CN110283361A - A kind of preparation method of the graphene fiber element aeroge of lanthanum-carried zirconium double metal - Google Patents
A kind of preparation method of the graphene fiber element aeroge of lanthanum-carried zirconium double metal Download PDFInfo
- Publication number
- CN110283361A CN110283361A CN201811602706.XA CN201811602706A CN110283361A CN 110283361 A CN110283361 A CN 110283361A CN 201811602706 A CN201811602706 A CN 201811602706A CN 110283361 A CN110283361 A CN 110283361A
- Authority
- CN
- China
- Prior art keywords
- lanthanum
- aeroge
- preparation
- fiber element
- microcrystalline cellulose
- 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
- B01J20/06—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
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- 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
- B01J20/28047—Gels
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- 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
-
- 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
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
- C08J2205/026—Aerogel, i.e. a supercritically dried gel
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Dispersion Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a kind of preparation method of the graphene fiber element aeroge of lanthanum-carried zirconium double metal, this method prepares graphene fiber element aeroge first；Then lanthanum salt and zirconates are dissolved in the aqueous solution containing hydrochloric acid and ethyl alcohol, graphene fiber element aeroge, segmentally heating stirring is added, obtained sample is added in NaOH solution after filtering and is stirred to react, it is washed after filtering, is dry, obtaining the graphene fiber element aeroge of lanthanum-carried zirconium double metal.Aeroge of the invention is by specific chemical key to fluorine, phosphorus specific adsorption, it can be in the case where a variety of interfering ions coexist, not by the interference of other ions, the fluorine and phosphorus in water removal can efficiently be removed, regeneration treatment is carried out after aeroge absorption, still keeps original adsorption capacity, while lanthanum, zirconium form hydroxide sediment by sodium hydroxide and increase the specific surface area of material, the toughness and intensity of structure are further increased, does not allow it in use easy to harden.
Description
Technical field
The present invention relates to a kind of preparation methods of the graphene fiber element aeroge of lanthanum-carried zirconium double metal, belong to adsorption material
Expect technical field.
Background technique
Aeroge, be it is a kind of liquid original in gel is removed or is replaced with gas, a kind of inside obtained from
Bulk multi-hole but the special gel for not changing some intrinsic essence such as original network structure or volume size, are water-settings
The product that glue or organogel are obtained after dry under the conditions of certain specific by certain method.Aerogel material is with gas
Body replaces liquid as decentralized medium, and using solid phase as the network skeleton of gel, gap structure has reached Nano grade.This
Kind continuous three-dimensional manometer network structure allows for aeroge and is provided with unique performance, such as high specific surface area, extremely-low density,
Low-k, lower thermal conductivity, unique optics and acoustical behavior etc., thus be often applied to wastewater treatment, catalyst and its
The fields such as carrier, absorption, energy storage.
Graphite oxide aerogel is mutually overlapped by a large amount of graphene synusia, and three-dimensional network is self-assembly of
Shape porous structure.There is a large amount of hole in graphite oxide aerogel, porosity can be up to 99.7%, wherein single hole
Diameter differed from several nanometers to a few micrometers.Graphite oxide aerogel has the characteristic of hydrophobic oleophilic oil, density 2.4mg/cm3
Graphite oxide aerogel 226 is up to the saturated extent of adsorption for the organic solvent that density is 0.788~1.595g/cm3~
567g/g.The advantages of porous network shape structure and biggish specific surface area for having due to graphite oxide aerogel, so can
With with this aeroge under the action of physical absorption come contain in drainage it is smaller than graphite oxide aerogel aperture size
Organic dye molecule or other impurities, to achieve the purpose that purified water.But the building of three-dimensional grapheme structural body only according to
It is acted on by the weak electrostatic interaction of graphene film interlayer, hydrogen bond or pi-pi bond, it is difficult to realize the high mechanics of three-dimensional grapheme structural body
Performance, mechanical strength is lower, is easily broken after adsorption saturation.
Current aeroge is largely and not have effect to phosphorus, fluorine for adsorbing organic material, the fluoride pollution in water
It is a global environmental problem.According to the regulation of the World Health Organization, the fluorinion concentration in drinking water is not to be exceeded
1.0mg/L.Excessively high fluorine ion will lead to fluorine poisoning, den tal fluorosis, fluorosis of bone, thyroid gland wound, the diseases such as kidney damage in reference water
Disease.The theory of conservation culture at present also focuses more on drinking water safety by everybody wide-scale distribution, the public.Current existing fluorine removal skill
Art mainly has coagulant sedimentation, absorption method, membrane separation process, ion-exchange, electrocoagulation, electroosmose process etc..These methods exist
Removal efficiency is low, device complexity, problem at high cost, it is difficult to promote in practice.Only absorption method is more commonly used, and efficient
Adsorbent is the key that absorption method.
Common adsorbent mainly active aluminium oxide, molecular sieve, rare-earth adsorbent and natural macromolecule adsorbent etc..
However, these adsorbents can be all dissolved under conditions of pH is less than 1, and the F meeting adsorbed up under conditions of pH is greater than 8
It is desorbed.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provide a kind of lanthanum-carried zirconium double metal graphene fiber element aeroge and
Preparation method.
Technical scheme is as follows:
A kind of graphene fiber element aeroge of lanthanum-carried zirconium double metal, the aeroge is with graphene fiber element airsetting
Glue is carrier, and supported on carriers has the hydroxide sediment of lanthanum and zirconium.
A kind of preparation method of the microcrystalline cellulose graphene aerogel of lanthanum-carried zirconium double metal, comprises the following steps that
(1) graphene oxide is taken and is dispersed in water, obtain graphene oxide dispersion, microcrystalline cellulose is taken and is scattered in water
In, microcrystalline cellulose dispersion liquid is obtained, graphene oxide dispersion is added dropwise in microcrystalline cellulose dispersion liquid and obtains mixed liquor, is adjusted
Ammonium hydroxide is added in pH, ultrasound, heated sealed 10-16 hours at 90-100 DEG C, solids is impregnated, cleaning, freeze-drying obtains
Graphene fiber element aeroge；
(2) lanthanum salt and zirconates are dissolved in the aqueous solution containing hydrochloric acid and ethyl alcohol, aeroge, segmentally heating is then added
Stirring, obtained sample are added in NaOH solution after filtering and are stirred to react, and wash after filtering, is dry, obtain the double gold of lanthanum-carried zirconium
The graphene fiber element aeroge of category.
Preferred according to the present invention, in step (1), the concentration of graphene oxide dispersion is 0.5-1.0g/100mL, institute
The graphene oxide stated is to be made using Hemmer method.
Preferred according to the present invention, in step (1), the concentration of microcrystalline cellulose dispersion liquid is 0.5-1.0g/100mL.
It is preferred according to the present invention, in step (1), body that graphene oxide dispersion is mixed with microcrystalline cellulose dispersion liquid
Product ratio are as follows: (1-2): (1-2).
Preferred according to the present invention, in step (1), adjusting pH is to adjust pH to neutrality, institute using the NaOH solution of 1mol/L
The ultrasound stated is ice-bath ultrasonic 30min, and ice bath temperature is 0 DEG C.
Preferred according to the present invention, in step (1), the additional amount of ammonium hydroxide and the volume ratio of mixed liquor are 0.5-1.5:100,
The mass concentration of ammonium hydroxide is 25~28%.
Preferred according to the present invention, in step (1), soaking time is 48 hours, is changed during immersion water 2-3 times, and freezing is dry
The dry time is 44-50h.
Preferred according to the present invention, in step (1), microcrystalline cellulose is to be prepared as follows to obtain: by fibrous raw material
It is mixed with sodium hydroxide solution, heating reaction 1-2h, the concentrated sulfuric acid adjusts pH to neutrality, and cleaning, drying to constant weight will be fine after drying
It ties up in raw material soaking sulfuric acid, heating hydrolysis, adjusts pH to neutrality again, wash, is dry, obtaining microcrystalline cellulose.
It is further preferred that fibrous raw material is cotton fiber, the mass concentration of sodium hydroxide solution is 1-3%, fibrous raw material
With the mass volume ratio of sodium hydroxide solution are as follows: 5-20:1, g/L, heating reaction temperature are 40-60 DEG C, and adjusting pH uses dense
The concentration of sulfuric acid is 0.5mol/L.
It is further preferred that after dry fibrous raw material and sulfuric acid mass volume ratio are as follows: 5-20:1, g/L, the quality of sulfuric acid
Concentration is 6-10%, and hydrolysis temperature is 75-85 DEG C, and adjusting pH again is to be adjusted to neutrality with the NaOH of 1mol/L.
Preferred according to the present invention, the lanthanum salt is LaCl3, the zirconates is ZrOCl2·8H2O。
Preferred according to the present invention, the volume fraction of hydrochloric acid is 4-6% in the aqueous solution containing hydrochloric acid and ethyl alcohol, ethyl alcohol
Volume fraction is 20-30%.
It is preferred according to the present invention, the mass volume ratio of the additional amount of lanthanum salt and the aqueous solution containing hydrochloric acid and ethyl alcohol are as follows:
100-135:1, g/L, the mass volume ratio of the additional amount of zirconates and the aqueous solution containing hydrochloric acid and ethyl alcohol are as follows: 120-150:1, g/
The mass ratio of L, aeroge and lanthanum salt is 1:2-4.
It is preferred according to the present invention, in step (2), segmentally heating be first 50 DEG C heating stirring 12 hours, then 60
It is stirred 6 hours at DEG C.
It is preferred according to the present invention, in step (2), the mass volume ratio of filtered sample and NaOH solution are as follows: 5-
30g/100mL, the concentration of NaOH solution are 0.25moL/L.
The application of the graphene fiber element aeroge of lanthanum-carried zirconium double metal, for not removed waste water by other ion interferences
Middle fluorine and phosphorus, the additional amount of aeroge are 0.01-0.1g/100mL solution.
Present invention technical characterstic compared with the prior art and effect:
1, the microcrystalline cellulose graphene aerogel of lanthanum-carried zirconium double metal of the invention by specific chemical key to fluorine,
Phosphorus specific adsorption can efficiently can go to remove water in the case where a variety of interfering ions coexist, not by the interference of other ions
In fluorine and phosphorus.
2, the microcrystalline cellulose graphene aerogel of lanthanum-carried zirconium double metal of the invention is to fluorine, phosphorus large amount of adsorption, removal
It is high-efficient.
3, the microcrystalline cellulose graphene aerogel of lanthanum-carried zirconium double metal of the invention, lanthanum, zirconium are heavy by hydroxide
The form of starch is supported in the hole and lamella of graphene fiber element aeroge, while also a small amount of lanthanum ion, zirconium ion,
Adsorption capacity is powerful, carries out regeneration treatment after aeroge absorption, still keeps original adsorption capacity.
4, the present invention helps the lamella of graphene oxide to separate, lanthanum, zirconium pass through hydrogen by hydro-thermal method using hydrochloric acid and ethyl alcohol
Sodium oxide molybdena forms hydroxide sediment to the further reaming of graphene fiber element aeroge, increases the specific surface area of material,
Adsorption capacity further enhances, while the hydroxide sediment of lanthanum and zirconium is supported on graphene fiber element aeroge hole and piece
The toughness and intensity of structure are further increased in layer, does not allow it easy to harden, long service life.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) figure of aeroge prepared by the embodiment of the present invention 1；
Fig. 2 is the XRD diagram of aeroge prepared by the embodiment of the present invention 1.
Fig. 3 is the adsorption isotherm (adsorbent dosage: 0.5g/L) of aeroge prepared by the embodiment of the present invention 1.
Fig. 4 be the embodiment of the present invention 1 prepare aeroge adsorption dynamics adsorption kinetics figure (adsorbent dosage: 0.5g/L, fluorine from
Sub- concentration 50mg/L).
Specific embodiment
Below with reference to embodiment, the present invention will be further described, and non-elaborate is existing by this field in embodiment
Technology.
Embodiment 1
A kind of preparation method of the microcrystalline cellulose graphene aerogel of lanthanum-carried zirconium double metal, comprises the following steps that
(1) 0.5g raw cotton is mixed with the sodium hydroxide solution that 1L mass fraction is 2%, 50 DEG C of heating 2h of oil bath are used
The concentrated sulfuric acid of 0.5mol/L adjusts pH to neutrality, washes with water clean, 80 DEG C of dryings to constant weight；By the cotton fiber 0.5g after drying
It is soaked in the sulfuric acid that 1L mass fraction is 8%, 80 DEG C of heating stirrings use microcrystalline cellulose up to being hydrolyzed to microcrystalline cellulose
The NaOH of 1mol/L is adjusted to neutrality, filtering washing, dry to constant weight, obtains microcrystalline cellulose；
(2) microcrystalline cellulose graphene aerogel is prepared
0.7g is taken to be scattered in 100mL deionized water, ultrasonic 30min, crystallite the graphene oxide made from Hemmer method
Cellulose 0.7g is scattered in 100mL deionized water, ultrasonic 30min, and graphene oxide dispersion is added drop-wise to crystallite fibre dropwise
It ties up in plain dispersion liquid, obtains mixed liquor, mixed liquor is adjusted into pH to neutrality using the NaOH solution of 1mol/L, ice-bath ultrasonic at 0 DEG C
Mixed liquor is transferred in hydrothermal reaction kettle by 30min, and the ammonium hydroxide that 2mL mass concentration is 25~28%, 95 DEG C of heated sealeds are added
12 hours, obtained hydrogel is impregnated 48 hours in deionized water, during which changes water 3 times, obtain microcrystalline cellulose graphene
Hydrogel is freeze-dried 48h by hydrogel, and graphene fiber element aeroge is made.
(3) the double load graphene fiber element aeroges of lanthanum zirconium are prepared.
By 6.0gLaCl3With 7.5g ZrOCl2·8H2O be dissolved in 60mL contain hydrochloric acid (5%, v/v) and ethyl alcohol (25%,
V/v in aqueous solution), aeroge 2g obtained is added, first 50 DEG C heating stirring 12 hours, then stirring 6 is small at 60 DEG C
When, it is added in the NaOH solution of 100mL 0.25moL under room temperature and stirs 12 hours after sample is filtered, after sample filtering,
It is cleaned with deionized water to neutrality, it is dry at 60 DEG C, the double load graphene fiber element aeroges of lanthanum zirconium are made.
Embodiment 2
The adsorbent 0.05g of embodiment 1 is added in the Fluorinse that 100mL concentration is 50mg/L (pH=3), 25 DEG C
Lower absorption 12h, after adsorption equilibrium, unit mass adsorbent reaches 34.2mg/g to the adsorbance of fluorine ion.Illustrate the adsorbent
With very high adsorption capacity.
Embodiment 3
The adsorbent 0.05g of embodiment 1 is added in 100mL fluoride solution, wherein sulphur radical ion is added, sulfate radical from
Sub- molar concentration is 200 times of fluorine ion, and the removal rate of fluorine ion is 80% at this time, shows that adsorbent has very fluorine ion
Strong selective absorption effect.
Embodiment 4
The 1g adsorbent of embodiment 1 is filled into the adsorption column that diameter is 10cm to the competitive Adsorption reality for carrying out fluorine ion
It tests, fluorinion concentration 20mg/L, other competing ions are NO3Concentration is 200mg/L, sulfate concentration 300mg/L, humic
Acid concentration is 10mg/L.As a result the bed volume that the accessible liquor capacity of adsorbent is 100 times is shown, shows that adsorbent is higher
Adsorption effect has the ability of processing actual complex waste water, is not influenced by other ions.
Comparative example 1
A kind of preparation method of lanthanum-carried microcrystalline cellulose graphene aerogel, step (1), step (2) same to embodiment
1, the difference is that:
LaCl is only added in step (3)3, it is added without ZrOCl2·8H2O。
Comparative example 2
A kind of preparation method for the microcrystalline cellulose graphene aerogel loading zirconium, step (1), step (2) same to embodiment
1, the difference is that:
ZrOCl is only added in step (3)28H2O is added without LaCl3。
Comparative example 3
A kind of adsorbent is the mixture of 0.5g hydrous zirconia gel and 0.5g hydrous zirconium oxide(HZO).
Comparative example 4
A kind of adsorbent is graphene fiber element aeroge made from 1 step of embodiment (2).
Experimental example 1
The 1g adsorbent of the 1g adsorbent of embodiment 1 and comparative example 1-3 is filled to the adsorption column for being 10cm to diameter respectively
The middle competitive Adsorption experiment for carrying out fluorine ion, fluorinion concentration 20mg/L or phosphate radical 30mg/L (being remembered with P), concentration other
Competing ions are NO3Concentration is 200mg/L, sulfate concentration 300mg/L, humic acid concentration 10mg/L, comparison absorption effect
Fruit, the results are shown in Table 1:
Table 1
Experimental example 2,
Comparative example 1,2,3,4 carries out specific surface area and adsorbance measurement, and experimental result is as shown in table 2 below.
Table 2
| Project | Specific surface area | Adsorbance |
| Embodiment 1 | 82.15m2/g | 34.2mg/g |
| Comparative example 1 | 42.19m2/g | 13.2mg/g |
| Comparative example 2 | 45.25m2/g | 11.1mg/g |
| Comparative example 3 | 33.34m2/g | 16.7mg/g |
| Comparative example 4 | 65.32m2/g | 15.4mg/g |
It can be seen from Table 1 that in phosphate radical, NO3, sulfate radical, humic acid interference under, the embodiment of the present invention 1 is still
There is very strong Adsorption ability, comparative example 1 lanthanum-carried microcrystalline cellulose graphene aerogel and comparison to fluorine and phosphorus
The microcrystalline cellulose graphene aerogel of example 2 load zirconiums is far smaller than the present invention to the Adsorption of fluorine and phosphorus, although comparison
3 effect of example and effect of the present invention are similar, but comprehensive specific surface area, the specific surface area of comparative example 3 be far smaller than it is of the invention, separately
Outside, in use, comparative example 3 is easy hardened, needs to increase usage amount, is just able to maintain initial adsorption effect, comparative example 4
Although 3 large specific surface area of relative contrast's example, the adsorption effect and comparative example 3 to fluorine and phosphorus are suitable, to sum up, airsetting of the invention
Glue by specific chemical key to fluorine, phosphorus specific adsorption, can in the case where a variety of interfering ions coexist, not by other from
The interference of son, can efficiently remove fluorine and phosphorus in water removal, and lanthanum, zirconium are supported on graphene fibre by way of hydroxide sediment
In the hole and lamella for tieing up plain aeroge, while there are also a small amount of lanthanum ions, zirconium ion, and adsorption capacity is powerful, after aeroge absorption
Regeneration treatment is carried out, original adsorption capacity is still kept, prior lanthanum, zirconium form hydroxide sediment by sodium hydroxide
The specific surface area of material is increased, adsorption capacity further enhances, while the hydroxide sediment of lanthanum and zirconium is supported on graphite
The toughness and intensity of structure are further increased in alkene cellulose aerogels hole and lamella, do not allow it easy to harden.
Embodiment 5
A kind of preparation method of the microcrystalline cellulose graphene aerogel of lanthanum-carried zirconium double metal, step (1), step (2)
By the progress of embodiment 1, the difference is that:
The additional amount of step (3) aeroge is 3g.
Embodiment 6
A kind of preparation method of the microcrystalline cellulose graphene aerogel of lanthanum-carried zirconium double metal, step (1), step (2)
By the progress of embodiment 1, the difference is that:
Step (3) is by 6.0gLaCl3With 7.5g ZrOCl2·8H2O is dissolved in 50mL and contains hydrochloric acid (5%, v/v) and ethyl alcohol
In the aqueous solution of (25%, v/v), aeroge 2g obtained is added.
Claims (10)
1. a kind of graphene fiber element aeroge of lanthanum-carried zirconium double metal, the aeroge is with graphene fiber element aeroge
For carrier, supported on carriers has the hydroxide sediment of lanthanum and zirconium.
2. a kind of preparation method of the microcrystalline cellulose graphene aerogel of lanthanum-carried zirconium double metal, comprises the following steps that
(1) graphene oxide is taken and is dispersed in water, obtain graphene oxide dispersion, microcrystalline cellulose is taken and is dispersed in water,
Microcrystalline cellulose dispersion liquid is obtained, graphene oxide dispersion is added dropwise in microcrystalline cellulose dispersion liquid and obtains mixed liquor, adjusts pH,
Ammonium hydroxide is added in ultrasound, heated sealed 10-16 hours at 90-100 DEG C, solids is impregnated, cleaning, freeze-drying obtains graphite
Alkene cellulose aerogels；
(2) lanthanum salt and zirconates are dissolved in the aqueous solution containing hydrochloric acid and ethyl alcohol, aeroge is then added, segmentally heating is stirred
It mixes, obtained sample is added in NaOH solution after filtering and is stirred to react, and washs after filtering, is dry, obtaining lanthanum-carried zirconium double metal
Graphene fiber element aeroge.
3. preparation method according to claim 2, which is characterized in that in step (1), the concentration of graphene oxide dispersion
For 0.5-1.0g/100mL, the graphene oxide is to be made using Hemmer method, and the concentration of microcrystalline cellulose dispersion liquid is
0.5-1.0g/100mL, the volume ratio that graphene oxide dispersion is mixed with microcrystalline cellulose dispersion liquid are as follows: (1-2): (1-2),
Adjusting pH is that pH is adjusted using the NaOH solution of 1mol/L to neutrality, and the ultrasound is ice-bath ultrasonic 30min, ice bath temperature 0
DEG C, the volume ratio of the additional amount of ammonium hydroxide and mixed liquor is 0.5-1.5:100, and the mass concentration of ammonium hydroxide is 25~28%, when immersion
Between be 48 hours, changed during immersion water 2-3 times, sublimation drying 44-50h.
4. preparation method according to claim 2, which is characterized in that in step (1), microcrystalline cellulose is by the following method
It is prepared: fibrous raw material is mixed with sodium hydroxide solution, heating reaction 1-2h, the concentrated sulfuric acid adjusts pH to neutrality, and cleaning is done
It is dry to be impregnated in sulfuric acid fibrous raw material after drying, heating hydrolysis to constant weight, adjust pH to neutrality again, it is washing, dry, obtain crystallite
Cellulose.
5. the preparation method according to claim 4, which is characterized in that fibrous raw material is cotton fiber, sodium hydroxide solution
Mass concentration is 1-3%, the mass volume ratio of fibrous raw material and sodium hydroxide solution are as follows: 5-20:1, g/L heat reaction temperature
It is 40-60 DEG C, the concentration for adjusting the concentrated sulfuric acid that pH is used is 0.5mol/L；The mass volume ratio of fibrous raw material and sulfuric acid after drying
Are as follows: 5-20:1, g/L, the mass concentration of sulfuric acid are 6-10%, and hydrolysis temperature is 75-85 DEG C, and adjusting pH again is with 1mol/L's
NaOH is adjusted to neutrality.
6. preparation method according to claim 2, which is characterized in that the lanthanum salt is LaCl3, the zirconates is
ZrOCl2·8H2O。
7. preparation method according to claim 2, which is characterized in that the body of hydrochloric acid in the aqueous solution containing hydrochloric acid and ethyl alcohol
Fraction is 4-6%, and the volume fraction of ethyl alcohol is 20-30%.
8. preparation method according to claim 2, which is characterized in that the additional amount of lanthanum salt and the water containing hydrochloric acid and ethyl alcohol
The mass volume ratio of solution are as follows: 100-135:1, g/L, the mass body of the additional amount of zirconates and the aqueous solution containing hydrochloric acid and ethyl alcohol
Product ratio are as follows: the mass ratio of 120-150:1, g/L, aeroge and lanthanum salt is 1:2-4.
9. preparation method according to claim 2, which is characterized in that in step (2), segmentally heating is first to heat at 50 DEG C
Stirring 12 hours, is then stirred 6 hours at 60 DEG C.
10. preparation method according to claim 2, which is characterized in that in step (2), filtered sample and NaOH are molten
The mass volume ratio of liquid are as follows: 5-30g/100mL, the concentration of NaOH solution are 0.25moL/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811602706.XA CN110283361A (en) | 2018-12-26 | 2018-12-26 | A kind of preparation method of the graphene fiber element aeroge of lanthanum-carried zirconium double metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811602706.XA CN110283361A (en) | 2018-12-26 | 2018-12-26 | A kind of preparation method of the graphene fiber element aeroge of lanthanum-carried zirconium double metal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110283361A true CN110283361A (en) | 2019-09-27 |
Family
ID=68001088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811602706.XA Pending CN110283361A (en) | 2018-12-26 | 2018-12-26 | A kind of preparation method of the graphene fiber element aeroge of lanthanum-carried zirconium double metal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110283361A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111330550A (en) * | 2020-03-27 | 2020-06-26 | 神华神东煤炭集团有限责任公司 | Zr/La co-modified cross-linked chitosan, preparation method and application thereof |
| CN111732148A (en) * | 2020-06-29 | 2020-10-02 | 河海大学 | System for retrieve phosphate in follow surface eutrophic water |
| CN113083214A (en) * | 2021-03-30 | 2021-07-09 | 山东大学 | Preparation method of mesoporous zirconium/lanthanum double hydroxide fiber and application of mesoporous zirconium/lanthanum double hydroxide fiber in purification of phosphate wastewater |
| CN114686472A (en) * | 2020-12-31 | 2022-07-01 | 中国石油化工股份有限公司 | Immobilized nitrobacteria and immobilization method thereof |
| CN115725209A (en) * | 2023-01-05 | 2023-03-03 | 曹阳 | Nano composite coating and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105013450A (en) * | 2015-08-04 | 2015-11-04 | 西南科技大学 | Double metal loaded sodium alginate/carboxymethylcellulose double-functional microballoon adsorbing material and preparation method thereof |
| CN105566659A (en) * | 2015-12-25 | 2016-05-11 | 郑州轻工业学院 | Graphene oxide/nano cellulose aerogel and preparation method and application thereof |
| CN106544539A (en) * | 2015-09-16 | 2017-03-29 | 弘大科技（北京）股份公司 | A kind of aeroge-metallic composite and its preparation method and application |
| CN108579626A (en) * | 2018-04-26 | 2018-09-28 | 南京林业大学 | The preparation method of Cellulose nanocrystal body/graphene/polyvinyl alcohol aeroge |
-
2018
- 2018-12-26 CN CN201811602706.XA patent/CN110283361A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105013450A (en) * | 2015-08-04 | 2015-11-04 | 西南科技大学 | Double metal loaded sodium alginate/carboxymethylcellulose double-functional microballoon adsorbing material and preparation method thereof |
| CN106544539A (en) * | 2015-09-16 | 2017-03-29 | 弘大科技（北京）股份公司 | A kind of aeroge-metallic composite and its preparation method and application |
| CN105566659A (en) * | 2015-12-25 | 2016-05-11 | 郑州轻工业学院 | Graphene oxide/nano cellulose aerogel and preparation method and application thereof |
| CN108579626A (en) * | 2018-04-26 | 2018-09-28 | 南京林业大学 | The preparation method of Cellulose nanocrystal body/graphene/polyvinyl alcohol aeroge |
Non-Patent Citations (3)
| Title |
|---|
| WEIYANDU 等: "Selective removal of phosphate by dual Zr and La hydroxide/cellulose-based bio-composites", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| XIAO WEI等: "Green synthesis of hybrid graphene oxide/microcrystalline celluloseaerogels and their use as superabsorbents", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
| YANANSHANG 等: "Highly selective and efficient removal of fluoride from aqueous solution by Zrsingle bondLa dual-metal hydroxide anchored bio-sorbents", 《JOURNAL OF CLEANER PRODUCTION》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111330550A (en) * | 2020-03-27 | 2020-06-26 | 神华神东煤炭集团有限责任公司 | Zr/La co-modified cross-linked chitosan, preparation method and application thereof |
| CN111330550B (en) * | 2020-03-27 | 2023-06-02 | 神华神东煤炭集团有限责任公司 | Zr/La co-modified crosslinked chitosan, preparation method and application thereof |
| CN111732148A (en) * | 2020-06-29 | 2020-10-02 | 河海大学 | System for retrieve phosphate in follow surface eutrophic water |
| CN114686472A (en) * | 2020-12-31 | 2022-07-01 | 中国石油化工股份有限公司 | Immobilized nitrobacteria and immobilization method thereof |
| CN114686472B (en) * | 2020-12-31 | 2023-07-28 | 中国石油化工股份有限公司 | Immobilized nitrifying bacteria and immobilization method thereof |
| CN113083214A (en) * | 2021-03-30 | 2021-07-09 | 山东大学 | Preparation method of mesoporous zirconium/lanthanum double hydroxide fiber and application of mesoporous zirconium/lanthanum double hydroxide fiber in purification of phosphate wastewater |
| CN115725209A (en) * | 2023-01-05 | 2023-03-03 | 曹阳 | Nano composite coating and preparation method thereof |
| CN115725209B (en) * | 2023-01-05 | 2023-12-22 | 曹阳 | Nano composite coating and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110283361A (en) | A kind of preparation method of the graphene fiber element aeroge of lanthanum-carried zirconium double metal | |
| Dai et al. | 3D macroscopic superhydrophobic magnetic porous carbon aerogel converted from biorenewable popcorn for selective oil-water separation | |
| CN110496609B (en) | Graphene oxide/hydroxyapatite nanowire multifunctional adsorption aerogel and preparation method thereof | |
| Liu et al. | Fabrication of functional biomass carbon aerogels derived from sisal fibers for application in selenium extraction | |
| CN105566659B (en) | A kind of graphene oxide/nano-cellulose aerogel and its preparation method and application | |
| Xiong et al. | A 3D titanate aerogel with cellulose as the adsorption-aggregator for highly efficient water purification | |
| Li et al. | Fabrication of cellulose aerogel from wheat straw with strong absorptive capacity | |
| CN102824898B (en) | Three-dimensional porous pressure-resistant and expansion-limiting type bentonite adsorbing material and preparation method thereof | |
| CN106944005A (en) | A kind of depth removes resin-base nano compound adsorbent of Micro fluoride and its preparation method and application | |
| CN111250056B (en) | Chitosan/graphite phase carbon nitride/titanium dioxide nanofiber membrane and preparation method and application thereof | |
| Qiao et al. | Construction of hierarchically porous chitin microspheres via a novel Dual-template strategy for rapid and High-capacity removal of heavy metal ions | |
| Meng et al. | Structural control of silica aerogel fibers for methylene blue removal | |
| CN110652962A (en) | Three-dimensional porous graphene/attapulgite composite aerogel and preparation method thereof | |
| CN111889066A (en) | PH response controlled release hollow mesoporous silica nanoparticle and preparation method thereof | |
| Wang et al. | Three-dimensional graphene/La (OH) 3-nanorod aerogel adsorbent by self-assembly process for enhanced removal and recovery of phosphate in wastewater | |
| CN108046254A (en) | A kind of corncob derives active carbon electrode material and preparation method thereof | |
| CN110917825B (en) | Composite aerogel moisture absorption material and preparation method and application thereof | |
| CN107511130A (en) | A kind of zeolite-loaded nano-tourmaline material and its preparation method and application | |
| CN110102265A (en) | For the load zirconium biology compound adsorbent and regeneration method of removing fluor in water and application | |
| Sun et al. | Mesoporous silica–carbon composites fabricated by a universal strategy of hydrothermal carbonization: controllable synthesis and applications | |
| CN110156038B (en) | Microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve and preparation method and application thereof | |
| Mkrtchyan et al. | Comparative analysis of the adsorption kinetics of the methylene blue dye on graphene aerogel and activated coconut carbon | |
| CN1724344A (en) | Preparing multipurpous carbon with regular constructure and high ratio surface area by mould board carbonizing process | |
| CN106732795A (en) | A kind of fiber/CNT/BiFeO3Three-dimensional recyclable efficient catalytic material and its preparation and application | |
| CN106622177A (en) | Spherical porous adsorbent based on carbon nanotubes as well as preparation method and application of spherical porous adsorbent |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190927 |