CN108079948A - A kind of preparation method of galapectite, carbon and the compound arsenic removing agent of ferriferrous oxide nano - Google Patents
A kind of preparation method of galapectite, carbon and the compound arsenic removing agent of ferriferrous oxide nano Download PDFInfo
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- CN108079948A CN108079948A CN201711426708.3A CN201711426708A CN108079948A CN 108079948 A CN108079948 A CN 108079948A CN 201711426708 A CN201711426708 A CN 201711426708A CN 108079948 A CN108079948 A CN 108079948A
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- 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
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- 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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- 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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- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
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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
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- 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
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
Abstract
The preparation method of a kind of galapectite, carbon and the compound arsenic removing agent of ferriferrous oxide nano, is related to water-treatment technology field.Galapectite, carbon and ferriferrous oxide nano composite material arsenic removing agent are successfully prepared using high-temperature calcination and coprecipitation, experimental procedure is simple, easy to operate, is characterized using means such as SEM, XRD, XPS, BET.Criticize optimal arsenic removal parameter and absorption property that adsorption experiment has inquired into arsenic removing agent, the result shows that for arsenic solution As (III), the As (V) of 5 mg/L while there is higher removal efficiency to initial concentration under pH 7,0.5 mg/mL of adsorbent amount, 60 min, product specific surface area of the present invention is high simultaneously has typical microcellular structure, and regenerability is good, non-secondary pollution, application easy to spread.
Description
Technical field
The invention belongs to water-treatment technology fields, and in particular to the technology of preparing of water body arsenic scavenging material.
Background technology
Arsenic (As) is one of element most toxic in the world, is prevalent in soil, water and air.Usually with
As2S2, As2S3, As2O3And C6H5AsO, i.e., respectively red arsenic, yellow arsenic, arsenic and benzene arsenic oxide, arsenic different according to form
Inorganic arsenic and organo-arsenic can be divided into, different according to chemical valence, arsenic can be divided into pentavalent arsenic As (V) and trivalent arsenic As (III) again,
Wherein trivalent inorganic arsenic poison highest.Due to the hypertoxicity and migration characteristic of arsenic, arsenic pollution serious threat to the strong of the mankind
Health and living environment, therefore, water body arsenic pollution have caused worldwide extensive concern.
The standard of Arsenic in Drinking Water is reduced to 10 ppb, U.S. environment by World Safety Organization (WHO) from 50 ppb
Protection administration (USEPA) and China's current standard all define, and the content standard of Arsenic in Drinking Water is 10 ppb.Therefore, how
Effectively, the arsenic easily removed in water body is the important topic for being related to human health.
Existing arsenic pollution method includes absorption method, chemical flocculation precipitation method, ion-exchange, membrane separation process etc., wherein
It is verified that for most economical efficient, simple and practicable processing method, all kinds of sorbing materials are developed absorption method by researcher,
Many results of study show that rare earth can be effective with clay material, metal-base composites, chitosan-based material and active material
The arsenic of water body middle and high concentration is removed, because they have inorganic arsenic very strong affinity, however there is also certain for such material
The defects of, such as adsorb it is not thorough enough, adsorption efficiency compared with it is slow, adsorption capacity is low, cost is higher, cannot reach drinking water standard, and
It is low to the highest trivalent inorganic arsenic removal efficiency of toxicity.
Nano material has many advantages, such as very strong adsorption capacity since size is small, specific surface area is high, nano material pair
Many metal ions have very strong adsorption capacity, are also concerned, are with a wide range of applications in terms of wastewater treatment.But
Since nano material is mostly in These powdered adsorbents input water body, it is difficult to recycle, cause secondary pollution and nanometer material
Material is easily reunited since size is small, the shortcomings such as cause removal efficiency low.Therefore, how overcome the deficiencies in the prior art is current water
Processing technology field urgent problem.
The content of the invention
In order to solve the problems in the existing technology, the present invention proposes a kind of available for arsenic removal, angstrom beneficial to recycling
The preparation method of Lip river stone, carbon and the compound arsenic removing agent of ferriferrous oxide nano.
The present invention comprises the following steps：
1）Galapectite is scattered in ethyl alcohol, obtains the alcohol suspending liquid of galapectite；
2）Phenolic resin is dissolved in ethyl alcohol, and adds in methenamine, obtains phenol resin solution；
3）The alcohol suspending liquid of galapectite is added dropwise on sponge, phenol resin solution is added dropwise after to be dried, it is dry；
4）By step 3）Products therefrom is placed in Muffle furnace and calcines, and obtains calcining solid product；
5）Calcining solid product is mixed with molysite aqueous solution；
6）To step 5）Aqueous slkali is added in gained mixture, and is reacted in atmosphere of inert gases, then produces reaction
Object obtains solid formation through Magneto separate；
7）Solid formation is washed with deionized water to neutrality, it is freeze-dried, it is compound to obtain galapectite, carbon and ferriferrous oxide nano
Arsenic removing agent.
The present invention is successfully prepared nanocomposite, compared with prior art, this hair with high-temperature calcination and coprecipitation
Bright nanocomposite obtained overcomes the problem of nano material reunion inactivation, secondary pollution water body and existing arsenic removal is difficult
Problem has preferable water body arsenic absorption property, has higher removal efficiency to water body arsenic, and can effectively remove trivalent arsenic simultaneously
And pentavalent arsenic, preparation process are easy reliable, the production cycle is shorter, beneficial to batch production to be applied in actual water process.
Further, the mixing quality ratio of phenolic resin and methenamine of the present invention is 1~10: 1, the phenolic aldehyde tree
The solid-to-liquid ratio of lipoprotein solution is 1~1: 20.Be conducive to the quick dissolving of phenolic resin under this ratio.
The calcining heat is 800~1000 DEG C, and the time is 15~30 min.Be conducive to prepare sample under this temperature, time
The high temperature cabonization process of product.
The molysite be ferric sulfate, ferric nitrate, iron chloride, ferric oxalate, ferrous sulfate, frerrous chloride or ferric acetate in extremely
Lack any one.These molysite are the common drug in laboratory, cheap, are readily available, can substantially reduce production cost.
The mixing quality ratio of the molysite and high-temperature calcination solid product is 1~10: 1.By changing molysite and natural ore deposit
The ratio of native galapectite, the pattern and adsorption efficiency of controllable composite material, to obtain best product.
The concentration of the aqueous slkali is 0.5~5 mol/L.The concentration of aqueous slkali can effectively control generation in the range
Fe3O4。
The alkali be sodium hydroxide, potassium hydroxide, sodium acid carbonate or ammonium hydroxide at least any one.These alkali are reality
The common drug in room is tested, it is cheap, it is readily available, and can effectively control generation Fe3O4。
Description of the drawings
Fig. 1 is HNTs (a), HNTs/C (b) and HNTs/C/Fe3O4(c) XRD diagram.
Fig. 2 is HNTs/C and HNTs/C/Fe3O4The Raman figures of nanocomposite.
Fig. 3 is HNTs/C/Fe3O4The full spectrograms of XPS of nanocomposite.
Fig. 4 is HNTs/C/Fe3O4The XPS spectrum figure of Fe 2p in nanocomposite.
The SEM that Fig. 5 is HNTs/C schemes.
Fig. 6 is HNTs/C/Fe3O4The SEM figures of nanocomposite.
Fig. 7 is HNTs/C/Fe3O4The BET figures of nanocomposite.
Fig. 8 is As2O3AFS canonical plottings.
Fig. 9 is HNTs, HNTs/C and HNTs/C/Fe3O4Adsorption efficiency comparison diagram.
Figure 10 is arsenic solution initial concentration（Low concentration）To the influence figure of material arsenic removal efficiency.
Figure 11 is arsenic solution initial concentration（High concentration）To the influence figure of material arsenic removal efficiency.
Figure 12 is influence figure of the adsorbent amount to material arsenic removal efficiency.
Figure 13 is influence figure of the pH value of solution to material arsenic removal efficiency.
Figure 14 is influence figure of the adsorption time to material arsenic removal efficiency.
Figure 15 is HNTs/C/Fe3O4Nanocomposite arsenic removal recycles efficiency chart.
Specific embodiment
With reference to embodiment, the present invention is described in further detail.
First, the preparation process of galapectite, carbon and ferriferrous oxide composite material：
Embodiment 1：
(1) 5 g natural ore soil galapectites are scattered in 500 mL ethanol solutions.
(2) 5 g phenolic resin and 0.5 g methenamines are dissolved in 100 mL ethanol solutions.
(3) scattered galapectite solution is first dropped evenly on sponge, after to be dried, continues to drop evenly institute in (2)
Phenol resin solution is obtained, it is dry.
(4) products therefrom in (3) is placed in 1000 DEG C of 30 min of high-temperature calcination in Muffle furnace and obtains black solid product.
(5) product in 10 g (4) adds in in the mixed molysite solution of iron chloride and ferrous sulfate (metal salt quality is
30 g), and 250 rpm/min mechanical agitations make ionizable metal salt uniformly, fully be contacted with galapectite.
(6) inert nitrogen gas is passed through in (5), continues to stir the oxygen in removing system.
(7) 0.5 mol/L ammonia spirits, 50 mL is added dropwise in (6), continues to stir with the speed of 150~300 rpm/min
Mixing makes it fully react.
(8) reaction product in (7) is placed under magnetic force, solid formation is separated from solution, and uses deionization
Water washing is freeze-dried to obtain composite material for several times to neutrality.
Embodiment 2：
(1) 5 g natural ore soil galapectites are scattered in 500 mL ethanol solutions.
(2) 5 g phenolic resin and 1 g methenamines are dissolved in 100 mL ethanol solutions.
(3) scattered galapectite solution is first dropped evenly on sponge, after to be dried, continues to drop evenly institute in (2)
Phenol resin solution is obtained, it is dry.
(4) products therefrom in (3) is placed in 1000 DEG C of 30 min of high-temperature calcination in Muffle furnace and obtains black solid product.
(5) product in 10 g (4) adds in in the mixed molysite solution of ferric sulfate, frerrous chloride (metal salt quality is
30 g), and 250 rpm/min mechanical agitations make ionizable metal salt uniformly, fully be contacted with galapectite.
(6) inert nitrogen gas is passed through in (5), continues to stir the oxygen in removing system.
(7) 0.5 mol/L sodium hydrate aqueous solutions, 50 mL is added dropwise in (6), with the speed of 150~300 rpm/min
Continuing stirring makes it fully react.
(8) reaction product in (7) is placed under magnetic force, solid formation is separated from solution, and uses deionization
Water washing is freeze-dried to obtain composite material for several times to neutrality.
Embodiment 3：
(1) 5 g natural ore soil galapectites are scattered in 500 mL ethanol solutions.
(2) 5 g phenolic resin and 0.5 g methenamines are dissolved in 120 mL ethanol solutions.
(3) scattered galapectite solution is first dropped evenly on sponge, after to be dried, continues to drop evenly institute in (2)
Phenol resin solution is obtained, it is dry.
(4) products therefrom in (3) is placed in 800 DEG C of 30 min of high-temperature calcination in Muffle furnace and obtains black solid product.
(5) by (metal salt quality is 30 in the mixed molysite solution of product addition ferric sulfate and ferric acetate in 5 g (4)
G), 250 rpm/min mechanical agitations make ionizable metal salt uniformly, fully be contacted with galapectite.
(6) inert nitrogen gas is passed through in (5), continues to stir the oxygen in removing system.
(7) to 1 mol/L sodium bicarbonate aqueous solutions, 20 mL is added dropwise in (6), with the speed of 150~300 rpm/min after
Continuous stirring makes it fully react.
(8) reaction product in (7) is placed under magnetic force, solid formation is separated from solution, and uses deionization
Water washing is freeze-dried to obtain composite material for several times to neutrality.
Embodiment 4：
(1) 5 g natural ore soil galapectites are scattered in 500 mL ethanol solutions.
(2) 5 g phenolic resin and 1 g methenamines are dissolved in 120 mL ethanol solutions.
(3) scattered galapectite solution is first dropped evenly on sponge, after to be dried, continues to drop evenly institute in (2)
Phenol resin solution is obtained, it is dry.
(4) products therefrom in (3) is placed in 1000 DEG C of 15 min of high-temperature calcination in Muffle furnace and obtains black solid product.
(5) by (metal salt quality is 50 in the mixed molysite solution of product addition ferric nitrate, frerrous chloride in 5 g (4)
G), 250 rpm/min mechanical agitations make ionizable metal salt uniformly, fully be contacted with galapectite.
(6) inert nitrogen gas is passed through in (5), continues to stir the oxygen in removing system.
(7) to 2 mol/L sodium hydrate aqueous solutions, 10 mL is added dropwise in (6), with the speed of 150~300 rpm/min after
Continuous stirring makes it fully react.
(8) reaction product in (7) is placed under magnetic force, solid formation is separated from solution, and uses deionization
Water washing is freeze-dried to obtain composite material for several times to neutrality.
Embodiment 5：
(1) 5 g natural ore soil galapectites are scattered in 500 mL ethanol solutions.
(2) 5 g phenolic resin and 1 g methenamines are dissolved in 150 mL ethanol solutions.
(3) scattered galapectite solution is first dropped evenly on sponge, after to be dried, continues to drop evenly institute in (2)
Phenol resin solution is obtained, it is dry.
(4) products therefrom in (3) is placed in 1000 DEG C of 15 min of high-temperature calcination in Muffle furnace and obtains black solid product.
(5) by (metal salt quality is 20 in the mixed molysite solution of product addition iron chloride and ferric acetate in 10 g (4)
G), 250 rpm/min mechanical agitations make ionizable metal salt uniformly, fully be contacted with galapectite.
(6) inert nitrogen gas is passed through in (5), continues to stir the oxygen in removing system.
(7) to 3 mol/L potassium hydroxide aqueous solutions, 10 mL is added dropwise in (6), with the speed of 150~300 rpm/min after
Continuous stirring makes it fully react.
(8) reaction product in (7) is placed under magnetic force, solid formation is separated from solution, and uses deionization
Water washing is freeze-dried to obtain composite material for several times to neutrality.
Embodiment 6：
(1) 5 g natural ore soil galapectites are scattered in 500 mL ethanol solutions.
(2) 5 g phenolic resin and 1 g methenamines are dissolved in 50 mL ethanol solutions.
(3) scattered galapectite solution is first dropped evenly on sponge, after to be dried, continues to drop evenly institute in (2)
Phenol resin solution is obtained, it is dry.
(4) products therefrom in (3) is placed in 1000 DEG C of 30 min of high-temperature calcination in Muffle furnace and obtains black solid product.
(5) by (metal salt quality is 10 in the mixed molysite solution of product addition iron chloride and ferric acetate in 10 g (4)
G), 250 rpm/min mechanical agitations make ionizable metal salt uniformly, fully be contacted with galapectite.
(6) inert nitrogen gas is passed through in (5), continues to stir the oxygen in removing system.
(7) 0.5 mol/L ammonia spirits, 50 mL is added dropwise in (6), continues to stir with the speed of 150~300 rpm/min
Mixing makes it fully react.
(8) reaction product in (7) is placed under magnetic force, solid formation is separated from solution, and uses deionization
Water washing is freeze-dried to obtain composite material for several times to neutrality.
2nd, the characterization for the composite material that preparation obtains：
By taking the sample in case study on implementation 1 as an example, prepared material is characterized respectively using Powder X-ray Diffractometer, such as
Shown in Fig. 1, three curves are respectively (a) HNTs, (b) HNTs/C and (c) HNTs/C/Fe in Fig. 13O4The XRD of composite material
Figure.
Comparison (a), (b), (c) three curves are visible：The characteristic absorption peak that 2 θ are HNTs at 20.1 ° and 24.9 ° weakens
, this is because halloysite nanotubes enter inside porous carbon materials and Fe3O4It is supported on the surface of HNTs/C；It is bent from (c)
Significantly occurs Fe in line3O4Characteristic absorption peak（JCPDS 19-0629）, respectively correspond to 2 θ for 35.4 °, 43.3 °, 57.2
°、62.6 °.Further illustrate that trielement composite material is successfully prepared.
Composite material is characterized using the Raman image instrument of model GX-PT-2412, as shown in Figure 2.In Fig. 2
Two curves represent HNTs/C and HNTs/C/Fe respectively3O4Raman spectrum.
From Fig. 2, it is apparent that in 1341 cm-1With 1580 cm-1Wave number corresponds to disordered carbon band D peak bands and sp respectively2
Hydridization carbon ribbon G peaks band；It can be seen that from the relative intensity ratios at two peaks and add in Fe3O4I afterwardsD/IGRelative intensity ratios increase
It is big, illustrate Fe3O4There is interaction between carbon, affect orderly, the disordered structure of carbon, further prove tri compound
Material preparation success.
Composite material is characterized using model ESCALAB 250Xi x-photoelectron spectroscopies, as shown in Figure 3.Figure
3 be HNTs/C/Fe3O4The full spectrograms of XPS of trielement composite material, Fig. 4 are the XPS collection of illustrative plates of Fe 2p in trielement composite material.
From the full spectrogram of Fig. 3, it is apparent that peak value divides in 73.99,102.08,284.08,530.95,711.5ev
It is not the O since Al 2p, Si 2p, C 1s, O 1s, Fe 2p are generated（A）, O 1s, Si 2p, Al 2p elements illustrate composite wood
The presence of galapectite in material.Fe 2p1/2 and Fe 2p3/2 Photoelectron peaks appear in 724.1ev and 710.5ev in Fig. 4.Fe
The peak of 2p3/2 is concentrated mainly on 710.5ev, is due to Fe3+It is caused.Also, do not have between Fe 2p1/2 and Fe 2p3/2
Fe2+、Fe3+Feature satellites, illustrate in composite material be not present Fe2O3, further prove composite material in loaded be
Fe3O4, illustrate HNTs/C/Fe3O4Trielement composite material is successfully prepared.
Using the scanning electron microscope (SEM) of model XL-30E to HNTs/C, HNTs/C/Fe3O4Composite material point
Morphology characterization has not been carried out, as shown in Figure 5,6.
As can be seen from Figure 5 carbon has been wrapped in galapectite surface.Comparison diagram 5,6 is it can be found that there is granular Fe3O4It is raw
Into and be supported on galapectite pipe or be supported on galapectite surface package carbon on, illustrate HNTs/C and HNTs/C/Fe3O4It is compound
Material preparation success.
Nitrogen adsorption desorption has been carried out to trielement composite material using the specific-surface area detection instrument of model 3H-2000PS2
Thermoisopleth measures, as shown in Figure 7.
As can be seen from Figure 7 prepared composite material has preferable nitrogen adsorption desorption performance, from HNTs/C/
Fe3O4Nitrogen adsorption desorption isothermal curve find out that, when relative pressure is relatively low, adsorption desorption capacity is increased very fast, illustrates material
Material has smaller pore structure, with reference to graph of pore diameter distribution as can be seen that the pore-size distribution of material is less than 1 nm, further proves material
Material has preferable microcellular structure.
Fig. 8 is As2O3AFS standard curves.It is accurate to measure 0.0,0.1,0.2,0.3,0.4,0.5,0.6,0.7 mL's
As2O3Standard solution (1 μ g/mL) is separately added into 2 mL of hydrochloric acid of 6 mol/L, the sulphur of 50 g/L in the volumetric flask of 10 mL
1 mL of urea-ascorbic acid, distilled water are settled to 10 mL, wherein containing As2O3Concentration is respectively 0,10,20,30,40,50,60,70
ng/mL.After standing 10 min, it is measured with atomic fluorescence spectrophotometer.The fluorescence intensity level of each standard serial solution is read, with
As therein2O3Concentration is abscissa, and corresponding fluorescence intensity level is ordinate, draws standard curve.Standard curve for I=
184.0969C+43.5175 wherein I is fluorescence intensity, C is arsenic concentration.Gained equation of linear regression R2It is worth for 0.99924, says
The bright standard curve linear relationship is good, can be used as standard working curve application.
Identical experiment carried out using composite material made from above-mentioned other embodiments respectively, as a result similar embodiment 1
Sample.
3rd, HNTs/C/Fe3O4Composite material is for the research of arsenic removal (III), arsenic (V) efficiency：
1、HNTs、HNTs/C、HNTs/C/Fe3O4Adsorption efficiency compares：
Fig. 9 is HNTs, HNTs/C, HNTs/C/Fe3O4The adsorption efficiency comparison diagram of three kinds of materials.Using model PF7 type atoms
Fluorescent spectrophotometer measuring fluorescence intensity, so as to calculate adsorption rate.
As can be seen from the figure compared with pure HNTs, the arsenic removal advantage of HNTs/C composite materials is not obvious, and HNTs/C/
Fe3O4Composite material to the removal efficiency of arsenic (III), arsenic (V) apparently higher than HNTs and HNTs/C, this is because Fe3O4Addition
Improve the arsenic removal performance of composite material, it was demonstrated that HNTs/C/Fe3O4There is composite material higher arsenic removal performance study to be worth.
2nd, the influence of As initial concentration solutions：
Figure 10,11 respectively low concentration and High Concentration of Arsenic solution are to HNTs/C/Fe3O4Nanocomposite arsenic removal (III), arsenic
(V) the influence figure of efficiency.Fluorescence intensity is measured using model PF7 types atomic fluorescence spectrophotometer, so as to calculate adsorption rate.
As can be seen from Figure 10 HNTs/C/Fe3O4The arsenic removal efficiency of composite material is first raised with the rise presentation of concentration
The trend balanced afterwards, adsorption capacity are raised with the rise of arsenic solution concentration, but with the rise of concentration, adsorption capacity one
It is straight to rise, illustrate to adsorb and be not up to saturation state, the arsenic removal efficiency of arsenic (III), arsenic (V) be distinguished less, removal efficiency is equal
It is higher；As can be seen from Figure 11 downward trend after the arsenic removal efficiency of composite material is first raised as the rise of concentration is presented,
The adsorption capacity of arsenic (V) is raised with the rise of arsenic solution concentration, and the adsorption capacity of arsenic (III) is with arsenic solution concentration
Rise gradually gently tends to balance.Removal effect tends to balance when due to concentration being 5 mg/L, illustrates under the concentration adsorbent profit
It is higher with rate.
3rd, the influence of adsorbent amount：
Figure 12 is adsorbent amount to HNTs/C/Fe3O4Composite material removes the influence figure of arsenic ion, using model PF7 types
Atomic fluorescence spectrophotometer measures fluorescence intensity, so as to calculate adsorption rate.
As seen from the figure, with the increase of adsorbent amount, removal efficiency first rises to tend to balance afterwards, in 0.1mg/L-
0.5 mg/L adsorption efficiencies rise apparent, hereafter vary less, this is because, with the increase of adsorbent amount, arsenic in solution
The effective active site that ion can contact increases, thus adsorption efficiency increases, and with the further increase of adsorbent amount, it is molten
Arsenic ion absorption is complete in liquid, thus adsorption efficiency tends to balance.In 0.5 mg/mL, removal effect tends to balance, and illustrates this
Adsorbent utilization rate is higher under adsorbent amount.
4th, the influence of pH value：
Figure 13 is pH value to HNTs/C/Fe3O4Composite material removes the influence figure of arsenic ion, glimmering using model PF7 type atoms
Light photometric determination fluorescence intensity, so as to calculate adsorption rate.
As can be seen from Figure, it is preferable to the removal efficiency of arsenic (V) with the increase material of pH, illustrate that pH removes arsenic (V)
Except efficiency influences less；In pH 5-8, material is higher to the removal efficiency of arsenic (III), this is because in acid condition, H+
Protonation the effective active site of adsorbent surface is reduced, cause adsorption efficiency low, and in alkaline conditions, be
By OH-Absorption competition effect occupy the contact site of adsorbent surface and cause.
5th, the influence of adsorption time：
Figure 14 is adsorption time to HNTs/C/Fe3O4The influence figure of composite material removal efficiency.
As can be observed from Figure, removal efficiency increase at any time and increase, rise in 60 min it is very fast after tend to
Balance, removal efficiency rises again in 480-720 min, after reach balance, this is because the aperture of material is smaller, with when
Between increase, arsenic ion has time enough to enter in material hole in solution, therefore removal efficiency improves again, when in solution
After arsenic ion absorption completely, removal efficiency tends to balance, and whole removal efficiency is higher.Influence of the time to absorption the result shows that
The sorbing material can reach preferable removal effect in a short period of time, be very beneficial for practical application.
6th, circular regeneration performance：
Figure 15 is HNTs/C/Fe3O4Sorbing material arsenic removal recycles efficiency chart.
As shown in figure 15, still there is higher removal effect to arsenic (III), arsenic (V) recycling after 5 times material, point
Do not reach the removal efficiency of 85 % and 98 %, illustrate that the material has preferable circular regeneration performance, before there is preferable application
Scape.
Above each experimental study HNTs/C/Fe3O4The optimal arsenic removal parameter and absorption property of composite material, the results showed that
It is same for arsenic solution arsenic (III), the arsenic (V) of 5 mg/L to initial concentration under pH 7,0.5 mg/mL of adsorbent amount, 60 min
When with higher removal efficiency, respectively reach 98%, 99%, and regenerability is good, non-secondary pollution, application easy to spread.
Claims (7)
1. the preparation method of a kind of galapectite, carbon and the compound arsenic removing agent of ferriferrous oxide nano, it is characterised in that including following step
Suddenly：
1）Galapectite is scattered in ethyl alcohol, obtains the alcohol suspending liquid of galapectite；
2）Phenolic resin is dissolved in ethyl alcohol, and adds in methenamine, obtains phenol resin solution；
3）The alcohol suspending liquid of galapectite is added dropwise on sponge, phenol resin solution is added dropwise after to be dried, it is dry；
4）By step 3）Products therefrom is placed in Muffle furnace and calcines, and obtains calcining solid product；
5）Calcining solid product is mixed with molysite aqueous solution；
6）To step 5）Aqueous slkali is added in gained mixture, and is reacted in atmosphere of inert gases, then produces reaction
Object obtains solid formation through Magneto separate；
7）Solid formation is washed with deionized water to neutrality, it is freeze-dried, it is compound to obtain galapectite, carbon and ferriferrous oxide nano
Arsenic removing agent.
2. preparation method according to claim 1, it is characterised in that：The mixing quality of the phenolic resin and methenamine
Than being 1~1: 20 for the solid-to-liquid ratio of 1~10: 1, the phenol resin solution.
3. preparation method according to claim 1, it is characterised in that：The calcining heat is 800~1000 DEG C, and the time is
15~30 min.
4. preparation method according to claim 1, it is characterised in that：The molysite for ferric sulfate, ferric nitrate, iron chloride,
In ferric oxalate, ferrous sulfate, frerrous chloride or ferric acetate at least any one.
5. the preparation method according to claim 1 or 4, it is characterised in that：The molysite and high-temperature calcination solid product
Mixing quality ratio is 1~10: 1.
6. preparation method according to claim 1, it is characterised in that：The concentration of the aqueous slkali is 0.5~5 mol/L.
7. the preparation method according to claim 1 or 6, it is characterised in that：The alkali is sodium hydroxide, potassium hydroxide, carbon
In sour hydrogen sodium or ammonium hydroxide at least any one.
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| CN111111615A (en) * | 2019-12-27 | 2020-05-08 | 扬州大学 | Preparation method of coralline-like charcoal/hydrated iron oxide composite arsenic removal agent |
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