CN110193344A - A kind of aromatic modified zeolite adsorbent material of cation seperation column [5] and its preparation method and application - Google Patents
A kind of aromatic modified zeolite adsorbent material of cation seperation column [5] and its preparation method and application Download PDFInfo
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Abstract
The present invention provides aromatic modified zeolite adsorbent materials of a kind of cation seperation column [5] and its preparation method and application, belong to adsorbent material technical field.The aromatic modified zeolite adsorbent material of cation seperation column [5] provided by the invention includes zeolite and cation seperation column [5] aromatic hydrocarbons for being carried on zeolite surface and interlayer, the present invention is modified zeolite using cation seperation column [5] aromatic hydrocarbons, cation seperation column [5] aromatic hydrocarbons is set to be carried on zeolite surface and interlayer by charge interaction, so that zeolite has more positive electricity active sites, can equilibrium zeolite negative electricity structure generated due to same lattice metathesis, and increase ion exchange site.Embodiment the result shows that, the aromatic modified zeolite adsorbent material of cation seperation column [5] provided by the invention for organic anionic dyes adsorb when, 85% is up to the removal rate of dyestuff.
Description
Technical field
The present invention relates to adsorbent material technical field, in particular to a kind of aromatic modified zeolite adsorption material of cation seperation column [5]
Material and its preparation method and application.
Background technique
With the fast development of the industries such as cosmetics, rubber, plastics, textile and paper, water environment pollution situation is increasingly tight
It is high.Organic dye waste water is considered as one of main industrial pollution source in the world today.For textile industry, need to consume every year
700000 tons of dyestuffs.Organic dye waste water complicated component, strong toxicity and organic dye molecule are difficult to remove.Therefore, untreated
Organic dye waste water is the one of the major reasons of water pollution.
Organic dyestuff is broadly divided into anionic dye, the dye of positive ion and non-ionic dye.Methyl orange
(C14H14N3NaO3S, abbreviation MO) it is one of representative of organic anionic dyes, there is carcinogenic and mutagenicity, human body can be caused
Shock, increased heart rate, jaundice, vomiting and tissue necrosis.So far, it has been found that the sides of many removal anionic dyes
Method, including oxidation, UF membrane, condensation, absorption, electronation and biological treatment.Wherein, absorption method is since its is easy to operate and clear
Except rate height, it is considered to be a kind of cheap effective method.
Zeolite is widely used in water environment and controls because its is various in style, rich reserves, cheap, processing technology are simple
Reason.Zeolite has unique aluminosilicate framework structure, has uniform cellular structure and hole abundant in crystals, and
With very strong ion exchange and absorption property.However, zeolite can generate permanent negative electricity knot due to same lattice metathesis
Structure, it is weaker to the removal ability of organic anionic dyes that this will lead to zeolite.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of aromatic modified zeolite adsorbent material of cation seperation column [5] and its systems
Preparation Method and application.The aromatic modified zeolite adsorbent material of cation seperation column [5] provided by the invention has organic anionic dyes
Excellent adsorption effect.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of aromatic modified zeolite adsorbent material of cation seperation column [5], including zeolite and it is carried on zeolite
Cation seperation column [5] aromatic hydrocarbons on surface and interlayer；
Cation seperation column [5] aromatic hydrocarbons has structure shown in Formulas I:
Preferably, the partial size of the zeolite is 1~100 mesh.
The present invention provides the preparation methods of the aromatic modified zeolite adsorbent material of above-mentioned cation seperation column [5], including following step
It is rapid:
Zeolite and cation seperation column [5] arene solution are mixed, successively shaken, washed and is dried, obtain cation seperation column
[5] aromatic modified zeolite adsorbent material.
Preferably, the mass concentration of cation seperation column [5] arene solution is 0.5~20g/L.
Preferably, the quality of the zeolite and the volume ratio of cation seperation column [5] arene solution are 0.5~1g:10mL.
Preferably, the time of the concussion be 5~for 24 hours.
Preferably, the temperature of the drying is 40~200 DEG C.
The present invention provides the aromatic modified zeolite adsorbent materials of above-mentioned cation seperation column [5] in absorption organic anionic dyes
Application.
Preferably, the dosage of the aromatic modified zeolite adsorbent material of cation seperation column [5] is 3~20g/L when the absorption；It is described
The mass concentration of organic anionic dyes is 20~300mg/L when absorption；The pH value of the organic anionic dyes is 2~12.
Preferably, the time of the absorption is 10~960min.
The present invention provides a kind of aromatic modified zeolite adsorbent material of cation seperation column [5], including zeolite and it is carried on zeolite
Cation seperation column [5] aromatic hydrocarbons on surface and interlayer；Cation seperation column [5] aromatic hydrocarbons has structure shown in Formulas I.The present invention using sun from
Sub- column [5] aromatic hydrocarbons is modified zeolite, so that cation seperation column [5] aromatic hydrocarbons is carried on zeolite surface and layer by charge interaction
Between so that zeolite have more positive electricity active sites, can equilibrium zeolite due to same lattice metathesis generate negative electricity structure, and
Increase ion exchange site.Meanwhile the aromatic modified zeolite adsorbent material of cation seperation column [5] provided by the invention has biggish ratio
Surface area and good thermal stability.Embodiment the result shows that, the aromatic modified zeolite absorption of cation seperation column [5] provided by the invention
When material is adsorbed for organic anionic dyes, 85% is up to the removal rate of dyestuff.
The present invention provides the preparation method of the aromatic modified zeolite adsorbent material of above-mentioned cation seperation column [5], this method is at low cost
Honest and clean, raw material sources are extensive, simple easily operated, easy to industrialized production.
Detailed description of the invention
Fig. 1 is the SEM figure of cation seperation column [5] aromatic hydrocarbons, zeolite and the aromatic modified zeolite adsorbent material of cation seperation column [5],
In (a) be that the SEM of cation seperation column [5] aromatic hydrocarbons schemes, (b) scheme for the SEM of zeolite, (c) inhaled for cation seperation column [5] aromatic modified zeolite
The SEM of enclosure material schemes；
Fig. 2 is the infrared absorption of cation seperation column [5] aromatic hydrocarbons, zeolite and the aromatic modified zeolite adsorbent material of cation seperation column [5]
Spectrogram；
Fig. 3 is the XRD spectrum of cation seperation column [5] aromatic hydrocarbons, zeolite and the aromatic modified zeolite adsorbent material of cation seperation column [5]；
Fig. 4 is the thermogravimetric analysis of cation seperation column [5] aromatic hydrocarbons, zeolite and the aromatic modified zeolite adsorbent material of cation seperation column [5]
Figure；
The zeolite and WPA5/ZE that Fig. 5 is different-grain diameter are to the removal rate variation diagram of MO；
Fig. 6 is removal rate variation diagram of the adsorbent material after the WPA5 solution modification of various concentration to MO；
Fig. 7 be under different adsorption times WPA5/ZE to the removal rate variation diagram of MO；
Fig. 8 be various concentration MO solution under WPA5/ZE to the removal rate variation diagram of MO；
Fig. 9 be under different pH value MO solution WPA5/ZE to the removal rate variation diagram of MO；
The linear graph of pseudo- First order dynamic model and pseudo-second-order equation model when Figure 10 is WPA/ZE absorption MO, wherein
(a) it is pseudo- First order dynamic model linear graph, is (b) pseudo-second-order equation model linear graph；
Figure 11 is Langmuir the and Freundlich isotherm model curve of WPA/ZE absorption MO, wherein (a) is
Langmuir isotherm model curve (b) is Freundlich isotherm model curve.
Specific embodiment
The present invention provides a kind of aromatic modified zeolite adsorbent material of cation seperation column [5], including zeolite and it is carried on zeolite
Cation seperation column [5] aromatic hydrocarbons on surface and interlayer；
Cation seperation column [5] aromatic hydrocarbons has structure shown in Formulas I:
In the present invention, the partial size of the zeolite is preferably 1~100 mesh, more preferably 30~90 mesh.The present invention is to described
The source of zeolite does not have special requirement, uses the natural zeolite or artificial zeolite of this field conventional commercial.
In the present invention, cation seperation column [5] aromatic hydrocarbons is to pass through methylene bridges in phenyl ring contraposition to disubstituted benzenes
Made of five-membered copolymer, substituent group be-OCH2CH2N(CH3)3.The present invention does not have the source of the cation seperation column [5] aromatic hydrocarbons
Have special requirement, using this field conventional commercial cation seperation column [5] aromatic hydrocarbons or voluntarily prepare.When voluntarily prepare sun from
When sub- column [5] aromatic hydrocarbons, the preparation method preferably includes following steps:
(1) under the effect of the catalyst, so that (2- hydroxyethyl) ether of quinhydrones two and carbon tetrabromide is carried out substitution reaction, obtain
Intermediate product A；
(2) under the effect of the catalyst, so that intermediate product A and paraformaldehyde is carried out annulation, obtain intermediate product B；
(3) make intermediate product B and trimethylamine that substitution reaction occur, obtain cation seperation column [5] aromatic hydrocarbons.
In the present invention, the catalyst in the step (1) is preferably triphenylphosphine, the quinhydrones two (2- hydroxyethyl)
The molar ratio of ether, carbon tetrabromide and catalyst is preferably 10:24:24.In the present invention, substitution reaction in the step (1)
Solvent is preferably acetonitrile, and in a specific embodiment of the present invention, it is preferable to use steaming acetonitrile again, the temperature of the substitution reaction is preferred
For room temperature, the time is preferably 8h；The substitution reaction preferably carries out under nitrogen protection.In the present invention, the tool of above-mentioned raw materials
Body feed way is preferred are as follows: under nitrogen protection, by (2- hydroxyethyl) ether of quinhydrones two and triphenylphosphine dissolved in steaming acetonitrile again
In, it activates at room temperature 15 minutes, the acetonitrile solution of carbon tetrabromide is then added under ice bath, adds, is opened after adding in 5 minutes
Begin to calculate the substitution reaction time.
After the completion of the substitution reaction of the step (1), after the present invention is it is also preferable to include the substitution reaction liquid is carried out
Reason, the post-processing preferably include following steps:
Ice water is added into the substitution reaction liquid, obtains crystal, is successively filtered, washs, recrystallizes and does later
It is dry, obtain intermediate product A solid.
In the present invention, the volume ratio of the substitution reaction liquid and ice water is preferably 3:2.In the present invention, the washing
Preferably include the once washing successively carried out and secondary washing, the once washing is preferably the mixing of methanol and water with detergent
Liquid, the volume ratio of methanol and water is preferably 3:2 in the mixed liquor；The secondary washing is preferably petroleum ether with detergent.?
In the present invention, the recrystallization is preferably methanol with solvent；The drying is preferably dried in vacuo.
In the present invention, the catalyst in the step (2) is preferably boron trifluoride diethyl ether, the compound A, poly
The molar ratio of formaldehyde and catalyst is preferably 1:3:1.In the present invention, the annulation solvent in the step (2) is preferred
For 1,2- dichloroethanes, the temperature of the annulation is preferably room temperature, and the time is preferably 3h；The annulation is preferably in nitrogen
It is carried out under gas shielded；Before carrying out annulation, the present invention preferably grinds the paraformaldehyde.In the present invention, on
The feed way for stating raw material is preferred are as follows: compound A is dissolved in 1,2- dichloroethanes, after grinding is added under nitrogen protection
Paraformaldehyde activates 30 minutes at room temperature；Boron trifluoride diethyl ether is added dropwise under ice bath, removes ice bath, carries out annulation, this
Since invention calculate the cyclic reaction time removing after ice bath.
After the completion of the annulation of the step (2), the present invention further preferably includes after carrying out to the annulation liquid
Reason, the post-processing preferably include following steps:
Into the annulation liquid plus reaction is quenched water, is successively extracted, dried, be concentrated and purified later, obtained
To intermediate product B solid.
In the present invention, the extraction is preferably saturated salt solution with reagent；The present invention, which preferably passes through, is added desiccant
Reaction solution extracted is dried in mode, and the desiccant is preferably anhydrous sodium sulfate；In the present invention, the concentration is excellent
It is selected as being concentrated under reduced pressure, the purifying is preferably column chromatography separating purification, and the mobile phase of the pillar layer separation is preferably petroleum ether
With the mixed liquor of methylene chloride, the volume ratio of the petroleum ether and methylene chloride is preferably 1:2.
In the present invention, the molar ratio of the intermediate product B in the step (3) and trimethylamine is preferably 0.13:5.1；Institute
It states the substitution reaction in step (3) preferably to carry out under nitrogen protection, the temperature of the substitution reaction is preferably 85 DEG C, and the time is excellent
It is selected as 12~for 24 hours；The substitution reaction is preferably ethyl alcohol with solvent.In the present invention, the feed way of above-mentioned raw materials is preferred are as follows:
Intermediate product B is dissolved in ethyl alcohol, under nitrogen protection, the ethanol solution of trimethylamine is added dropwise, carries out substitution reaction.
After the completion of the substitution reaction of the step (3), the present invention further preferably includes the post-processing to the substitution reaction liquid,
The post-processing preferably includes following steps:
The substitution reaction liquid is successively distilled, extracted and is concentrated, cation seperation column [5] aromatic hydrocarbon solid is obtained.
In the present invention, the mode of the distillation is preferably evaporated under reduced pressure；The concrete operations of the extraction are preferred are as follows: will steam
Solid after evaporating is soluble in water, using chloroform extraction, collects water layer；The number of the extraction is preferably 3 times.In the present invention
In, the mode of the concentration is preferably concentrated under reduced pressure.
In the present invention, the preparation process of cation seperation column [5] aromatic hydrocarbons is as shown in formula a:
The present invention is modified zeolite using cation seperation column [5] aromatic hydrocarbons, makes cation seperation column [5] by charge interaction
Aromatic hydrocarbons is carried on zeolite surface and interlayer so that zeolite have more positive electricity active sites, can equilibrium zeolite due to same lattice
Metathesis generates negative electricity structure, and increases ion exchange site.
The present invention provides the preparation methods of the aromatic modified zeolite adsorbent material of above-mentioned cation seperation column [5], including following step
It is rapid:
Zeolite and cation seperation column [5] arene solution are mixed, successively shaken, washed and is dried, obtain cation seperation column
[5] aromatic modified zeolite adsorbent material.
The present invention preferably successively washs the zeolite before mixing zeolite and cation seperation column [5] arene solution
And drying.In the present invention, the washing is preferably water with detergent；The present invention can be removed miscellaneous on zeolite by washing
Matter.In the present invention, the temperature of the drying is preferably 50 DEG C；The present invention does not have special requirement to the time of the drying,
It can be by the Zeolite dehydration after washing to constant weight.
In the present invention, the mass concentration of cation seperation column [5] arene solution is preferably 0.5~20g/L, more preferably
4~15g/L, most preferably 8g/L；The solvent of cation seperation column [5] arene solution is preferably water.In the present invention, the boiling
The quality of stone and the volume ratio of cation seperation column [5] arene solution are preferably 0.5g:10mL.
The present invention does not have special requirement to the mixed mode, uses hybrid mode well known to those skilled in the art
, specifically such as it is stirred；In the present invention, the time of the concussion be preferably 5~for 24 hours；In the present invention, described to wash
Washing with detergent is preferably water, and the number of the washing is preferably 5~10 times.In the present invention, the temperature of the drying is preferred
It is 40~200 DEG C, preferably 50 DEG C；The present invention does not have special requirement to the time of the drying, by Zeolite dehydration to constant weight
?.
The present invention provides the aromatic modified zeolite adsorbent materials of above-mentioned cation seperation column [5] in absorption organic anionic dyes
Application.The present invention does not have particular/special requirement to the type of the organic anionic dyes, is specifically as follows methyl orange, bromine cresols
Purple, orange N, orange V and fluorescein sodium etc..
In the present invention, when the absorption dosage of the aromatic modified zeolite adsorbent material of cation seperation column [5] be preferably 3~
20g/L, more preferably 8g/L；The mass concentration of organic anionic dyes is preferably 20~300mg/L when the absorption, more preferably
For 100~200mg/L；The pH value of the organic anionic dyes is preferably 2~12, and more preferably 4~10.In the present invention,
The time of the absorption is preferably 10~960min, more preferably 60~840min, most preferably 240~720min；The suction
Attached temperature is preferably room temperature.
Below with reference to embodiment to the aromatic modified zeolite adsorbent material of cation seperation column provided by the invention [5] and its preparation side
Method and application are described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
The preparation of cation seperation column [5] aromatic hydrocarbons:
(1) under nitrogen protection, by quinhydrones two (2- hydroxyethyl) ether (1.98g, 10mmol) and triphenylphosphine (6.30g,
24mmol) 40mL is dissolved in steam in acetonitrile again, at room temperature activate 15 minutes, under ice bath be added carbon tetrabromide (7.96g,
Acetonitrile solution (20mL) 24mmol), add in 5 minutes, reacts at room temperature 8 hours, and TLC is shown after the reaction was completed, is obtained
Between product A；It is slowly added to 40mL ice water into reaction solution, obtains a large amount of white crystals, filtering uses first to remove insoluble matter
Alcohol and water mixed liquid (3:2v/v) wash white solid, then remove the complete triphenylphosphine of unreacted with petroleum ether, use first
Alcohol is recrystallized, and vacuum drying obtains white intermediate product A solid；
(2) intermediate product A (0.65g, 2.0mmol) is dissolved in 1, the 2- dichloroethanes of 25mL, is added under nitrogen protection
Paraformaldehyde (0.18g, 6.0mmol) after grinding activates 30 minutes at room temperature；Boron trifluoride diethyl ether is added dropwise under ice bath
(0.26mL, 2.0mmol) removes ice bath, reacts 3 hours at room temperature, obtains bottle green reaction solution, and TLC display has been reacted
Cheng Hou obtains intermediate product B；Into reaction solution plus reaction is quenched in water, extracts (3 × 8mL) using saturated salt solution, use is anhydrous
Sodium sulphate is dry, is concentrated under reduced pressure, with column chromatography separating purification (petroleum ether/methylene chloride=1:2), obtains white intermediate product B
Solid, yield 47%；
(3) intermediate product B (0.21g, 0.13mmol) is dissolved in 30mL ethyl alcohol, under nitrogen protection, is added dropwise three
The ethanol solution (33%, 1.52mL, 5.1mmol) of methylamine is refluxed overnight at 85 DEG C, and TLC is shown after the reaction was completed, obtain sun from
Sub- column [5] aromatic hydrocarbons；Reaction solution is evaporated under reduced pressure, excess of solvent is removed, obtained solid is dissolved in 15mL deionized water,
With chloroform extraction (3 × 20mL), collect water layer, be concentrated under reduced pressure colorless and transparent cation seperation column [5] aromatic hydrocarbon solid, yield are
95%.
Embodiment 2
Zeolite (abbreviation ZE) is rinsed with water completely, 50 DEG C drying to constant weight, is added in 1g zeolite (30 mesh of partial size)
Cation seperation column [5] aromatic hydrocarbons (referred to as WPA5) solution of 10mL 10/L vibrates 24 hours, at room temperature after being cleaned zeolite with water
Drying to constant weight at 50 DEG C, obtains the aromatic modified zeolite adsorbent material (abbreviation WPA5/ZE) of cation seperation column [5].
SEM scanning electricity is carried out to cation seperation column [5] aromatic hydrocarbons, zeolite and the aromatic modified zeolite adsorbent material of cation seperation column [5]
Mirror analysis, gained microscopic appearance figure as shown in Figure 1, wherein (a) be cation seperation column [5] aromatic hydrocarbons SEM scheme, (b) be zeolite SEM
Figure (c) is schemed for the SEM of cation seperation column [5] aromatic modified zeolite adsorbent material.By in Fig. 1 it is found that WPA5 have irregular lines
Planar structure, zeolite then has non-uniform laminated structure, and the slot line between lamella is high-visible, and WPA5/ZE
The irregular spherical structure of volume increase is shown, and gully possessed by script zeolite is also filled.WPA5/ZE and WPA5 and
The size and shape of zeolite have larger difference, and which demonstrate the formation of the aromatic modified zeolite adsorbent material of cation seperation column [5].
The infrared suction of FTIR is carried out to cation seperation column [5] aromatic hydrocarbons, zeolite and the aromatic modified zeolite adsorbent material of cation seperation column [5]
Spectrum analysis is received, gained infrared absorpting light spectra is as shown in Figure 2.As seen from Figure 2,474cm-1Place is that the bending of Si-O key is shaken
It is dynamic, 539.42cm-1The stretching vibration of the expression Si-O-Al at place.In 794.46cm-1The absorption peak at place shows Si-OH in zeolite
The bending vibration of upper-OH, in 1098.84cm-1The absorption of vibrations at place shows the stretching vibration of zeolite structured middle Si-O-.?
3333.87cm-1Place observed the characteristic peak of-OH, 3619.86cm-1What the absorption peak expression at place was generated in conjunction with Si by-OH
Stretching vibration.In addition, 1209.84cm in the infrared absorption spectrum of WPA5-1The peak at place is the stretching vibration of C-N key.1404cm-1
The peak value at place corresponds to CH3-N+Bending vibration, and 1484.36cm-1Peak value expression-the CH at place2-N+The scissoring vibration of key.
CH in WPA53-N+With-CH2-N+Vibration can be found in the infrared absorption peak of modified zeolite adsorbing material, and in zeolite not
Absorption peak in the range is deposited, this shows that the aromatic modified zeolite adsorbent material of cation seperation column [5] is successfully prepared.
X-ray diffraction is carried out to cation seperation column [5] aromatic hydrocarbons, zeolite and the aromatic modified zeolite adsorbent material of cation seperation column [5]
Analysis, gained XRD spectrum are as shown in Figure 3.As seen from Figure 3, WPA5 has amorphous structure.And zeolite 12.36 °,
20.85 °, 21.97 °, 23.59 °, 24.86 °, 26.62 °, 27.65 °, 36.07 °, 36.52 °, 39.45 °, 50.15 ° and 59.93 °
Place produces main crystal diffraction peak.Notable feature of the zeolite at 27.65 ° and 36.52 ° is not observed in WPA5/ZE
Peak, and the phenomenon that all diffraction maximums of zeolite show decrease in WPA5/ZE.It is therefore shown that having between WPA5 and zeolite
There is stronger interaction.
Thermogravimetric analysis is carried out to cation seperation column [5] aromatic hydrocarbons, zeolite and the aromatic modified zeolite adsorbent material of cation seperation column [5],
Gained TG curve is as shown in Figure 4.A small amount of combination water and trip when as seen from Figure 4, from room temperature to 290 DEG C, in WPA5
It is constantly lost from water, which is 11.84wt%.Heating within the scope of 300~390 DEG C leads to the degradation of WPA5
(64.88wt%), the stage are main weight loss.The weightlessness (28.49wt%) occurred within the scope of 390~780 DEG C is taken off
The decomposition of WPA5 is shown.For zeolite, entire heating process has little effect (4.05%) to weight loss.And
The total weight loss of WPA5/ZE is 8.89wt%, illustrates that the aromatic modified zeolite adsorbent material of cation seperation column [5] has good heat
Stability.It is worth noting that, the total weight loss of WPA5/ZE is much smaller than WPA5, showing can after WPA5 is loaded on zeolite
To improve the thermal stability of WPA5.
Embodiment 3
The zeolite of different-grain diameter size is divided into ten groups using standard sub-sieve, respectively 10 mesh, 20 mesh, 30 mesh, 40 mesh,
50 mesh, 60 mesh, 70 mesh, 80 mesh, 90 mesh and 100 mesh.Every group of zeolite takes 1g, respectively by cation seperation column [5] virtue of 10mL 10g/L
Hydrocarbon solution, which is added to, to be mixed and is vibrated in every group of zeolite 24 hours, removes supernatant and with milli-Q water, finally by zeolite in
It dries at 50 DEG C to constant weight, obtains the aromatic modified zeolite adsorbent material of cation seperation column [5].
Then 25mL is added in the conical flask of 50mL tool plug in the zeolite and WPA5/ZE for weighing 0.5g different-grain diameter respectively
Methyl orange (MO) solution of 100mg/L measures ultra-violet absorption spectrum after vibrating 12h at room temperature, then bent by the standard of MO
Line determines the concentration variation of absorption front and back MO.
WPA5/ZE indicates the adsorbance (qe) and removal rate (R) of MO with Formulas I, Formula II respectively:
In Formulas I, C0Indicate the initial concentration of MO in solution, mg/L；
CeIndicate the concentration of MO when adsorption equilibrium, mgL-1；
V indicates the volume of MO, L；
W indicates the quality of zeolite, g；
In Formula II, C0Indicate the initial concentration of MO in solution, mg/L；
CeIndicate the concentration of MO when adsorption equilibrium, mgL-1。
The zeolite and WPA5/ZE of different-grain diameter are as shown in Figure 5 to the removal rate of MO.As shown in Figure 5, removal of the zeolite to MO
Rate is very limited, and average removal rate is about 4%, and is greatly improved with the modified zeolite of WPA5 to the removal rate of MO.This be by
In the surface and hole that WPA5 loads to zeolite by charge interaction, so that zeolite has more positive electricity active sites,
This is highly beneficial to removal organic anionic dyes MO.When partial size is reduced to 30 mesh from 10 mesh, removal rate of the WPA5/ZE to MO
It is continuously improved, removal rate reaches 85% when 30 mesh.As partial size continues to reduce, WPA5/ZE gradually decreases the removal rate of MO.Boiling
The reduction of stone particle increases the specific surface area of zeolite, this for more WPA5 molecules be integrated on zeolite provide more from
Son exchange site.But continue to reduce with partial size, space steric effect is also enhancing, and is unfavorable for the knot of WPA5 and zeolite surface
It closes, therefore the removal rate of MO reduces.
Embodiment 4
Prepare the WPA5 solution of different solubility, concentration range be 0.5 to 20g/L (respectively 0.5,1,1.5,2,2.5,3,
3.5,4,4.5,5,5.5,6,6.5,7,7.5,8,8.5,9,9.5,10,12,14,16,18,20g/L).With various concentration
WPA5 is modified that (wherein the quality of the zeolite liquid volume ratio molten with cation seperation column [5] aromatic hydrocarbons is to zeolite (partial size be 30 mesh)
0.5g:10mL), it is then cleaned with ultrapure water and is dried at 50 DEG C to constant weight, obtained the aromatic modified zeolite of cation seperation column [5] and inhale
Enclosure material.
Zeolite adsorbent material of the 0.5g after the WPA5 solution modification of various concentration is weighed respectively in the taper of 50mL tool plug
In bottle, methyl orange (MO) solution of 25mL 100mg/L is then added, measures ultra-violet absorption spectrum after vibrating 12h at room temperature,
Then the concentration variation of absorption front and back MO is determined by the standard curve of MO.
WPA5/ZE is calculated to the removal rate (R) of MO according to the method for embodiment 3, and acquired results are as shown in Figure 6.It can by Fig. 6
Know, zeolite is 4.4% to the removal rate of MO, and the zeolite after 0.5g/L WPA5 solution modification is 16.2% to the removal rate of MO.
With the increase of WPA5 concentration, WPA5/ZE is consequently increased the removal rate of MO.When WPA5 concentration reaches 3.5g/L, WPA5/
ZE reaches 81.4% to the removal rate of MO.With continuing to increase for WPA5 concentration, modified zeolite is slow to the removal rate of methyl orange
Increase, but this trend is not significant.When WPA5 concentration reaches 8g/L, WPA5/ZE reaches 84.6% to the removal rate of MO.
Embodiment 5
The 2 aromatic modified zeolite adsorbent material of gained cation seperation column [5] of 0.5g embodiment is weighed in the band plug conical flask of 50mL
In, and 25mL 100mg/L MO solution is added, then vibrate at room temperature the different time (10,20,30,40,50,60,90,
120、150、180、210、240、270、300、330、360、420、480、540、600、660、720、780、840、900、
960min).WPA5/ZE is calculated to the removal rate of MO according to the method in embodiment 3, and acquired results are as shown in Figure 7.
As seen from Figure 7, with the increase of adsorption time, removal rate increases therewith.The quick absorption portion of 0~150min
Dividing is due to internal diffusional resistance deficiency and a large amount of adsorption sites；When adsorption time reaches 150min, WPA5/ZE removes MO
Except rate is 75.45%；After 150min, the concentration of MO is gradually decreased, and the concentration gradient between solution and zeolite surface is caused to reduce.
At this point, diffusional resistance starts to increase, WPA5/ZE rises very slow to the removal rate of MO, and in 960min, removal rate reaches
81.51%.
Embodiment 6
Prepare MO solution (20,40,60,80,100,120,140,160,180,200,250,300mg/ of various concentration
L), 12 parts of embodiments, the 2 aromatic modified zeolite adsorbent material of gained cation seperation column [5] is weighed, every part of 0.5g is respectively placed in 50mL's
In band plug conical flask, and the MO solution of the above-mentioned various concentration of 25mL is added, measures UV absorption light after vibrating 12h at room temperature
Then spectrum determines the concentration variation of absorption front and back MO by the standard curve of MO.WPA5/ is calculated according to the method in embodiment 3
For ZE to the removal rate and adsorbance of MO, acquired results are as shown in Figure 8.
As shown in Figure 8, WPA5/ZE increases the adsorbance of MO with the increase of initial concentration, but removal rate is with first
The increase of beginning concentration and reduce, this is because the upper active site quantity of WPA5/ZE is constantly reduced with the progress of absorption.
Embodiment 7
The aqueous solution of different pH value (2~12) is mixed by HCl and NaOH, then prepares 100mg/L using the solution
MO solution, weighs 11 parts of embodiments, the 2 aromatic modified zeolite adsorbent material of gained cation seperation column [5], and every part of 0.5g is respectively placed in
In the band plug conical flask of 50mL, and the MO solution of the above-mentioned different pH value of 25mL is added, measures ultraviolet suction after vibrating 12h at room temperature
Spectrum is received, the concentration variation of absorption front and back MO is then determined by the standard curve of MO.It is calculated according to the method in embodiment 3
For WPA5/ZE to the removal rate of MO, acquired results are as shown in Figure 9.
As seen from Figure 9, in the range of pH2~12, " M " shape is presented to the removal rate of MO in WPA5/ZE, and in pH=
Reach maximum value when 5.Then, in pH=7, removal rate is minimized.However, removal rate increase is simultaneously as pH from 7 increases to 9
And reach local maximum in pH=9.As pH is continued growing, the quantity of the attracted by surfaces OH-ion of WPA5/ZE is more than
MO, this is also that WPA5/ZE has the main reason for low removal rate at a high ph.
The adsorption dynamics adsorption kinetics of the aromatic modified zeolite adsorbent material of 8 cation seperation column of embodiment [5]
Pseudo- first order kinetics and pseudo-second-order equation model are usually used in studying the adsorption mechanism of adsorbent material.Pseudo- first-level model
Have been widely used for the absorption behavior of research solid-liquid system.The linear forms of pseudo- First order dynamic model are as shown in formula III:
In formula III, qt: the adsorbance under time t, mgg-1；
qe: adsorbance when balance, mgg-1；
k1: pseudo- single order rate constant, min-1；
T: adsorption time, min.
The linear forms of pseudo-second-order equation model are as shown in formula IV:
In formula IV, qe: adsorbance when balance, mgg-1；
k2: pseudo- second order rate constant, min-1；
T: adsorption time, min.
Second order rate constants k2With equilibrium adsorption capacities qeIt can be obtained by the curve of t/qt-t.
The linear graph of pseudo- First order dynamic model and pseudo-second-order equation model when WPA/ZE absorption MO is as shown in Figure 10,
Related coefficient is calculated to be listed in Table 1 below.It can be by the linear regression coeffficient R of fitting a straight line come judgment experiment and theoretical fitting journey
Degree.In addition, the experiment adsorbance q obtained by comparing experimentE, expWith the theoretical adsorption capacity q for calculating acquisitionE, calBetween it is close
Degree is also used as judging one of reference of fitting degree of kinetic model.For pseudo- First order dynamic model,
Coefficient R2(0.966) lower, theoretical adsorption capacity qE, cal(2.08) with experiment adsorbance qE, exp(4.04) between exist compared with
Large deviation.And the R of pseudo-second-order equation model2It is worth the R that (0.996) is greater than pseudo- First order dynamic model2Value, pseudo-second-order equation
The theoretical adsorption capacity q of modelE, cal(3.88) close to experiment value.Therefore, pseudo-second-order equation model can better describe WPA5/
Absorption behavior of the ZE to MO.
The kinetic parameter of 1 WPA5/ZE of table absorption MO
The Adsorption thermodynamics of the aromatic modified zeolite adsorbent material of 9 cation seperation column of embodiment [5]
Study Adsorption thermodynamics between disclosing adsorbent-adsorbate interaction and adsorption system design for very
It is important.For Langmuir and Freundlich isotherm model since parameter is few, form is simple, intends solid-liquid system absorption behavior
Conjunction degree is higher and is used widely.
Langmuir adsorption isotherm equation is shown as a formula V:
The equation of Formula V linear change is as shown in Formula IV:
In Formula IV, Ce: the concentration of solute, mgL when adsorption equilibrium-1；
qe: adsorbance when balance, mgg-1；
qm: the maximal absorptive capacity of adsorbent, mgg-1；
KL: Langmuir coefficient, Lmg-1。
Separation factor or balance parameters are as shown in Formula VII:
In Formula VII, KL: Langmuir coefficient, Lmg-1；
C0: the initial concentration of MO, mg/L in solution；
If RL>1, isothermal shape be it is unfavorable, work as RL=1, then isothermal shape is linear, if 0<
RL < 1 item be it is suitable, RL=0 is then irreversible.
Freundlich isotherm model is the empirical equation of multi-molecular absorption, has certain versatility.It is the most frequently used
Tellurium determination formula as shown in Formula VIII:
qe=KFCe 1/nFormula VIII；
In Formula VIII, KF: Freundlich adsorption isotherm constant, L/g；
Ce: the concentration of solute, mgL when adsorption equilibrium-1。
The isothermal linear forms of Freundlich are as shown in Formula IX:
KF: Freundlich adsorption isotherm constant, L/g；
Ce: the concentration of solute, mgL when adsorption equilibrium-1。
Figure 11 is Langmuir the and Freundlich isotherm model curve that WPA/ZE adsorbs MO.Calculate phase relation ordered series of numbers
In table 2.
The thermodynamic parameter of 2 WPA5/zeolite of table absorption MO
As shown in Table 2, the related coefficient (0.98) of Langmuir model is greater than Freundlich model (0.968), explanation
Langmuir model can better describe absorption of the WPA/ZE to MO.
As seen from the above embodiment, cation seperation column [5] aromatic hydrocarbons successfully can be loaded to boiling by method provided by the invention
Shi Shang, the aromatic modified good thermal stability of zeolite adsorbent material of gained cation seperation column [5] are adsorbed for organic anionic dyes
When, 85% or more is up to the removal rate of dyestuff.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of aromatic modified zeolite adsorbent material of cation seperation column [5], which is characterized in that including zeolite and be carried on zeolite surface
With cation seperation column [5] aromatic hydrocarbons of interlayer；
Cation seperation column [5] aromatic hydrocarbons has structure shown in Formulas I:
2. the aromatic modified zeolite adsorbent material of cation seperation column [5] according to claim 1, which is characterized in that the zeolite
Partial size be 1~100 mesh.
3. the preparation method of any one of the claim 1~2 aromatic modified zeolite adsorbent material of cation seperation column [5], feature
It is, comprising the following steps:
Zeolite and cation seperation column [5] arene solution are mixed, successively shaken, washed and is dried, cation seperation column [5] virtue is obtained
Hydrocarbon modified zeolite adsorbing material.
4. preparation method according to claim 3, which is characterized in that the quality of cation seperation column [5] arene solution is dense
Degree is 0.5~20g/L.
5. preparation method according to claim 3 or 4, which is characterized in that the quality of the zeolite and cation seperation column [5] virtue
The volume ratio of hydrocarbon solution is 0.5~1g:10mL.
6. preparation method according to claim 3, which is characterized in that the time of the concussion be 5~for 24 hours.
7. preparation method according to claim 3, which is characterized in that the temperature of the drying is 40~200 DEG C.
8. the aromatic modified zeolite adsorbent material of cation seperation column described in claim 1~2 any one [5] or claim 3~7 times
The aromatic modified zeolite adsorbent material of cation seperation column [5] of a preparation method of anticipating preparation answering in absorption organic anionic dyes
With.
9. application according to claim 8, which is characterized in that the aromatic modified zeolite of cation seperation column [5] is inhaled when the absorption
The dosage of enclosure material is 3~20g/L；The mass concentration of organic anionic dyes is 20~300mg/L when the absorption；It is described to have
The pH value of machine anionic dye is 2~12.
10. application according to claim 8, which is characterized in that the time of the absorption is 10~960min.
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