CN106925225A - A kind of functional mesoporous adsorbent of molecular sieve of histidine and its application in the treatment of waste water - Google Patents
A kind of functional mesoporous adsorbent of molecular sieve of histidine and its application in the treatment of waste water Download PDFInfo
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Abstract
Application the present invention relates to a kind of functional mesoporous adsorbent of molecular sieve and its in the treatment of waste water.Specifically, the present invention relates to one kind with molecular sieve MCM 41 as matrix, with histidine as functional reagent, the functional mesoporous molecular sieve of histidine prepared by two step graftings, the histidine by the grafting on the surface of molecular sieve MCM 41, significantly improves the adsorption capacity of material heavy metal ion.The adsorbent preparation process is simple, low cost, good stability is a kind of very promising wastewater treatment material containing heavy metal ion.
Description
Technical field
The invention belongs to advanced composite material (ACM) technical field, and in particular to a kind of preparation of modified mesoporous molecular sieve adsorbent
Method and application process.
Background technology
With the fast development of human society, the living standard of people is stepped up, while the environmental problem of facing mankind
Also it is increasingly serious.Protect and improve the ecological environment, realize the sustainable development of human society, be that the whole mankind is urgent and arduousness is appointed
Business.And the fast development of modern industry causes the discharge capacity of industrial wastewater to sharply increase, water pollution is serious, and waste water treatment turns into
Significant problem urgently to be resolved hurrily.Waste water containing heavy metal ion be maximum to human health risk and to ecological environmental pollution most
One of serious industrial wastewater, they can be by empty gas and water, soil, especially by food chain, to the physical and mental health of the mankind
Bring serious harm.Therefore, heavy metal wastewater thereby how is effectively administered, has caused the extensive concern of countries in the world.
The difference in source and composition according to heavy metal wastewater thereby, its processing mode also difference.According to handling principle
Difference, the processing method of heavy metal wastewater thereby is commonly divided into Physical, chemical method, physical-chemical process and the major class of bioanalysis four.Its
In commonly use processing method have chemical precipitation method, exchanger resin method and absorption method etc..
In recent years, absorption method due to process is simple, low cost, it is efficient the advantages of, got in the process field of heavy metal wastewater thereby
More to be paid close attention to by people.It is adsorbent wherein to use activated carbon more.It is attempted to research and develop more cheap, more efficient suction at present
Attached dose is further improved adsorption efficiency and reduces cost to replace activated carbon.
Ordered meso-porous silicon oxide material has a regular adjustable pore passage structure, big specific surface area and adsorption capacity high,
It is a kind of preferable sorbing material.The modified organo-functional group of common mesopore molecular sieve includes NH2-、SH-And COOH-Deng them
Lone pair electrons can be provided, can be matched with heavy metal ions in wastewater.Modified mesopore molecular sieve passes through organic functions
The effect heavy metal ion such as complexing, ion exchange of group shows good adsorption effect, therefore how to mesopore molecular sieve
It is modified to improve the focus that the adsorption effect of heavy metal ion is this area research.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of process is simple, modified mesoporous molecular sieve absorption with low cost
The preparation method of agent, the novel absorption material being prepared using the method has energy of adsorption higher to the heavy metal in waste water
Power.
The purpose of the present invention is achieved through the following technical solutions：
There is provided a kind of histidine functional mesoporous adsorbent of molecular sieve first, its with molecular sieve MCM-41 as matrix, with histidine
It is functional reagent, by grafting obtained from grafting histidine on the surface of molecular sieve MCM-41；The adsorbent has
Following structural formula：
Wherein, MCM-41 represents Mesoporous silica MCM 41 type molecular sieve.
Further, the specific surface area of the functional mesoporous adsorbent of molecular sieve of described histidine is 653 m2 g-1, averagely
Pore size is 2.76nm, and pore volume is 0.45 m3 g-1。
Further, the preparation method of the functional mesoporous adsorbent of molecular sieve of the histidine is two step graftings, specifically
Step is：
（1）, by raw molecule sieve MCM-41 and 3- chloropropyl triethoxysilanes in mass ratio 1：1-3 is dissolved in drying solvent,
Pyroreaction 6-72 hours under atmosphere of inert gases；Through dry toluene, absolute ethyl alcohol after isolated solid crude product elder generation
Repeatedly washing, obtains raw material Cl-MCM-41 after vacuum drying；Described pyroreaction temperature is 50 ~ 180 DEG C, and described drying is molten
Agent is one or more in toluene, chlorobenzene, dimethylbenzene or dichloro-benzenes；
（2）, by step（1）The Cl-MCM-41 and L-Histidine in mass ratio 1 for obtaining：1-6 is dissolved in reaction dissolvent, reaction temperature
It is 20-100 DEG C to spend, after reacting 6-72 hours, isolated solid crude product；After deionized water washing, histidine function is obtained
Change mesoporous molecular sieve adsorbent；Described reaction dissolvent is ethylenediamine, triethylamine, isopropylamine or triethanolamine and water mixed solution
In one or more.
Step（1）Described in raw molecule sieve MCM-41 can be according to document（Chen C, Li H, Davis M E.
Studies on mesoporous materials：I.Synthesis and characterization of MCM-41
[J] .Microporous Materials, 1993,2 (1)：17–26）Methods described is synthesized.
Above-mentioned preparation method is more preferably following steps：
（1）76mL deionized waters and 8mL 2mol/L NaOH solutions are mixed, then to addition 1.6g template CTAB in solution,
Stir at room temperature to template CTAB and all dissolve；Then 7.6g tetraethyl orthosilicates are weighed, are added drop-wise in solution, at room temperature after
Continuous stirring reaction 1h；Reacted mixed liquor is placed in high-pressure hydrothermal reaction kettle, 100 DEG C are warming up to, stood at such a temperature
Crystallization 3 days；Then solid matter filtering, the washing to neutrality, re-dry that will be obtained；Finally dried sample is warming up to
550 DEG C, and 6h is calcined at such a temperature to remove template template, the solid product for obtaining as Mesoporous silica MCM 41；
（2）2.5g Mesoporous silica MCM 41s and the dry toluene of 150mL are mixed in anhydrous and oxygen-free bottle, logical nitrogen is then vacuumized
Gas；5mL 3- chloropropyl triethoxysilanes are slowly added dropwise under normal temperature in anhydrous and oxygen-free bottle, 100 DEG C are then warmed up to, at this
At a temperature of react 24h；Solid product is finally dried through filtering, and successively with dry toluene, absolute ethanol washing, obtains one
Product Cl-MCM-41 after step grafting；
（3）Weigh 8g histidines to be dissolved in the deionized water of 200mL, the solution is mixed with 2g Cl-MCM-41, then to mixed
Middle addition 8mL triethylamines in solution are closed, 35 DEG C is then heated to, at such a temperature stirring reaction 24h；Finally cross filter solid product
Thing, and wash with water, finally give the functional mesoporous adsorbent of molecular sieve of histidine.
Heavy metal ion of the above-mentioned functional mesoporous adsorbent of molecular sieve of histidine in wastewater treatment is used to adsorb waste water,
Such as can apply to waste water, steel and non-ferrous metal metallurgy waste water, mine wastewater and part the chemical industry enterprise of machining discharge
In the heavy metal ion adsorbed field of industry waste water；Heavy metal ion in the waste water is Cr3+、Co2+、Ni2+、Cu2+、Zn2+Or
Cd2+In one or more, it is preferable to above-mentioned ionic adsorption effect.
Further, the functional mesoporous adsorbent of molecular sieve dosage of histidine is 2g L-1, mixing speed is 150rpm,
Adsorption time is 10min, and adsorption temp is 25 DEG C.
Further, the pH of the waste water is controlled to 3-7；More preferably 5-6.
Further, the heavy metal ion initial concentration scope in described waste water is not higher than 150 mg L-1, it is preferable over
Not higher than 50 mg L-1。
The functional mesoporous adsorbent of molecular sieve of histidine prepared by the present invention, to the Cr in waste water3+、Co2+、Ni2+Deng a huge sum of money
Category ion has good suction-operated；Modified mesoporous molecular sieve adsorbent chemical stability is good, it is easy to separate, cost is low
Advantage, is a kind of very promising waste water sorbing material.
Brief description of the drawings
Fig. 1 is the FTIR infrared test spectrograms of MCM-41, Cl-MCM-41 and His-MCM-41 prepared by embodiment 2；
Fig. 2 is the nitrogen adsorption desorption curve figure of Cl-MCM-41 and His-MCM-41 prepared by embodiment 3.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Embodiment 1：The preparation of the functional mesoporous adsorbent of molecular sieve of histidine
（1）To addition 76mL deionized waters and 8mL NaOH (2M) solution in the 250mL there-necked flasks equipped with magnetic agitation rotor,
Again to 1.6g template CTAB are added in solution, stirred at room temperature to template under magnetic stirring apparatus effect and all dissolved.So
After weigh 7.6g tetraethyl orthosilicates, be slowly dropped in there-necked flask, stirring reaction 1h is continued at room temperature.By reacted mixing
Liquid is placed in the high-pressure hydrothermal reaction kettle of polytetrafluoroethylene (PTFE), is put into baking oven, is warming up to 100 DEG C, and crystallization 3 is stood at such a temperature
My god.Then solid matter filtering, the washing that will be obtained are to neutrality, then are put into baking oven and dry.Finally dried sample is put
To in resistance box, 550 DEG C are warming up to, and are calcined 6h at such a temperature to remove template.Resulting solid product is Jie
Porous materials MCM-41.
（2）To addition 2.5g Mesoporous silica MCM 41s in the 250mL anhydrous and oxygen-frees bottle equipped with magnetic agitation rotor, then measure
Then the dry toluene solutions of 150mL vacuumize logical nitrogen in triplicate in bottle.2.5mL 3- chlorine third is slowly added dropwise under normal temperature
Then ethyl triethoxy silicane alkane be warmed up to 100 DEG C in anhydrous and oxygen-free bottle, and 24h is reacted at such a temperature.Solid product passes through
Filter, and it is successively multiple with dry toluene, absolute ethanol washing, drying in drying box is finally put into, after obtaining a step grafting
Product Cl-MCM-41, yield is 42%.
（3）2g Cl-MCM-41 are taken in the there-necked flask of the 500mL equipped with magnetic agitation rotor.Weigh the dissolving of 2g histidines
In the deionization of 200mL, it is subsequently poured into there-necked flask.Again to 8mL triethylamines are added in there-necked flask, 35 DEG C are then heated to,
Stirring reaction 24h at such a temperature.Solid product is finally filtered, and with substantial amounts of water washing repeatedly, finally gives histidine work(
Mesoporous molecular sieve adsorbent can be changed, yield is 26%.
The functional mesoporous adsorbent of molecular sieve specific surface area of gained histidine is 483 m2 g-1, mean pore size is
2.55nm, pore volume is 0.40 m3 g-1。
Embodiment 2：The preparation of the functional mesoporous adsorbent of molecular sieve of histidine
（1）With embodiment 1.
（2）To addition 2.5g Mesoporous silica MCM 41s in the 250mL anhydrous and oxygen-frees bottle equipped with magnetic agitation rotor, then measure
Then the dry toluene solutions of 150mL vacuumize logical nitrogen in triplicate in bottle.5mL 3- chloropropyls are slowly added dropwise under normal temperature
Then triethoxysilane is warmed up to 100 DEG C in anhydrous and oxygen-free bottle, and 24h is reacted at such a temperature.Solid product through filtering,
And it is successively multiple with dry toluene, absolute ethanol washing, drying in drying box is finally put into, obtain the product after a step grafting
Cl-MCM-41, yield is 88%.
（3）2g Cl-MCM-41 are taken in the there-necked flask of the 500mL equipped with magnetic agitation rotor.Weigh the dissolving of 8g histidines
In the deionized water of 200mL, it is subsequently poured into there-necked flask.Again to 8mL triethylamines are added in there-necked flask, 35 are then heated to
DEG C, stirring reaction 24h at such a temperature.Solid product is finally filtered, and with substantial amounts of water washing repeatedly, finally gives histidine
Functional mesoporous adsorbent of molecular sieve, yield is 93%.
The functional mesoporous adsorbent of molecular sieve specific surface area of gained histidine is 653 m2 g-1, mean pore size is
2.76nm, pore volume is 0.45 m3 g-1.The XRD x ray diffration pattern xs of gained MCM-41, Cl-MCM-41 and His-MCM-41 are in 2 θ
=1.1 ° or so have a strong peak, there is three weak diffraction maximums between 2 θ=3 ° ~ 5 °, indicate modified material and still remain with Jie
The two-dimentional hexagonal structure that porous molecular sieve material has, with the degree of order higher.Gained MCM-41, Cl-MCM-41 and His-
The FTIR infrared tests spectrogram of MCM-41 as shown in Figure 1, shows that each product smoothly synthesizes.
Embodiment 3：The preparation of the functional mesoporous adsorbent of molecular sieve of histidine
（1）With embodiment 1.
（2）To addition 2.5g Mesoporous silica MCM 41s in the 250mL anhydrous and oxygen-frees bottle equipped with magnetic agitation rotor, then measure
Then the dry toluene solutions of 150mL vacuumize logical nitrogen in triplicate in bottle.7.5mL 3- chlorine third is slowly added dropwise under normal temperature
Then ethyl triethoxy silicane alkane be warmed up to 100 DEG C in anhydrous and oxygen-free bottle, and 24h is reacted at such a temperature.Solid product passes through
Filter, and it is successively multiple with dry toluene, absolute ethanol washing, drying in drying box is finally put into, after obtaining a step grafting
Product Cl-MCM-41, yield is 87%.
（3）2g Cl-MCM-41 are taken in the there-necked flask of the 500mL equipped with magnetic agitation rotor.Weigh 12g histidines molten
Solution is subsequently poured into there-necked flask in the deionized water of 200mL.Again to 8mL triethylamines are added in there-necked flask, 35 are then heated to
DEG C, stirring reaction 24h at such a temperature.Solid product is finally filtered, and with substantial amounts of water washing repeatedly, finally gives histidine
Functional mesoporous adsorbent of molecular sieve, yield is 90%.
The functional mesoporous adsorbent of molecular sieve specific surface area of gained histidine is 644 m2 g-1, mean pore size is
2.75nm, pore volume is 0.43 m3 g-1.The nitrogen adsorption desorption curve figure of gained Cl-MCM-41 and His-MCM-41 such as accompanying drawing 2
It is shown.The equilibrium adsorption capacity of His-MCM-41 materials is reduced more before modified, show reference area reduce, illustrate organo-functional group into
Work(has been grafted onto on the surface of mesoporous material.
Embodiment 4：The preparation of the functional mesoporous adsorbent of molecular sieve of histidine
（1）With embodiment 1.
（2）To addition 2.5g Mesoporous silica MCM 41s in the 250mL anhydrous and oxygen-frees bottle equipped with magnetic agitation rotor, then measure
Then the dry toluene solutions of 150mL vacuumize logical nitrogen in triplicate in bottle.5mL 3- chloropropyls are slowly added dropwise under normal temperature
Then triethoxysilane is warmed up to 50 DEG C in anhydrous and oxygen-free bottle, and 24h is reacted at such a temperature.Solid product through filtering, and
Absolute ethanol washing with dry toluene, repeatedly, be finally put into drying in drying box, obtain the product after a step grafting successively
Cl-MCM-41, yield is 52%.
（3）2g Cl-MCM-41 are taken in the there-necked flask of the 500mL equipped with magnetic agitation rotor.Weigh the dissolving of 8g histidines
In the deionized water of 200mL, it is subsequently poured into there-necked flask.Again to 8mL triethylamines are added in there-necked flask, 20 are then heated to
DEG C, stirring reaction 24h at such a temperature.Solid product is finally filtered, and with substantial amounts of water washing repeatedly, finally gives histidine
Functional mesoporous adsorbent of molecular sieve, yield is 67%.
The functional mesoporous adsorbent of molecular sieve specific surface area of gained histidine is 620 m2 g-1, mean pore size is
2.73nm, pore volume is 0.44 m3 g-1。
Embodiment 5：The preparation of the functional mesoporous adsorbent of molecular sieve of histidine
（1）With embodiment 1.
（2）To addition 2.5g Mesoporous silica MCM 41s in the 250mL anhydrous and oxygen-frees bottle equipped with magnetic agitation rotor, then measure
Then the dry toluene solutions of 150mL vacuumize logical nitrogen in triplicate in bottle.5mL 3- chloropropyls are slowly added dropwise under normal temperature
Then triethoxysilane is warmed up to 100 DEG C in anhydrous and oxygen-free bottle, and 6h is reacted at such a temperature.Solid product through filtering, and
Absolute ethanol washing with dry toluene, repeatedly, be finally put into drying in drying box, obtain the product after a step grafting successively
Cl-MCM-41, yield is 61%.
（3）2g Cl-MCM-41 are taken in the there-necked flask of the 500mL equipped with magnetic agitation rotor.Weigh the dissolving of 8g histidines
In the deionized water of 200mL, it is subsequently poured into there-necked flask.Again to 8mL triethylamines are added in there-necked flask, 35 are then heated to
DEG C, stirring reaction 6h at such a temperature.Solid product is finally filtered, and with substantial amounts of water washing repeatedly, finally gives histidine
Functional mesoporous adsorbent of molecular sieve, yield is 63%.
The functional mesoporous adsorbent of molecular sieve specific surface area of gained histidine is 589 m2 g-1, mean pore size is
2.68nm, pore volume is 0.41 m3 g-1。
Embodiment 6：The preparation of the functional mesoporous adsorbent of molecular sieve of histidine
（1）With embodiment 1.
（2）To addition 2.5g Mesoporous silica MCM 41s in the 250mL anhydrous and oxygen-frees bottle equipped with magnetic agitation rotor, then measure
Then the dry toluene solutions of 150mL vacuumize logical nitrogen in triplicate in bottle.5mL 3- chloropropyls are slowly added dropwise under normal temperature
Then triethoxysilane is warmed up to 100 DEG C in anhydrous and oxygen-free bottle, and 72h is reacted at such a temperature.Solid product through filtering,
And it is successively multiple with dry toluene, absolute ethanol washing, drying in drying box is finally put into, obtain the product after a step grafting
Cl-MCM-41, yield is 85%.
（3）2g Cl-MCM-41 are taken in the there-necked flask of the 500mL equipped with magnetic agitation rotor.Weigh the dissolving of 8g histidines
In the deionized water of 200mL, it is subsequently poured into there-necked flask.Again to 8mL triethylamines are added in there-necked flask, 35 are then heated to
DEG C, stirring reaction 72h at such a temperature.Solid product is finally filtered, and with substantial amounts of water washing repeatedly, finally gives histidine
Functional mesoporous adsorbent of molecular sieve, yield is 93%.
The functional mesoporous adsorbent of molecular sieve specific surface area of gained histidine is 651 m2 g-1, mean pore size is
2.76nm, pore volume is 0.43 m3 g-1。
Embodiment 7：The preparation of the functional mesoporous adsorbent of molecular sieve of histidine
（1）With embodiment 1.
（2）To addition 2.5g Mesoporous silica MCM 41s in the 250mL anhydrous and oxygen-frees bottle equipped with magnetic agitation rotor, then measure
Then the dry chlorobenzene solutions of 150mL vacuumize logical nitrogen in triplicate in bottle.5mL 3- chloropropyls are slowly added dropwise under normal temperature
Then triethoxysilane is warmed up to 100 DEG C in anhydrous and oxygen-free bottle, and 24h is reacted at such a temperature.Solid product through filtering,
And it is successively multiple with dry toluene, absolute ethanol washing, drying in drying box is finally put into, obtain the product after a step grafting
Cl-MCM-41, yield is 82%.
（3）2g Cl-MCM-41 are taken in the there-necked flask of the 500mL equipped with magnetic agitation rotor.Weigh the dissolving of 8g histidines
In the deionized water of 200mL, it is subsequently poured into there-necked flask.Again to 8mL ethylenediamines are added in there-necked flask, 35 are then heated to
DEG C, stirring reaction 24h at such a temperature.Solid product is finally filtered, and with substantial amounts of water washing repeatedly, finally gives histidine
Functional mesoporous adsorbent of molecular sieve, yield is 89%.
The functional mesoporous adsorbent of molecular sieve specific surface area of gained histidine is 648 m2 g-1, mean pore size is
2.75nm, pore volume is 0.44 m3 g-1。
Embodiment 8：The preparation of the functional mesoporous adsorbent of molecular sieve of histidine
（1）With embodiment 1.
（2）To addition 2.5g Mesoporous silica MCM 41s in the 250mL anhydrous and oxygen-frees bottle equipped with magnetic agitation rotor, then measure
Then the dry xylene solutions of 150mL vacuumize logical nitrogen in triplicate in bottle.5mL 3- chlorine third is slowly added dropwise under normal temperature
Then ethyl triethoxy silicane alkane be warmed up to 100 DEG C in anhydrous and oxygen-free bottle, and 24h is reacted at such a temperature.Solid product passes through
Filter, and it is successively multiple with dry toluene, absolute ethanol washing, drying in drying box is finally put into, after obtaining a step grafting
Product Cl-MCM-41, yield is 80%.
（3）2g Cl-MCM-41 are taken in the there-necked flask of the 500mL equipped with magnetic agitation rotor.Weigh the dissolving of 8g histidines
In the deionized water of 200mL, it is subsequently poured into there-necked flask.Again to 8mL isopropylamines are added in there-necked flask, 35 are then heated to
DEG C, stirring reaction 24h at such a temperature.Solid product is finally filtered, and with substantial amounts of water washing repeatedly, finally gives histidine
Functional mesoporous adsorbent of molecular sieve, yield is 87%.
The functional mesoporous adsorbent of molecular sieve specific surface area of gained histidine is 648 m2 g-1, mean pore size is
2.73nm, pore volume is 0.46 m3 g-1。
Embodiment 9：The preparation of the functional mesoporous adsorbent of molecular sieve of histidine
（1）With embodiment 1.
（2）To addition 2.5g Mesoporous silica MCM 41s in the 250mL anhydrous and oxygen-frees bottle equipped with magnetic agitation rotor, then measure
Then the dry dichlorobenzene solutions of 150mL vacuumize logical nitrogen in triplicate in bottle.5mL 3- chlorine third is slowly added dropwise under normal temperature
Then ethyl triethoxy silicane alkane be warmed up to 100 DEG C in anhydrous and oxygen-free bottle, and 24h is reacted at such a temperature.Solid product passes through
Filter, and it is successively multiple with dry toluene, absolute ethanol washing, drying in drying box is finally put into, after obtaining a step grafting
Product Cl-MCM-41, yield is 81%.
（3）2g Cl-MCM-41 are taken in the there-necked flask of the 500mL equipped with magnetic agitation rotor.Weigh the dissolving of 8g histidines
In the deionization of 200mL, it is subsequently poured into there-necked flask.Again to 8mL triethanolamines are added in there-necked flask, 35 are then heated to
DEG C, stirring reaction 24h at such a temperature.Solid product is finally filtered, and with substantial amounts of water washing repeatedly, finally gives histidine
Functional mesoporous adsorbent of molecular sieve, yield is 85%.
The functional mesoporous adsorbent of molecular sieve specific surface area of gained histidine is 642 m2 g-1, mean pore size is
2.73nm, pore volume is 0.45 m3 g-1。
Embodiment 10：The preparation of the functional mesoporous adsorbent of molecular sieve of histidine
（1）With embodiment 1.
（2）To addition 2.5g Mesoporous silica MCM 41s in the 250mL anhydrous and oxygen-frees bottle equipped with magnetic agitation rotor, then measure
Then the dry dichlorobenzene solutions of 150mL vacuumize logical nitrogen in triplicate in bottle.5mL 3- chlorine third is slowly added dropwise under normal temperature
Then ethyl triethoxy silicane alkane be warmed up to 180 DEG C in anhydrous and oxygen-free bottle, and 24h is reacted at such a temperature.Solid product passes through
Filter, and it is successively multiple with dry toluene, absolute ethanol washing, drying in drying box is finally put into, after obtaining a step grafting
Product Cl-MCM-41, yield is 84%.
（3）2g Cl-MCM-41 are taken in the there-necked flask of the 500mL equipped with magnetic agitation rotor.Weigh the dissolving of 8g histidines
In the deionization of 200mL, it is subsequently poured into there-necked flask.Again to 8mL triethanolamines are added in there-necked flask, 100 are then heated to
DEG C, stirring reaction 24h at such a temperature.Solid product is finally filtered, and with substantial amounts of water washing repeatedly, finally gives histidine
Functional mesoporous adsorbent of molecular sieve, yield is 87%.
The functional mesoporous adsorbent of molecular sieve specific surface area of gained histidine is 649 m2 g-1, mean pore size is
2.74nm, pore volume is 0.45 m3 g-1。
Embodiment 11：The functional mesoporous adsorbent of molecular sieve absorption heavy metals ion test of histidine
Concentration is taken for 50mg L-1Heavy metal ion solution, it is 6 to adjust solution ph with watery hydrochloric acid and sodium hydroxide solution；Weigh
The functional mesoporous adsorbent of molecular sieve of histidine prepared by 0.02g examples 2 in the above-mentioned solution of 10mL, low whipping speed
It is 150 rpm, adsorption reaction is carried out under the conditions of 25 DEG C of temperature（Adsorption time 10min）.The functional mesoporous molecular sieve of histidine is inhaled
The adsorption rate of attached dose of heavy metal ion is as follows：
| Heavy metal ion | Cr3+ | Co2+ | Ni2+ | Cu2+ | Zn2+ | Cd2+ |
| Adsorption rate | 75.68% | 39.78% | 53.82% | 99.92% | 58.55% | 58.92% |
Embodiment 12：The functional mesoporous adsorbent of molecular sieve absorption heavy metals ion test of histidine
Concentration is taken for 150mg L-1Heavy metal ion solution, it is 6 to adjust solution ph with watery hydrochloric acid and sodium hydroxide solution；Claim
The functional mesoporous adsorbent of molecular sieve of histidine prepared by 0.02g examples 2 is taken in the above-mentioned solution of 10mL, in stirring speed
It is 150 rpm to spend, and adsorption reaction is carried out under the conditions of 25 DEG C of temperature（Adsorption time 10min）.The functional mesoporous molecular sieve of histidine
The adsorption rate of adsorbent heavy metal ion is as follows：
| Heavy metal ion | Cr3+ | Co2+ | Ni2+ | Cu2+ | Zn2+ | Cd2+ |
| Adsorption rate | 34.21% | 16.52% | 24.06% | 47.94% | 30.92% | 38.31% |
Embodiment 13：The functional mesoporous adsorbent of molecular sieve absorption heavy metals ion test of histidine
Concentration is taken for 10mg L-1Heavy metal ion solution, it is 6 to adjust solution ph with watery hydrochloric acid and sodium hydroxide solution；Weigh
The functional mesoporous adsorbent of molecular sieve of histidine prepared by 0.02g examples 2 in the above-mentioned solution of 10mL, low whipping speed
It is 150 rpm, adsorption reaction is carried out under the conditions of 25 DEG C of temperature（Adsorption time 10min）.The functional mesoporous molecular sieve of histidine is inhaled
The adsorption rate of attached dose of heavy metal ion is as follows：
| Heavy metal ion | Cr3+ | Co2+ | Ni2+ | Cu2+ | Zn2+ | Cd2+ |
| Adsorption rate | 98.79% | 70.13% | 66.26% | 99.99% | 98.12% | 96.58% |
Embodiment 14：The functional mesoporous adsorbent of molecular sieve absorption heavy metals ion test of histidine
Concentration is taken for 50mg L-1Heavy metal ion solution, it is 3 to adjust solution ph with watery hydrochloric acid and sodium hydroxide solution；Weigh
The functional mesoporous adsorbent of molecular sieve of histidine prepared by 0.02g examples 2 in the above-mentioned solution of 10mL, low whipping speed
It is 150 rpm, adsorption reaction is carried out under the conditions of 25 DEG C of temperature（Adsorption time 10min）.The functional mesoporous molecular sieve of histidine is inhaled
The adsorption rate of attached dose of heavy metal ion is as follows：
| Heavy metal ion | Cr3+ | Co2+ | Ni2+ | Cu2+ | Zn2+ | Cd2+ |
| Adsorption rate | 7.29% | 3.18% | 5.14% | 52.48% | 19.47% | 2.53% |
Embodiment 15：The functional mesoporous adsorbent of molecular sieve absorption heavy metals ion test of histidine
Concentration is taken for 50mg L-1Heavy metal ion solution, it is 7 to adjust solution ph with watery hydrochloric acid and sodium hydroxide solution；Weigh
The functional mesoporous adsorbent of molecular sieve of histidine prepared by 0.02g examples 2 in the above-mentioned solution of 10mL, low whipping speed
It is 150 rpm, adsorption reaction is carried out under the conditions of 25 DEG C of temperature（Adsorption time 10min）.The functional mesoporous molecular sieve of histidine is inhaled
The adsorption rate of attached dose of heavy metal ion is as follows：
| Heavy metal ion | Cr3+ | Co2+ | Ni2+ | Cu2+ | Zn2+ | Cd2+ |
| Adsorption rate | 70.79% | 39.28% | 50.86% | 99.90% | 57.95% | 57.71% |
Embodiment 16：The functional mesoporous adsorbent of molecular sieve absorption heavy metals ion test of histidine
Concentration is taken for 50mg L-1Heavy metal ion solution, it is 6 to adjust solution ph with watery hydrochloric acid and sodium hydroxide solution；Weigh
The functional mesoporous adsorbent of molecular sieve of histidine prepared by 0.02g examples 2 in the above-mentioned solution of 10mL, low whipping speed
It is 150 rpm, adsorption reaction is carried out under the conditions of 25 DEG C of temperature（Adsorption time 5min）.The functional mesoporous molecular sieve adsorption of histidine
The adsorption rate of agent heavy metal ion is as follows：
| Heavy metal ion | Cr3+ | Co2+ | Ni2+ | Cu2+ | Zn2+ | Cd2+ |
| Adsorption rate | 74.64% | 39.63% | 52.60% | 99.87% | 57.92% | 58.10% |
Embodiment 17：The functional mesoporous adsorbent of molecular sieve absorption heavy metals ion test of histidine
Concentration is taken for 50mg L-1Heavy metal ion solution, it is 6 to adjust solution ph with watery hydrochloric acid and sodium hydroxide solution；Weigh
The functional mesoporous adsorbent of molecular sieve of histidine prepared by 0.02g examples 2 in the above-mentioned solution of 10mL, low whipping speed
It is 150 rpm, adsorption reaction is carried out under the conditions of 25 DEG C of temperature（Adsorption time 120min）.The functional mesoporous molecular sieve of histidine is inhaled
The adsorption rate of attached dose of heavy metal ion is as follows：
| Heavy metal ion | Cr3+ | Co2+ | Ni2+ | Cu2+ | Zn2+ | Cd2+ |
| Adsorption rate | 75.76% | 39.86% | 53.88% | 99.94% | 58.61% | 58.98% |
Claims (10)
1. the functional mesoporous adsorbent of molecular sieve of a kind of histidine, it is characterised in that described functional mesoporous molecular sieve be with
Molecular sieve MCM-41 be matrix, with histidine as functional reagent, by grafting on the surface of molecular sieve MCM-41 grafting group
Obtained from propylhomoserin；The adsorbent has following structural formula：
Wherein, MCM-41 represents Mesoporous silica MCM 41 type molecular sieve.
2. the functional mesoporous adsorbent of molecular sieve of histidine according to claim 1, it is characterised in that described histidine
The specific surface area of functional mesoporous adsorbent of molecular sieve is 653 m2 g-1, mean pore size is 2.76nm, and pore volume is 0.45
m3 g-1。
3. the functional mesoporous adsorbent of molecular sieve of histidine according to claim 1 and 2, it is characterised in that described group of ammonia
The preparation method of acid functionalization mesoporous molecular sieve adsorbent is two step graftings, is concretely comprised the following steps：
（1）, by raw molecule sieve MCM-41 and 3- chloropropyl triethoxysilanes in mass ratio 1：1-3 is dissolved in drying solvent,
Pyroreaction 6-72 hours under atmosphere of inert gases；Through dry toluene, absolute ethyl alcohol after isolated solid crude product elder generation
Repeatedly washing, obtains raw material Cl-MCM-41 after vacuum drying；Described pyroreaction temperature is 50 ~ 180 DEG C, and described drying is molten
Agent is one or more in toluene, chlorobenzene, dimethylbenzene or dichloro-benzenes；
（2）, by step（1）The Cl-MCM-41 and L-Histidine in mass ratio 1 for obtaining：1-6 is dissolved in reaction dissolvent, reaction temperature
It is 20-100 DEG C to spend, after reacting 6-72 hours, isolated solid crude product；After deionized water washing, histidine function is obtained
Change mesoporous molecular sieve adsorbent；Described reaction dissolvent is ethylenediamine, triethylamine, isopropylamine or triethanolamine and water mixed solution
In one or more.
4. the functional mesoporous adsorbent of molecular sieve of histidine described in claim 3, it is characterised in that preparation method includes as follows
Step：
（1）76mL deionized waters and 8mL 2mol/L NaOH solutions are mixed, then to addition 1.6g template CTAB in solution,
Stir at room temperature to template CTAB and all dissolve；Then 7.6g tetraethyl orthosilicates are weighed, are added drop-wise in solution, at room temperature after
Continuous stirring reaction 1h；Reacted mixed liquor is placed in high-pressure hydrothermal reaction kettle, 100 DEG C are warming up to, stood at such a temperature
Crystallization 3 days；Then solid matter filtering, the washing to neutrality, re-dry that will be obtained；Finally dried sample is warming up to
550 DEG C, and 6h is calcined at such a temperature to remove template template, the solid product for obtaining as Mesoporous silica MCM 41；
（2）2.5g Mesoporous silica MCM 41s and the dry toluene of 150mL are mixed in anhydrous and oxygen-free bottle, logical nitrogen is then vacuumized
Gas；5mL 3- chloropropyl triethoxysilanes are slowly added dropwise under normal temperature in anhydrous and oxygen-free bottle, 100 DEG C are then warmed up to, at this
At a temperature of react 24h；Solid product is finally dried through filtering, and successively with dry toluene, absolute ethanol washing, obtains one
Product Cl-MCM-41 after step grafting；
（3）Weigh 8g histidines to be dissolved in the deionized water of 200mL, the solution is mixed with 2g Cl-MCM-41, then to mixed
Middle addition 8mL triethylamines in solution are closed, 35 DEG C is then heated to, at such a temperature stirring reaction 24h；Finally cross filter solid product
Thing, and wash with water, finally give the functional mesoporous adsorbent of molecular sieve of histidine.
5. any described functional mesoporous adsorbent of molecular sieve of histidine of claim 1-4 application in the treatment of waste water, its
It is characterised by, the functional mesoporous adsorbent of molecular sieve of histidine is used to adsorb the heavy metal ion in waste water.
6. the functional mesoporous adsorbent of molecular sieve of histidine according to claim 5 application in the treatment of waste water, it is special
Levy and be, the functional mesoporous adsorbent of molecular sieve dosage of histidine is 2g L-1, mixing speed is 150rpm, and adsorption time is
10min, adsorption temp is 25 DEG C.
7. the functional mesoporous adsorbent of molecular sieve of histidine according to claim 5 application in the treatment of waste water, it is special
Levy and be, the pH of the waste water is controlled to 3-7.
8. the functional mesoporous adsorbent of molecular sieve of histidine according to claim 7 application in the treatment of waste water, it is special
Levy and be, the pH of the waste water is controlled to 5-6.
9. the functional mesoporous adsorbent of molecular sieve of histidine according to claim 5 application in the treatment of waste water, it is special
Levy and be, the heavy metal ion in the waste water is Cr3+、Co2+、Ni2+、Cu2+、Zn2+Or Cd2+In one or more.
10. the functional mesoporous adsorbent of molecular sieve of histidine according to claim 5 application in the treatment of waste water, it is special
Levy and be, the heavy metal ion initial concentration scope in described waste water is not higher than 150 mg L-1, it is preferable over not higher than 50
mg L-1。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110170312A (en) * | 2019-05-30 | 2019-08-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of ammonia nitrogen adsorbent based on Chitosan-coated SBA-15 mesopore molecular sieve and products thereof and application |
| CN110562997A (en) * | 2019-08-10 | 2019-12-13 | 桂林理工大学 | in-situ separation and enrichment method for critical metal arsenic and lead in non-ferrous metal tailings |
| CN115554986A (en) * | 2022-09-20 | 2023-01-03 | 华南理工大学 | Metal organic framework material with efficient adsorption effect and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1404917A (en) * | 2002-11-15 | 2003-03-26 | 中国科学院山西煤炭化学研究所 | Method for preparing hydrosulfuryl functional MCM-48 mesic molecular sieve |
| CN101972632A (en) * | 2010-10-27 | 2011-02-16 | 南开大学 | method for preparing aminopropyl-MCM-41 for adsorbing heavy metal ions in waste water |
| CN102241406A (en) * | 2010-05-11 | 2011-11-16 | 哈尔滨工业大学 | Carboxylated MCM-41 mesoporous molecular sieve for adsorbing heavy metal ions, and preparation method thereof |
| CN102423685A (en) * | 2011-10-27 | 2012-04-25 | 浙江师范大学 | Method for preparing amino functional MCM-48 mesoporous material |
| CN102614828A (en) * | 2012-04-23 | 2012-08-01 | 中国科学院上海硅酸盐研究所 | Cysteine modified sba-15 mesoporous material and preparation method thereof |
| CN102642825A (en) * | 2012-04-16 | 2012-08-22 | 天津师范大学 | Histidine-functionalized carbon nanotube and preparation method and application thereof |
| US20140186250A1 (en) * | 2012-07-19 | 2014-07-03 | The United States Of America | Carbonyl functionalized porous inorganic oxide adsorbents and methods of making and using the same |
| CN104226238A (en) * | 2014-09-15 | 2014-12-24 | 淮阴师范学院 | Preparation method and adsorption method of Ni<2+> adsorbent |
-
2017
- 2017-03-17 CN CN201710158543.XA patent/CN106925225B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1404917A (en) * | 2002-11-15 | 2003-03-26 | 中国科学院山西煤炭化学研究所 | Method for preparing hydrosulfuryl functional MCM-48 mesic molecular sieve |
| CN102241406A (en) * | 2010-05-11 | 2011-11-16 | 哈尔滨工业大学 | Carboxylated MCM-41 mesoporous molecular sieve for adsorbing heavy metal ions, and preparation method thereof |
| CN101972632A (en) * | 2010-10-27 | 2011-02-16 | 南开大学 | method for preparing aminopropyl-MCM-41 for adsorbing heavy metal ions in waste water |
| CN102423685A (en) * | 2011-10-27 | 2012-04-25 | 浙江师范大学 | Method for preparing amino functional MCM-48 mesoporous material |
| CN102642825A (en) * | 2012-04-16 | 2012-08-22 | 天津师范大学 | Histidine-functionalized carbon nanotube and preparation method and application thereof |
| CN102614828A (en) * | 2012-04-23 | 2012-08-01 | 中国科学院上海硅酸盐研究所 | Cysteine modified sba-15 mesoporous material and preparation method thereof |
| US20140186250A1 (en) * | 2012-07-19 | 2014-07-03 | The United States Of America | Carbonyl functionalized porous inorganic oxide adsorbents and methods of making and using the same |
| CN104226238A (en) * | 2014-09-15 | 2014-12-24 | 淮阴师范学院 | Preparation method and adsorption method of Ni<2+> adsorbent |
Non-Patent Citations (2)
| Title |
|---|
| 徐东耀等: "氨基修饰介孔氧化硅处理含镉废水的工艺研究", 《中国煤炭》 * |
| 秦庆东: "《介孔硅材料吸附水中污染物技术与原理》", 30 September 2015 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110170312A (en) * | 2019-05-30 | 2019-08-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of ammonia nitrogen adsorbent based on Chitosan-coated SBA-15 mesopore molecular sieve and products thereof and application |
| CN110562997A (en) * | 2019-08-10 | 2019-12-13 | 桂林理工大学 | in-situ separation and enrichment method for critical metal arsenic and lead in non-ferrous metal tailings |
| CN115554986A (en) * | 2022-09-20 | 2023-01-03 | 华南理工大学 | Metal organic framework material with efficient adsorption effect and preparation method and application thereof |
| CN115554986B (en) * | 2022-09-20 | 2023-08-25 | 华南理工大学 | Metal organic framework material with efficient adsorption effect and preparation method and application thereof |
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