CN107570119B - A kind of stalk adsorbent for heavy metal preparation method with half interpenetrating network structure - Google Patents
A kind of stalk adsorbent for heavy metal preparation method with half interpenetrating network structure Download PDFInfo
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Abstract
The stalk adsorbent for heavy metal preparation method with half interpenetrating network structure that the present invention relates to a kind of, first using ultrasonic pretreated straw, then the graft modification of acrylic acid is carried out to it, acrylic acid modified stalk and functional monomer are finally subjected to graft copolymerization, prepare the stalk adsorbent for heavy metal with half interpenetrating network structure and contents of many kinds of heavy metal ion adsorption group, it is 100~1000mg/L heavy metal ion aqueous solution for initial concentration, the heavy metal ion adsorbed capacity of stalk adsorbent for heavy metal with half interpenetrating network structure reaches 40~500mg/g, 60~120min reaches adsorption equilibrium, it can be widely applied to heavy metal ion adsorbed separation and heavy metal ion pollution control etc..
Description
One, technical field
The stalk adsorbent for heavy metal preparation method with half interpenetrating network structure that the present invention relates to a kind of, the present invention
The stalk adsorbent for heavy metal with half interpenetrating network structure of preparation is suitable for the adsorbing separation of heavy metal ion, can be wide
It is general to be applied to heavy metal ion adsorbed, separation of heavy metal ions purification and heavy metal ion environmental pollution improvement etc..
Two, background technique
With the raising of global industry degree, environmental pollution is on the rise, and wherein water pollution has seriously affected people's
Production and living, industrial wastewater are the main source of heavy metal pollution of water body, many industrial process, such as plating, process hides, mining, steel-making,
Dyeing etc., can generate waste water largely containing heavy metal ion, such as Cd2+、Cu2+、Pb2+、Ni2+、As3+、Hg2+、Cr3+、Co2+And Co3+
Deng, by heavy metal cannot by biology degrade, after the industrial wastewater of heavy metal ion enters water body environment, aquatic life can be caused
Object poisoning, and be enriched in human body by food chain, the health of human body is threatened, therefore heavy metal is excessive rich in food chain
Rally causes very big harm to natural environment and human health.The improvement of heavy metal ion-containing waste water is always concerned by people
Key points and difficulties, there are many method for handling effluent containing heavy metal ions, and advantage and disadvantage are individually present, and wherein chemical Treatment plating contains zinc
Waste water has the advantages that small investment, processing technique are easily grasped, the disadvantage is that consumption chemical materials, the sludge of generation are not easy to discharge；From
Sub- exchange process treating capacity is big, but resin vulnerable to pollution, and operating cost is high；Though absorption method adsorption capacity is big, adsorbent material is used
Service life is short, must regenerate, operating cost is high.Therefore, domestic and foreign scholars are exploring and are studying a kind of efficient heavy ion removing
Method.Result of study in recent years shows the exploitation and use of cost effective chemical treatment medicament, is to solve heavy metal wastewater thereby dirt
The good approach of dye problem.
High hydroscopic resin is a kind of new functional macromolecule material through appropriately crosslinked and with three-dimensional net structure, is contained
A large amount of hydroxyl, carboxyl, sulfonic group and amide groups, these groups have very strong chelation to heavy metal ion.Therefore, high to inhale
Water-base resin serves not only as water-absorbing-retaining material, is also used as the chelating agent of metal ion, carries out to heavy metal ion
Enrichment, separation and recycling.The carragheen of the preparations such as Pourjavadi/suction of the Sodium Polyacrylate high hydroscopic resin to copper nitrate solution
Attached capacity reaches 1.27mmol/g, and the adsorption capacity of acetic acid copper solution reaches 14.8mmol/g, and the adsorption capacity of cobalt acetate solution reaches
14.7mmol/g, Patel etc. are using the cationic high hydroscopic resin of microwave-assisted polymerization preparation to Ni2+And Cu2+Adsorption capacity
It is up to 688.58and 376.62mg/g respectively, Roy etc. uses PEGDA to be prepared for gathering for crosslinking agent, Redox System At Low Temperature polymerization
Acrylic acid high hydroscopic resin, to Cr6+、Ni2+、Cu2+And Pb2+Adsorption capacity be respectively 41.1mg/g, 58.2mg/g, 43.1mg/
G and 81.2mg/g, Singh etc. are prepared for polyacrylic acid/acrylamide/sodium humate high hydroscopic resin using aqueous solution polymerization,
It was found that working as Cu2+Initial concentration is 320 and 1000mg/L, Cu2+Adsorption capacity is respectively 269mg/L and 299mg/L.The system such as Bulut
Standby bentonite complex high absorbent resin is to Pb2+、Ni2+、Cd2+And Cu2+Adsorption capacity be respectively 666.67mg/g,
270.27mg/g, 416.6mg/g 7 and 222.22mg/g,Etc. being prepared for the compound height of starch graft polyacrylate/bentonite
Water-absorbing resin, find pH=4 when to high hydroscopic resin Cu2+And Pb2+Adsorption capacity it is maximum, and Cu2+Adsorption capacity is higher than Pb2+。
Polyacrylic acid water-absorbing resin, which is made, using water solution polymerization process in Xie Jianjun etc. has good complexing, unitary gold to heavy metal ion
Belonging to balance liquid absorbency rate in solion is 160~190g/g, to single Pb2+Adsorption capacity reach as high as 187mg/g, put down
The adsorbance that weighs sequence are as follows: Pb2+>Cd2+>Ni2+>Cu2+>Zn2+>Mn2+>Cr3+.He Ming etc. is to acrylic acid-acrylamide high water absorption
Property resin is in different Cd2+Absorption property under concentration is studied, and finds adsorption capacity with Cd2+After concentration increase first increases
It reduces, in Cd2+Adsorption capacity is up to 269.75mg/g in the range of concentration is 2-3mmol/L.He Ming etc. is to acrylic acid-the third
Acrylamide super absorbent resin is in different Cd2+Absorption property under concentration is studied, and adsorption capacity is with Cd2+Concentration increases
First increase reduces afterwards, in Cd2+Adsorption capacity is up to 269.75mg/g in the range of concentration is 2-3mmol/L.The discovery such as Wang Pin
Ion concentration is bigger, and acid/acrylic amide type high hydroscopic resin is to Cd2+、Cu2+And Ni2+Adsorbance it is also bigger, maximal absorptive capacity difference
Reach 1.66mmol/g, 3.42mmol/g and 1.31mmol/g.Resin is presented centainly in the mixed solution of 3 heavy metal species ions
Selective absorption, adsorbance size is followed successively by Cu2+>Cd2+>Ni2+.3 kinds of resin adsorption Cu2+Afterwards in the HCl solution of 1mol/L
When desorption 3min, desorption rate respectively reaches 98.62%, 98.45% and 83.87%.Xie Jianjuns etc. are to make kaolin/wood by oneself
Quality sodium sulfonate-g- acrylic acid-acrylamide composite high-water-absorptivresin resin (KLPAAM) is raw material, has investigated resin in heavy metal
Absorbent in ion salt solution, discovery metal ion solution concentration, pH value significantly affect KLPAAM composite highly-absorbent resin
Absorbent.Reverb woods etc. inquires into influence of the different group resins to heavy metal ion adsorbed performance, finds binary resin pair
Heavy metal ion adsorbed effect is best, and resin is Cd to the size order of single heavy metal ion adsorption capacity2+>Cu2+>Ni2+>
Pb2+, maximum adsorption capacity is followed successively by 331.80mg/g, 182.82mg/g, 165.79mg/g, 23.89mg/g, absorbent according to
Secondary is Pb2+>Ni2+>Cu2+>Cd2+。
In order to which the cost and better building porous three-dimensional network structure, the Recent study that reduce high hydroscopic resin are main
Graft copolymerization is carried out with various polymer monomers by modified plant cellulose and synthesizes composite highly-absorbent resin, therefore stalk is multiple
It closes high hydroscopic resin and is increasingly becoming research hotspot both domestic and external.Wheat stalk is carried out oxygenation pretreatment by Xie etc., then with acrylic acid
Nitrogenous and boron super absorbent resin has been synthesized with attapulgite graft copolymerization, and has had studied the release characteristics of nitrogen and boron.Feng Zhi
The multiplying power that the high hydroscopic resin that prosperous equal sunflower stalk marrow and acrylic acid and acrylic amide graft copolymerization obtain inhales distilled water is 293
Times, inhale tap water multiplying power be 154 times, inhale physiological saline multiplying power be 31 times, Tan Fengzhi etc. corn stover is pre-processed after with
Acrylic graft copolymer prepares super absorbent resin, and water absorption rate is up to 291g/g, and absorption salt ratio reaches 49g/g.Wangdan etc.
It is raw material using Wheat Straw, acrylic acid, acrylamide and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC), passes through grafting
Copolymerization amphiprotic absorbent resin inhales distilled water and reaches 853g/g, suction physiological saline for 118g/g.Guo Yan etc. is by wheat stalk
Alkaline boiling pretreatment is carried out, agricultural high-hygroscopicity resin is synthesized with acrylic acid, acrylic amide graft copolymerization, deionized water is absorbed and reaches
412g/g, the aqueous solution for absorbing w (compound fertilizer)=0.1% reach 126g/g.The Wheat Straw such as Liu Wei and cornstalk and acrylic acid
Graft copolymerization prepares super absorbent resin, and wherein the water absorbent rate of the water-absorbing resins of Wheat Straw preparation is close to 200, cornstalk system
The water absorbent rate of standby water-absorbing resins is close to 150.It pays loyalty etc. and be grafted altogether by corn stover and acrylic acid and its sodium salt
It is poly-, the optimum condition of polymerization reaction has tentatively been found out, better performances, cheap product have been made.Ten thousand great waves etc. are by corn
It is compound with acrylic acid, acrylamide and sodium styrene sulfonate progress aqueous solution graft copolymerization preparation corn stover after stalk pretreatment
Super absorbent resin, when straw content is 10%, straw composite super absorbent resin water suction 10min water absorption rate reaches balance for discovery
The 58% of water absorption rate, water suction 50min straw composite super absorbent resin water suction reach balance, the nearly 350g/g of equilibrium water absorption.Wan Tao
It balances and inhales Deng the straw composite super absorbent resin for preparing maleic anhydride modified stalk and acrylic acid and acrylic amide graft copolymerization
Water rate and balance salt absorbing rate can respectively reach 400~1000 times and 30~80 times, the gel strength of water absorbent gel up to 5~
Water retention after 25Pa.s, 80~90 DEG C of water absorbent gel dry 200min is 15~40%.
The preparation method of straw composite super absorbent resin is mainly first gelatinized stalk, inorganic acid, inorganic base or acid
Acid anhydride processing, then with corresponding function monomer reaction, have not been reported the acrylic acid with half interpenetrating network structure both at home and abroad at present and change
The preparation of property stalk adsorbent for heavy metal and its heavy metal ion adsorbed performance study.
Three, summary of the invention
In view of this, the object of the invention is to provide a kind of stalk heavy metal ion with half interpenetrating network structure
Sorbent preparation method.First using ultrasonic pretreated straw, the graft modification of acrylic acid is then carried out to it, acrylic acid is changed
Property stalk and functional monomer carry out graft copolymerization, preparation have half interpenetrating network structure and contents of many kinds of heavy metal ion adsorption group
Stalk adsorbent for heavy metal, by half interpenetrating network structure adjust polymer network elasticity and extensibility, pass through
Acrylic acid modified stalk realizes the graft copolymerization of stalk and functional monomer, improves the compatibility of stalk and polymeric matrix, mentions
The dispersing uniformity of high stalk in a polymer matrix.
Purpose according to the present invention proposes a kind of stalk adsorbent for heavy metal system with half interpenetrating network structure
Preparation Method, feature have following processing step:
A) stalk is washed with deionized, dry after crush, sieve takes 100~200 mesh stalk powders, by stalk powder plus
Enter to n,N-Dimethylformamide, be placed in ultrasonic cleaner ultrasound and pre-process 1~6 hour, the pretreated stalk of ultrasound is hanged
Supernatant liquid is transferred to three-necked flask, and acrylic acid, N, N'- dicyclohexyl carbodiimide and 4-dimethylaminopyridine is added, is warming up to
25~50 DEG C of 2~6h of reaction, are cooled to room temperature, filtering, ethanol washing 3~5 times, dry, crush, obtain acrylic acid modified straw
Stalk；N,N-Dimethylformamide, stalk, acrylic acid mass ratio be 100:5~20:2~10, acrylic acid, N, N'- dicyclohexyl
The molar ratio of carbodiimides and 4-dimethylaminopyridine: 1:0.5~1:0.1~0.5；
B) NaOH is dissolved in 200mL deionized water, acrylic acid is slowly dropped to NaOH aqueous solution in ice bath, stirring is anti-
0.5~2h is answered, part is obtained and neutralizes acrylic acid aqueous solution；By acrylic acid modified stalk, acrylamide, polyvinylpyrrolidone and
Crosslinking agent is added to part and neutralizes acrylic acid aqueous solution, stirs evenly, and is warming up to 50~60 DEG C, and redox initiator is added,
Initiated polymerization 3~5 hours, product is washed 3~5 times with dehydrated alcohol, 80 DEG C of drying crush, obtain having Semi-IPN
The stalk adsorbent for heavy metal of network structure；The molar ratio of acrylic acid and NaOH are 1:0.5~0.8；Acrylic acid and propylene
The mass ratio of amide is 1~5:1~5；Crosslinking agent accounts for the 0.1~0.8% of acrylic acid and acrylamide monomer quality total amount；Oxidation
Reduction initiator accounts for the 0.1%~2.0% of acrylic acid and acrylamide monomer quality total amount；The molar ratio of Oxidizing and Reducing Agents
For 1~2:1；Polyvinylpyrrolidone accounts for the 5~20% of acrylic acid and acrylamide monomer quality total amount；Acrylic acid modified stalk
Account for the 5~30% of acrylic acid and acrylamide monomer quality total amount；
It c) is 100~1000mg/L heavy metal ion aqueous solution, the straw with half interpenetrating network structure for initial concentration
The heavy metal ion adsorbed capacity of stalk adsorbent for heavy metal reaches 40~500mg/g, and 60~120min reaches adsorption equilibrium.
Stalk used in the present invention be selected from corn stover, wheat stalk, soybean stalk, rice straw, jowar stalk and
Cotton stalk.
Ultrasonic cleaner frequency used in the present invention is 20~80kHz, power is 300~3000W.
Crosslinking agent used in the present invention is selected from N, N '-methylene-bisacrylamide, ethylene glycol diacrylate, a contracting second
Diol acrylate, tirethylene glycol double methacrylate, 1,3- propylene glycol double methacrylate, trimethylolpropane tris acrylic acid
Ester, pentaerythritol triacrylate, glycidyl methacrylate and polyethyleneglycol diacrylate.
Redox initiator used in the present invention includes Oxidizing and Reducing Agents, and oxidant is selected from ammonium persulfate, mistake
Potassium sulfate and sodium peroxydisulfate, reducing agent are selected from sodium hydrogensulfite, sodium sulfite, sodium thiosulfate and ferrous sulfate.
Heavy metal ion used in the present invention is selected from Cd2+、Cu2+、Pb2+、Ni2+、Cr3+And Cr6+。
Advantages of the present invention and effect are:
1) polymerization reaction directly carries out in aqueous solution, and non-environmental-pollution, method is simple, is not necessarily to nitrogen protection, because
This eliminates nitrogen device, reduces the Meteorological of equipment.
2) it by acrylic acid modified stalk, realizes the graft copolymerization of stalk and functional monomer, improves stalk and polymer
The compatibility of matrix improves the dispersing uniformity of stalk in a polymer matrix.
3) acrylic acid modified stalk and functional monomer are subjected to graft copolymerization, preparation has half interpenetrating network structure and more
The stalk adsorbent for heavy metal of heavy metal species ionic adsorption group adjusts polymer network by half interpenetrating network structure
Elastic and extensibility further increases the weight of stalk adsorbent for heavy metal by the synergistic effect of a variety of adsorption groups
Adsorption of metal ions performance；
4) with agricultural crop straw, this natural material prepares agricultural crop straw adsorbent for heavy metal, has life cycle
Chain is short, it is discarded after can the environmentally protective advantage such as natural degradation, that is, take full advantage of inexhaustible regenerated resources, and solve straw
The environomental pollution source that stalk burns realizes agriculture to current China's crop straw burning and heavy metal ion bring environmental pollution is administered
The comprehensive utilization of crop material and agricultural sustainable development have important, have huge social benefit, environmental benefit and economy
Benefit.
The heavy metal ion adsorbed rate of stalk adsorbent for heavy metal of the present invention and adsorption capacity measurement side
Method is as follows.
It is heavy metal ion aqueous solution and the 0.2g drying of 100-1000mg/L, finely ground stalk heavy metal ion by concentration
Adsorbent is put into 250mL conical flask, is subsequently placed in oscillator and is vibrated absorption, and oscillation samples after a certain period of time, using atom
Absorption spectrometer measures the absorbance of sample, and each sample is measured 3 times and is averaged, heavy metal ion adsorbed amount qtHold with absorption
Measure qeIt is calculated as follows respectively:
qt(mg/g)={ (C0-Ct)V}/m (1)
qe(mg/g)={ (C0-Ce)V}/m (2)
Wherein C0、CtAnd CeRespectively heavy metal ion initial concentration, oscillation absorption certain time concentration of heavy metal ion,
Heavy metal ion adsorbed equilibrium concentration (mg.L-1), V are liquor capacity (L), and m is the quality of stalk adsorbent for heavy metal
(g)。
Four, specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is further explained, but it is of the invention
Content be not limited solely to the following examples.
Embodiment 1:
Cotton stalk is washed with deionized, dry after crush, sieve take 100 mesh cotton stalk powder, by 5g cotton straw
Stalk powder is added to 100mL n,N-Dimethylformamide, is placed in that frequency is 50kHz, power is that 1000W ultrasonic cleaner is super
Sound preconditioning 1 hour, the pretreated cotton stalk suspension of ultrasound is transferred to three-necked flask, 2g acrylic acid, 2.87g is added
N, N'- dicyclohexyl carbodiimide and 0.34g 4-dimethylaminopyridine are warming up to 25 DEG C of reaction 6h, are cooled to room temperature, mistake
Filter ethanol washing 5 times, dries, crushes, obtain acrylic acid modified cotton stalk.
9g NaOH is dissolved in 200mL deionized water, 24g acrylic acid is slowly dropped to NaOH aqueous solution in ice bath,
It is stirred to react 2h, part is obtained and neutralizes acrylic acid aqueous solution；The acrylic acid modified cotton stalk of 12g, 16g acrylamide, 2g are gathered
Vinylpyrrolidone and 0.12g ethylene glycol diacrylate are added to part and neutralize acrylic acid aqueous solution, stir evenly, are warming up to
60 DEG C, 0.48g ammonium persulfate and 0.16g sodium hydrogensulfite is added, initiated polymerization 3 hours, product is washed with dehydrated alcohol
It washs 3 times, 80 DEG C of drying crush, the cotton stalk adsorbent for heavy metal with half interpenetrating network structure obtained, for initial
Concentration is the Cd of 100mg/L2+、Ni2+、Pb2+And Cu2+Aqueous solution, cotton stalk adsorbent for heavy metal Cd2+、Ni2+、Pb2+With
Cu2+Adsorption capacity respectively reaches 46mg/g, 40mg/g, 65mg/g and 52mg/g, and 120min reaches adsorption equilibrium.
Embodiment 2:
Broomcorn straw is washed with deionized, dry after crush, sieve take 200 mesh broomcorn straw powder, by 20g sorghum stalks
Stalk powder is added to 100mL n,N-Dimethylformamide, is placed in that frequency is 50kHz, power is 600W ultrasonic cleaner ultrasound
The pretreated broomcorn straw suspension of ultrasound is transferred to three-necked flask, 10g acrylic acid, 28.66g is added by pretreatment 3 hours
N, N'- dicyclohexyl carbodiimide and 8.48g 4-dimethylaminopyridine are warming up to 40 DEG C of reaction 3.5h, are cooled to room temperature,
Filtering ethanol washing 3 times, dries, crushes, obtain acrylic acid modified broomcorn straw.
7.2g NaOH is dissolved in 200mL deionized water, it is water-soluble that 20g acrylic acid is slowly dropped to NaOH in ice bath
Liquid is stirred to react 0.5h, obtains part and neutralizes acrylic acid aqueous solution；By the acrylic acid modified broomcorn straw of 10g, 20g acrylamide,
8g polyvinylpyrrolidone and 0.08g diethylene glycol double methacrylate are added to part and neutralize acrylic acid aqueous solution, and stirring is equal
It is even, it is warming up to 60 DEG C, is added 0.36g sodium peroxydisulfate and 0.12g sodium hydrogensulfite, initiated polymerization 3 hours, by product nothing
Water-ethanol washs 5 times, and 80 DEG C of drying crush, obtain the broomcorn straw adsorbent for heavy metal with half interpenetrating network structure,
The Cu for being 300mg/L for initial concentration2+、Ni2+、Cr3+And Cr6+Aqueous solution, broomcorn straw adsorbent for heavy metal Cu2+、
Ni2+、Cr3+And Cr6+Adsorption capacity respectively reaches 124mg/g, 102mg/g, 89mg/g and 75mg/g, and it is flat that 105min reaches absorption
Weighing apparatus.
Embodiment 3:
Soybean stalk is washed with deionized, dry after crush, sieve take 200 mesh soybean stalk powders, by the big beanstalk of 10g
Stalk powder is added to 100mL n,N-Dimethylformamide, is placed in that frequency is 30kHz, power is 300W ultrasonic cleaner ultrasound
The pretreated soybean stalk suspension of ultrasound is transferred to three-necked flask, 5g acrylic acid, 10.03gN is added by pretreatment 6 hours,
N'- dicyclohexyl carbodiimide and 2.12g 4-dimethylaminopyridine are warming up to 50 DEG C of reaction 2h, are cooled to room temperature, filtering,
It ethanol washing 5 times, dries, crushes, obtain acrylic acid modified soybean stalk.
5.4g NaOH is dissolved in 200mL deionized water, it is water-soluble that 16g acrylic acid is slowly dropped to NaOH in ice bath
Liquid is stirred to react 1h, obtains part and neutralizes acrylic acid aqueous solution；By the acrylic acid modified soybean stalk of 6g, 24g acrylamide, 6g
Polyvinylpyrrolidone and 0.10g tirethylene glycol double methacrylate are added to part and neutralize acrylic acid aqueous solution, stir evenly,
It is warming up to 50 DEG C, is added 0.54g potassium peroxydisulfate and 0.18g sodium thiosulfate, initiated polymerization 5 hours, by product with anhydrous
Ethanol washing 3 times, 80 DEG C of drying crush, obtain the soybean stalk adsorbent for heavy metal with half interpenetrating network structure, right
In the Pb that initial concentration is 600mg/L2+、Cu2+、Cd2+And Ni2+Aqueous solution, soybean stalk adsorbent for heavy metal Pb2+、Cu2 +、Cd2+And Ni2+Adsorption capacity respectively reaches 256mg/g, 194mg/g, 176mg/g and 144mg/g, and 90min reaches adsorption equilibrium.
Embodiment 4:
Wheat stalk is washed with deionized, dry after crush, sieve take 100 mesh wheat stalk powder, by 8g Wheat Straw
Stalk powder is added to 100mL n,N-Dimethylformamide, is placed in that frequency is 50kHz, power is 600W ultrasonic cleaner ultrasound
The pretreated wheat stalk suspension of ultrasound is transferred to three-necked flask, 4g acrylic acid, 8.02g N is added by pretreatment 3 hours,
N'- dicyclohexyl carbodiimide and 1.70g 4-dimethylaminopyridine are warming up to 30 DEG C of reaction 5h, are cooled to room temperature, filtering,
It ethanol washing 3 times, dries, crushes, obtain acrylic acid modified wheat stalk.
9g NaOH is dissolved in 200mL deionized water, 24g acrylic acid is slowly dropped to NaOH aqueous solution in ice bath,
It is stirred to react 2h, part is obtained and neutralizes acrylic acid aqueous solution；By the acrylic acid modified wheat stalk of 8g, 16g acrylamide, the poly- second of 8g
Alkene pyrrolidone and 0.16g 1,3-PD double methacrylate are added to part and neutralize acrylic acid aqueous solution, stir evenly, and rise
Temperature is to 50 DEG C, addition 0.60g potassium peroxydisulfate and 0.20g sodium sulfite, and initiated polymerization 5 hours, by product dehydrated alcohol
Washing 5 times, 80 DEG C of drying, crushes, the wheat stalk adsorbent for heavy metal with half interpenetrating network structure is obtained, for first
Beginning concentration is the Pb of 800mg/L2+、Cu2+、Cd2+And Cr3+Aqueous solution, wheat stalk adsorbent for heavy metal Pb2+、Cu2+、Cd2+
And Cr3+Adsorption capacity respectively reaches 376mg/g, 245mg/g, 206mg/g and 136mg/g, and 75min reaches adsorption equilibrium.
Embodiment 5:
Corn stover is washed with deionized, dry after crush, sieve take 200 mesh maize straw powders, by 15g corn stalk
Stalk powder is added to 100mL n,N-Dimethylformamide, is placed in that frequency is 50kHz, power is 800W ultrasonic cleaner ultrasound
The pretreated corn stover suspension of ultrasound is transferred to three-necked flask, 8g acrylic acid, 18.34g N is added by pretreatment 2 hours,
N'- dicyclohexyl carbodiimide and 4.07g 4-dimethylaminopyridine are warming up to 25 DEG C of reaction 6h, are cooled to room temperature, filtering,
It ethanol washing 5 times, dries, crushes, obtain acrylic acid modified corn stover.
7.5g NaOH is dissolved in 200mL deionized water, it is water-soluble that 22g acrylic acid is slowly dropped to NaOH in ice bath
Liquid is stirred to react 2h, obtains part and neutralizes acrylic acid aqueous solution；By the acrylic acid modified corn stover of 4g, 18g acrylamide, 6g
Polyvinylpyrrolidone and 0.10g N, N '-methylene-bisacrylamide are added to part and neutralize acrylic acid aqueous solution, and stirring is equal
It is even, it is warming up to 50 DEG C, is added 0.62g ammonium persulfate and 0.21g sodium hydrogensulfite, initiated polymerization 5 hours, by product nothing
Water-ethanol washs 3 times, and 80 DEG C of drying crush, obtain the corn stover adsorbent for heavy metal with half interpenetrating network structure,
The Pb for being 1000mg/L for initial concentration2+、Cu2+、Cd2+And Ni2+Aqueous solution, magnetic polymer adsorbent for heavy metal Pb2 +、Cu2+、Cd2+And Ni2+Adsorption capacity respectively reaches 500mg/g, 322mg/g, 264mg/g and 209mg/g, and 60min reaches absorption
Balance.
Claims (5)
1. a kind of stalk adsorbent for heavy metal preparation method with half interpenetrating network structure, it is characterised in that there is following work
Skill step:
Stalk is washed with deionized, dry after crush, sieve take 100~200 mesh stalk powders, stalk powder is added to N,
Dinethylformamide is placed in ultrasonic cleaner ultrasound and pre-processes 1~6 hour, and the pretreated stalk suspension of ultrasound is turned
Three-necked flask is moved on to, acrylic acid, N, N'- dicyclohexyl carbodiimide and 4-dimethylaminopyridine is added, is warming up to 25~50
DEG C reaction 2~6h, be cooled to room temperature, filter, ethanol washing 3~5 times, dry, crush, obtain acrylic acid modified stalk；N,N-
Dimethylformamide, stalk, acrylic acid mass ratio be 100:5~20:2~10, acrylic acid, N, N'- dicyclohexyl carbonization two
The molar ratio of imines and 4-dimethylaminopyridine: 1:0.5~1:0.1~0.5；
NaOH is dissolved in 200mL deionized water, acrylic acid is slowly dropped to NaOH aqueous solution in ice bath, is stirred to react 0.5
~2h obtains part and neutralizes acrylic acid aqueous solution；By acrylic acid modified stalk, acrylamide, polyvinylpyrrolidone and crosslinking
Agent is added to part and neutralizes acrylic acid aqueous solution, stirs evenly, and is warming up to 50~60 DEG C, and redox initiator is added, and causes
Polymerization reaction 3~5 hours, product is washed 3~5 times with dehydrated alcohol, 80 DEG C of drying are crushed, obtained with semi-intercrossing network
The stalk adsorbent for heavy metal of structure；The molar ratio of acrylic acid and NaOH are 1:0.5~0.8；Acrylic acid and acrylamide
Mass ratio be 1~5:1~5；Crosslinking agent accounts for the 0.1~0.8% of acrylic acid and acrylamide monomer quality total amount；Redox
Initiator accounts for the 0.1%~2.0% of acrylic acid and acrylamide monomer quality total amount；The redox initiator includes oxidation
Agent and reducing agent, the molar ratio of Oxidizing and Reducing Agents are 1~2:1；Oxidant is selected from ammonium persulfate, potassium peroxydisulfate and persulfuric acid
Sodium, reducing agent are selected from sodium hydrogensulfite, sodium sulfite, sodium thiosulfate and ferrous sulfate；Polyvinylpyrrolidone accounts for acrylic acid
With the 5~20% of acrylamide monomer quality total amount, acrylic acid modified stalk accounts for acrylic acid and acrylamide monomer quality total amount
5~30%；
It is 100~1000mg/L heavy metal ion aqueous solution for initial concentration, the stalk huge sum of money with half interpenetrating network structure
Belong to the heavy metal ion adsorbed capacity of ion adsorbent and reach 40~500mg/g, 60~120min reaches adsorption equilibrium.
2. a kind of stalk adsorbent for heavy metal preparation side with half interpenetrating network structure according to claim 1
Method, it is characterised in that: the stalk is selected from corn stover, wheat stalk, soybean stalk, rice straw, jowar stalk and cotton
Chopped straw stalk.
3. a kind of stalk adsorbent for heavy metal preparation side with half interpenetrating network structure according to claim 1
Method, it is characterised in that: the ultrasonic cleaner frequency is 20~80kHz, power is 300~3000W.
4. a kind of stalk adsorbent for heavy metal preparation side with half interpenetrating network structure according to claim 1
Method, it is characterised in that: the crosslinking agent is selected from N, N '-methylene-bisacrylamide, ethylene glycol diacrylate, a contracting second two
Alcohol double methacrylate, tirethylene glycol double methacrylate, 1,3- propylene glycol double methacrylate, trimethylolpropane tris acrylic acid
Ester, pentaerythritol triacrylate, glycidyl methacrylate and polyethyleneglycol diacrylate.
5. a kind of stalk adsorbent for heavy metal preparation side with half interpenetrating network structure according to claim 1
Method, it is characterised in that: the heavy metal ion is selected from Cd2+、Cu2+、Pb2+、Ni2+、Cr3+And Cr6+。
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