CN104448131A - Preparation method of porous magnetic polyacrylamide (PAM) microsphere adsorbent - Google Patents
Preparation method of porous magnetic polyacrylamide (PAM) microsphere adsorbent Download PDFInfo
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- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 93
- 239000004005 microsphere Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003463 adsorbent Substances 0.000 title abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 238000007598 dipping method Methods 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- -1 polymeric polylol Chemical compound 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 150000005846 sugar alcohols Polymers 0.000 claims description 10
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 5
- 239000003637 basic solution Substances 0.000 claims description 5
- 239000004160 Ammonium persulphate Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000004159 Potassium persulphate Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000593 microemulsion method Methods 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 3
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 239000000975 dye Substances 0.000 abstract description 41
- 239000002351 wastewater Substances 0.000 abstract description 17
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract description 12
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 12
- 125000002091 cationic group Chemical group 0.000 abstract description 11
- 238000001179 sorption measurement Methods 0.000 abstract description 11
- 238000005406 washing Methods 0.000 abstract description 5
- PGSADBUBUOPOJS-UHFFFAOYSA-N neutral red Chemical compound Cl.C1=C(C)C(N)=CC2=NC3=CC(N(C)C)=CC=C3N=C21 PGSADBUBUOPOJS-UHFFFAOYSA-N 0.000 abstract description 4
- 229920006395 saturated elastomer Polymers 0.000 abstract description 2
- 239000012670 alkaline solution Substances 0.000 abstract 1
- ZXJXZNDDNMQXFV-UHFFFAOYSA-M crystal violet Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1[C+](C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZXJXZNDDNMQXFV-UHFFFAOYSA-M 0.000 abstract 1
- 229960001235 gentian violet Drugs 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 15
- 239000002594 sorbent Substances 0.000 description 13
- 230000000274 adsorptive effect Effects 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 239000002250 absorbent Substances 0.000 description 6
- 230000002745 absorbent Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 241000405217 Viola <butterfly> Species 0.000 description 2
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000009514 concussion Effects 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- SMEROWZSTRWXGI-HVATVPOCSA-N lithocholic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)CC1 SMEROWZSTRWXGI-HVATVPOCSA-N 0.000 description 2
- 239000006249 magnetic particle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000000452 restraining effect Effects 0.000 description 2
- MECHNRXZTMCUDQ-RKHKHRCZSA-N vitamin D2 Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)/C=C/[C@H](C)C(C)C)=C\C=C1\C[C@@H](O)CCC1=C MECHNRXZTMCUDQ-RKHKHRCZSA-N 0.000 description 2
- 235000001892 vitamin D2 Nutrition 0.000 description 2
- 239000011653 vitamin D2 Substances 0.000 description 2
- 208000026817 47,XYY syndrome Diseases 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- SMEROWZSTRWXGI-UHFFFAOYSA-N Lithocholsaeure Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)CC2 SMEROWZSTRWXGI-UHFFFAOYSA-N 0.000 description 1
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
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- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 235000019600 saltiness Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
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- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to a preparation method of a porous magnetic polyacrylamide (PAM) microsphere adsorbent. The method comprises the following steps: carrying out initiated polymerization on a PAM monomer synthesis liquid containing acrylamide, polymeric polylol, N,N-methylene bisacrylamide, an initiator and water in a form of a liquid drop, so as to obtain porous PAM microspheres; dipping the porous PAM microspheres into a mixed solution of Fe<2+> and Fe<3+> to reach dipping balance; separating to obtain PAM microspheres containing iron ions, and washing with deionized water; and dipping the microspheres into an alkaline solution, so as to obtain porous magnetic PAM microspheres. The porous magnetic PAM microspheres prepared by the method have strong adsorption action on cationic dyes, and have high saturated adsorption capacity on the cationic dyes, such as methylene blue, toluylene red and gentian violet, with various concentrations. The adsorption capacity of the adsorbent provided by the invention on the cationic dyes is over 10 times that of a traditional adsorbent under the same condition. The chromaticity of an adsorbed dye solution can be up to or close to the chromaticity requirement of domestic water, and zero emission of dye wastewater is achieved.
Description
Technical field
The present invention relates to a kind of preparation method of porous magnetic polyacrylamide PAM microsphere adsorbing agent of effective removal waste water cationic dyestuff, belong to adsorption technology field.
Background technology
Dye industry is one of important industry of fine chemical industry, and product is mainly used in the painted of textile printing and dyeing and timber, paper, leather, food etc.The dyestuff output of China accounts for more than 60% of global ultimate production, and kind is more than 1200 kinds, and the quantity discharged of waste water from dyestuff accounts for 2% of China's trade effluent total release, and quantity discharged is very large.Waste water from dyestuff does not have many materials biodegradable or produce the features such as obvious restraining effect to biology because its colourity is high, toxic organic pollutant content is high, saltiness is high, in waste water, cause huge pollution to environment.
In view of grave danger that waste water from dyestuff causes for environment and human body health, the treatment process of waste water from dyestuff is also varied.At present, the method for dye wastewater treatment mainly contains: biological degradation method, flocculence, high-level oxidation technology and absorption method etc.But aforesaid method is because of himself feature or defect, and it has many restrictions in the engineer applied of reality.Such as, a lot of dyestuff has comparatively significantly restraining effect to enzyme in biological degradation method and bacterium, causes biological degradation efficiency not high; Flocculence can produce a large amount of mud when dye wastewater treatment, and this may cause the pollution to environment; High-level oxidation technology all has higher requirement to physico-chemical properties etc. such as the pH of catalyzer and waste water, and actually operating costly, causes its practical application to be restricted.Moreover, dye species is various and towards anti-light solution, anti-oxidant, antibiooxidation future development, and this causes relying on oxidation technology dye wastewater treatment to become more and more difficult.Absorption method is because of its high efficiency and operation is comparatively simple, low cost and other advantages, and it highlights advantage gradually in the industrial difficult degradation waste water from dyestuff of process.At present, research about sorbent material is a lot, the kind of sorbent material is also varied, industrial application more still based on gac, in actual applications, the main drawback of gac is solid-liquid separation and regeneration comparatively difficulty, and this also causes its application to be restricted, moreover, gac is larger for the difference fluctuation of adsorptive capacity also because of selection of organic dye.In addition, what all the other application were more both comprises the low value product such as resin, clay, zeolite, wilkinite, flyash and sawdust, also comprise the novel material such as Graphene, MOFs, however due to cost is higher or due to adsorptive capacity not plateau because of, its application is all restricted.
Patent CN 101284223A discloses a kind of preparation method of magnetic porous carbon adsorbent, in basic solution, obtain metal hydroxides colloid and mix with resin solution, obtain resin/hydroxide colloid compound system, prepare through charing and activation except after desolventizing.But the magnetic porous carbon adsorbent prepared through this method to the adsorptive capacity of methylene radical orange and rhodamine B only less than 50mg/g.Patent CN 103447014A discloses the preparation method of a kind of polyacrylic acid/13X adsorbent of molecular sieve, 13X molecular sieve is added under agitation in polyacrylic acid solution, again through calcining, pulverizing obtains polyacrylic acid/13X adsorbent of molecular sieve, but this method can reach 90% for the clearance of waste water from dyestuff Methylene Blue, the removal completely to methylene blue can not be reached, moreover, the saturated extent of adsorption that this method does not introduce the sorbent material obtained is how many, and this all limits its application.Patent CN 103303998A discloses a kind of method based on lithocholate gel adsorption cationic dye wastewater, its maximal absorptive capacity for methylene blue reaches 870mg/g, but lithocholic acid is the product of biological metabolism, its source and price all limit its space of applying in dye wastewater treatment.Thus, develop a kind of cheapness, be easy to regenerate, adsorptive capacity is large and the preparation method being conducive to the sorbent material realizing waste water from dyestuff zero release possesses good prospect.
Summary of the invention
The object of the invention is the preparation method providing a kind of porous magnetic polyacrylamide PAM microsphere adsorbing agent in order to improve the deficiencies in the prior art; The present invention is especially for the Cationic organic dyes removed with positive charge in waste water, its cationic dyestuff for different concns scope all has extremely strong adsorption, and the colourity of the waste water from dyestuff after absorption reaches or close to the standard (GB T5750-2006) of domestic water.Magnetic PAM microsphere adsorbing agent after absorption with simple method desorption and regeneration, can be able to reuse.
Technical scheme of the present invention is: a kind of preparation method of porous magnetic polyacrylamide PAM microsphere adsorbing agent; Its concrete steps are as follows: will containing acrylamide, polymerized polyalcohol, N, the PAM monomer synthesize liquid of N-methylene-bisacrylamide, initiator and water composition, with the form initiated polymerization of drop, be separated by polymerization initiation under the effect of polymerized polyalcohol and obtain multi-hole type PAM microballoon; Porous PAM microballoon be impregnated in Fe
2+and Fe
3+mixing solutions in, reach dipping balance, be separated the PAM microballoon that obtains containing iron ion, with deionized water wash, then microballoon be placed in basic solution, flood 0.5-2h under 60-100 DEG C of condition, PAM magnetic porous microspheres can be obtained; The mass percentage that wherein in PAM monomer synthesize liquid, each component and each component account for synthesis liquid total amount is respectively: acrylamide (AM) 5-30%, polymerized polyalcohol 2.5-40%, water 24-92.05%, N,N methylene bis acrylamide (MBAM) 0.05-5%, initiator (APS) 0.4-1%.
Preferably above-mentioned polymerized polyalcohol is the polyvalent alcohol soluble in water such as polyoxyethylene glycol (PEG, molecular weight 400-20000), polypropylene glycol or polyvinyl alcohol.Preferably described initiator is ammonium persulphate, Potassium Persulphate or water-soluble light trigger azo-bis-isobutyrate hydrochloride etc.Preferably described linking agent is the conventional internal crosslinker such as N,N methylene bis acrylamide or N hydroxymethyl acrylamide.
Above-mentionedly form the means of drop with monomer synthesize liquid in the form initiated polymerization of drop and be preferably Microfluidic droplet technical process and (be generally coaxial flow microchannel, T-shaped microchannel, double-Y shaped microchannel, flow focusing type microchannel), microemulsion method (reverse microemulsion process) or liquid droplet ejection method etc.; The mode of trigger monomer polyreaction is thermal-initiated polymerization or light initiation polymerization (UV-light).
Preferred above-mentioned Fe
2+and Fe
3+mixing solutions in total Fe ionic concn at 0.1-1mol/L; Fe in mixing solutions
2+with Fe
3+mol ratio be 0.5-2:1.It is preferably 1-5 time by the PAM microballoon deionized water wash number of times being impregnated with Fe ion.
Preferably PAM microballoon is flooded in 60-100 DEG C of alkali lye, dipping time 0.5-2h.Preferably described alkali lye is KOH, NaOH or ammoniacal liquor; Concentration of lye is 0.1-1mol/L.
Beneficial effect:
(1) the invention provides a kind of preparation method cationic dyestuff being had to superpower adsorbing porous magnetic PAM microsphere adsorbing agent.
(2) porous magnetic PAM microsphere adsorbing agent of the present invention all has very high adsorptive capacity for the cationic dye wastewater of different concns.As, it can reach 1900mg/g, far above sorbent materials such as commercially available gacs, in table 8 to the methylene blue solution adsorptive capacity with 300mg/L.
(3) porous magnetic PAM microballoon of the present invention can be used for the zero release realizing waste water from dyestuff, for Sewage advanced treatment.As, 5mg microsphere adsorbing agent is joined in 50mL methylene blue solution, do not measure the existence of methylene blue with ultraviolet-visible spectrophotometer inspection after absorption, detecting its colourity with platinum cobalt colourimeter is 11 °, meet the chromaticity requirements (15 ° of domestic water, GB T5750-2006), see Fig. 5.
(4) preparation method of porous magnetic PAM microsphere adsorbing agent of the present invention is simple, and environmental friendliness is with low cost, be convenient to actually operating, it, in wider temperature and pH scope (temperature 15-50 DEG C, pH 4-10), all has very strong adsorption to cationic dyestuff.
(5) PAM magnetic porous microspheres sorbent material of the present invention can utilize the quick desorption of acidity alcohol solution after absorbing dye, and desorption rate is close to 100%.Test its recycling efficiency with the microballoon of the methylene blue solution of 10mg/L test after desorption, after six absorption, the adsorption rate of microballoon to methylene blue remains on more than 95%.
Accompanying drawing explanation
Fig. 1 is the SEM picture of porous magnetic PAM microballoon (P1) prepared by embodiment 1, wherein a: amplify 40 times, b: amplify 400 times, c: amplify 5000 times, d: amplify 10000 times, e: amplify 50000 times, f: amplify 70000 times;
Fig. 2 is the FT-IR figure of porous magnetic PAM microballoon (P1) prepared by embodiment 1;
Fig. 3 is the XRD figure of porous magnetic PAM microballoon (P1) prepared by embodiment 1;
The electron microscopic picture of porous magnetic PAM microballoon P6, P7, P8, P9 that Fig. 4 embodiment 6-9 prepares; Wherein a, b are the surface tissue picture of sample P 6, and c, d are the surface tissue picture of sample P 7, and e, f are the surface tissue picture of sample P 8, and g, h are the surface tissue picture of sample P 9;
Fig. 5 methylene blue, Viola crystallina, the contrast photo of toluylene red three kinds of dye mixture solution before and after the absorption of porous magnetic microballoon.
Embodiment
Following examples illustrate the present invention, do not restrict the present invention.
Embodiment 1
Preparation PAM monomer synthesize liquid 10g, containing AM 10%, N,N methylene bis acrylamide 0.4%, ammonium persulphate 0.4%, PEG-4000 (molecular weight 4000) 10%, rest part is deionized water.Using this monomer synthesize liquid as disperse phase, whiteruss is external phase, disperse phase flow velocity is 0.4mL/h, external phase flow velocity is 4mL/h, by coaxial flow microchannel drop generating device, and diameter of inner pipe 0.11mm, outer tube diameter 0.5mm, initiated polymerization at 86 DEG C, the reaction times is 80s, collects obtain porous PAM microballoon with dehydrated alcohol.The porous PAM microballoon obtained to be impregnated in concentration be 0.1mol/L mol ratio is the Fe of 2:1
3+and Fe
2+mixing solutions in, reach dipping balance, by the deionized water wash 3 times of the PAM microballoon containing iron ion, then be placed in basic solution, 1h is flooded under 100 DEG C of conditions, utilize magnetic field that microballoon is separated with basic solution, by washing with alcohol 2-3 time, drying just can obtain porous magnetic PAM microsphere adsorbing agent, be designated as P1, its SEM schemes as shown in Figure 1, and its FT-IR schemes as shown in Figure 2, and its XRD figure as shown in Figure 3; Microsphere average grain diameter is 200 μm, and water absorbent rate is 14 times, and in magnetic microsphere, PAM massfraction is 71.3%, and magnetic particle massfraction is 11.5%, and Bound moisture massfraction is 17.2%.Microspherulite diameter can be made to carry out modulation at 0.1 μm of-1.5mm by the inner and outer tubes internal diameter changing flow velocity and coaxial flow micro-channel device.
Embodiment 2-5
Prepare porous magnetic PAM microballoon according to experimental technique described in embodiment 1, but the content changing AM is respectively 5%, 15%, 20% and 30%, the amount of deionized water makes corresponding change, and all the other conditions are constant.Be designated as P2, P3, P4, P5 respectively according to the porous magnetic PAM microballoon obtained accordingly, wherein massfraction shared by PAM increases along with the massfraction increase of AM, refers to table 1.
Embodiment 6-9
Prepare porous magnetic PAM microballoon according to experimental technique described in embodiment 1, but the content changing N,N methylene bis acrylamide is respectively 0.05%, 0.1%, 1% and 2%, the amount of deionized water makes corresponding change, and all the other conditions are constant.Be designated as P6, P7, P8, P9 respectively according to the sorbent microspheres obtained accordingly, change the consumption of linking agent, the surface tissue of the sorbent microspheres obtained can change, and refers to Fig. 4.
Embodiment 10-16
Prepare porous magnetic PAM microballoon according to experimental technique described in embodiment 1, but the content changing PEG-4000 is respectively 0,2.5%.5%, 7.5%, 15%, 20% and 30%, the amount of deionized water makes corresponding change, and all the other conditions are constant.P10, P11, P12, P13, P14, P15, P16 is designated as respectively according to the sorbent microspheres obtained accordingly, the concentration of PEG changes and can have an impact to the water absorbent rate of the sorbent microspheres obtained, its water absorbent rate can increase along with the increase of PEG-4000 content, refers to table 2.
Embodiment 17-21
Porous magnetic PAM microballoon is prepared according to experimental technique described in embodiment 1, but the kind changing polymerized polyalcohol uses PEG-400, PEG-1000, PEG-20000, propylene glycol and polyvinyl alcohol (PVA) to replace PEG-4000 respectively, and the concentration of polymerized polyalcohol maintains 10%.The microsphere adsorbing agent obtained is designated as P17, P18, P19, P20, P21.Affect similar to the concentration changing polyoxyethylene glycol, the kind changing polymerized polyalcohol also can have an impact to the water absorbent rate of sorbent microspheres, refers to table 3.
Embodiment 22-24
Prepare porous magnetic PAM microballoon according to experimental technique described in embodiment 1, but post processing mode is different, the porous PAM microballoon obtained to be impregnated in concentration be 0.1mol/L mol ratio is the Fe being respectively 1:1,2:1 and 1:2
3+and Fe
2+mixing solutions in, reach dipping balance, PAM microballoon containing iron ion be impregnated under 100 DEG C of conditions 1h in the NaOH solution of 0.1mol/L, utilize magnetic field that microballoon is separated with NaOH solution, by washing with alcohol 2-3 time, the dry porous magnetic PAM microsphere adsorbing agent that just can obtain different post-treatment condition and prepare, is designated as P22, P23, P24.Change Fe in steeping fluid
3+and Fe
2+the saturation magnetic moment of ratio regular meeting to magnetic microsphere have an impact, namely the magnetic power of magnetic microsphere is had an impact.Refer to table 4.
Embodiment 25-27
Prepare porous magnetic PAM microballoon according to experimental technique described in embodiment 1, but post processing mode is different, the porous PAM microballoon obtained to be impregnated in concentration be 0.1mol/L, 0.5mol/L and 1mol/L mol ratio is 2:1Fe
3+and Fe
2+mixing solutions in, reach dipping balance, PAM microballoon containing iron ion be impregnated under 100 DEG C of conditions 1h in the NaOH solution of 0.1mol/L, utilize magnetic field that microballoon is separated with NaOH solution, by washing with alcohol 2 times, the dry porous magnetic PAM microsphere adsorbing agent that just can obtain different post-treatment condition and prepare, is designated as P25, P26, P27.Change Fe ionic concn in steeping fluid to have an impact to magnetic particle massfraction in microsphere adsorbing agent.Refer to table 5.
Embodiment 28,29
Prepare porous magnetic PAM microballoon according to the method described in embodiment 1, but adopt Potassium Persulphate, Potassium Persulfate to replace ammonium persulphate as initiator respectively, the porous magnetic PAM microballoon prepared is designated as P28, P29 respectively.It is to be noted and adopt Potassium Persulphate, Potassium Persulfate as initiator, required polymerization reaction time can shorten, and is 20s, 50s respectively.
Embodiment 30
According to the method preparation PAM monomer solution described in embodiment 1, change the thermal initiator in embodiment 1 into water-soluble light trigger azo-bis-isobutyrate hydrochloride, massfraction 0.4%, employing uv-light polymerization reacts, light application time is 15s, all the other treatment steps are with embodiment 1, and the porous magnetic PAM microballoon adopting this method to prepare is designated as P30, and the porous magnetic PAM microballoon obtained is similar with P1 in nature.
Embodiment 32,33
Porous magnetic PAM microballoon is prepared according to the method described in embodiment 1, using PAM monomer synthesize liquid as disperse phase, whiteruss is external phase, and disperse phase flow velocity is 0.4mL/h, and external phase flow velocity is 4mL/h, by coaxial flow microchannel drop generating device, diameter of inner pipe 0.11mm, outer tube diameter 0.5mm, initiated polymerization at 86 DEG C, reaction times is 80s, collects obtain porous PAM microballoon with dehydrated alcohol.The porous PAM microballoon obtained to be impregnated in concentration be 0.1mol/L mol ratio is the Fe of 2:1
3+and Fe
2+mixing solutions in, reach dipping balance, by the deionized water wash 3 times of the PAM microballoon containing iron ion, KOH, ammoniacal liquor is adopted to replace NaOH solution as different from Example 1, dipping temperature is 60 DEG C, time is 2 hours, 2 groups of PAM microballoons embodiment 32,33 obtained impregnated in KOH, ammoniacal liquor respectively, dipping temperature is 20 DEG C, time is 2 hours, obtain 2 groups of porous magnetic PAM microballoons, with embodiment 1, are designated as P32, P33 by all the other steps respectively, and the porous magnetic PAM microballoon obtained is similar with P1 in nature.
Embodiment 34
According to method preparation PAM monomer solution described in embodiment 1, T-shaped micro-channel device is adopted to replace coaxial flow microchannel drop generating device respectively, T-shaped microchannel internal diameter is 0.5mm, PAM monomer synthesize liquid is as disperse phase, flow velocity is 0.4mL/h, whiteruss is consistent as all the other conditions and embodiment 1, the porous magnetic PAM microsphere sample adopting this method to prepare is designated as P31, the porous magnetic PAM microballoon obtained with embodiment 1 unlike, the median size of P34 is 0.5mm, slightly larger than the sample particle diameter that embodiment obtains.
Embodiment 32-34
According to method preparation PAM monomer synthesize liquid 10g described in embodiment 1, adopt microemulsion method to prepare PAM microballoon, be scattered in the there-necked flask that 100g whiteruss is housed, mechanical stirring also carries out N
2protection.Regulate mechanical mixing speed 100r/min, 400r/min, 1000r/min respectively, prepare three groups of PAM microballoons be impregnated in concentration is respectively 0.1mol/L mol ratio is the Fe of 2:1
3+and Fe
2+mixing solutions in, reach dipping balance, by the deionized water wash 3 times of the PAM microballoon containing iron ion, then be placed in the NaOH solution of 0.8mol/L, 1h is placed under 100 DEG C of conditions, utilize magnetic field that microballoon is separated with NaOH solution, by washing with alcohol 2 times, drying just can obtain 3 groups of porous magnetic PAM microsphere adsorbing agents, be designated as P35, P36, P37, the median size of three groups of microballoons is followed successively by 530 μm, 377 μm, 251 μm.It is to be noted than microflow control technique, the particle size distribution range of the microballoon adopting microemulsion method to prepare is wider.
By the result of following absorption test case, the absorption property of the porous magnetic PAM microballoon that the present invention obtains is explained
Absorption test case 1
Get the microsphere adsorbing agent of the quality m=5mg prepared by embodiment 1 respectively, add v=200ml starting point concentration c
0for the methylene blue of 5mg/L, 10mg/L, 30mg/L, 60mg/L, 100mg/L and 300mg/L, Viola crystallina and neutral red solution, in neutral conditions, temperature 30 DEG C, keep concussion to adsorption equilibrium, in the process, ultraviolet-visible spectrophotometer is used to measure dye strength c in solution over time, according to
v can calculate the adsorptive capacity of microballoon to different concns dye solution.Porous magnetic PAM microsphere adsorbing agent is as shown in table 6 for the adsorptive capacity of different dyes, the adsorptive capacity of other sorbent material that contrast table 8 is listed, and visible porous magnetic PAM microsphere adsorbing agent has very high adsorptive capacity for Liquidity limit dyestuff.Absorption test case 2
Get the microsphere adsorbing agent 15mg prepared by embodiment 1 respectively, add v=50ml c
0the methylene blue solution of=10mg/L, neutral red solution, the mixing solutions of aldrich mixture and three kinds of dyestuffs, temperature 30 DEG C, keep concussion to adsorption equilibrium, be separated microsphere adsorbing agent, by the solution centrifugal after absorption, ultraviolet-visible spectrophotometer and platinum cobalt colourimeter is adopted to detect residual dye concentration and the colourity of the rear different solutions of absorption respectively, result is as shown in table 7, it can thus be appreciated that, the chromaticity requirements 15 ° that the colourity of fuel solution after the absorption of porous magnetic PAM microballoon substantially reaches or specifies close to domestic water standard (GB T5750-2006), this method visible is conducive to the zero release realizing cationic dye wastewater, see Fig. 5.
The content of each component in table 1 magnetic microsphere sorbent material P2-5
The water absorbent rate of table 2 microsphere adsorbing agent P10-16
The water absorbent rate of table 3 microsphere adsorbing agent P17-21
The saturation magnetic moment of table 4 microsphere adsorbing agent P22-24
Each constituent mass mark in table 5 microsphere adsorbing agent P25-27
Table 6 porous magnetic PAM microballoon is for the adsorptive capacity of different dyes
The colourity of table 7 different dyes solution after the absorption of porous magnetic microballoon
Other common adsorbents of table 8 is for the adsorptive capacity of different dyes
Claims (9)
1. the preparation method of a porous magnetic polyacrylamide PAM microsphere adsorbing agent; Its concrete steps are as follows: by the PAM monomer synthesize liquid formed containing acrylamide, polymerized polyalcohol, N,N methylene bis acrylamide, initiator and water, with the form initiated polymerization of drop, obtain multi-hole type PAM microballoon; Porous PAM microballoon be impregnated in Fe
2+and Fe
3+mixing solutions in, reach dipping balance, be separated the PAM microballoon that obtains containing iron ion, with deionized water wash, then microballoon be placed in basic solution, flood 0.5-2h under 60-100 DEG C of condition, PAM magnetic porous microspheres can be obtained; The mass percentage that wherein in PAM monomer synthesize liquid, each component and each component account for synthesis liquid total amount is respectively: acrylamide 5-30%, polymerized polyalcohol 2.5-40%, water 24-92.05%, N,N methylene bis acrylamide 0.05-5%, initiator 0.4-1%.
2., according to preparation method according to claim 1, it is characterized in that described polymerized polyalcohol is polyoxyethylene glycol, polypropylene glycol or polyvinyl alcohol.
3., according to preparation method according to claim 1, it is characterized in that described initiator is ammonium persulphate, Potassium Persulphate or azo-bis-isobutyrate hydrochloride.
4., according to preparation method according to claim 1, it is characterized in that described linking agent is N,N methylene bis acrylamide or N hydroxymethyl acrylamide.
5., according to preparation method according to claim 1, it is characterized in that the means of monomer synthesize liquid formation drop in the form initiated polymerization with drop are Microfluidic droplet method, microemulsion method or liquid droplet ejection method; The mode of trigger monomer polyreaction is thermal-initiated polymerization or light initiation polymerization.
6., according to preparation method according to claim 1, it is characterized in that Fe
2+and Fe
3+mixing solutions in total Fe ionic concn at 0.1-1mol/L; Fe in mixing solutions
2+with Fe
3+mol ratio be 0.5-2:1.
7., according to preparation method according to claim 1, it is characterized in that the PAM microballoon deionized water wash number of times by being impregnated with Fe ion is 1-5 time.
8., according to preparation method according to claim 1, it is characterized in that PAM microballoon to flood in 60-100 DEG C of alkali lye, dipping time 0.5-2h.
9., according to preparation method according to claim 1, it is characterized in that described alkali lye is KOH, NaOH or ammoniacal liquor; Concentration of lye is 0.1-1mol/L.
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