CN102350297B - Adsorbent, preparation method and application thereof - Google Patents
Adsorbent, preparation method and application thereof Download PDFInfo
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- CN102350297B CN102350297B CN2011102700635A CN201110270063A CN102350297B CN 102350297 B CN102350297 B CN 102350297B CN 2011102700635 A CN2011102700635 A CN 2011102700635A CN 201110270063 A CN201110270063 A CN 201110270063A CN 102350297 B CN102350297 B CN 102350297B
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Abstract
The invention discloses an adsorbent, a preparation method and an application thereof. The adsorbent is a porous iron oxide phosphate micron ball, has a shape of a honeycomb porous micron ball and has a grain size of 18-25 microns. Compared with the prior art, the adsorbent has the advantages that a simple water heating method is adopted, monomer ferric trichloride is taken as an iron source, a reaction temperature is low and a reaction time is short, thereby being beneficial to industrial production in large scope. When the iron oxide phosphate micron ball prepared by using the preparation method provided by the invention is applied to the production of dye absorption and heavy metal ion absorption, compared with the prior art, the iron oxide phosphate micron ball can effectively absorb various dyes and heavy metal ions under a condition of normal temperature and normal pressure, due to a surface porous structure, a large specific surface area and a large aperture of the iron oxide phosphate micron ball. Besides, the iron oxide phosphate micron ball is excellent in reusability and high in industrial use value.
Description
Technical field
The present invention relates to micro Nano material, preparation method and application thereof, particularly ternary compound phosphoric acid oxygen iron multi-pore micron ball, preparation method and application thereof.
Background technology
Due to the fast development of industry, the water that heavy metal ion and organic pollution cause pollutes and human health and biological existence has been consisted of serious threat in recent years.In water treatment, absorption method commonly used is come deep purifying water quality.Traditional adsorbent comprises active carbon, activated coal, coke, cinder, polymeric adsorbent etc., but the problem such as that these adsorbents exist respectively is expensive, adsorption capacity is not high, applicable pH value scope is narrower, mechanical strength is low makes their range of application be restricted.Adsorbent how to seek novel function admirable is the large problem that present water treatment field needs to be resolved hurrily.In modern industry, organic dyestuff is widely used in dyeing of dyeing such as paper, plastics, textile, food, cosmetics etc.Also contain gas chromatography and noxious material in its industrial wastewater, the color of dyestuff can suppress the transmission of sunlight in water simultaneously, reduces the photosynthesis of water body green plants, thereby has destroyed the ecological balance in water, has caused serious environmental problem.The problem of environmental pollution that brings in order to solve industrial and agricultural production has bibliographical information, adopt titanium doped magnetic iron ore as adsorbent can remove methylene blue in water (learn leading edge, 2008,15,151-154), adsorb and reach adsorption equilibrium after 30 minutes, its adsorption rate is about 91%.Although adsorption efficiency is higher, the time that reaches adsorption equilibrium is longer.Also someone adopts shitosan as adsorbent (spectroscopy and spectrum analysis, 2005,25,698 – 700), can adsorb expeditiously organic dyestuff safranine T in 20 minutes, but affected by pH larger due to it, therefore should determine applicable elements according to concrete water quality characteristic in practice.In addition, in numerous environmental pollutions, heavy metal can not be by natural degradation due to self, and then easily enters human body by food chain, the serious harm mankind's health.Cu
2+, Cd
2+Be considered to heavy metal contaminants main in water resource, searching can be removed them effectively from water resource material seems particularly important.Metal oxide and active carbon often have good adsorption capacity, thereby can be used as the adsorbent of heavy metal ion in environmental improvement.α-Fe as graduate nanometer sheet assembling
2O
3(J. Phys. Chem. C., 2008,112,6253-6257) in 60 minutes, can remove in water about 50% pollutant.Recently, some unconventional ABSORBENTS ABSORPTION adsorption of metal ions have also shown good adsorption capacity.Bibliographical information utilizes the active carbon (Bioresource Technology., 2008,99,492 – 501) of olivine preparation of zinc chloride activation to Cd
2+The adsorption capacity of ion is 0.68mg/g, and the time that reaches the maximum saturation adsorbance is 90 minutes, and the Capacity Ratio of absorption is lower.We are the synthetic Ni of seminar
12P
5(CrystEngComm, 2010,12,1568-1575) to Cd
2+Adsorption capacity be 3.05 mg/g, the time of absorption is 30 minutes, than the adsorption capacity of traditional adsorbent, obvious enhancing is arranged.Aluminium hydroxide to heavy metal ion adsorbed (spectrographic laboratory, 2010,27, studies show that 498-412), when initial concentration reaches certain value, probably at 4 hours, Cd
2+Ion reaches adsorption equilibrium, and adsorption capacity is 4.80mg/g, although adsorption capacity is larger, the time that reaches adsorption equilibrium is long.Utilize in the research of sludge absorption heavy metal ion copper, zinc, cadmium (the Guangdong chemical industry, 2010,3,207-209), mud is to Cu
2+Ion selectively very high adsorbed 15 minutes, and the adsorption efficiency of copper ion has just reached 94.3%, and adsorption capacity is 22.47mg/g (Cu before absorption
2+Ion concentration is 50mg/l).In general, the concentration of initial heavy metal ion is low-down in actual applications.Therefore, for selecting suitable adsorbent, the ability that moves down the removing heavy metals ion at low concentration is a kind of better standard.Chinese patent CN 1544347 discloses a kind of method that use 335 type weak-base anion-exchange resins are processed copper in wastewater from phthalocyanine green production, and technique is simple, small investment, and instant effect, but pretreated process is more loaded down with trivial details, and recycling rate of waterused is not high.Chinese patent CN 101890337A discloses a kind of metal ion nanoadsorbent, and the adsorption efficiency of cadmium ion has been reached 99%, and the time of absorption is 30 minutes, but the capacity of absorption is little, thereby is difficult to realize large-scale use.The adsorbent of reporting in above-mentioned document and patent is absorbing dye or heavy metal ion solely.
Summary of the invention
First purpose of the present invention is to provide the new adsorbent of a kind of absorbing dye simultaneously and heavy metal ion.
Second purpose of the present invention is the preparation method of above-mentioned adsorbent
The 3rd purpose of the present invention is the application of above-mentioned adsorbent.
The technical scheme of first goal of the invention that the present invention solves is: a kind of new adsorbent, described adsorbent are cellular phosphoric acid oxygen iron micron ball, and pattern is the micron ball of honeycomb porous, and its particle diameter is the 18-25 micron.
The preparation method of described new adsorbent is: with soluble sources, soluble ferric iron salt and reducing agent are dissolved in distilled water, after stirring, intensification 100-180 ℃, reacted 2-20 hour, and be cooled to room temperature, with absolute ethyl alcohol and deionized water washing several, 50-60 С is dried to constant weight in vacuum drying chamber, gets final product.
The mol ratio 1:1-10:3-5 of soluble ferric iron salt, reducing agent, soluble sources.
Described soluble ferric iron salt is ferric trichloride, ferric sulfate, and ferric nitrate, its chemical formula is respectively FeCl
3.3H
2O, Fe
2(SO
4)
3,Fe (NO
3)
3.9H
2O。
Described reducing agent is urea CO (NH
2)
2
Described phosphorus source is Na
2HPO
4, K
2HPO
4, (NH
4)
2HPO
4
The prepared cellular phosphoric acid of the present invention oxygen iron micron ball to Dye Adsorption and heavy metal ion adsorbed aspect application.
In uniform temperature and water, under the reducing agent effect, the micron ball that redox reaction generates phosphoric acid oxygen iron occurs in the molysite of solubility and hydrophosphate.As structure directing agent, alkali-metal hydrophosphate provides the phosphorus source in chemical reaction with appropriate reducing agent.When reacting, reducing agent as the structure directing agent effect under, generate nucleus, further be copolymerized into micron ball, due to the effect of gas at spherical surface, structure directing agent auxiliary is so generate cavernous phosphoric acid oxygen iron micron ball.In addition, excessive or very few hydrophosphate can change the remaining ionic species of system significantly, the molysite of excessive solubility can not be combined with hydrophosphate fully, and the low reactant that can not make of temperature participates in reaction fully, all can be unfavorable for the formation of phosphoric acid oxygen iron multi-pore micron ball.
The present invention has compared with prior art used simple hydrothermal method, and source of iron is the simple substance ferric trichloride, and the temperature and time of reaction is all shorter, is more conducive to industry and produces on a large scale.The phosphoric acid oxygen iron micron ball that the present invention is made is in Dye Adsorption and heavy metal ion adsorbed production, compared with prior art, due to its porous surface structure, specific area is large, the aperture is large, just can well adsorb many kinds of dyestuffs and heavy metal ion under normal temperature and normal pressure, reusability is good, and industrial application is worth high.
This patent not only can adsorb also Adsorption of Heavy Metal Ions well of organic dyestuff by the synthetic cellular phosphoric acid oxygen iron micron ball of simple hydro-thermal method, wherein adsorbs methylene blue dye 3 minutes, and adsorption efficiency has just reached 94.81%; In 30 minutes, Cd
2+Ion concentration drops to 1.25mg/L, Cu by the front 10mg/L of absorption
2+Ion concentration drops to 0.6mg/L by the front 10mg/L of absorption.As calculated, this adsorbent is to Cd
2+Adsorption capacity be 21.9mg/g, to Cu
2+The adsorption capacity of ion is 23.5mg/g.And adsorb after 50min minute, the concentration of two kinds of ions is almost constant, means that the time that adsorbing reaches capacity namely reaches adsorption equilibrium is shorter.At this moment, Cd
2+And Cu
2+Adsorption efficiency be respectively 97.13% and 97.81%.Show that the synthetic cellular phosphoric acid oxygen iron micron ball of this patent has the ability of selective absorption heavy metal preferably; Circulate after 5 times, Cu
2+Remove that efficient still remains 74%, Cd
2+Be 92%.Present adsorbent is not reported in document and patent.As a kind of novel adsorbent, this material preparation method is simple, and is with low cost, and advantages of good adsorption effect can be recycled, and application prospect is preferably arranged in water pollution control.
Description of drawings
Fig. 1 is the X-ray powder diffraction pattern of embodiment 1 gained micron ball.
Fig. 2 is the energy spectrogram (EDS) of embodiment 1 gained micron ball.
Fig. 3 is SEM (SEM) photo of embodiment 1 gained micron ball.
Fig. 4 is SEM (SEM) photo of embodiment 2 gained micron balls.
Fig. 5 is SEM (SEM) photo of embodiment 3 gained micron balls.
Fig. 6 is SEM (SEM) photo of embodiment 4 gained micron balls.
Fig. 7 is the picture of embodiment 1 gained micron ball absorbing dye.
Fig. 8 is embodiment 1 gained micron ball Adsorption of Heavy Metal Ions Cu
2+The picture of ion.
Fig. 9 is embodiment 1 gained micron ball Adsorption of Heavy Metal Ions Cd
2+The picture of ion.
Figure 10 is that embodiment 1 gained micron ball is to Cu
2+Ion and Cd
2+The change in concentration that the different adsorption times of ion cause.
Figure 11 is that embodiment 1 gained micron ball is to Cu
2+Ion and Cd
2+The adsorption isotherm of ion.
Figure 12 is that embodiment 1 gained micron ball is to Cu
2+Ion and Cd
2+The relation between efficient and cycle-index of removing of ion.
The specific embodiment
Embodiment 1:
Urea CO (NH with 0.1 gram
2)
2, the dibastic sodium phosphate of 1mmol ferric trichloride and 4mmol is dissolved in 20 ml waters, and vigorous stirring is poured the gained mixed solution in the stainless steel autoclave of 25 milliliters of polytetrafluoroethylene (PTFE) as liner after mixing, and is heated to 160 ℃ of reactions 12 hours.After reaction finishes, this autoclave is cooled to room temperature, alternately wash the gained light yellow product for several times with absolute ethyl alcohol and deionized water, 60 С are dry in vacuum drying chamber, as shown in Figure 3, products therefrom has the porous calcium phosphate oxygen iron micron ball of absorbing dye and heavy metal ion, and its pattern is the micron ball of honeycomb porous, and its particle diameter is the 18-25 micron.
With product (Cu K alpha ray, λ=0.154060 nm, the sweep speed 0.02 of Japanese Shimadzu XRD-6000 type x-ray powder diffraction instrument to enforcement experiment 1
o/ s) carry out phase to identify, as shown in fig. 1.Contrast JCPDS standard card (74-1443), all diffraction maximums and Fe
4(PO
4)
2The O monoclinic system fits like a glove.Because diffraction maximum is very strong, illustrate that product has degree of crystallinity preferably.Fig. 2 elementary analysis demonstration makes and contains Fe, O, P, Na, Cu and C element in product, and wherein Elements C derives from the physical absorption to carbon in air, and element Na derives from the reactant dibastic sodium phosphate, and element Cu comes from the copper sheet that supports sample.By to the calculated by peak area of this power spectrum as can be known, the atom number of Fe and P and O is than very near 4:2:9, thereby illustrates that this material that we obtain is exactly phosphoric acid oxygen iron.
Embodiment 2:
Urea CO (NH with 0.1 gram
2)
2, the dibastic sodium phosphate of 1mmol ferric sulfate and 4mmol is dissolved in 20 ml waters, and vigorous stirring is poured the gained mixed solution in the stainless steel autoclave of 25 milliliters of polytetrafluoroethylene (PTFE) as liner after mixing, and is heated to 160 ℃ of reactions 12 hours.After reaction finishes, this autoclave is cooled to room temperature, alternately wash the gained light yellow product for several times with absolute ethyl alcohol and deionized water, 60 С are dry in vacuum drying chamber, as shown in Figure 4, products therefrom has the porous calcium phosphate oxygen iron micron ball of absorbing dye and heavy metal ion equally, and its pattern is the micron ball of the honeycomb porous of sheet composition.
Embodiment 3:
Urea CO (NH with 0.1 gram
2)
2, the dibastic sodium phosphate of 1mmol ferric nitrate and 4mmol is dissolved in 20 ml waters, and vigorous stirring is poured the gained mixed solution in the stainless steel autoclave of 25 milliliters of polytetrafluoroethylene (PTFE) as liner after mixing, and is heated to 160 ℃ of reactions 12 hours.After reaction finishes, this autoclave is cooled to room temperature, alternately wash the gained light yellow product for several times with absolute ethyl alcohol and deionized water, 60 С are dry in vacuum drying chamber, as shown in Figure 5, products therefrom has the porous calcium phosphate oxygen iron micron ball of absorbing dye and heavy metal ion equally, and its pattern is the micron ball of the honeycomb porous of sheet composition.
Embodiment 4:
Urea CO (NH with 0.82 gram
2)
2The dibastic sodium phosphate of 1mmol ferric trichloride and 6mmol (the mol ratio 1:13:6 of soluble ferric iron salt, reducing agent, soluble sources) is dissolved in 20 ml waters, vigorous stirring, the gained mixed solution is poured in the stainless steel autoclave of 25 milliliters of polytetrafluoroethylene (PTFE) as liner after mixing, be heated to 160 ℃ of reactions 12 hours.After reaction finishes, this autoclave is cooled to room temperature, alternately wash the gained light yellow product for several times with absolute ethyl alcohol and deionized water, 60 С are dry in vacuum drying chamber, as shown in Figure 6, products therefrom is no longer cavernous phosphoric acid oxygen iron micron ball, but a kind of aggregated particle with matsurface makes it no longer have the performance of absorbing dye and heavy metal ion.Thereby we draw, and the molar ratio of reactant is different over the pattern of the product that certain scope obtains, and performance is also just different.
Embodiment 5:
The product that the embodiment 1 of 0.015 gram is made joins in the beaker of 100ml, the safranine T that measures 50ml concentration and be 10mg/l joins in this beaker, ultrasonic 2min makes it dissolve complete, stir successively in the dark 1min, 2min, 3min, 5min, 10min, 20min, and collect respectively the sample of 1min, 2min, 3min, 5min, 10min, 20min with centrifuge tube, then survey its ultraviolet.Same method is changed to methylene blue to dyestuff safranine T.Shown in Figure 7,3 minutes adsorption efficiencies of absorption methylene blue dye have just reached 94.81%, and the time of absorption is short, and the efficient of absorption is high.Thereby verify out that products therefrom is the porous calcium phosphate oxygen iron micron ball with good absorbing dye.
Embodiment 6:
The product that the embodiment 1 of 0.02 gram is made joins in the beaker of 100ml, gets the Cu that concentration is 10mg/l
2+The solution 50ml of ion joins in this beaker, and ultrasonic 30min stirs 30min and gets its sample afterwards.This sample is placed in centrifuge tube centrifugal, gets supernatant.Last using plasma Atomic Emission Spectrometer AES has been measured heavy metal ion Cu
2+The variation of the emission spectrum before and after being adsorbed.As can be seen from Figure 8, embodiment 1 gained phosphoric acid oxygen iron micron ball Adsorption of Cu
2+After ion 30 minutes, drop to 0.6mg/l by concentration 10mg/l before absorption.To Cu
2+The adsorption capacity of ion is 23.5mg/g.
Embodiment 7:
The product that the embodiment 1 of 0.02 gram is made joins in the beaker of 100ml, gets the Cd that concentration is 10mg/l
2+The solution 50ml of ion joins in this beaker, and ultrasonic 30min stirs 30min and gets its sample afterwards.This sample is placed in centrifuge tube centrifugal, gets supernatant.The using plasma Atomic Emission Spectrometer AES has been measured heavy metal ion Cd
2+The variation of the emission spectrum before and after being adsorbed.As can be seen from Figure 9, embodiment 1 gained phosphoric acid oxygen iron micron ball absorption Cd
2+After ion 30 minutes, drop to 1.25mg/l by concentration 10mg/l before absorption.To Cd
2+The adsorption capacity of ion is 21.9mg/g.
Embodiment 8:
The product that the embodiment 1 of 0.02 gram is made joins in the beaker of 100ml, gets the Cu that concentration is 10mg/l
2+Ion, Cd
2+The mixed solution 50ml of ion joins in this beaker, and ultrasonic 30min gets 5 samples after stirring successively 10min, 20min, 30min, 50min, 100min.5 samples are placed in centrifuge tube centrifugal, get supernatant.The using plasma Atomic Emission Spectrometer AES has been measured heavy metal ion Cu
2+, Cd
2+The variation of the emission spectrum before and after being adsorbed.As shown in figure 10, adsorb after 50min minute, the concentration of two kinds of ions is almost constant, means that the time that adsorbing reaches capacity namely reaches adsorption equilibrium is shorter.At this moment, Cd
2+And Cu
2+Adsorption efficiency be respectively 97.13% and 97.81%.
Embodiment 9:
The product that the embodiment 1 of 0.02 gram is made joins in the beaker of 100ml, and getting concentration is the Cu of 10mg/l, 20 mg/l, 30 mg/l, 40 mg/l, 50 mg/l, 60 mg/l
2+Ion, Cd
2+The mixed solution 50ml of ion joins in this beaker, and ultrasonic 30min stirs successively 30min and gets 6 samples afterwards.6 samples are placed in centrifuge tube centrifugal, get supernatant.The using plasma Atomic Emission Spectrometer AES has been measured heavy metal ion Cu
2+, Cd
2+The variation of the emission spectrum before and after being adsorbed.Thereby at Cu
2+Ion, Cd
2+Under the different mass concentration of ion, calculate this adsorbent to their different adsorption capacities.Shown in Figure 11, along with the increase of initial concentration of heavy metal ion, the ability that removes of current adsorbent increases until maximum.
Embodiment 10:
The product that the embodiment 1 of 0.02 gram is made joins in the beaker of 100ml, gets the Cu that concentration is 10mg/l
2+Ion, Cd
2+The mixed solution 50ml of ion joins in this beaker, and ultrasonic 30min stirs successively 30min and gets its sample afterwards.2 samples are placed in centrifuge tube centrifugal, get supernatant.The using plasma Atomic Emission Spectrometer AES has been measured heavy metal ion Cu
2+, Cd
2+The variation of the emission spectrum before and after being adsorbed.Then the sample cleaning, drying of using is for the first time taken identical quality 0.02g, identical with top operating procedure, measure heavy metal ion Cu
2+, Cd
2+The variation of the emission spectrum before and after being adsorbed.Shown in Figure 12, after repeating 5 times, Cu
2+Remove that efficient still remains approximately 74%, Cd
2+Be approximately 92%.
By top series of experiments, the checking products therefrom is the porous calcium phosphate oxygen iron micron ball with good Adsorption of Heavy Metal Ions, and the time of this adsorbent Adsorption of Heavy Metal Ions is short, good reproducibility, adsorption efficiency is high, and cost is low, cheap and easy to get, have good prospects for commercial application.
Claims (2)
1. adsorbent, it is characterized in that: described adsorbent is cellular phosphoric acid oxygen iron micron ball, and pattern is the micron ball of honeycomb porous, and its particle diameter is the 18-25 micron;
The preparation method of described adsorbent is: with soluble sources, soluble ferric iron salt and reducing agent are dissolved in distilled water, after stirring, intensification 100-180 ℃, reacted 2-20 hour, and be cooled to room temperature, with absolute ethyl alcohol and deionized water washing several, 50-60 С is dried to constant weight in vacuum drying chamber, gets final product;
The mol ratio 1:1-10:3-5 of described soluble ferric iron salt, reducing agent, soluble sources;
Described soluble ferric iron salt is ferric trichloride, ferric sulfate, and ferric nitrate, its chemical formula is respectively FeCl
3.3H
2O, Fe
2(SO
4)
3,Fe (NO
3)
3.9H
2O;
Described reducing agent is urea CO (NH
2)
2;
Described phosphorus source is Na
2HPO
4, K
2HPO
4, (NH
4)
2HPO
4
Adsorbent claimed in claim 1 to Dye Adsorption and heavy metal ion adsorbed aspect application.
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| CN104418400B (en) * | 2013-08-20 | 2017-02-08 | 天津大学 | Iron-based nano-alloy and application thereof in adsorption of cesium |
| CN106316882B (en) * | 2016-07-27 | 2018-01-30 | 中国计量科学研究院 | A kind of preparation method of electron level acetonitrile |
| CN108658644A (en) * | 2018-07-04 | 2018-10-16 | 中国科学院南京土壤研究所 | Metal-organic framework material class fertilizer and preparation method thereof |
Citations (3)
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|---|---|---|---|---|
| CN1606472A (en) * | 2001-12-21 | 2005-04-13 | 室町化学株式会社 | Adsorbent for phosphoric acid |
| CN1610648A (en) * | 2001-11-07 | 2005-04-27 | 诺尔斯海德公司 | Method of synthesising crystalline microporous metalloaluminophosphate from solid substrates |
| CN1748857A (en) * | 2005-08-19 | 2006-03-22 | 天津理工大学 | Process for preparing phosphate radical adsorber |
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| WO2009150232A2 (en) * | 2008-06-13 | 2009-12-17 | Novartis Ag | Manufacture process for the preparation of an iron containing phosphate adsorbent |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1610648A (en) * | 2001-11-07 | 2005-04-27 | 诺尔斯海德公司 | Method of synthesising crystalline microporous metalloaluminophosphate from solid substrates |
| CN1606472A (en) * | 2001-12-21 | 2005-04-13 | 室町化学株式会社 | Adsorbent for phosphoric acid |
| CN1748857A (en) * | 2005-08-19 | 2006-03-22 | 天津理工大学 | Process for preparing phosphate radical adsorber |
Non-Patent Citations (2)
| Title |
|---|
| Reaction mechanisms of tridymite iron phosphate with lithium ions in the low-voltage range;Tae-Gon Kim et al.;《Electrochimica Acta》;20070823;第53卷;第1843–1849页 * |
| Tae-Gon Kim et al..Reaction mechanisms of tridymite iron phosphate with lithium ions in the low-voltage range.《Electrochimica Acta》.2007,第53卷第1843–1849页. |
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Effective date of registration: 20201119 Address after: 226600 Haian Industrial Park, Jiangsu, Nantong Patentee after: NANTONG ZHONGXING MAGNETIC INDUSTRIAL Co.,Ltd. Address before: 241000 Wuhu Road, Yijiang District, Anhui, Patentee before: ANHUI NORMAL University |