CN103212374A - Stratified hydroxide composite material and preparation method thereof - Google Patents
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Abstract
The invention provides a stratified hydroxide composite material and a preparation method thereof, wherein the stratified hydroxide composite material is obtained by reacting a stratified hydroxide with sulfonatocalixarene. Compared with the prior art, the composite material of stratified hydroxide and calixarene provided by the invention has the advantages of high specific surface area, porosity and the like of the stratified hydroxide, and meanwhile, the composite material is also capable of realizing selective absorption for phenol organic materials by means of the unique cavity structure of the calixarene compound, and the hydrophily and hydrophobicity of the cavity and the side-chain substituent group.
Description
Technical field
The invention belongs to new material and water and pollute the inorganic agent technical field, relate in particular to a kind of layered hydroxide composite and preparation method thereof.
Background technology
Shortage of water resources and water pollution seriously are one of significant problems of facing of current society.Sewage is carried out certain improvement, and making it to reach the standard of utilizing again is one of method that addresses this problem.At present, the improvement to the general pollutant of sewage has both at home and abroad all obtained achievement preferably, can reach the purpose of reuse basically according to demand.But the improvement of the persistence organic pollutant (POPs) of trace remains a difficult problem in the water.In the water environment high toxicity of POPs, three cause the effect and the endocrine desiccation produced serious environmental problem.Chlorophenols is exactly that a class exists commonplace POPs, and it extensively is present in the industrial wastewaters such as oil refining, plastics, rubber, medicine, iron and steel, and in addition 2, the 4-chlorophenesic acid also is widely used in the manufacturing of pesticide and herbicide.The maximum permissible concentration of aldehydes matter is 0.002mg/L in the general provision surface water, and when the concentration of phenol in the water body was 0.1～0.2mg/L, the flesh of fish can produce the phenol flavor, and concentration Gao Shike makes fish kill.If people's long-term drinking contains phenol water, can cause giddy, anaemia and various neurological symptom, even poison.
The method of handling the phenols organic pollution can be divided three classes: physics method, chemical method and bioanalysis.Wherein, the absorption method flow process in the physics method is the simplest, and adsorbance is big, and treatment effect is also stable.Absorption method mainly is that the strong absorption property that utilizes some porous adsorbent high-specific surface areas to show is removed the absorption of the aldehydes matter in the waste water, adsorbent commonly used has NACF, chitin, shitosan and macroporous absorbent resin etc., but these adsorbents do not have selectivity to pollutant.
Layered double hydroxide (LDH) is extremely important anionic type laminated material, different anions is introduced the LDH that interlayer can obtain the organic anion intercalation, and this type of material has extensive use in fields such as storage, drug delivery and the release of optics, catalysis, biomolecule, bio-sensing, sewage disposal, electrochemical sensings.
The hydroxide with hydrotalcite layered structure that layered double hydroxide is made up of bivalent metal ion and trivalent metal ion claims mixed metal hydroxides again; Layered double hydroxide has the shepardite lamellar structure, laminate is owing to trivalent metal ion isomorphous substitution bivalent metal ion has positive charge, anionic electric charge of the object that interlayer can exchange and laminate positive charge balance, make layered double hydroxide be electroneutral, layered double hydroxide has bigger anion-exchange capacity (AEC, 2～3mep/g), acceptant object anion, therefore can be used to the metal and the organic pollution that exist with the anion form in the adsorbed water body, but this type of material shortage has limited range of application to the selectivity of guest molecule.
Organic/inorganic composite material is a research field of rising and have development potentiality in the materials chemistry recently, it is to combine by synergy organifying compound and inorganic matter in nanometer range, double grading with organic compounds and inorganic matter, combination property is better than each one-component, be the research focus in materials chemistry field in recent years, receive much concern always.
The present invention considers layered hydroxide and the macrocyclic compound calixarenes with molecular recognition characteristic are compounded to form composite.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of layered hydroxide composite and preparation method thereof, and this composite has better adsorption capability and selectivity to phenol organic matter.
The invention provides a kind of layered hydroxide composite, obtain by layered hydroxide and the reaction of sulfonation calixarenes.
Preferably, described sulfonation calixarenes is sulfonation cup [a 4] aromatic hydrocarbons.
Preferably, described sulfonation calixarenes is sulfonation thia cup [a 4] aromatic hydrocarbons.
Preferably, layered hydroxide is Mg-Al layered double hydroxide or Zn-Al layered double hydroxide.
Preferably, layered hydroxide is Mg-Al-CO
3Layered double hydroxide or Zn-Al-CO
3Layered double hydroxide.
The present invention also provides a kind of preparation method of layered hydroxide composite, comprising:
A) with the layered hydroxide roasting, obtain composite oxides;
B) described composite oxides, sulfonation calixarenes are mixed with water, obtain the layered hydroxide composite after the reaction.
Preferably, the temperature of described roasting is 400 ℃～500 ℃, and the time of roasting is 2～4h.
Preferably, the mass ratio of described composite oxides and sulfonation calixarenes is 1:(0.3～3).
Preferably, the time of reaction is 40～50h described step B).
Preferably, described step B) be specially:
The sulfonation calixarenes is mixed with water, add described composite oxides, obtain the layered hydroxide composite after the reaction.
The invention provides a kind of layered hydroxide composite and preparation method thereof, this layered hydroxide composite is obtained by layered hydroxide and the reaction of sulfonation calixarenes.Compared with prior art, the present invention is the composite of layered hydroxide and calixarenes, this composite has advantages such as high specific area of layered hydroxide and porous, simultaneously, it also can utilize the hydrophilic and hydrophobic of cavity structure, cavity and the side chain substituents group of calixarene compound uniqueness, realizes the selective absorption to phenol organic matter.
Experimental result shows that layered hydroxide composite of the present invention can reach 119.0mg/g to the phenolic compound adsorbance.
Description of drawings
The ZnAl-CO of Fig. 1 for obtaining in the embodiment of the invention 1
3The X-ray diffractogram of layered double hydroxide, composite oxides and layered hydroxide composite;
The ZnAl-CO of Fig. 2 for obtaining in the embodiment of the invention 1
3The X-ray diffractogram of the layered hydroxide composite that obtains among layered double hydroxide, the embodiment 1～embodiment 4;
Fig. 3 is the ZnAl-CO that obtains among sulfonation thia cup of the present invention [4] aromatic hydrocarbons, the embodiment 1
3The infrared spectrogram of the layered hydroxide composite that obtains among layered double hydroxide, the embodiment 1～embodiment 4;
Fig. 4 is the X-ray diffractogram of absorption front and back layered hydroxide composite among the embodiment of the invention 5～7, the embodiment 9～11.
The specific embodiment
The invention provides a kind of layered hydroxide composite, obtain by layered hydroxide and the reaction of sulfonation calixarenes.
Wherein, layered hydroxide is that layered hydroxide well known to those skilled in the art gets final product, and there is no special restriction.Layered hydroxide described in the present invention is preferably Mg-Al layered double hydroxide or Zn-Al layered double hydroxide, more preferably Mg-Al-CO
3Layered double hydroxide or Zn-Al-CO
3Layered double hydroxide.
Layered hydroxide is that a class is filled the layer stylolitization compound that commutative anion constitutes by positively charged metal hydroxides thing layer and interlayer.By static or hydrogen bond action, this more weak interaction force makes interlayer anion have interchangeability between interlayer anion and laminate, the target anion can be introduced interlayer by ion-exchange method and obtain required layered hydroxide.
Layered hydroxide has good ion-exchange performance, and has advantages such as high-specific surface area, porous and stability, therefore has suction-operated.
Calixarenes is a class cyclic oligomer that is formed by connecting at the phenolic hydroxyl group ortho position by methylene by phenol units (general four to eight), form a series of complexs that comprise different object types by changing the big I in its cave, so be called as the third generation main body macrocyclic compound after supramolecular chemistry relay ring dextrin, the crown ether, the length that can collect crown ether and cyclodextrin can form the Subjective and Objective inclusion compound with particle and neutral molecule.The calixarenes of sulfonation described in the present invention is that sulfonation calixarenes well known to those skilled in the art gets final product, and there is no special restriction, is preferably sulfonation cup [4] aromatic hydrocarbons, more preferably sulfonation thia cup [4] aromatic hydrocarbons.
The sulfonation calixarenes has selectivity to guest molecule, but because it is water-soluble, in the aqueous solution, can lose because of dissolving, can't be used for water pollutant absorption as adsorbent alone, the layered hydroxide composite that the reaction of itself and layered hydroxide obtains can layered hydroxide and the advantage of calixarenes, overcome defective separately, thereby make composite can utilize the advantage of layered hydroxide porous and high-specific surface area, can utilize the cavity structure of calixarene compound uniqueness again, the hydrophilic and hydrophobic of cavity and side chain substituents group is realized the selective absorption to phenol organic matter.
The present invention also provides the preparation method of above-mentioned hydroxide composite, comprising: A) with the layered hydroxide roasting, obtain composite oxides; B) described composite oxides, sulfonation calixarenes are mixed with water, obtain the layered hydroxide composite after the reaction.
All raw materials of the present invention do not have special restriction to its source, buy on market or homemadely all can.Layered hydroxide and sulfonation calixarenes are all same as above, do not repeat them here; Described water is preferably the exhaust water that carries out exhaust through inert gas such as nitrogen, can avoid the influence of gas such as water oxygen gas to layered hydroxide.
The preparation method of layered hydroxide and sulfonation calixarenes all adopts method well known to those skilled in the art to be prepared and gets final product, and there is no special restriction.
The present invention utilizes roasting hydration method that macrocyclic compound sulfonation calixarenes is inserted between the stratiform hydroxide layer.This method is to be based upon on the characteristic basis of layered hydroxide " memory effect ", layered hydroxide is at high temperature carried out roasting form composite oxides, then its anionic solution with the desire embedding is carried out exchange reaction to obtain the layered hydroxide composite.This method can be eliminated the slaine inorganic anion with organic anion competition intercalation.
Layered hydroxide has " memory effect ", and the composite oxides that form after the roasting can recover original layer structure again in anion solutions at a certain temperature.Sintering temperature described in the present invention is preferably 400 ℃～550 ℃, and more preferably 400 ℃～500 ℃, the time of roasting is preferably 2～4h, more preferably 3～4h.
According to the present invention, described step B) be specially: the sulfonation calixarenes is mixed with water, add described composite oxides, obtain the layered hydroxide composite after the reaction.The quality of described composite oxides and sulfonation calixarenes is 1:(0.3～3), be preferably 1:(0.5～2); After mixing with water, described composite oxides, sulfonation calixarenes preferably under stirring condition, react; The time of reacting is 40～50h, is preferably 45～50h.
The present invention is presoma with the layered hydroxide, utilize simple, easy-operating method to introduce the macrocyclic compound calixarenes and obtain the layered hydroxide composite at the layered hydroxide interlayer, realize the combination of inorganic laminated main body chemistry and interlayer housing chemistry, the composite that obtains has phenol organic matter selects absorption property preferably.
Experimental result shows that layered hydroxide composite of the present invention can reach 119.0mg/g to the phenolic compound adsorbance.
In order to further specify the present invention, layered hydroxide composite provided by the invention and preparation method thereof is described in detail below in conjunction with embodiment.
Used reagent is commercially available in following examples.
1.1 with 10mmol(1.363g) ZnCl
2, 5mmol(1.207g) AlCl
36H
2O, 35mmol(2.102g) urea mixes with 1L water, under 100 ℃ of counterflow conditions, after continuing to stir 24h, sedimentation and filtration, with deionized water and absolute ethanol washing, 40 ℃ of vacuum drying obtain ZnAl-CO
3Layered double hydroxide.
1.2 with the ZnAl-CO that obtains in 1.1
3Layered double hydroxide roasting 4h under 400 ℃ of conditions in air obtains composite oxides.
1.3 0.1g sulfonation thia cup [4] aromatic hydrocarbons is joined in the 10ml exhaust water, add the composite oxides that obtain among the 0.1g1.2 then, sealing, magnetic agitation 48h, centrifugation is with exhaust water washing three times, place air drying, obtain the layered hydroxide composite.
Utilize the ZnAl-CO of X-ray diffractometer to obtaining in 1.1
3Layered double hydroxide, the layered hydroxide composite that obtains in the composite oxides and 1.3 that obtain in 1.2 is analyzed, and obtains X-ray diffractogram, and as Fig. 1 and shown in Figure 2, wherein a is ZnAl-CO among Fig. 1
3Layered double hydroxide, b are composite oxides, and c is the hydroxide composite that obtains in 1.3, and c ' is the partial enlarged drawing of c, and a is ZnAl-CO among Fig. 2
3Layered double hydroxide, c are the hydroxide composite that obtains in 1.3, and c ' is the partial enlarged drawing of c.As shown in Figure 1, ZnAl-CO
3The interlamellar spacing of layered double hydroxide is 0.75nm, diffraction maximum is sharp-pointed, show the sample good crystallinity, laminate is arranged regular, and the diffraction maximum of wide in range metal oxide appears in the composite oxides after the roasting, illustrates that layer structure is destroyed, and by serial diffraction maximum occurring at 2.05nm, 1.06nm, 0.75nm and 0.53nm place among the c, illustrate that calixarenes enters the layered double hydroxide interlayer, formed the hydroxide composite, interlamellar spacing is 2.05nm.
Utilize the ZnAl-CO of infrared spectrometer to obtaining in 1.1
3The layered hydroxide composite that obtains in layered double hydroxide, sulfonation thia cup [4] aromatic hydrocarbons and 1.3 is analyzed, and obtains its infrared spectrogram, and as shown in Figure 3, wherein a is that sulfonation thia cup [4] aromatic hydrocarbons, f are the ZnAl-CO that obtains in 1.1
3Layered double hydroxide, c are the layered hydroxide composite that obtains in 1.3.By c as seen, at 3431cm
-1The absorption at place is the stretching vibration peak of association hydroxyl; 1635cm
-1The place belongs to the H-O-H flexural vibrations of water; At 1362cm
-1The place can be observed CO
3 2-Vibration, this is that interlayer is residual fraction CO still because roasting is incomplete
3 2-, rebuild the residual CO in back
3 2-There is interlayer, so CO occurs in the infared spectrum of composite
3 2-Characteristic absorption; 1173cm
-1The place is the characteristic absorption of sulfonate radical, with the bimodal (1197cm of splitting in sulfonation thia cup [4] aromatic hydrocarbons
-1And 1153cm
-1) compare, become a wide in range strong vibration, illustrate that sulfonation thia cup [4] aromatic hydrocarbons successfully inserts ZnAl-CO
3The layered double hydroxide interlayer.
Embodiment 2
2.1 with 10mmol(1.363g) ZnCl
2, 5mmol(1.207g) AlCl
36H
2O, 35mmol(2.102g) urea mixes with 1L water, under 100 ℃ of counterflow conditions, after continuing to stir 24h, sedimentation and filtration, with deionized water and absolute ethanol washing, 40 ℃ of vacuum drying obtain ZnAl-CO
3Layered double hydroxide.
2.2 with the ZnAl-CO that obtains in 2.1
3Layered double hydroxide roasting 4h under 400 ℃ of conditions in air obtains composite oxides.
2.3 0.05g sulfonation thia cup [4] aromatic hydrocarbons is joined in the 10ml exhaust water, add the composite oxides that obtain among the 0.1g2.2 then, sealing, magnetic agitation 48h, centrifugation is with exhaust water washing three times, place air drying, obtain the layered hydroxide composite.
Utilize X-ray diffractometer that the layered hydroxide composite that obtains in 2.3 is analyzed, obtain its X-ray diffractogram, as shown in Figure 2, wherein b is the layered hydroxide composite that obtains in 2.3.
Utilize infrared spectrometer that the layered hydroxide composite that obtains in 2.3 is analyzed, obtain its infrared spectrogram, as shown in Figure 3, wherein b is the layered hydroxide composite that obtains in 2.3.
Embodiment 3
3.1 with 10mmol(1.363g) ZnCl
2, 5mmol(1.207g) AlCl
36H
2O, 35mmol(2.102g) urea mixes with 1L water, under 100 ℃ of counterflow conditions, after continuing to stir 24h, sedimentation and filtration, with deionized water and absolute ethanol washing, 40 ℃ of vacuum drying obtain ZnAl-CO
3Layered double hydroxide.
3.2 with the ZnAl-CO that obtains in 3.1
3Layered double hydroxide roasting 4h under 400 ℃ of conditions in air obtains composite oxides.
3.3 0.15g sulfonation thia cup [4] aromatic hydrocarbons is joined in the 10ml exhaust water, add the composite oxides that obtain among the 0.1g3.2 then, sealing, magnetic agitation 48h, centrifugation is with exhaust water washing three times, place air drying, obtain the layered hydroxide composite.
Utilize X-ray diffractometer that the layered hydroxide composite that obtains in 3.3 is analyzed, obtain its X-ray diffractogram, as shown in Figure 2, wherein d is the layered hydroxide composite that obtains in 3.3, and d ' is its partial enlarged drawing.
Utilize infrared spectrometer that the layered hydroxide composite that obtains in 3.3 is analyzed, obtain its infrared spectrogram, as shown in Figure 3, wherein d is the layered hydroxide composite that obtains in 3.3.
4.1 with 10mmol(1.363g) ZnCl
2, 5mmol(1.207g) AlCl
36H
2O, 35mmol(2.102g) urea mixes with 1L water, under 100 ℃ of counterflow conditions, after continuing to stir 24h, sedimentation and filtration, with deionized water and absolute ethanol washing, 40 ℃ of vacuum drying obtain ZnAl-CO
3Layered double hydroxide.
4.2 with the ZnAl-CO that obtains in 4.1
3Layered double hydroxide roasting 4h under 400 ℃ of conditions in air obtains composite oxides.
4.3 0.2g sulfonation thia cup [4] aromatic hydrocarbons is joined in the 10ml exhaust water, add the composite oxides that obtain among the 0.1g4.2 then, sealing, magnetic agitation 48h, centrifugation is with exhaust water washing three times, place air drying, obtain the layered hydroxide composite.
Utilize X-ray diffractometer that the layered hydroxide composite that obtains in 4.3 is analyzed, obtain its X-ray diffractogram, as shown in Figure 2, wherein e is the layered hydroxide composite that obtains in 4.3, and e ' is its partial enlarged drawing.
Utilize infrared spectrometer that the layered hydroxide composite that obtains in 4.3 is analyzed, obtain its infrared spectrogram, as shown in Figure 3, wherein e is the layered hydroxide composite that obtains in 4.3.
5.1 compound concentration is 2 of 0.5mg/ml, 3-dimethyl phenol solution.
Place centrifuge tube 5.2 get the hydroquinones solution that obtains among the 5ml5.1, add the layered hydroxide composite that obtains among the 0.03g embodiment 1, sooner or later rock centrifuge tube 2～3min every day, adsorb after three days, centrifugal filtration keeps filtrate, absorption back solid sample washing three times, air drying is collected, and measures the concentration of the solution after solution absorbs simultaneously, sees Table 1.
Utilize X-ray diffractometer that the layered hydroxide composite that embodiment 5 absorbs front and back is analyzed, obtain its X-ray diffractogram, as shown in Figure 4, wherein, a is the layered hydroxide composite before absorbing, a ' is its partial enlarged drawing, and b is the layered hydroxide composite after absorbing, and b ' is its partial enlarged drawing.As seen from Figure 4, compare with the layered hydroxide composite before the absorption, because aldehydes matter enters in the cavity of layered hydroxide composite, it is big that the layered hydroxide composite interlamellar spacing after the absorption becomes.
Embodiment 6
6.1 compound concentration is 2 of 1.0mg/ml, 3-dimethyl phenol solution.
Place centrifuge tube 6.2 get the hydroquinones solution that obtains among the 5ml6.1, add the layered hydroxide composite that obtains among the 0.03g embodiment 1, sooner or later rock centrifuge tube 2～3min every day, adsorb after three days, centrifugal filtration keeps filtrate, absorption back solid sample washing three times, air drying is collected, and measures the concentration of the solution after solution absorbs simultaneously, sees Table 1.
Utilize X-ray diffractometer that the layered hydroxide composite after absorbing in 6.2 is analyzed, obtain its X-ray diffractogram, shown in c among Fig. 4, c ' is its partial enlarged drawing.
Embodiment 7
7.1 compound concentration is 2 of 1.5mg/ml, 3-dimethyl phenol solution.
Place centrifuge tube 7.2 get the hydroquinones solution that obtains among the 5ml7.1, add the layered hydroxide composite that obtains among the 0.03g embodiment 1, sooner or later rock centrifuge tube 2～3min every day, adsorb after three days, centrifugal filtration keeps filtrate, absorption back solid sample washing three times, air drying is collected, and measures the concentration of the solution after solution absorbs simultaneously, sees Table 1.
Utilize X-ray diffractometer that the layered hydroxide composite after absorbing in 7.2 is analyzed, obtain its X-ray diffractogram, shown in d among Fig. 4, d ' is its partial enlarged drawing.
Embodiment 8
8.1 compound concentration is 2 of 2.0mg/ml, 3-dimethyl phenol solution.
Place centrifuge tube 8.2 get the hydroquinones solution that obtains among the 5ml8.1, add the layered hydroxide composite that obtains among the 0.03g embodiment 1, sooner or later rock centrifuge tube 2～3min every day, adsorb after three days, centrifugal filtration keeps filtrate, absorption back solid sample washing three times, air drying is collected, and measures the concentration of the solution after solution absorbs simultaneously, sees Table 1.
Table 1 layered hydroxide composite absorption 2, the data before and after the 3-dimethyl phenol solution
Embodiment 9
9.1 compound concentration is the hydroquinones solution of 0.5mg/ml.
Place centrifuge tube 9.2 get the hydroquinones solution that obtains among the 5ml9.1, add the layered hydroxide composite that obtains among the 0.03g embodiment 1, sooner or later rock centrifuge tube 2～3min every day, adsorb after three days, centrifugal filtration keeps filtrate, absorption back solid sample washing three times, air drying is collected, and measures the concentration of the solution after solution absorbs simultaneously, sees Table 2.
Utilize X-ray diffractometer that the layered hydroxide composite after absorbing in 9.2 is analyzed, obtain its X-ray diffractogram, shown in e among Fig. 4, e ' is its partial enlarged drawing.As shown in Figure 4, the interlamellar spacing maximum of the layered hydroxide composite in 9.2 after the absorption is 2.16nm.
10.1 compound concentration is the hydroquinones solution of 1.0mg/ml.
Place centrifuge tube 10.2 get the hydroquinones solution that obtains among the 5ml10.1, add the layered hydroxide composite that obtains among the 0.03g embodiment 1, sooner or later rock centrifuge tube 2～3min every day, adsorb after three days, centrifugal filtration keeps filtrate, absorption back solid sample washing three times, air drying is collected, and measures the concentration of the solution after solution absorbs simultaneously, sees Table 2.
Utilize X-ray diffractometer that the layered hydroxide composite after absorbing in 10.2 is analyzed, obtain its X-ray diffractogram, shown in f among Fig. 4, f ' is its partial enlarged drawing.
Embodiment 11
11.1 compound concentration is the hydroquinones solution of 1.5mg/ml.
Place centrifuge tube 11.2 get the hydroquinones solution that obtains among the 5ml11.1, add the layered hydroxide composite that obtains among the 0.03g embodiment 1, sooner or later rock centrifuge tube 2～3min every day, adsorb after three days, centrifugal filtration keeps filtrate, absorption back solid sample washing three times, air drying is collected, and measures the concentration of the solution after solution absorbs simultaneously, sees Table 2.
Utilize X-ray diffractometer that the layered hydroxide composite after absorbing in 11.2 is analyzed, obtain its X-ray diffractogram, shown in g among Fig. 4, g ' is its partial enlarged drawing.
Embodiment 12
12.1 compound concentration is the hydroquinones solution of 2.0mg/ml.
Place centrifuge tube 12.2 get the hydroquinones solution that obtains among the 5ml12.1, add the layered hydroxide composite that obtains among the 0.03g embodiment 1, sooner or later rock centrifuge tube 2～3min every day, adsorb after three days, centrifugal filtration keeps filtrate, absorption back solid sample washing three times, air drying is collected, and measures the concentration of the solution after solution absorbs simultaneously, sees Table 2.
Data before and after the table 2 layered hydroxide composite absorption hydroquinones
From table 1 and table 2 as can be seen, the layered hydroxide composite all has suction-operated to two kinds of phenol, with 2, the 3-dimethyl phenol is compared, the layered hydroxide composite is better to the absorption of hydroquinones, and the maximum adsorption rate is 90.4%, and maximal absorptive capacity is 119.0mg/g; To 2, the maximum adsorption rate of 3-dimethyl phenol is 87.4%, and maximal absorptive capacity is 97.8mg/g.Increase with the phenols solution concentration reduces the layered hydroxide composite to the adsorption rate of two kinds of aldehydes matters, and adsorbance increases to increasing with the phenols solution concentration.The pH of both phenols solution of absorption back all becomes greatly, and this is that after by the absorption of the layered hydroxide composite of alkalescence, acid aldehydes matter enters the composite interlayer, and hydrogen ion concentration is reduced because aldehydes matter solution is acidity, the increase of pH value.
The above only is a preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a layered hydroxide composite is characterized in that, is obtained by layered hydroxide and the reaction of sulfonation calixarenes.
2. layered hydroxide composite according to claim 1 is characterized in that, described sulfonation calixarenes is sulfonation cup [a 4] aromatic hydrocarbons.
3. layered hydroxide composite according to claim 1 is characterized in that, described sulfonation calixarenes is sulfonation thia cup [a 4] aromatic hydrocarbons.
4. layered hydroxide composite according to claim 1 is characterized in that, layered hydroxide is Mg-Al layered double hydroxide or Zn-Al layered double hydroxide.
5. layered hydroxide composite according to claim 1 is characterized in that, layered hydroxide is Mg-Al-CO
3Layered double hydroxide or Zn-Al-CO
3Layered double hydroxide.
6. the preparation method of a layered hydroxide composite is characterized in that, comprising:
A) with the layered hydroxide roasting, obtain composite oxides;
B) described composite oxides, sulfonation calixarenes are mixed with water, obtain the layered hydroxide composite after the reaction.
7. preparation method according to claim 6 is characterized in that, the temperature of described roasting is 400 ℃～500 ℃, and the time of roasting is 2～4h.
8. preparation method according to claim 6 is characterized in that, the mass ratio of described composite oxides and sulfonation calixarenes is 1:(0.3～3).
9. preparation method according to claim 6 is characterized in that, described step B) in the reaction time be 40～50h.
10. preparation method according to claim 6 is characterized in that, described step B) be specially:
The sulfonation calixarenes is mixed with water, add described composite oxides, obtain the layered hydroxide composite after the reaction.
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| CN104437384A (en) * | 2014-11-05 | 2015-03-25 | 沈阳大学 | Compound modified bentonite |
| CN105642263A (en) * | 2014-11-14 | 2016-06-08 | 辽宁奥克化学股份有限公司 | A preparing method of a modified layered bi-metal oxide |
| CN111892131A (en) * | 2020-07-14 | 2020-11-06 | 上海大学 | Device and method for treating wastewater by using electrolysis combined with biochar-LDH composite material |
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