CN108940226A - A kind of biological material adsorbent and the preparation method and application thereof for heavy metals removal - Google Patents
A kind of biological material adsorbent and the preparation method and application thereof for heavy metals removal Download PDFInfo
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- CN108940226A CN108940226A CN201810938637.3A CN201810938637A CN108940226A CN 108940226 A CN108940226 A CN 108940226A CN 201810938637 A CN201810938637 A CN 201810938637A CN 108940226 A CN108940226 A CN 108940226A
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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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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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
- B01J20/0203—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
- B01J20/0274—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 characterised by the type of anion
- B01J20/0281—Sulfates of compounds other than those provided for in B01J20/045
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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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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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
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Abstract
The invention discloses under certain condition, using cellulose acetate substrate as raw material, by 95% dense formic acid dissolution process, cellogel solution is obtained.With basic zirconium chloride (ZrOCl2) and phosphoric acid (H3PO4) it is reaction raw materials, under the conditions of pH=1 and temperature are 35 DEG C, amorphous phosphoric acid zirconium white color colloidal suspensions are obtained by inorganic polymer composite flocculant；Cellogel solution is chemically reacted with basic zirconium phosphate suspension, and stretching vibration superposition occurs for the oxygen of the hydroxyl on the Zr metal ion in basic zirconium phosphate and cellulose acetate on the position C-2, forms cellulose acetate-basic zirconium phosphate；Dichlorodiphenyl Acetate cellulose-basic zirconium phosphate is acidified, and the ion-exchange performance of adsorbent is improved.Cellulose acetate-zirconium phosphate sorbent prepared by the present invention has absorption Pb2+、Zn2+High-efficient, the advantages that adsorption capacity is big, treatment effect is stablized, using not generating secondary pollution, and operate it is convenient.
Description
Technical field
The present invention relates to a kind of biological material adsorbents for heavy metals removal, belong to environmental protection technical field,
It is specifically a kind of to be directed to a kind of biological material adsorbent and the preparation method and application thereof for heavy metals removal.
Background technique
Cadmium, chromium, lead, copper, zinc and mercury are common heavy metal water body pollution objects.Heavy metal element is very steady in the environment
It is fixed, it will not decompose, and be difficult to remove.Heavy metal element realizes the movement in ecological environment by the migration between substance.
Once human body has taken in heavy metal element by certain mode, heavy metal element will be accumulated in vivo, be not easy to be discharged, equivalance
After tiring out to a certain extent, each organ of human body will be damaged.
Cellulose is that the most abundant natural reproducible high-molecular compound of reserves, chemical structure are by polyhydroxy in nature
The polymer long-chain molecule that β-dehydrated glucose unit of base is formed by connecting through ehter bond (C-O-C).Strand is piled up so that fine
Plain space structure is tieed up staggeredly to be spaced by crystalline state and amorphous state and constituted, and the hydroxyl (- OH) in crystalline phase can forming quantity Pang
Big hydrogen bond causes cellulose to be difficult to dissolve in conventional organic solvent, so that the application of cellulose is extremely restricted.Pass through
Processing is modified to cellulose and obtains derivative product, expands the application range of cellulose.In the derivative of cellulose, vinegar
Acid cellulose is using wider cellulose organic ester, it is to be catalyzed cotton fiber or lumber fibre with acetic acid or aceticanhydride
A kind of thermoplastic resin for being esterified under agent effect, and being obtained.The presence of hydroxyl and carbonyl in cellulose acetate, to heavy metal
There is strong affinity, therefore can be used as the adsorbent of heavy metal.Since cellulose acetate can be with microballoon, sheet, film and solution
Etc. different forms occur, further improve the popularity of flexibility and the application of cellulose acetate functionalization.
Basic zirconium phosphate is the novel and multifunctional material of one kind gradually to grow up in recent years, it had both had similar to amberlite
The ion-exchange performance of rouge, while there is the performance of the shape-selective absorption and catalysis as zeolite again.In addition, basic zirconium phosphate also has
Higher thermal stability, mechanical strength and preferable acid-proof alkaline, and sizable specific surface area can be provided, therefore
Field of environment protection has very big application prospect.Basic zirconium phosphate has amorphous and two kinds of forms of crystalline form, wherein crystalline form basic zirconium phosphate
There are many crystal structure types, with alpha zirconium phosphate (molecular formula Zr(HPO4)2·H2O is abbreviated as α-ZrP) it is most representative.α-
ZrP is a kind of cationic lamellar compound with strong ion-exchange capacity, has regular veneer structure and designability.It is brilliant
There is-HPO in body structure4Group exists ,-HPO4Hydroxyl in group is connected with the crystallization water with hydrogen bond, there is good chemical stability
And it is non-toxic.Corresponding layer-pillared compound can be formed after some objects of its Intercalation reaction such as ion, molecule or atom.Due to phosphorus
Sour zirconium class layer-pillared compound has potential shape-selective absorption property, become the ion-exchanger of the great attractive prospect of one kind and
By domestic and foreign scholars' extensive concern.It, just can not be into when exchange ion diameter is greater than interlamellar spacing due to being limited by interlamellar spacing
Enter and swapped in layer with proton, therefore α-ZrP only has selectivity to certain metal ions, ZrP is to alkali gold according to the literature
Belong to and alkaline-earth metal has good absorption property.
Due to the low cost of cellulose acetate nanocomposite, easy processing, using wide, renewable, recycled etc.
Feature has larger application prospect, and amorphous basic zirconium phosphate is the inorganic ion exchanger of tetravalent metal hydrochlorate, has high selection
Property, high thermal stability and hydrophobic character, are superior adsorbents to heavy metal, but in practical applications due to amorphous basic zirconium phosphate
Grain is superfine, adsorbs for heavy metal water body, because fluid resistance and head loss practicability are poor, therefore amorphous basic zirconium phosphate is born
Being loaded on porous adsorbing material can be with this problem of effective solution.Therefore load basic zirconium phosphate is carried out by Dichlorodiphenyl Acetate cellulose to change
Property processing, to improve the removal ability of heavy metal ion.It yet there are no cellulose acetate-zirconium phosphate nano composite material phase
Close report.
Summary of the invention
The purpose of the present invention is to provide a kind of cellulose acetate for heavy metals removal-zirconium phosphate nano composite materials
Preparation method, for heavy metal Pb (II), Zn(II) ion has the function of selective exchange adsorption.A kind of system provided by the invention
The method of standby cellulose acetate-zirconium phosphate nano composite material, utilizes basic zirconium chloride and phosphoric acid solution in acid condition first
Reaction prepares basic zirconium phosphate；Then cellulose acetate solution and phosphoric acid zirconium solution hybrid reaction in dense formic acid are dissolved in and prepares acetic acid
Cellulose-basic zirconium phosphate；Cellulose acetate-basic zirconium phosphate is finally placed on HNO3H is formed in solution+Form.
To achieve the above object, the invention adopts the following technical scheme:
A kind of biological material adsorbent and preparation method thereof for heavy metals removal, comprising the following steps:
(1) prepared by basic zirconium phosphate: the basic zirconium chloride (ZrOCl for being 0.1mol/L by concentration2) and 0.1mol/L phosphoric acid (H3PO4) molten
Liquid 1:(0.5 ~ 2 by volume) it is mixed under continual stirring conditions, pH of mixed is adjusted with the ammonia spirit of 0.5mol/L
Value is 1, and adjustment mixeding liquid temperature is 35 DEG C, and mixed liquor is stirred 30min in the blender that speed is 200r/min, obtains phosphorus
Sour zirconium suspension；
(2) cellulose acetate-basic zirconium phosphate preparation: cellulose acetate is dissolved in the dense formic acid that mass fraction is 95%, obtains matter
The cellogel that concentration is 10 ~ 40g/L is measured, the basic zirconium phosphate prepared in step (1) is added to continuous stirring and suspends
In liquid, 4h is continuously stirred, mixing speed is 50 ~ 100r/min.After the completion of stirring, resulting mixed liquor is stood for 24 hours, it is during which even
You rock solution.After the completion of standing, it is separated by filtration to obtain sediment, and excessive reagent is washed with deionized, obtains white
Sediment;
(3) white depositions cellulose acetate-basic zirconium phosphate acidification: are added to the nitric acid (HNO that concentration is 0.1mol/L3) solution
Middle balance for 24 hours, is acidified product.Then it is separated by filtration sediment, excessive acid is washed with deionized, finally in 80 DEG C of baking
It is dry in case, obtain cellulose acetate-zirconium phosphate nano composite material.
A kind of biological material adsorbent for heavy metals removal is obtained prepared by above-mentioned preparation method.
Concrete application method of the invention: the heavy metal Pb that mass concentration is 50mg/L is respectively configured2+And Zn2+Nitric acid
Salting liquid.Adjustment is 25 DEG C containing Pb or Zn solution temperature, measures 25ml and is put into hard straight plastic tube, it is above-mentioned that 0.05 ~ 0.1g is added
The adsorbent of acidification shakes 2h on 120r/min oscillator, is filtered with filter needle tubing, uses after diluting 20000 times step by step
Atomic fluorescence spectrophotometer measures adsorption equilibrium concentration, calculates its adsorption capacity and adsorption efficiency.
Reaction mechanism of the invention: (1) basic zirconium chloride (ZrOCl2) and phosphoric acid (H3PO4) it in pH=1 and temperature is 35 DEG C of items
Under part, basic zirconium phosphate white gum suspension is obtained by inorganic polymer composite flocculant；(2) be dissolved in cellulose acetate in dense formic acid with
Basic zirconium phosphate suspension is chemically reacted, the hydroxyl on the Zr metal ion in basic zirconium phosphate and cellulose acetate on the position C-2
Stretching vibration superposition occurs for oxygen, forms cellulose acetate-basic zirconium phosphate；(3) Dichlorodiphenyl Acetate cellulose-basic zirconium phosphate is acidified,
Improve the ion-exchange performance of adsorbent.
Fig. 1 is a kind of biological material adsorbent for heavy metals removal and its preparation reaction mechanism schematic diagram.
The beneficial effects of the present invention are:
(1) present invention is that basic material prepares adsorbent with native cellulose, and raw material is agricultural wastes, from a wealth of sources, valence
Lattice are cheap, environmental-friendly.And cellulose acetate preparation method is simple, equipment requirement is low, is convenient for large-scale production;
(2) present invention is modified processing using basic zirconium phosphate as support materials with cellulose acetate, forms " organic and inorganic " and combines
Material.Since amorphous basic zirconium phosphate is to Pb2+、Zn2+With preferable adsorption effect and higher adsorptive selectivity, but it is amorphous
The particle that phosphoric acid bores is superfine, and average grain diameter is 1 ~ 20 μm, fluid resistance and pressure when directly applying to the removal of Heavy Metals in Waters
Head loss is very big, and the practicability is poor, and cellulose acetate has a porous structure, and hydroxyl on its position C-2, C-3 and C-6 and
Ester bond has typical primary and secondary alcohol reaction property, has more adsorption sites for heavy metal.Therefore, these act on so that
Dichlorodiphenyl Acetate cellulose-basic zirconium phosphate has absorption Pb2+、Zn2+It is high-efficient, adsorption capacity is big, treatment effect stablize the advantages that;
(3) biomass new material adsorbent prepared by the present invention is using organic material cellulose acetate and inorganic material basic zirconium phosphate as base
It is prepared by plinth material, using not generating secondary pollution, and operate it is convenient.
Detailed description of the invention
Fig. 1 is a kind of biological material adsorbent for heavy metals removal and its preparation reaction mechanism schematic diagram.
Specific embodiment
Specific embodiments of the present invention will be further explained below.It should be noted that for these implementations
The explanation of mode is used to help understand the present invention, but and does not constitute a limitation of the invention.In addition, invention described below
Technical characteristic involved in each embodiment can be combined with each other as long as they do not conflict with each other.
Embodiment 1:
Basic zirconium chloride (the ZrOCl for being 0.1mol/L by concentration2) and 0.1mol/L phosphoric acid (H3PO4) solution is by volume
100ml:50ml is mixed under continual stirring conditions, and adjusting mixed liquor pH value with the ammonia spirit of 0.5mol/L is 1, adjustment
Mixeding liquid temperature is 35 DEG C, and mixed liquor is stirred 30min in the blender that speed is 200r/min, obtains basic zirconium phosphate suspension
Liquid；
Cellulose acetate is dissolved in the dense formic acid that mass fraction is 95%, obtains the cellulose acetate that mass concentration is 10g/L
Gel takes 25ml gel solution to be added in the basic zirconium phosphate suspension of preparation with continuous stirring, continuously stirs 4h, mixing speed
For 50r/min.After the completion of stirring, resulting mixed liquor is stood for 24 hours, during which rocks solution once in a while.After the completion of standing, filtering point
From obtaining sediment, and excessive reagent is washed with deionized, obtains white depositions；
White depositions are added to the nitric acid (HNO that concentration is 0.1mol/L3) balance for 24 hours in solution, it is acidified product.Then
It is separated by filtration sediment, excessive acid is washed with deionized, it is finally dry in 80 DEG C of baking oven, obtain cellulose acetate-
Zirconium phosphate nano composite material；
The heavy metal Pb that mass concentration is 50mg/L is respectively configured2+And Zn2+Nitrate solution.Adjust the temperature containing Pb or Zn solution
Degree is 25 DEG C, measures 25ml and is put into hard straight plastic tube, the adsorbent of the above-mentioned acidification of 0.05g is added, in 120r/min oscillator
Upper concussion 2h is filtered with filter needle tubing, and it is dense to measure adsorption equilibrium with atomic fluorescence spectrophotometer after 20000 times of dilution step by step
Degree, is computed to Pb2+Adsorption efficiency be 91.46%, adsorption capacity 22.87mg/g, to Zn2+Adsorption efficiency be
86.32%, adsorption capacity 19.69mg/g.
Embodiment 2:
Basic zirconium chloride (the ZrOCl for being 0.1mol/L by concentration2) and 0.1mol/L phosphoric acid (H3PO4) solution 75ml by volume:
75ml is mixed under continual stirring conditions, and adjusting mixed liquor pH value with the ammonia spirit of 0.5mol/L is 1, adjusts mixed liquor
Temperature is 35 DEG C, and mixed liquor is stirred 30min in the blender that speed is 200r/min, obtains basic zirconium phosphate suspension；
Cellulose acetate is dissolved in the dense formic acid that mass fraction is 95%, obtains the cellulose acetate that mass concentration is 20g/L
Gel takes 25ml gel solution to be added in the basic zirconium phosphate suspension of preparation with continuous stirring, continuously stirs 4h, mixing speed
For 70r/min.After the completion of stirring, resulting mixed liquor is stood for 24 hours, during which rocks solution once in a while.After the completion of standing, filtering point
From obtaining sediment, and excessive reagent is washed with deionized, obtains white depositions；
White depositions are added to the nitric acid (HNO that concentration is 0.1mol/L3) balance for 24 hours in solution, it is acidified product.Then
It is separated by filtration sediment, excessive acid is washed with deionized, it is finally dry in 80 DEG C of baking oven, obtain cellulose acetate-
Zirconium phosphate nano composite material；
The heavy metal Pb that mass concentration is 50mg/L is respectively configured2+And Zn2+Nitrate solution.Adjust the temperature containing Pb or Zn solution
Degree is 25 DEG C, measures 25ml and is put into hard straight plastic tube, the adsorbent of the above-mentioned acidification of 0.05g is added, in 120r/min oscillator
Upper concussion 2h is filtered with filter needle tubing, and it is dense to measure adsorption equilibrium with atomic fluorescence spectrophotometer after 20000 times of dilution step by step
Degree, is computed to Pb2+Adsorption efficiency be 92.52%, adsorption capacity 23.03mg/g, to Zn2+Adsorption efficiency be
88.47%, adsorption capacity 20.31mg/g.
Embodiment 3:
Basic zirconium chloride (the ZrOCl for being 0.1mol/L by concentration2) and 0.1mol/L phosphoric acid (H3PO4) solution 50ml by volume:
100ml is mixed under continual stirring conditions, and adjusting mixed liquor pH value with the ammonia spirit of 0.5mol/L is 1, adjustment mixing
Liquid temperature is 35 DEG C, and mixed liquor is stirred 30min in the blender that speed is 200r/min, obtains basic zirconium phosphate suspension；
Cellulose acetate is dissolved in the dense formic acid that mass fraction is 95%, obtains the cellulose acetate that mass concentration is 30g/L
Gel takes 25ml gel solution to be added in the basic zirconium phosphate suspension of preparation with continuous stirring, continuously stirs 4h, mixing speed
For 85r/min.After the completion of stirring, resulting mixed liquor is stood for 24 hours, during which rocks solution once in a while.After the completion of standing, filtering point
From obtaining sediment, and excessive reagent is washed with deionized, obtains white depositions；
White depositions are added to the nitric acid (HNO that concentration is 0.1mol/L3) balance for 24 hours in solution, it is acidified product.Then
It is separated by filtration sediment, excessive acid is washed with deionized, it is finally dry in 80 DEG C of baking oven, obtain cellulose acetate-
Zirconium phosphate nano composite material；
The heavy metal Pb that mass concentration is 50mg/L is respectively configured2+And Zn2+Nitrate solution.Adjust the temperature containing Pb or Zn solution
Degree is 25 DEG C, measures 25mL and is put into hard straight plastic tube, the adsorbent of the above-mentioned acidification of 0.1g is added, on 120r/min oscillator
2h is shaken, is filtered with filter needle tubing, measures adsorption equilibrium concentration with atomic fluorescence spectrophotometer after diluting 20000 times step by step,
It is computed to Pb2+Adsorption efficiency be 95.47%, adsorption capacity is 24.82 mg/g, to Zn2+Adsorption efficiency be 89.53%,
Adsorption capacity is 20.96 mg/g.
Embodiment 4:
Basic zirconium chloride (the ZrOCl for being 0.1mol/L by concentration2) and 0.1mol/L phosphoric acid (H3PO4) solution 75ml by volume:
75ml is mixed under continual stirring conditions, and adjusting mixed liquor pH value with the ammonia spirit of 0.5mol/L is 1, adjusts mixed liquor
Temperature is 35 DEG C, and mixed liquor is stirred 30min in the blender that speed is 200r/min, obtains basic zirconium phosphate suspension；
Cellulose acetate is dissolved in the dense formic acid that mass fraction is 95%, obtains the cellulose acetate that mass concentration is 40g/L
Gel takes 25ml gel solution to be added in the basic zirconium phosphate suspension of preparation with continuous stirring, continuously stirs 4h, mixing speed
For 100r/min.After the completion of stirring, resulting mixed liquor is stood for 24 hours, during which rocks solution once in a while.After the completion of standing, filtering
Isolated sediment, and excessive reagent is washed with deionized, obtain white depositions；
White depositions are added to the nitric acid (HNO that concentration is 0.1mol/L3) balance for 24 hours in solution, it is acidified product.Then
It is separated by filtration sediment, excessive acid is washed with deionized, it is finally dry in 80 DEG C of baking oven, obtain cellulose acetate-
Zirconium phosphate nano composite material；
The heavy metal Pb that mass concentration is 50mg/L is respectively configured2+And Zn2+Nitrate solution.Adjust the temperature containing Pb or Zn solution
Degree is 25 DEG C, measures 25ml and is put into hard straight plastic tube, the adsorbent of the above-mentioned acidification of 0.075g is added, in 120r/min oscillator
Upper concussion 2h is filtered with filter needle tubing, and it is dense to measure adsorption equilibrium with atomic fluorescence spectrophotometer after 20000 times of dilution step by step
Degree, is computed to Pb2+Adsorption efficiency be 93.22%, adsorption capacity is 23.96 mg/g, to Zn2+Adsorption efficiency be
87.26%, adsorption capacity 20.03mg/g.
Embodiment 5:
Basic zirconium chloride (the ZrOCl for being 0.1mol/L by concentration2) and 0.1mol/L phosphoric acid (H3PO4) solution 50ml by volume:
100ml is mixed under continual stirring conditions, and adjusting mixed liquor pH value with the ammonia spirit of 0.5mol/L is 1, adjustment mixing
Liquid temperature is 35 DEG C, and mixed liquor is stirred 30min in the blender that speed is 200r/min, obtains basic zirconium phosphate suspension；
Cellulose acetate is dissolved in the dense formic acid that mass fraction is 95%, obtains the cellulose acetate that mass concentration is 30g/L
Gel takes 25ml gel solution to be added in the basic zirconium phosphate suspension of preparation with continuous stirring, continuously stirs 4h, mixing speed
For 70r/min.After the completion of stirring, resulting mixed liquor is stood for 24 hours, during which rocks solution once in a while.After the completion of standing, filtering point
From obtaining sediment, and excessive reagent is washed with deionized, obtains white depositions；
White depositions are added to the nitric acid (HNO that concentration is 0.1mol/L3) balance for 24 hours in solution, it is acidified product.Then
It is separated by filtration sediment, excessive acid is washed with deionized, it is finally dry in 80 DEG C of baking oven, obtain cellulose acetate-
Zirconium phosphate nano composite material；
The heavy metal Pb that mass concentration is 50mg/L is respectively configured2+And Zn2+Nitrate solution.Adjust the temperature containing Pb or Zn solution
Degree is 25 DEG C, measures 25ml and is put into hard straight plastic tube, the adsorbent of the above-mentioned acidification of 0.075g is added, in 120r/min oscillator
Upper concussion 2h is filtered with filter needle tubing, and it is dense to measure adsorption equilibrium with atomic fluorescence spectrophotometer after 20000 times of dilution step by step
Degree, is computed to Pb2+Adsorption efficiency be 92.06%, adsorption capacity 22.87mg/g, to Zn2+Adsorption efficiency be
90.51%, adsorption capacity 21.98mg/g.
Embodiment 6:
Basic zirconium chloride (the ZrOCl for being 0.1mol/L by concentration2) and 0.1mol/L phosphoric acid (H3PO4) solution 50ml by volume:
100ml is mixed under continual stirring conditions, and adjusting mixed liquor pH value with the ammonia spirit of 0.5mol/L is 1, adjustment mixing
Liquid temperature is 35 DEG C, and mixed liquor is stirred 30min in the blender that speed is 200r/min, obtains basic zirconium phosphate suspension；
Cellulose acetate is dissolved in the dense formic acid that mass fraction is 95%, obtains the cellulose acetate that mass concentration is 20g/L
Gel takes 25ml gel solution to be added in the basic zirconium phosphate suspension of preparation with continuous stirring, continuously stirs 4h, mixing speed
For 50r/min.After the completion of stirring, resulting mixed liquor is stood for 24 hours, during which rocks solution once in a while.After the completion of standing, filtering point
From obtaining sediment, and excessive reagent is washed with deionized, obtains white depositions；
White depositions are added to the nitric acid (HNO that concentration is 0.1mol/L3) balance for 24 hours in solution, it is acidified product.Then
It is separated by filtration sediment, excessive acid is washed with deionized, it is finally dry in 80 DEG C of baking oven, obtain cellulose acetate-
Zirconium phosphate nano composite material；
The heavy metal Pb that mass concentration is 50mg/L is respectively configured2+And Zn2+Nitrate solution.Adjust the temperature containing Pb or Zn solution
Degree is 25 DEG C, measures 25ml and is put into hard straight plastic tube, the adsorbent of the above-mentioned acidification of 0.05g is added, in 120r/min oscillator
Upper concussion 2h is filtered with filter needle tubing, and it is dense to measure adsorption equilibrium with atomic fluorescence spectrophotometer after 20000 times of dilution step by step
Degree, is computed to Pb2+Adsorption efficiency be 91.55%, adsorption capacity 22.33mg/g, to Zn2+Adsorption efficiency be
88.47%, adsorption capacity 20.78mg/g.
Embodiment 7:
Basic zirconium chloride (the ZrOCl for being 0.1mol/L by concentration2) and 0.1mol/L phosphoric acid (H3PO4) solution is by volume
100ml:50ml is mixed under continual stirring conditions, and adjusting mixed liquor pH value with the ammonia spirit of 0.5mol/L is 1, adjustment
Mixeding liquid temperature is 35 DEG C, and mixed liquor is stirred 30min in the blender that speed is 200r/min, obtains basic zirconium phosphate suspension
Liquid；
Cellulose acetate is dissolved in the dense formic acid that mass fraction is 95%, obtains the cellulose acetate that mass concentration is 40g/L
Gel takes 25ml gel solution to be added in the basic zirconium phosphate suspension of preparation with continuous stirring, continuously stirs 4h, mixing speed
For 85r/min.After the completion of stirring, resulting mixed liquor is stood for 24 hours, during which rocks solution once in a while.After the completion of standing, filtering point
From obtaining sediment, and excessive reagent is washed with deionized, obtains white depositions；
White depositions are added to the nitric acid (HNO that concentration is 0.1mol/L3) balance for 24 hours in solution, it is acidified product.Then
It is separated by filtration sediment, excessive acid is washed with deionized, it is finally dry in 80 DEG C of baking oven, obtain cellulose acetate-
Zirconium phosphate nano composite material；
The heavy metal Pb that mass concentration is 50mg/L is respectively configured2+And Zn2+Nitrate solution.Adjust the temperature containing Pb or Zn solution
Degree is 25 DEG C, measures 25ml and is put into hard straight plastic tube, the adsorbent of the above-mentioned acidification of 0.1g is added, on 120r/min oscillator
2h is shaken, is filtered with filter needle tubing, measures adsorption equilibrium concentration with atomic fluorescence spectrophotometer after diluting 20000 times step by step,
It is computed to Pb2+Adsorption efficiency be 94.38%, adsorption capacity 24.16mg/g, to Zn2+Adsorption efficiency be 89.09%, inhale
Attached capacity is 21.38mg/g.
Claims (3)
1. a kind of biological material adsorbent and preparation method thereof for heavy metals removal, it is characterised in that include the following steps
It is:
(1) prepared by basic zirconium phosphate: the basic zirconium chloride (ZrOCl for being 0.1mol/L by concentration2) and 0.1mol/L phosphoric acid (H3PO4) molten
Liquid 1:(0.5 ~ 2 by volume) it is mixed under continual stirring conditions, pH of mixed is adjusted with the ammonia spirit of 0.5mol/L
Value is 1, and adjustment mixeding liquid temperature is 35 DEG C, and mixed liquor is stirred 30min in the blender that speed is 200 r/min, is obtained
Basic zirconium phosphate suspension；
(2) cellulose acetate-basic zirconium phosphate preparation: cellulose acetate is dissolved in the dense formic acid that mass fraction is 95%, obtains matter
The cellogel that concentration is 10 ~ 40g/L is measured, the basic zirconium phosphate prepared in step (1) is added to continuous stirring and suspends
In liquid, 4h is continuously stirred, mixing speed is 50 ~ 100r/min；After the completion of stirring, resulting mixed liquor is stood for 24 hours, it is during which even
You rock solution；After the completion of standing, it is separated by filtration to obtain sediment, and excessive reagent is washed with deionized, obtains white
Sediment；
(3) white depositions cellulose acetate-basic zirconium phosphate acidification: are added to the nitric acid (HNO that concentration is 0.1mol/L3) solution
Middle balance for 24 hours, is acidified product, is then separated by filtration sediment, excessive acid is washed with deionized, finally in 80 DEG C of baking
It is dry in case, obtain cellulose acetate-zirconium phosphate nano composite material.
2. a kind of biological material adsorbent for heavy metals removal made from preparation method according to claim 1 is answered
With, it is characterised in that: cellulose acetate-basic zirconium phosphate is acidified dosage of the nanocomposite for water phase removal of heavy metal ions and is
2~4 g/L。
3. a kind of biological material adsorbent and preparation method thereof for heavy metals removal according to claim 1,
Be characterized in that: cellulose acetate described in step (3)-basic zirconium phosphate souring soln can be nitric acid, hydrochloric acid, phosphoric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201810938637.3A CN108940226A (en) | 2018-08-17 | 2018-08-17 | A kind of biological material adsorbent and the preparation method and application thereof for heavy metals removal |
Applications Claiming Priority (1)
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| CN110743629A (en) * | 2019-10-29 | 2020-02-04 | 南方科技大学 | Ion exchange membrane and preparation method and application thereof |
| CN117599742A (en) * | 2023-11-29 | 2024-02-27 | 河北地质大学 | Synthesis method of zirconium phosphate coating material with core-shell structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110743629A (en) * | 2019-10-29 | 2020-02-04 | 南方科技大学 | Ion exchange membrane and preparation method and application thereof |
| CN117599742A (en) * | 2023-11-29 | 2024-02-27 | 河北地质大学 | Synthesis method of zirconium phosphate coating material with core-shell structure |
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