CN110523369A - The method and application of the one doped meso-porous silica membrane of step fabricated in situ lanthana nano particle - Google Patents
The method and application of the one doped meso-porous silica membrane of step fabricated in situ lanthana nano particle Download PDFInfo
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- CN110523369A CN110523369A CN201910749222.6A CN201910749222A CN110523369A CN 110523369 A CN110523369 A CN 110523369A CN 201910749222 A CN201910749222 A CN 201910749222A CN 110523369 A CN110523369 A CN 110523369A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
Abstract
The invention belongs to material preparation technology and separation technology field, disclose the method and application of an a kind of doped meso-porous silica membrane of step fabricated in situ lanthana nano particle.The present invention is with natural biomass Cellulose nanocrystal (CNCs) for template, tetraethyl orthosilicate (TEOS) is silicon source, lanthanum nitrate hexahydrate is lanthanum source, lanthanum nitrate/CNCs/ silica composite films are prepared using in-situ method, CNCs template is removed using calcining, and aoxidizing lanthanum nitrate is lanthana, a step obtains the doped meso-porous silica membrane of lanthana nano particle.The phosphoric acid in water body is adsorbed with succusion, there is excellent absorption property.Advantages of the present invention: a doped meso-porous silica membrane of step in-situ method lanthana nano particle is obtained with simple preparation method, with good meso-hole structure, biggish specific surface area and stable active site, to have biggish adsorption capacity, material is environmentally protective, it is compared to powder body material, membrane adsorbent is recyclable, easily reuses.
Description
Technical field
The invention belongs to material preparation and separation technology fields, are related to a kind of fabricated in situ lanthana nano particle doping Jie
The method of hole silica membrane and purposes for the phosphate anion in adsorbing separation water body.
Background technique
The domestic lake in China, rivers are numerous, and water body environment protection has very important status in our national lifes.
There are many environmental pollutions, such as the pollution of polluted by nitrogen, phosphorus, heavy metal pollution etc. in the water body of nature.Wherein phosphorus pollution is more
From containing phosphatization fertilizer and organophosphorus pesticide production and use, cyanideless electro-plating industry and phosphorous chemical industry caused by it is unprocessed
Waste water, exhaust gas and waste residue.In our daily lifes, used washing powder is mostly Powdered Detergent Containing Phosphate, although phosphorus therein
Hydrochlorate can enhance the ability of the removal spot of washing powder, but be likely to result in phosphorus pollution.It is widely used in agricultural production to contain
Phosphatization fertilizer and pesticide.A large amount of phosphorous sanitary sewage is discharged into the natural waters such as great rivers, is significantly increased in water body
The content of phosphorus, seriously destroys Water quality.Not only in people's daily life, it can make phosphorus-containing wastewater that can arrange under the effect of human activity
Enter lake, in rivers.And some natural causes can also make in water body P elements be enriched with, as rainwash and land erosion,
Depositing dust, rainfall, snowfall, soil erosion and groundwater activities etc..China part phosphorus pollutes more serious lake pollution investigation and grinds
Study carefully the results show that having into the P elements in water body in lake nearly 64% from municipal wastewater.Municipal sewage cannot obtain effectively
Purification, this will result directly in Urban Water Shortage Problem of Cities.Although phosphorus be in our human life activities cannot or one of scarce element,
P elements are the important composition elements for constituting biological cell, it participates in setting up cell membrane, various biological enzyme and inhereditary material nucleosides
Acid.It also constitutes atriphos (ATP), is the Energy supply material of our human bodies, and when our activities need energy, it will be by
Release is to maintain our normal vital movements.But if the content of phosphorus is more than that certain standard (0.02mg/L) is just held in water body
Easily lead to water eutrophication phenomenon.The oxygen content of water body reduces, so that many aquatiles are dead, greatly destroys water body ring
Border.Therefore, it seeks and cleanly and efficiently reduces or remove the enrichment of phosphorus in water body, the method for preventing water eutrophication phenomenon becomes
When previous big research hotspot.
Previous numerous studies report the related water process such as method, membrane separation process, chemical precipitation method, crystallization of biology
Technology can be applied to phosphatic elimination in water body, but these methods have many limitations.For example, the method for biology needs very much
Specific environmental factor, such as temperature, pH；Chemical precipitation method is easy to be secondarily contaminated；Crystallization method is difficult to recycle.
Summary of the invention
In view of the problems of the existing technology, the invention proposes combine absorption method and membrane separation process in water removal
The method of phosphorus.Mesoporous silicon material have very big specific surface area, biggish aperture and uniform pore structure, separation, absorption and
There is very big application in the fields such as catalysis.Mesoporous silicon material large specific surface area, aperture are adjustable, orderly hole on nano-scale
Many characteristics such as road structure and surface group are functionalisable and receive researchers and widely pay close attention to, become functional material side
The hot spot of face research.
The present invention is mesoporous the two of the lanthana nano particle doping that a kind of pair of phosphate anion has larger adsorption capacity
The preparation method of silicon oxide film, using biological material Cellulose nanocrystal (CNCs) as template, tetraethyl orthosilicate (TEOS)
For silicon source, the mesoporous silica film of situ study synthesis lanthanum oxide doping is utilized.The lanthanum oxide doping of preparation it is mesoporous
Silica membrane can be used as a kind of adsorbent material for being selectively adsorbing and separating phosphate radical.One step in-situ synthesis lanthana is received
The method of the doped meso-porous silica membrane of rice grain, steps are as follows:
Step 1: hydrolyzing cotton using sulfuric acid solution, prepare Cellulose nanocrystal CNCs suspension.Take certain volume
CNCs suspension sequentially adds a certain amount of deionized water and tetraethyl orthosilicate (TEOS), then to water-bath in flask
It is heated to certain temperature, stirring condition makes tetraethyl orthosilicate (TEOS) hydrolysis a few hours, then, slowly to above-mentioned suspension
Drop adds a certain amount of lanthanum nitrate hexahydrate aqueous solution, continues after stirring a few hours, finally, above-mentioned mixed liquor is poured into poly- four
In vinyl fluoride culture dish, and it is put into solvent flashing in water bath with thermostatic control and obtains lanthanum nitrate/Cellulose nanocrystal/bis- at transparent membrane
Si oxide compound film；
Step 2: lanthanum nitrate/Cellulose nanocrystal/silica composite films will be obtained and be put into Muffle furnace, in certain temperature
Degree is lower to calcine certain time, and the mesoporous silica film of lanthana nano particle doping is made.
In step 1, Cellulose nanocrystal suspension, deionized water, tetraethyl orthosilicate, lanthanum nitrate hexahydrate aqueous solution
Amount ratio is 45.5~62.5mL:87.5~104.5mL:8~16mL:4~12mL；The Cellulose nanocrystal suspension it is dense
Degree is 10wt%；The concentration of lanthanum nitrate hexahydrate aqueous solution is 0.5g/mL.
In step 1, at 40~60 DEG C, hydrolysis time is controlled in 4~12h water-bath heating and temperature control.
, in step 1, mixing time control is in 2~6h after 0.5g/mL lanthanum nitrate hexahydrate aqueous solution is added.
In step 1, the diameter of the polytetrafluoroethylene (PTFE) culture dish is 9~10cm, is added in polytetrafluoroethylene (PTFE) culture dish
The volume of mixed solution is 15~20mL, and water bath with thermostatic control temperature is controlled at 25~35 DEG C.
In step 2, heating rate when lanthanum nitrate/Cellulose nanocrystal/silica composite films calcining is 2~5
℃·min-1, calcination temperature is 550~650 DEG C, and calcination time is 8~10h.
Lanthana nano particle in the doped meso-porous silica membrane of in-situ synthesis lanthana nano particle in the present invention
Diameter be 5-10nm, mass percent of the lanthana nano particle in composite membrane is about 38.43%~65.19%, oxidation
The macropore range of the doped meso-porous silica membrane of lanthanum nano particle in situ is 7.9-10.1nm.
The doped meso-porous silica membrane application of lanthana nano particle produced by the present invention is the phosphoric acid of adsorbed water body
Radical ion, and containing other interfering ions such as Cl-、NO3 -Or SO4 2-Phosphate radical waste water in, still have for phosphate radical good
Good absorption property shows that the doped meso-porous silica membrane of lanthana nano particle has fine anti-interference and selectivity.
The doped meso-porous silica membrane absorption of a kind of step in-situ synthesis lanthana nano particle produced by the present invention
It is had the technical effect that brought by phosphate radical in separation water body
(1) it is put forward for the first time a kind of side being prepared in situ in the doped meso-porous silicon dioxide film of lanthana nano particle by a step
Method, this method is simply green, prepares material and inexpensively operates and is easy to get, and the period is shorter, at low cost, has practicability and good economy
Benefit.
(2) there is biggish specific surface area using lanthanum oxide doping mesoporous silicon dioxde film made from a step in-situ method, is situated between
Pore structure is stablized, and is not easy to collapse.
(3) lanthana active site is introduced into mesoporous silicon fiml by a step in-situ method, fully ensures that active site is uniform
And Stable distritation is in mesoporous silicon fiml, and solves the problems, such as that lanthana is revealed in water body.
A kind of doped meso-porous silica membrane of above-mentioned step fabricated in situ lanthana nano particle is applied to adsorbed water body
Phosphate anion, specific method carries out as steps described below:
(1) membrane material is added in 200mg/L phosphate aqueous solution, using the pH to 4 of hydrochloric acid conditioning solution, at 25 DEG C
In water bath with thermostatic control after oscillation absorption a period of time, supernatant liquor is taken to determine phosphoric acid solution by inductively-coupled plasma spectrometer
Ultimate density, and calculate adsorbance.If the mixed liquor volume being added is V (L), it is added adsorbent mass W (g), matches molten
The initial concentration of liquid is C0(mg/L), its concentration is C after certain time absorptiont(mg/L), then adsorbance qt(mg/g) are as follows:
qt=V (C0-Ct)/W
(2) membrane material application is containing other interfering ions such as NO3 -(200mg/L)、SO4 2-(200mg/L) or Cl-
In the phosphate waste of (200mg/L), pH value of solution is transferred to 4, after vibrating for 24 hours in 25 DEG C of water bath with thermostatic control, removes supernatant liquor,
Residual concentration is surveyed, adsorbance is calculated.
Detailed description of the invention
Fig. 1 is the scanning of the 1 doped meso-porous silica membrane Sample 1 of in-situ synthesis lanthana nano particle of example
Electron microscope；
Fig. 2 is the transmission of the 1 doped meso-porous silica membrane Sample 1 of in-situ synthesis lanthana nano particle of example
Electron microscope；
Fig. 3 is the XRD light of the 1 doped meso-porous silica membrane Sample 1 of in-situ synthesis lanthana nano particle of example
Spectrogram；
Fig. 4 is that 1~4 doped meso-porous silica membrane of in-situ synthesis lanthana nano particle of example (is respectively designated as
Sample 1, Sample 2, Sample 3, Sample 4) N2Adsorption-desorption isothermal and graph of pore diameter distribution.
Fig. 5 is that 1~4 doped meso-porous silica membrane of in-situ synthesis lanthana nano particle of example (is respectively designated as
Sample 1, Sample 2, Sample 3, Sample 4) under different time to the adsorption effect figure of phosphate radical.
Fig. 6 is that 1~4 doped meso-porous silica membrane of in-situ synthesis lanthana nano particle of example (is respectively designated as
Sample 1, Sample 2, Sample 3, Sample 4) in the presence of disturbance ion to the Adsorption Effect figure of phosphate radical.
Specific embodiment
Below with reference to specific implementation example, the present invention will be further described.
Embodiment 1
(1) cotton is hydrolyzed using sulfuric acid solution, prepares 10wt% Cellulose nanocrystal CNCs suspension, takes 45.5mL's
CNCs suspension sequentially adds the deionized water of 104.5mL and the tetraethyl orthosilicate (TEOS) of 8mL, then extremely in flask
It is heated to 40 DEG C in water-bath, tetraethyl orthosilicate (TEOS) hydrolysis 12h is made under stirring condition, then, to above-mentioned suspension
Liquid be slowly added dropwise 4mL concentration be 0.5g/mL lanthanum nitrate hexahydrate aqueous solution, continue stir 2h after above-mentioned mixed liquor is poured into it is more
A diameter is that the mixed liquor in the polytetrafluoroethylene (PTFE) culture dish of 9cm, in each polytetrafluoroethylene (PTFE) culture dish is 15mL, will then be gathered
Tetrafluoroethene culture dish is placed in rectangular digital display water bath with thermostatic control that solvent flashing finally acquires nitric acid at transparent membrane at 25 DEG C
Lanthanum/Cellulose nanocrystal/silica composite films；
(2) lanthanum nitrate/Cellulose nanocrystal/silica composite films obtained in step 1 are put into Muffle furnace and are calcined,
10h is calcined at 550 DEG C, heating rate is 2 DEG C of min-1, the mesoporous dioxy of final obtained lanthana nano particle in situ doping
SiClx film, thereon, mass percent of the lanthana nano particle in composite membrane are 38.43%, are named as Sample 1.
The scanning electron microscope (SEM) photograph of the Sample 1 prepared in attached drawing 1 of the invention according to example 1, as can be seen from the figure membrane material
Expect that surface has meso-hole structure, and is uniformly distributed lanthana nano particle；
The transmission plot of the Sample 1 prepared in attached drawing 2 of the invention according to example 1, as can be seen from the figure lanthana is received
The general 5-10nm of the diameter of rice grain；
In attached drawing 3 of the invention according to example 1 prepare Sample 1 XRD spectrum, it can be seen from the figure that 25 ° and
45 ° of peak corresponds respectively to the characteristic diffraction peak of silica and lanthana；
The Sample 1 prepared in attached drawing 4 of the invention according to example 1, it can be seen that the specific surface area of Sample 1 is
220m2/ g, average pore size 7.9nm.
The Sample 1 prepared in attached drawing 5 of the invention according to example 1 is applied to the phosphate anion of adsorbed water body not
With the adsorption effect figure of time, as seen from the figure, phosphatic adsorption capacity is about 20.365mg/g, and adsorbent was at first 200 minutes
Quickly, the subsequent rate of adsorption is slack-off for the interior rate of adsorption, probably reaches adsorption equilibrium after 6 hours.
The Sample 1 prepared in attached drawing 6 of the invention according to example 1, and containing other interfering ions such as NO3 -、
SO4 2-、Cl-Phosphate radical waste water in, still there is good absorption property for phosphate radical, the adsorption capacity of reservation reaches 86%,
Show that the doped meso-porous silica membrane of lanthana nano particle has fine anti-interference and selectivity.
Embodiment 2
(1) cotton is hydrolyzed using sulfuric acid solution, prepares 10wt% Cellulose nanocrystal CNCs suspension, takes the CNCs of 50mL
Suspension sequentially adds the deionized water of 100mL and the tetraethyl orthosilicate (TEOS) of 16mL, then to water-bath in flask
In be heated to 50 DEG C, tetraethyl orthosilicate (TEOS) hydrolysis 12h is made under stirring condition, then, Xiang Shangshu suspension is slow
The lanthanum nitrate hexahydrate aqueous solution that 12mL concentration is 0.5g/mL is added dropwise, continue to stir above-mentioned mixed liquor is poured into after 6h it is multiple straight
Diameter is that the mixed liquor in the polytetrafluoroethylene (PTFE) culture dish of 9.5cm, in each polytetrafluoroethylene (PTFE) culture dish is 17.5mL, will then be gathered
Tetrafluoroethene culture dish is placed in rectangular digital display water bath with thermostatic control that solvent flashing finally acquires nitric acid at transparent membrane at 30 DEG C
Lanthanum/Cellulose nanocrystal/silica composite films；
(2) lanthanum nitrate/Cellulose nanocrystal/silica composite films obtained in step 1 are put into Muffle furnace and are calcined,
9h is calcined at 600 DEG C, heating rate is 3 DEG C of min-1, the mesoporous dioxy of final obtained lanthana nano particle in situ doping
SiClx film, thereon, mass percent of the lanthana nano particle in composite membrane are 48.36%, are named as Sample 2.
The Sample 2 prepared in attached drawing 4 of the invention according to example 2, it can be seen that the specific surface area of Sample 2 is
166m2/ g, aperture 8.7nm.
The Sample 2 prepared in attached drawing 5 of the invention according to example 2 is applied to the phosphate anion of adsorbed water body not
With the adsorption effect figure of time, as seen from the figure, phosphatic adsorption capacity is about 29.72mg/g, and adsorbent is in first 200 minutes
Quickly, the subsequent rate of adsorption is slack-off for the rate of adsorption, probably reaches adsorption equilibrium after 6 hours.
The Sample 2 prepared in attached drawing 6 of the invention according to example 2, and containing other interfering ions such as NO3 -、
SO4 2-、Cl-Phosphate radical waste water in, still there is good absorption property for phosphate radical, the adsorption capacity of reservation reaches 85%,
Show that the doped meso-porous silica membrane of lanthana nano particle has fine anti-interference and selectivity.
Embodiment 3
(1) cotton is hydrolyzed using sulfuric acid solution, prepares 10wt% Cellulose nanocrystal CNCs suspension, takes 62.5mL's
CNCs suspension sequentially adds the deionized water of 87.5mL and the tetraethyl orthosilicate (TEOS) of 8mL, then to water in flask
It is heated to 60 DEG C in bath, tetraethyl orthosilicate (TEOS) hydrolysis 4h is made under stirring condition, then, Xiang Shangshu suspension is slow
It is slow that the lanthanum nitrate hexahydrate aqueous solution that 8mL concentration is 0.5g/mL is added dropwise, continue to stir above-mentioned mixed liquor is poured into after 6h it is multiple straight
Diameter is that the mixed liquor in the polytetrafluoroethylene (PTFE) culture dish of 10cm, in each polytetrafluoroethylene (PTFE) culture dish is 20mL, then by poly- four
Vinyl fluoride culture dish is placed in rectangular digital display water bath with thermostatic control that solvent flashing finally acquires nitric acid at transparent membrane at 35 DEG C
Lanthanum/Cellulose nanocrystal/silica composite films；
(2) lanthanum nitrate/Cellulose nanocrystal/silica composite films obtained in step 1 are put into Muffle furnace and are calcined,
8h is calcined at 650 DEG C, heating rate is 4 DEG C of min-1, the mesoporous dioxy of final obtained lanthana nano particle in situ doping
SiClx film, thereon, mass percent of the lanthana nano particle in composite membrane are 55.52%, are named as Sample 3.
The Sample 3 prepared in attached drawing 4 of the invention according to example 3, it can be seen that the specific surface area of Sample 3 is
122m2/ g, aperture 9.9nm.
The Sample3 prepared in attached drawing 5 of the invention according to example 3 is applied to the phosphate anion of adsorbed water body in difference
The adsorption effect figure of time, as seen from the figure, phosphatic adsorption capacity are about 39.00mg/g, and adsorbent is in preceding 200 minutes interior suctions
Quickly, the subsequent rate of adsorption is slack-off for attached rate, probably reaches adsorption equilibrium after 6 hours.
The Sample 3 prepared in attached drawing 6 of the invention according to example 3, and containing other interfering ions such as NO3 -、
SO4 2-、Cl-Phosphate radical waste water in, still there is good absorption property for phosphate radical, the adsorption capacity of reservation reaches 90%,
Show that the doped meso-porous silica membrane of lanthana nano particle has fine anti-interference and selectivity.
Embodiment 4
(1) cotton is hydrolyzed using sulfuric acid solution, prepares 10wt% Cellulose nanocrystal CNCs suspension, takes 62.5mL's
CNCs suspension sequentially adds the deionized water of 87.5mL and the tetraethyl orthosilicate (TEOS) of 8mL, then to water in flask
It is heated to 60 DEG C in bath, tetraethyl orthosilicate (TEOS) hydrolysis 8h is made under stirring condition, then, Xiang Shangshu suspension is slow
It is slow that the lanthanum nitrate hexahydrate aqueous solution that 12mL concentration is 0.5g/mL is added dropwise, continue to stir above-mentioned mixed liquor is poured into after 6h it is multiple
Diameter is that the mixed liquor in the polytetrafluoroethylene (PTFE) culture dish of 10cm, in each polytetrafluoroethylene (PTFE) culture dish is 20mL, will then be gathered
Tetrafluoroethene culture dish is placed in rectangular digital display water bath with thermostatic control that solvent flashing finally acquires nitric acid at transparent membrane at 35 DEG C
Lanthanum/Cellulose nanocrystal/silica composite films；
(2) lanthanum nitrate/Cellulose nanocrystal/silica composite films obtained in step 1 are put into Muffle furnace and are calcined,
8h is calcined at 650 DEG C, heating rate is 5 DEG C of min-1, the mesoporous dioxy of final obtained lanthana nano particle in situ doping
SiClx film, thereon, mass percent of the lanthana nano particle in composite membrane are 65.19%, are named as Sample 4.
The Sample 4 prepared in attached drawing 4 of the invention according to example 4, it can be seen that the specific surface area of Sample 3 is
114m2/ g, aperture 10.1nm.
The Sample 4 prepared in attached drawing 5 of the invention according to example 4 is applied to the phosphate anion of adsorbed water body not
With the adsorption effect figure of time, as seen from the figure, phosphatic adsorption capacity is about 48.21mg/g, and adsorbent is in first 200 minutes
Quickly, the subsequent rate of adsorption is slack-off for the rate of adsorption, probably reaches adsorption equilibrium after 6 hours.
The Sample 4 prepared in attached drawing 6 of the invention according to example 4, and containing other interfering ions such as NO3 -、
SO4 2-、Cl-Phosphate radical waste water in, still there is good absorption property for phosphate radical, the adsorption capacity of reservation reaches 90%,
Show that the doped meso-porous silica membrane of lanthana nano particle (Sample 4) has fine anti-interference and selectivity.
Claims (8)
1. the method for a doped meso-porous silica membrane of step fabricated in situ lanthana nano particle, which is characterized in that including such as
Lower step:
Step 1: hydrolyzing cotton using sulfuric acid solution, prepare Cellulose nanocrystal CNCs suspension；Take the CNCs of certain volume outstanding
Supernatant liquid sequentially adds a certain amount of deionized water and tetraethyl orthosilicate (TEOS), is then heated to water-bath in flask
Certain temperature, stirring condition make tetraethyl orthosilicate (TEOS) hydrolysis a few hours, then, slowly add to above-mentioned hanging drop
A certain amount of lanthanum nitrate hexahydrate aqueous solution continues after stirring a few hours, finally, above-mentioned mixed liquor is poured into polytetrafluoroethylene (PTFE)
In culture dish, and it is put into solvent flashing in water bath with thermostatic control and obtains lanthanum nitrate/Cellulose nanocrystal/silica at transparent membrane
Composite membrane；
Step 2: lanthanum nitrate/Cellulose nanocrystal/silica composite films will be obtained and be put into Muffle furnace, temperature programming to calcining
Temperature calcines certain time at a certain temperature, and the mesoporous silica film of lanthana nano particle doping is made.
2. the side of the doped meso-porous silica membrane of step in-situ synthesis lanthana nano particle as described in claim 1
Method, which is characterized in that in step 1, Cellulose nanocrystal suspension, deionized water, tetraethyl orthosilicate and lanthanum nitrate hexahydrate
The amount ratio of aqueous solution is 45.5~62.5mL:87.5~104.5mL:8~16mL:4~12mL；The Cellulose nanocrystal is outstanding
The concentration of supernatant liquid is 10wt%；The concentration of lanthanum nitrate hexahydrate aqueous solution is 0.5g/mL.
3. the side of the doped meso-porous silica membrane of step in-situ synthesis lanthana nano particle as described in claim 1
Method, which is characterized in that in step 1, at 40~60 DEG C, hydrolysis time is controlled in 4~12h water-bath heating and temperature control.
4. the side of the doped meso-porous silica membrane of step in-situ synthesis lanthana nano particle as described in claim 1
Method, which is characterized in that in step 1, mixing time control is in 2~6h after 0.5g/mL lanthanum nitrate hexahydrate aqueous solution is added.
5. the side of the situ study synthesis doped meso-porous silica membrane of lanthana nano particle as described in claim 1
Method, which is characterized in that in step 1, the diameter of the polytetrafluoroethylene (PTFE) culture dish is 9~10cm, and polytetrafluoroethylene (PTFE) training is added
The volume for supporting mixed solution in ware is 15~20mL, and water bath with thermostatic control temperature is controlled at 25~35 DEG C.
6. the side of the doped meso-porous silica membrane of step in-situ synthesis lanthana nano particle as described in claim 1
Method, it is characterised in that in step 2, the heating rate of temperature programming is 2~5 DEG C of min-1, calcination temperature is 550~650 DEG C, is forged
The burning time is 8~10h.
7. a kind of doped meso-porous silica membrane of lanthana nano particle, which is characterized in that be by claim 1~6 times
What one preparation method obtained, the mesoporous range of the doped meso-porous silica membrane of lanthana nano particle in situ is
7.9-10.1nm, the diameter 5-10nm of lanthana nano particle, lanthana nano particle are doped meso-porous in lanthana nano particle
Mass percent in silica membrane is 38.43%~65.19%.
8. a kind of doped meso-porous silica membrane of lanthana nano particle as claimed in claim 7 is applied to adsorbed water body
The purposes of phosphate anion.
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| CN201910749222.6A CN110523369A (en) | 2019-08-14 | 2019-08-14 | The method and application of the one doped meso-porous silica membrane of step fabricated in situ lanthana nano particle |
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| CN201910749222.6A CN110523369A (en) | 2019-08-14 | 2019-08-14 | The method and application of the one doped meso-porous silica membrane of step fabricated in situ lanthana nano particle |
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040050795A1 (en) * | 2002-09-18 | 2004-03-18 | Park Jae Kwang | Removal of arsenic and other anions using novel adsorbents |
| CN102985365A (en) * | 2010-04-09 | 2013-03-20 | 不列颠哥伦比亚大学 | Inorganic mesoporous materials with chiral nematic structures and preparation method thereof |
| CN104136113A (en) * | 2011-10-24 | 2014-11-05 | 梅塔材料技术有限责任公司 | Porous composite media for removing phosphorus from water |
| CN104667882A (en) * | 2015-02-13 | 2015-06-03 | 江苏大学 | Preparation and application of nano-structure composite adsorption material |
| CN104692389A (en) * | 2015-02-13 | 2015-06-10 | 江苏大学 | Preparation of nanostructured material |
| US20160008396A1 (en) * | 2002-05-24 | 2016-01-14 | Spectrum Pharmaceuticals, Inc. | Rare earth metal compounds, methods of making, and methods of using the same |
| CN106964317A (en) * | 2017-03-21 | 2017-07-21 | 河北师范大学 | A kind of double amido modified mesoporous silicon materials of lanthanum load and preparation method thereof |
| CN106964318A (en) * | 2017-03-17 | 2017-07-21 | 江苏大学 | A kind of mesoporous silicon fiml and its an one step preparation method and purposes |
| CN109201018A (en) * | 2018-08-21 | 2019-01-15 | 江苏大学 | A kind of preparation method and purposes of the mesoporous carbon film of La doped |
| CN109603785A (en) * | 2018-12-18 | 2019-04-12 | 安徽工业大学 | It is a kind of to remove arsenic, phosphorus adsorbent and preparation method thereof in water removal simultaneously |
-
2019
- 2019-08-14 CN CN201910749222.6A patent/CN110523369A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160008396A1 (en) * | 2002-05-24 | 2016-01-14 | Spectrum Pharmaceuticals, Inc. | Rare earth metal compounds, methods of making, and methods of using the same |
| US20040050795A1 (en) * | 2002-09-18 | 2004-03-18 | Park Jae Kwang | Removal of arsenic and other anions using novel adsorbents |
| CN102985365A (en) * | 2010-04-09 | 2013-03-20 | 不列颠哥伦比亚大学 | Inorganic mesoporous materials with chiral nematic structures and preparation method thereof |
| CN104136113A (en) * | 2011-10-24 | 2014-11-05 | 梅塔材料技术有限责任公司 | Porous composite media for removing phosphorus from water |
| CN104667882A (en) * | 2015-02-13 | 2015-06-03 | 江苏大学 | Preparation and application of nano-structure composite adsorption material |
| CN104692389A (en) * | 2015-02-13 | 2015-06-10 | 江苏大学 | Preparation of nanostructured material |
| CN106964318A (en) * | 2017-03-17 | 2017-07-21 | 江苏大学 | A kind of mesoporous silicon fiml and its an one step preparation method and purposes |
| CN106964317A (en) * | 2017-03-21 | 2017-07-21 | 河北师范大学 | A kind of double amido modified mesoporous silicon materials of lanthanum load and preparation method thereof |
| CN109201018A (en) * | 2018-08-21 | 2019-01-15 | 江苏大学 | A kind of preparation method and purposes of the mesoporous carbon film of La doped |
| CN109603785A (en) * | 2018-12-18 | 2019-04-12 | 安徽工业大学 | It is a kind of to remove arsenic, phosphorus adsorbent and preparation method thereof in water removal simultaneously |
Non-Patent Citations (4)
| Title |
|---|
| EMMANUELAWATI, IRENE ET AL.: ""Low-cost and large-scale synthesis of functional porous materials for phosphate removal with high performance"", 《NANOSCAL》 * |
| LIU, ENXIU ET AL.: ""Fabrication of phosphate functionalized chiral nematic mesoporous silica films for the efficient and selective adsorption of lanthanum ions"", 《JOURNAL OF MOLECULAR LIQUIDS》 * |
| 汪纯: ""镧改性的多孔硅吸附磷的研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 茹静等: "纳米纤维素基吸附材料", 《化学进展》 * |
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