CN104645945A - Wheat straw bio-based ion exchange type adsorbing material and preparation method thereof - Google Patents
Wheat straw bio-based ion exchange type adsorbing material and preparation method thereof Download PDFInfo
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- CN104645945A CN104645945A CN201510085395.4A CN201510085395A CN104645945A CN 104645945 A CN104645945 A CN 104645945A CN 201510085395 A CN201510085395 A CN 201510085395A CN 104645945 A CN104645945 A CN 104645945A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/44—Materials comprising a mixture of organic materials
- B01J2220/445—Materials comprising a mixture of organic materials comprising a mixture of polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
Abstract
The invention discloses a wheat straw bio-based ion exchange type adsorbing material and a preparation method thereof. The preparation method comprises the following steps: selecting wheat straws as the raw material, grafting monomer molecules with initiating groups to the surfaces of the wheat straws, and thermally initializing transfer of surface atom free groups so as to realize the chain growth of a polymer monomer, and thus obtaining the wheat straw bio-based ion exchange type adsorbing material with high grafting ratio and high adsorbing capacity. The wheat straw bio-based ion exchange type adsorbing material can be applied for enriching and recovering rear-earth ions of rare earth mineral and metallurgical wastewater, and can be regenerated and reused for many times. A reasonable resource utilization way of the wheat straws is developed, linear chain polymers are grafted on the surfaces of substrates by utilizing a thermal initiation technique in a chemical bonding manner, and the adsorbing material has the characteristics of stable performances, high grafting amount, large adsorption capacity, high adsorption speed, easiness in regeneration and the like, the ideas of recycling waste materials and treating a waste with another waste are achieved, and the social benefits and the economic benefits are remarkable.
Description
Technical field
The present invention relates to natural biomass sill and surface-functionalized technical field of modification thereof, be specifically related to a kind of Wheat Straw bio-based ion-exchange type sorbing material and preparation method thereof.
Background technology
China is a large agricultural country, and wheat has distribution, nearly 700,000,000 tons of annual stalk output in the most area of China, and the agricultural crop straw that quantity is so surprising, especially how Wheat Straw is treated as a problem merited attention.In recent years, along with country labor force transfer, energy consumption structure improve and the application of all kinds of alternative materials, add the reasons such as stalk comprehensive utilization cost is high, less economical, industrialization level is low, start to have occurred provincialism, seasonality, structural stalk surplus, after annual wheat harvest, owing to stacking stalk nowhere, stalk is often piled the edge of a field, roadside or on-site incineration by villagers.Containing a large amount of organic matters in Wheat Straw, phosphorus content is high, and incomplete combustion then has little carbon granules and generates, and burning the raging opium caused can spread dozens of kilometres, affects sight line, serious threat traffic safety.The smog simultaneously formed can shroud for a long time and not easily be dispersed on high, produces larger air pollution, and long-term breathing is unfavorable for the health of people, the more important thing is the waste causing resource.Wheat Straw is a kind of important reproducible living resources, if process rationally, just can create a large amount of wealth of society, if dealt with improperly, then can cause great harm to social economy and environment.For this reason, State Council has issued " General Office of the State Council is about accelerating to advance the suggestion of agricultural crop straw comprehensive utilization " (Office of the State Council is sent out [2008] No. 105) file to accelerate to advance stalk comprehensive utilization, the construction of promotion resource-conserving and environment-friendly society.Therefore be power with technological innovation, the Appropriate application approach of exploitation Wheat Straw is a behave of benefiting the nation and the people.
In the last few years along with the fast development of China's industrialization and urbanization level, all kinds of waste water discharged in a large number, caused the heavy metal pollution problem in water body day by day serious, urgently to be resolved hurrily.Absorption and ion-exchange are most widely used the treatment process also the most effectively removing each metal ion species in water at present.At present, the chemical products such as the resin/fiber prepared for raw material with non-renewable fossil energy are the most common on market, are also most widely used ion exchange materials; But along with the consumption of fossil energy and the day by day serious of environmental pollution, utilizing natural reproducible resource, the friendly product of development environment and technology will become the inexorable trend of scientific research.Because agriculture and forestry organic waste material has the features such as hole is many, specific area is large, surface reactive material is many, many scholars by agriculture and forestry organic waste material directly or by the modified heavy metal be used in adsorbed water of certain methods, achieve desirable effect, it is that raw material prepares anion adsorbent for removing anionic dye that patent CN101693188A discloses a kind of employing agricultural wastes wheat straw waste, epoxychloropropane and dimethylamine; Patent CN 102671632A discloses one, and to choose sesame stalk be raw material, then citric acid is used to carry out chemical modification to it, form a large amount of carboxy functional group on sesame stalk surface, finally make a kind of low-cost bio adsorbent dye of positive ion to good adsorbent effect; Patent CN 102423695A disclose a kind of can be degradable stalk cellulose-poly-hydroxy Al salt dephosphorization adsorbent and manufacture method; Patent CN 101862642A discloses a kind of preparation method and application etc. of amphoteric chelate sorbent containing agricultural straw.Wheat Straw is the class that in agriculture and forestry organic waste material, output is maximum, has impayable cost advantage relative to other materials.From the build of material, from microcosmic to macroscopic view, the cellulose linear molecule be cross-linked by hydrogen chain and multistage fibre pipe form wheat straw tube wall, final formation hollow pipe build, surface active groups, except the primary hydroxyl group in cellulose basic structural unit (cellobiose) and secondary hydroxyl group, also has phenolic hydroxyl group and methoxyl group.Therefore, functional graft modification can be carried out to Wheat Straw surface, give its ion-exchange performance and be used as water treatment absorbent, reach and turn waste into wealth, the object of the treatment of wastes with processes of wastes against one another, there is significant Social and economic benef@.
The method of Wheat Straw being carried out to graft modification has a lot, mainly contains chemical graft, high-energy radiation grafting, plasma grafting and Graft copolymerization etc.High-energy radiation and plasma grafting reaction relatively rapid, grafting scope can control, but to the condition of grafting and equipment requirement higher, and have injury to material main body.UV-irradiation technology grafting efficiency is high, is to adopt more method at present, but there is illumination dark space, and material backlight face and inner surface are difficult to cause, and cause grafting uneven.Though above grafting method can realize grafting object, there is the common fault that grafting cost is high, not easily realize large-scale production.Chemical graft adopts heat to cause usually, and equipment is simple, can carry out amplifications and produce, but conventional method is by initator dispersion in the solution, and reaction is once carry out, and very easily generation autohemagglutination and reaction condition is wayward, causes the problems such as percent grafting is low, monomer utilization ratio is low.
Summary of the invention
The object of the invention is to provide that a kind of percent grafting is high, adsorption capacity large, environmental friendliness, reused Wheat Straw bio-based sorbing material and preparation method thereof.
For achieving the above object, the technical solution used in the present invention is: a kind of Wheat Straw bio-based ion-exchange type sorbing material, take Wheat Straw as raw material, adopt surface modifying method, monomer molecule with initiating group is received Wheat Straw surface, with the method (ATRP) of heat initiation surface atom radical transfer polymerization, the copolymer long-chain that polymer monomer is formed is grafted to Wheat Straw surface again, obtains the Wheat Straw bio-based ion-exchange type sorbing material of rich surface containing carboxylate radical adsorption group.
According to such scheme, the described monomer molecule with initiating group is bromo isobutyl acylbromide.
According to such scheme, described polymer monomer is Sodium methacrylate, PAA or sodium p styrene sulfonate.
According to such scheme, described surface modifying method comprises the following steps: be immersed in by Wheat Straw in activation process liquid I and soak 6 ~ 24h, then filter, be washed to neutrality, drying for standby, must disappear brilliant Wheat Straw; The brilliant Wheat Straw that disappears obtained is added in DMF solvent, then drips bromo isobutyl acylbromide and pyridine, under magnetic agitation, at 25 ~ 60 DEG C of reaction 6 ~ 24h, rinse with oxolane, acetone, then spend deionized water, suction filtration, drying, obtain bromination Wheat Straw.
According to such scheme, described activation process liquid I is the NaOH aqueous solution or the NaOH aqueous solution/alcohol mixeding liquid, and the concentration of NaOH is 10 ~ 30wt%.
According to such scheme, described in the disappear solid-to-liquid ratio of brilliant Wheat Straw and DMF solvent be 1:(30 ~ 60) g/ml; The solid-to-liquid ratio of brilliant Wheat Straw and bromo isobutyl acylbromide of disappearing is 1:(3 ~ 6) g/mL; The volume ratio of bromo isobutyl acylbromide and pyridine is (6 ~ 1): 1.
According to such scheme, described heat causes surface atom radical transfer polymerization and comprises the following steps: add in polymer monomer solution by bromination Wheat Straw, dispersed with stirring, then slowly drip N, N, N', N ", N "-pentamethyl-diethylenetriamine, and pass into N
2, deaeration, then adds CuBr and CuBr
2powder, under sealing and stirring condition, at 25 ~ 60 DEG C of reaction 0.5 ~ 24h, then successively through boiling water, acetone, hydrochloric acid/alcohol mixeding liquid cleaning, then through washing suction filtration to neutral.
According to such scheme, the concentration of described polymer monomer solution is 10 ~ 50wt%; The solid-to-liquid ratio of bromination Wheat Straw and polymer monomer solution solution is 10 ~ 50g/L; Bromination Wheat Straw and N, N, N', N ", N " solid-to-liquid ratio of-pentamethyl-diethylenetriamine is 1:(0.6 ~ 3.6) g/ml; Bromination Wheat Straw, CuBr, CuBr
2mass ratio be 1:(0.225 ~ 1.35): (0.045 ~ 0.27).
The preparation method of above-mentioned a kind of Wheat Straw bio-based ion-exchange type sorbing material, specifically comprises the steps:
1) Wheat Straw cleaned, dry, carry out pulverizing or cutting;
2) by step 1) process the Wheat Straw that obtains and be immersed in activation process liquid I and soak 6 ~ 24h, then filter, be washed to neutrality, drying for standby, must disappear brilliant Wheat Straw;
3) the brilliant Wheat Straw that disappears obtained is added N, in dinethylformamide solvent, then bromo isobutyl acylbromide and pyridine is dripped, under magnetic agitation, at 25 ~ 60 DEG C of reaction 6 ~ 24h, rinse with oxolane, acetone, then spend deionized water, suction filtration, drying, obtain bromination Wheat Straw;
4) add in polymer monomer solution by the bromination Wheat Straw obtained, dispersed with stirring, then slowly drips N, N, N', N ", N "-pentamethyl-diethylenetriamine, and pass into N
2, deaeration, then adds CuBr and CuBr
2powder, under sealing and stirring condition, at 25 ~ 60 DEG C of reaction 0.5 ~ 24h, then successively through boiling water, acetone, hydrochloric acid/alcohol mixeding liquid cleaning, then through washing suction filtration to neutral;
5) by step 4) product that obtains is immersed in oscillation treatment 0.1 ~ 6h in sodium treatment fluid II, then washes suction filtration to neutral, after drying described Wheat Straw bio-based ion-exchange type sorbing material.
According to such scheme, described sodium treatment fluid II is the NaOH aqueous solution, and concentration is 1 ~ 10wt%; In described hydrochloric acid/alcohol mixeding liquid, the volume ratio of hydrochloric acid and ethanol is 5:1, and the concentration of hydrochloric acid is 5 ~ 20wt%.
According to such scheme, described Sodium methacrylate, PAA, sodium p styrene sulfonate can be commercially available chemical reagent, in also can being undertaken by alkaline solutions such as the NaOH solution of methacrylic acid, PAA or p styrene sulfonic acid and equimolar amounts and sodium make the transition and be prepared from.
Compared with prior art, beneficial effect of the present invention is:
1) before graft modification is carried out to Wheat Straw, activation process liquid is adopted to disappear brilliant process to Wheat Straw, destroy the hydrogen bond between cellulose in Wheat Straw, reach the effect reducing surface molecules degree of crystallinity, increase modifier molecules accessibility, improve the reactivity of Wheat Straw surface hydroxyl.
2) by initiating group is bonded to Wheat Straw material surface in advance, the chain growth of polymer monomer is realized again in the mode of surface in situ initiation atomic radicals transfer, there is homopolymers few, monomer utilization ratio is high, the features such as grafting amount is controlled, high percent grafting can be obtained, the ion exchange material of high adsorption capacity.
3) way adopting hot polymerization to cause, has grafting even, and equipment is simple, is easy to the advantage of carrying out large-scale production.
4) Wheat Straw is as a kind of main agricultural wastes, have thing source abundant, inexpensive, renewable, be easy to the features such as degraded, this invention exploits the reasonable resource utilization ways of Wheat Straw, achieve turn waste into wealth, the theory of the treatment of wastes with processes of wastes against one another, there is significant Social and economic benef@.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the invention will be further described, in accompanying drawing:
Fig. 1 is the brilliant Wheat Straw (a) that disappears described in the embodiment of the present invention 1, bromination Wheat Straw (b), after grafting Wheat Straw (c) ESEM with can spectrogram.
Fig. 2 is the brilliant Wheat Straw (a) that disappears described in the embodiment of the present invention 1, bromination Wheat Straw (b), the infared spectrum of Wheat Straw (c) after grafting.
Fig. 3 is that the obtained Wheat Straw bio-based ion-exchange type sorbing material of the embodiment of the present invention 1 is to the repeat performance of cerium ion.
Detailed description of the invention
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
In following examples, as no specific instructions, the reagent of employing is commercially available chemical reagent.Described polymer monomer solution selects sodium methacrylate solution, in being undertaken by the methacrylic acid solution of equimolar amounts and NaOH solution and sodium make the transition and be prepared from.Described Wheat Straw is common agricultural discarded object.
Embodiment 1
A kind of Wheat Straw bio-based ion-exchange type sorbing material, its preparation method comprises the following steps:
1) Wheat Straw is cleaned post-drying, be placed in plant pulverizer and pulverize, cross 80 mesh sieves and get Wheat Straw fine fibre.
2) Wheat Straw fine fibre is immersed in 24h in the NaOH solution of 15wt%, carry out the brilliant process that disappears, then filtered water is washed till neutrality, and must disappear brilliant Wheat Straw, drying for standby.
3) take the 1g brilliant Wheat Straw that disappears to add 50mL N is housed, in the round-bottomed flask of dinethylformamide, instillation 4mL bromo isobutyl acylbromide and 1mL pyridine, under magnetic agitation condition, at 60 DEG C of reaction 24h, after having reacted, rinse with oxolane, acetone, then with excessive deionized water washing suction filtration, be dried to constant weight under room temperature, obtain the surperficial bromination Wheat Straw being connected to initiating group.
4) sodium transition is carried out in the NaOH solution neutralization first 12mL methacrylic acid being dissolved in 20mL equimolar amounts, obtain the sodium methacrylate solution that concentration is 40wt%, then 0.6g bromination Wheat Straw is added, dispersed with stirring, slowly drips 0.72mLN, N, N', N ", N "-pentamethyl-diethylenetriamine, and pass into N
210min, deaeration, adds 0.27g CuBr and 0.054gCuBr
2under sealing and stirring condition, at 40 DEG C of reaction 12h, after having reacted, with boiling water, acetone wash residual methacrylic acid monomer, organic reagent and homopolymers, use the ion of hydrochloric acid/alcohol mixeding liquid (concentration of hydrochloric acid is 10wt%, and hydrochloric acid and ethanol contend are than being 5:1) cleaning material surface attachment again, washing suction filtration is to neutral.
5) by step 4) product that obtains is immersed in the NaOH solution of 5wt% 1h activation of vibrating, and then washes suction filtration to neutral, after 65 DEG C of dryings Wheat Straw bio-based ion-exchange type sorbing material (after grafting Wheat Straw).
Disappear brilliant Wheat Straw (a), bromination Wheat Straw (b), and after grafting, Wheat Straw (c) ESEM be shown in Fig. 1 with energy spectrogram.Can obviously find out from figure, after grafting, the surface of Wheat Straw becomes smooth, has significantly regular graft, and graft is grafted on Wheat Straw substrate surface uniformly.
Disappear brilliant Wheat Straw (a), bromination Wheat Straw (b), and after grafting, Wheat Straw (c) infrared spectrum is shown in Fig. 2.Can find out in figure that C=O is at 1732cm
-1stretching vibration peak, prove that bromo isobutyl acylbromide (BIBB) successfully anchors to bromination Wheat Straw surface, 1380cm in Fig. 2 (c)
-1and 1532cm
-1cOO
-group symmetry and asymmetrical stretching vibration peak, illustrate that sodium polymethacrylate has been grafted to Wheat Straw substrate surface.
Embodiment 2
A kind of Wheat Straw bio-based ion-exchange type sorbing material, its preparation method comprises the following steps:
1) Wheat Straw is cleaned post-drying, be placed in plant pulverizer and pulverize, cross 80 mesh sieves and get Wheat Straw fine fibre.
2) Wheat Straw fine fibre is immersed in 6h in the NaOH solution of 25wt% and carries out the brilliant process that disappears, then filtered water is washed till neutrality, and must disappear brilliant Wheat Straw, drying for standby.
3) take the 1.0g brilliant Wheat Straw that disappears to add 30mL N is housed, in the round-bottomed flask of dinethylformamide, instillation 3mL bromo isobutyl acylbromide and 1mL pyridine, under magnetic agitation condition, at 25 DEG C of reaction 24h, after having reacted, rinse with oxolane, acetone, then with excessive deionized water washing suction filtration, be dried to constant weight under room temperature, obtain the bromination Wheat Straw that surface is connected to initiating group.
4) sodium transition is carried out in the NaOH solution neutralization first 6mL methacrylic acid being dissolved in 20mL equimolar amounts, obtain the sodium methacrylate solution that concentration is 25wt%, then 0.3g bromination Wheat Straw is added, dispersed with stirring, slowly drips 1.08mLN, N, N', N ", "-pentamethyl-diethylenetriamine passes into N at mixture to N
210min, deaeration, adds 0.405g CuBr and 0.081g CuBr
2under sealing and stirring condition, at 30 DEG C of reaction 24h, after having reacted, with boiling water, acetone wash residual methacrylic acid monomer, organic reagent and homopolymers, use the ion of hydrochloric acid/alcohol mixeding liquid (concentration of hydrochloric acid is 5wt%, and hydrochloric acid and ethanol contend are than being 5:1) cleaning material surface attachment again, washing suction filtration is to neutral.
5) by step 4) product that obtains is immersed in the NaOH solution of 2wt% 6h activation of vibrating, and then washes suction filtration to neutral, after 65 DEG C of dryings Wheat Straw bio-based ion-exchange type sorbing material.
Embodiment 3
A kind of Wheat Straw bio-based ion-exchange type sorbing material, its preparation method comprises the following steps:
1) Wheat Straw is cleaned post-drying, be placed in plant pulverizer and pulverize, cross 80 mesh sieves and get Wheat Straw fine fibre.
2) Wheat Straw fine fibre is immersed in 24h in the NaOH solution of 10wt% and carries out the brilliant process that disappears, then filtered water is washed till neutrality, and must disappear brilliant Wheat Straw, drying for standby.
3) take the 1g brilliant Wheat Straw that disappears to add 60mL N is housed, in the round-bottomed flask of dinethylformamide, instillation 6mL bromo isobutyl acylbromide and 2mL pyridine, under magnetic agitation condition, at 40 DEG C of reaction 12h, after having reacted, rinse with oxolane, acetone, then with excessive deionized water washing suction filtration, be dried to constant weight under room temperature, obtain the bromination Wheat Straw that surface is connected to initiating group.
4) the NaOH solution neutralization first 9mL methacrylic acid being dissolved in 20mL equimolar amounts is carried out sodium transition, obtaining 35wt% sodium methacrylate solution, then adding 0.9g bromination Wheat Straw, dispersed with stirring, slow dropping 2.16mLN, N, N', N ", N "-pentamethyl-diethylenetriamine, and pass into N
210min, deaeration, adds 0.81g CuBr and 0.162gCuBr
2under sealing and stirring condition, at 40 DEG C of reaction 6h, after having reacted, with boiling water, acetone wash residual methacrylic acid monomer, organic reagent and homopolymers, use the ion of hydrochloric acid/alcohol mixeding liquid (concentration of hydrochloric acid is 20wt%, and hydrochloric acid and ethanol contend are than being 5:1) cleaning material surface attachment again, washing suction filtration is to neutral.
5) by step 4) product that obtains is immersed in solution vibration 0.5h activation in the NaOH of 5wt%, then washes suction filtration to neutral, after 65 DEG C of dryings Wheat Straw bio-based ion-exchange type sorbing material.
Embodiment 4
A kind of Wheat Straw bio-based ion-exchange type sorbing material, its preparation method comprises the following steps:
1) Wheat Straw is cleaned post-drying, be placed in plant pulverizer and pulverize, cross 80 mesh sieves and get Wheat Straw fine fibre.
2) Wheat Straw fine fibre is immersed in 24h in the NaOH solution of 20wt%, carry out the brilliant process that disappears, then filtered water is washed till neutrality, and must disappear brilliant Wheat Straw, drying for standby.
3) take the 1g brilliant Wheat Straw that disappears to add 50mL N is housed, in the round-bottomed flask of dinethylformamide, instillation 4mL bromo isobutyl acylbromide and 1mL pyridine, under magnetic agitation condition, at 30 DEG C of reaction 24h, after having reacted, rinse with oxolane, acetone, then with excessive deionized water washing suction filtration, be dried to constant weight under room temperature, obtain the bromination Wheat Straw that surface is connected to initiating group.
4) sodium transition is carried out in the NaOH solution neutralization first 12mL methacrylic acid being dissolved in 20mL equimolar amounts, obtain the sodium methacrylate solution that concentration is 40wt%, then 1.2g bromination Wheat Straw is added, dispersed with stirring, slowly drips 1.44mLN, N, N', N ", N "-pentamethyl-diethylenetriamine, and pass into N
210min, deaeration, adds 0.54g CuBr and 0.108gCuBr
2under sealing and stirring condition, at 50 DEG C of reaction 8h, after having reacted, with boiling water, acetone wash residual methacrylic acid monomer, organic reagent and homopolymers, use the ion of hydrochloric acid/alcohol mixeding liquid (concentration of hydrochloric acid is 10wt%, and hydrochloric acid and ethanol contend are than being 5:1) cleaning material surface attachment again, washing suction filtration is to neutral.
5) by step 4) product that obtains is immersed in the NaOH solution of 5wt% 2h activation of vibrating, and is washed to neutrality, after 65 DEG C of dryings Wheat Straw bio-based ion-exchange type sorbing material.
Embodiment 5
A kind of preparation method's (amplification test) of Wheat Straw bio-based ion-exchange type sorbing material, comprises the following steps:
1) after Wheat Straw being cut into segment with agricultural gate shears, clean post-drying, keep the integral tubular build of Wheat Straw, obtain Wheat Straw short tube.
2) Wheat Straw short tube is immersed in 24h in the NaOH/ alcohol mixeding liquid of 15wt%, carry out the brilliant process that disappears, then filtered water is washed till neutrality, and must disappear brilliant Wheat Straw, drying for standby.
3) take the 1kg brilliant Wheat Straw that disappears to add 50L N is housed, in the reactor of dinethylformamide, 6L bromo isobutyl acylbromide (technical grade) and 2L pyridine is dripped with funnel, under the slow stirring condition of obtuse blade stirring bar, at 60 DEG C of reaction 24h, after having reacted, rinse with oxolane, acetone, then with excessive running water washing suction filtration, natural air drying under room temperature, obtains the bromination Wheat Straw that surface is connected to initiating group.
4) during the NaOH solution first 12L methacrylic acid being dissolved in 20L equimolar amounts is carried out and sodium transition, obtain the sodium methacrylate solution that concentration is 40wt%, then 600g bromination Wheat Straw is added, dispersed with stirring, slowly drips 720mLN, N, N', N ", N "-pentamethyl-diethylenetriamine (technical grade), and pass into N
210min, deaeration, adds 270g CuBr and 54g CuBr
2under sealing and stirring condition, at 40 DEG C of reaction 12h, after having reacted, with boiling water, acetone wash residual methacrylic acid monomer, organic reagent and homopolymers, use the ion of hydrochloric acid/alcohol mixeding liquid (concentration of hydrochloric acid is 5wt%, and hydrochloric acid and ethanol contend are than being 5:1) cleaning material surface attachment again, washing suction filtration is to neutral.
5) by step 4) product that obtains is immersed in the NaOH solution of 5wt% 3h activation of vibrating, and then washes suction filtration to neutral, after 65 DEG C of dryings Wheat Straw bio-based ion-exchange type sorbing material.
The performance test results:
Wheat Straw bio-based ion-exchange type sorbing material obtained for embodiment 1 ~ 5 is applied to the absorption and enrichment of carrying out rare earth ion, specifically comprise the following steps: be that conical flask put into by the Wheat Straw bio-based ion-exchange type sorbing material of M by quality, then in this conical flask, add concentration C
0for the Ce (NO) of 200mg/L
3solution, the addition making Wheat Straw bio-based ion-exchange type sorbing material is 0.5g/L, and vibrate 24h in constant temperature oscillator at 30 DEG C, after absorption terminates, measures Ce in solution
3+the ultimate density C of ion
e.Adopt ICP measuring method, calculate Ce
3+the adsorbance Q of ion
0=V* (C
0-C
e)/M, the results are shown in Table 1.
The ion exchange capacity of the Wheat Straw bio-based ion-exchange type sorbing material that table 1 embodiment 1 ~ 5 is obtained
| Wheat Straw base adsorbent | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Adsorbance Q 0(mg/g) | 308.08 | 237.92 | 244.48 | 228.32 | 281.66 |
In order to verify De contamination ability and the power of regeneration of the Wheat Straw bio-based ion-exchange type sorbing material that the present invention obtains, the Wheat Straw bio-based ion-exchange type sorbing material that Example 1 obtains is added to solid-to-liquid ratio 0.5g/L the Ce that 40ml concentration is 200mg/L
3+in solion, at 30 DEG C of vibration 12h in constant temperature oscillator, analyze and detect it to Ce
3+after the adsorbance of ion, be that the HCl solution of 0.2mol/L carries out De contamination experiment to adsorbing saturated sample by 40ml concentration, De contamination step is: vibrate 12h in 30 DEG C of constant temperature oscillators.After distilled water washing, put into the NaOH solution activation 1h that 20ml concentration is 5.0%, then extremely neutral with distilled water flushing.Repeat absorption and De contamination experiment, testing result is shown in Fig. 3.As can be seen from the figure, the absorption property of obtained Wheat Straw bio-based ion-exchange type sorbing material is stablized, to Ce after regenerating 8 times
3+the adsorption efficiency of ion still reaches more than 90%.
Testing result shows, the Wheat Straw bio-based ion-exchange type sorbing material that the present invention obtains has excellent absorption and regeneration performance.
The foregoing is only the preferred embodiment of the present invention, it should be pointed out that for the person of ordinary skill of the art, without departing from the concept of the premise of the invention, make some improvement and conversion, these all belong to protection scope of the present invention.
Claims (10)
1. a Wheat Straw bio-based ion-exchange type sorbing material, take Wheat Straw as raw material, adopt surface modifying method, monomer molecule with initiating group is received Wheat Straw surface, then is grafted to Wheat Straw surface with the copolymer long-chain that polymer monomer is formed by the method that heat causes surface atom radical transfer polymerization.
2. Wheat Straw bio-based ion-exchange type sorbing material according to claim 1, is characterized in that, the described monomer molecule with initiating group is bromo isobutyl acylbromide.
3. Wheat Straw bio-based ion-exchange type sorbing material according to claim 1, it is characterized in that, described polymer monomer is Sodium methacrylate, PAA or sodium p styrene sulfonate.
4. the Wheat Straw bio-based ion-exchange type sorbing material according to any one of claims 1 to 3, it is characterized in that, described surface modifying method comprises the following steps: be immersed in by Wheat Straw in activation process liquid I and soak 6 ~ 24h, then filter, be washed to neutrality, drying for standby, must disappear brilliant Wheat Straw; The brilliant Wheat Straw that disappears obtained is added in DMF solvent, then drips bromo isobutyl acylbromide and pyridine, under magnetic agitation, at 25 ~ 60 DEG C of reaction 6 ~ 24h, rinse with oxolane, acetone, then spend deionized water, suction filtration, drying, obtain bromination Wheat Straw.
5. preparation method according to claim 4, is characterized in that, described activation process liquid I is the NaOH aqueous solution or the NaOH aqueous solution/alcohol mixeding liquid, and the concentration of NaOH is 10 ~ 30wt%.
6. Wheat Straw bio-based ion-exchange type sorbing material according to claim 4, is characterized in that, described in the disappear solid-to-liquid ratio of brilliant Wheat Straw and DMF solvent be 1:(30 ~ 60) g/ml; The solid-to-liquid ratio of brilliant Wheat Straw and bromo isobutyl acylbromide of disappearing is 1:(3 ~ 6) g/mL; The volume ratio of bromo isobutyl acylbromide and pyridine is (6 ~ 1): 1.
7. Wheat Straw bio-based ion-exchange type sorbing material according to claim 4, it is characterized in that, described heat causes surface atom radical transfer polymerization and comprises the following steps: add in polymer monomer solution by bromination Wheat Straw, dispersed with stirring, then slowly drips N, N, N', N ", N "-pentamethyl-diethylenetriamine, and pass into N
2, deaeration, then adds CuBr and CuBr
2powder, under sealing and stirring condition, at 25 ~ 60 DEG C of reaction 0.5 ~ 24h, then successively through boiling water, acetone, hydrochloric acid/alcohol mixeding liquid cleaning, then through washing suction filtration to neutral.
8. Wheat Straw bio-based ion-exchange type sorbing material according to claim 7, is characterized in that, the concentration of described polymer monomer solution is 10 ~ 50wt%; The solid-to-liquid ratio of bromination Wheat Straw and polymer monomer solution solution is 10 ~ 50g/L; Bromination Wheat Straw and N, N, N', N ", N " solid-to-liquid ratio of-pentamethyl-diethylenetriamine is 1:(1.2 ~ 3.6) g/ml; Bromination Wheat Straw, CuBr, CuBr
2mass ratio be 1:(0.45 ~ 1.35): (0.09 ~ 0.27).
9. the preparation method of the Wheat Straw bio-based ion-exchange type sorbing material described in any one of claim 1 ~ 8, is characterized in that, comprise the steps:
1) Wheat Straw cleaned, dry, carry out pulverizing or cutting;
2) by step 1) process the Wheat Straw that obtains and be immersed in activation process liquid I and soak 6 ~ 24h, then filter, be washed to neutrality, drying for standby, must disappear brilliant Wheat Straw;
3) the brilliant Wheat Straw that disappears obtained is added N, in dinethylformamide solvent, then bromo isobutyl acylbromide and pyridine is dripped, under magnetic agitation, at 25 ~ 60 DEG C of reaction 6 ~ 24h, rinse with oxolane, acetone, then spend deionized water, suction filtration, drying, obtain bromination Wheat Straw;
4) add in polymer monomer solution by the bromination Wheat Straw obtained, dispersed with stirring, then slowly drips N, N, N', N ", N "-pentamethyl-diethylenetriamine, and pass into N
2, deaeration, then adds CuBr and CuBr
2powder, under sealing and stirring condition, at 25 ~ 60 DEG C of reaction 0.5 ~ 24h, then successively through boiling water, acetone, hydrochloric acid/alcohol mixeding liquid cleaning, then through washing suction filtration to neutral;
5) by step 4) product that obtains is immersed in oscillation treatment 0.1 ~ 6h in sodium treatment fluid II, then washes suction filtration to neutral, after drying described Wheat Straw bio-based ion-exchange type sorbing material.
10. preparation method according to claim 9, is characterized in that, described sodium treatment fluid II is the NaOH aqueous solution, and concentration is 1 ~ 10wt%; In described hydrochloric acid/alcohol mixeding liquid, the volume ratio of hydrochloric acid and ethanol is 5:1, and the concentration of hydrochloric acid is 5 ~ 20wt%.
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| CN105879849A (en) * | 2016-06-08 | 2016-08-24 | 四川大学 | Straw-based solid amine sulfur dioxide adsorbent and preparing and using methods thereof |
| CN106146758A (en) * | 2016-07-08 | 2016-11-23 | 中国地质大学（武汉） | A kind of ultraviolet light causes the method that sawdust surface grafting functional polymer prepares cation adsorbing material |
| CN106362712A (en) * | 2016-10-24 | 2017-02-01 | 中国地质大学（武汉） | Rice husk base ion-exchange adsorption material, preparation method thereof and application |
| CN110975832A (en) * | 2019-12-11 | 2020-04-10 | 安徽大学 | Straw-based hydrogel adsorbent for efficiently removing heavy metal ions and preparation method thereof |
| CN112717891A (en) * | 2019-10-14 | 2021-04-30 | 自然资源部天津海水淡化与综合利用研究所 | Preparation method of biochar with multiple heavy metal Cd adsorption sites |
| CN115532227A (en) * | 2022-10-12 | 2022-12-30 | 北京中岩大地环境科技有限公司 | Aluminum modified reed biochar, preparation method thereof and application thereof in wetland |
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| CN105879849A (en) * | 2016-06-08 | 2016-08-24 | 四川大学 | Straw-based solid amine sulfur dioxide adsorbent and preparing and using methods thereof |
| CN105879849B (en) * | 2016-06-08 | 2018-02-16 | 四川大学 | Straw base solid amine sulfur dioxide adsorbent and its preparation and application |
| CN106146758A (en) * | 2016-07-08 | 2016-11-23 | 中国地质大学（武汉） | A kind of ultraviolet light causes the method that sawdust surface grafting functional polymer prepares cation adsorbing material |
| CN106362712A (en) * | 2016-10-24 | 2017-02-01 | 中国地质大学（武汉） | Rice husk base ion-exchange adsorption material, preparation method thereof and application |
| CN112717891A (en) * | 2019-10-14 | 2021-04-30 | 自然资源部天津海水淡化与综合利用研究所 | Preparation method of biochar with multiple heavy metal Cd adsorption sites |
| CN110975832A (en) * | 2019-12-11 | 2020-04-10 | 安徽大学 | Straw-based hydrogel adsorbent for efficiently removing heavy metal ions and preparation method thereof |
| CN115532227A (en) * | 2022-10-12 | 2022-12-30 | 北京中岩大地环境科技有限公司 | Aluminum modified reed biochar, preparation method thereof and application thereof in wetland |
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