CN104874365B - Carboxymethyl cellulose ion insertion hydrotalcite-like composite material and preparation method and application - Google Patents
Carboxymethyl cellulose ion insertion hydrotalcite-like composite material and preparation method and application Download PDFInfo
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Abstract
Disclosure of the invention carboxymethyl cellulose ion insertion hydrotalcite-like composite material and preparation method and application, the chemical general formula of the composite is [M2+ 1‑xM3+ x(OH)2]x+(A‑)x·mH2O, wherein M2+For Zn2+、Ca2+Or Mg2+, M3+For Fe3+Or Al3+, M2+And M3+In brucite main layer board；A2‑For interlayer carboxymethyl cellulose anion；X is M3+/(M2++M3+) molar ratio, 0.1≤x≤0.33；Numbers of the m for interlayer hydrone, m=3 6.The hydrotalcite-like composite material of the present invention is using calcining graft process, will be enriched in adjacent hydroxyl carboxymethyl cellulose it is anion intercalated be assembled into houghite interlayer and prepare the hydrotalcite-like composite material with typical layers laminated structure as adsorbent, the selective absorption for being applied to water body mesoboric acid root anion is removed.The separation absorption of boron in waste water and desalinization can be used for as a kind of New Types of Environmental Materials.The product heat stability and mechanical stability height, environmental friendliness, and preparation process is simple, easily realize industrialization.
Description
Technical field
The invention belongs to technical field of inorganic-organic composite function material preparation, and in particular to a kind of carboxymethyl cellulose
Ion insertion hydrotalcite-like composite material and preparation method and application.
Background technology
As the development of economic society, current environment pollution become the significant challenge of facing mankind, various water pollutions are not
Disconnected aggravation, causes the continuous deterioration of ecological environment, drastically influence the Health and Living quality of people.Wherein, boron is used as one kind
Important industrial chemicals, practical application are extensive, but the boron pollution that waste water containing boron discharge is produced is urgently to be resolved hurrily.At present, can be used for point
Leave away inorganic adsorbent, organic polymer adsorbent and hybrid boron are can be divided mainly into except the adsorbent of boron in solution
Three kinds of adsorbent.Inorganic boron adsorbent has firm structure, good heat stability and relatively low preparation cost, but to boron
Adsorption capacity is relatively low and does not have specially good effect selectivity, is easily affected by coexisting ion.Organic adsorbent is with N- methyl glucose osamines
There is to boron specially good effect specificity and higher adsorption capacity for adsorption functional group, but due to the particularity and water in its structure it is insoluble
Property so as to the defect such as mechanical performance and hydrophilic difference is shown in actual applications, has had a strong impact on the performance of its performance.Now
In the urgent need to finding one kind or a class has high stability, selectivity high, with low cost and efficient quickly adsorbent is realizing
The efficient removal of boron is current absorption method except the focus and difficult point of boron research.Composite is the trend of modern material development, is passed through
The compound of multiple material function realizes performance complement and optimization, wherein organic/inorganic hybridization material be in compositional material families most
Dazzling nova.Chinese scholars attempt by by adjacent hydroxy compounds load or graft on mesoporous material or silica gel prepare have
Machine/inorganic hybridization boron adsorbent.
Cellulose is most ancient most abundant natural polymer on the earth, is that the inexhaustible mankind are most precious
Expensive natural reproducible resource.Carboxymethyl cellulose（CMC）It, with native cellulose as base stock, is used in the world today to be
The maximum cellulose species of widest in area, consumption.It is with low cost, through alkalization, etherification reaction and a kind of electrolyte for generating
Polymer.As carboxymethyl cellulose intramolecular contains many hydrophilic hydroxyls and carbonyl, therefore to metal ion and dyestuff
With certain adsorptivity.But the ability of its adion is not strong, it is necessary to made it have by chemical modification more or higher
Hydrophilic group, to reduces cost, improve performance so as to become adsorbing material of good performance.
Houghite（LDHs）, there is the double-metal hydroxide of layer structure as a class, because which has can modulation
The advantages of heat stability of composition, high surface adsorption property and uniqueness, causes the extensive concern of researcher.Work as LDHs
Interlayer ion is CO3 2-、NO3 -And Cl-Deng inorganic ionss when, the boron that brucite can be used in adsorbent solution, but adsorption capacity is not
It is high.In houghite interlayer, insert the organic acid such as tartaric acid, citric acid and malic acid and can be used to adsorb the metal ion in water.
Have been reported and Organic substance introducing houghite interlayer can be prepared into many function materials with property compared with precursor
Material.
Will be enriched in the new organic/inorganic that the carboxymethyl cellulose ion insertion of adjacent hydroxyl is prepared to houghite interlayer
Hydridization boron adsorbent will obtain significantly result.One side houghite interlayer is drawn due to carboxymethyl cellulose
Enter, act not only as adsorption activity center and selective absorption is produced to boron, and the interface polarity and chemistry of material can be improved
Microenvironment, increases interlamellar spacing, reduces surface energy, and absorbability can be significantly increased；On the other hand due to the inorganic material of houghite
The introducing of material matrix, can cause the adsorbing material to have higher mechanical stability and a heat stability, and be conducive to regeneration and
Recycle.Along with houghite and carboxymethyl cellulose both raw material sources extensively, low cost, and Environmental compatibility
It is good so that such adsorbent will have broad application prospects.However, yet there are no being related to carboxymethyl cellulose anion
The preparation of intercalation houghite and its report of absorption boron.
The content of the invention
It is an object of the invention to provide a kind of carboxymethyl cellulose intercalation houghite with low cost, easy to make is multiple
Condensation material, the material environment are friendly, and heat stability and mechanical stability are high, high to the adsorption capacity of boron at normal temperatures, can be used for
The separation of boron in water body is removed.
For achieving the above object, the technical solution adopted in the present invention is：
The hydrotalcite-like composite material of the present invention using calcining graft process, will be enriched in adjacent hydroxyl carboxymethyl cellulose it is cloudy from
Sub- intercalation is assembled into houghite interlayer and prepares the hydrotalcite-like composite material with typical layers laminated structure, and the product has
The features such as having heat stability and mechanical stability height, environmental friendliness, and preparation process is simple, easily realize industrialization.This kind has
A large amount of adjacent oh group in machine-inorganic composite materials can play chelating adsorption to boron, can be used for waste water and desalinization
The separation absorption of middle boron.The anion intercalated hydrotalcite-like materials of this kind of carboxymethyl cellulose are with existing boron adsorbent as removed boron resin
Etc. comparing, not only mechanical strength is big, preparation cost is low, boron adsorption capacity high, and has significant specially good effect to inhale to the boron in solution
Attached effect, is expected to industrially be applied as a kind of new boron specially good effect adsorbing material.
A kind of chemical general formula of carboxymethyl cellulose ion insertion hydrotalcite-like composite material of the present invention is
[M2+ 1-xM3+ x(OH)2]x+(A-)x·mH2O, wherein M2+For Zn2+、Ca2+Or Mg2+, M3+For Fe3+Or Al3+, M2+And M3+
In brucite main layer board；A2-For interlayer carboxymethyl cellulose anion；X is M3+/(M2++M3+) molar ratio, 0.1
≤x≤0.33；Numbers of the m for interlayer hydrone, m=3-6；The crystal structure of this kind of material is tied for the crystal of hydrotalcite-like materials
Structure；
A kind of preparation method of carboxymethyl cellulose ion insertion hydrotalcite-like composite material of the present invention, including with
Lower step：
1）Soluble divalent metal salt and trivalent metal salt are dissolved in deionized water by certain mol proportion, solution is stirred to obtain
A, wherein bivalence with trivalent metal metal ion mol ratio are（1~4）：1, bivalent metal ion concentration is 0.05 ~ 0.10 mol
L-1；
2）Under strong stirring, sodium hydroxide solution is dropwise added drop-wise in solution A, with sodium hydroxide solution adjust pH to 9 ~
10,1 ~ 3h is continuously stirred at room temperature, by gained mixture filtering and washing for several times to neutrality, gained filter cake is put into thermostatic drying chamber
Interior 80 ~ 120 DEG C of 4 ~ 6h of drying, obtain white solid B, i.e. layered double hydroxide material LDH；
3）Above-mentioned gained solid B is placed at 300 ~ 600 DEG C of Muffle furnace and is calcined after 3 ~ 5h, obtain white solid powder C, i.e. layer
Shape bimetal composite oxide LDO；
4）It is scattered in layered bi-metal composite oxides LDO obtained above in deionized water by a certain percentage, obtains outstanding
Turbid liquid D；
5）Sodium carboxymethyl cellulose solid is dissolved in distilled water, carboxymethylcellulose sodium solution E is obtained；
6）By above-mentioned steps 4）The LDO suspension D of middle gained, are mixed with a certain proportion of carboxymethylcellulose sodium solution E,
6 ~ 10h of mechanical agitation, keeps solution alkaline pH8 ~ 10 in flask；The hydro-thermal that said mixture is transferred to politef is brilliant
In change kettle, 12 ~ 20h of crystallization in 80 ~ 150 DEG C of baking ovens, is cooled to room temperature, and products obtained therefrom solid-liquid separation washs to neutrality 60～85
DEG C 2～10h of vacuum drying, obtains final product the anion intercalated hydrotalcite-like composite material of carboxymethyl cellulose, is designated as LDH-CMC.
Described divalent metal divalent metal salt is Zn2+、Ca2+Or Mg2+Nitrate, trivalent metal salt is Fe3+Or Al3 +Nitrate.
Described naoh concentration is 0.50 ~ 4.0 molL-1, the mixing speed of described strong stirring is 300～
450rpm。
Described sodium carboxymethyl cellulose is 1 with the mol ratio of trivalent salt:1~3:1.
Described layered bi-metal composite oxides LDO is 1% ~ 3% with the mass ratio of deionized water, described carboxymethyl
The concentration of sodium cellulosate solution E is 1% ~ 3%, and the volume ratio of described LDO suspensions D and carboxymethylcellulose sodium solution E is 1:1
~1:3。
Using chelating principle of the adjacent oh group to boron, by the carboxymethyl cellulose rich in adjacent oh group of above-mentioned preparation
Anion intercalated hydrotalcite-like composite material is gone as adsorbent, the selective absorption for being applied to water body mesoboric acid root anion
Remove.
The present invention has advantages below compared with prior art：
1）This technology there is specially good effect to select the boron in solution using what calcining graft process can synthesize particle diameter and morphology controllable
The LDH-CMC of absorbability is selected, so as to expand the type of boron adsorbent；In addition, the method resulting materials are integrally homogeneous, chemical group
Into adjustable on microcosmic with structure；
2）By the anion intercalated LDH-CMC for obtaining of carboxymethyl cellulose compared with common LDH, with more adjacent hydroxyls
Base group, can further improve the selectivity and adsorption capacity of product boron, can efficient absorption boron at short notice；LDH-CMC
With high mechanical strength compared with common CMC, the advantages of easily recovery；
3）The characteristics of inorganic, organic adsorbent is had concurrently using organic/inorganic composite material obtained by this technology, with traditional boron
Adsorbent is such as compared except the inorganic adsorbent such as organic adsorbent or hydrous oxide such as boron resin, with mechanical strength is big, absorption
The advantages of capacity height, specially good effect selectivity, low price；
4）This technology is simple and easy to do, pollution-free, practical, products obtained therefrom applied range.
Description of the drawings
Fig. 1 is the X-ray diffraction of Mg-Al-LDH, Mg-Al-LDO and Mg-Al-CMC in embodiment 1（XRD）Figure.
Fig. 2 is the Fourier transform infrared of Mg-Al-LDH, Mg-Al-LDO and Mg-Al-CMC in embodiment 1（FTIR）Figure.
Fig. 3 is that the thermogravimetric of Mg-Al-LDH and Mg-Al-CMC in embodiment 1 is weightless（TG-DSC）Figure.
Fig. 4 is the high-resolution field emission scanning electron microscope of Mg-Al-LDH, Mg-Al-LDO and Mg-Al-CMC in embodiment 1
（HRSEM）Figure.
Fig. 5 is the adsorption effect figure of Mg-Al-LDH, Mg-Al-LDO and Mg-Al-CMC to boron in embodiment 1.
Fig. 6 is adsorption effect comparison diagrams of the Mg-Al-CMC2 to boron in Mg-Al-CMC and embodiment 2 in embodiment 1.
Specific embodiment
Technical scheme is described further with reference to specific embodiment, but protection scope of the present invention
It is not limited to these embodiments.
Embodiment 1
（1）Mol ratio is the synthesis of 2 Mg-Al houghites：By 5.12g magnesium nitrates and 3.75g aluminum nitrates, it is dissolved in
100mL
Mixed solution is made in distilled water；Then 4g sodium hydroxide is dissolved in into 100mL distilled water and is made into mixed ammonium/alkali solutions.Will
Two solution are stirred continuously in the lower three-neck flask for instilling and having filled 100mL distilled water in room temperature.After completion of dropping, 1molL is used-1
Sodium hydroxide adjusts pH to 9-10, is continuously stirred at room temperature 2h.By gained mixture filtering and washing for several times to neutrality, gained is solid
Body is put in thermostatic drying chamber 80 DEG C and is dried 4h, obtains Mg-Al double-metal hydroxide Mg-Al-LDH.
（2）Mg-Al-LDH solids are positioned in Muffle furnace after calcining 4 hours at 450 DEG C, obtain white solid Mg-Al
Bimetallic oxide Mg-Al-LDO.
（3）The Mg-Al-LDO ultrasonic cleaners are scattered in 100mL distilled water and obtain Mg-Al-LDO suspensions.
（4）Weigh 4.5g sodium carboxymethyl cellulose（Abbreviation CMC）After dissolving in 100mL distilled water, it is added drop-wise to
In Mg-Al-LDO suspensions, mechanical agitation 4 hours keeps solution alkaline pH 9-10 in flask；It is mixed
Thing is transferred in the hydrothermal reaction kettle of politef crystallization 12 hours in 80 DEG C of baking ovens, filters, washs to neutrality, at 80 DEG C
Drying, grinding, obtains Mg-Al-CMC samples.
Fig. 1 is the X-ray diffraction of Mg-Al-LDH, Mg-Al-LDO and Mg-Al-CMC in embodiment 1（XRD）Figure.From figure
As can be seen that at 2 θ=11.26 °, 22.8 °, 34.34 °, 60.50 °, 61.64 °, products obtained therefrom Mg-Al-LDH shows class
The characteristic diffraction peak of brucite（003）、（006）、（009）、（110）, and prepared sample diffraction peak height and it is narrow, miscellaneous peak is very
It is few, illustrate that prepared houghite is the high single crystalline phase of degree of crystallinity.To obtain after the 400 DEG C of roastings of Mg-Al-LDH solids
Mg-Al-LDO, Mg-Al-LDH crystal characteristic diffraction maximums are wholly absent, while occurring in that bimetal composite oxide（LDO）'s
Characteristic diffraction peak.The Mg-Al-CMC that CMC intercalation Mg-Al-LDO are obtained, Mg-Al-LDH crystal characteristic peaks occur again, and
Substantially offset to low-angle, illustrate that the layer structure of houghite is restored, gained composite with houghite phase
Same crystal structure.
Fig. 2 is the Fourier transform infrared spectroscopy of Mg-Al-LDH, Mg-Al-LDO and Mg-Al-CMC in embodiment 1
（FTIR）Figure.In 3400cm in figure-1The relatively wide bands of a spectrum in place are physical absorption water or water of crystallization-OH vibrational bands and M-OH
Stretching band, in addition in 1630cm-1Also there are the weak bending vibration bands of a spectrum of water at place.In 780～890cm-1Place is M-O vibrations
Bands of a spectrum.After CMC is intercalation into Mg-Al-LDH, 1630 cm-1Nearby the vibration peak of water of crystallization substantially returns to level before roasting,
In 1380cm-1There are the symmetrical stretching vibration bands of a spectrum of carboxylate radical-COO-, and in 1040cm-1There are C-O stretching vibration peaks.FT-
IR spectrograms explanation CMC comes into the inter-layer position of Mg-Al-LDO, realizes carboxymethyl cellulose pillared hydrotalcite supramolecular structured
The intercalation assembling of structure.
Fig. 3 is weightless for the thermogravimetric of Mg-Al-LDH and Mg-Al-CMC（TG-DSC）Figure.As seen from the figure, Mg-Al-LDH is 110
DEG C or so discharge physical absorption water, the removing of 230 DEG C or so of endothermic peak for interlayer water of crystallization, 370 DEG C or so of correspondence
The decomposition combustion of interlayer Organic substance species.There are 3 significantly weightlessness platforms in correspondence said process, TG curves.Mg-Al-CMC
TG figures reflect 3 zero-g periods, room temperature loses surface adsorption water and intermediary water to 240 DEG C；257 ~ 380 DEG C crystallize for interlayer
The removing of water；440 DEG C or so the decomposition combustions for interlayer CMC, corresponding TG curves weight loss are larger；Comprehensive FTIR and TG-
Dsc analysis result understands that Mg-Al-CMC is not the simple composite of CMC and LDHs, but defines the nothing with intercalation configuration
There is stronger interaction between machine-organic supermolecular compound, and main, object.
Fig. 4 is the high-resolution field emission scanning electron microscope of Mg-Al-LDH, Mg-Al-LDO and Mg-Al-CMC in embodiment 1
（HRSEM）Figure.As seen from the figure, Mg-Al-LDH has leaveves load shape hierarchy, the Mg-Al-LDO obtained after calcining
Lamellar structure disappears, and granule/block shape is presented；And Mg-Al-CMC recovers uniformly laminated structure again.
Material is as follows to the absorption property method of testing of boron：
Under room temperature, Mg-Al-LDH, Mg-Al-LDO and the Mg-Al-CMC for weighing 0.1g respectively is added to 30 μ of 100mL
g·mL-1Sodium tetraborate simulated wastewater, it is 300 rmin to be placed on magnetic stirring apparatuss mixing speed-1, when reaction is different
Between point such as 20,40,60min until 8h is sampled, centrifugation takes supernatant azomethine hydrogen spectrophotometry its absorbance,
And calculate adsorption capacity q（mg·g-1）,
Formula（1）
In formula：C 0 For the concentration of Inorganic Boron in waste water before absorption, μ gmL-1；
CFor the concentration of Inorganic Boron in waste water in adsorption process, μ gmL-1；
VFor the cumulative volume of absorption system（mL）；
m 0 For the addition quality of adsorbent.
Fig. 5 is the adsorption effect figures of the Mg-Al-LDH and Mg-Al-CMC to boron in embodiment 1.It can be seen that Mg-
The adsorption capacity of Al-CMC will be apparently higher than Mg-Al-LDH, nearly 9 mgg of maximum adsorption capacity-1。
Embodiment 2
（1）Mol ratio is the synthesis of 3 Mg-Al houghites：By 7.68g magnesium nitrates and 3.75g aluminum nitrates, it is dissolved in
Mixed solution is made in 100mL distilled water；Then 5.6g sodium hydroxide is dissolved in into 100mL distilled water and is made into mixed base
Solution.Two solution are stirred continuously in the lower three-neck flask for instilling and having filled 100mL distilled water in room temperature.After completion of dropping, use
1mol·L-1Sodium hydroxide adjusts pH to 9-10, is continuously stirred at room temperature 2h.By gained mixture filtering and washing for several times, gained
Solid is put in thermostatic drying chamber 80 DEG C and is dried 4h, obtains Mg-Al-LDH2.
（2）Mg-Al-LDH2 solids are positioned in Muffle furnace after calcining 4 hours at 450 DEG C, obtain white solid Mg-
Al-LDO2。
（3）The Mg-Al-LDO2 ultrasonic cleaners are scattered in obtain Mg-Al-LDO2 in 100mL distilled water suspended
Liquid.（4）6.0g CMC are weighed after dissolving in 100mL distilled water, is added drop-wise in Mg-Al-LDO2 suspensions, machinery is stirred
Mix 4 hours, keep solution alkaline pH9-10 in flask；Be mixed thing be transferred to politef hydro-thermal it is anti-
Crystallization 12 hours, filtration, washing, the drying at 80 DEG C in 100 DEG C of baking ovens in kettle is answered, is ground, is obtained Mg-Al-CMC2 samples.
Fig. 6 is adsorption effect comparison diagrams of the Mg-Al-CMC2 to boron in Mg-Al-CMC and embodiment 2 in embodiment 1.
From the graph as can be seen that two kinds of composites are suitable to the adsorption capacity of boron, absorption of the Mg-Al-CMC2 to boron is held
Amount is slightly above Mg-Al-CMC, illustrates that this kind of material can be used as boron specific adsorbent adsorbing separation waste water or the boron in sea water.
The present invention is not limited to above-mentioned embodiment, it is every with of the invention with same or like technical scheme, fall
Enter within protection scope of the present invention.The technology not described in detail of the invention, shape, construction part are known technology.
Claims (6)
1. a kind of preparation method of carboxymethyl cellulose ion insertion hydrotalcite-like composite material：Characterized in that, the composite wood
The chemical general formula of material is [M2+ 1-xM3+ x(OH)2]x+(A-)x·mH2O, wherein M2+For Zn2+、Ca2+Or Mg2+, M3+For Fe3+Or Al3 +, M2+And M3+In brucite main layer board；A-For interlayer carboxymethyl cellulose anion；X is M3+/(M2++M3+) mole
Ratio, 0.1≤x≤0.33；Numbers of the m for interlayer hydrone, m=3-6；The crystal structure of this kind of material is hydrotalcite-like materials
Crystal structure；
The preparation method of described carboxymethyl cellulose ion insertion hydrotalcite-like composite material, comprises the following steps：
1）Soluble divalent metal salt and trivalent metal salt are dissolved in deionized water by certain mol proportion, solution A is stirred to obtain, its
Middle bivalence with trivalent metal metal ion mol ratio is（1~4）：1, bivalent metal ion concentration is 0.05 ~ 0.10 molL-1；
2）Under strong stirring, sodium hydroxide solution is dropwise added drop-wise in solution A, pH is adjusted to 9 ~ 10 with sodium hydroxide solution,
1 ~ 3h is continuously stirred at room temperature, by gained mixture filtering and washing for several times to neutrality, gained filter cake is put in thermostatic drying chamber
80 ~ 120 DEG C of 4 ~ 6h of drying, obtain white solid B, i.e. layered double hydroxide material LDH；
3）Above-mentioned gained solid B is placed at 300 ~ 600 DEG C of Muffle furnace and is calcined after 3 ~ 5h, obtain white solid powder C, i.e. stratiform double
Composite oxide of metal LDO；
4）It is scattered in layered bi-metal composite oxides LDO obtained above in deionized water by a certain percentage, obtains LDO and hang
Turbid liquid D；
5）Sodium carboxymethyl cellulose solid is dissolved in distilled water, carboxymethylcellulose sodium solution E is obtained；
6）By above-mentioned steps 4）The LDO suspension D of middle gained, are mixed with a certain proportion of carboxymethylcellulose sodium solution E, machinery
6 ~ 10h of stirring, keeps solution alkaline pH8 ~ 10 in flask；Said mixture is transferred to into the hydrothermal crystallizing kettle of politef
12 ~ 20h of crystallization in interior 80 ~ 150 DEG C of baking ovens, is cooled to room temperature, and products obtained therefrom solid-liquid separation washs to neutrality 60～85 DEG C very
2～10h of empty drying, obtains final product the hydrotalcite-like composite material of carboxymethyl cellulose intercalation, is designated as LDH-CMC.
2. preparation method according to claim 1, it is characterised in that described divalent metal salt is Zn2+、Ca2+Or Mg2+
Nitrate, trivalent metal salt is Fe3+Or Al3+Nitrate.
3. preparation method according to claim 1, it is characterised in that described naoh concentration is 0.50 ~ 4.0
mol·L-1, the mixing speed of described strong stirring is 300～450rpm.
4. preparation method according to claim 1, it is characterised in that described sodium carboxymethyl cellulose is rubbed with trivalent salt
You are than being 1:1~3:1.
5. preparation method according to claim 1, it is characterised in that described layered bi-metal composite oxides LDO with
The mass ratio of deionized water is 1% ~ 3%, and the concentration of described carboxymethylcellulose sodium solution E is 1% ~ 3%, and described LDO hangs
The volume ratio of turbid liquid D and carboxymethylcellulose sodium solution E is 1:1~1:3.
6. carboxymethyl cellulose ion insertion houghite composite wood obtained in a kind of preparation method according to claim 1
Application of the material in water body in the adsorbing separation of boron.
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