CN106824066A - Modified zirconium hydroxide composite adsorbing material of the 3D Graphenes of fluorine ion and preparation method thereof in a kind of removal rural potable water - Google Patents
Modified zirconium hydroxide composite adsorbing material of the 3D Graphenes of fluorine ion and preparation method thereof in a kind of removal rural potable water Download PDFInfo
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- CN106824066A CN106824066A CN201611264627.3A CN201611264627A CN106824066A CN 106824066 A CN106824066 A CN 106824066A CN 201611264627 A CN201611264627 A CN 201611264627A CN 106824066 A CN106824066 A CN 106824066A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
Abstract
The invention discloses modified zirconium hydroxide composite adsorbing material of a kind of 3D Graphenes for removing fluorine ion in rural potable water and preparation method thereof.The preparation method comprises the following steps:(1)Prepare graphene oxide;(2)Prepare 3D Graphene gels;(3)During 3D Graphene gels impregnated in into the mixed liquor that zirconium oxychloride solution and urea liquid are mixed to get, heating water bath is obtained the modified zirconium hydroxide composite adsorbing material of 3D Graphenes.Preparation process is simple of the present invention, raw material sources are extensive and with low cost, and the modified zirconium hydroxide composite adsorbing material of obtained 3D Graphenes is high to the adsorption capacity of fluorine ion, and fluorine removing rate is high;At room temperature, the modified zirconium hydroxide composite adsorbing material treatment of obtained 3D Graphenes removes water sample of the fluorinion concentration in 25~100mg/L, and removal efficiency can reach more than 85%.
Description
Technical field
The invention belongs to adsorbent water-treatment technology field, and in particular to the 3D of fluorine ion in a kind of removal rural potable water
Graphene is modified zirconium hydroxide composite adsorbing material and preparation method.
Background technology
Fluorine is the essential trace elements of the human body, and human body can be by drinking-water, food and breathing intake fluorine ion.Suitably, safety
Water in fluorinion concentration and total intake it is significant to pre- anti-caries and endemic fluorosis.China《Implement in rural area<It is raw
Sanitary standard for drinking water living>Criterion》Content of fluoride 1.0mg/ L are drinking water standard higher limit in middle regulation water, are lacking it
When he may be selected water source, the content of fluoride relaxes limit value for 1.5 mg/ L in drinking water, and high-fluorine water is more than the value.When
Fluorinated volume is in 1.0~1.5 mgL in drinking water-1, drink has slight harmful effect to human body for a long time;When fluorinated volume surpasses in water
Cross 1.5 mg L-1When, drink be susceptible to suffer from den tal fluorosis and fluorosis of bone for a long time.In general, the mgL of fluorinated volume 1.0~3.0-1When master
Show as den tal fluorosis, the graying calcification of tooth;The mgL of fluorinated volume 3.0~6.0-1When, fluorosis of bone can be caused, it is mainly shown as
Leg joint numbness, pain, knee joint enlargement;Fluorinated volume is more than 6.0 mgL-1When, you can cause disabling severe fluorine bone
Disease, shows as the even paralysis etc. of textured bone, hunch, overall pain, disability.Therefore fluorine contains in drinking water
Amount is not to be exceeded 1.0 mgL-1, in particular cases must not exceed 1.5 mgL-1。
In China, drink people in the countryside of the content of fluoride more than 1.5 mg/ L up to more than 5,000 ten thousand people, distribution compared with
Extensively throughout 29 provinces, autonomous regions and municipalities, the part province (autonomous region) of North China, East China, northeast and the Northwest is mainly distributed on.North China
The relative scale drunk high-fluorine water population absolute quantity, account for dangerous total population of drinking water all occupy national the first, belong to fluorine high
Water severely afflicated area.Wherein the Inner Mongol, Henan proportion all reach 45 %, and Tianjin is even up to 70 %, and fluorine high is drunk in East China
Water problems is more serious.
Both at home and abroad treatment fluoride waste method have various, common method mainly have the precipitation method, Coagulation Method, electrocoagulation,
Ion-exchange, electroosmose process, hyperfiltration and absorption method etc..The dosage of wherein medicament used by the precipitation method is big, and can not be by
Effectively utilize, the waste water after treatment is extremely difficult to national standard;The requirement of Coagulation Method pH values is high, big by anion effects, goes fluorine removal
It is unstable;Ion-exchange can simultaneously remove all of counter anion, but regenerate expensive;At electroosmose process and hyperfiltration
Reason high cost, also removes the part mineral matter beneficial to human body while fluorine removal;Absorption method is due to easy to operate, processing cost
Low, high treating effect, reproducible utilization has turned into one of main method of fluoride ion removing.At present, conventional adsorbent has work
Property aluminum oxide, activated carbon, titanium dioxide etc..
The present invention is first preparing raw material using cheap graphite powder, basic zirconium chloride and urea etc., using chemical reduction method
Method prepare the modified zirconium hydroxide composite adsorbing material of 3D Graphenes, be the fluorine ion absorber of high adsorption capacity, operation letter
Single, with low cost, preparation technology flow is simple, and it is a kind of brand-new drinking to remove fluorine ion in water removal using the sorbing material for preparing
Water fluoridation technology.
The content of the invention
Answered it is an object of the invention to provide a kind of modified zirconium hydroxide of 3D Graphenes for removing fluorine ion in rural potable water
Close sorbing material and preparation method thereof.Extensively, preparation process is simple, the 3D Graphenes of preparation are modified the preparation method raw material sources
Zirconium hydroxide composite adsorbing material adsorption capacity is high, and fluorine removing rate is high, so as to substantially reduce fluorine removal cost.
The purpose of the present invention is achieved through the following technical solutions.
The preparation side of the modified zirconium hydroxide composite adsorbing material of the 3D Graphenes of fluorine ion in a kind of removal rural potable water
Method, comprises the following steps:
(1)Under cryogenic, sodium nitrate is dissolved in the concentrated sulfuric acid, adds graphite powder, be uniformly mixing to obtain suspension;Ice
Under water bath condition, to potassium permanganate is added in suspension, after stirring, pure water dilution is added, carried out under the conditions of tepidarium anti-
Should;Reaction adds pure water again after terminating, and is slowly added to hydrogen peroxide, continues to stir, the product that will be obtained successively using hydrochloric acid and
Pure water carries out centrifuge washing, and freeze-drying obtains graphene oxide;
(2)The graphene oxide ultrasonic disperse that will be obtained obtains graphene oxide solution in water, adds sodium ascorbate, continues
After ultrasonic disperse is uniform, heating is stood under the conditions of hot bath, obtain 3D Graphene gels;
(3)After 3D Graphene gels are immersed in into the mixed solution being mixed to get by zirconium oxychloride solution and urea liquid, water-bath
Heating, cooling, after being dialysed in pure water, freeze-drying obtains the modified zirconium hydroxide composite adsorbing material of 3D Graphenes.
Further, step(1)In, the cryogenic conditions are under the conditions of 0 DEG C.
Further, step(1)In, the sodium nitrate is 1 with the solid-liquid ratio of the concentrated sulfuric acid:30~50g/mL.
Further, step(1)In, the sodium nitrate is 1 with the solid-liquid ratio of the concentrated sulfuric acid: 50g/mL.
Further, step(1)In, the graphite powder is 1 with the mass ratio of sodium nitrate:1.
Further, step(1)In, the potassium permanganate is 6 ~ 10 with the mass ratio of graphite powder:1.
Further, step(1)In, the potassium permanganate is 6 with the mass ratio of graphite powder:1.
Further, step(1)In, it is for the first time 3 ~ 5 with second ratio of the addition of pure water:9~11.
Further, step(1)In, it is for the first time 2 with second ratio of the addition of pure water:5.
Further, step(1)In, the temperature of the tepidarium is 30 ~ 40 DEG C.
Further, step(1)In, the temperature of the tepidarium is 35 DEG C.
Further, step(1)In, the time of the reaction is 0.5 ~ 1.5h.
Further, step(1)In, the time of the reaction is 0.5h.
Further, step(1)In, the mass concentration of the hydrogen peroxide is 30%.
Further, step(1)In, the addition of the hydrogen peroxide and second volume ratio of the addition of pure water are 3:
90~110。
Further, step(1)In, the addition of the hydrogen peroxide is with the volume ratio of second addition of pure water
3:100。
Further, step(1)In, it is 60min to add the mixing time after hydrogen peroxide.
Further, step(1)In, the mass concentration of the hydrochloric acid is 5%.
Further, step(2)In, the graphene oxide solution is 1 with the liquid ratio of sodium ascorbate:2~8mL/
mg。
Further, step(2)In, the time of graphene oxide ultrasonic disperse in water is 0.5 ~ 1.5h.
Further, step(2)In, the time of graphene oxide ultrasonic disperse in water is 1h.
Further, step(2)In, the time for continuing ultrasonic disperse is 5min.
Further, step(2)In, the temperature of the hot bath heating is 90 DEG C, and the time is 1 ~ 2h.
Further, step(2)In, the time of the heating water bath is 1.5h.
Further, step(3)In, the concentration of the zirconium oxychloride solution is 0.4 ~ 0.6mol/L.
Further, step(3)In, the concentration of the urea liquid is 4 ~ 6mol/L.
Further, step(3)In, after 3D Graphene gels impregnate 24h in the mixed solution of basic zirconium chloride and urea
Heating water bath is carried out again.
Further, step(3)In, the temperature of the heating water bath is 95 DEG C, and the time is 60 ~ 450min.
Further, step(3)In, the time dialysed in pure water is 24h.
Further, step(3)In, the time of the freeze-drying is 12 ~ 18h.
Further, step(3)In, the time of the freeze-drying is 15h.
Further, step(3)In, in the mixed solution be mixed to get by zirconium oxychloride solution and urea liquid, chlorine oxygen
It is 1 to change zirconium with the mol ratio of urea:100.
Compared with prior art, the invention has the advantages that and beneficial effect:
(1)Preparation process is simple of the present invention, raw material sources are extensive, cheap, and experimental operating conditions are gentle, to equipment requirement
It is low, the modified zirconium hydroxide composite adsorbing material physico-chemical property stabilization of 3D Graphenes of preparation, with good absorption and separation property
Energy;
(2)The modified zirconium hydroxide composite adsorbing material of 3D Graphenes prepared by the present invention has efficient absorption to the fluorine ion in water
Performance, adsorption time is short, and adsorption equilibrium is can reach after 145min is reacted;
(3)The pH scopes that the modified zirconium hydroxide composite adsorbing material of 3D Graphenes prepared by the present invention is applicable are wide, the pH in water body
For 3~9 when, in the water sample of 25~100mg/L, efficiency can reach more than 85%, be limited to better than existing removal fluorinion concentration
PH range adsorbents.
Brief description of the drawings
Fig. 1 is the ESEM of the modified zirconium hydroxide composite adsorbing material of 3D Graphenes prepared by embodiment 1(SEM)Figure.
Specific embodiment
Implementation of the invention is described further below in conjunction with example, but it will be understood by those skilled in the art that the present invention
Implementation and protection not limited to this.
Embodiment 1
The modified zirconium hydroxide composite adsorbing material of the 3D Graphenes of fluorine ion in a kind of removal rural potable water of the present embodiment
Prepare, comprise the following steps:
(1)Under the conditions of 0 DEG C, 0.5g sodium nitrate is dissolved in the 25mL concentrated sulfuric acids, adds 0.5g graphite powders and be stirred continuously shape
Into uniform suspension;Under the conditions of ice-water bath to solution in be slowly added to 3g potassium permanganate, to being slowly added in above-mentioned solution
40mL pure water, heats 1h under the conditions of 40 DEG C of hot baths, and question response adds 100mL pure water, 30% hydrogen peroxide 3mL is added dropwise after terminating,
Continue to stir 60min;5% hydrochloric acid is added to the product centrifuge washing in solution, then uses pure water product, finally freezed dry
Dry prepared graphene oxide;
(2)Graphene oxide obtains graphene oxide solution after ultrasound 1h in water, and 6mL graphene oxide solutions add 30mg
Sodium ascorbate, ultrasonic 5min makes its fully dispersed in the solution, after heating 2h is stood under the conditions of 90 DEG C of hot baths, obtains 3D
Graphene gel;
(3)0.4mol/L zirconium oxychloride solutions and 0.4mol/L urea liquids are made mixed liquor, basic zirconium chloride in mixed solution
It is 1 with the mol ratio of urea:100,3D Graphene gels be impregnated in into 24h, 95 DEG C of heating water bath solution in above-mentioned mixed liquor
90min, after after solution cooling, product is dialysed 24h, and freeze-drying 12h in pure water, and the modified hydroxide of 3D Graphenes is obtained
Zirconium composite adsorbing material.
The SEM figures of the modified zirconium hydroxide composite adsorbing material of 3D Graphenes are obtained as shown in figure 1, as shown in Figure 1, preparation
The modified zirconium hydroxide composite adsorbing material of 3D Graphenes has good 3D porous structures, and zirconium hydroxide can be more uniform
Be deposited in graphenic surface.
The modified zirconium hydroxide composite adsorption material of 3D Graphenes for adding 50mg to prepare in 250ml polytetrafluoroethylplastic plastics bottle
Material and 100ml initial concentrations are the fluorine ion simulated water sample of 25mg/L, and the pH of simulated water sample is 3.5, the 190r/ under 25 DEG C of normal temperature
Min is vibrated, and 3ml water samples are taken in different time, and keep in dark place water sample under the conditions of temperature is less than 4 DEG C.Obtain the composite adsorption material
Expect to the maximal absorptive capacity of fluorine ion to be 45.69mg/g, to fluorine ion initial concentration for the solution of 25mg/L adsorption equilibrium when
Between be 145min, fluoride ion removing efficiency can reach 97.4%.Composite after absorption fluorine ion is separated, during separation
Between reach good sedimentation effect after 180min.
Embodiment 2
(1)Under the conditions of 0 DEG C, 0.5g sodium nitrate is dissolved in the 25mL concentrated sulfuric acids, adds 0.5g graphite powders and be stirred continuously shape
Into uniform suspension;Under the conditions of ice-water bath to solution in be slowly added to 3g potassium permanganate, to being slowly added in above-mentioned solution
40mL pure water, heats 1h under the conditions of 40 DEG C of hot baths, and question response adds 100mL pure water, 30% hydrogen peroxide 3mL is added dropwise after terminating,
Continue to stir 60min;5% hydrochloric acid is added to the product centrifuge washing in solution, then uses pure water product, finally freezed dry
Dry prepared graphene oxide;
(2)Graphene oxide obtains graphene oxide solution after ultrasound 1h in water, and 6mL graphene oxide solutions add 30mg
Sodium ascorbate, ultrasonic 5min makes its fully dispersed in the solution, after heating 2h is stood under the conditions of 90 DEG C of hot baths, obtains 3D
Graphene gel;
(3)0.6mol/L zirconium oxychloride solutions and 0.6mol/L urea liquids are made mixed liquor, basic zirconium chloride in mixed solution
It is 1 with the mol ratio of urea:100,3D Graphene gels be impregnated in into 24h, 95 DEG C of heating water bath solution in above-mentioned mixed liquor
180min, after after solution cooling, product is dialysed 24h, and freeze-drying 12h in pure water, and the modified hydrogen-oxygen of 3D Graphenes is obtained
Change zirconium composite adsorbing material.
The SEM figures of the modified zirconium hydroxide composite adsorbing material of 3D Graphenes are obtained referring to Fig. 1, composite adsorbing material has good
Good 3D porous structures, and zirconium hydroxide more uniform can be deposited in graphenic surface.
The modified zirconium hydroxide composite adsorbing material of obtained 3D Graphenes be to pH 3.5 simulated water sample in fluorine ion most
Big adsorbance is 34.4mg/g, to fluorine ion initial concentration for the time of equilibrium adsorption of the solution of 25mg/L is 145min, fluorine from
Sub- removal efficiency can reach 78.8%.Composite after absorption fluorine ion is separated, is reached after disengaging time 180min good
Good sedimentation effect.
Embodiment 3
(1)Under the conditions of 0 DEG C, 0.5g sodium nitrate is dissolved in the 25mL concentrated sulfuric acids, adds 0.5g graphite powders and be stirred continuously shape
Into uniform suspension;Under the conditions of ice-water bath to solution in be slowly added to 3g potassium permanganate, to being slowly added in above-mentioned solution
40mL pure water, heats 1h under the conditions of 35 DEG C of hot baths, and question response adds 100mL pure water, 30% hydrogen peroxide 3mL is added dropwise after terminating,
Continue to stir 60min;5% hydrochloric acid is added to the product centrifuge washing in solution, then uses pure water product, finally freezed dry
Dry prepared graphene oxide;
(2)Graphene oxide obtains graphene oxide solution after ultrasound 1h in water, and 6mL graphene oxide solutions add 30mg
Sodium ascorbate, ultrasonic 5min makes its fully dispersed in the solution, after heating 2h is stood under the conditions of 90 DEG C of hot baths, obtains 3D
Graphene gel;
(3)0.5mol/L zirconium oxychloride solutions and 0.5mol/L urea liquids are made mixed liquor, basic zirconium chloride in mixed solution
It is 1 with the mol ratio of urea:100,3D Graphene gels be impregnated in into 24h, 95 DEG C of heating water bath solution in above-mentioned mixed liquor
300min, after after solution cooling, product is dialysed 24h, and freeze-drying 12h in pure water, and the modified hydrogen-oxygen of 3D Graphenes is obtained
Change zirconium composite adsorbing material.
The SEM figures of the modified zirconium hydroxide composite adsorbing material of 3D Graphenes are obtained referring to Fig. 1, composite adsorbing material has good
Good 3D porous structures, and zirconium hydroxide more uniform can be deposited in graphenic surface.
The modified zirconium hydroxide composite adsorbing material of obtained 3D Graphenes be to pH 3.5 simulated water sample in fluorine ion most
Big adsorbance is 23.56mg/g, to fluorine ion initial concentration for the time of equilibrium adsorption of the solution of 25mg/L is 325min, fluorine from
Sub- removal efficiency can reach 60.2%.Composite after absorption fluorine ion is separated, is reached after disengaging time 180min good
Good sedimentation effect.
Claims (9)
1. a kind of preparation method of the modified zirconium hydroxide composite adsorbing material of the 3D Graphenes for removing fluorine ion in rural potable water,
It is characterised in that it includes following steps:
(1)Under cryogenic, sodium nitrate is dissolved in the concentrated sulfuric acid, adds graphite powder, be uniformly mixing to obtain suspension;Ice
Under water bath condition, to potassium permanganate is added in suspension, after stirring, pure water dilution is added, carried out under the conditions of tepidarium anti-
Should;Reaction adds pure water again after terminating, and is slowly added to hydrogen peroxide, continues to stir, the product that will be obtained successively using hydrochloric acid and
Pure water carries out centrifuge washing, and freeze-drying obtains graphene oxide;
(2)The graphene oxide ultrasonic disperse that will be obtained obtains graphene oxide solution in water, adds sodium ascorbate, continues
After ultrasonic disperse is uniform, heating is stood under the conditions of hot bath, obtain 3D Graphene gels;
(3)After 3D Graphene gels are immersed in into the mixed solution being mixed to get by zirconium oxychloride solution and urea liquid, water-bath
Heating, cooling, after being dialysed in pure water, freeze-drying obtains the modified zirconium hydroxide composite adsorbing material of 3D Graphenes.
2. the modified zirconium hydroxide of a kind of 3D Graphenes for removing fluorine ion in rural potable water according to claim 1 is combined
The preparation method of sorbing material, it is characterised in that step(1)In, the cryogenic conditions are under the conditions of 0 DEG C;The sodium nitrate
It is 1 with the solid-liquid ratio of the concentrated sulfuric acid:30~50g/mL;The graphite powder is 1 with the mass ratio of sodium nitrate:1.
3. the modified zirconium hydroxide of a kind of 3D Graphenes for removing fluorine ion in rural potable water according to claim 1 is combined
The preparation method of sorbing material, it is characterised in that step(1)In, the potassium permanganate is 6 ~ 10 with the mass ratio of graphite powder:1;
It is for the first time 3 ~ 5 with second ratio of the addition of pure water:9~11;The temperature of the tepidarium is 30 ~ 40 DEG C;The reaction
Time is 0.5 ~ 1.5h;The mass concentration of the hydrogen peroxide is 30%;The addition of the hydrogen peroxide and second addition of pure water
The volume ratio of amount is 3:90~110;It is 60min to add the mixing time after hydrogen peroxide;The mass concentration of the hydrochloric acid is 5%.
4. the modified zirconium hydroxide of a kind of 3D Graphenes for removing fluorine ion in rural potable water according to claim 1 is combined
The preparation method of sorbing material, it is characterised in that step(1)In, the sodium nitrate is 1 with the solid-liquid ratio of the concentrated sulfuric acid: 50g/
mL;The potassium permanganate is 6 with the mass ratio of graphite powder:1;The temperature of the tepidarium is 35 DEG C;The time of the reaction is
0.5h;It is for the first time 2 with second ratio of the addition of pure water:5;The addition of the hydrogen peroxide and second addition of pure water
The volume ratio of amount is 3:100.
5. the modified zirconium hydroxide of a kind of 3D Graphenes for removing fluorine ion in rural potable water according to claim 1 is combined
The preparation method of sorbing material, it is characterised in that step(2)In, the liquid material of the graphene oxide solution and sodium ascorbate
Than being 1:2~8mL/mg;The time of graphene oxide ultrasonic disperse in water is 0.5 ~ 1.5h;It is described continue ultrasonic disperse when
Between be 5min;The temperature of the hot bath heating is 90 DEG C, and the time is 1 ~ 2h.
6. the modified zirconium hydroxide of a kind of 3D Graphenes for removing fluorine ion in rural potable water according to claim 1 is combined
The preparation method of sorbing material, it is characterised in that step(2)In, the time of graphene oxide ultrasonic disperse in water is 1h;Institute
The time for stating heating water bath is 1.5h.
7. the modified zirconium hydroxide of a kind of 3D Graphenes for removing fluorine ion in rural potable water according to claim 1 is combined
The preparation method of sorbing material, it is characterised in that step(3)In, the concentration of the zirconium oxychloride solution is 0.4 ~ 0.6mol/L;
The concentration of the urea liquid is 4 ~ 6mol/L;3D Graphene gels impregnate 24h in the mixed solution of basic zirconium chloride and urea
Carry out heating water bath again afterwards;The temperature of the heating water bath is 95 DEG C, and the time is 60 ~ 450min;The time of dialysis is in pure water
24h;The time of the freeze-drying is 12 ~ 18h.
8. the modified zirconium hydroxide of a kind of 3D Graphenes for removing fluorine ion in rural potable water according to claim 1 is combined
The preparation method of sorbing material, it is characterised in that step(3)In, the time of the freeze-drying is 15h.
9. the modified zirconium hydroxide of a kind of 3D Graphenes for removing fluorine ion in rural potable water according to claim 1 is combined
The preparation method of sorbing material, it is characterised in that step(3)In, by mixing that zirconium oxychloride solution and urea liquid are mixed to get
Close in solution, basic zirconium chloride is 1 with the mol ratio of urea:100.
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CN110102265A (en) * | 2019-04-04 | 2019-08-09 | 浙江树人学院(浙江树人大学) | For the load zirconium biology compound adsorbent and regeneration method of removing fluor in water and application |
CN112048100A (en) * | 2020-09-09 | 2020-12-08 | 巢湖市方太渔具有限责任公司 | Preparation method of fishing net thread quality enhancer |
CN113816479A (en) * | 2021-09-30 | 2021-12-21 | 南通大学 | Slow-release gel aluminum modified wood chip defluorinating agent and preparation method thereof |
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