CN104492374B - A kind of preparation method of ceria/calcium aluminum layered di-hydroxyl composite metal oxidate/absorbent charcoal composite material - Google Patents
A kind of preparation method of ceria/calcium aluminum layered di-hydroxyl composite metal oxidate/absorbent charcoal composite material Download PDFInfo
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Abstract
The preparation method that the invention discloses a kind of ceria/calcium aluminum layered di-hydroxyl composite metal oxidate/absorbent charcoal composite material, it is at a certain temperature activated carbon is carried out evacuation decompression, then it is rapidly added reaction solution, utilizes atm difference that reaction solution can be made quickly to immerse inside activated carbon；Again through ultrasonic wave added co-precipitation, a step Fast back-projection algorithm CeO2/ CaAl-LDHs/AC composite.CeO of the present invention2Common contaminant chromium, lead, fluorine and peacock green in water are not only had excellent absorption property by/CaAl-LDHs/AC composite, are also convenient for operation, it is easy to separate, and heat stability is high.
Description
One, technical field
The preparation method that the present invention relates to a kind of ceria/calcium aluminum layered di-hydroxyl composite metal oxidate/absorbent charcoal composite material, it is with activated carbon for carrier, under vacuum-heating-reduced pressure, adopting ultrasonic wave added coprecipitation to prepare, this material may be respectively used in chromium, lead, fluorine and malachite green dye in adsorption treatment aqueous solution.
Two, background technology
Calcium aluminum layered di-hydroxyl composite metal oxidate (CaAl-LDHs) is a kind of good sewage-treating agent, can be used for Organic substance (PingZhang, etal.JournalofColloidandInterfaceScience, 2012 such as Adsorption methyl orange, 365,110-116)；Dichromate ion (CrO can be removed through ion exchange4 2-) (YanlinLi, etal.ChemicalEngineeringJournal, 2013,218,295-302), arsenate (AsO4 3-) (CN103058338A).Due to CaAl-LDHs and fluorion (F-) electrostatic attraction force intensity be weaker than chemical bond, fluorine removing rate is relatively low, and this type of LDHs is of a size of micron order powder, and actually used being difficult to separates, and cost of water treatment is higher, easily causes secondary pollution.
Granular active carbon is the most cheap sewage-treating agent; there is highly developed porosity and internal surface area; of a relatively high mechanical strength and easy recyclability (SayedZiaMohammadi; etal.JournalofIndustrialandEngineeringChemistry; 2014; 37,465-472).Ceria (CeO2) in aqueous, the hydroxyl of surface adsorption can and F-Carry out ion exchange, it is possible to Absorptive complex wave metal ion (TaoZhang, etal.AppliedClayScience, 2013,72,117-123).If with activated carbon for carrier, the calcium aluminum layered di-hydroxyl composite metal oxidate/absorbent charcoal composite material (CeO of synthesis ceria doping2/ CaAl-LDHs/AC), separation will be beneficial to, reduce cost of water treatment.
The preparation method of existing absorbent charcoal carrier LDHs composite mainly has: ureal antigen (AgnieszkaMalak-Polaczyk, etal.EnergyFuels, 2010,24,3346-3351), hydro-thermal method (JianJu, etal.ElectrochimicaActa, 2012,78,569-575).Generated time is generally more than 12 hours, and the LDHs particle diameter formed is relatively big, easily blocks activated carbon capillary, reduces the adsorption effect of material.Although ultrasonic wave added coprecipitation can form LDHs (YuZhong, etal.JournalofHazardousMaterials, the 2013,250-251,345-353 of little particle diameter, bigger serface；YanlinLi, etal.ChemicalEngineeringJournal, 2013,218,295-302), but during practical operation, owing to solution can not immerse activated carbon inner surface rapidly, it is necessary to longer dip time, otherwise LDHs is only formed at activated carbon outer surface, can not be formed at inner surface, easily block duct.Therefore, it is necessary to a kind of method developing fast and effeciently synthesizing activity high-area carbon/layered di-hydroxyl composite metal oxidate composite.
Three, summary of the invention
It is desirable to provide a kind of ceria/calcium aluminum layered di-hydroxyl composite metal oxidate/absorbent charcoal composite material (is abbreviated as CeO2/ CaAl-LDHs/AC composite) preparation method, this composite is with activated carbon for carrier, with the composite obtained after ceria doping and modification calcium aluminum layered di-hydroxyl composite metal oxidate load.
Activated carbon is carried out evacuation decompression by the present invention at a certain temperature, is then rapidly added reaction solution, utilizes atm difference that reaction solution can be made quickly to immerse inside activated carbon；Again through ultrasonic wave added co-precipitation, a step Fast back-projection algorithm CeO2/ CaAl-LDHs/AC composite.CeO of the present invention2/ CaAl-LDHs/AC composite has excellent absorption property, can be directly used for processing pollutant common in water, such as chromium, lead, fluorine and peacock green etc..
CeO of the present invention2The preparation method of/CaAl-LDHs/AC composite comprises the steps:
1) Activated Carbon Pretreatment: the 50.0g activated carbon concentrated nitric acid normal temperature dipping of mass concentration 65% is processed 7 hours, to eliminate surface impurity, washs and dry；Activated carbon after being processed by 5.0-20.0g concentrated nitric acid immerses in acid solution A, with distilled water wash vacuum drying after supersound process, obtains the activated carbon of pretreatment, to strengthen the adhesion strength of follow-up LDHs material, is designated as AC.
Described acid solution A is four oxaloacetic acid solution, ethylenediamine tetraacetic oxaloacetic acid solution or diamino-acetic acid solution, and the concentration of described acid solution A is 0.001-0.01mol/L.
The temperature of supersound process is room temperature, and the time is 0.5-3 hour.
2) preparation of composite: be immediately placed in mixed solution B after the activated carbon of pretreatment is carried out vacuum-heating-reduced pressure treatment, reaction solution is made quickly to immerse inside activated carbon, regulating pH value by pH adjusting agent is 5-10, carry out ultrasonic wave added coprecipitation reaction, with distilled water wash vacuum drying after ageing, obtain CeO2/ CaAl-LDHs/AC composite.
The vacuum of described vacuum-heating-reduced pressure treatment is 0.02-0.08MPa, and temperature is 60-150 DEG C, and the time is 0.5-3 hour.
Described mixed solution B is the mixed solution of the nitrate of calcium, aluminum and cerium or sulfate, and in mixed solution B, the mol ratio of calcium, aluminum and cerium is 7:1:1-1:3:5, and in mixed solution B, the concentration of calcium is 0.001-0.01mol/L.
The activated carbon of pretreatment and the mass ratio of mixed solution B are 1:1-30.
Described pH adjusting agent is the NaOH solution of 1.0mol/L.
Ultrasonic power during ultrasonic wave added coprecipitation reaction is 20-100W, and temperature is 30-100 DEG C, and the time is 0.5-3 hour.
The time of ageing process is 1-3 hour, and Aging Temperature is 90-150 DEG C.
[CeO of the present invention2The absorption property test of/CaAl-LDHs/AC composite]
(1) potassium dichromate (K is used2Cr2O7), lead acetate [(CH3COO)2Pb·3H2O], sodium fluoride (NaF) and peacock green (C23H25ClN2), preparing chromium, lead, fluorine and peacock green content respectively is the solution for standby of 1000mg/L.Solution all thus stock solution dilution gained needed for subsequent experimental.
(2) CeO prepared by the present invention2/ CaAl-LDHs/AC composite, as adsorbent, is added separately in the solution of the chromium of concentration known, lead, fluorine and peacock green, measures its adsorbance respectively after stirring 2 hours.By testing the change of concentration before and after absorption, it is judged that adsorption effect.
[the analysis method of chromium, lead, fluorine and peacock green]
Chromium (Cr2O7 2-) analyze: dinitrodiphenyl carbazide spectrphotometric method for measuring: solution to be measured for 0.5mL is added in 50mL volumetric flask, it is diluted with water to graticule, add the sulfuric acid solution of 1.0mL mass concentration 49% and the phosphoric acid solution of 1.0mL mass concentration 42.5%, shake up, add 2mL dinitrodiphenyl carbazide, shake up, be diluted with water to graticule.After colour developing 5-10min, at 540nm wavelength place, use 10mm cuvette, make reference with water, measure absorbance.
Plumbous (Pb2+) analyze: take 20.0mL solution to be measured, add 10.0mL hexamethylenetetramine-hydrochloric acid buffer solution (pH=5.4), add 2 xylenol orange, carry out titration with 0.001mol/LEDTA solution.
Fluorine (F-) analyze: take 10.0mL solution to be measured in the plastics volumetric flask of 50.0mL, (compound method of mixing buffer solution is: add 500mL water in 1000mL beaker to add 20.0mL mixing buffer solution, 57.0mL glacial acetic acid, 58.0gNaCl, 12.0g sodium citrate, being adjusted to pH value of solution with 1.0mol/LNaOH subsequently is 5.0, adds water and is settled to 1000mL).Being subsequently poured in plastic beaker, be placed under fluoride ion selective electrode, stirring measures, the potential value shown by grapher.
Peacock green: take 5.0mL solution to be measured in 50.0mL volumetric flask, be settled to scale.With ultraviolet-uisible spectrophotometer at 617nm place mensuration absorbance.
Compared with the prior art, advantages of the present invention has:
(1) present invention adopts vacuum-heating-decompression method, makes reaction solution quickly immerse inside activated carbon, then adopts ultrasonic wave added coprecipitation, a step Fast back-projection algorithm CeO2/ CaAl-LDHs/AC composite, technique is simple and quick, relative to existing method, energy-conserving and environment-protective.
(2) CeO prepared by the present invention2/ CaAl-LDHs/AC composite, has concentrated CeO2, CaAl-LDHs and activated carbon advantage, not only common contaminant chromium, lead, fluorine and peacock green in water are had excellent absorption property, are also convenient for operation, it is easy to separate.
(3) single CeO2High with CaAl-LDHs cost when actual sewage processes, the present invention adopts cheap activated carbon to be carrier, prepared CeO2/ CaAl-LDHs/AC composite adsorption effect is better, and cost performance is high, economical and effective.
(4) relative to activated carbon and acid treatment activated carbon (AC), CeO of the present invention2The heat stability of/CaAl-LDHs/AC composite significantly improves.
Four, accompanying drawing explanation
Fig. 1 is the field emission scanning electron microscope figure of associated materials.Wherein in figure, A is the activated carbon (AC) of pretreatment；In figure, B is without vacuum-heating-reduced pressure treatment, the CeO being directly immersed in mixed solution B by the activated carbon of pretreatment to generate for ultrasonic 1 hour2/ CaAl-LDHs/AC composite；In figure, C is the CeO that the inventive method prepares2/ CaAl-LDHs/AC composite；In figure, D is the enlarged drawing of C in figure.As seen from the figure: the surface smoother of the activated carbon (AC) of pretreatment, irregular loose structure (in figure A) is become；Directly within ultrasonic 1 hour, CeO is generated without vacuum-heating-reduced pressure treatment2During/CaAl-LDHs/AC (in figure B), although the visible intercalation material of activated carbon outer surface, but inner surface does not observe intercalation material (in figure B illustration)；And adopt CeO prepared by the inventive method2/ CaAl-LDHs/AC composite (in figure C), the intercalation material (in figure D in C and figure) that activated carbon surfaces externally and internally is all evenly distributed as seen, and duct do not block.
Fig. 2 is AC (a) and CeO of the present invention2The X-crystallogram of/CaAl-LDHs/AC composite (b).On curve a, the characteristic peak of AC is positioned at 22.4 °, the diffraction maximum of corresponding 002.On curve b, it is positioned at the diffraction maximum of 10.1 °, 29.2 °, 38.2 ° and the peak of 47.8 ° upper 003,009,012 and 018 of corresponding CaAl-LDHs respectively, show that this material has crystal diffraction peak and the layer structure (YanlinLi of di-hydroxyl composite metal oxidate, etal.ChemicalEngineeringJournal, 2013,218,295-302).24.5 the diffraction maximum in C002 face on ° still visible AC, 32.7 ° and 56.2 ° is CeO2Characteristic peak (TaoZhang, etal.AppliedClayScience, 2013,72,117-123).
Fig. 3 is CeO of the present invention2The X-photoelectron spectroscopy figure of/CaAl-LDHs/AC composite.Al as seen from Figure 32p(75.2eV)、Alloss(114.1eV)、Al2s(120.1eV)、C1s(284.8eV)、Ca2p(347.8eV)、N1s(400.0eV)、O1s(532.6eV) and Ce3dThe characteristic peak of (883.3,899.2,901.6 and 917.3eV), containing Ca, Al, Ce, N, O and C element in illustrative material, in conjunction with Fig. 1 and Fig. 2, it was shown that CeO2/ CaAl-LDHs/AC is formed.
Fig. 4 is AC (a) and CeO of the present invention2The infrared spectrogram of/CaAl-LDHs/AC composite (b).On curve a, 1643cm-1Locate as the asymmetrical stretching vibration peak of carboxyl (-COOH) on AC.On curve b, 3426cm-1For the stretching vibration peak of hydroxyl (-OH), 1636cm-1Place is the bending vibration peak of hydrone, 1396cm-1Place is nitrate anion (NO3 -) characteristic absorption peak, 890cm-1For the stretching vibration peak of cerium-oxygen (Ce-O), 710cm-1Stretching vibration peak (RezaPournajaf, etal.CeramicsInternational, 2014,40,8687-8692) for cerium-oxygen-cerium (Ce-O-Ce), it was shown that CeO2/ CaAl-LDHs/AC is formed.
Fig. 5 is activated carbon (a), AC (b) and CeO of the present invention2The thermogravimetric analysis figure of/CaAl-LDHs/AC composite (c).From curve a it can be seen that the quality of original activity charcoal loses 17.62% between 42-126 DEG C, for elimination residual moisture；8.45% is lost, for carbonization pyrolytic process between 135-285 DEG C；Between 632-897 DEG C, substantially, weight-loss ratio 49.79%, for calcining and decomposing process for weightlessness.On curve b, it is 7.91% that the quality of AC is lost between 43-160 DEG C, deviates from residual moisture for it；6.55% is lost, for the sour catabolic process of its absorption between 236-377 DEG C；15.65% is lost, for calcining and decomposing process between 635-897 DEG C.On curve c, CeO2The quality of/CaAl-LDHs/AC only loses 3.2% between 49-130 DEG C, mainly caused by the desorption of intermediary water and physical absorption water, now still keeps layer structure；Losing 12.8% between 130-420 DEG C, mainly caused by the elimination of laminate hydroxyl, now the layer structure of layered double hydroxide is destroyed gradually；9.09% is lost, mainly caused by the decomposition of nitrate anion between 420-583 DEG C；5.86% is lost, for calcining and decomposing process between 685-897 DEG C.Above-mentioned thermogravimetric analysis data shows: relative to activated carbon and acid treatment activated carbon (AC), CeO of the present invention2The heat stability of/CaAl-LDHs/AC composite significantly improves.
Five, detailed description of the invention
Embodiment 1:
CeO in the present embodiment2The preparation method of/CaAl-LDHs/AC composite is as follows:
1) Activated Carbon Pretreatment
The 50.0g activated carbon salpeter solution normal temperature dipping of mass concentration 65% is processed 7 hours, to eliminate surface impurity, washs and dry；Activated carbon after being processed by 10.0g salpeter solution immerses in the four oxaloacetic acid solution of 50.0mL0.001mol/L, under room temperature ultrasonic 1 hour, with distilled water wash vacuum drying after taking-up, obtains the activated carbon of pretreatment, is designated as AC.
2) preparation of composite
At 80 DEG C, 10.0gAC is carried out after vacuum-heating-decompression (vacuum 0.02MPa) processes 1 hour, add immediately in 80.0mL mixed solution B, regulating pH value by the NaOH solution of 1.0mol/L is 9.3, ultrasonic wave added co-precipitation 1 hour when ultrasonic power 60W, temperature 30 DEG C subsequently, last it is cooled to room temperature 105 DEG C of constant temperature ageings after 1 hour, with distilled water wash vacuum drying, obtains CeO2/ CaAl-LDHs/AC composite.
Described mixed solution B is the mixed solution of calcium nitrate, aluminum nitrate and cerous sulfate, and in mixed solution B, the concentration of calcium nitrate is 0.01mol/L, and the mol ratio of calcium nitrate, aluminum nitrate and cerous sulfate is 1:1:1.
CeO prepared by 0.05g the present embodiment2/ CaAl-LDHs/AC composite is added separately in the aqueous solution that 25.0mL concentration is the chromium of 100.0mg/L, lead, fluorine and peacock green, measures adsorbance after stirring 2 hours.
Embodiment 2:
CeO in the present embodiment2The preparation method of/CaAl-LDHs/AC composite is as follows:
1) Activated Carbon Pretreatment
The 50.0g activated carbon salpeter solution normal temperature dipping of mass concentration 65% is processed 7 hours, to eliminate surface impurity, washs and dry；Activated carbon after being processed by 5.0g salpeter solution immerses in the diamino-acetic acid solution of 50.0mL0.01mol/L, under room temperature ultrasonic 2 hours, with distilled water wash vacuum drying after taking-up, obtains the activated carbon of pretreatment, is designated as AC.
2) preparation of composite
At 100 DEG C, 5.0gAC is carried out after vacuum-heating-decompression (vacuum 0.08MPa) processes 2 hours, add immediately in 100.0mL mixed solution B, regulating pH value by the NaOH solution of 1.0mol/L is 7.5, ultrasonic wave added co-precipitation 1 hour when ultrasonic power 40W, temperature 40 DEG C subsequently, last it is cooled to room temperature 90 DEG C of constant temperature ageings after 2 hours, with distilled water wash vacuum drying, obtains CeO2/ CaAl-LDHs/AC composite.
Described mixed solution B is the mixed solution of calcium nitrate, aluminum nitrate and cerous sulfate, and in mixed solution B, the concentration of calcium nitrate is 0.001mol/L, and the mol ratio of calcium nitrate, aluminum nitrate and cerous sulfate is 1:3:5.
CeO prepared by 0.05g the present embodiment2/ CaAl-LDHs/AC composite is added separately in the aqueous solution that 25.0mL concentration is the chromium of 100.0mg/L, lead, fluorine and peacock green, measures adsorbance after stirring 2 hours.
Embodiment 3:
CeO in the present embodiment2The preparation method of/CaAl-LDHs/AC composite is as follows:
1) Activated Carbon Pretreatment
The 50.0g activated carbon salpeter solution normal temperature dipping of mass concentration 65% is processed 7 hours, to eliminate surface impurity, washs and dry；Activated carbon after being processed by 20.0g salpeter solution immerses in the ethylenediamine tetraacetic oxaloacetic acid solution of 100.0mL0.002mol/L, ultrasonic half an hour under room temperature, with distilled water wash vacuum drying after taking-up, obtains the activated carbon of pretreatment, is designated as AC.
2) preparation of composite
At 100 DEG C, 20.0gAC is carried out after vacuum-heating-decompression (vacuum 0.05MPa) processes 2 hours, add immediately in 100.0mL mixed solution B, regulating pH value by the NaOH solution of 1.0mol/L is 7.5, ultrasonic wave added co-precipitation 30 minutes when ultrasonic power 90W, temperature 50 C subsequently, last it is cooled to room temperature 120 DEG C of constant temperature ageings after 1.0 hours, with distilled water wash vacuum drying, obtains CeO2/ CaAl-LDHs/AC composite.
Described mixed solution B is the mixed solution of calcium sulfate, aluminum sulfate and cerous sulfate, and in mixed solution B, the concentration of calcium sulfate is 0.006mol/L, and the mol ratio of calcium sulfate, aluminum sulfate and cerous sulfate is 1:3:5.
CeO prepared by 0.05g the present embodiment2/ CaAl-LDHs/AC composite is added separately in the aqueous solution that 25.0mL concentration is the chromium of 100.0mg/L, lead, fluorine and peacock green, measures adsorbance after stirring 2 hours.
【CeO2The absorption property of/CaAl-LDHs/AC composite compares]
Material forms: calculated CeO by inductively coupled plasma luminescent spectrum2In/CaAl-LDHs/AC composite, the mol ratio of calcium aluminum cerium is: Ca:Al:Ce=5.44:1.99:1 to 4.87:2.33:1.
From table 1: CeO of the present invention2Concentration is the chromium of 100.0mg/L, lead, fluorine and peacock green by/CaAl-LDHs/AC composite, and within two hours, adsorption efficiency is up to 91.7%, 98.2%, 80.6% and 97.8%.
From table 2: CeO of the present invention2/ CaAl-LDHs/AC composite to the maximal absorptive capacity of chromium, lead, fluorine and peacock green up to 83.1mg/g, 131.6mg/g, 62.2mg/g and 420.2mg/g.
From table 3: CeO of the present invention2/ CaAl-LDHs/AC composite is good in aqueous solution, the maximal absorptive capacity of chromium, lead, fluorine and peacock green is compared with the adsorption effect of other material.
Table 1AC, CaAl-LDHs/AC and CeO2/ CaAl-LDHs/AC is to the adsorption efficiency (neutrality, room temperature 25 DEG C, adsorption time 2 hours) that concentration is 100.0mg/L difference pollutant
Table 2AC, CaAl-LDHs/AC and CeO2/ the CaAl-LDHs/AC maximal absorptive capacity (neutrality, room temperature 25 DEG C, adsorption time 2 hours) to different pollutant
Table 3 CeO of the present invention2/ CaAl-LDHs/AC and other LDHs, the maximal absorptive capacity (mg/g) of each pollutant is compared by absorbent charcoal material.
Claims (8)
1. the preparation method of ceria/calcium aluminum layered di-hydroxyl composite metal oxidate/absorbent charcoal composite material, it is characterised in that comprise the following steps:
1) Activated Carbon Pretreatment: the 50.0g activated carbon concentrated nitric acid normal temperature dipping of mass concentration 65% is processed 7 hours, washs and dry；Activated carbon after being processed by 5.0-20.0g concentrated nitric acid immerses in acid solution A, with distilled water wash vacuum drying after supersound process, obtains the activated carbon of pretreatment；Described acid solution A is ethylenediamine tetraacetic oxaloacetic acid solution or diamino-acetic acid solution, and the concentration of described acid solution A is 0.001-0.01mol/L；
2) preparation of composite: be immediately placed in mixed solution B after the activated carbon of pretreatment is carried out vacuum-heating-reduced pressure treatment, reaction solution is made quickly to immerse inside activated carbon, regulating pH value by pH adjusting agent is 5-10, carry out ultrasonic wave added coprecipitation reaction, with distilled water wash vacuum drying after ageing, obtain CeO2/ CaAl-LDHs/AC composite；Described mixed solution B is the mixed solution of the nitrate of calcium, aluminum and cerium or sulfate, and in mixed solution B, the mol ratio of calcium, aluminum and cerium is 7:1:1-1:3:5.
2. method according to claim 1, it is characterised in that:
In step 1), the temperature of supersound process is room temperature, and the time is 0.5-3 hour.
3. method according to claim 1, it is characterised in that:
The vacuum of described vacuum-heating-reduced pressure treatment is 0.02-0.08MPa, and temperature is 60-150 DEG C, and the time is 0.5-3 hour.
4. method according to claim 1, it is characterised in that:
In described mixed solution B, the concentration of calcium is 0.001-0.01mol/L.
5. method according to claim 1, it is characterised in that:
The activated carbon of pretreatment and the mass ratio of mixed solution B are 1:1-30.
6. method according to claim 1, it is characterised in that:
Described pH adjusting agent is the NaOH solution of 1.0mol/L.
7. method according to claim 1, it is characterised in that:
Ultrasonic power during ultrasonic wave added coprecipitation reaction is 20-100W, and temperature is 30-100 DEG C, and the time is 0.5-3 hour.
8. method according to claim 1, it is characterised in that:
The time of ageing process is 1-3 hour, and Aging Temperature is 90-150 DEG C.
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| KR101823083B1 (en) * | 2016-09-07 | 2018-01-30 | 주식회사 케이씨텍 | Surface-modified colloidal ceria abrasive particle, preparing method of the same and polishing slurry composition comprising the same |
| CN112138630B (en) * | 2019-06-28 | 2022-11-15 | 江汉大学 | Fluorinated graphene/cerium dioxide-magnesium aluminum-layered double hydroxide and preparation method and application thereof |
| CN111821948B (en) * | 2020-07-16 | 2022-06-03 | 常熟理工学院 | Preparation method of defluorination adsorbent based on flour |
| CN113318709A (en) * | 2021-06-04 | 2021-08-31 | 董鹏 | Oil stain adsorbent and preparation method thereof |
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