CN108114703A - A kind of chitosan-rare earth composite membrane and preparation method and application - Google Patents
A kind of chitosan-rare earth composite membrane and preparation method and application Download PDFInfo
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- CN108114703A CN108114703A CN201711392477.9A CN201711392477A CN108114703A CN 108114703 A CN108114703 A CN 108114703A CN 201711392477 A CN201711392477 A CN 201711392477A CN 108114703 A CN108114703 A CN 108114703A
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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
- B01J20/22—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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0207—Compounds of Sc, Y or Lanthanides
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
- B01J20/28038—Membranes or mats made from fibers or filaments
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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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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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
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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Abstract
The present invention relates to a kind of chitosan rare earth composite membranes and preparation method and application, belong to water-treatment technology field.Preparation method includes：Chitosan solution is reacted with earth solution in the environment of crosslinking agent presence, obtains chitosan rare earth crosslinking mixed liquor, then vacuum defoamation, film forming, drying.The preparation method is simple for process, simple operation, production cost are low, is suitble to produce and prepare chitosan rare earth composite membrane on a large scale.The chitosan rare earth composite membrane large specific surface area that is prepared by the above method, stable structure, advantages of good adsorption effect, nonhazardous, safety and environmental protection.It uses it in water, can effectively reduce the content of fluorine ion in water.
Description
Technical field
The present invention relates to water treatment field, and more particularly to a kind of chitosan-rare earth composite membrane and preparation method thereof is with answering
With.
Background technology
Fluorine element is a kind of essential element of skeleton health, and suitable fluorine contributes to the heavily fortified point of tooth and bone
Gu the generation of saprodontia is reduced, but the fluorine of long-term excess intake then generates human body larger harm, such as ligament calcification, sclerotin
Loose, anchylosis etc. can also make one disability when serious.According to《GB5749-2006》National Specification, China
Content of fluoride in Drinking Water must not be higher than 1.0mg/L.Su Qingzhen (developing tendency of removal of fluoride from drinking and its mechanism, electric power ring
It protects in border.The 6th phase of volume 36) current 27 provinces, municipalities and autonomous regions in China are reported, totally 7,226 ten thousand people quote fluorine-containing exceeded
Water.
Therefore, content of fluoride ion has become one that China ensures town and country water safety effectively in control Drinking Water
Vital task.Mainly have currently for the method for reducing fluorine content in water：Chemical precipitation method, ion-exchange, coagulant sedimentation,
Absorption method, electro-osmosis method, membrane separation process etc., wherein with the research of absorption method and being most widely used.
Therefore, efficient, cheap, easy regeneration is developed, the high-quality sorbing material of environment-friendly and green becomes key.
The content of the invention
The first object of the present invention is the preparation method for providing a kind of chitosan-rare earth composite membrane, the preparation method work
Skill is simple, simple operation, production cost are low, is suitble to produce and prepare chitosan-rare earth composite membrane on a large scale.
The second object of the present invention is to provide a kind of chitosan-rare earth composite membrane, is prepared by above-mentioned preparation method
, the chitosan-rare earth composite membrane large specific surface area, stable structure, advantages of good adsorption effect, nonhazardous, safety and environmental protection.
The second object of the present invention is to provide a kind of application of above-mentioned chitosan-rare earth composite membrane, use it in water,
The content of fluorine ion in water can effectively be reduced.
The present invention is solved its technical problem and is realized using following technical scheme：
The present invention proposes a kind of preparation method of chitosan-rare earth composite membrane, comprises the following steps：Chitosan solution with it is dilute
Native solution reacts in the environment of crosslinking agent presence, obtains chitosan-rare earth crosslinking mixed liquor, then through vacuum defoamation, film forming, do
It is dry, obtain chitosan-rare earth composite membrane.
Rare earth in earth solution contains at least one of lanthanum element and Ce elements.
Preferably, lanthanum element is provided by the substance containing lanthanum chloride.
Preferably, Ce elements are provided by the substance containing cerous nitrate.
Preferably, concentration of the rare earth in earth solution is 1-5wt%.
The present invention also proposes a kind of chitosan-rare earth composite membrane, by the preparation method system of above-mentioned chitosan-rare earth composite membrane
It is standby and obtain.
The present invention also proposes a kind of application of above-mentioned chitosan-rare earth composite membrane namely uses it in water reducing water
Middle content of fluoride ion.
The advantageous effect of chitosan-rare earth composite membrane that present pre-ferred embodiments provide and preparation method and application
It is：
Chitosan-rare earth composite membrane that present pre-ferred embodiments provide has significant advantage in terms of fluorine removal, when
With higher absorption property, compared with traditional defluorination material such as bone black, zeolite, activated alumina, saturated extent of adsorption
Bigger；Second is that there is higher selectivity to fluorine ion, sulfate ion, nitrate ion and chlorion present in solution etc.
It is smaller to its Adsorption Effect.The chitosan-rare earth composite membrane large specific surface area, stable structure, advantages of good adsorption effect, nonhazardous, peace
Loopful is protected.
Its preparation method is simple for process, simple operation, production cost are low, be suitble to it is large-scale produce and prepare chitosan-
Rare earth composite membrane.It uses it in water, can effectively reduce the content of fluorine ion in water.
Specific embodiment
It, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, builds according to normal condition or manufacturer
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Chitosan-rare earth composite membrane of the embodiment of the present invention and preparation method and application is specifically described below.
Chitosan provided in an embodiment of the present invention-rare earth composite membrane main component includes chitosan and rare earth.Wherein, shell gathers
Sugar is in alkaline conditions by a kind of derivative formed after deacetylation by chitin, and deacetylation is generally in 65%-
It is unique a large amount of existing alkaline polysaccharides in nature between 90%.Since chitosan has biodegradable, extremely strong flocculation
Effect, the features such as precipitability is good, and it is nontoxic, environmentally friendly, therefore chitosan as main component is prepared and answered by the embodiment of the present invention
Film is closed, conventional adsorbent can be overcome to be difficult to harmless treatment, easily cause the shortcomings that secondary pollution.
The hydroxyl and amino contained in chitosan molecule has the effects that excellent chelant, charge neutrality, adsorption bridging, rare earth
Compound has the characteristics that large amount of adsorption, toxicity are low.According to Lewis acid-base theories, rare earth ion belongs to hard acid class, hard with belonging to
The coordination atoms such as oxygen, fluorine, the nitrogen of bases have stronger coordination ability.Rare earth ion loaded into high mechanical strength, is easily shaped
On matrix, can not only the excellent suction fluorine performance of rare earth ion be utilized, but also it can be reused.And chitosan molecule structure
In contain substantial amounts of-NH2It, therefore can be as the excellent carrier of rare earth ion with-OH.
Specifically, the preparation method of chitosan-rare earth composite membrane may include following steps in the embodiment of the present invention：Chitosan
Solution is reacted with earth solution in the environment of crosslinking agent presence, obtains chitosan-rare earth crosslinking mixed liquor.
Wherein, chitosan solution is that chitosan is dissolved in acid solution so that chitosan is abundant, release activity into
Point.
Optionally, above-mentioned acid solution can for example include aqueous acetic acid, aqueous hydrochloric acid solution and aqueous citric acid solution
In any one, be preferably acetic acid.When selecting acetic acid as acid solution, acetic acid is preferably formulated to mass concentration as 1-5%
Aqueous acetic acid for use namely aqueous acetic acid in acetic acid concentration be 1-5wt%.
It is preferred that after chitosan is dissolved in acid solution, plasticizer can be added in, to improve the physical characteristic of chitosan solution.
It is preferred that the quality of chitosan and plasticizer is 100：5-20, within this range, the plasticization effect that plasticizer rises are optimal.
Optionally, plasticizer includes the alcohol that C atomicities are no more than 6.Preferably, the C atomicities of above-mentioned alcohol are no more than 4.More
Preferably, above-mentioned alcohol includes at least one of glycerine, propylene glycol, butanediol and polyethylene glycol.
Rare earth in earth solution contains at least one of lanthanum element and Ce elements, and lanthanum element and Ce elements are more other dilute
Earth elements have more excellent suction fluorine ability after being combined with chitosan.Preferably, lanthanum element is carried by the substance containing lanthanum chloride
For；Ce elements are provided by the substance containing cerous nitrate, and lanthanum chloride and cerous nitrate can make chitosan-rare earth composite membrane to fluorine ion
With higher selectivity and suction fluorine ability, and sulfate ion, nitrate ion and chlorion etc. can be reduced, it is adsorbed
It influences.
Preferably, concentration of the rare earth in earth solution is 1-5wt%.Chitosan and earth solution in chitosan solution
In rare earth mass ratio be 100：1-5.Under this proportioning, the combination between chitosan solution and earth solution is better.
Optionally, the crosslinking agent in the embodiment of the present invention includes glutaraldehyde.Crosslinking agent and the shell in chitosan solution
The amount ratio of glycan is 3-10mL：1g.
It is preferred that crosslinking agent is to be added under conditions of shearing is scattered to chitosan solution and the mixed liquor of earth solution
In.Wherein, shearing is scattered to be carried out under conditions of 5000-9000rpm.Disperse by using high speed shear, rare earth can be made
Material disperses more uniformly, so as to the complex more stablized, while crosslinking degree can be made more equal in chitosan
It is even, avoid the occurrence of partial cross-linking phenomenon.
With reference to the dosage and property of crosslinking agent, according to chitosan molecule amount it is too big, the viscosity mistake of solution system will be made
Greatly, the cooperation for causing rare earth material and chitosan is uneven, while crosslinking operation is made to be difficult to complete；According to chitosan molecule
Amount is too small, then the mechanical strength of finally formed composite membrane can be caused inadequate, easy to dissolve in water.Therefore, the present invention is implemented
The viscosity of chitosan in example is preferably 0.25-0.65Pas, and concentration of the chitosan in chitosan solution is 0.5-3wt%,
So that chitosan has stable structure with the composite membrane that rare earth is formed.
Further, the chitosan of gained-rare earth composite membrane is subjected to vacuum defoamation, film forming and drying successively, you can
To chitosan-rare earth composite membrane.
Preferably, dry using freeze-drying, drying time can be 20-28h.It can be kept away by using freeze-drying mode
Fenestra hole caused by exempting from heated drying shrinks and situations such as collapses, so as to obtain structural integrity, large specific surface area, advantages of good adsorption effect
Chitosan-rare earth composite membrane.
Hold, the preparation-obtained chitosan of the preparation method provided through the embodiment of the present invention-rare earth composite membrane except
There is significant advantage in terms of fluorine：First, the chitosan-rare earth composite membrane has higher absorption property, with traditional fluorine removal
Material such as bone black, zeolite, activated alumina etc. are compared, saturated extent of adsorption bigger；Second, the chitosan-rare earth composite membrane pair
Fluorine ion has higher selectivity, and sulfate ion, nitrate ion and chlorion present in solution etc. adsorb shadow to it
Sound is smaller.
In addition, the embodiment of the present invention additionally provides a kind of application of chitosan-rare earth composite membrane, water can be also used it for
In, to reduce content of fluoride ion in water.Specifically, above-mentioned chitosan-rare earth composite membrane can be soaked in water, it is preferable that shell
The mass ratio of glycan-rare earth composite membrane and water is 1：50-2000, soaking time may be configured as 15-30h, also can be according to actual need
Shorten or extend.
The feature and performance of the present invention are described in further detail with reference to embodiments.
Embodiment 1
Chitosan solution is dissolved in to be configured to mass fraction in the acetum that mass fraction is 2wt% be 0.5wt%'s
Then chitosan solution adds in glycerine plasticizing.Wherein the viscosity of chitosan is the mass ratio of 0.46Pas, chitosan and glycerine
For 100：8.
By rare earth powder it is soluble in water be made into mass fraction be 1wt% earth solution.Wherein, rare earth powder includes chlorination
The mass ratio of lanthanum powder and cerous nitrate powder, chitosan and rare earth powder is 100：2.
Under stirring condition, above-mentioned earth solution is slowly added dropwise into above-mentioned chitosan solution, obtains chitosan-rare earth
Mixed liquor.Under the high speed shear situation of 6000rpm, glutaraldehyde progress is slowly added dropwise into above-mentioned chitosan-rare earth mixed liquor
Crosslinking obtains chitosan-rare earth crosslinking mixed liquor.Wherein, the amount ratio of chitosan and glutaraldehyde is 1g：5mL.
By above-mentioned chitosan-rare earth crosslinking mixed liquor vacuum defoamation, film liquid is obtained into.It is poured into above-mentioned into film liquid in mold,
Freeze forming in refrigerator is placed in, is then handled for 24 hours to get to dry chitosan-rare earth composite membrane with freeze drier.
Chitosan-rare earth composite membrane is packed into cloth bag, after sealing, cloth bag is put into drinking water, wherein composite membrane and drink
It is 20 with the mass ratio of water：2000, the content of fluorine ion in detection water is sampled in different time sections, testing standard is according to document
《Absorption of the cerium modification of chitosan microballoon to fluorine ion》In method.
Embodiment 2
Chitosan solution is dissolved in the acetum that mass fraction is 2wt% and is configured to the shell that mass fraction is 2wt%
Then glycan solution adds in glycerine plasticizing.Wherein the viscosity of chitosan is 0.35Pas, and the mass ratio of chitosan and glycerine is
100：8.
By rare earth powder it is soluble in water be made into mass fraction be 3wt% earth solution.Wherein, rare earth powder includes chlorination
The mass ratio of lanthanum powder and cerous nitrate powder, chitosan and rare earth powder is 100：3.
Under stirring condition, above-mentioned earth solution is slowly added dropwise into above-mentioned chitosan solution, obtains chitosan-rare earth
Mixed liquor.Under the high speed shear situation of 7000rpm, glutaraldehyde progress is slowly added dropwise into above-mentioned chitosan-rare earth mixed liquor
Crosslinking obtains chitosan-rare earth crosslinking mixed liquor.Wherein, the amount ratio of chitosan and glutaraldehyde is 1g：7mL.
By above-mentioned chitosan-rare earth crosslinking mixed liquor vacuum defoamation, film liquid is obtained into.It is poured into above-mentioned into film liquid in mold,
Freeze forming in refrigerator is placed in, is then handled for 24 hours to get to dry chitosan-rare earth composite membrane with freeze drier.
Chitosan-rare earth composite membrane is packed into cloth bag, after sealing, cloth bag is put into drinking water, wherein composite membrane and drink
It is 30 with the mass ratio of water：2000, the content of fluorine ion in detection water is sampled in different time sections, testing standard is according to document
《Absorption of the cerium modification of chitosan microballoon to fluorine ion》In method.
Embodiment 3
Chitosan solution is dissolved in the acetum that mass fraction is 2wt% and is configured to the shell that mass fraction is 4wt%
Then glycan solution adds in glycerine plasticizing.Wherein the viscosity of chitosan is 0.3Pas, and the mass ratio of chitosan and glycerine is
100：15.
By rare earth powder it is soluble in water be made into mass fraction be 5wt% earth solution.Wherein, rare earth powder includes chlorination
The mass ratio of lanthanum powder and cerous nitrate powder, chitosan and rare earth powder is 100：4.
Under stirring condition, above-mentioned earth solution is slowly added dropwise into above-mentioned chitosan solution, obtains chitosan-rare earth
Mixed liquor.Under the high speed shear situation of 8000rpm, glutaraldehyde progress is slowly added dropwise into above-mentioned chitosan-rare earth mixed liquor
Crosslinking obtains chitosan-rare earth crosslinking mixed liquor.Wherein, the amount ratio of chitosan and glutaraldehyde is 1g：8mL.
By above-mentioned chitosan-rare earth crosslinking mixed liquor vacuum defoamation, film liquid is obtained into.It is poured into above-mentioned into film liquid in mold,
Freeze forming in refrigerator is placed in, is then handled for 24 hours to get to dry chitosan-rare earth composite membrane with freeze drier.
Chitosan-rare earth composite membrane is packed into cloth bag, after sealing, cloth bag is put into drinking water, wherein composite membrane and drink
It is 50 with the mass ratio of water：2000, the content of fluorine ion in detection water is sampled in different time sections, testing standard is according to document
《Absorption of the cerium modification of chitosan microballoon to fluorine ion》In method.
Embodiment 4
Chitosan solution is dissolved in the acetum that mass fraction is 1wt% and is configured to the shell that mass fraction is 3wt%
Then glycan solution adds in glycerine plasticizing.Wherein the viscosity of chitosan is 0.25Pas, and the mass ratio of chitosan and glycerine is
100：5.
By rare earth powder it is soluble in water be made into mass fraction be 2wt% earth solution.Wherein, rare earth powder includes chlorination
The mass ratio of lanthanum powder and cerous nitrate powder, chitosan and rare earth powder is 100：1.
Under stirring condition, above-mentioned earth solution is slowly added dropwise into above-mentioned chitosan solution, obtains chitosan-rare earth
Mixed liquor.Under the high speed shear situation of 5000rpm, glutaraldehyde progress is slowly added dropwise into above-mentioned chitosan-rare earth mixed liquor
Crosslinking obtains chitosan-rare earth crosslinking mixed liquor.Wherein, the amount ratio of chitosan and glutaraldehyde is 1g：3mL.
By above-mentioned chitosan-rare earth crosslinking mixed liquor vacuum defoamation, film liquid is obtained into.It is poured into above-mentioned into film liquid in mold,
Freeze forming in refrigerator is placed in, then with freeze drier processing 20h to get to dry chitosan-rare earth composite membrane.
Chitosan-rare earth composite membrane is packed into cloth bag, after sealing, cloth bag is put into drinking water, wherein composite membrane and drink
It is 50 with the mass ratio of water：2500, the content of fluorine ion in detection water is sampled in different time sections, testing standard is according to document
《Absorption of the cerium modification of chitosan microballoon to fluorine ion》In method.
Embodiment 5
Chitosan solution is dissolved in to be configured to mass fraction in the acetum that mass fraction is 5wt% be 1.5wt%'s
Then chitosan solution adds in glycerine plasticizing.Wherein the viscosity of chitosan is the mass ratio of 0.65Pas, chitosan and glycerine
For 100：20.
By rare earth powder it is soluble in water be made into mass fraction be 4wt% earth solution.Wherein, rare earth powder includes chlorination
The mass ratio of lanthanum powder and cerous nitrate powder, chitosan and rare earth powder is 100：5.
Under stirring condition, above-mentioned earth solution is slowly added dropwise into above-mentioned chitosan solution, obtains chitosan-rare earth
Mixed liquor.Under the high speed shear situation of 9000rpm, glutaraldehyde progress is slowly added dropwise into above-mentioned chitosan-rare earth mixed liquor
Crosslinking obtains chitosan-rare earth crosslinking mixed liquor.Wherein, the amount ratio of chitosan and glutaraldehyde is 1g：10mL.
By above-mentioned chitosan-rare earth crosslinking mixed liquor vacuum defoamation, film liquid is obtained into.It is poured into above-mentioned into film liquid in mold,
Freeze forming in refrigerator is placed in, then with freeze drier processing 28h to get to dry chitosan-rare earth composite membrane.
Chitosan-rare earth composite membrane is packed into cloth bag, after sealing, cloth bag is put into drinking water, wherein composite membrane and drink
It is 50 with the mass ratio of water：10000, the content of fluorine ion in detection water is sampled in different time sections, testing standard is according to document
《Absorption of the cerium modification of chitosan microballoon to fluorine ion》In method.
Embodiment 6
The present embodiment and embodiment 3 difference lies in：Acid solution in the present embodiment is aqueous hydrochloric acid solution.
Embodiment 7
The present embodiment and embodiment 3 difference lies in：Acid solution in the present embodiment is aqueous citric acid solution.
Embodiment 8
The present embodiment and embodiment 3 difference lies in：Plasticizer in the present embodiment contains glycerine and propylene glycol.
Embodiment 9
The present embodiment and embodiment 3 difference lies in：Plasticizer in the present embodiment contains glycerine, butanediol and poly- second two
Alcohol.
Embodiment 10
The present embodiment and embodiment 3 difference lies in：Plasticizer in the present embodiment contains glycerine, propylene glycol, butanediol
And polyethylene glycol.
Test example 1
It repeats to implement above-described embodiment 1-10, obtains enough chitosans-rare earth composite membrane.By taking embodiment 1-3 as an example,
Control group 1 and control group 2 are set, wherein, control group 1 is using bone black as sorbing material, and control group 2 is using activated alumina as suction
Enclosure material.
Tests below is carried out to embodiment 1-3 and control group 1-2：
Embodiment 1-3 is prepared to the active oxygen of chitosan-rare earth composite membrane, the bone black of control group 1 and control group 2 of gained
Change aluminium and adsorption treatment is carried out for 24 hours respectively to drinking water under the same conditions, according to document《Cerium modification of chitosan microballoon is to fluorine
The absorption of ion》In method measure the content of fluorine ion in each group sample before and after adsorption treatment, the results are shown in Table 1.
1 result of the test of table
As can be seen from Table 1 chitosan-processed drinking water of rare earth composite membrane is provided using 1-3 of the embodiment of the present invention
In content of fluoride ion be decreased obviously, and embodiment 1-3 provide chitosan-rare earth composite membrane adsorption effect significantly better than pair
The adsorption effect for the active alundum (Al2O3) that adsorption effect and control group 2 according to the bone black of 1 offer of group provide.
In addition, identical examination is carried out to the chitosan obtained by embodiment 4-10-rare earth composite membrane according to the method for test example 1
It tests, result of the test is consistent with the result of the test of embodiment 1-3, shows that chitosan-rare earth obtained by embodiment 4-10 is compound
The adsorption effect of film is substantially better than the adsorption effect of control group 1 and control group 2.
To sum up, the preparation method of chitosan provided by the invention-rare earth composite membrane is simple for process, simple operation, is produced into
This is low, is suitble to produce and prepare chitosan-rare earth composite membrane on a large scale.The chitosan that the method for being prepared as described above is prepared-
Rare earth composite membrane large specific surface area, stable structure, advantages of good adsorption effect, nonhazardous, safety and environmental protection.It uses it in water, it can be effective
Reduce the content of fluorine ion in water.
Embodiments described above is part of the embodiment of the present invention, instead of all the embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without creative efforts
Every other embodiment, belongs to the scope of protection of the invention.
Claims (10)
1. the preparation method of a kind of chitosan-rare earth composite membrane, which is characterized in that comprise the following steps：Chitosan solution with it is dilute
Native solution reacts in the environment of crosslinking agent presence, obtains chitosan-rare earth crosslinking mixed liquor, then through vacuum defoamation, film forming, do
It is dry, obtain chitosan-rare earth composite membrane；
Rare earth in the earth solution contains at least one of lanthanum element and Ce elements；
Preferably, the lanthanum element is provided by the substance containing lanthanum chloride；
Preferably, the Ce elements are provided by the substance containing cerous nitrate；
Preferably, concentration of the rare earth in the earth solution is 1-5wt%.
2. the preparation method of chitosan according to claim 1-rare earth composite membrane, which is characterized in that the chitosan is molten
Liquid is obtained through following steps：Chitosan is dissolved in acid solution, then adds in plasticizer；
Preferably, the acid solution is the aqueous acetic acid that mass concentration is 1-5%.
3. the preparation method of chitosan according to claim 2-rare earth composite membrane, which is characterized in that the chitosan
Viscosity is that the concentration of 0.25-0.65Pas and/or the chitosan in the chitosan solution is 0.5-3wt%.
4. the preparation method of chitosan according to claim 2-rare earth composite membrane, which is characterized in that the plasticizer bag
Include the alcohol that C atomicities are no more than 6；
Preferably, the C atomicities of the alcohol are no more than 4；
Preferably, the alcohol includes at least one of glycerine, propylene glycol, butanediol and polyethylene glycol；
Preferably, the quality of the chitosan and the plasticizer is 100：5-20.
5. the preparation method of chitosan according to claim 1-rare earth composite membrane, which is characterized in that the chitosan is molten
The mass ratio of chitosan in liquid and the rare earth in the earth solution is 100：1-5.
6. the preparation method of chitosan according to claim 1-rare earth composite membrane, which is characterized in that the crosslinking agent bag
Include glutaraldehyde；
Preferably, the amount ratio of the crosslinking agent and the chitosan in the chitosan solution is 3-10mL：1g.
7. the preparation method of chitosan according to claim 1-rare earth composite membrane, which is characterized in that the crosslinking agent is
In being added under conditions of shearing is scattered to the mixed liquor of the chitosan solution and the earth solution；
Preferably, shearing is scattered is carried out under conditions of 5000-9000rpm.
8. a kind of chitosan-rare earth composite membrane, which is characterized in that the chitosan-rare earth composite membrane is appointed by such as claim 1-7
The preparation method of chitosan-rare earth composite membrane described in one is prepared.
9. the application of chitosan as claimed in claim 8-rare earth composite membrane, which is characterized in that the chitosan-rare earth is compound
Film is used in water reduce content of fluoride ion in water.
10. application according to claim 9, which is characterized in that the chitosan-rare earth composite membrane is soaked in water；
Preferably, the mass ratio of the chitosan-rare earth composite membrane and water is 1：50-2000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711392477.9A CN108114703A (en) | 2017-12-19 | 2017-12-19 | A kind of chitosan-rare earth composite membrane and preparation method and application |
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| CN113354084A (en) * | 2021-08-03 | 2021-09-07 | 大唐环境产业集团股份有限公司 | Water treatment filler, preparation method thereof and circulating cooling water treatment process using filler |
| CN116237023A (en) * | 2023-05-11 | 2023-06-09 | 清有生态科技(上海)有限公司 | Chitosan-based defluorinating agent and preparation method thereof |
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