CN110433766A - A kind of modified mesoporous silicon fiml and its preparation method and application greatly of lanthanum - Google Patents
A kind of modified mesoporous silicon fiml and its preparation method and application greatly of lanthanum Download PDFInfo
- Publication number
- CN110433766A CN110433766A CN201910646162.5A CN201910646162A CN110433766A CN 110433766 A CN110433766 A CN 110433766A CN 201910646162 A CN201910646162 A CN 201910646162A CN 110433766 A CN110433766 A CN 110433766A
- Authority
- CN
- China
- Prior art keywords
- silicon fiml
- lanthanum
- mesoporous silicon
- modified
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0207—Compounds of Sc, Y or Lanthanides
-
- 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
-
- 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
-
- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Nanotechnology (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to material preparation technology and separation technology field, the application of the absorption of phosphorus in a kind of modified preparation method of mesoporous silicon fiml greatly of lanthanum and its water body.The present invention is using natural biomass Cellulose nanocrystal as template, tetramethoxy-silicane is silicon source, CNCs/ silica composite films are prepared using solvent volatilization self-assembly method, CNCs template is removed using acid wash, big mesoporous silicon dioxde film is formed, lanthanum is modified in the surface of big mesoporous silicon fiml using the method calcined after ethanol evaporation method later.The phosphoric acid in water body is adsorbed with succusion, there is excellent absorption property.Advantages of the present invention: the modified big mesoporous silicon fiml of lanthanum is obtained since meso-hole structure is larger with simple preparation method, about 20nm, it is modified to be conducive to later period surface, mesoporous obstruction is not easily caused, there is bigger lanthanum load capacity, to there is 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 preparation method of modified big mesoporous silicon fiml of lanthanum,
More particularly to a kind of preparation method of the new adsorbent for water pollution processing, and applied to the phosphorus in adsorbing separation water body
Acid ion.
Background technique
Although water resource is abundant on the earth, about 70% area is covered with water on the earth, and freshwater resources quite lack,
Account for the 2.53% of global total water.The normal life of our mankind also be unable to do without the demand of fresh water.But recent years is with industry
Development and the improvement of people's living standards, a large amount of untreated industrial wastewaters and urban sewage discharge cause in water body
Water pollution problems very serious.Especially a large amount of phosphorus-containing wastewaters are discharged into water body, lead to water eutrophication.Water body richness battalion
Feedingization leads to deteriorating water quality, and aquatile is dead, and the putrefaction of dead body generates stench, damages us and lives the natural environment in place, into
And our daily lifes are influenced, it also will cause sizable wasting of resources.Previous literature research the 22 of national the Grate Lakes region
The eutrophic extent in a typical case lake, result of study is shown, during 2010-2011,59.1% typical lake is in
Different degrees of eutrophic state.It is higher that water eutrophication problem is mainly derived from the nitrogen and phosphorus element content in water body, such as
The content of phosphorus is more than 0.023mg/L in fruit water body, is easy for leading to water eutrophication.Water eutrophication to environment, agricultural,
Fishery or even civil plantation have considerable influence.It will lead to algae and planktonic organism excessive multiplication, oxygen content of water drop
Low, a large amount of fish are dead, and then influence the income of fishermen.And the dead corruption of fish generates stench, can also seriously break
The environment that bad persons live.The drinking-water of citizen can be also affected by it, and water factory's decontamination procedure is added, and it is clean to be difficult purification.Institute
It is necessary with studying a kind of materials purification water quality of the P elements in adsorbed water body.
Nowadays there are many researchs to report relevant water treatment technology, such as bioanalysis, chemical precipitation method, crystallization and absorption
The methods of be all applied to the removal of phosphoric acid, but these method limitations are a lot of.Such as biological method needs many specific rings
Border factor；Chemical precipitation method easily causes secondary pollution；Method for crystallising is difficult to recycle.In contrast, adsorbing separation skill is utilized
Art carry out water body in phosphate adsorption have the advantages that it is many such as applied widely, be conducive to recycling and it is reusable, adsorb
Agent makes the phosphoric acid processing method of great application prospect for the high treating effect of water body.
Mesoporous silicon material is common adsorbent in adsorption method, and wherein mesoporous silicon material has certain superiority, is situated between
Hole silica membrane material shows outstanding absorption property due to huge specific surface area, a large amount of meso-hole structures.It can incite somebody to action
It is applied to the P elements in adsorbed water body.Pure mesoporous silicon dioxde film material is not very greatly, through lanthanum to the adsorption capacity of phosphorus
It is modified to greatly increase its absorption property.But the aperture of mesoporous silicon dioxde film material is smaller at present, absorption property compared with
Difference, adsorption rate are slow.
Summary of the invention
The present invention is the preparation method that a kind of pair of phosphate anion has the modified big mesoporous silicon fiml of the lanthanum of larger adsorption capacity,
It is silicon source with positive quanmethyl silicate (TMOS) using Cellulose nanocrystal (CNCs) as template, acid wash closes after removing removing template
At big mesoporous silicon membrane material, a kind of adsorbent material can be used as separating phosphate radical.The present invention prepares material therefor green inexpensively,
Belong to environmentally friendly material, and preparation method is simple, there is significant economic benefit.
Resulting mesoporous silicon dioxde film is tested with chiral liquid crystal nematic structure, bright iris is presented.Gained film
Material has biggish meso-hole structure, is conducive to the phosphorus in quick adsorption separation water body, and lanthanum active site is conducive to selective suction
Attached separation of phosphorus.
A kind of preparation method of the modified big mesoporous silicon fiml of lanthanum, steps are as follows:
Step 1: Cellulose nanocrystal CNCs is prepared using sulphuric acid hydrolysis medical absorbent cotton, it is spare；
Step 2: Cellulose nanocrystal prepared by step 1 is ultrasonically treated, and a certain amount of DEXTROSE ANHYDROUS is added, so
It is placed on magnetic stirring apparatus and is allowed to uniformly mixed, the positive quanmethyl silicate TMOS of silicon precursor is added later and continues stirring hydrolysis,
It pours into polytetrafluoroethylene (PTFE) culture dish, drying film forming, obtains Cellulose nanocrystal/silica composite films A in a water bath；Step
3: Cellulose nanocrystal/silica composite films A that step 2 obtains is placed in removal Cellulose nanocrystal mould in sulfuric acid solution
Plate obtains big mesoporous silicon fiml B；
Step 4: the big mesoporous silicon fiml B that step 3 is obtained is placed in a beaker, rear that lanthanum nitrate hexahydrate and ethyl alcohol mixing is added
Solution, using the modified silicon fiml of ethanol evaporation method, is finally placed in baking oven in water bath chader and obtains modified big mesoporous silicon fiml C；
Step 5: the modification silicon fiml C mesoporous greatly that step 4 obtains being placed in Muffle furnace and is calcined, it is modified to obtain final product lanthanum
Big mesoporous silicon fiml D.
In step 1, prepare Cellulose nanocrystal CNCs the step of are as follows: it is molten that medical absorbent cotton is placed in 40~60wt% sulfuric acid
In liquid, 35~55 DEG C of stirrings hydrolyze 1~3h, and the hydrolysis to inhibit cellulose is diluted by a large amount of ultrapure waters；Overnight stand layering,
Supernatant liquor is outwelled, Cellulose nanocrystal dispersion liquid is centrifugated, washing；White suspension after centrifuge separation is transferred to
It dialyses in dialysis membrane, the molecular cut off of the dialysis membrane is 11000~15000, and dialysis time is 1~5 day；Until pH value etc.
In 2.4, dilution, ultrasound obtains the Cellulose nanocrystal suspension that mass percentage concentration is 3%~5%.
In step 2, the Cellulose nanocrystal, DEXTROSE ANHYDROUS and positive quanmethyl silicate amount ratio are 10~20mL:
The μ of 100~200mg:400~1000 L.The ultrasonic time is 10~30min；Whipping temp after glucose is added is 20~30
DEG C, the time is 0.5~1.5h；Whipping temp after positive quanmethyl silicate is added dropwise is 20~30 DEG C, and the time is 2~3h.The baking
Dry film forming are as follows: in polytetrafluoroethylene (PTFE) culture dish, 20~30 DEG C of water-baths are dried 2~7 days.
In step 3, the process that Cellulose nanocrystal template is removed in sulfuric acid solution are as follows: by cellulose nanometer
The volume ratio of water-bath 5~15 days in sulfuric acid solution crystalline substance/silica composite films A, the concentrated sulfuric acid of sulfuric acid solution and water be 1:4~
1:2, bath temperature are controlled at 70~90 DEG C.
In step 4, the big mesoporous silicon fiml B, ethyl alcohol, lanthanum nitrate hexahydrate amount ratio be 1g:50~200mL:0.3
~6g, bath temperature are 40~80 DEG C, and duration of oscillation is 12~36h, are dried in an oven later, oven temperature control 60~
100℃。
In step 5, obtained modification silicon fiml C mesoporous greatly is placed in Muffle furnace, initially with 5~10 DEG C of min-1It is warming up to
100 DEG C, 1~3h is kept, then with 5~10 DEG C of min-1500~600 DEG C are warming up to, 5~8h is kept, obtains final product
The modified big mesoporous silicon fiml D of lanthanum.
The modified big mesoporous silicon fiml of lanthanum prepared by the present invention is for the phosphate radical in adsorbing separation water body.
Heretofore described Cellulose nanocrystal (CNCs) is to be hydrolyzed to generate by medical absorbent cotton, is a kind of biology
Matter template.
Heretofore described positive quanmethyl silicate (TMOS) is used as silicon source, generates silicon dioxide film substrate.
Heretofore described glucose, effect is to increase the toughness of film for anticracking.
Heretofore described lanthanum nitrate hexahydrate is to be modified big mesoporous silicon membrane material and can be used for selective absorption point
From phosphorus.
The modified big mesoporous silicon fiml of above-mentioned lanthanum is applied to the phosphate anion of adsorbed water body, specific method as steps described below into
Row:
(1) anhydrous potassium dihydrogenphosphate is weighed, configures phosphate standard liquid, concentration 200mg/L with ultrapure water.It accurately weighs
20mg silicon fiml adsorbent is placed in 10mL colorimetric cylinder, and the pH value using hydrochloric acid and sodium hydrate regulator solution makes in the range of 2.0
To 11.0, adsorption process vibrates 24 hours in 25 DEG C of constant temperature gas bath, after take supernatant liquor to pass through inductively coupled plasma body
Spectrometer determines the ultimate density of phosphoric acid solution, and calculates adsorbance.
(2) anhydrous potassium dihydrogenphosphate is weighed, configures phosphate standard liquid, concentration 200mg/L with ultrapure water.By 20mg membrane material
Material adsorbent is added in the colorimetric cylinder of 10mL, is demarcated with the phosphoric acid solution of pH=4 to 10mL.It is small to be placed in oscillation 24 in constant temperature gas bath
When, setting temperature is 20 to 40 DEG C, and supernatant liquor is taken to determine the final of phosphoric acid solution by inductively-coupled plasma spectrometer
Concentration, and calculate adsorbance.
(3) anhydrous potassium dihydrogenphosphate is weighed, configures phosphate standard liquid, concentration 200mg/L with ultrapure water.By standard solution
It is diluted to the phosphoric acid solution of various concentration (10,25,50,75,100,125,150,175,200mg/L), and adjusts the pH of solution
It is 4.It weighs 20mg silicon fiml adsorbent to be added in 10mL colorimetric cylinder, is demarcated with various concentration phosphoric acid solution to 10mL, set
It is vibrated 24 hours for 25 DEG C in constant temperature gas bath, 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 W (L), the initial concentration of matched solution 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
(4) it weighs 20mg membrane material to be added in 10mL colorimetric cylinder, be demarcated with 200mg/L phosphate solution to 10mL.It will
After colorimetric cylinder is placed in 25 DEG C of constant temperature gas bath oscillation 5,15,30,60,90,120,180,270,360,720min, take upper layer clear
Liquid determines the ultimate density of phosphoric acid solution by inductively-coupled plasma spectrometer, and calculates adsorbance.
(5) a series of phosphate solution (F with counter anion are prepared with standard solution (pH=4,25 DEG C)-, Cl-,
NO3 -And SO4 2-Sodium-salt form) solution, with obtain ultimate density be every kind of anion 150mg/L.20mg membrane material is added
In 10mL colorimetric cylinder, demarcated with the phosphate solution of preparation to 10mL.Supernatant liquor is taken to pass through inductively coupled plasma spectrometry
Instrument determines the ultimate density of phosphoric acid solution, and calculates adsorbance.
Technological merit of the invention:
(1) present invention utilizes existing fibers a large amount of in nature with biomass cellulose nanocrystalline (CNCs) for template
Element is used as initial preparation material, cheap and easy to get, environmentally protective, has such as high-purity, high polymerization degree, high-crystallinity, Gao Qinshui
The advantages that property, high Young's modulus, high intensity, hyperfine structure and high transparency.
(2) go the big mesoporous silicon dioxde film after removing template that there is high specific surface area and biggish mesoporous pore size
(20nm) is conducive to the further modification of material, loads more lanthanas and do not easily cause mesoporous obstructing problem, be conducive to more
The acquisition of high-adsorption-capacity, and big meso-hole structure is conducive to improve the rate of absorption, to improve adsorption efficiency.
(3) it is modified using two-step method to carry out surface to mesoporous silicon fiml by the present invention, and lanthanum active site is introduced into mesoporous, can be with
Guarantee being uniformly distributed for active site.
(4) membrane material prepared, which is compared to powder body material, has the advantages that be easily recycled and reuse.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of big mesoporous silicon fiml prepared by the present invention；
Fig. 2 is the transmission electron microscope picture of big mesoporous silicon fiml prepared by the present invention；
Fig. 3 is the infrared conversion spectrum figure of Fourier of modification prepared by the present invention silicon fiml mesoporous greatly；
Fig. 4 is that lanthanum prepared by the present invention is modified mesoporous silicon fiml at different pH to the influence diagram of the adsorbance of phosphate radical.
Fig. 5 is that lanthanum prepared by the present invention is modified mesoporous silicon fiml under different time to the adsorption effect figure of phosphate radical.
Fig. 6 is the adsorption effect figure of the modified mesoporous silicon fiml of lanthanum prepared by the present invention in various concentration phosphate solution.
Specific embodiment
Below with reference to specific implementation example, the present invention will be further described.
Embodiment 1
(1) it weighs 10g medical absorbent cotton to be dissolved in the sulfuric acid solution of 40wt% concentration, and is stirred at 35 DEG C
3h.Later, so that it is stopped hydrolytic process with the cellulose of 2000 milliliters of cold ultrapure water dilution hydrolysis, and stand 12h.Give up
Remaining white fiber element is carried out centrifugal treating by layer clear liquid.Then, the white suspension being centrifuged out is washed with deionized water
3 times are washed to remove soluble cellulosic material, is subsequently placed in bag filter (molecular cut off 11000-15000) 2~5 days
(until pH=2.4 of suspension).The solid product finally obtained dilutes in water, and is passing through ultrasonic treatment dispersion using preceding
10 minutes, being diluted to mass percent concentration was 3%.
(2) CNCs suspension (pH=2.4) obtained in the step 1 of 15mL is ultrasonically treated 10min.100mg is anhydrous
Glucose is added in CNCs and stirs 0.5h at 20 DEG C, and mixture suspension is added in 400 μ L tetramethoxy-silicanes (TMOS) later
In.Mixture suspension stirs 1.5h at 20 DEG C.Later, uniform mixture pours into polystyrene culture dish (d=90mm)
In and be dried at room temperature for.In 20 DEG C of water-baths slow evaporation 2~3 days to form complete CNCs/ silica composite films A,
Abbreviation CSF.
(3) Cellulose nanocrystal/silica composite films A that step (2) obtain is placed in water-bath 5 days in sulfuric acid solution,
Obtain big mesoporous silicon fiml B, abbreviation MSF；
Wherein, the volume ratio of the concentrated sulfuric acid of sulfuric acid solution and water is 1:4, and bath temperature is controlled at 80 DEG C.
(4) the 1g silicon fiml B mesoporous greatly that synthesis obtains in step (3) is added in beaker, after will be dissolved with 0.3482g's
The 100mL ethyl alcohol of lanthanum nitrate hexahydrate is added in beaker, 40 DEG C of water-bath oscillation 12h is placed the beaker, later in 60 DEG C of baking ovens
It is dry；
(5) the modified big mesoporous silicon fiml of step (4) is placed in Muffle furnace, initially with 5 DEG C of min-1It is warming up to 100
DEG C, 1h is kept, later with 5 DEG C of min-1500 DEG C are warming up to, 5h is kept, obtains the modified big mesoporous silicon fiml D of final product lanthanum, letter
La-MSF-20 (Si/La molar ratio is referred to as 20:1).
(6) the modified big mesoporous silicon fiml of lanthanum is subjected to optimal adsorption pH test.
Anhydrous potassium dihydrogenphosphate is weighed, configures phosphate standard liquid, concentration 200mg/L with ultrapure water.Accurately weigh 20mg
Silicon fiml adsorbent is placed in 10mL colorimetric cylinder, using the pH value of hydrochloric acid and sodium hydrate regulator solution make in the range of 2.0 to
11.0, adsorption process vibrates 24 hours in 25 DEG C of constant temperature gas bath, after take supernatant liquor pass through inductively coupled plasma body light
Spectrometer determines the ultimate density of phosphoric acid solution, and calculates adsorbance, and obtaining Optimal pH is 3 or 4.
(7) the modified big mesoporous silicon fiml of lanthanum is subjected to optimal adsorption temperature test.
Anhydrous potassium dihydrogenphosphate is weighed, configures phosphate standard liquid, concentration 200mg/L with ultrapure water.By 20mg membrane material
Adsorbent is added in the colorimetric cylinder of 10mL, is demarcated with the phosphoric acid solution of pH=4 to 10mL.It is small to be placed in oscillation 24 in constant temperature gas bath
When, setting temperature is 20~40 DEG C, and supernatant liquor is taken to determine the final of phosphoric acid solution by inductively-coupled plasma spectrometer
Concentration, and calculate adsorbance.
(8) the modified big mesoporous silicon fiml of lanthanum is subjected to the assessment of thermoisopleth absorption property.
Potassium dihydrogen phosphate is accurately weighed, 200mg/L phosphate standard liquid is configured to.Standard solution is diluted to various concentration
The phosphoric acid solution of (10,25,50,75,100,125,150,175,200mg/L), and the pH for adjusting solution is 4.Weigh 20mg film
Material is added in 10mL colorimetric cylinder, is demarcated with various concentration phosphoric acid solution to 10mL, is shaken in 25 DEG C of constant temperature gas bath
After swinging 24 hours, supernatant liquor is taken to determine the ultimate density of phosphoric acid solution by inductively-coupled plasma spectrometer, and calculate
Adsorbance.If the mixed liquor volume being added is W (L), the initial concentration of matched solution is C0(mg/L), after certain time absorption
Its concentration is Ct(mg/L), then the adsorbance q of filmt(mg/g) are as follows:
qt=V (C0-Ct)/W
(9) the modified big mesoporous silicon fiml of lanthanum is subjected to dynamic analysis test.
It accurately weighs 20mg membrane material to be added in 10mL colorimetric cylinder, be demarcated with 200mg/L phosphate solution to 10mL.It will
After colorimetric cylinder is placed in 25 DEG C of constant temperature gas bath oscillation 5,15,30,60,90,120,180,270,360,720min, take upper layer clear
Liquid determines the ultimate density of phosphoric acid solution by inductively-coupled plasma spectrometer, and calculates adsorbance.
(10) the modified big mesoporous silicon fiml of lanthanum is subjected to coexisting ion absorption test.
A series of phosphate solution (F with counter anion are prepared with standard solution (pH=4,25 DEG C)-, Cl-, NO3 -
And SO4 2-Sodium-salt form) solution, with obtain ultimate density be every kind of anion 150mg/L.20mg membrane sample is added
In 10mL colorimetric cylinder, demarcated with the phosphate solution of preparation to 10mL.Supernatant liquor is taken to pass through inductively coupled plasma spectrometry
Instrument determines the ultimate density of phosphoric acid solution, and calculates adsorbance.
Embodiment 2
(1) it weighs 10g medical absorbent cotton to be dissolved in the sulfuric acid solution of 50wt% concentration, and is stirred at 45 DEG C
2h.Later, so that it is stopped hydrolytic process with the cellulose of 2000 milliliters of cold ultrapure water dilution hydrolysis, and stand 12h.Give up
Remaining white fiber element is carried out centrifugal treating by layer clear liquid.Then, the white suspension being centrifuged out is washed with deionized water
3 times are washed to remove soluble cellulosic material, is subsequently placed in bag filter (molecular cut off 11000-15000) 2~5 days
(until pH=2.4 of suspension).The solid product finally obtained dilutes in water, and is passing through ultrasonic treatment dispersion using preceding
10 minutes, being diluted to mass percent concentration was 3.5%.
(2) CNCs suspension (pH=2.4) obtained in the step 1 of 15mL is ultrasonically treated 10min.150mg is anhydrous
Glucose is added in CNCs and stirs 1h at 25 DEG C, and 600 μ L tetramethoxy-silicanes (TMOS) are added in mixture suspension later.
Mixture suspension stirs 2h at 25 DEG C.Later, uniform mixture pour into polystyrene culture dish (d=90mm) and
It dries at room temperature.In 25 DEG C of water-baths slow evaporation 2~3 days to form complete CNCs/ silica composite films A, referred to as
CSF。
(3) Cellulose nanocrystal/silica composite films that step (2) obtain are placed in water-bath 7 days in sulfuric acid solution, obtained
To big mesoporous silicon fiml B, abbreviation MSF；
Wherein, the volume ratio of the concentrated sulfuric acid of sulfuric acid solution and water is 1:3, and bath temperature is controlled at 85 DEG C.
(4) the 1g silicon fiml mesoporous greatly that synthesis obtains in step (3) is added in beaker, after will be dissolved with 0.6964g's
The 100mL ethyl alcohol of lanthanum nitrate hexahydrate is added in beaker, 60 DEG C of water-bath oscillations is placed the beaker for 24 hours, later in 80 DEG C of baking ovens
It is dry；
(5) the modified big mesoporous silicon fiml of step (4) is placed in Muffle furnace, initially with 10 DEG C of min-1It is warming up to 100
DEG C, 2h is kept, later with 10 DEG C of min-1550 DEG C are warming up to, 6h is kept, obtains the modified big mesoporous silicon fiml D of final product lanthanum, letter
La-MSF-10 (Si/La molar ratio is referred to as 10:1).
(6) the modified big mesoporous silicon fiml of lanthanum is subjected to optimal adsorption pH test.
Anhydrous potassium dihydrogenphosphate is weighed, configures phosphate standard liquid, concentration 200mg/L with ultrapure water.Accurately weigh 20mg
Silicon fiml adsorbent is placed in 10mL colorimetric cylinder, using the pH value of hydrochloric acid and sodium hydrate regulator solution make in the range of 2.0 to
11.0, adsorption process vibrates 24 hours in 25 DEG C of constant temperature gas bath, after take supernatant liquor pass through inductively coupled plasma body light
Spectrometer determines the ultimate density of phosphoric acid solution, and calculates adsorbance, and obtaining Optimal pH is 3 or 4.
(7) the modified big mesoporous silicon fiml of lanthanum is subjected to optimal adsorption temperature test.
Anhydrous potassium dihydrogenphosphate is weighed, configures phosphate standard liquid, concentration 200mg/L with ultrapure water.By 20mg membrane material
Adsorbent is added in the colorimetric cylinder of 10mL, is demarcated with the phosphoric acid solution of pH=4 to 10mL.It is small to be placed in oscillation 24 in constant temperature gas bath
When, setting temperature is 20~40 DEG C, and supernatant liquor is taken to determine the final of phosphoric acid solution by inductively-coupled plasma spectrometer
Concentration, and calculate adsorbance.
(8) the modified big mesoporous silicon fiml of lanthanum is subjected to the assessment of thermoisopleth absorption property.
Potassium dihydrogen phosphate is accurately weighed, 200mg/L phosphate standard liquid is configured to.Standard solution is diluted to various concentration
The phosphoric acid solution of (10,25,50,75,100,125,150,175,200mg/L), and the pH for adjusting solution is 4.Weigh 20mg film
Material is added in 10mL colorimetric cylinder, is demarcated with various concentration phosphoric acid solution to 10mL, is shaken in 25 DEG C of constant temperature gas bath
After swinging 24 hours, supernatant liquor is taken to determine the ultimate density of phosphoric acid solution by inductively-coupled plasma spectrometer, and calculate
Adsorbance.If the mixed liquor volume being added is W (L), the initial concentration of matched solution is C0(mg/L), after certain time absorption
Its concentration is Ct(mg/L), then the adsorbance q of filmt(mg/g) are as follows:
qt=V (C0-Ct)/W
(9) the modified big mesoporous silicon fiml of lanthanum is subjected to dynamic analysis test.
It accurately weighs 20mg membrane material to be added in 10mL colorimetric cylinder, be demarcated with 200mg/L phosphate solution to 10mL.It will
After colorimetric cylinder is placed in 25 DEG C of constant temperature gas bath oscillation 5,15,30,60,90,120,180,270,360,720min, take upper layer clear
Liquid determines the ultimate density of phosphoric acid solution by inductively-coupled plasma spectrometer, and calculates adsorbance.
(10) the modified big mesoporous silicon fiml of lanthanum is subjected to coexisting ion absorption test.
A series of phosphate solution (F with counter anion are prepared with standard solution (pH=4,25 DEG C)-, Cl-, NO3 -
And SO4 2-Sodium-salt form) solution, with obtain ultimate density be every kind of anion 150mg/L.20mg membrane sample is added
In 10mL colorimetric cylinder, demarcated with the phosphate solution of preparation to 10mL.Supernatant liquor is taken to pass through inductively coupled plasma spectrometry
Instrument determines the ultimate density of phosphoric acid solution, and calculates adsorbance.
Embodiment 3
(1) it weighs 10g medical absorbent cotton to be dissolved in the sulfuric acid solution of 60wt% concentration, and is stirred at 50 DEG C
1.5h.Later, so that it is stopped hydrolytic process with the cellulose of 2000 milliliters of cold ultrapure water dilution hydrolysis, and stand 12h.Give up
Remaining white fiber element is carried out centrifugal treating by supernatant liquor.Then, the white suspension deionized water that will be centrifuged out
The washing 3 times cellulosic materials soluble with removing, are subsequently placed in 2~5 in bag filter (molecular cut off 11000-15000)
Its (until pH=2.4 of suspension).The solid product finally obtained dilutes in water, and is passing through ultrasonic treatment point using preceding
It dissipates 10 minutes, being diluted to mass percent concentration is 4%.
(2) CNCs suspension (pH=2.4) obtained in the step 1 of 15mL is ultrasonically treated 30min.200mg is anhydrous
Glucose is added in CNCs and stirs 1.5h at 30 DEG C, and mixture suspension is added in 800 μ L tetramethoxy-silicanes (TMOS) later
In.Mixture suspension stirs 3h at 30 DEG C.Later, uniform mixture pours into polystyrene culture dish (d=90mm)
And it is dried at room temperature for.In 30 DEG C of water-baths slow evaporation 2~3 days to form complete CNCs/ silica composite films A, letter
Claim CSF.
(3) Cellulose nanocrystal/silica composite films that step (2) obtain are placed in water-bath 11 days in sulfuric acid solution,
Obtain big mesoporous silicon fiml B, abbreviation MSF；
Wherein, the volume ratio of the concentrated sulfuric acid of sulfuric acid solution and water is 1:2, and bath temperature is controlled at 90 DEG C.
(4) the 1g silicon fiml mesoporous greatly that synthesis obtains in step (3) is added in beaker, after will be dissolved with 1.3928g's
The 100mL ethyl alcohol of lanthanum nitrate hexahydrate is added in beaker, 80 DEG C of water-bath oscillation 36h is placed the beaker, later in 90 DEG C of baking ovens
It is dry；
(5) the modified big mesoporous silicon fiml of step (4) is placed in Muffle furnace, initially with 7 DEG C of min-1It is warming up to 100
DEG C, 3h is kept, later with 7 DEG C of min-1600 DEG C are warming up to, 8h is kept, obtains the modified big mesoporous silicon fiml D of final product lanthanum, letter
La-MSF-5 (Si/La molar ratio is referred to as 5:1).
(6) the modified big mesoporous silicon fiml of lanthanum is subjected to optimal adsorption pH test.
Anhydrous potassium dihydrogenphosphate is weighed, configures phosphate standard liquid, concentration 200mg/L with ultrapure water.Accurately weigh 20mg
Silicon fiml adsorbent is placed in 10mL colorimetric cylinder, using the pH value of hydrochloric acid and sodium hydrate regulator solution make in the range of 2.0 to
11.0, adsorption process vibrates 24 hours in 25 DEG C of constant temperature gas bath, after take supernatant liquor pass through inductively coupled plasma body light
Spectrometer determines the ultimate density of phosphoric acid solution, and calculates adsorbance, and obtaining Optimal pH is 3 or 4.
(7) the modified big mesoporous silicon fiml of lanthanum is subjected to optimal adsorption temperature test.
Anhydrous potassium dihydrogenphosphate is weighed, configures phosphate standard liquid, concentration 200mg/L with ultrapure water.By 20mg membrane material
Adsorbent is added in the colorimetric cylinder of 10mL, is demarcated with the phosphoric acid solution of pH=4 to 10mL.It is small to be placed in oscillation 24 in constant temperature gas bath
When, setting temperature is 20~40 DEG C, and supernatant liquor is taken to determine the final of phosphoric acid solution by inductively-coupled plasma spectrometer
Concentration, and calculate adsorbance.
(8) the modified big mesoporous silicon fiml of lanthanum is subjected to the assessment of thermoisopleth absorption property.
Potassium dihydrogen phosphate is accurately weighed, 200mg/L phosphate standard liquid is configured to.Standard solution is diluted to various concentration
The phosphoric acid solution of (10,25,50,75,100,125,150,175,200mg/L), and the pH for adjusting solution is 4.Weigh 20mg film
Material is added in 10mL colorimetric cylinder, is demarcated with various concentration phosphoric acid solution to 10mL, is shaken in 25 DEG C of constant temperature gas bath
After swinging 24 hours, supernatant liquor is taken to determine the ultimate density of phosphoric acid solution by inductively-coupled plasma spectrometer, and calculate
Adsorbance.If the mixed liquor volume being added is W (L), the initial concentration of matched solution is C0(mg/L), after certain time absorption
Its concentration is Ct(mg/L), then the adsorbance q of filmt(mg/g) are as follows:
qt=V (C0-Ct)/W
(9) the modified big mesoporous silicon fiml of lanthanum is subjected to dynamic analysis test.
It accurately weighs 20mg membrane material to be added in 10mL colorimetric cylinder, be demarcated with 200mg/L phosphate solution to 10mL.It will
After colorimetric cylinder is placed in 25 DEG C of constant temperature gas bath oscillation 5,15,30,60,90,120,180,270,360,720min, take upper layer clear
Liquid determines the ultimate density of phosphoric acid solution by inductively-coupled plasma spectrometer, and calculates adsorbance.
(10) the modified big mesoporous silicon fiml of lanthanum is subjected to coexisting ion absorption test.
A series of phosphate solution (F with counter anion are prepared with standard solution (pH=4,25 DEG C)-, Cl-, NO3 -
And SO4 2-Sodium-salt form) solution, with obtain ultimate density be every kind of anion 150mg/L.20mg membrane sample is added
In 10mL colorimetric cylinder, demarcated with the phosphate solution of preparation to 10mL.Supernatant liquor is taken to pass through inductively coupled plasma spectrometry
Instrument determines the ultimate density of phosphoric acid solution, and calculates adsorbance.
Fig. 1 is the scanning electron microscope (SEM) photograph of big mesoporous silicon fiml prepared by the present invention: the as can be seen from the figure mesoporous knot of the plane of film
Structure.
Fig. 2 is the transmission electron microscope picture of big mesoporous silicon fiml prepared by the present invention: as can be seen from the figure the composite membrane is mesoporous
Structure.
Fig. 3 is the Fourier Transform Infrared Spectroscopy figure of material prepared by the present invention: due to the load of La, big mesoporous silicon fiml table
Face 955cm-1The silanol bonds at place disappear, 1389cm-1Neighbouring small peak is due to remaining nitrate after calcining.
Fig. 4 is adsorption capacity figure of the adsorbent prepared by the present invention at different pH: as can be seen from the figure film is best
Adsorbing pH is 4, and maximum adsorption capacity is about 50mg/g.
Fig. 5 is adsorption capacity figure of the adsorbent prepared by the present invention under different adsorption times；We can from figure
To material, quickly, the subsequent rate of adsorption is slack-off for the rate of adsorption in first 200 minutes, probably reaches adsorption equilibrium after 6 hours.
Fig. 6 is adsorption capacity figure of the adsorbent prepared by the present invention in the phosphate of various concentration, it can be seen that with
The increase of solution concentration, adsorption capacity gradually increase.
Claims (10)
1. a kind of preparation method of the modified big mesoporous silicon fiml of lanthanum, which comprises the steps of:
Step 1: Cellulose nanocrystal CNCs is prepared using sulphuric acid hydrolysis medical absorbent cotton, it is spare；
Step 2: Cellulose nanocrystal prepared by step 1 is ultrasonically treated, and a certain amount of DEXTROSE ANHYDROUS is added, then sets
In being allowed to uniformly mixed on magnetic stirring apparatus, the positive quanmethyl silicate TMOS of silicon precursor is added later and continues stirring hydrolysis, pours into
In polytetrafluoroethylene (PTFE) culture dish, drying film forming, obtains Cellulose nanocrystal/silica composite films A in a water bath；
Step 3: Cellulose nanocrystal/silica composite films A that step 2 obtains being placed in removal cellulose in sulfuric acid solution and is received
Rice crystal template obtains big mesoporous silicon fiml B；Step 4: the big mesoporous silicon fiml B that step 3 is obtained is placed in a beaker, rear that six water are added
Lanthanum nitrate and alcohol mixed solution are closed, in water bath chader, using the modified silicon fiml of ethanol evaporation method, is finally placed in baking oven and obtains
To modified big mesoporous silicon fiml C；
Step 5: the modification silicon fiml C mesoporous greatly that step 4 obtains being placed in Muffle furnace and is calcined, modified big Jie of final product lanthanum is obtained
Hole silicon fiml D.
2. a kind of preparation method of the modified big mesoporous silicon fiml of lanthanum as described in claim 1, which is characterized in that in step 1, preparation
The step of Cellulose nanocrystal CNCs are as follows: medical absorbent cotton is placed in 40~60wt% sulfuric acid solution, 35~55 DEG C of stirring water
1~3h is solved, the hydrolysis to inhibit cellulose is diluted by a large amount of ultrapure waters；Overnight stand layering, outwells supernatant liquor, to fiber
The nanocrystalline dispersion liquid centrifuge separation of element, washing；White suspension after centrifuge separation is transferred in dialysis membrane and is dialysed, it is described
The molecular cut off for analysing film is 11000~15000, and dialysis time is 1~5 day；Until pH value is equal to 2.4, dilution, ultrasound is obtained
The Cellulose nanocrystal suspension for being 3%~5% to mass percentage concentration.
3. a kind of preparation method of the modified big mesoporous silicon fiml of lanthanum as described in claim 1, which is characterized in that described in step 2
Cellulose nanocrystal, DEXTROSE ANHYDROUS, positive quanmethyl silicate amount ratio be the μ of 10~20mL:100~200mg:400~1000
L。
4. a kind of preparation method of the modified big mesoporous silicon fiml of lanthanum as described in claim 1, which is characterized in that described in step 2
Ultrasonic time is 10~30min；Whipping temp after the addition glucose is 20~30 DEG C, and the time is 0.5~1.5h；It is described
Whipping temp after positive quanmethyl silicate is added dropwise is 20~30 DEG C, and the time is 2~3h.
5. a kind of preparation method of the modified big mesoporous silicon fiml of lanthanum as described in claim 1, which is characterized in that described in step 2
Drying film forming are as follows: in polytetrafluoroethylene (PTFE) culture dish, 20~30 DEG C of water-baths are dried 2~7 days.
6. a kind of preparation method of the modified big mesoporous silicon fiml of lanthanum as described in claim 1, which is characterized in that described in step 3
In sulfuric acid solution remove Cellulose nanocrystal template process are as follows: by Cellulose nanocrystal/silica composite films A in sulphur
The volume ratio of water-bath 5~15 days in acid solution, the concentrated sulfuric acid of sulfuric acid solution and water is 1:4~1:2, bath temperature control 70~
90℃。
7. a kind of preparation method of the modified big mesoporous silicon fiml of lanthanum as described in claim 1, which is characterized in that described in step 4
Big mesoporous silicon fiml B, ethyl alcohol, lanthanum nitrate hexahydrate amount ratio be 1g:50~200mL:0.3~6g, bath temperature be 40~
80 DEG C, duration of oscillation is 12~36h, is dried in an oven later, and oven temperature is controlled at 60~100 DEG C.
8. a kind of preparation method of the modified big mesoporous silicon fiml of lanthanum as described in claim 1, which is characterized in that in step 5, will
To modification silicon fiml C mesoporous greatly be placed in Muffle furnace, initially with 5~10 DEG C of min-1100 DEG C are warming up to, 1~3h is kept, then exists
With 5~10 DEG C of min-1500~600 DEG C are warming up to, 5~8h is kept, obtains the modified big mesoporous silicon fiml D of final product lanthanum.
9. a kind of modified big mesoporous silicon fiml of lanthanum that the preparation method as described in any one of claim 1~8 obtains, which is characterized in that
The mesoporous silicon fiml is chiral liquid crystal nematic structure, has well-regulated big meso-hole structure.
10. a kind of modified big mesoporous silicon fiml of lanthanum as claimed in claim 9 is used for the phosphate anion in selective absorption water body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910646162.5A CN110433766A (en) | 2019-07-17 | 2019-07-17 | A kind of modified mesoporous silicon fiml and its preparation method and application greatly of lanthanum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910646162.5A CN110433766A (en) | 2019-07-17 | 2019-07-17 | A kind of modified mesoporous silicon fiml and its preparation method and application greatly of lanthanum |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110433766A true CN110433766A (en) | 2019-11-12 |
Family
ID=68430676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910646162.5A Pending CN110433766A (en) | 2019-07-17 | 2019-07-17 | A kind of modified mesoporous silicon fiml and its preparation method and application greatly of lanthanum |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110433766A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022160824A1 (en) * | 2021-01-28 | 2022-08-04 | 青岛科技大学 | Preparation method for novel solid electrolyte |
Citations (6)
| 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 |
| 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 |
| 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 |
-
2019
- 2019-07-17 CN CN201910646162.5A patent/CN110433766A/en active Pending
Patent Citations (6)
| 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 |
| 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 |
| 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 |
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"", 《NANOSCALE》 * |
| 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》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022160824A1 (en) * | 2021-01-28 | 2022-08-04 | 青岛科技大学 | Preparation method for novel solid electrolyte |
| US11777146B2 (en) | 2021-01-28 | 2023-10-03 | Qingdao University Of Science And Technology | Preparation method of solid electrolyte |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107694510B (en) | Method for removing methylene blue in printing and dyeing wastewater by two-dimensional magnetic MXene | |
| CN105236507B (en) | The method that the adsorbent being combined using beta cyclodextrin chitosan and walnut shell charcoal removes the Cr VI in waste water | |
| CN106334524B (en) | Nucleocapsid structure layered double hydroxide compound particle preparation method and application | |
| CN102580689B (en) | Anionic dye adsorbent as well as preparation method and application thereof | |
| CN113457474B (en) | Nanofiber membrane material, preparation method and application thereof | |
| CN106111060B (en) | A kind of modification biological carbon composite and its preparation and application | |
| Caprarescu et al. | Commercial gooseberry buds extract containing membrane for removal of methylene blue dye from synthetic wastewaters | |
| CN108129547A (en) | A kind of method for extracting zoogloea extracellular polymeric | |
| US11577220B2 (en) | Cellulose nanocrystal-supported sodium alginate adsorbent | |
| CN108745289A (en) | The preparation method and application of LDH and SWCNT nanocomposites | |
| CN109110863A (en) | Utilize the method for fortimicin in chemical activation/micro-wave digestion activation biological carbon materials removal water body | |
| CN110433766A (en) | A kind of modified mesoporous silicon fiml and its preparation method and application greatly of lanthanum | |
| CN112371077A (en) | Simplified synchronous denitrification and dephosphorization adsorbent and preparation method thereof | |
| CN103933946B (en) | Adsorbent of bacterial cellulose loaded lanthanum metal compound, preparation and application thereof | |
| CN106268673B (en) | A kind of preparation method of amino modified chitosan composite adsorbing material | |
| Yang et al. | Polyacrylamide grafted cellulose as an eco-friendly flocculant: efficient removal of organic dye from aqueous solution | |
| CN105935582B (en) | A kind of preparation method and application of graphene sorbing material | |
| CN105647772B (en) | Aging hastening method based on foraging white spirit agent | |
| CN108249425B (en) | Method for preparing graphene quantum dots by using molecular sieve | |
| CN109200990A (en) | A kind of preparation method and its usage of the lanthanum coordination functional mesoporous silicon dioxide film of diamino | |
| CN106215882B (en) | It is a kind of for handling the preparation method of the watermelon peel adsorbent of waste water from dyestuff | |
| CN109364960A (en) | A kind of macropore TiO of wide spectrum excitation2Optic catalytic composite material and preparation method thereof | |
| CN109201018A (en) | A kind of preparation method and purposes of the mesoporous carbon film of La doped | |
| Rahman et al. | The effect of various acids to the gelation process to the silica gel characteristic using organic silica | |
| CN113893841A (en) | Barium titanate nano material for piezoelectric catalytic degradation of trace organic pollutants in water and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191112 |
|
| RJ01 | Rejection of invention patent application after publication |