CN103881033A - Preparation method of crop straw dye adsorption material - Google Patents
Preparation method of crop straw dye adsorption material Download PDFInfo
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Abstract
The invention relates to a preparation method of a crop straw dye adsorption material. The preparation method is characterized by comprising the process steps of adding straw powder into N, N-dimethylformamide, putting into an ultrasonic cleaning tank to perform ultrasonic treatment for 20-60 minutes at 30-50 DEG C, then adding phytic acid and urea into the system, heating to 50-90 DEG C, reacting for 2-6 hours, then cooling a product to the room temperature, precipitating, washing, drying and crushing to obtain phytic acid modified straw; neutralizing itaconic acid by using NaOH, then adding the phytic acid modified straw, acrylamide, vinyl pyrrolidone and a crosslinking agent, fully stirring for 30 minutes, then gradually heating to 50-60 DEG C, and finally slowly dropwise adding a redox initiator into a polymerization system to initiate a polymerization reaction for 3-5 hours; and after polymerization, precipitating, washing and drying to obtain the crop straw dye adsorption material. The adsorption capacity of the crop straw dye adsorption material to a cationic dye aqueous solution with the initial concentration of 200-2000mg/L is 195-1400mg/g, the decolorization rate of the crop straw dye adsorption material is 55-90%, and the crop straw dye adsorption material can reach adsorption equilibrium after 100-200 minutes of room temperature adsorption, and can be widely applied to the adsorption, separation and purification of cationic dyes, the environmental pollution control of cationic dye wastewater, and the like.
Description
Technical field
The present invention relates to the preparation method of the dye adsorption material of a kind of agricultural crop straw, the dye adsorption material of agricultural crop straw prepared by the present invention is applicable to fractionation by adsorption and the decolouring etc. of cationic dyestuff, can be widely used in the environmental pollution improvement of absorption, separation, purification and the cationic dyestuff waste water of cationic dyestuff etc.
Background technology
Waste water from dyestuff is the colorful wastewater that contains dyestuff, be mainly derived from dye and dye intermediate production industry and weaving, leather, papermaking, rubber, plastics, makeup, the different industries such as pharmacy and food, has that composition is complicated, a water yield and change of water quality is large, colourity is high, COD and the feature such as BOD concentration is high, suspended substance is many, recalcitrant substance is many, is one of more unmanageable trade effluent.In addition, waste water from dyestuff not only has obvious colourity, affects sense organ, and in waste water, contain water body or the poisonous and hazardous pollutent of human body, if waste water from dyestuff is without processing directly discharge, the destruction that can cause water ecological setting, venomous injurant enters food chain, can affect the health of human body.Therefore effectively dye wastewater treatment using has become society and has needed badly the problem of solution.
The method of dye wastewater treatment using mainly contains chemistry, biology, Physical etc. at present.Precipitation flocculence is simple to operate, and cost is low, but a large amount of mud that produce increase operation cost.When Treatment of Wastewater by Electrolysis, consumption electricity and metal electric maximum dose are large.Photochemical catalytic oxidation is only effective to lower concentration waste water from dyestuff.More single and the microorganism of biological process selectivity is to environment sensitive.Absorption method is simple to operate, and cost is low, effective, and sorbent material is easy to recycle.Conventional sorbent material has gac, mineral, resene sorbent material etc.Charcoal absorption power is strong, and clearance is high, but cost is high, general only for the lower treatment of dyeing wastewater of concentration or advanced treatment.Mineral comprise natural zeolite, wilkinite etc., and its ion-exchange capacity and absorption property are better, but active low, regeneration difficulty.And resene sorbent treatment efficiency is high, can regenerate under certain condition, after regeneration, still can keep efficient, be applicable to the processing of waste water from dyestuff.
High hydrophilous resin has the advantage such as circulation absorption and environment friendly that loading capacity is large, adsorption rate is fast, good.In addition, the three-dimensional crosslinked network structure and function functional group of High hydrophilous resin makes it have hypertonicity and good ionic adsorption, and therefore High hydrophilous resin causes people's concern gradually as the research of dye adsorption resin.The use modified attapulgites such as Wang Yongsheng obtain the absorption of composite highly-absorbent resin for methylene blue dye with poly-(acrylic acid-acrylamide) graft copolymerization, and 60 DEG C time, adsorptive capacity reaches 1273mg/g.Li Shengfang is the absorption for Crystal Violet Dye by compound amylose starch poly-(vinylformic acid-acrylamide-methacrylic ester) resin, show that its adsorption process meets Langmuir model and accurate second-order kinetic equation.Paulino etc. have studied modification pectinose and the absorption property of polyacrylic acid-acrylic amide graft copolymerization composite highly-absorbent resin to methylene blue dye, and maximum adsorption capacity is 48mg/g, and percent of decolourization is 98%.The employing vinylformic acid High hydrophilous resins such as reverb woods are studied the adsorption effect of 3 kinds of cationic dyestuff-malachite greens, methylene blue and toluylene reds, find containing carboxyl and the more High hydrophilous resin of sulfonic group to three kinds dye adsorption better, adsorption rate all exceedes 90%.
In order to reduce the cost of High hydrophilous resin and better to build porous three-dimensional network structure, research in recent years is mainly carried out the synthetic composite highly-absorbent resin of graft copolymerization by the plant cellulose after modification and various polymer monomer, and therefore stalk composite highly-absorbent resin becomes study hotspot both domestic and external gradually.Wheat stalk is carried out alkali pre-treatment by Xie etc., then synthesized nitrogenous and super absorbent resin boron with vinylformic acid and attapulgite graft copolymerization, and studied the release characteristics of nitrogen and boron.The multiplying power that the High hydrophilous resin that the use sunflower stalk marrows such as Feng Zhixin and vinylformic acid and acrylic amide graft copolymerization obtain is inhaled distilled water is 293 times, the multiplying power of inhaling tap water is 154 times, the multiplying power of inhaling physiological saline is 31 times, Tan Fengzhi etc. will prepare super absorbent resin with acrylic graft copolymer after maize straw pre-treatment, water-intake rate is up to 291g/g, and absorption salt ratio reaches 49 g/g.It is raw material that wangdans etc. utilize Wheat Straw, vinylformic acid, acrylamide and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC), synthesizes amphiprotic absorbent resin by graft copolymerization, and suction distilled water reaches 853g/g, suction physiological saline is 118g/g.Wheat stalk is carried out alkaline boiling pre-treatment by Guo Yan etc., with vinylformic acid, the synthetic agricultural high-hygroscopicity resin of acrylic amide graft copolymerization, absorbs deionized water and reach 412g/g, and the aqueous solution that absorbs w (Chemical Mixed Fertilizer)=0.1% reaches 126g/g.The use Wheat Straws such as Liu Wei and cornstalk and acrylic graft copolymer are prepared super absorbent resin, and the water absorbent rate of the absorbent resin that wherein prepared by Wheat Straw approaches 200, and the water absorbent rate of absorbent resin prepared by cornstalk approaches 150.Pay loyal grade maize straw and vinylformic acid and sodium salt thereof are carried out to graft copolymerization, tentatively found out the top condition of polyreaction, made better performances, cheap product.Wan Tao etc. prepare maize straw composite high-water uptake resin by carrying out aqueous solution graft copolymerization with vinylformic acid, acrylamide and Sodium styrene sulfonate after maize straw pre-treatment, find in the time that straw content is 10%, the stalk composite highly-absorbent resin 10 min water-intake rates that absorb water reach 58% of equilibrium water absorption, the 50 min stalk composite highly-absorbent resin water suctions that absorb water reach balance, the nearly 350 g/g of equilibrium water absorption.The stalk composite highly-absorbent resin equilibrium water absorption that Wan Tao etc. prepare maleic anhydride modified stalk and vinylformic acid and acrylic amide graft copolymerization and balance salt absorbing rate can reach respectively 400～1000 times and 30～80 times, the gel-strength of water absorbent gel reaches 5～25Pa.s, and the water retention after 80～90 DEG C of dry 200min of water absorbent gel is 15～40%.
The preparation method of stalk composite highly-absorbent resin first carries out gelatinization, acid, alkali or acid anhydrides processing to stalk at present, again with corresponding function monomer reaction, water suction, water conservation and the suction salt performance of main research stalk composite highly-absorbent resin, and the applied research of absorption property to dyestuff is less, have not been reported both at home and abroad about the preparation of the dye adsorption material of phytic acid modified straw and the adsorption applications research to cationic dyestuff solution thereof at present.
Summary of the invention
In view of this, object of the present invention is exactly in the preparation method that the dye adsorption material of a kind of agricultural crop straw is provided.Adopt phytic acid graft modification stalk, utilize in phytic acid molecule the chemical reaction of 6 phosphate groups and stalk molecule chain hydroxyl, on stalk molecule chain, introduce phytic acid group, strengthen the hydrogen bond action between modified straw and polymeric matrix, improved the degree of scatter of modified straw at High hydrophilous resin matrix.Meanwhile the negatively charged ion phosphate group number of phytic acid unit is many, can be used as complexing ion and negatively charged ion and cationic dyestuff and produces complexing absorption and electrostatic adhesion, improves the cationic dyestuff absorption property of the dye adsorption material of agricultural crop straw.
According to object of the present invention, the method for the dye adsorption material of a kind of agricultural crop straw has been proposed, its feature has following processing step:
A) stalk is cut into fragment, with deionized water wash 3～4 times, put at 80 DEG C, baking oven and dry, pulverize, sieve is got 100-200 object stalk powder, stalk powder is joined in DMF, be placed in 30～50 DEG C of supersound process of ultrasonic cleaner 20～60 minutes, then phytic acid and urea are joined in above-mentioned system, be warmed up to 50～90 DEG C, after reaction 2～6h, product be cooled to room temperature, filter, washing with alcohol 3～5 times, in 70～80 DEG C of baking ovens, dry, pulverize, obtain phytic acid modified straw; The mass ratio of stalk powder, phytic acid, urea and DMF is 10～30:5～15:0.5～3:100;
B) a certain amount of solid NaOH is dissolved in 250mL deionized water, then in ice bath, methylene-succinic acid is slowly added drop-wise in the NaOH aqueous solution, fully stir, reaction 0.5～2h, the mol ratio of methylene-succinic acid and NaOH is 1:1～1.6;
C) in above-mentioned solution, add phytic acid modified straw, acrylamide, vinyl pyrrolidone and linking agent, fully stir 30min, be warming up to gradually 50～60 DEG C, then redox initiator be slowly added drop-wise in polymerization system, initiated polymerization 3～5 hours; The mass ratio of methylene-succinic acid, acrylamide and vinyl pyrrolidone is 1～5:5～10:1～5; Linking agent accounts for 0.1～0.8% of methylene-succinic acid, acrylamide and vinylpyrrolidone monomer quality total amount; Redox initiator accounts for 0.5%～2.0% of methylene-succinic acid, acrylamide and vinylpyrrolidone monomer quality total amount; Phytic acid modified straw accounts for 5～30% of methylene-succinic acid, acrylamide and vinylpyrrolidone monomer quality total amount;
D) dye adsorption synthetic agricultural crop straw material is precipitated with ethanol, washing with alcohol 3～5 times, 70～80 DEG C of oven dry, pulverize and obtain particulate state, the dye adsorption material of lurid agricultural crop straw, the cationic dyestuff adsorption from aqueous solution capacity that is 200～2000mg/l to starting point concentration reaches 195～1400mg/g, percent of decolourization reaches 55～90%, and room temperature absorption 100～200min reaches adsorption equilibrium.
Stalk used in the present invention is selected from maize straw, wheat stalk, soybean stalk, rice straw, jowar stalk and cotton stalk.
Ultrasonic cleaner frequency used in the present invention is that 20～80kHz, power are 300～3000W.
Linking agent used in the present invention is selected from N,N methylene bis acrylamide, ethylene glycol diacrylate, diethylene glycol double methacrylate, tirethylene glycol double methacrylate, 1,3-PD double methacrylate and polyethyleneglycol diacrylate.
Redox initiator used in the present invention comprises Oxidizing and Reducing Agents, and the mol ratio of Oxidizing and Reducing Agents is 1～2:1.Oxygenant is selected from ammonium persulphate, Potassium Persulphate and Sodium Persulfate, and reductive agent is selected from sodium bisulfite, S-WAT and Sulfothiorine.
Cationic dyestuff used in the present invention is selected from that monovalent cation dyestuff methylene blue, Viola crystallina, cationic blue FGL, cationic blue G, Stigma Croci T, Cationic Pure Blue GB, cationic pink FF, positively charged ion orange R, Cationic Yellow X-6G, cationic pink fg, Cationic Bright Yellow 7GL, positively charged ion are scarlet, cationic yellow 2RL, Basic blue RL, cationic blue X-GRL, cationic blue and divalent cation dyestuff methyl green.
Advantage of the present invention and effect are:
1) reaction is directly carried out in the aqueous solution, non-environmental-pollution, and method is simple, without nitrogen protection, therefore saved nitrogen device, reduced the Meteorological of equipment;
2) adopt phytic acid graft modification stalk, utilize in phytic acid molecule the chemical reaction of 6 phosphate groups and stalk molecule chain hydroxyl, on stalk molecule chain, introduce phytic acid group, strengthen the hydrogen bond action between modified straw and polymeric matrix, improved the degree of scatter of modified straw at High hydrophilous resin matrix.Meanwhile the negatively charged ion phosphate group number of phytic acid unit is many, can be used as complexing ion and negatively charged ion and cationic dyestuff and produces complexing absorption and electrostatic adhesion, improves the absorption property of the dye adsorption material of agricultural crop straw to cationic dyestuff;
3) prepare the dye adsorption material of phytic acid modified straw with this natural materials of agricultural crop straw, have life cycle chain can natural degradation after short, discarded etc. environmental protection advantage, take full advantage of inexhaustible renewable resource, solve again the environomental pollution source of crop straw burning, the environmental pollution bringing administering current China crop straw burning and dyeing waste water, realize the comprehensive utilization of agricultural crop straw and agricultural sustainable development and have importantly, there is huge social benefit, environmental benefit and economic benefit.
Dye adsorption speed, equilibrium adsorption capacity and the percent of decolourization measuring method of the dye adsorption material of agricultural crop straw of the present invention are as follows.
The cationic dyestuff solution that is 200-2000mg.L-1 by concentration and 0.2g are dry, the dye adsorption material of agricultural crop straw of porphyrize is put into 250mL Erlenmeyer flask, then be placed in vibrator vibration absorption, after vibration certain hour, sample, adopt the absorbancy of ultraviolet/visible spectrophotometer at cationic dyestuff maximum absorption wave strong point working sample, each sample measurement is averaged for 3 times, cationic dyestuff adsorptive capacity
q t , equilibrium adsorption capacity
q eand percent of decolourization
k d be calculated as follows respectively:
q t (mg/g)={(
C 0-
C t)
V}/
m (1)
q e (mg/g)={(
C 0-
C e)
V}/
m (2)
K d ={(
C 0-
C e) /
C 0}×100% (3)
Wherein
c 0,
c t, and
c ebe respectively cationic dyestuff starting point concentration, vibration absorption certain hour cationic dyestuff concentration, cationic dyestuff adsorption equilibrium concentration (mg.L-1),
vfor liquor capacity (L),
mfor the quality (g) of the dye adsorption material of agricultural crop straw.
Embodiment
In order to understand better the present invention, further set forth content of the present invention below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
embodiment 1:
Maize straw is cut into fragment, with deionized water wash 4 times, put at 80 DEG C, baking oven and dry, pulverize, sieve is got 200 object maize straw powder, 20g maize straw powder is joined in 200g DMF to 50 DEG C of supersound process of ultrasonic cleaner that to be placed in frequency and to be 50kHz, power be 500W 20 minutes, then 15g phytic acid and 2g urea are joined in above-mentioned system, be warmed up to 60 DEG C, after reaction 5h, product be cooled to room temperature, filter, washing with alcohol 5 times, in 80 DEG C of baking ovens, dry, pulverize, obtain phytic acid corn straw modification, 5gNaOH is dissolved in 250mL deionized water, then in ice bath, 10g methylene-succinic acid is slowly added drop-wise in the NaOH aqueous solution, fully stir, after reaction 2h, add 13.8g phytic acid corn straw modification, 30g acrylamide, 6g vinyl pyrrolidone and 0.23g N, N '-methylene-bisacrylamide, fully stir 30min, be warming up to gradually 60 DEG C, then 0.46g ammonium persulphate and 0.15g sodium bisulfite are slowly added drop-wise in polymerization system, initiated polymerization precipitated dye adsorption synthetic maize straw material after 5 hours with ethanol, washing with alcohol 3 times, 80 DEG C of oven dry, pulverize and obtain particulate state, the dye adsorption material of lurid maize straw, the Degradation of Cationic Dye Crystal Violet adsorption from aqueous solution capacity that is 200mg/L to starting point concentration reaches 195mg/g, percent of decolourization reaches 80%, room temperature absorption 100min reaches adsorption equilibrium.
embodiment 2:
Wheat stalk is cut into fragment, with deionized water wash 3 times, put at 80 DEG C, baking oven and dry, pulverize, sieve is got 100 object wheat stalk powder, 60g wheat stalk powder is joined in 200g DMF, and being placed in frequency is that 30kHz, power are 30 DEG C of supersound process of 300W ultrasonic cleaner 60 minutes, then 30g phytic acid and 6g urea are joined in above-mentioned system, be warmed up to 80 DEG C, after reaction 3h, product be cooled to room temperature, filter, washing with alcohol 5 times, in 70 DEG C of baking ovens, dry, pulverize, obtain phytic acid modification wheat stalk, 4.8gNaOH is dissolved in 250mL deionized water, then in ice bath, 15g methylene-succinic acid is slowly added drop-wise in the NaOH aqueous solution, fully stir, after reaction 2h, add 9g phytic acid modification wheat stalk, 20g acrylamide, 10g vinyl pyrrolidone and 0.36g ethylene glycol diacrylate, fully stir 30min, be warming up to gradually 50 DEG C, then 0.33g Sodium Persulfate and 0.13g S-WAT are slowly added drop-wise in polymerization system, initiated polymerization precipitated dye adsorption synthetic wheat stalk material after 5 hours with ethanol, washing with alcohol 4 times, 80 DEG C of oven dry, pulverize and obtain particulate state, the dye adsorption material of lurid wheat stalk, the cationic dyestuff cationic blue G adsorption from aqueous solution capacity that is 500mg/L to starting point concentration reaches 460mg/g, percent of decolourization reaches 78%, room temperature absorption 150min reaches adsorption equilibrium.
embodiment 3:
Jowar stalk is cut into fragment, with deionized water wash 4 times, put at 80 DEG C, baking oven and dry, pulverize, sieve is got 200 object jowar stalk powders, 30g jowar stalk powder is joined in 200g DMF, and being placed in frequency is that 80kHz, power are that 50 DEG C of 3000W ultrasonic cleaners carry out supersound process 40 minutes, then 20g phytic acid and 3.5g urea are joined in above-mentioned system, be warmed up to 90 DEG C, after reaction 2h, product be cooled to room temperature, filter, washing with alcohol 3 times, in 80 DEG C of baking ovens, dry, pulverize, obtain phytic acid modification jowar stalk, 8gNaOH is dissolved in 250mL deionized water, then in ice bath, 20g methylene-succinic acid is slowly added drop-wise in the NaOH aqueous solution, fully stir, after reaction 0.5h, add 7.2g phytic acid modification jowar stalk, 20g acrylamide, 8g vinyl pyrrolidone and 0.192g diethylene glycol double methacrylate, fully stir 30min, be warming up to gradually 60 DEG C, then 0.71g Potassium Persulphate and 0.25g sodium bisulfite are slowly added drop-wise in polymerization system, initiated polymerization precipitated the synthetic dye adsorption material of jowar stalk after 5 hours with ethanol, washing with alcohol 3 times, 80 DEG C of oven dry, pulverize and obtain particulate state, the dye adsorption material of lurid jowar stalk, the cationic dyestuff aqueous solution of methylene blue loading capacity that is 2000mg/L to starting point concentration reaches 1400mg/g, percent of decolourization reaches 55%, room temperature absorption 200min reaches adsorption equilibrium.
embodiment 4:
Soybean stalk is cut into fragment, with deionized water wash 4 times, put at 80 DEG C, baking oven and dry, pulverize, sieve is got 100 object soybean stalk powder, 25g soybean stalk powder is joined in 200g DMF, and being placed in frequency is that 20kHz, power are 30 DEG C of supersound process of 500W ultrasonic cleaner 60 minutes, then 15g phytic acid and 2.5g urea are joined in above-mentioned system, be warmed up to 50 DEG C, after reaction 6h, product be cooled to room temperature, filter, washing with alcohol 5 times, in 80 DEG C of baking ovens, dry, pulverize, obtain phytic acid modified soybean stalk, 5gNaOH is dissolved in 250mL deionized water, then in ice bath, 15g methylene-succinic acid is slowly added drop-wise in the NaOH aqueous solution, fully stir, after reaction 2h, add 2.4g phytic acid modified soybean stalk, 25g acrylamide, 8g vinyl pyrrolidone and 0.384g 1, ammediol double methacrylate, fully stir 30min, be warming up to gradually 55 DEG C, then 0.56g ammonium persulphate and 0.32g Sulfothiorine are slowly added drop-wise in polymerization system, initiated polymerization precipitated dye adsorption synthetic soybean stalk material after 4 hours with ethanol, washing with alcohol 4 times, 70 DEG C of oven dry, pulverize and obtain particulate state, the dye adsorption material of lurid soybean stalk, the cationic dyestuff cationic pink FF adsorption from aqueous solution capacity that is 300mg/L to starting point concentration reaches 292mg/g, percent of decolourization reaches 85%, room temperature absorption 100min reaches adsorption equilibrium.
embodiment 5:
Rice straw is cut into fragment, with deionized water wash 4 times, put at 80 DEG C, baking oven and dry, pulverize, sieve is got 100 object rice straw powder, 40g rice straw powder is joined in 200g DMF, and being placed in frequency is that 50kHz, power are 50 DEG C of supersound process of 300W ultrasonic cleaner 40 minutes, then 25g phytic acid and 4.0g urea are joined in above-mentioned system, be warmed up to 90 DEG C, after reaction 2h, product be cooled to room temperature, filter, washing with alcohol 3 times, in 80 DEG C of baking ovens, dry, pulverize, obtain phytic acid modified straw stalk, 10gNaOH is dissolved in 250mL deionized water, then in ice bath, 10g methylene-succinic acid is slowly added drop-wise in the NaOH aqueous solution, fully stir, after reaction 2h, add 7.5g phytic acid modified straw stalk, 40g acrylamide, 5g vinyl pyrrolidone and 0.23g polyethyleneglycol diacrylate, fully stir 30min, be warming up to gradually 60 DEG C, then 0.21g ammonium persulphate and 0.07g sodium bisulfite are slowly added drop-wise in polymerization system, initiated polymerization precipitated dye adsorption synthetic rice straw material after 3 hours with ethanol, washing with alcohol 5 times, 80 DEG C of oven dry, pulverize and obtain particulate state, the dye adsorption material of lurid rice straw, the scarlet adsorption from aqueous solution capacity of the cationic dyestuff positively charged ion that is 250mg/L to starting point concentration reaches 210mg/g, percent of decolourization reaches 90%, room temperature absorption 120min reaches adsorption equilibrium.
embodiment 6:
Cotton stalk is cut into fragment, with deionized water wash 4 times, put at 80 DEG C, baking oven and dry, pulverize, sieve is got 100 object cotton stalk powder, 50g cotton stalk powder is joined in 200g DMF, and being placed in frequency is that 50kHz, power are 50 DEG C of supersound process of 500W ultrasonic cleaner 40 minutes, then 10g phytic acid and 1g urea are joined in above-mentioned system, be warmed up to 70 DEG C, after reaction 4h, product be cooled to room temperature, filter, washing with alcohol 5 times, in 70 DEG C of baking ovens, dry, pulverize, obtain phytic acid modification cotton stalk, 10gNaOH is dissolved in 250mL deionized water, then in ice bath, 18g methylene-succinic acid is slowly added drop-wise in the NaOH aqueous solution, fully stir, after reaction 1h, add 12.5g phytic acid modified straw stalk, 25g acrylamide, 7g vinyl pyrrolidone and 0.05g tirethylene glycol double methacrylate, fully stir 30min, be warming up to gradually 60 DEG C, then 0.38g Sodium Persulfate and 0.15g Sulfothiorine are slowly added drop-wise in polymerization system, initiated polymerization precipitated dye adsorption synthetic rice straw material after 4 hours with ethanol, washing with alcohol 3 times, 80 DEG C of oven dry, pulverize and obtain particulate state, the dye adsorption material of lurid rice straw, the cationic dyestuff methyl green adsorption from aqueous solution capacity that is 1000mg/L to starting point concentration reaches 650mg/g, percent of decolourization reaches 58%, room temperature absorption 180min reaches adsorption equilibrium.
Claims (6)
1. a preparation method for the dye adsorption material of agricultural crop straw, is characterized in that having following processing step:
Stalk is cut into fragment, with deionized water wash 3～4 times, put at 80 DEG C, baking oven and dry, pulverize, sieve is got 100-200 object stalk powder, stalk powder is joined in DMF, be placed in 30～50 DEG C of supersound process of ultrasonic cleaner 20～60 minutes, then phytic acid and urea are joined in above-mentioned system, be warmed up to 50～90 DEG C, after reaction 2～6h, product be cooled to room temperature, filter, washing with alcohol 3～5 times, in 70～80 DEG C of baking ovens, dry, pulverize, obtain phytic acid modified straw; The mass ratio of stalk powder, phytic acid, urea and DMF is 10～30:5～15:0.5～3:100;
A certain amount of solid NaOH is dissolved in 250mL deionized water, then in ice bath, methylene-succinic acid is slowly added drop-wise in the NaOH aqueous solution, fully stir, reaction 0.5～2h, the mol ratio of methylene-succinic acid and NaOH is 1:1～1.6;
In above-mentioned solution, add phytic acid modified straw, acrylamide, vinyl pyrrolidone and linking agent, fully stir 30min, be warming up to gradually 50～60 DEG C, then redox initiator is slowly added drop-wise in polymerization system, initiated polymerization 3～5 hours; The mass ratio of methylene-succinic acid, acrylamide and vinyl pyrrolidone is 1～5:5～10:1～5; Linking agent accounts for 0.1～0.8% of methylene-succinic acid, acrylamide and vinylpyrrolidone monomer quality total amount; Redox initiator accounts for 0.5%～2.0% of methylene-succinic acid, acrylamide and vinylpyrrolidone monomer quality total amount; Phytic acid modified straw accounts for 5～30% of methylene-succinic acid, acrylamide and vinylpyrrolidone monomer quality total amount;
Dye adsorption synthetic agricultural crop straw material is precipitated with ethanol, washing with alcohol 3～5 times, 70～80 DEG C of oven dry, pulverize and obtain particulate state, the dye adsorption material of lurid agricultural crop straw, the cationic dyestuff adsorption from aqueous solution capacity that is 200～2000mg/l to starting point concentration reaches 195～1400mg/g, percent of decolourization reaches 55～90%, and room temperature absorption 100～200min reaches adsorption equilibrium.
2. the preparation method of the dye adsorption material of a kind of agricultural crop straw according to claim 1, is characterized in that: described stalk is selected from maize straw, wheat stalk, soybean stalk, rice straw, jowar stalk and cotton stalk.
3. the preparation method of the dye adsorption material of a kind of agricultural crop straw according to claim 1, is characterized in that: described ultrasonic cleaner frequency is that 20～80kHz, power are 300～3000W.
4. the preparation method of the dye adsorption material of a kind of agricultural crop straw according to claim 1, it is characterized in that: described linking agent is selected from N, N-methylene-bisacrylamide, ethylene glycol diacrylate, diethylene glycol double methacrylate, tirethylene glycol double methacrylate, 1,3-PD double methacrylate and polyethyleneglycol diacrylate.
5. the preparation method of the dye adsorption material of a kind of agricultural crop straw according to claim 1, it is characterized in that: described redox initiator comprises Oxidizing and Reducing Agents, the mol ratio of Oxidizing and Reducing Agents is 1～2:1, oxygenant is selected from ammonium persulphate, Potassium Persulphate and Sodium Persulfate, and reductive agent is selected from sodium bisulfite, S-WAT and Sulfothiorine.
6. the preparation method of the dye adsorption material of a kind of agricultural crop straw according to claim 1, is characterized in that: described cationic dyestuff is selected from that monovalent cation dyestuff methylene blue, Viola crystallina, cationic blue FGL, cationic blue G, Stigma Croci T, Cationic Pure Blue GB, cationic pink FF, positively charged ion orange R, Cationic Yellow X-6G, cationic pink fg, Cationic Bright Yellow 7GL, positively charged ion are scarlet, cationic yellow 2RL, Basic blue RL, cationic blue X-GRL, cationic blue and divalent cation dyestuff methyl green.
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| JP2017113709A (en) * | 2015-12-24 | 2017-06-29 | 株式会社日本触媒 | Surfactant carrier |
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| CN113860512A (en) * | 2021-09-14 | 2021-12-31 | 镇江同源胜环境科技有限公司 | Indigenous algicidal bacteria activating agent and method for preventing cyanobacterial bloom by using same |
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| CN104162413A (en) * | 2014-09-18 | 2014-11-26 | 苏州新协力环保科技有限公司 | Novel preparation method of rape stalk cellulose adsorbent |
| JP2017113709A (en) * | 2015-12-24 | 2017-06-29 | 株式会社日本触媒 | Surfactant carrier |
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| CN107349909B (en) * | 2017-07-21 | 2019-09-20 | 成都理工大学 | A kind of preparation method of magnetism stalk cellulose dye sorbent |
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| CN110841611B (en) * | 2019-09-30 | 2021-11-09 | 浙江海洋大学 | Application of modified mussel shell to adsorption of methylene blue |
| CN111268842A (en) * | 2020-02-25 | 2020-06-12 | 濮阳市盛源能源科技股份有限公司 | Sewage treatment method |
| CN111268842B (en) * | 2020-02-25 | 2022-05-20 | 濮阳市盛源能源科技股份有限公司 | Sewage treatment method |
| CN111704130A (en) * | 2020-06-28 | 2020-09-25 | 南通大学 | Preparation method of blue algae biochar for purifying cationic yellow dye wastewater |
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