CN108031433A - A kind of preparation method of mesoporous calcium silicates load nano zero-valence iron composite material - Google Patents
A kind of preparation method of mesoporous calcium silicates load nano zero-valence iron composite material Download PDFInfo
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- CN108031433A CN108031433A CN201711342503.7A CN201711342503A CN108031433A CN 108031433 A CN108031433 A CN 108031433A CN 201711342503 A CN201711342503 A CN 201711342503A CN 108031433 A CN108031433 A CN 108031433A
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- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/70—Treatment of water, waste water, or sewage by reduction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The present invention relates to a kind of preparation method of mesoporous calcium silicates load nano zero-valence iron composite material.It is of the invention first using soluble calcium salt and silicate as raw material, cetyl trimethylammonium bromide or the mixture of itself and tetramethylammonium hydroxide are template, the oxygen being trapped in mesoporous calcium silicates hole is removed using the flower-shaped mesoporous calcium silicates of ultrasonic wave added Template synthesis, then evacuated and nitrogen displacement；Then in the presence of the mesoporous calcium silicates of deoxidation, using sodium borohydride reduction molysite fabricated in situ nano zero valence iron and it is supported in the opening of the channel and duct of mesoporous calcium silicates, the mesoporous calcium silicates load nano zero-valence iron composite material of synthesis Zero-valent Iron high degree of dispersion.The present invention not only increases the dispersiveness and stability of nano zero valence iron, overcome the reunion of nano zero valence iron, absorption, decomposition and removal effect of the material to pollutant are also improved at the same time, and resulting materials are organic compound contaminated to organic pollution and heavy metal and heavy metal to be respectively provided with preferable removal ability.
Description
Technical field
The present invention relates to heavy metal containing wastewater treatment field, more particularly, to a kind of mesoporous silicon for heavy metal containing wastewater treatment
The preparation method of sour calcium load nano zero-valence iron composite material.
Background technology
With the increase developed rapidly with population of industrial and agricultural production, to the value volume and range of product of the pollutant of environmental emission
Increase therewith, caused the water pollution being on the rise.Typical pollutant such as heavy metal ion, dyestuff, pigment, phenolic material
Matter, antibiotic etc., these materials rarely have single form presence in the environment, but are interacted by multiple pollutant, mutual shadow
Ring, forming component is more complicated, more intractable combined pollution.And existing processing method is directed to Single Pollution more, to by a variety of
The processing method for the combined pollution that pollutant is formed is very few, and the processing method of especially synchronous removal multiple pollutant is still few
See.Common practice is that different pollutants are handled by different step using distinct methods, finally can be only achieved processing requirement.
Obviously, these traditional processing method techniques are more complicated, hardly possible control, and processing cost is higher.Heavy metal pollution is one global
Environmental problem.Due to the high toxicity of heavy metal, non-biodegradable, the chronicity and concealment of pollution, environment and people are given birth to
Property safety is ordered to threaten seriously, in particular with the fast development of modern industry, heavy metal is more to be existed in the form of combined pollution,
Intractability bigger.Therefore, carry out novel heavy metal wastewater treatment material, material is handled especially for heavy-metal composite pollution thing
The research and development of material, are of great significance the improvement for promoting heavy metal pollution.
So far, various heavy wastewater treatment method has been have developed both at home and abroad, such as chemical precipitation method (hydroxide, vulcanization
Thing, chelate precipitation), ferrite process, absorption method, ion-exchange, membrane filtration it is (ultrafiltration, enhancing ultrafiltration, nanofiltration, reverse osmosis, electric
Dialysis), floatation and electrochemical method (electric flocculation, electric flotation, electro-deposition) etc..But these methods all have some disadvantages,
Still lack pervasive effective administering method at present.Compared with other processing methods, since absorption method is to utilize porosity or high ratio
Suction-operated of the surface area solid material to heavy metal ions in wastewater and the method for removing heavy metal, are adapted to various differences
Heavy metal wastewater thereby, particularly low concentration wastewater and waste water advanced treating, and its is easy to operate, advantage of lower cost, because
This, is a kind of economic, effectively and most process for treating heavy-metal waste water of application value.
It is the performance of adsorbent using Heavymetal Wastewater Treatment by Adsorption key.Nano material compares table since particle diameter is small
Area is big, and surface energy is high, and surface also has the hydroxyl that can be largely bonded with cation, and inside diffusional resistance phenomenon is not present,
Therefore, there is stronger adsorption capacity to heavy metal ion, be a kind of sorbing material for having huge applications prospect, in recent years by
Step is as the hot spot studied.At present, the nano material applied to heavy metal containing wastewater treatment can be divided into the absorption of inorganic and organic nano
Material, based on inorganic nano material, such as nano-TiO2, nanometer delafossite (CuFeO2), nano magnetic iron oxide and its modified production
Thing and nano zero valence iron etc..Although nano adsorption material has preferable adsorption effect, there are problems with：(1) due to than
Surface area is big, and surface energy is high, is easy to reunite and form offspring, reduces using effect；(2) it is more when using to be scattered in powder
In processing solution, since particle is tiny, difficulty is separated after adsorbing heavy metal.In nano adsorption material, nano zero valence iron (nZVI)
Not only there is higher specific surface area and stronger adsorption capacity, but also due to its electrode potential E0(Fe2+/ Fe)=- 0.44V,
With stronger reducing power, there is higher reactivity and catalytic activity to many kinds of substance：(1) can be with bromate, nitric acid
A variety of inorganic matter reaction generation bromides such as salt, NH4 +And N2；(2) can be by Cu2+、Ag+Replaced etc. torpescence heavy metal, will
CrO4 2-、UO2 2+Etc. the stronger heavy metal ion of oxidisability or compound reduction fix, be successfully processed Cd, Pb, Ag, Ni,
The heavy metal pollution such as As, Zn, Cu, Cr (VI), Mo (VI) and U (VI)；(3) hydrogenation can occur with the azo bond in dye molecule to break
Split or made by light electrolysis dye decolored；(4) organic pollution deoxidization, degradation such as metronidazole etc. is made.Therefore, nZVI extensively should
In reparation for water body and heavy metal in soil and organic pollution.Although nZVI is to various heavy, inorganic matter and organic
The treatment effect of pollutant is good, advantage is obvious, but in actual application, nZVI in itself there are it is obvious the defects of：(1)
The nano-colloid property of nZVI particles, high surface energy and ferromagnetism inherently, stabilizing it property is poor and oxidizable, easy group
It is poly-, reactivity and transfer ability in media as well are reduced, shortens service life；(2) with H in reaction process+Disappear
Consumption, iron (hydrogen) oxide of generation and the heavy metal contaminants of co-precipitation etc. are covered in the surface of Fe, hinder Fe and pollutant
Between electronics transfer so that the progress of retarded reaction；(3) nZVI and it is dissolved in the excessive Fe of water3+Ion pair environment also has
Certain toxicity.Therefore, appropriate method and suitable material are selected, prepares that performance is stable, reactivity is high and to environment
Harmless loaded nano Zero-valent Iron is its using effect of raising and promotes and applies the key issue that must be solved.Clearly for
NZVI with high reaction activity can hinder it using in the material such as surface cladding or modification organic polymer to improve stability
Electronics transfer between pollutant, is made nanofiber or nanotube difficulty is very big, more feasible method is to load nZVI
To suitable porous material.
The content of the invention
For the problem that above-mentioned heavy metal containing wastewater treatment there are the problem of, the advantages of nano zero valence iron and exist, the present invention
A kind of preparation method of mesoporous calcium silicates load nano zero-valence iron composite material is provided, its main feature is that：(1) ultrasonic wave added mould is used
Plate method prepares the flower-shaped mesoporous calcium silicates being made of microplate；(2) using flower-shaped mesoporous calcium silicates as carrier, fabricated in situ nano zero-valence
Iron, makes the Zero-valent Iron of generation be dispersed in opening of the channel or the duct of calcium silicates, improves the stability of Zero-valent Iron；(3) mesoporous silicon
Sour calcium since with large specific surface area, there is stronger affinity and adsorption capacity to heavy metal and some other pollutant,
Pollutant can be effectively adsorbed, while the Zero-valent Iron on the calcium silicates loaded is to some pollutants of absorption, especially reproducibility
Material and organic matter have stronger decomposition, reducing power, the pollutant of absorption can be made to decompose, reduce and degrade, into one
Step improves the removal effect to pollutant.
Mesoporous calcium silicates load nano zero-valence iron composite material prepared by the method for the present invention not only increases nano zero valence iron
Dispersiveness and stability, and due to being supported on mesoporous calcium silicates, enhance the absorption property to polluter, therefore,
Absorption to pollution, degradation capability are enhanced, enhances the removal effect to pollutant.And preparation process is simple, bar is reacted
Part is gentle, easily controllable, and production efficiency is high, new pollution is not produced, easy to popularize.
To achieve the above object, the preparation method of mesoporous calcium silicates load nano zero-valence iron composite material, including following step
Suddenly：
(1) distilled water and template are added to reactor for 1: 0.04~0.06 by the mass ratio of distilled water and template
In, dissolving is sufficiently stirred under ultrasound condition at 45~60 DEG C；Again by the mass ratio of calcium salt and distilled water for 0.1~0.15: 1 to
Calcium salt is added in reactor, 1~1.5h of stirring and dissolving under ultrasonic wave auxiliary；Then by the ratio between amount of calcium salt and silicate material
Weigh silicate for 1: 1.0~1.1, silicate plus distilled water be configured to the solution of 0.8~1mol/L, under agitation in 1~
It is slowly added into 2h in above-mentioned reactor, is then stirred for 2~3h；Then still aging 15~24h, with anhydrous second after suction filtration
Alcohol 20~30min of soaking and stirring, then filter, so repeatedly 5~6 times, then it is washed with distilled water again 3~5 times, is drying to obtain Jie
Hole calcium silicates；
(2) mesoporous calcium silicates obtained by step (1) is added in reactor, be placed in vacuum drying chamber and vacuumize 8~
15min, logical nitrogen to normal pressure, is then shut off nitrogen, then vacuumizes, so repeatedly 2~5 times, finally leads to nitrogen to normal pressure, opens
Vacuum drying chamber, rapid sealing reactor are spare；
(3) using the mixed solution of ethanol and water as solvent, Fe is prepared3+Concentration is the iron salt solutions of 0.075~0.1mol/L,
Then 20~30min of logical nitrogen flooding oxygen, it is spare；
(4) it is 0.015~0.02 by step (2) intermediary hole calcium silicates and the mass volume ratio of step (3) iron salt solutions:
1g/ml measures the iron salt solutions in step (3), is added in the reactor of step (2), then 0.5~1h of ultrasonic disperse；Continue
Nitrogen is passed through, under agitation by sodium borohydride and Fe3+The ratio between the amount of material be slowly added dropwise 0.3~0.4mol/L's for 2~3: 1
Sodium borohydride aqueous solution, solution are gradually converted into black, after being added dropwise, are stirred for 5~10min；Then 5~10min is stood,
Product is filtered, first rinses 3~5 times again with alcohol flushing 2~3 times with water, it is dry it is black in the solid matter with white, i.e.,
Product.
Further, dry to be dried in vacuo in step (1), temperature is 50~60 DEG C, when the time is 15~24 small.
Further, the preferred three-necked bottle of reactor of step (1) and step (2), more preferably with reflux condensing tube, constant pressure
The three-necked bottle of dropping funel and mechanical stirring device.
Further, in step (1), the template is that the ratio between amount of cetyl trimethylammonium bromide or material is
1.1~1.0: 1 cetyl trimethylammonium bromide and the mixture of tetramethylammonium hydroxide.
Further, in step (1), the calcium salt is soluble calcium nitrate or calcium chloride；The silicon
Hydrochlorate is soluble sodium metasilicate.
Further, in step (2), the nitrogen is high pure nitrogen.
Further, in step (3), the molysite is ferric sulfate or iron chloride, is that analysis is pure.
Further, in step (3), in the mixed solution of ethanol and water, the volume ratio of ethanol and water is 3: 7.
Further, in step (4), the sodium borohydride aqueous solution is to be dissolved in logical nitrogen with the pure sodium borohydride of analysis
Drive in the distilled water of 30~40min of oxygen and be formulated.
Further, in step (4), the rate of addition of sodium borohydride aqueous solution is 10~15 drops/min.
Further, in step (4), the slurry is the distilled water for boiling 4~8min, and is passed through after the cooling period
30~40min of nitrogen；The ethanol of washing is absolute ethyl alcohol, and 20~30min of logical nitrogen flooding oxygen.
Further, dry to be dried in vacuo in step (4), temperature is 35~45 DEG C.
The present invention relates to a kind of preparation method of mesoporous calcium silicates load nano zero-valence iron composite material.First with solubility
Calcium salt and silicate are raw material, cetyl trimethylammonium bromide or cetyl trimethylammonium bromide and tetramethylammonium hydroxide
Mixture be template, flower-shaped mesoporous calcium silicates form by microplate accumulation using ultrasonic wave added Template synthesis, then by taking out very
Empty and nitrogen displacement removes the oxygen being trapped in mesoporous calcium silicates hole；Then the iron salt solutions through logical nitrogen deoxidation are added to and filled
In the reactor of the mesoporous calcium silicates of deoxidation, sodium borohydride, which is added dropwise, reduces molysite, is supported on fabricated in situ nano zero valence iron
In the opening of the channel and duct of mesoporous calcium silicates, the mesoporous calcium silicates load nano zero valence iron composite wood of synthesis Zero-valent Iron high degree of dispersion
Material, improves the dispersiveness and stability of nano zero valence iron, while improves absorption, decomposition and removal of the material to pollutant and make
With.
Compared with prior art, the present invention has following beneficial technique effect：
(1) present invention has synthesized more regular, more uniform flower-shaped Jie of pore distribution using ultrasonic wave auxiliary template method first
Hole calcium silicates, favourable places are provided for the load of nano zero valence iron；By vacuumizing repeatedly and nitrogen displacement, effectively remove
The oxygen being trapped in hole, interference is eliminated for the in-situ reducing synthesis of latter step nano zero valence iron.
(2) in the presence of mesoporous calcium silicates, in-situ reducing synthesis nano zero valence iron, is conducive to utilize mesoporous silicic acid the present invention
The effect of the net electric field of calcium microplate makes Zero-valent Iron be formed, grown at opening of the channel and loads, so that Zero-valent Iron is more evenly distributed.
(3) the mesoporous calcium silicates load nano zero-valence iron composite material that the present invention synthesizes has higher specific surface area, institute
The advantage for playing two kinds of components of calcium silicates and Zero-valent Iron can be cooperateed with by obtaining material, particularly heavy so as to improve to pollutant
The adsorption capacity of metal；The removal effect to the pollutant of oxidisability is improved at the same time, thus is significantly improved to pollutant, it is special
It is not the removal effect of heavy metal-organic matter combined pollution.
(4) present invention efficiently solves the agglomeration traits of nano zero valence iron, improve nano zero valence iron stability and
Dispersiveness；The product of acquisition have concurrently reduction to the absorption property of pollutant particularly heavy metal and to oxidative pollutant, point
Removal effect is solved, improves the removal effect to pollutant；Meanwhile also improve the adaptation for preparing sorbing material to pollutant
Property, open up extensively application range.
(5) product of the present invention has universality to contents of many kinds of heavy metal ion and organic matter, particularly suitable for by heavy metal and having
The processing of the complicated pollution such as combined pollution that machine thing is formed, can simplify adsorption treatment process, reduce cost for wastewater treatment, have
Wide application value.
Brief description of the drawings
Fig. 1 is the preparation process FB(flow block) that the mesoporous calcium silicates of product of the present invention loads nano zero-valence iron composite material；
Fig. 2 is the X-ray diffraction that mesoporous calcium silicates prepared by the embodiment of the present invention 1 loads nano zero-valence iron composite material
Figure；
Fig. 3 is the scanning electron microscope (SEM) photograph that mesoporous calcium silicates prepared by the embodiment of the present invention 1 loads nano zero-valence iron composite material；
Fig. 4 is the transmission electron microscope picture that mesoporous calcium silicates prepared by the embodiment of the present invention 1 loads nano zero-valence iron composite material.
Embodiment
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings.
The preparation process FB(flow block) of the present invention is as shown in Figure 1.Embodiment 1~7 loads nano zero-valence for mesoporous calcium silicates
The preparation embodiment of iron composite material；Embodiment 8~10 loads nano zero-valence iron composite material pair for the mesoporous calcium silicates prepared
The removal capacity of heavy metal and organic pollution.
Embodiment 1
(1) distilled water 248g and 14.88g cetyl trimethylammonium bromide is taken to add 500mL bands reflux condensing tube, constant pressure
In dropping funel and churned mechanically three-necked bottle, it is placed in supersonic wave cleaning machine and is fully dissolved at 50 DEG C, add 24.80g
Four water-calcium nitrate, the stirring and dissolving 1.25h under ultrasonic wave auxiliary；Then nine water sodium metasilicate of 29.85g is weighed, adds distilled water to prepare
Into the solution of 0.8mol/L, it is slowly added into 2h with constant pressure funnel in three-necked bottle, 3h is stirred for after dripping off；In room temperature
Under still aging 24h, then filter, then 30min is stirred with soaked in absolute ethyl alcohol, then filter, so repeatedly 6 times, then use again
Distill water washing 5 times；Dry 24h is placed in 50 DEG C of vacuum drying chambers, obtains mesoporous calcium silicates 11.95g.
(2) mesoporous calcium silicates prepared by the step of weighing 2.3232g (1) is added to 500mL bands reflux condensing tube, constant pressure is dripped
In liquid funnel and churned mechanically three-necked bottle, it is placed in vacuum drying chamber and vacuumizes 10min, leads to nitrogen to normal pressure, be then shut off
Nitrogen, then vacuumize, so repeatedly 3 times, finally lead to nitrogen to normal pressure, open vacuum drying chamber, it is spare to be stoppered plug rapidly；
(3) 1.7418g ferric sulfate is weighed, Fe is configured to for 3: 7 ethanol water dissolving with ethanol and water volume ratio3+It is dense
Spend the Fe for 0.075mol/L3+Solution 116.2mL, then logical nitrogen flooding oxygen 20min, spare；
(4) Fe prepared by step (3)3+Solution be added in step (2) through logical nitrogen deoxidation equipped with mesoporous calcium silicates
In three-necked bottle, ultrasonic disperse 1h on ultrasonic wave is subsequently placed in；Nitrogen is continually fed into, is matched somebody with somebody under agitation with 0.9887g sodium borohydrides
Into 0.3mol/L sodium borohydride aqueous solution 87.1mL, rate of addition is 12 drops/min, and solution is gradually converted into black, be added dropwise
After, 10min is stirred for, then stands 5min, product is filtered, first 5 times is rinsed with water and uses alcohol flushing again 3 times, finally
It is dry in 40 DEG C of vacuum drying chamber, obtain it is black in the solid matter with white, i.e. product 2.7193g, Fe contents are
17.11%.
X-ray diffraction, scanning electron microscope and transmission electron microscope analysis are carried out to product prepared by embodiment 1, as a result as Fig. 2~
Shown in Fig. 4.Wherein, mesoporous calcium silicates is denoted as MCS, and mesoporous calcium silicates load nano zero-valence iron composite material is denoted as nZVI/MCS.
From Fig. 2, it is apparent that the diffraction maximum of mesoporous calcium silicates load nano zero-valence iron composite material and mesoporous silicic acid
Calcium is substantially similar, but 2 θ be 44-45 ° there is Zero-valent Iron characteristic diffraction peak (QI LIANG WANG, SHANE SNYDER,
JUNGWOO KIM, AND HEECHUL CHOI.Aqueous Ethanol modified Nanoscale Zerovalent
Iron in Bromate Reduction:Synthesis, Characterization, and
Reactivity.Environ.Sci.Technol.2009,43,3292-3299), show to have succeeded in mesoporous calcium silicates negative
Carry nano zero valence iron.As seen from Figure 3, zero-valent iron particle is distributed in surface, opening of the channel or the duct of mesoporous calcium silicates.From
Fig. 4 is it will be clear that zero-valent iron particle ratio is relatively uniformly dispersed throughout among calcium silicates sheet thin slice.These analysis result tables
Bright, nano zero valence iron is preferably supported on mesoporous calcium silicates.
Embodiment 2
(1) distilled water 248g and 12.4g cetyl trimethylammonium bromide is taken to add 500mL bands reflux condensing tube, constant pressure
In dropping funel and churned mechanically three-necked bottle, it is placed in supersonic wave cleaning machine and is fully dissolved at 60 DEG C, add 29.76g
Four water-calcium nitrate, the stirring and dissolving 1.5h under ultrasonic wave auxiliary；Then nine water sodium metasilicate of 37.60g is weighed, adds distilled water to be configured to
The solution of 0.9mol/L, is slowly added into three-necked bottle in 1.5h with constant pressure funnel, and 2.5h is stirred for after dripping off；In room
Still aging 18h, then filters under temperature, then stirs 25min with soaked in absolute ethyl alcohol, then filters, so repeatedly 5 times, Ran Houzai
It is washed with distilled water 4 times；Dry 18h is placed in 60 DEG C of vacuum drying chambers, obtains mesoporous calcium silicates 14.07g.
(2) mesoporous calcium silicates prepared by the step of weighing 2.3232g (1) is added to 500mL bands reflux condensing tube, constant pressure is dripped
In liquid funnel and churned mechanically three-necked bottle, it is placed in vacuum drying chamber and vacuumizes 10min, leads to nitrogen to normal pressure, be then shut off
Nitrogen, then vacuumize, so repeatedly 3 times, finally lead to nitrogen to normal pressure, open vacuum drying chamber, it is spare to be stoppered plug rapidly；
(3) 2.3224g ferric sulfate is weighed, Fe is configured to for 3: 7 ethanol water dissolving with ethanol and water volume ratio3+It is dense
Spend the Fe for 0.1mol/L3+Solution 116.2mL, then logical nitrogen flooding oxygen 25min, spare；
(4) Fe prepared by step (3)3+Solution be added in step (2) through logical nitrogen deoxidation equipped with mesoporous calcium silicates
In three-necked bottle, ultrasonic disperse 0.75h on ultrasonic wave is subsequently placed in；Nitrogen is continually fed into, under agitation with 1.3183g sodium borohydrides
The sodium borohydride aqueous solution 99.6mL for the 0.35mol/L being made into, rate of addition are 15 drops/min, and solution is gradually converted into black,
After being added dropwise, 8min is stirred for, then stands 5min, product is filtered, first rinsed 3 times with water and use alcohol flushing again 3 times, most
It is dry in 40 DEG C of vacuum drying chamber afterwards, obtain it is black in the solid matter with white, i.e. product 2.8413g, Fe contents are
21.24%.
Embodiment 3
(1) 248g distilled water and 9.92g cetyl trimethylammonium bromides is taken to add 500mL bands reflux condensing tube, constant pressure
In dropping funel and churned mechanically three-necked bottle, it is placed in supersonic wave cleaning machine and is fully dissolved at 45 DEG C, add 37.20g
Four water-calcium nitrate, the stirring and dissolving 1.5h under ultrasonic wave auxiliary；Then nine water sodium metasilicate of 49.23g is weighed, adds distilled water to be configured to
The solution of 1mol/L, is slowly added into three-necked bottle in 2h with constant pressure funnel, and 3h is stirred for after dripping off；It is quiet at room temperature
Ageing 20h is put, is then filtered, then 20min is stirred with soaked in absolute ethyl alcohol, then is filtered, so repeatedly 5 times, then again with distillation
Water washing 5 times；Dry 24h is placed in 55 DEG C of vacuum drying chambers, obtains mesoporous calcium silicates 17.83g.
(2) mesoporous calcium silicates prepared by the step of weighing 2.3232g (1) is added to 500mL bands reflux condensing tube, constant pressure is dripped
In liquid funnel and churned mechanically three-necked bottle, it is placed in vacuum drying chamber and vacuumizes 10min, leads to nitrogen to normal pressure, be then shut off
Nitrogen, then vacuumize, so repeatedly 3 times, finally lead to nitrogen to normal pressure, open vacuum drying chamber, it is spare to be stoppered plug rapidly；
(3) 2.7869g ferric sulfate is weighed, Fe is configured to for 3: 7 ethanol water dissolving with ethanol and water volume ratio3+It is dense
Spend the Fe for 0.08mol/L3+Solution 174.2mL, then logical nitrogen flooding oxygen 30min, spare；
(4) Fe prepared by step (3)3+Solution be added in step (2) through logical nitrogen deoxidation equipped with mesoporous calcium silicates
In three-necked bottle, ultrasonic disperse 0.5h on ultrasonic wave is subsequently placed in；Nitrogen is continually fed into, under agitation with 1.0546g sodium borohydrides
The sodium borohydride aqueous solution 92.9mL for the 0.3mol/L being made into, rate of addition are 10 drops/min, and solution is gradually converted into black, drop
After adding, 5min is stirred for, then stands 5min, product is filtered, first rinsed 4 times with water and use alcohol flushing again 3 times, finally
It is dry in 35 DEG C of vacuum drying chamber, obtain it is black in the solid matter with white, i.e. product 2.97593g, Fe contents are
23.35%.
Embodiment 4
(1) 248g distilled water and 14.88g cetyl trimethylammonium bromides and tetramethylammonium hydroxide composite mould plate agent are taken
(the amount ratio of the two material is 1.1: 1) adds 500mL bands reflux condensing tube, constant pressure funnel and churned mechanically three-necked bottle
In, it is placed in supersonic wave cleaning machine and is fully dissolved at 60 DEG C, add 24.80g four water-calcium nitrates, is stirred under ultrasonic wave auxiliary
Mix dissolving 1h；Then nine water sodium metasilicate of 29.84g is weighed, adds distilled water to be configured to the solution of 0.8mol/L, is dripped in 1h with constant pressure
Liquid funnel is slowly added into three-necked bottle, and 2h is stirred for after dripping off；Still aging 15h at room temperature, then filters, then with anhydrous
Ethanol soaking and stirring 30min, then filter, so repeatedly 5 times, then it is washed with distilled water again 3 times；It is placed in 60 DEG C of vacuum drying chambers
Middle dry 15h, obtains mesoporous calcium silicates 11.77g.
(2) mesoporous calcium silicates prepared by the step of weighing 2.3232g (1) is added to 500mL bands reflux condensing tube, constant pressure is dripped
In liquid funnel and churned mechanically three-necked bottle, it is placed in vacuum drying chamber and vacuumizes 10min, leads to nitrogen to normal pressure, be then shut off
Nitrogen, then vacuumize, so repeatedly 3 times, finally lead to nitrogen to normal pressure, open vacuum drying chamber, it is spare to be stoppered plug rapidly；
(3) 3.0965g ferric sulfate is weighed, Fe is configured to for 3: 7 ethanol water dissolving with ethanol and water volume ratio3+It is dense
Spend the Fe for 0.1mol/L3+Solution 154.9mL, then logical nitrogen flooding oxygen 25min, spare；
(4) Fe prepared by step (3)3+Solution be added in step (2) through logical nitrogen deoxidation equipped with mesoporous calcium silicates
In three-necked bottle, ultrasonic disperse 1h on ultrasonic wave is subsequently placed in；Nitrogen is continually fed into, is matched somebody with somebody under agitation with 1.7577g sodium borohydrides
Into 0.35mol/L sodium borohydride aqueous solution 132.7mL, rate of addition is 12 drops/min, and solution is gradually converted into black, drop
After adding, 8min is stirred for, then stands 5min, product is filtered, first rinsed 5 times with water and use alcohol flushing again 2 times, finally
It is dry in 40 DEG C of vacuum drying chamber, obtain it is black in the solid matter with white, i.e. product 3.0112g, Fe contents are
26.87%.
Embodiment 5
(1) 248g distilled water and 14.88g cetyl trimethylammonium bromides and tetramethylammonium hydroxide composite mould plate agent are taken
(the amount ratio of the two material is 1.0: 1) adds 500mL bands reflux condensing tube, constant pressure funnel and churned mechanically three-necked bottle
In, it is placed in supersonic wave cleaning machine and is fully dissolved at 60 DEG C, add 24.80g anhydrous calcium chlorides, is stirred under ultrasonic wave auxiliary
Mix dissolving 1.5h；Then 27.28g anhydrous sodium metasilicates are weighed, adds distilled water to be configured to the solution of 1.0mol/L, constant pressure is used in 2h
Dropping funel is slowly added into three-necked bottle, and 3h is stirred for after dripping off；Still aging 24h at room temperature, then filters, then with nothing
Water-ethanol soaking and stirring 20min, then filter, so repeatedly 6 times, then it is washed with distilled water again 4 times；It is placed in 55 DEG C of vacuum drying
Dry 24h, obtains mesoporous calcium silicates 25.46g in case.
(2) mesoporous calcium silicates prepared by the step of weighing 2.3232g (1) is added to 500mL bands reflux condensing tube, constant pressure is dripped
In liquid funnel and churned mechanically three-necked bottle, it is placed in vacuum drying chamber and vacuumizes 10min, leads to nitrogen to normal pressure, be then shut off
Nitrogen, then vacuumize, so repeatedly 3 times, finally lead to nitrogen to normal pressure, open vacuum drying chamber, it is spare to be stoppered plug rapidly；
(3) 2.5811g ferric sulfate is weighed, Fe is configured to for 3: 7 ethanol water dissolving with ethanol and water volume ratio3+It is dense
Spend the Fe for 0.1mol/L3+Solution 129.1mL, then logical nitrogen flooding oxygen 30min, spare；
(4) Fe prepared by step (3)3+Solution be added in step (2) through logical nitrogen deoxidation equipped with mesoporous calcium silicates
In three-necked bottle, ultrasonic disperse 1h on ultrasonic wave is subsequently placed in；Nitrogen is continually fed into, is matched somebody with somebody under agitation with 1.4651g sodium borohydrides
Into 0.3mol/L sodium borohydride aqueous solution 129.1mL, rate of addition is 10 drops/min, and solution is gradually converted into black, drop
After adding, 10min is stirred for, then stands 5min, product is filtered, first rinsed 4 times with water and use alcohol flushing again 3 times, most
It is dry in 45 DEG C of vacuum drying chamber afterwards, obtain it is black in the solid matter with white, i.e. product 2.9735g, Fe contents are
22.35%.
Embodiment 6
(1) 248g distilled water and 13.64g cetyl trimethylammonium bromides is taken to add 500mL bands reflux condensing tube, constant pressure
In dropping funel and churned mechanically three-necked bottle, it is placed in supersonic wave cleaning machine and is fully dissolved at 60 DEG C, add 37.20g
Calcium chloride hexahydrate, the stirring and dissolving 1.5h under ultrasonic wave auxiliary；Then 22.80g anhydrous sodium metasilicates are weighed, add distilled water to be configured to
The solution of 1.0mol/L, is slowly added into three-necked bottle in 2h with constant pressure funnel, and 3h is stirred for after dripping off；At room temperature
Still aging 24h, then filters, then stirs 25min with soaked in absolute ethyl alcohol, then filters, so repeatedly 6 times, then again with steaming
Distilled water is washed 5 times；Dry 24h is placed in 60 DEG C of vacuum drying chambers, obtains mesoporous calcium silicates 19.14g.
(2) mesoporous calcium silicates prepared by the step of weighing 2.3232g (1) is added to 500mL bands reflux condensing tube, constant pressure is dripped
In liquid funnel and churned mechanically three-necked bottle, it is placed in vacuum drying chamber and vacuumizes 10min, leads to nitrogen to normal pressure, be then shut off
Nitrogen, then vacuumize, so repeatedly 3 times, finally lead to nitrogen to normal pressure, open vacuum drying chamber, it is spare to be stoppered plug rapidly；
(3) 2.512g ferric trichlorides are weighed, Fe is configured to for 3: 7 ethanol water dissolving with ethanol and water volume ratio3+
Concentration is the Fe of 0.1mol/L3+Solution 154.9mL, then logical nitrogen flooding oxygen 30min, spare；
(4) Fe prepared by step (3)3+Solution be added in step (2) through logical nitrogen deoxidation equipped with mesoporous calcium silicates
In three-necked bottle, ultrasonic disperse 1h on ultrasonic wave is subsequently placed in；Nitrogen is continually fed into, is matched somebody with somebody under agitation with 1.4648g sodium borohydrides
Into 0.35mol/L sodium borohydride aqueous solution 110.6mL, rate of addition is 10 drops/min, and solution is gradually converted into black, drop
After adding, 5min is stirred for, then stands 5min, product is filtered, first rinsed 4 times with water and use alcohol flushing again 3 times, finally
It is dry in 40 DEG C of vacuum drying chamber, obtain it is black in the solid matter with white, i.e. product 3.0721g, Fe contents are
26.13%.
Embodiment 7
(1) 248g distilled water and 12.40g cetyl trimethylammonium bromides is taken to add 500mL bands reflux condensing tube, constant pressure
In dropping funel and churned mechanically three-necked bottle, it is placed in supersonic wave cleaning machine and is fully dissolved at 55 DEG C, add 29.76g
Calcium chloride hexahydrate, the stirring and dissolving 1.25h under ultrasonic wave auxiliary；Then 16.58g anhydrous sodium metasilicates are weighed, add distilled water to prepare
Into the solution of 0.9mol/L, it is slowly added into 2h with constant pressure funnel in three-necked bottle, 2h is stirred for after dripping off；In room temperature
Under still aging 24h, then filter, then 30min is stirred with soaked in absolute ethyl alcohol, then filter, so repeatedly 5 times, then use again
Distill water washing 5 times；Dry 20h is placed in 60 DEG C of vacuum drying chambers, obtains mesoporous calcium silicates 15.33g.
(2) mesoporous calcium silicates prepared by the step of weighing 2.3232g (1) is added to 500mL bands reflux condensing tube, constant pressure is dripped
In liquid funnel and churned mechanically three-necked bottle, it is placed in vacuum drying chamber and vacuumizes 10min, leads to nitrogen to normal pressure, be then shut off
Nitrogen, then vacuumize, so repeatedly 3 times, finally lead to nitrogen to normal pressure, open vacuum drying chamber, it is spare to be stoppered plug rapidly；
(3) 4.1863g ferric chloride (FeCl36H2O)s are weighed, dissolve preparation with ethanol and water volume ratio for 3: 7 ethanol water
Into Fe3+Concentration is the Fe of 0.09mol/L3+Solution 172.1mL, then logical nitrogen flooding oxygen 30min, spare；
(4) Fe prepared by step (3)3+Solution be added in step (2) through logical nitrogen deoxidation equipped with mesoporous calcium silicates
In three-necked bottle, ultrasonic disperse 1h on ultrasonic wave is subsequently placed in；Nitrogen is continually fed into, is matched somebody with somebody under agitation with 1.7577g sodium borohydrides
Into 0.4mol/L sodium borohydride aqueous solution 116.2mL, rate of addition is 12 drops/min, and solution is gradually converted into black, drop
After adding, 5min is stirred for, then stands 5min, product is filtered, first rinsed 5 times with water and use alcohol flushing again 3 times, finally
It is dry in 40 DEG C of vacuum drying chamber, obtain it is black in the solid matter with white, i.e. product 3.1111g, Fe contents are
26.62%.
Embodiment 8
The mesoporous calcium silicates prepared with embodiment 1 is loaded nano zero valence iron (nZVI/MCS), mesoporous calcium silicates (MCS) and received
Rice Zero-valent Iron (nZVI) is test specimen, their removal effects to methyl orange and hexachloro-benzene is detected respectively, as a result such as the institute of table 1
Show.
1 sintetics of table compares the removal effect of methyl orange and hexachloro-benzene
As it can be seen from table 1 nZVI has preferable removal effect to methyl orange and hexachloro-benzene, nZVI tools are primarily due to
There is very strong reproducibility, can effectively deoxidization, degradation methyl orange and hexachloro-benzene.Mesoporous calcium silicates MCS relies primarily on suction-operated removal
Methyl orange and hexachloro-benzene, and the surface memory of MCS is stronger, the methyl orange weak to polarity and hexachloro-benzene affinity are poor.And it is being situated between
Hole calcium silicates has loaded 17.11% Zero-valent Iron, significantly improves its removal rate to methyl orange and hexachloro-benzene, substantially with approaching
The effect of nano zero valence iron, and the wherein amount of iron is fewer than nZVI very much, only 25.66mg/L.
Embodiment 9
The mesoporous calcium silicates prepared with embodiment 3 is loaded nano zero valence iron (nZVI/MCS), mesoporous calcium silicates (MCS) and received
Rice Zero-valent Iron (nZVI) is test specimen, detects them respectively to heavy metal ion Cr6+、Mn2+、Cu2+、Ni2+、Pb2+And Cd2+'s
Removal effect, concentration of heavy metal ion are 75mg/L, and the results are shown in Table 2.
2 sintetics of table compares the removal effect of heavy metal ion
| Sample | pH | Dosage (mg/L) | Cr6+ | Mn2+ | Cu2+ | Ni2+ | Pb2+ | Cd2+ |
| nZVI | 4.32 | 260 | 87.17 | 75.41 | 99.81 | 79.78 | 97.82 | 99.01 |
| MCS | 5.17 | 300 | 57.34 | 79.82 | 98.38 | 91.43 | 99.75 | 99.13 |
| nZVI/MCS | 5.23 | 300 | 97.83 | 93.11 | 100 | 96.75 | 99.99 | 100 |
From table 2 it can be seen that nano zero valence iron (nZVI) is to Cu2+、Pb2+And Cd2+Etc. there is preferable removal effect, to Cr6 +、Mn2+And Ni2+Removal effect it is poor；MCS is to Cu2+、Ni2+、Pb2+And Cd2+Deng there is higher removal rate；When in calcium silicates
During the nano zero valence iron of upper load 23.35%, to Cr6+、Mn2+、Cu2+、Ni2+、Pb2+And Cd2+There is good removal effect.This
It is because nZVI relies primarily on the high-specific surface area of Zero-valent Iron and strong reducing power, to Cu2+、Pb2+And Cd2+Except Adsorption
Outside, also reduction removes；MCS relies primarily on these ions the effects such as physical absorption, surface coordination and ion exchange absorption
Remove removing heavy metals；And nZVI/MCS has then gathered the advantages of both nZVI and MCS, therefore, have to these heavy metals good
Adsorption effect.
Embodiment 10
The mesoporous calcium silicates prepared with embodiment 3 is loaded nano zero valence iron (nZVI/MCS), mesoporous calcium silicates (MCS) and received
Rice Zero-valent Iron (nZVI) is test specimen, detects them respectively to Cu2+- methyl orange, Cu2+The removal effect of-hexachloro-benzene combined pollution
Fruit, wherein Cu2+It is 80mg/L with methyl orange, the concentration of hexachloro-benzene, the results are shown in Table 3.
3 sintetics of table compares the removal effect of heavy metal-organic matter combined pollutant
Table 3 the result shows that, mesoporous calcium silicates loads nano zero valence iron nZVI/MCS to Cu2+- methyl orange, Cu2+- hexachloro-benzene
Heavy metal and organic matter have good removal effect in combined pollution, hence it is evident that better than MCS, are slightly better than nZVI.This is because, will
NZVI is supported on MCS, reduces the reunion of nZVI, improves activity, while the also absorption of MCS, surface coordination and ion
Exchange interaction so that nZVI/MCS significantly improves the removal ability of heavy metal-organic matter combined pollution.
The foregoing is merely the preferred embodiments of the present invention, and according to the above-mentioned design, those skilled in the art are also
Can to the process conditions of preparation, various modification can be adapted and conversion, these similar conversion and modification belong to the reality of the present invention
Matter.
Claims (10)
1. a kind of preparation method of mesoporous calcium silicates load nano zero-valence iron composite material, it is characterised in that comprise the following steps：
(1) distilled water and template are added in reactor for 1: 0.04~0.06 by the mass ratio of distilled water and template,
Dissolving is sufficiently stirred under ultrasound condition at 45~60 DEG C；Again by the mass ratio of calcium salt and distilled water for 0.1~0.15: 1 to anti-
Answer and calcium salt is added in device, 1~1.5h of stirring and dissolving under ultrasonic wave auxiliary；Then it is by the ratio between amount of calcium salt and silicate material
1: 1.0~1.1 weigh silicate, silicate plus distilled water are configured to the solution of 0.8~1mol/L, under agitation in 1~2h
Inside it is slowly added into above-mentioned reactor, is then stirred for 2~3h；Then still aging 15~24h, uses absolute ethyl alcohol after suction filtration
20~30min of soaking and stirring, then filter, so repeatedly 5~6 times, then it is washed with distilled water again 3~5 times；It is drying to obtain mesoporous
Calcium silicates；
(2) mesoporous calcium silicates obtained by step (1) is added in reactor, is placed in vacuum drying chamber and vacuumizes 8~15min,
Logical nitrogen is then shut off nitrogen to normal pressure, then vacuumizes, so repeatedly 2~5 times, finally leads to nitrogen to normal pressure, opens vacuum and do
Dry case, sealing reactor are spare；
(3) using the mixed solution of ethanol and water as solvent, Fe is prepared3+Concentration is the iron salt solutions of 0.075~0.1mol/L, then
Logical 20~30min of nitrogen flooding oxygen, it is spare；
(4) it is 0.015~0.02: 1g/ml by the mass volume ratio of step (2) intermediary hole calcium silicates and step (3) iron salt solutions
The iron salt solutions in step (3) are measured, are added in the reactor of step (2), then 0.5~1h of ultrasonic disperse；It is continually fed into
Nitrogen, under agitation by sodium borohydride and Fe3+The ratio between the amount of material be 2~3: the 1 boron hydrogen that 0.3~0.4mol/L is slowly added dropwise
Change sodium water solution, solution is gradually converted into black, after being added dropwise, is stirred for 5~10min；Then 5~10min is stood, will be produced
Thing filters, and first rinses 3~5 times again with alcohol flushing 2~3 times with water, it is dry it is black in the solid matter with white, that is, produce
Thing.
2. the preparation method of mesoporous calcium silicates load nano zero-valence iron composite material according to claim 1, its feature exist
In in step (1), the template is ten that the ratio between amount of cetyl trimethylammonium bromide or material is 1.1~1.0: 1
The mixture of six alkyl trimethyl ammonium bromides and tetramethylammonium hydroxide.
3. the preparation method of mesoporous calcium silicates load nano zero-valence iron composite material according to claim 1, its feature exist
In in step (1), the calcium salt is soluble calcium nitrate or calcium chloride；The silicate is soluble
Sodium metasilicate.
4. the preparation method of mesoporous calcium silicates load nano zero-valence iron composite material according to claim 1, its feature exist
In the reactor in step (1) and step (2) is three-necked bottle.
5. the preparation method of mesoporous calcium silicates load nano zero-valence iron composite material according to claim 1, its feature exist
In dry to be dried in vacuo in step (1), temperature is 50~60 DEG C, when the time is 15~24 small.
6. the preparation method of mesoporous calcium silicates load nano zero-valence iron composite material according to claim 1, its feature exist
In in step (3), the molysite is ferric sulfate or iron chloride.
7. the preparation method of mesoporous calcium silicates load nano zero-valence iron composite material according to claim 1, its feature exist
In in step (3), in the mixed solution of ethanol and water, the volume ratio of ethanol and water is 3: 7.
8. the preparation method of mesoporous calcium silicates load nano zero-valence iron composite material according to claim 1, its feature exist
In in step (4), the sodium borohydride aqueous solution is the distillation that sodium borohydride is dissolved in 30~40min of logical nitrogen flooding oxygen
It is formulated in water；The rate of addition of sodium borohydride aqueous solution is 10~15 drops/min.
9. the preparation method of mesoporous calcium silicates load nano zero-valence iron composite material according to claim 1, its feature exist
In in step (4), the slurry is the distilled water for boiling 4~8min, and is passed through 30~40min of nitrogen after the cooling period；
The ethanol of washing is absolute ethyl alcohol, and 20~30min of logical nitrogen flooding oxygen.
10. the preparation method of mesoporous calcium silicates load nano zero-valence iron composite material according to claim 1, its feature exist
In dry to be dried in vacuo in step (4), temperature is 35~45 DEG C.
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Application publication date: 20180515 |