CN104448131B - 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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- 239000004005 microsphere Substances 0.000 title claims abstract description 103
- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003463 adsorbent Substances 0.000 title abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- -1 iron ions Chemical class 0.000 claims abstract description 8
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012670 alkaline solution Substances 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- 150000005846 sugar alcohols Polymers 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 238000000593 microemulsion method Methods 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 239000011806 microball Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 39
- 239000002351 wastewater Substances 0.000 abstract description 19
- 238000001179 sorption measurement Methods 0.000 abstract description 12
- 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 11
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 11
- 125000002091 cationic group Chemical group 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 3
- 230000000694 effects Effects 0.000 abstract description 2
- 229920006395 saturated elastomer Polymers 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 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
- 239000012530 fluid Substances 0.000 abstract 1
- 229960001235 gentian violet Drugs 0.000 abstract 1
- 229920005862 polyol Polymers 0.000 abstract 1
- 150000003077 polyols Chemical class 0.000 abstract 1
- 230000008859 change Effects 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000002594 sorbent Substances 0.000 description 5
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 229940057995 liquid paraffin Drugs 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 235000019394 potassium persulphate Nutrition 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 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
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-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
- 230000007547 defect Effects 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 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
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 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 description 1
- KVYRCBOUKXJXDK-UHFFFAOYSA-N 3,4-dimethylphenazine-1,2-diamine hydrochloride Chemical compound Cl.C1=CC=CC2=NC3=C(C)C(C)=C(N)C(N)=C3N=C21 KVYRCBOUKXJXDK-UHFFFAOYSA-N 0.000 description 1
- 208000026817 47,XYY syndrome Diseases 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- 241001062009 Indigofera Species 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
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 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
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 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
- 239000010919 dye waste Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 235000013305 food Nutrition 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
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000006249 magnetic particle Substances 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
- 239000004530 micro-emulsion Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010298 pulverizing process 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
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Polymerisation Methods In General (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention relates to a preparation method of a porous magnetic Polyacrylamide (PAM) microsphere adsorbent, which is characterized in that PAM monomer synthetic fluid consisting of acrylamide, polymeric polyol, N-methylene bisacrylamide, an initiator and water is subjected to a polymerization reaction initiated in a form of liquid drops to obtain porous PAM microspheres; impregnating porous PAM microspheres in Fe2+And Fe3+The mixed solution is soaked in the solution to be balanced, PAM microspheres containing iron ions are obtained by separation, washed by deionized water and soaked in alkaline solution, and then PAM magnetic porous microspheres are obtained; the porous magnetic PAM microspheres prepared by the method have strong adsorption effect on cationic dyes, and have high saturated adsorption capacity on cationic dyes with various concentrations, such as methylene blue, neutral red, gentian violet and the like. The adsorption capacity of the cationic dye is that of the traditional adsorbent under the same conditionsMore than 10 times. The chroma of the dye solution after adsorption can reach or approach the chroma requirement of domestic water, and the zero discharge of dye wastewater is favorably realized.
Description
Technical field
The porous magnetic polyacrylamide PAM that the present invention relates to a kind of effective removal waste water cationic dyestuff is micro-
The preparation method of ball adsorbent, belongs to adsorption technology field.
Background technology
Dye industry is one of important industry of fine chemical industry, product be mainly used in textile printing and dyeing and timber,
The coloring of paper, leather, food etc..The dyestuff yield of China accounts for more than the 60% of whole world total output, and kind surpasses
Crossing 1200 kinds, the discharge capacity of waste water from dyestuff accounts for the 2% of China's industrial wastewater total release, and discharge capacity is the biggest.
Waste water from dyestuff is because having many materials not in its colourity height, toxic organic pollutant content height, salinity height, waste water
Biodegradable or biology is produced the feature such as obvious inhibiting effect, environment is caused huge pollution.
Grave danger environment and human body health caused in view of waste water from dyestuff, the process of waste water from dyestuff
Method is the most varied.At present, the method processing waste water from dyestuff mainly has: biological degradation method, flocculence, height
Level oxidation technology and absorption method etc..But, said method is because of himself feature or defect, and it is actual
Engineer applied suffers from many restrictions.Such as, enzyme in biological degradation method and antibacterial are had the brightest by a lot of dyestuffs
Aobvious inhibitory action, causes biodegradation inefficient；Flocculence can produce substantial amounts of when processing waste water from dyestuff
Mud, this may result in the pollution to environment；High-level oxidation technology is to physics and chemistry such as the pH of catalyst and waste water
Character etc. all have higher requirement, and practical operation costly, causes its actual application to be restricted.The most such as
This, dye species is various and develops towards anti-light solution, antioxidation, antibiooxidation direction, and this results in relying on oxygen
Change technical finesse waste water from dyestuff and become more and more difficult.Absorption method is because of its high efficiency and operates relatively simple, one-tenth
The advantages such as this is low, it gradually highlights advantage in terms of processing industry difficult degradation waste water from dyestuff.Currently, with respect to suction
The research of attached dose is a lot, and the kind of adsorbent is the most varied, commercial Application more still based on activated carbon,
In actual applications, the major defect of activated carbon is solid-liquid separation and regeneration more difficulty, and this also causes it to apply
Being restricted, moreover, activated carbon is also bigger because of the different fluctuations of selection for the adsorbance of organic dyestuff.
In addition, what remaining application was more both includes resin, clay, zeolite, bentonite, flyash and sawdust
Deng low value product, also include the new material such as Graphene, MOFs, but or due to relatively costly or due to adsorbance
Not plateau because of, its application is all restricted.
Patent CN 101284223A discloses the preparation method of a kind of magnetic porous carbon adsorbent, molten in alkalescence
Liquid obtain metal hydroxides colloid and mixes with resin solution, obtaining resin/hydroxide colloid complex
System, prepares through carbonization and activation after removing solvent.But the magnetic porous carbon adsorbent prepared through this method
To methylene orange and the adsorbance of 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, adds under agitation in polyacrylic acid solution
Enter 13X molecular sieve, then through calcining, pulverizing obtains polyacrylic acid/13X adsorbent of molecular sieve, but should
Method can reach 90% for the clearance of waste water from dyestuff Methylene Blue, and can not reach methylene blue is complete
Removing, moreover, it is how many that this method does not introduce the saturated extent of adsorption of the adsorbent obtained, and this all limits
Its application.Patent CN 103303998A discloses a kind of useless based on the lithocholate gel adsorption dye of positive ion
The method of water, it reaches 870mg/g for the maximal absorptive capacity of methylene blue, but lithocholic acid is biological metabolism
Product, its source and price all limit its space applied in terms of dye wastewater treatment.Thus, exploitation
A kind of cheap, to be prone to regeneration, adsorbance big and be advantageously implemented the preparation side of adsorbent of waste water from dyestuff zero-emission
Method possesses good prospect.
Summary of the invention
The invention aims to improve the deficiencies in the prior art and provide a kind of porous magnetic polyacrylamide
The preparation method of PAM microsphere adsorbing agent；Present invention is particularly directed to remove in waste water the cation with positive charge have
Organic dye, it is respectively provided with extremely strong adsorption for the dye of positive ion of variable concentrations scope, the dye after absorption
The colourity of material waste water reaches or close to the standard (GB T5750-2006) of domestic water.Magnetic PAM after absorption
Microsphere adsorbing agent can be able to reuse with simple method desorption and regeneration.
The technical scheme is that the preparation side of a kind of porous magnetic polyacrylamide PAM microsphere adsorbing agent
Method；Its specifically comprise the following steps that by containing acrylamide, polymerized polyalcohol, N,N methylene bis acrylamide,
PAM monomer synthesis liquid, the in droplets initiated polymerization of initiator and water composition, polymerized polyalcohol
Effect under by polymerization cause be separated obtain porous type PAM microsphere；Porous PAM microsphere be impregnated in
Fe2+And Fe3+Mixed solution in, reach dipping balance, isolated contains the PAM microsphere of iron ion, use
Deionized water wash, then microsphere is placed in alkaline solution, impregnate 0.5-2h under the conditions of 60-100 DEG C,
To PAM magnetic porous microspheres；Wherein in PAM monomer synthesis liquid, each component and each component account for synthesis liquid total amount
Weight/mass percentage composition be respectively as follows: 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%.
The most above-mentioned polymerized polyalcohol be Polyethylene Glycol (PEG, molecular weight 400-20000), polypropylene glycol or
The polyhydric alcohol that polyvinyl alcohol etc. are soluble in water.Preferably described initiator is Ammonium persulfate., potassium peroxydisulfate or water-soluble
Property light trigger azo-bis-isobutyrate hydrochloride etc..Preferably described cross-linking agent is N,N methylene bis acrylamide
Or the conventional internal crosslinker such as N hydroxymethyl acrylamide.
In above-mentioned initiated polymerization in droplets, the means of monomer synthesis liquid formation drop are preferably miniflow
Control drop technique method (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 side of trigger monomer polyreaction
Formula is thermal-initiated polymerization or light initiation polymerization (ultraviolet light).
The most above-mentioned Fe2+And Fe3+Mixed solution in total Fe ion concentration at 0.1-1mol/L；Mixed solution
Middle Fe2+With Fe3+Mol ratio be 0.5-2:1.Preferably will be impregnated with the PAM microsphere deionization of Fe ion
Water washing times is 1-5 time.
Preferably PAM microsphere is impregnated in 60-100 DEG C of alkali liquor, dip time 0.5-2h.Preferably described alkali
Liquid is KOH, NaOH or ammonia；Concentration of lye is 0.1-1mol/L.
Beneficial effect:
(1) the invention provides one has superpower adsorbing porous magnetic PAM microsphere to adsorb in the dye of positive ion
The preparation method of agent.
(2) porous magnetic PAM microsphere adsorbing agent of the present invention all has for the cationic dye wastewater of variable concentrations
The highest adsorbance.As, it can reach 1900mg/g to the methylene blue solution adsorbance with 300mg/L,
Far above adsorbents such as commercially available activated carbons, it is shown in Table 8.
(3) porous magnetic PAM microsphere of the present invention can be used for realizing the zero-emission of waste water from dyestuff, deep for waste water
Degree processes.As, 5mg microsphere adsorbing agent is joined in 50mL methylene blue solution, after absorption with ultraviolet-
Visible spectrophotometer inspection does not measures the existence of methylene blue, and detecting its colourity with platinum cobalt colorimeter is 11 °, symbol
Close the chromaticity requirements (15 °, GB T5750-2006) of domestic water, see Fig. 5.
(4) preparation method of porous magnetic PAM microsphere adsorbing agent of the present invention is simple, environmental friendliness, low cost
Honest and clean, it is simple to practical operation, it is the most right in wider temperature and pH scope (temperature 15-50 DEG C, pH 4-10)
The dye of positive ion has the strongest adsorption.
(5) PAM magnetic porous microspheres adsorbent of the present invention available acidity alcohol solution after absorbing dye is quick
Desorption, desorption rate is close to 100%.The microsphere test after desorption is tested with the methylene blue solution of 10mg/L
It reuses efficiency, and after six times adsorb, microsphere is maintained at more than 95% to the adsorption rate of methylene blue.
Accompanying drawing explanation
Fig. 1 is the SEM picture of porous magnetic PAM microsphere (P1) of embodiment 1 preparation, 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 microsphere (P1) of embodiment 1 preparation；
Fig. 3 is the XRD figure of porous magnetic PAM microsphere (P1) of embodiment 1 preparation；
The electron microscopic picture of porous magnetic PAM microsphere P6, P7, P8, P9 that Fig. 4 embodiment 6-9 prepares；
Wherein a, b are the surface texture picture of sample P 6, and c, d are the surface texture picture of sample P 7, and e, f are sample
The surface texture picture of P8, g, h are the surface texture picture of sample P 9；
Fig. 5 methylene blue, Gentian Violet, three kinds of dye mixture solution of dimethyl diaminophenazine chloride are before and after porous magnetic microsphere adsorbs
Contrast photo.
Detailed description of the invention
The present invention is illustrated by following example, does not restricts the present invention.
Embodiment 1
Preparation PAM monomer synthesis liquid 10g, containing AM 10%, N,N methylene bis acrylamide 0.4%, over cure
Acid ammonium 0.4%, PEG-4000 (molecular weight 4000) 10%, remainder is deionized water.Close with this monomer
Becoming liquid as dispersion phase, liquid paraffin is continuous phase, and dispersion phase flow velocity is 0.4mL/h, and continuous phase flow velocity is 4
ML/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, the response time is 80s, collects with dehydrated alcohol and obtains porous PAM microsphere.
The porous PAM microsphere obtained be impregnated in concentration be 0.1mol/L mol ratio be the Fe of 2:13+And Fe2+Mixed
Close in solution, reach dipping balance, the PAM microsphere containing iron ion is washed with deionized 3 times, then
It is placed in alkaline solution, under the conditions of 100 DEG C, impregnates 1h, utilize magnetic field to make microsphere separate with alkaline solution,
By washing with alcohol 2-3 time, it is dried and just can get porous magnetic PAM microsphere adsorbing agent, be designated as P1, its SEM
Figure as it is shown in figure 1, its FT-IR figure as in figure 2 it is shown, its XRD figure as shown in Figure 3；Microsphere average grain diameter
Being 200 μm, water absorbent rate is 14 times, and in magnetic microsphere, PAM mass fraction is 71.3%, magnetic particle
Mass fraction is 11.5%, is 17.2% in conjunction with water quality mark.By changing flow velocity and coaxial flow microchannel
The inner and outer tubes internal diameter of device can make microspherulite diameter carry out modulation at 0.1 μm-1.5mm.
Embodiment 2-5
Prepare porous magnetic PAM microsphere according to experimental technique described in embodiment 1, but change the content of AM respectively
Being 5%, 15%, 20% and 30%, the amount of deionized water makes corresponding change, and remaining condition is constant.Foundation
The porous magnetic PAM microsphere that this method obtains is designated as P2, P3, P4, P5, wherein quality shared by PAM respectively
Mark increases along with the mass fraction of AM and increases, and refers to table 1.
Embodiment 6-9
Prepare porous magnetic PAM microsphere according to experimental technique described in embodiment 1, but change N, N-di-2-ethylhexylphosphine oxide third
The content of acrylamide is respectively 0.05%, 0.1%, 1% and 2%, and the amount of deionized water makes corresponding change,
Remaining condition is constant.It is designated as P6, P7, P8, P9 respectively according to the sorbent microspheres obtained accordingly, changes and hand over
The consumption of connection agent, the surface texture of the sorbent microspheres obtained can change, refer to Fig. 4.
Embodiment 10-16
Prepare porous magnetic PAM microsphere according to experimental technique described in embodiment 1, but change the content of PEG-4000
It is respectively 0,2.5%.5%, 7.5%, 15%, 20% and 30%, the amount of deionized water makes corresponding change,
Remaining condition is constant.According to the sorbent microspheres that obtains accordingly be designated as respectively P10, P11, P12, P13, P14,
P15, P16, the concentration of PEG produces change can produce 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
Prepare porous magnetic PAM microsphere according to experimental technique described in embodiment 1, but change the kind of polymerized polyalcohol
Class replaces with PEG-400, PEG-1000, PEG-20000, propylene glycol and polyvinyl alcohol (PVA) respectively
PEG-4000, the concentration of polymerized polyalcohol maintains 10%.The microsphere adsorbing agent obtained be designated as P17, P18,
P19、P20、P21.Similar to the concentration impact changing Polyethylene Glycol, the kind changing polymerized polyalcohol also can
The water absorbent rate of sorbent microspheres is produced impact, refers to table 3.
Embodiment 22-24
Prepare porous magnetic PAM microsphere according to experimental technique described in embodiment 1, but post processing mode is different, will
It is 0.1mol/L mol ratio for respectively 1:1,2:1 and 1:2 that the porous PAM microsphere obtained impregnated in concentration
Fe3+And Fe2+Mixed solution in, reach dipping balance, by the PAM microsphere containing iron ion in 100 DEG C
Under the conditions of impregnated in 1h in the NaOH solution of 0.1mol/L, utilize magnetic field to make microsphere separate with NaOH solution,
By washing with alcohol 2-3 time, it is dried the porous magnetic PAM microsphere that just available different post-treatment conditions are prepared and inhales
Attached dose, it is designated as P22, P23, P24.Change Fe in impregnation liquid3+And Fe2+Ratio regular meeting magnetic microsphere is satisfied
Produce impact with magnetic moment, i.e. the magnetic power of magnetic microsphere is produced impact.Refer to table 4.
Embodiment 25-27
Prepare porous magnetic PAM microsphere according to experimental technique described in embodiment 1, but post processing mode is different, will
It is that 0.1mol/L, 0.5mol/L and 1mol/L mol ratio is that the porous PAM microsphere obtained impregnated in concentration
2:1Fe3+And Fe2+Mixed solution in, reach dipping balance, by the PAM microsphere containing iron ion in 100 DEG C
Under the conditions of impregnated in 1h in the NaOH solution of 0.1mol/L, utilize magnetic field to make microsphere separate with NaOH solution,
By washing with alcohol 2 times, it is dried the porous magnetic PAM microsphere that just available different post-treatment conditions are prepared and inhales
Attached dose, it is designated as P25, P26, P27.In change impregnation liquid, Fe ion concentration can be to magnetic grain in microsphere adsorbing agent
Protonatomic mass mark produces impact.Refer to table 5.
Embodiment 28,29
Prepare porous magnetic PAM microsphere according to the method described in embodiment 1, but be respectively adopted potassium peroxydisulfate, mistake
Two potassium sulfate replace Ammonium persulfate. to be designated as respectively as initiator, the porous magnetic PAM microsphere prepared
P28、P29.It is to be noted and use potassium peroxydisulfate, potassium persulfate as initiator, required polymerization is anti-
Can shorten between Ying Shi, be 20s, 50s respectively.
Embodiment 30
Prepare PAM monomer solution according to the method described in embodiment 1, change the thermal initiator in embodiment 1 into water
Soluble photoinitiator azo-bis-isobutyrate hydrochloride, mass fraction 0.4%, use uv-light polymerization reaction,
Light application time is 15s, and remaining processes step with embodiment 1, the porous magnetic PAM that this method will be used to prepare
Microsphere is designated as P30, and the porous magnetic PAM microsphere obtained is similar with P1 in nature.
Embodiment 32,33
Porous magnetic PAM microsphere is prepared, using PAM monomer synthesis liquid as dispersion according to the method described in embodiment 1
Phase, liquid paraffin is continuous phase, and dispersion phase flow velocity is 0.4mL/h, and continuous phase flow velocity is 4mL/h, by same
Axial flow microchannel drop generating device, diameter of inner pipe 0.11mm, outer tube diameter 0.5mm, cause at 86 DEG C
Polyreaction, the response time is 80s, collects with dehydrated alcohol and obtains porous PAM microsphere.Many by obtaining
Hole PAM microsphere impregnated in concentration be 0.1mol/L mol ratio be the Fe of 2:13+And Fe2+Mixed solution in,
Reach dipping balance, the PAM microsphere containing iron ion is washed with deionized 3 times, with embodiment 1 not
Same is to use KOH, ammonia to replace NaOH solution, and dipping temperature is 60 DEG C, and the time is 2 hours, will
2 groups of PAM microspheres that embodiment 32,33 obtains impregnated in KOH, ammonia respectively, and dipping temperature is 20 DEG C,
Time is 2 hours, and obtain 2 groups of porous magnetic PAM microspheres, with embodiment 1, are designated as by remaining step respectively
P32, P33, the porous magnetic PAM microsphere obtained is similar with P1 in nature.
Embodiment 34
According to method preparation PAM monomer solution described in embodiment 1, it is respectively adopted T-shaped micro-channel device and replaces coaxial
Stream microchannel drop generating device, T-shaped microchannel internal diameter be 0.5mm, PAM monomer synthesis liquid as dispersion phase,
Flow velocity is 0.4mL/h, and liquid paraffin keeps consistent as remaining condition with embodiment 1, uses this method to be prepared into
To porous magnetic PAM microsphere sample be designated as P31, different from the porous magnetic PAM microsphere that embodiment 1 obtains
, the mean diameter of P34 is 0.5mm, the sample particle diameter obtained slightly larger than embodiment.
Embodiment 32-34
According to method preparation PAM monomer synthesis liquid 10g described in embodiment 1, microemulsion method is used to prepare PAM microsphere,
Being scattered in the there-necked flask equipped with 100g liquid paraffin, mechanical agitation also carries out N2Protection.Adjust respectively
Prepare three groups of PAM microspheres are divided by joint mechanical agitation rotating speed 100r/min, 400r/min, 1000r/min
Not impregnated in concentration be 0.1mol/L mol ratio be the Fe of 2:13+And Fe2+Mixed solution in, reach dipping flat
Weighing apparatus, is washed with deionized the PAM microsphere containing iron ion 3 times, then is placed in the NaOH of 0.8mol/L
In solution, under the conditions of 100 DEG C, place 1h, utilize magnetic field to make microsphere separate with NaOH solution, use ethanol
Wash 2 times, be dried and just can get 3 groups of porous magnetic PAM microsphere adsorbing agents, be designated as P35, P36, P37,
The mean diameter of three groups of microspheres is followed successively by 530 μm, 377 μm, 251 μm.It is to be noted than micro-fluidic
Technology, the particle size distribution range of the microsphere that employing microemulsion method is prepared is wider.
By the result of following absorption test case, the absorption property of the porous magnetic PAM microsphere obtaining the present invention gives
With explanation
Absorption test case 1
Take the microsphere adsorbing agent of quality m=5mg prepared by embodiment 1 respectively, add v=200ml initial concentration
c0For 5mg/L, 10mg/L, 30mg/L, 60mg/L, 100mg/L and 300mg/L methylene blue,
Gentian Violet and neutral red solution, in neutral conditions, temperature 30 DEG C, holding concussion to adsorption equilibrium,
During this, ultraviolet-visible spectrophotometer is used to measure the dye strength c in solution over time, root
According toV can calculate the microsphere adsorbance to variable concentrations dye solution.Porous magnetic PAM
Microsphere adsorbing agent is as shown in table 6 for the adsorbance of different dyes, other adsorbent that contrast table 8 is listed
Adsorbance, it is seen that porous magnetic PAM microsphere adsorbing agent has the highest adsorbance for Liquidity limit dyestuff.
Absorption test case 2
Take the microsphere adsorbing agent 15mg prepared by embodiment 1 respectively, add v=50ml c0The methylene of=10mg/L
Base indigo plant solution, neutral red solution, aldrich mixture and the mixed solution of three kinds of dyestuffs, temperature 30 DEG C, protect
Hold and shake to adsorption equilibrium, separate microsphere adsorbing agent, the solution centrifugal after adsorbing, it is respectively adopted ultraviolet-visible
Spectrophotometer and platinum cobalt colorimeter detect residual dye concentration and colourity, the result such as table of different solutions after adsorbing
Shown in 7, it follows that the colourity of the fuel solution after porous magnetic PAM microsphere adsorbs basically reaches or connects
The chromaticity requirements 15 ° that nearly domestic water standard (GB T5750-2006) specifies, it is seen that this method is advantageously implemented sun
The zero-emission of ionic dye waste water, is shown in Fig. 5.
The content of each component in table 1 magnetic microsphere adsorbent 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 microsphere is for the adsorbance of different dyes
Table 7 is the colourity of different dyes solution after porous magnetic microsphere adsorbs
Other common adsorbents of table 8 is for the adsorbance of different dyes
Claims (7)
1. a preparation method for porous magnetic polyacrylamide PAM microsphere adsorbing agent, its specifically comprise the following steps that by
The PAM being made up of acrylamide, polymerized polyalcohol, N,N methylene bis acrylamide, initiator and water is mono-
Body synthesis liquid, in droplets initiated polymerization, obtain porous type PAM microsphere；Porous PAM is micro-
Ball impregnated in Fe2+And Fe3+Mixed solution in, reach dipping balance, isolated contains the PAM of iron ion
Microsphere, is washed with deionized, then is placed in alkaline solution by microsphere, impregnates 0.5-2h under the conditions of 60-100 DEG C,
I.e. can get PAM magnetic porous microspheres；Wherein in PAM monomer synthesis liquid, each component and each component account for synthesis liquid
The weight/mass percentage composition of total amount be respectively as follows: 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 the preparation method described in claim 1, it is characterised in that described polymerized polyalcohol be Polyethylene Glycol,
Polypropylene glycol or polyvinyl alcohol.
3. according to the preparation method described in claim 1, it is characterised in that described initiator is Ammonium persulfate., over cure
Acid potassium or azo-bis-isobutyrate hydrochloride.
4. according to the preparation method described in claim 1, it is characterised in that single in initiated polymerization in droplets
It is Microfluidic droplet method, microemulsion method or liquid droplet ejection method that body synthesis liquid forms the means of drop；Trigger monomer gathers
The mode closing reaction is thermal-initiated polymerization or light initiation polymerization.
5. according to the preparation method described in claim 1, it is characterised in that Fe2+And Fe3+Mixed solution in total Fe
Ion concentration is at 0.1-1mol/L；Fe in mixed solution2+With Fe3+Mol ratio be 0.5-2:1.
6. according to the preparation method described in claim 1, it is characterised in that the PAM microsphere being impregnated with Fe ion is used
Deionized water wash number of times is 1-5 time.
7. according to the preparation method described in claim 1, it is characterised in that described alkaline solution be KOH solution,
NaOH solution or ammonia；Alkaline solution concentration is 0.1-1mol/L.
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| CN106434621A (en) * | 2016-10-28 | 2017-02-22 | 华北电力大学 | Method for immobilizing laccase on polyacrylamide-coated magnetic nano particles and application of method |
| CN108545798A (en) * | 2018-04-27 | 2018-09-18 | 苏州科技大学 | Water treatment agent of high-efficiency environment friendly and preparation method thereof |
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| CN110739143B (en) * | 2018-07-18 | 2022-10-28 | 苏州为度生物技术有限公司 | Method for preparing magnetic shell-core microspheres based on distillation precipitation method |
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| CN111468081A (en) * | 2020-04-14 | 2020-07-31 | Tcl华星光电技术有限公司 | Magnetic polymer microsphere, preparation method thereof and dye adsorbent |
| CN114471446B (en) * | 2020-10-27 | 2023-12-08 | 中国石油化工股份有限公司 | Adsorption material, preparation method thereof, treatment method of dye wastewater and application thereof |
| CN115193414B (en) * | 2021-04-09 | 2024-07-12 | 中国科学院理化技术研究所 | Application of heterogeneous porous polymer microsphere in dye adsorption |
| CN113368841B (en) * | 2021-06-12 | 2022-07-01 | 中国科学院青岛生物能源与过程研究所 | Method for preparing magnetic multi-effect adsorbent by utilizing enzymolysis residues through dry method |
| CN115386136B (en) * | 2022-08-30 | 2023-07-28 | 南京大学 | Preparation method and application of aminated polyacrylamide foam adsorbent |
| CN115819403B (en) * | 2022-09-27 | 2024-06-25 | 安徽普利药业有限公司 | Preparation method of pantoprazole sodium |
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