CN201283290Y - Poly-m-phenylenediamine absorption block embedded by polyvinyl alcohol - Google Patents

Abstract

The utility model discloses a poly phenylene-diamine adsorption block embedded by polyvinyl alcohol, which comprises a random coil shaped framework structure which is formed by polyvinyl alcohol, and poly phenylene-diamine powder is distributed in the framework structure. The poly phenylene-diamine adsorption block embedded by polyvinyl alcohol can be used to absorb heavy metal ions, in particular to lead ions.

Description

The poly m-phenylene diamine Attraction block of polyvinyl alcohol embedding

Technical field

The utility model relates to the Industrial Wastewater Treatment material, is specifically related to the poly m-phenylene diamine Attraction block of polyvinyl alcohol embedding.

Background technology

Lead ion itself has sizable toxicity as a kind of heavy metal ion, will cause very big harm to environment if will contain the direct discharging of waste liquid of lead ion, therefore need handle the waste liquid of discharging.Adopt the synthetic poly m-phenylene diamine of chemical oxidative polymerization that lead ion is had good adsorption performance (Mei-Rong Huang, Qian-Yun Peng, Xin-Gui Li.Rapid and Effective Adsorption of Lead Ions on Fine PolyphenylenediamineMicroparticles.Chemistry, A European Journal, 2006,12,4341-4350.Huang Meirong, cloud use of Pb ion absorbent of polyphenylene diamine before the Li upstart, Peng, publication number: CN1840235).But, the nascent polymer that generates has inconvenience because originally as Powdered, directly using.Therefore, be necessary its embedding is become the above particle of millimeter level, so that Separation of Solid and Liquid makes it have real practical application potentiality in the Industrial Wastewater Treatment field.

Embedding medium commonly used has sodium alginate, PVA (polyvinyl alcohol), polyacrylamide, gelatin, carragheen etc.Wherein polyvinyl alcohol is a kind of novel fixation support, have intensity height, good, the antimicrobial capacity of decomposition of chemical stability strong, to series of advantages such as microorganism are nontoxic, cheap, be a kind of embedded material with practical potentiality.At home and abroad obtained in recent years than extensive studies.At present the embedding of polyvinyl alcohol generally is to make crosslinking agent with boric acid, can make the mechanical strength height of embedding bead owing to crosslinked effect like this, long service life, and good springiness.But the meeting of crosslinked action simultaneously makes embedding bead inside generate fine and close network structure, has influenced the mass-transfer performance of bead.Adopt the crosslinked embedding method of polyvinyl alcohol-boric acid to come the embedding poly m-phenylene diamine, the absorption property of adsorbent descends with Powdered comparing to some extent after the embedding.Constantly there is the people that the crosslinked embedding method of polyvinyl alcohol-boric acid is improved in recent years, has the people to overcome polyvinyl alcohol-H as additive with sodium alginate ₃BO ₃The shortcoming of method immobilization balling-up difficulty (Li Feng, Lv Xiwu, Yan Wei. polyvinyl alcohol is as the research of immobilized cell embedding medium, Chinese water supply and drainage, 2000,16 (12): 14-17).Someone adds CaCO ₃Increase the permeability of granule of polyvinyl alcohol.In polyvinyl alcohol, add SiO ₂, not only can increase the proportion of particle, reduce the rising phenomenon in system ball and processing procedure, and can generate CaOSiO with the calcium salt that adds ₂Glue can further increase particle operation stability (Min Hang, Zheng Yaotong, Qian Zeshu, etc. the polyvinyl alcohol embedding anaerobic activated sludge is handled the optimal condition research of waste water, environmental science, 1994,15 (5): 10 ~ 14).Someone adopts the time-delay embedding method to make the network of prepared immobilization gel particle closely knit evenly, and twine interconnects.This make the water-soluble dilatancy of particle obtained inhibition to a certain degree (Shi Hanchang is etc. the improvement of polyvinyl alcohol-boric acid process for fixation for Li Huazi, Wang Jianlong. Research of Environmental Sciences, 2002,12 (5): 25-27).Below all be the improved trial of on the basis of making crosslinking agent with boric acid, carrying out, but also do not make crosslinking agent and use the report of polyvinyl alcohol merely as embedding medium without boric acid.

The utility model content

The purpose of this utility model just provides a kind of poly m-phenylene diamine Attraction block of operating the polyvinyl alcohol embedding simple and easy, with low cost, that adsorption effect is excellent, and this Attraction block is little to the adsorbent of poly m-phenylene diamine performance impact after embedding.

For realizing above purpose, the utility model is achieved through the following technical solutions:

A kind of poly m-phenylene diamine Attraction block of polyvinyl alcohol embedding, Attraction block comprise the skeleton structure of the random coil shape of being made up of polyvinyl alcohol, are furnished with the poly m-phenylene diamine powder between skeleton structure.

Preferable, the particle diameter (full-size) of the poly m-phenylene diamine Attraction block of above-mentioned polyvinyl alcohol embedding is 5-30mm.

Above-mentioned Attraction block can adopt following method preparation:

It is 7.5%～8.5% solution that polyvinyl alcohol is made weight content, according to poly m-phenylene diamine and polyvinyl alcohol weight ratio is that 0.8～2:1 joins poly m-phenylene diamine in the described poly-vinyl alcohol solution and mixes, dry, when poly m-phenylene diamine was joined poly-vinyl alcohol solution, keeping the temperature of solution was 25～50 ℃.

Preferable, poly m-phenylene diamine and polyvinyl alcohol weight ratio are 1.4～1.8:1.

The beneficial effects of the utility model: the poly m-phenylene diamine Attraction block of the direct embedding of polyvinyl alcohol of the present utility model, preparation is simple, and is with low cost.This Attraction block not only has certain mechanical performance, and mass-transfer performance is good, can keep the heavy metal ion adsorbed performance of Powdered adsorbent largely.Take all factors into consideration cost of material, cost of manufacture and absorption property, have very big potential actual application value with the adsorbent of poly m-phenylene diamine of polyvinyl alcohol embedding.Be significant in the application of water treatment field for the exploitation poly m-phenylene diamine.

The prepared breakage rate with the poly m-phenylene diamine powder sorbent of polyvinyl alcohol embedding of the utility model adopts following method to measure:

The adsorbent of poly m-phenylene diamine with polyvinyl alcohol embedding that makes in the utility model is made bulk, accurately taking by weighing 0.10g is put in the 50mL distilled water, in 30 ℃ water bath with thermostatic control, stir 24h, filter, take out and weigh after the intact adsorbent of poly m-phenylene diamine with polyvinyl alcohol embedding dries naturally, calculate breakage rate according to the weight change before and after handling.Get its mean value by twice parallel laboratory test.

Adsorbent of poly m-phenylene diamine adsorpting lead ion adsorption capacity and clearance with polyvinyl alcohol embedding that the utility model is prepared adopt static adsorptive method to detect, and step is as follows:

Take by weighing and contain 50mg with the adsorbent of poly m-phenylene diamine of polyvinyl alcohol embedding, place that to contain 25mL concentration be 487.3mgL ^-1The conical flask of lead nitrate solution in, 20～40 ℃ of following stirring and adsorbing 2 hours, filter, with remaining Pb in the complexometric titration filtrate ²⁺Concentration C '.Calculate adsorbents adsorb capacity Q (mg g respectively according to formula (1) and (2) ^-1) and clearance q (%).

$Q=\frac{(487.3-C\′)\×0.025}{0.05}$

$q=\frac{(487.3-C\′)}{487.3}\×100\%---\left(2\right)$

Adsorbent of poly m-phenylene diamine absorption mercury ion adsorption capacity and clearance with polyvinyl alcohol embedding that the utility model is prepared adopt static adsorptive method to detect, and step is as follows:

Take by weighing and contain 50mg with the adsorbent of poly m-phenylene diamine of polyvinyl alcohol embedding, place that to contain 25mL concentration be 398mgL ^-1The conical flask of mercuric nitrate solution in, 20～40 ℃ of following stirring and adsorbing 1～30 minute, filter, with remaining Hg in the complexometric titration filtrate ²⁺Concentration C.Calculate adsorbents adsorb capacity Q (mg g respectively according to formula (3) and (4) ^-1) and clearance q (%).

$Q=\frac{(398-C)\×0.025}{0.05}---\left(3\right)$

$q=\frac{(398-C)}{398}\×100\%---\left(4\right)$

Description of drawings

The poly m-phenylene diamine Attraction block schematic diagram of Fig. 1 polyvinyl alcohol embedding

The skeleton schematic diagram of the poly m-phenylene diamine Attraction block of Fig. 2 polyvinyl alcohol embedding

The specific embodiment

The poly m-phenylene diamine Attraction block of polyvinyl alcohol embedding as shown in Figure 1, it is block that Attraction block is, and the about 10mm of particle diameter, Attraction block comprise the skeleton structure 1 of the random coil shape of being made up of polyvinyl alcohol, the skeleton structure schematic diagram is furnished with poly m-phenylene diamine powder 2 as shown in Figure 2 between skeleton structure.

Poly m-phenylene diamine in the above-mentioned Attraction block adopts following method preparation:

0.08mol (8.652g) monomer m-phenylene diamine (MPD) is dissolved in the 200mL distilled water, ultrasonic 3～5 minutes, impel it fully to dissolve, then monomer solution is placed 30 ℃ of water-baths, balance half an hour.The oxidant ammonium persulfate of 0.08mol (18.256g) is dissolved in the 100mL distilled water, also it is maintained 30 ℃.This ammonium persulfate solution is added in the above-mentioned monomer solution.Reacted 24 hours, suction filtration, and with distilled water wash products in funnel, until using BaCl ₂Solution check sulfate radical-free ion.Drain after cleaning, product was descended dry 3 days at 50 ℃, obtain poly m-phenylene diamine, productive rate 80.6%.

The poly m-phenylene diamine Attraction block of above-mentioned polyvinyl alcohol embedding adopts the following proposal preparation:

The 4g polyvinyl alcohol is dissolved in the 46mL90 ℃ of left and right sides hot water, after waiting to dissolve it is cooled to about 40 ℃, be mixed with the poly-vinyl alcohol solution that weight concentration is 8wt%.Measure this poly-vinyl alcohol solution of 10mL to the 200mL beaker, add 0.8g poly m-phenylene diamine powder, stir and ultrasonic processing about 20 minutes with glass bar, impel the two to mix, 40 ℃ of left and right sides cross-linking reactions were carried out 24 hours.This mixed liquid is poured in the culture dish of clean drying, made it sprawl thick flat board into about 5mm.After 40 ℃ of dryings, then film is divided into square block standby of 10mm.Through breakage rate test, be 10.2% with the adsorbent of poly m-phenylene diamine breakage rate of polyvinyl alcohol embedding.Detecting through static adsorptive method, is 487.3mgL without the adsorbent of poly m-phenylene diamine with polyvinyl alcohol embedding of swelling to the 25mL initial concentration ^-1 Mercuric nitrate absorption 2 hours, recording adsorption capacity is 181.03mg/g, clearance is 74.30%.

The bulk that obtains adopts static adsorptive method to detect with adsorbent of poly m-phenylene diamine swelling in distilled water of polyvinyl alcohol embedding after 4 hours, and recording 25mL concentration is 487.3mgL ^-1The adsorption capacity of plumbi nitras be 183.27mg/g, clearance is 75.22%; Swelling time changes 6 hours into, adopts static adsorptive method to detect, and adsorption capacity is 188.00mg/g, and clearance is 77.16%; Swelling time changes 8 hours into, adopts static adsorptive method to detect, and adsorption capacity is 190.58mg/g, and clearance is 78.22%; Swelling time changes 10 hours into, adopts static adsorptive method to detect, and adsorption capacity is 190.61mg/g, and clearance is 78.23%.

Without the adsorbent of poly m-phenylene diamine with polyvinyl alcohol embedding of swelling, be 398mgL to the 25mL initial concentration ^-1Mercuric nitrate adsorb 1 minute, 5 minutes, 10 minutes, 15 minutes, 30 minutes respectively after, adsorption capacity is respectively 118mg/g, 156mg/g, 185mg/g, 187mg/g, 189mg/g, clearance is respectively 59%, 78%, 92%, 93%, 94%.

Claims (2)

1. the poly m-phenylene diamine Attraction block of a polyvinyl alcohol embedding is characterized in that, described Attraction block comprises the skeleton structure of the random coil shape of being made up of polyvinyl alcohol, is furnished with the poly m-phenylene diamine powder between skeleton structure.

2. the poly m-phenylene diamine Attraction block of polyvinyl alcohol embedding according to claim 1 is characterized in that the particle diameter of the poly m-phenylene diamine Attraction block of described polyvinyl alcohol embedding is 5-30mm.

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