CN110102265A - For the load zirconium biology compound adsorbent and regeneration method of removing fluor in water and application - Google Patents
For the load zirconium biology compound adsorbent and regeneration method of removing fluor in water and application Download PDFInfo
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- CN110102265A CN110102265A CN201910272712.1A CN201910272712A CN110102265A CN 110102265 A CN110102265 A CN 110102265A CN 201910272712 A CN201910272712 A CN 201910272712A CN 110102265 A CN110102265 A CN 110102265A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
Abstract
The invention discloses a kind of for the load zirconium biology compound adsorbent and regeneration method of removing fluor in water and application, which is prepared by basic zirconium chloride, fairy shrimp chorion, sodium hydroxide, ethyl alcohol；The load zirconium biology compound adsorbent can be applied to removal Micro fluoride ion, and when there are when other coexisting ions, be still able to maintain biggish adsorption capacity and more highly selective in water body；When through the processed fluorine containing waste water of load zirconium biology compound adsorbent, when being discharged fluorinion concentration higher than 1.0mg/L, stopping is adsorbed, and is regenerated with NaOH and NaCl mixed solution to it.Load zirconium biology compound adsorbent of the invention has good defluorination effect production technology easy to control, lower production costs, can stablize and save 1 year or so time, and can be applied to drinking water.
Description
Technical field
The invention belongs to water-treatment technology field, in particular to a kind of load zirconium biology compound adsorbent for removing fluor in water
And regeneration method and application.
Background technique
Fluorine is one of the essential trace elements of the human body, is usually present in big gas and water and soil with combining form, and people
The fluoride pollution for caused by is principal element.Fluoride pollution be mainly derived from glass manufacturing industry, metal-processing industry, chemical industry,
The high-technology industries such as semiconductors manufacture.When these direct discharging of waste water are by serious polluted underground water, if long-term drinking is high
Concentration fluorinated water will affect metabolism of the human body to calcium, phosphorus, make organism metabolism and physiological function that obstacle occur, to cause fluorine spot
Some fluorine poisoning symptoms such as tooth, fluorosis of bone.It is counted according to the World Health Organization (WHO), China, India, Pakistan and Thailand etc.
The universal high fluorine of the surface water of state.Especially in China, the exploitation of fluorine mine, metal smelt, aluminium processing, coke, glass, electronics, plating, change
Containing the fluoride of high concentration in the waste water of the industries such as fertilizer, pesticide discharge, the pollution of environment is caused.Current industry is fluorine-containing useless
Water discharge standard is 10.0mg/L, and it is widely distributed that the direct emission of high fluorine industrial wastewater results in Fluorine Containing Groundwater.According to " life drink
With water hygiene standard " (GB5749-2006) regulation, it is 1.0mg/L that fluoride concentration limit value is drunk in the existing life in China.But China
North China, the northwest universal fluorine content of wide geographic area underground water are exceeded, and some areas are even as high as 4.0~8.0mg/L, are region drinks
One of popular extensive, serious country of harm of water fluorine poisoning.Especially in northwest arid area, there are about 8 million peoples to drink fluorine-containing matter
Exceeded water is measured, the endemic fluorosis disease thus caused is throughout 29 provinces, cities and autonomous regions.
In the past 30 years, a large amount of research has been carried out to the processing of fluorinated water both at home and abroad, to defluorinating process and relevant basis
Theoretical research also has made some progress.The key for eliminating drinking-water endemic fluorosis at present is to change water, harness the river and drops fluorine
It is up to standard.Common defluorination method mainly has absorption method, electrocoagulation, hyperfiltration, ion-exchange, chemical precipitation method and coagulation
Sedimentation etc..In these methods, the processing of electrocoagulation and chemical precipitation method suitable for various amounts of fluoride in drinking water；By the way that stone is added
Ash, calcium chloride or aluminide etc. and F-Form gelatinous precipitate；The two is during processing, more demanding to the pH value of water quality,
And the problems such as electrocoagulation is there is also aluminum plate electrodes passivation, and power consumption is big.Although hyperfiltration and ion-exchange can be with
Achieve the purpose that fluorine removal, but efficiency is lower, lack selectivity, and waste water quality is required stringent.Due to absorption method cost compared with
It is low, and defluorination effect is preferable, so the important method of always fluoride wastewater treatment；And the selection of adsorbent removes absorption
Fluorine is most important.Therefore exploiting economy, adsorption capacity are high, preparation process is simple, easy to operate, are suitable for various concentration, difference
The adsorption-defluorination material of hardness, different pH value will be the key that drinking water drop fluorine is promoted, it may have great environment and economic meaning
Justice.
Zirconium oxide is a kind of novel lamellar mesoporous material developed in recent years.Not only there is biggish absorption to hold for it
Amount, while having excellent heat, chemical stability and good dynamic performance again, it is extremely difficult to be dissolved in water and acid, it is environmental-friendly simultaneously
And biggish specific surface area can be provided.Zirconium oxide is widely used in the research of environmental area as a kind of multifunctional material
In.But zirconium oxide exists in the form of inorganic particle, directly apply to column absorption or other fluidised form systems in often generate it is higher
Pressure drop, exist be separated by solid-liquid separation difficult, fluid resistance it is big apply bottleneck.To solve this problem, carrier immobilized skill is utilized
The inorganic particles such as zirconium oxide are supported and prepare loaded complex function adsorbent material in porous carrier surface, can both solve nothing by art
The difficult technical bottleneck of machine adsorbent separation, and can effectively realize the immobilization of inorganic adsorbent particle and nanosizing.
Common carrier polarization in current carrier immobilized technology, active carbon, hypercrosslinked polymeric resin class carrier etc. are main
Will be based on micropore, the very thin microcellular structure of such complex function adsorbent material carrier hinders absorption mass-transfer efficiency, is applied to height
The low disadvantage of work adsorption capacity is shown in fast (20~100BV/h) fluidised form adsorption system；And for zeolite, macroreticular resin class
Carrier duct is wider, although composite material absorption mass-transfer performance is beneficial, its macroporous structure often leads to the inorganic adsorbent being loaded into
Agent generates particle growth and local agglomeration, and then nanometer size effect lacks, and adsorption capacity is lower.Therefore, how rationally
In conjunction with carrier surface pore structure, improving composite functional material work utilization efficiency is the key that solve such material further to develop
Problem.
Fairy shrimp (Artemia) belongs to Crustaceans, is the important Food organism resources of culture fishery, is almost distributed in
All salt pans and salt lake with high salt all over the world.Brine shrimp eggs can resist dry, with high salt, radiation for a long time, high fever, freezing, lack
The extreme environments such as oxygen, and acid and alkali-resistance, the fairy shrimp chorion survival ability outstanding to its play vital protective effect.
It is numerous that brine shrimp eggs as a kind of living resources have that bio-compatibility is good, cheap, environmental-friendly, stability is excellent etc.
Advantage, with unique cavernous structure, progressive ladder distribution is presented in surface duct, be can be used as carrier material and is developed compound life
Object adsorbent.Compared with conventional carrier material, special its internal layer duct area of advanced formula pore distribution one side of fairy shrimp chorion
There is similar active carbon to enrich microcellular structure in domain, can be realized inorganic adsorbent nano-pore template effect, promote nano particle point
Scattered and adsorption activity；On the other hand, outer channel is roomy, and the progressive distribution of space reduction formula can greatly improve absorption mass transfer speed
Rate.Porous nano template effect can be had concurrently as carrier using brine shrimp eggs and macropore strengthens mass transfer effect double action mechanism,
There is higher work utilization efficiency compared with conventional composite materials.
Basic zirconium chloride is a kind of Typical transition metal oxide, and the effective component of manufactured adsorbent is ZrO2, hydration
ZrO2The fluorine ion in higher Selective adsorption adsorption aqueous solution is shown, to generate complex compound H not soluble in water2
[ZrF6] (chemical equation 1,2).Using brine shrimp eggs as carrier, sufficiently by the distinctive advanced formula cellular structure of carrier to nanometer
Adsorbent orifice plate strengthens dispersion effect and macropore strengthens mass transfer characteristic, and immobilized zirconium oxide prepares biological complex function adsorbent material.
ZrOCl2+XH2O=ZrO2·(X-1)H2O+2HCl chemical formula 1
ZrO2+6F-+4H2O=H2[ZrF6]+6OH-Chemical formula 2
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to which it is compound to provide a kind of load zirconium biology for removing fluor in water
Adsorbent and regeneration method and application.
The purpose of the present invention is achieved through the following technical solutions: a kind of load zirconium biology for removing fluor in water is compound
Adsorbent, it is prepared by the following method to obtain:
(1) basic zirconium chloride is dissolved in the water, the mass volume ratio of zirconium oxide and water is 5~20g:150mL, adjusts pH value
To 6~7, white precipitate is generated；After 50~70 DEG C of heating water baths activate 2h, is filtered, be washed to neutrality with distillation, finally
White solid is put into baking oven, in 100~110 DEG C of 1~2h of drying, is taken out, it is cooling, active zirconia is obtained, is crushed spare.
(2) fairy shrimp chorion spends ionized water and cleans to neutrality, is dried for standby.
(3) active zirconia that 3~5g step (1) obtains and the fairy shrimp chorion that 3~5g step (2) obtains are added
In 100~150mL ethanol solution, 4~6h of room temperature ultrasound.Then, 4~6h of magnetic agitation carries out in-situ precipitate reaction,
Zirconium hydroxide is generated in brine shrimp eggs housing hole road, and chorion is made all to sink to container bottom, and chorion compound is obtained by filtration, is used in combination
Deionized water is cleaned to neutrality.
(4) the chorion compound that step (3) obtains is placed in 50~70 DEG C of drying boxes dry 8~12h, promotes fairy shrimp
Zirconium hydroxide in chorion duct is decomposed into zirconium oxide, and the load zirconium biology compound adsorbent for removing fluor in water is made.
Further, in the step (1), pH value is adjusted with the sodium hydroxide that concentration is 20wt%.
Further, the supersonic frequency in step (3) is 60~100HZ.
The invention also discloses a kind of regeneration method of above-mentioned load zirconium biology compound adsorbent for removing fluor in water, when containing
For fluorine sewage after this is used for the load zirconium biology compound adsorbent processing of removing fluor in water, the fluorinion concentration of water outlet is higher than 1.0mg/L
When, stop adsorption operations, which is regenerated, regeneration method includes following
Step: NaOH and NaCl mixed aqueous solution is consolidated by being filled with the column for the load zirconium biology compound adsorbent for being used for removing fluor in water
Fixed bed adsorbent equipment, NaOH mass concentration are that 3~5%, NaCl mass concentration is 2~3%, and control regeneration velocity is 1BV/h, temperature
25 DEG C of degree, can regenerate completely through 4~35BV desorption reaction, and adsorbent material need to be rinsed with clear water to neutral i.e. recyclable after regeneration
It uses.
The invention also discloses a kind of purposes of above-mentioned load zirconium biology compound adsorbent for removing fluor in water, this is used for water
The load zirconium biology compound adsorbent of middle fluorine removal can be used for removing Micro fluoride ion, specifically: by fluorine containing waste water with 10~
60BV/h flow velocity passes through the column preventing fixed bed adsorber for being filled with the load zirconium biology compound adsorbent for removing fluor in water, purification
Fluorine containing waste water.
Further, at 15~55 DEG C, pH is controlled in 6~8 ranges for the temperature control of the fluorine containing waste water.
The beneficial effects of the present invention are: the invention has the following advantages over the prior art:
(1) basic zirconium chloride is loaded into brine shrimp eggs shell channel surfaces by the present invention, sufficiently by chorion porous nano template and
Macropore strengthens mass transfer double action mechanism, high-performance complex function adsorbent material is developed, to greatly promote the work of such material
Make efficiency and application space, so that fairy shrimp chorion obtained is carried zirconium biology compound adsorbent has good defluorination effect, can have
Fluorine in effect removal water body；
(2) production technology is easy to control, lower production costs, when preservation 1 year or so can be stablized by carrying zirconium biology compound adsorbent
Between；
(3) material can be applied to drinking water, surface water and other water bodys by fluoride pollution, can efficiently go in water removal
Fluorine ion realizes the purification and security control of fluorinated water.
Detailed description of the invention
Fig. 1 is basic zirconium chloride (ZrOCl2) porous pattern scanning figure；
Fig. 2 is that fairy shrimp chorion carries zirconium traversing of probe electron microscope (SEM), wherein (a) is to carry chorion scanning electron microscope before zirconium
Figure is (b) chorion scanning electron microscope (SEM) photograph after load zirconium；
Fig. 3 is that fairy shrimp chorion carries transmission electron microscope picture (TEM) before and after zirconium, wherein (a) is to carry chorion transmission electron microscope before zirconium
Figure is (b) chorion transmission electron microscope picture after load zirconium；
Fig. 4 is that fairy shrimp chorion carries energy spectrum diagram (EDS) before and after zirconium, wherein (a) carries chorion energy spectrum diagram before zirconium, after (b) carrying zirconium
Chorion energy spectrum diagram；
Fig. 5 is the measurement schematic diagram for carrying zirconium biology compound adsorbent fluorine removal capacity.
Specific embodiment
The present invention is further described in conjunction with the accompanying drawings and embodiments.Following examples to further illustrate the present invention, but
It is not so limited the scope of the invention.
Embodiment 1: the preparation 1 of zirconium biology compound adsorbent is carried
By 4g basic zirconium chloride (ZrOCl2) be dissolved in 100mL water, after blender stirring, 20% sodium hydroxide is added,
PH to 6.5 is adjusted with dilute hydrochloric acid.In 70 DEG C of heating water baths, white depositions are filtered, and with distilled water flushing sediment
To neutrality, then in 110 DEG C of drying 1h, cooling is simultaneously crushed.Fairy shrimp chorion 4g is weighed, is cleaned with deionized water to neutrality, is dried
It is dry.Treated active zirconia and fairy shrimp chorion are placed in 100mL ethanol solution, it is ultrasonic at normal temperature
4h, supersonic frequency 60HZ.Magnetic agitation 4h later carries out in-situ precipitate reaction, generates hydroxide in brine shrimp eggs housing hole road
Zirconium, and chorion is made all to sink to container bottom.Chorion compound is taken out in filtering, wash with distilled water several times, until neutrality.In 50
Dry 12h in DEG C drying box, is made fairy shrimp chorion and carries zirconium biology compound adsorbent.
Embodiment 2: the preparation 2 of zirconium biology compound adsorbent is carried
By 15g basic zirconium chloride (ZrOCl2) be dissolved in 150mL water, after blender stirring, 20% sodium hydroxide is added,
PH to 7.0 is adjusted with dilute hydrochloric acid.50 DEG C of heating water baths are subsequently placed in, white depositions are filtered, and use distilled water flushing
Sediment is to neutrality, and then in 100 DEG C of drying 2h, cooling is simultaneously crushed.Fairy shrimp chorion 5g is weighed, is cleaned with deionized water into
Property, drying.By treated active zirconia and fairy shrimp chorion, it is placed in 150mL ethanol solution, at normal temperature
Ultrasonic 6h, supersonic frequency 100HZ.Magnetic agitation 5h later carries out in-situ precipitate reaction, generates hydrogen in brine shrimp eggs housing hole road
Zirconium oxide, and chorion is made all to sink to container bottom.Chorion compound is taken out in filtering, wash with distilled water several times, until neutrality.
In 8h dry in 70 DEG C of drying boxes, fairy shrimp chorion is made and carries zirconium biology compound adsorbent.
Embodiment 3: fluorine ion and regeneration 1 in water removal are gone using zirconium biology compound adsorbent is carried
The above-mentioned load zirconium biology compound adsorbent of 6g is placed in glass adsorption column (12 × 220mm of ф), fluorine-containing contaminant water (F-
=1.5mg/L and SO4 2-=100mg/L, Cl-=100mg/L, NO3 -=100mg/L, pH=6) from top to bottom downstream through being equipped with
The adsorption column of Biocomposite material, temperature are controlled at 15 DEG C, flow velocity 10BV/h, and fluorinion concentration is discharged after adsorbent is handled and is existed
1.0mg/L is hereinafter, treating capacity is up to 1000BV.(F after obvious leakage occurs in absorption-> 1.0mg/L), stop absorption.With
(NaOH mass concentration is 3% for 50mLNaOH and NaCl mixed solution；NaCl mass concentration 2%) regeneration, controlling regeneration velocity is
1BV/h, can regenerate completely (desorption rate is up to 99%) through 4BV desorption reaction by 25 DEG C of temperature.Regenerate the compound suction of rear bearing zirconium biology
Attached dose is cleaned to neutrality with deionized water and can be used continuously.
Embodiment 4: fluorine ion and regeneration 2 in water removal are gone using zirconium biology compound adsorbent is carried
The above-mentioned load zirconium biology compound adsorbent of 15g is placed in glass adsorption column (24 × 220mm of ф), fluorine-containing contaminant water
(F-=3.0mg/L and SO4 2-=200mg/L, Cl-=100mg/L, NO3 -=160mg/L, pH=8) from top to bottom downstream through
Adsorption column equipped with Biocomposite material, temperature are controlled at 55 DEG C, flow velocity 60BV/h, and it is dense that fluorine ion is discharged after adsorbent is handled
Degree is in 1.0mg/L hereinafter, treating capacity is up to 400BV.(F after obvious leakage occurs in absorption-> 1.0mg/L), stop absorption.With
(NaOH mass concentration is 5% for 50mLNaOH and NaCl mixed solution；NaCl mass concentration 3%) regeneration, controlling regeneration velocity is
1BV/h, can regenerate completely (desorption rate is up to 99%) through 35BV desorption reaction by 25 DEG C of temperature.It is compound to regenerate rear bearing zirconium biology
Adsorbent is cleaned to neutrality with deionized water and be can be used continuously.
Embodiment 5: influence of the zirconium biology compound adsorbent dosage to defluorination effect is carried
It takes respectively and carries zirconium biology compound adsorbent 0.10g, 0.20g, 0.30g, 0.40g, 0.50g, 50mL, 10mg/L is added
Fluoride waste in, set mixing time as 10min, total ionic strength adjustment-buffer (TISAB) (sodium chloride 58g, lemon be then added
Lemon acid sodium 0.357g is in 800mL water, acetic acid 57mL on the rocks, and adjusting pH value with 50% sodium hydroxide solution is 5.0, is diluted to
1000mL) 50mL does blank with 50mg/L fluorine ion standard solution and liquid is added, so that fluoride removing rate is measured, as a result such as table 1.By table 1
It is found that dosage has a significant effect to fluoride ion removing rate, fluorinion concentration is set to be down to 1.0mg/L hereinafter, then needing investment about
The load zirconium biology compound adsorbent of 8 ‰ (mass ratioes).
Table 1: influence of the zirconium biology compound adsorbent dosage to fluoride removing rate is carried
| Dosage (g) | Residual F-It measures (mg/L) | Fluoride removing rate (%) |
| 0.10 | 3.09 | 69.1 |
| 0.20 | 2.69 | 73.8 |
| 0.30 | 1.18 | 88.2 |
| 0.40 | 0.82 | 91.8 |
| 0.50 | 0.71 | 92.9 |
Influence of the embodiment 6:pH value to fluoride ion removing rate
The water sample 50mL that the fluorinated volume of different pH value is 10mg/L, each 0.4g that is added is taken to carry zirconium biology composite adsorption respectively
Agent does blank with 50mg/L fluorine ion standard solution and liquid is added, the results are shown in Table 2.It can be seen that pH value is by 2.0~10.00 ranges to fluorine
Ion remaval influences less, to illustrate that carry zirconium biology compound adsorbent is not influenced the adsorptivity of fluorine ion by pH value substantially.
Influence of the table 2:pH value to fluoride removing rate
| PH value | Residual F-It measures (mg/L) | Fluoride removing rate (%) |
| 2.15 | 1.05 | 89.5 |
| 3.14 | 1.03 | 89.7 |
| 4.36 | 0.80 | 92.0 |
| 5.17 | 0.72 | 92.8 |
| 6.16 | 0.68 | 93.2 |
| 7.24 | 0.75 | 92.5 |
| 8.65 | 0.72 | 92.8 |
| 9.14 | 0.72 | 92.8 |
| 10.16 | 0.80 | 92.0 |
Embodiment 7: the measurement of zirconium biology compound adsorbent fluorine removal capacity is carried
The water of 50mL difference fluorinated volume is taken, each load zirconium biology compound adsorbent that same amount is added surveys its adsorbance, such as Fig. 5.
As can be seen from the results, it is increased with the concentration of fluorine ion in water, fluoride removing quantity is also being gradually increased, and illustrates that carrying zirconium biology compound adsorbent has
Stronger adsorption capacity.
Embodiment 8: the stability of defluorination effect
In the water for being 10mg/L to fluorinated volume, the load zirconium biology compound adsorbent of about 8 ‰ (mass ratioes) of addition, stirring 15~
20min stands 2~48h, measures the fluoride removing rate of different sedimentation times.Through comparing, defluorination effect is without significant change.And it precipitates
12h or more is placed, fluoride removing rate illustrates to carry fluorine ion in zirconium biology compound adsorbent and water and form complex compound up to 95.0% or more
It is extremely stable afterwards, fluorine ion is not discharged into water.
Embodiment 9: the performance characterization of zirconium biology compound adsorbent is carried
The results show that the immobilized preceding brine shrimp eggs shell inner surfaces of pores of precipitating is smooth, nearly outer layer aperture reaches scanning electron microscopic observation,
Duct is open；Deep layer aperture is small, aretation.There is large, medium and small, the progressive ladder distribution (Fig. 2 a) of duct presentation in hole.It carries
Chorion duct becomes smaller (Fig. 2 b) after zirconium, it was demonstrated that zirconium oxide has succeeded immobilized to chorion inner surfaces of pores；Another is noteworthy characterized by
Central construct region (periphery aporate area be it is original it is untreated fall coating film layer) duct is only on the basis of original size
It reduces, no particle agglomeration and duct clogging, zirconium oxide arrives chorion inner surfaces of pores so that coating method is immobilized, it was demonstrated that duct is in
The fairy shrimp chorion of existing progressive ladder distribution is compared with conventional carrier material, and there is macropore to strengthen mass transfer effect mechanism of action,
Clear superiority is shown compared with conventional carriers material.
For transmission electron microscope observing the results show that fairy shrimp chorion is before carrying zirconium (Fig. 3 a), chorion does not have the plaque-like particle of brown,
Transparency is higher；After carrying zirconium (Fig. 3 b), there is apparent black splotch particle in chorion, granular size be about 10~50nm it
Between, it can affirm that fairy shrimp chorion plays porous nano template action.
Energy Dispersive Spectroscopy is analyzed as the result is shown (Fig. 4), Zr element level after fairy shrimp chorion sample fringe area is immobilized
It is higher in entire composition, it is only second to Ca and occupies second；And in contrast, immobilized preceding sample scattering region has no Zr element.Energy
Amount spectroscopic scatterometer analysis result further confirms that zirconium oxide has succeeded in the immobilized duct to chorion.
Claims (6)
1. a kind of load zirconium biology compound adsorbent for removing fluor in water, which is characterized in that it is prepared by the following method to obtain:
(1) basic zirconium chloride is dissolved in the water, the mass volume ratio of zirconium oxide and water is 5~20g:150mL, adjusts pH value to 6
~7, generate white precipitate；It after 50~70 DEG C of heating water baths activate 2h, is filtered, is washed to neutrality with distillation, finally will
White solid is put into baking oven, in 100~110 DEG C of 1~2h of drying, is taken out, cooling, is obtained active zirconia, is crushed spare.
(2) fairy shrimp chorion spends ionized water and cleans to neutrality, is dried for standby.
(3) active zirconia that 3~5g step (1) obtains and fairy shrimp chorion that 3~5g step (2) obtains are added 100~
In 150mL ethanol solution, 4~6h of room temperature ultrasound.Then, 4~6h of magnetic agitation carries out in-situ precipitate reaction, in the good year
Generate zirconium hydroxide in worm's ovum housing hole road, and chorion made all to sink to container bottom, chorion compound is obtained by filtration, and spend from
Sub- water is cleaned to neutrality.
(4) the chorion compound that step (3) obtains is placed in 50~70 DEG C of drying boxes dry 8~12h, promotes fairy shrimp chorion
Zirconium hydroxide in duct is decomposed into zirconium oxide, and the load zirconium biology compound adsorbent for removing fluor in water is made.
2. the preparation method for the load zirconium biology compound adsorbent of removing fluor in water according to claim 1, which is characterized in that
In the step (1), pH value is adjusted with the sodium hydroxide that concentration is 20wt%.
3. the preparation method for the load zirconium biology compound adsorbent of removing fluor in water according to claim 1, which is characterized in that
Supersonic frequency in step (3) is 60~100HZ.
4. the regeneration method described in a kind of claim 1 for the load zirconium biology compound adsorbent of removing fluor in water, which is characterized in that
The load zirconium biology compound adsorbent for being used for removing fluor in water is filled with the following steps are included: NaOH and NaCl mixed aqueous solution are passed through
Column preventing fixed bed adsorber, NaOH mass concentration is that 3~5%, NaCl mass concentration is 2~3%, control regeneration velocity be
1BV/h, can regenerate completely through 4~35BV desorption reaction by 25 DEG C of temperature, and adsorbent material need to be rinsed with clear water to neutrality after regeneration
It can be recycled.
5. the purposes described in a kind of claim 1 for the load zirconium biology compound adsorbent of removing fluor in water, which is characterized in that the use
It can be used for removing Micro fluoride ion in the load zirconium biology compound adsorbent of removing fluor in water, specifically: by fluorine containing waste water with 10
~60BV/h flow velocity passes through the column preventing fixed bed adsorber for being filled with the load zirconium biology compound adsorbent for removing fluor in water, only
Change fluorine containing waste water.
6. purposes according to claim 5, which is characterized in that the control of the temperature of the fluorine containing waste water is at 15~55 DEG C, pH
Control is in 6~8 ranges.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111111612A (en) * | 2019-12-19 | 2020-05-08 | 燕山大学 | Preparation and use method of magnetic porous biochar for removing chromium in water |
| CN111729649A (en) * | 2020-06-23 | 2020-10-02 | 南京大学 | High-selectivity anion adsorbent and preparation method and application thereof |
| CN114797792A (en) * | 2022-05-25 | 2022-07-29 | 浙江树人学院 | Preparation method and application of magnetic biochar-based composite adsorbent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111111612A (en) * | 2019-12-19 | 2020-05-08 | 燕山大学 | Preparation and use method of magnetic porous biochar for removing chromium in water |
| CN111111612B (en) * | 2019-12-19 | 2022-06-03 | 燕山大学 | Preparation and use method of magnetic porous biochar for removing chromium in water |
| CN111729649A (en) * | 2020-06-23 | 2020-10-02 | 南京大学 | High-selectivity anion adsorbent and preparation method and application thereof |
| CN111729649B (en) * | 2020-06-23 | 2022-03-18 | 南京大学 | High-selectivity anion adsorbent and preparation method and application thereof |
| CN114797792A (en) * | 2022-05-25 | 2022-07-29 | 浙江树人学院 | Preparation method and application of magnetic biochar-based composite adsorbent |
| CN114797792B (en) * | 2022-05-25 | 2023-10-24 | 浙江树人学院 | Preparation method and application of magnetic biochar-based composite adsorbent |
| CN115318250A (en) * | 2022-08-18 | 2022-11-11 | 自然资源部天津海水淡化与综合利用研究所 | Fumaric acid modified zirconium-loaded gel ball and preparation method and application thereof |
| CN115318250B (en) * | 2022-08-18 | 2023-06-27 | 自然资源部天津海水淡化与综合利用研究所 | Fumaric acid modified zirconium-carrying gel ball and preparation method and application thereof |
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