CN108993436A - A kind of modified cellulose adsorbent for heavy metal and preparation method thereof - Google Patents
A kind of modified cellulose adsorbent for heavy metal and preparation method thereof Download PDFInfo
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- CN108993436A CN108993436A CN201811061633.8A CN201811061633A CN108993436A CN 108993436 A CN108993436 A CN 108993436A CN 201811061633 A CN201811061633 A CN 201811061633A CN 108993436 A CN108993436 A CN 108993436A
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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
- 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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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Abstract
The invention discloses a kind of modified cellulose adsorbent for heavy metal and preparation method thereof, using ion liquid dissolving cellulose, then cellulose is subjected to etherification reaction, it is re-introduced into reproducibility group sulfinic acid base, it is finally that cellulose and sodium alginate is compound, obtain a kind of modified cellulose adsorbent for heavy metal；It wherein dissolves and contains aspartic acid and glutamic acid in cellulose ionic liquid.Adsorbent of the present invention has both the function that ion exchange and reduction are carried out to heavy metal ion, thus high to heavy metal ion removal rate；And preparation process is simple, Non-toxic, production cost is low, has good application value at heavy metal ion adsorbed aspect.
Description
Technical field
The present invention relates to technical field of sewage, more particularly, to a kind of modified cellulose adsorbent for heavy metal and
Preparation method.
Technical background
With the continuous acceleration of Chinese Industrialization, the industry for being related to heavy metals emission is more and more, including mining, gold
Belong to smelting, chemical industry, printing and dyeing, leather, pesticide, feed etc., along with some contaminating enterprises illegal exploitation, exceeded blowdown the problems such as
It is prominent, so that heavy metal pollution event high-incidence situation is occurred.Water pollution caused by the unreasonable discharge of industrial wastewater always is
One serious environmental problem, heavy metal ion have very high toxicity in low concentration, can accumulate, draw in biologic artifact
Play a series of imbalances and disease.Therefore, separation removes heavy metal ion for environmental protection and human health from industrial wastewater
There is vital effect.Currently, for heavy metal processing method mainly have chemical precipitation method, active carbon adsorption, from
Sub- exchange process etc..Chemical precipitation method mainly uses lime stone class alkaline matter, so that heavy metal ion is generated precipitation and separation and comes out, but
From the mud that the heavy metal ion that water body is separated is deposited to river bed again, still cause damages to environmental and biological materials；It is living
Property carbon adsorption and ion-exchange can be very good to isolate heavy metal from water body, but its cost is too high, using also by
Limitation.In recent years, using natural macromolecular material as heavy metal absorbent separating beavy metal by more and more researchers
Concern, wherein the adsorbent material that resourceful, the inexpensive, native cellulose that is easy to get is matrix is concerned.
In cellulosic molecule contain a large amount of polar group-hydroxyl, and native cellulose fibre have large specific surface area,
Multi-cellular structure has good heavy metal adsorption potentiality.Modified cellulose heavy metal absorbent passes through alkalization activation, oxygen
One of change, crosslinking and graft copolymerization or a variety of reactions are modified cellulose, and what is obtained has abundant amino-functional
Modified cellulose rolling into a ball, can be used for heavy metal in water absorption.By the modification to hydroxyl in cellulose macromolecule, introducing has
The functional group of good heavy metal adsorption performance, makes it have higher heavy metal adsorption.
Reduction adsorption is restored and is adsorbed to oxidizing substance using the reproducibility group in adsorbent.Sulfinic acid
Base is a kind of strong reducing property group, has preferable reproducibility, has the heavy metal ion of oxidisability, such as Cr to part6+, As5 +, Pt2+And trichloroacetic acid, chloroform, the oxidizing substances such as tetrachloro-ethylene, there is preferable removal to act on.Nakagawa etc. uses titanium dioxide
Thiocarbamide restores nitrobenzene, obtains almost quantitative aniline.Meanwhile thiourea dioxide can also restore the carbonyls such as aldehyde, ketone
For corresponding alcohol, sulfide is reduced to mercaptan or thioether.
The prior art such as Authorization Notice No. is the Chinese invention patent of 102500339 B of CN, is disclosed a kind of containing sulfinic acid
Reproducibility spherical cellulose adsorbent of base and preparation method thereof, using ion liquid dissolving cellulose, then altogether by grafting
Poly- reaction, and introduce reproducibility group, prepare partial size be 4.5-5.2mm, specific surface area 180-780m2The reproducibility ball of/g
Shape cellulose adsorbent.Preparation process of the invention is simple, Non-toxic.Product is degraded with preferable reduction adsorption antibiont
Ability, and cellulosic material is from a wealth of sources, it is cheap, therefore can be in the absorption and drinking water chlorination pair of heavy metal ion
Preferable economic benefit and environmental benefit are generated in terms of the removal of product.However, this method preparation adsorbent to heavy metal from
The ion exchange of son is small compared with weak thus adsorption capacity.
Summary of the invention
The purpose of the present invention is to provide a kind of modified cellulose adsorbent for heavy metal and preparation method thereof；The absorption
Agent has both the function that ion exchange and reduction are carried out to heavy metal ion, thus high to heavy metal ion removal rate；The adsorbent
Preparation process is simple, Non-toxic, and production cost is low.
The technical solution that the present invention is taken to achieve the above object are as follows:
A kind of preparation method of modified cellulose adsorbent for heavy metal, using ion liquid dissolving cellulose, to fibre
Dimension element successively carries out etherification reaction, reduction reaction, finally that cellulose and sodium alginate is compound to get modified cellulose absorption
Agent.Specifically includes the following steps:
Paper pulp fiber or cotton fiber are dissolved in 90-120 DEG C of ionic liquid by S1, and forming mass fraction is 1-7.5%
Cellulose-ionic liquid solution；Above-mentioned solution is cooled to 70-90 DEG C, sequentially adds ammonium hydroxide, epoxychloropropane and hexadecane
Base trimethylammonium bromide stirs, filtering, and deionized water and dehydrated alcohol washing is respectively adopted in filter cake, dry, obtains cation and changes
Property cellulose；Raw material and its parts by weight are: paper pulp fiber or cotton fiber: 1.3-6.0 parts；Ionic liquid: 55.5-75.0 parts；
Ammonium hydroxide: 3.2-18.0 parts；Epoxychloropropane: 0.3-1.0 parts；Cetyl trimethylammonium bromide: 0.01-0.03 parts；With tradition
Cellulose solvent compare, ionic liquid has the advantages that low volatility, recoverable, thermal property are stable, avoids organic
Pollution caused by solvent, and ionic liquid is cellulose non-derivative solvent, and cellulose need not activate can be directly
Mixed dissolution not only increases reaction rate, and can control the distribution of the degree of substitution and functional group of derivative, for
Uniform high-substitution cellulose derivative is produced to be of great significance；
S2 is equipped with stirring, in the reactor for inside setting constant temperature system, be added sulfinic acid based compound, aldehyde, acid catalyst and
Distilled water reacts 1-3h under the conditions of 20-50 DEG C, and the cation-modified cellulose of step S1 is added, anti-under the conditions of 40-70 DEG C
1-4h is answered, room temperature is down to, takes out, washes and dry the reproducibility cellulose to get the base containing sulfinic acid；Raw material and its parts by weight
It is: cation-modified cellulose: 0.6-6.5 parts；Sulfinic acid based compound: 3.0-19.5 parts；Aldehyde: 3.0-23.0 parts；Acid catalysis
Agent: 0.4-6.0 parts；Distilled water: 45.0-93.0 parts；Sulfinic acid base is a kind of strong reducing property group, has preferable reproducibility,
There is the heavy metal ion of oxidisability, such as Cr to part6+, As5+, Pt2+And trichloroacetic acid, chloroform, the oxidisability object such as tetrachloro-ethylene
Matter has preferable removal to act on；
S3 will be by etherificate, the cellulose of modified with reduction, sodium alginate, proline and titanium dioxide with 1:0.9-1.1:
The mass ratio of 0.5-0.8:0.1-0.4 is added to the 1- allyl -3- methylimidazole chlorine for being equivalent to 10-12 times of parts by weight of cellulose
In salt dissolving, lead to nitrogen, 90-100 DEG C of stirring is cooled to 50-60 DEG C, obtains mixed liquor, draws mixed liquor and instills deionization dropwise
It in water, filters, washs, it is dry, obtain modified cellulose adsorbent for heavy metal；There is collaboration to make for proline and titanium dioxide
With cellulose surface hydrophobic group can be increased, so that adsorbent is easy to separate from water body after having adsorbed heavy metal ion
Without causing secondary pollution, while cellulose surface cellular structure can be improved, so that cellulose surface functionalization group counterweight
While metal ion carries out ion exchange or reduction, cellulose duct can adsorb other macromolecule contaminants, sufficiently
Adsorbent is improved to the efficiency of sewage purification；On the other hand, it is capable of stability, the mechanical strength of reinforcing fiber element, is conducive to
It prolongs its service life, reduces industrialization cost.
Preferably, paper pulp fiber be bamboo, bagasse, straw, wheat straw, hybrid giant napier, splendid achnatherum, Qu Liu, toothed oak wood, poplar,
Reed, Eucalyptus, the alkaline process or sulfate pulping of birch or masson pine and the paper pulp after chemistry or bio-bleaching；Cotton fiber
It is cotton linter or absorbent cotton.
Preferably, step S1 intermediate ion liquid be [BMIM] Cl, [AMIM] Cl, [EMIM] Cl, [HeMIM] Cl, BPC,
One of BDTAC.
Preferably, the aspartic acid and 2.0- that are 1.5-3.0% containing mass fraction in step S1 intermediate ion liquid
The special presence of 4.5% glutamic acid, aspartic acid and glutamic acid, one can weaken in cellulosic molecule and intermolecular hydrogen
Key reduces cellulose molecular chain stability to reduce the crystallinity of cellulose, is conducive to infiltration of the ionic liquid in cellulose
It thoroughly and spreads, improves ionic liquid to the solubility of cellulose, and then improve reaction rate；Secondly cellulose surface can be made more
More hydroxyl exposures, to increase the density that functionalized reagent is reacted with hydroxyl, while can increase cellulose surface anion
Group not only improves the etherification reaction on subsequent fiber element surface, and can retain a part of negative electrical charge, so that cellulose has two
Property, the functionalization group of cellulose surface is enriched, is greatly improved cellulose to the adsorption capacity of heavy metal ion.
Preferably, sulfinic acid based compound is thiourea dioxide, sodium toluene sulfinate, sodium dithionite, benzene Asia
One of sodium sulfonate, rongalite.
Preferably, aldehyde is one of formaldehyde, methyl nonyl acetaldehyde, glutaraldehyde, acetaldehyde, octanal, glyoxal, hexanal.
Preferably, acid catalyst is one of sulfuric acid, hydrochloric acid, nitric acid, acetic acid, phosphoric acid, ethanedioic acid, acrylic acid or several
Kind.
Compared with the prior art, the advantages of the present invention are as follows:
1) present invention prepares adsorbent by carrier of cellulose, and raw material sources are extensive, cheap, environmental-friendly, and
Preparation method is simple, reaction condition is mild, and equipment requirement is low, is convenient for large-scale production；
2) present invention uses ion liquid dissolving cellulose, and compared with traditional cellulose solvent, ionic liquid has low
The stable advantage of volatility, recoverable, thermal property, avoids pollution caused by organic solvent, and ionic liquid is
Cellulose non-derivative solvent, cellulose need not activation can directly mixed dissolution, not only increase reaction rate, and
The distribution that can control the degree of substitution and functional group of derivative has for producing uniform high-substitution cellulose derivative
It is significant；
3) present invention adds aspartic acid in ionic liquid and glutamic acid, one can be improved ionic liquid to cellulose
Solubility, be conducive to improve reaction rate；Secondly the more hydroxyl exposures of cellulose surface can be made, to increase functionalization
The density that reagent is reacted with hydroxyl, while cellulose surface anionic group can be increased, not only improve subsequent fiber element surface
Etherification reaction, and a part of negative electrical charge can be retained, so that cellulose has both sexes, enrich the functionalization of cellulose surface
Group is greatly improved cellulose to the adsorption capacity of heavy metal ion.
Specific embodiment
The present invention program is described further below by embodiment:
Embodiment 1:
A kind of preparation method of modified cellulose adsorbent for heavy metal, using ion liquid dissolving cellulose, to fibre
Dimension element successively carries out etherification reaction, reduction reaction, finally that cellulose and sodium alginate is compound to get modified cellulose absorption
Agent.Specifically includes the following steps:
(1) 0.2 kilogram of absorbent cotton and 12.0 kilograms of ionic liquids ([BMIM] Cl) are put into reactor, in 90 DEG C of conditions
Lower dissolution 4h forms cellulose-ionic liquid solution that mass fraction is 1.12%；Above-mentioned solution is cooled to 70 DEG C, successively
1.2 kilograms of ammonium hydroxide, 0.06 kilogram of epoxychloropropane and 0.002 kilogram of cetyl trimethylammonium bromide, constant temperature magnetic force is added to stir
20h to be mixed, is filtered, deionized water is respectively adopted in filter cake and dehydrated alcohol washs 2 times, and it is dry in 50 DEG C of vacuum ovens, obtain sun
Ion modification cellulose；Compared with traditional cellulose solvent, ionic liquid has low volatility, recoverable, thermal property
Stable advantage avoids pollution caused by organic solvent, and ionic liquid is cellulose non-derivative solvent, cellulose
Need not activation can directly mixed dissolution, not only increase reaction rate, and can control the degree of substitution of derivative with
And the distribution of functional group, it is of great significance for the high-substitution cellulose derivative for producing uniform；
In above-mentioned ionic liquid containing mass fraction be 1.5% aspartic acid and 2.0% glutamic acid, aspartic acid and
The special presence of glutamic acid, one can weaken in cellulosic molecule and intermolecular hydrogen bonding, reduces cellulose molecular chain stability
To reduce the crystallinity of cellulose, be conducive to infiltration and diffusion of the ionic liquid in cellulose, improve ionic liquid to fibre
The solubility of element is tieed up, and then improves reaction rate；Secondly the more hydroxyl exposures of cellulose surface can be made, to increase function
The density that reagent is reacted with hydroxyl can be changed, while cellulose surface anionic group can be increased, not only improve subsequent fiber element
The etherification reaction on surface, and a part of negative electrical charge can be retained, so that cellulose has both sexes, enrich the function of cellulose surface
Group can be changed, be greatly improved cellulose to the adsorption capacity of heavy metal ion；
(2) equipped with stirring, in the reactor for inside setting constant temperature system, 3.0 kilograms of thiourea dioxides and 91.4 kilograms are added
Distilled water, open stirring, by 0.4 kilogram of concentrated sulfuric acid with and 1.6 kilograms of water be made into 20% solution, above-mentioned reaction system is added
In, the formaldehyde that 3.0 kilograms of contents are 37% is added, reacts 1h at 20 °C, it is obtained that 0.6 kilogram of step (1) is added
Cation-modified cellulose reacts 1h under the conditions of 40 DEG C, is down to room temperature, takes out, washes and dry to get the base containing sulfinic acid
Reproducibility cellulose adsorbent；Sulfinic acid base is a kind of strong reducing property group, has preferable reproducibility, has oxidation to part
The heavy metal ion of property, such as Cr6+, As5+, Pt2+And trichloroacetic acid, chloroform, the oxidizing substances such as tetrachloro-ethylene have and preferably go
Except effect；
(3) by modified with reduction cellulose, sodium alginate, proline and titanium dioxide with the mass ratio of 1:0.9:0.5:0.1
It is added in the 1- allyl -3- methylimidazole chlorate for being equivalent to 10 times of parts by weight of cellulose, leads to nitrogen, 90 DEG C of constant temperature magnetic force
3h is stirred, 50 DEG C is cooled to, obtains mixed liquor, mixed liquor is drawn with the syringe that bore is 0.6mm, is instilled be equipped with dropwise
It in the beaker of deionized water, filters, deionized water washing, it is dry in 50 DEG C of vacuum ovens, obtain modified cellulose heavy metal
Ion adsorbent；Proline and titanium dioxide have synergistic effect, can increase cellulose surface hydrophobic group, so that adsorbent exists
It has adsorbed heavy metal ion to be easy to separate from water body without causing secondary pollution later, while cellulose surface hole can be improved
Road structure, while so that cellulose surface functionalization group carries out ion exchange or reduction to heavy metal ion, cellulose hole
Road can adsorb other macromolecule contaminants, substantially increase adsorbent to the efficiency of sewage purification；On the other hand, can
Stability, the mechanical strength of reinforcing fiber element are conducive to extend its service life, reduce industrialization cost.
Embodiment 2:
A kind of preparation method of modified cellulose adsorbent for heavy metal, using ion liquid dissolving cellulose, to fibre
Dimension element successively carries out etherification reaction, reduction reaction, finally that cellulose and sodium alginate is compound to get modified cellulose absorption
Agent.Specifically includes the following steps:
(1) 4.0 kilograms of absorbent cotton and 81.9 kilograms of ionic liquids ([EMIM] Cl) are put into reactor, in 110 DEG C of items
3h is dissolved under part, forms cellulose-ionic liquid solution that mass fraction is 4.66%；Above-mentioned solution is cooled to 80 DEG C, according to
12.2 kilograms of ammonium hydroxide of secondary addition, 0.6 kilogram of epoxychloropropane and 0.08 kilogram of cetyl trimethylammonium bromide, constant temperature magnetic force stir
22h to be mixed, is filtered, deionized water is respectively adopted in filter cake and dehydrated alcohol washs 3 times, and it is dry in 50 DEG C of vacuum ovens, obtain sun
Ion modification cellulose；In above-mentioned ionic liquid containing mass fraction be 2.0% aspartic acid and 3.5% glutamic acid；
(2) equipped with stirring, in the reactor for inside setting constant temperature system, be added 14.9 kilograms of sodium toluene sulfinate and and
56.6 kilograms of distilled water open stirring, and 1.5 kilograms of acetic acid and 13.5 kilograms of distilled water are made into 10% solution, are added above-mentioned
In reaction system, the glutaraldehyde that 8.3 kilograms of contents are 50% is added, 2h is reacted under the conditions of 40 DEG C, 5.2 kilograms of steps is added
(1) cation-modified cellulose made from reacts 2h under the conditions of 60 DEG C, is down to room temperature, takes out, washes and dry to get containing
The reproducibility cellulose adsorbent of sulfinic acid base；
(3) modified with reduction cellulose, sodium alginate, proline and titanium dioxide are added with the mass ratio of 1:1:0.6:0.3
Enter into the 1- allyl -3- methylimidazole chlorate for being equivalent to 11 times of parts by weight of cellulose, lead to nitrogen, 90 DEG C of constant temperature magnetic force stir
3h is mixed, 50 DEG C is cooled to, obtains mixed liquor, draws mixed liquor with the syringe that bore is 0.6mm, is instilled to be equipped with dropwise and be gone
In the beaker of ionized water, filter, deionized water washing is dry in 50 DEG C of vacuum ovens, obtain modified cellulose heavy metal from
Sub- adsorbent.
Embodiment 3:
A kind of preparation method of modified cellulose adsorbent for heavy metal, using ion liquid dissolving cellulose, to fibre
Dimension element successively carries out etherification reaction, reduction reaction, finally that cellulose and sodium alginate is compound to get modified cellulose absorption
Agent.Specifically includes the following steps:
(1) 6.0 kilograms of absorbent cotton and 75.0 kilograms of ionic liquids ([AMIM] Cl) are put into reactor, in 120 DEG C of items
2h is dissolved under part, forms cellulose-ionic liquid solution that mass fraction is 7.35%；Above-mentioned solution is cooled to 90 DEG C, according to
12.2 kilograms of ammonium hydroxide of secondary addition, 0.6 kilogram of epoxychloropropane and 0.08 kilogram of cetyl trimethylammonium bromide, constant temperature magnetic force stir
It mixes for 24 hours, filtering, deionized water is respectively adopted in filter cake and dehydrated alcohol washs 3 times, and it is dry in 60 DEG C of vacuum ovens, obtain sun
Ion modification cellulose；In above-mentioned ionic liquid containing mass fraction be 3.0% aspartic acid and 4.5% glutamic acid；
(2) equipped with stirring, in the reactor for inside setting constant temperature system, 19.5 kilograms of sodium dithionites and 38.0 thousand are added
Gram distilled water water opens stirring, by 6.0 kilograms of concentrated nitric acids with and 7.0 kilograms of water be made into 30% solution, above-mentioned reactant is added
In system, the glyoxal that 23.0 kilograms of contents are 40% is added, reacts 3h under the conditions of 50 DEG C, 6.5 kilograms of step (1) systems are added
The cation-modified cellulose obtained, reacts 4h under the conditions of 70 DEG C, is down to room temperature, takes out, and washes and dries to get containing sulfinic acid
The reproducibility cellulose adsorbent of base；
(3) by modified with reduction cellulose, sodium alginate, proline and titanium dioxide with the mass ratio of 1:1.1:0.8:0.4
It is added in the 1- allyl -3- methylimidazole chlorate for being equivalent to 12 times of parts by weight of cellulose, leads to nitrogen, 100 DEG C of constant temperature magnetic
Power stirs 4h, is cooled to 60 DEG C, obtains mixed liquor, draws mixed liquor with the syringe that bore is 0.8mm, is instilled dress dropwise
Having in the beaker of deionized water, filters, deionized water is washed, and it is dry in 60 DEG C of vacuum ovens, obtain a modified cellulose huge sum of money
Belong to ion adsorbent.
Comparative example 1:
For dissolving in the ionic liquid of cellulose without containing aspartic acid and glutamic acid in step (1), rest part and
Embodiment 2 is completely the same.
Comparative example 2:
Proline and titanium dioxide will be added without in step (3) in cellulose recombination process, rest part and embodiment 2 are complete
It is complete consistent.
By product of the present invention to Cr containing heavy metal ion6+Waste water adsorbed, the results are shown in Table 1；Comparative example 1-2 product pair
Cr6+Removal rate is below embodiment 2, shows the special presence of aspartic acid and glutamic acid, being capable of promotion functions reagent and hydroxyl
Base reaction, while increasing cellulose surface anionic group, the etherification reaction of cellulose surface is not only improved, and one can be retained
Partial negative charge enriches the functionalization group of cellulose surface, is greatly improved cellulose pair so that cellulose has both sexes
The adsorption capacity of heavy metal ion；And proline and titanium dioxide have synergistic effect, can promote cellulose surface functionalization
Group carries out ion exchange or reduction to heavy metal ion.
1 product of the present invention of table is to Cr6+Removal rate
| Product | Cr6+Removal rate |
| Embodiment 1 | 90.92 |
| Embodiment 2 | 96.39 |
| Embodiment 3 | 92.64 |
| Comparative example 1 | 81.33 |
| Comparative example 2 | 89.15 |
Routine operation in operation of the present invention step is well known to those skilled in the art, herein without repeating.
Technical solution of the present invention is described in detail in embodiment described above, it should be understood that the above is only
For specific embodiments of the present invention, it is not intended to restrict the invention, all any modifications made in spirit of the invention,
Supplement or similar fashion substitution etc., should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of preparation method of modified cellulose adsorbent for heavy metal, using ion liquid dissolving cellulose, to fiber
Element successively carries out etherification reaction, reduction reaction, finally that cellulose and sodium alginate is compound to get modified cellulose adsorbent,
It is characterized by: containing aspartic acid and glutamic acid in the ionic liquid.
2. a kind of preparation method of modified cellulose adsorbent for heavy metal according to claim 1, it is characterised in that:
It is described that etherification reaction step is carried out to cellulose are as follows: paper pulp fiber or cotton fiber are dissolved in 90-120 DEG C of ionic liquid,
Form cellulose-ionic liquid solution that mass fraction is 1-7.5%；Solution is cooled to 70-90 DEG C, sequentially add ammonium hydroxide,
Epoxychloropropane and cetyl trimethylammonium bromide stir, and filtering, deionized water is respectively adopted in filter cake and dehydrated alcohol is washed
It washs, it is dry, obtain cation-modified cellulose.
3. a kind of preparation method of modified cellulose adsorbent for heavy metal according to claim 1, it is characterised in that:
The raw material for participating in etherification reaction and its parts by weight are: paper pulp fiber or cotton fiber: 1.3-6.0 parts；Ionic liquid:
55.5-75.0 parts；Ammonium hydroxide: 3.2-18.0 parts；Epoxychloropropane: 0.3-1.0 parts；Cetyl trimethylammonium bromide: 0.01-
0.03 part.
4. a kind of preparation method of modified cellulose adsorbent for heavy metal according to claim 1, it is characterised in that:
The ionic liquid is one of [BMIM] Cl, [AMIM] Cl, [EMIM] Cl, [HeMIM] Cl, BPC, BDTAC.
5. a kind of preparation method of modified cellulose adsorbent for heavy metal according to claim 1, it is characterised in that:
Glutamic acid containing aspartic acid and 2.0-4.5% that mass fraction is 1.5-3.0% in the ionic liquid.
6. a kind of preparation method of modified cellulose adsorbent for heavy metal according to claim 1, it is characterised in that:
It is described that reduction reaction step is carried out to cellulose are as follows: by sulfinic acid based compound, aldehyde, acid catalyst and distilled water, at 20-50 DEG C
Under the conditions of react 1-3h, cation-modified cellulose is added, reacts 1-4h under the conditions of 40-70 DEG C, is down to room temperature, takes out fiber
The reproducibility cellulose to get the base containing sulfinic acid is washed and dried to element.
7. a kind of preparation method of modified cellulose adsorbent for heavy metal according to claim 1, it is characterised in that:
The raw material for participating in reduction reaction and its parts by weight are: cation-modified cellulose: 0.6-6.5 parts；Sulfinic acid base chemical combination
Object: 3.0-19.5 parts；Aldehyde: 3.0-23.0 parts；Acid catalyst: 0.4-6.0 parts；Distilled water: 45.0-93.0 parts.
8. a kind of preparation method of modified cellulose adsorbent for heavy metal according to claim 1, it is characterised in that:
It is described by cellulose and sodium alginate composite steps are as follows: will pass through etherificate, the cellulose of modified with reduction, sodium alginate, proline
1- allyl -3- methylimidazole chlorate is added to the mass ratio of 1:0.9-1.1:0.5-0.8:0.1-0.4 with titanium dioxide
In, lead to nitrogen, 90-100 DEG C of stirring is cooled to 50-60 DEG C, obtains mixed liquor, mixed liquor is instilled in deionized water dropwise, take out
Filter is washed, dry, obtains modified cellulose adsorbent for heavy metal.
9. weight made from a kind of described in any item preparation methods of modified cellulose adsorbent for heavy metal of claim 1-8
Metal ion adsorbent.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110523393A (en) * | 2019-09-24 | 2019-12-03 | 陕西科技大学 | A kind of thiourea dioxide modification of chitosan and preparation method thereof |
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| CN102500339A (en) * | 2011-12-05 | 2012-06-20 | 福州大学 | Reductive spherical cellulose adsorbent containing sulfinyl and preparation method thereof |
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