials can be made to produce complexing action, or be oxidized to chromic salt etc., cause adopting conventional alkaline chemical precipitation method to be difficult to the stable national standard reaching total Cr concentration≤1.5mg/L.For low concentration heavy metal water, treatment process conventional at present has absorption method, ion exchange method etc., these class methods are due to restrictions such as the interference by concurrents such as high in salt in waste water, high organics, selective adsorption cannot be carried out to chromium, in addition the problem such as investment and running cost is higher, complicated operation, is difficult to implement at leather-making enterprises.
Along with the development of nanotechnology, in leather chemicals, the exploitation of nano material has become the focus of research, organic-inorganic nanocomposite materials with the obligate absorption of chromium in show special advantage, but nanocomposite applications is not also had related products and application at present in the advanced treatment of process hides tanning waste water, and by nano leather chemical the excellent properties that goes out of surface, for lower concentration provides a kind of possible containing the advanced treatment of chrome tanning waste water.
Summary of the invention
The present invention aims to provide the nano-compound adsorbent preparation method of a kind of direct process containing chrome tanning waste water, this sorbent material both had surface adsorption, there is again the trapping of polymer electronics, there is the nano-compound adsorbent of nano effect simultaneously, the nano-compound adsorbent using the present invention to prepare directly can process lower concentration in acid condition containing chrome tanning waste water, can not produce secondary pollution, cost is lower, simple to operate.
For achieving the above object, the technical solution used in the present invention is:
1, by nano titanium oxide (TiO 2) add in four-hole boiling flask, add 100ml deionized water to disperse, make the solution that mass concentration is 2%-8%, at constant temperature 30 DEG C, 60min is stirred with 800r/min, left undisturbed overnight, next day, at 50 DEG C, add 17 ~ 23g diallyldimethylammonium chloride (DMDAAC), abundant stirring, ultrasonication, stand-by.
2, the acrylamide (AM) of 19 ~ 25g and Hydroxyethyl acrylate (HEA) mixed solution are added constant pressure funnel, AM:HEA mass ratio is 1:0.7 ~ 1:1.3,7 ~ 13g methacrylic acid (MAA) is added in second dropping funnel, initiator potassium persulfate adds in the 3rd dropping funnel, and add-on is 2% ~ 8% of monomer total mass, is warming up to 60 ~ 90 DEG C, stirring velocity is 100 ~ 300r/min, drip monomer and initiator, 1h is added dropwise to complete, isothermal reaction 1 ~ 3h simultaneously.
3, after reaction terminates, cooling, adjust ph is 3 ~ 9, obtained vinylic polymers/nano titanium oxide P(DMDAAC-MAA-AM-HEA)/TiO 2solution.
4, at ambient temperature, by the P(DMDAAC-MAA-AM-HEA of preparation)/TiO 2; Be placed in vacuum drying oven, dry rear grinding, then cross 100-150 mesh sieve for 40 DEG C, obtained P(DMDAAC-MAA-AM-HEA)/TiO 2powder.
The present invention has prepared P(DMDAAC-MAA-AM-HEA with aqueous free radical polymerization)/TiO 2nano-compound adsorbent, this sorbent material comprises amino, carboxyl, hydroxyl, titanium dioxide nano-particle etc., form colloidal solid by the chromium ion in the adsorption of Low Concentration Chrome Tanning Wastewater such as ionic linkage, hydrogen bond, Fan get Hua Li, nano titania effect, produce " bridge formation " effect between particles, form a kind of reticulated structure and precipitate, thus show very strong adsorptive power, not only there is physical adsorption in this process, but also there is the trapping of polymer electronics and flocculation, there is nano effect simultaneously.Experiment records sorbent material of the present invention and directly processes lower concentration in acid condition containing chrome tanning waste water, and clearance can reach 95.0-98.6%, and sink to the bottom rapidly, can not produce secondary pollution, Financial cost is low, simple to operate, stable.
Embodiment
Below in conjunction with embodiment, the present invention will be described in detail.
Embodiment 1:
1, by nano titanium oxide (TiO 2) add in four-hole boiling flask, add 100ml deionized water to disperse, make the solution that mass concentration is 5%, at constant temperature 30 DEG C, 60min is stirred with 800r/min, left undisturbed overnight, next day, at 50 DEG C, add 20g diallyldimethylammonium chloride (DMDAAC), abundant stirring, ultrasonication, stand-by.
2, the acrylamide (AM) of 22g and Hydroxyethyl acrylate (HEA) mixed solution are added constant pressure funnel, AM:HEA mass ratio is 1:0.7, added by 10g methacrylic acid (MAA) in second dropping funnel, initiator potassium persulfate adds in the 3rd dropping funnel, and add-on is 5% of monomer total mass, be warming up to 80 DEG C, stirring velocity is, 200r/min, drips monomer and initiator simultaneously, 1h is added dropwise to complete, isothermal reaction 2.5h.
3, after reaction terminates, cooling, adjust ph is 7, obtained P(DMDAAC-MAA-AM-HEA)/TiO 2solution.
4, at ambient temperature, by the P(DMDAAC-MAA-AM-HEA of preparation)/TiO 2; Be placed in vacuum drying oven, dry rear grinding, then cross 100-150 mesh sieve for 40 DEG C, obtained P(DMDAAC-MAA-AM-HEA)/TiO 2powder.
Embodiment 2:
1, by nano titanium oxide (TiO 2) add in four-hole boiling flask, add 100ml deionized water to disperse, make the solution that mass concentration is 8%, at constant temperature 30 DEG C, 60min is stirred with 800r/min, left undisturbed overnight, next day, at 50 DEG C, add 17g diallyldimethylammonium chloride (DMDAAC), abundant stirring, ultrasonication, stand-by.
2, the acrylamide (AM) of 19g and Hydroxyethyl acrylate (HEA) mixed solution are added constant pressure funnel, AM:HEA mass ratio is 1:1, added by 7g methacrylic acid (MAA) in second dropping funnel, initiator potassium persulfate adds in the 3rd dropping funnel, and add-on is 3% of monomer total mass, be warming up to 70 DEG C, stirring velocity is, 200r/min, drips monomer and initiator simultaneously, 1h is added dropwise to complete, isothermal reaction 3h.
3, after reaction terminates, cooling, adjust ph is 7, obtained P(DMDAAC-MAA-AM-HEA)/TiO 2solution.
4, at ambient temperature, by the P(DMDAAC-MAA-AM-HEA of preparation)/TiO 2; Be placed in vacuum drying oven, dry rear grinding, then cross 100-150 mesh sieve for 40 DEG C, obtained P(DMDAAC-MAA-AM-HEA)/TiO 2powder.
Embodiment 3:
1, by nano titanium oxide (TiO 2) add in four-hole boiling flask, add 100ml deionized water to disperse, make the solution that mass concentration is 6%, at constant temperature 30 DEG C, 60min is stirred with 800r/min, left undisturbed overnight, next day, at 50 DEG C, add 22g diallyldimethylammonium chloride (DMDAAC), abundant stirring, ultrasonication, stand-by.
2, the acrylamide (AM) of 25g and Hydroxyethyl acrylate (HEA) mixed solution are added constant pressure funnel, AM:HEA mass ratio is 1:1.1, added by 12g methacrylic acid (MAA) in second dropping funnel, initiator potassium persulfate adds in the 3rd dropping funnel, and add-on is 4% of monomer total mass, be warming up to 90 DEG C, stirring velocity is, 200r/min, drips monomer and initiator simultaneously, 1h is added dropwise to complete, isothermal reaction 2.5h.
3, after reaction terminates, cooling, adjust ph is 8, obtained P(DMDAAC-MAA-AM-HEA)/TiO 2solution.
4, at ambient temperature, by the P(DMDAAC-MAA-AM-HEA of preparation)/TiO 2; Be placed in vacuum drying oven, dry rear grinding, then cross 100-150 mesh sieve for 40 DEG C, obtained P(DMDAAC-MAA-AM-HEA)/TiO 2powder.
Embodiment 4
1, by nano titanium oxide (TiO 2) add in four-hole boiling flask, add 100ml deionized water to disperse, make the solution that mass concentration is 5%, at constant temperature 30 DEG C, 60min is stirred with 800r/min, left undisturbed overnight, next day, at 50 DEG C, add 23g diallyldimethylammonium chloride (DMDAAC), abundant stirring, ultrasonication, stand-by.
2, the acrylamide (AM) of 23g and Hydroxyethyl acrylate (HEA) mixed solution are added constant pressure funnel, AM:HEA mass ratio is 1:1.1, added by 12g methacrylic acid (MAA) in second dropping funnel, initiator potassium persulfate adds in the 3rd dropping funnel, and add-on is 7% of monomer total mass, be warming up to 85 DEG C, stirring velocity is, 300r/min, drips monomer and initiator simultaneously, 1h is added dropwise to complete, isothermal reaction 2.5h.
3, after reaction terminates, cooling, adjust ph is 9, obtained P(DMDAAC-MAA-AM-HEA)/TiO 2solution.
4, at ambient temperature, by the P(DMDAAC-MAA-AM-HEA of preparation)/TiO 2; Be placed in vacuum drying oven, dry rear grinding, then cross 100-150 mesh sieve for 40 DEG C, obtained P(DMDAAC-MAA-AM-HEA)/TiO 2powder.
Embodiment 5:
1, by nano titanium oxide (TiO 2) add in four-hole boiling flask, add 100ml deionized water to disperse, make the solution that mass concentration is 3%, at constant temperature 30 DEG C, 60min is stirred with 800r/min, left undisturbed overnight, next day, at 50 DEG C, add 19g diallyldimethylammonium chloride (DMDAAC), abundant stirring, ultrasonication, stand-by.
2, the acrylamide (AM) of 24g and Hydroxyethyl acrylate (HEA) mixed solution are added constant pressure funnel, AM:HEA mass ratio is 1:0.8, added by 12g methacrylic acid (MAA) in second dropping funnel, initiator potassium persulfate adds in the 3rd dropping funnel, and add-on is 7% of monomer total mass, be warming up to 90 DEG C, stirring velocity is, 200r/min, drips monomer and initiator simultaneously, 1h is added dropwise to complete, isothermal reaction 1.5h.
3, after reaction terminates, cooling, adjust ph is 4, obtained P(DMDAAC-MAA-AM-HEA)/TiO 2solution.
4, at ambient temperature, by the P(DMDAAC-MAA-AM-HEA of preparation)/TiO 2; Be placed in vacuum drying oven, dry rear grinding, then cross 100-150 mesh sieve for 40 DEG C, obtained P(DMDAAC-MAA-AM-HEA)/TiO 2powder.
Embodiment 6:
1, by nano titanium oxide (TiO 2) add in four-hole boiling flask, add 100ml deionized water to disperse, make the solution that mass concentration is 3%, at constant temperature 30 DEG C, 60min is stirred with 800r/min, left undisturbed overnight, next day, at 50 DEG C, add 21g diallyldimethylammonium chloride (DMDAAC), abundant stirring, ultrasonication, stand-by.
2, the acrylamide (AM) of 23g and Hydroxyethyl acrylate (HEA) mixed solution are added constant pressure funnel, AM:HEA mass ratio is 1:1.2, added by 9g methacrylic acid (MAA) in second dropping funnel, initiator potassium persulfate adds in the 3rd dropping funnel, and add-on is 7% of monomer total mass, be warming up to 90 DEG C, stirring velocity is, 200r/min, drips monomer and initiator simultaneously, 1h is added dropwise to complete, isothermal reaction 3h.
3, after reaction terminates, cooling, adjust ph is 5, obtained P(DMDAAC-MAA-AM-HEA)/TiO 2solution.
4, at ambient temperature, by the P(DMDAAC-MAA-AM-HEA of preparation)/TiO 2; Be placed in vacuum drying oven, dry rear grinding, then cross 100-150 mesh sieve for 40 DEG C, obtained P(DMDAAC-MAA-AM-HEA)/TiO 2powder.
Experimental data (following data are the mean value of three actual measurements):

Claims (1)

1. directly process, containing a nano-compound adsorbent preparation method for chrome tanning waste water, is characterized in that: the step of this preparation method is as follows:
(1), nano titanium oxide is added in four-hole boiling flask, add 100mL deionized water to disperse, make the solution that mass concentration is 2%-8%, at constant temperature 30 DEG C, 60min is stirred with 800r/min, left undisturbed overnight, next day, at 50 DEG C, add 17 ~ 23g diallyldimethylammonium chloride, abundant stirring, ultrasonication, stand-by;
(2), the acrylamide of 19 ~ 25g and Hydroxyethyl acrylate mixed solution are added constant pressure funnel, acrylamide: Hydroxyethyl acrylate mass ratio is 1:0.7 ~ 1:1.3,7 ~ 13g methacrylic acid is added in second dropping funnel, initiator potassium persulfate adds in the 3rd dropping funnel, and add-on is 2% ~ 8% of monomer total mass, is warming up to 60 ~ 90 DEG C, stirring velocity is 100 ~ 300r/min, drip monomer and initiator, 1h is added dropwise to complete, isothermal reaction 1 ~ 3h simultaneously;
(3), after reaction terminates, cooling, adjust ph is 3 ~ 9, obtained vinylic polymers/nanometer titanium dioxide titanium solution;
(4), at ambient temperature, by the vinylic polymers/nano titanium oxide of preparation; Be placed in vacuum drying oven, dry rear grinding, then cross 100-150 mesh sieve for 40 DEG C, obtained P(DMDAAC-MAA-AM-HEA)/TiO 2powder.
CN201310447811.1A 2013-09-27 2013-09-27 A kind of direct process is containing the nano-compound adsorbent preparation method of chrome tanning waste water Active CN103450393B (en)

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WO2006007001A1 (en) * 2004-06-17 2006-01-19 Kemira Oyj Cationic polymers containing 2-mhydrocyethyl-methacrylic as promoters for asa sizing
CN101619366A (en) * 2009-07-21 2010-01-06 陕西科技大学 Preparation method of amphoteric vinyl polymer/ZnO nanocomposite tanning agent
CN101864022A (en) * 2010-06-17 2010-10-20 陕西科技大学 Method for preparing vinyl polymer/inorganic nanoparticle composite tanning agent by in-situ cyclopolymerization method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006007001A1 (en) * 2004-06-17 2006-01-19 Kemira Oyj Cationic polymers containing 2-mhydrocyethyl-methacrylic as promoters for asa sizing
CN101619366A (en) * 2009-07-21 2010-01-06 陕西科技大学 Preparation method of amphoteric vinyl polymer/ZnO nanocomposite tanning agent
CN101864022A (en) * 2010-06-17 2010-10-20 陕西科技大学 Method for preparing vinyl polymer/inorganic nanoparticle composite tanning agent by in-situ cyclopolymerization method

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