CN103127938A - Preparation method of silicon-aluminum iron carbonyl composite catalysts with utilization of iron-bearing waste - Google Patents
Preparation method of silicon-aluminum iron carbonyl composite catalysts with utilization of iron-bearing waste Download PDFInfo
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- CN103127938A CN103127938A CN2013100474056A CN201310047405A CN103127938A CN 103127938 A CN103127938 A CN 103127938A CN 2013100474056 A CN2013100474056 A CN 2013100474056A CN 201310047405 A CN201310047405 A CN 201310047405A CN 103127938 A CN103127938 A CN 103127938A
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Abstract
The invention discloses a preparation method of silicon-aluminum iron carbonyl composite catalysts with utilization of iron-bearing waste. The preparation method of the silicon-aluminum iron carbonyl composite catalysts with utilization of the iron-bearing waste includes the following steps: (1) placing grinding wheel gray iron filings in a beaker, adding dilute nitric acid solutions to the beaker, placing the beaker in a constant-temperature vibrator to vibrate the beaker at constant temperature, and (2) adjusting the pH value of the reaction system to 12, continuing vibrating the beaker at the constant temperature for 30 minutes, then aging the sample, obtaining solid bodies through centrifugal separation, washing the solid bodies to be neutral, drying the solid bodies, grinding the solid bodies, and obtaining the silicon-aluminum iron carbonyl composite catalysts. The silicon-aluminum iron carbonyl composite catalysts produced through the preparation method of the silicon-aluminum iron carbonyl composite catalysts with utilization of the iron-bearing waste can effectively absorb, and catalytically degrade dyes, and have the advantages of being wide in pH application rang, and recoverable in use.
Description
[technical field]
The present invention is specifically related to a kind of method of utilizing iron-contained waste material to prepare sial iron carbonyl composite catalyst.
[background technology]
Usually can produce a large amount of iron-contained waste materials in some industrial production, the resource that takes up room, contaminated environment affect human health.Iron-holder as the mine tailing that produces in ironmaking processes, dedusting ash, slag, tar slag, blast furnace slag etc. is all larger, and wherein the iron-holder of blast furnace dedusting ash is up to 45%, and the iron-holder in steel-smelting sewage sludge is generally 50%.The generation of iron-contained waste material is also usually arranged in the dedusting ash in iron ore production, deduster in addition, if can the recycling iron-contained waste material not only can protection of the environment, also reduced the waste of resource.
FeOOH is one of modal earth's surface nonmetallic mineral, extensively is present in the natural environments such as soil and water deposit.FeOOH exists with multiple isomerism bodily form formula, difference according to its structural property, can be divided into goethite (alpha-feooh), akaganeite (β-FeOOH), lepidocrocite (γ-FeOOH), and six side's lepidocrocites (δ-FeOOH) etc., its stability descends successively.Alpha-feooh is the oxyhydroxide of modal iron, and can both form in various environment.It is the primary product of low-alloy steel corrosion.In recent years, the preparation of unidirectional alpha-feooh nano particle receives much concern, this structure has anisotropic form and many good physicochemical properties, have larger specific area and special crystallographic plane, these special character might strengthen its catalytic activity, expand it in the application of surround lighting catalytic field.
And preparation alpha-feooh most important raw material is exactly source of iron, and in existing research mainly with pure chemistry reagent Fe (NO
3)
3, Fe (Cl)
3, Fe (Cl)
2, FeSO
4Deng as Fe
2+Or Fe
3+Source of iron prepare FeOOH, utilize iron-contained waste material to prepare the research of FeOOH and few.(main component is as Fe take pyrite cinder in its master's research paper for Chen Liqin
2O
3) be raw material, extract ferrous sulfate, the preparation nano α-FeOOH is as α-Fe
2O
3Precursor.(main component is SiO to the use such as Li steam power plant dedusting ash
2, Al
2O
3, Fe
2O
3Deng), the iron in the dedusting ash is as source of iron, and other materials have prepared the amorphous FeOOH of load as stent support FeOOH, and experimental result shows that it has larger specific area, and As is had suction-operated preferably; Be applied to simultaneously light and help in the Fenton system, process the methyl orange of 50mg/L, just can reach 100% and decolour in 80min.Although these researchs have obtained certain achievement, for traditional F enton Fenton (FeOOH/H
2O
2) technology still exists restriction: 1) applicable pH range is little, generally effective oxidative degradation pollutant under slant acidity (pH=2-3) condition; 2) H
2O
2Utilization rate is low; 3) course of reaction easily produces iron mud or the catalyst recovery utilization rate is low.Difference due to contained element kind and content in different iron-contained waste materials, the iron carbonyl catalyst that causes preparing has different absorption and photocatalysis characteristic, therefore studies the extensive concern that different iron-contained waste materials prepare the domestic and international researcher of research attraction of iron carbonyl composite catalyst.
[summary of the invention]
Technical problem to be solved by this invention is to provide the method for utilizing iron-contained waste material to prepare sial iron carbonyl composite catalyst, adsoption catalysis degradation of dye and incretion interferent effectively, and have advantages of wide and recyclable the recycling of the pH scope of application.
The present invention solves the problems of the technologies described above by the following technical programs: a kind of method of utilizing iron-contained waste material to prepare sial iron carbonyl composite catalyst comprises the following steps:
(1) emery wheel ash iron filings are placed in beaker, add dilute nitric acid solution, be placed in the isothermal vibration device, isothermal vibration;
(2) the pH value with reaction system is adjusted to 12, continues isothermal vibration 30min, then sample is aging; Then centrifugation goes out solid, is washed with distilled water to neutrality, and oven dry is ground, and obtains sial iron carbonyl composite catalyst.
Further, the iron-holder of described emery wheel ash iron filings is greater than 10%, and emery wheel ash iron filings derive from the iron-contained waste material of auto parts machinery factory, blast furnace dedusting ash, steel-smelting sewage sludge, slag.
Further, the concentration of described rare nitric acid is 1.0mol/L.
Further, the temperature of the isothermal vibration in described step (1) is 55 ℃, and the concussion time is 2h.
Further, the pH value with reaction system in described step (2) is adjusted to 12, is the pH value that adopts the sodium hydroxide solution conditioned reaction system of 2.5mol/L.
Further, the aging temperature in described step (2) is 55 ℃, and ageing time is 2 days.
Further, the temperature of the oven dry in described step (2) is 90 ℃.
Beneficial effect of the present invention is: (1) utilizes iron-contained waste material emery wheel ash successfully to prepare sial iron carbonyl composite catalyst, turns waste into wealth to open up new approach for the recycling of iron-contained waste material; (2) the sial iron carbonyl composite catalyst that makes can efficient adsorption catalytic degradation dyestuff and incretion interferent, and has advantages of wide and recyclable the recycling of the pH scope of application.
[description of drawings]
The invention will be further described in conjunction with the embodiments with reference to the accompanying drawings.
Fig. 1 is the iron carbonyl catalyst scanning electron microscope (SEM) photograph that in the present invention, the pure reagent ferric nitrate makes.
Fig. 2 is the sial iron carbonyl composite catalyst scanning electron microscope (SEM) photograph that medium plain emery wheel ash of the present invention makes.
[specific embodiment]
A kind of method of utilizing iron-contained waste material to prepare sial iron carbonyl composite catalyst takes 1.0g emery wheel ash iron filings in the 250mL polytetrafluoroethylene beaker, adds the salpeter solution of 100mL1.0mol/L, is placed in the isothermal vibration case, in 55 ℃ of concussion 2h; Regulate pH to 12 with the 2.5mol/L sodium hydroxide solution again, continue stopping concussion, aging 2d under 55 ℃ after concussion 30min under 55 ℃.Centrifugation goes out solid, is washed with distilled water to neutrality, and then oven dry under 90 ℃ namely gets product, grinds standby.
Take 10.1g AR ferric nitrate, prepare according to the method described above iron carbonyl.Carry out scanning electron microscope analysis by the FeOOH to two kinds of different source of iron preparations, investigate its crystal formation and pattern difference, as illustrated in fig. 1 and 2.Can find out, under identical preparation method, sial iron carbonyl composite catalyst with emery wheel ash and the preparation of pure reagent ferric nitrate all has crystalline structure preferably, mostly form bar-shaped or acicular texture, yet the sial iron carbonyl composite catalyst by emery wheel ash preparation is comprised of acicular texture and amorphous less agglomerated particle, thereby when making it have catalytic capability and have a better adsorption capacity.
Adopt following method to investigate sial iron carbonyl composite catalyst that the present invention makes to the decoloration performance of the dye of positive ion, anionic dye and zwitterionic dyestuff.
One, the decoloration performance of sial iron carbonyl composite catalyst to the dye of positive ion
Take 3 parts of 0.05g sial iron carbonyl composite catalyst powder, then with 3 kinds of dyes of positive ion of 50mL20mg/L: methylene blue, crystal violet, safranine T, drop into respectively in 3 parts of sial iron carbonyl composite catalyst powder, regulate respectively the pH to 6.5 of three parts of reaction systems with the salpeter solution of 0.1M and the NaOH solution of 0.1M again, add 1mL H
2O
2Carry out the adsoption catalysis oxidation reaction, its absorbance is measured in certain hour sampling in interval after 0.45 μ m membrane filtration.Wherein, the test wavelength of methylene blue, crystal violet, safranine T is respectively: 660nm, 590nm, 550nm, investigate sial iron carbonyl composite catalyst catalysis H
2O
2Degraded to the dye of positive ion.Under pH6.5, reaction 1h, sial iron carbonyl composite catalyst catalysis H
2O
2Percent of decolourization to 3 kinds of dyes of positive ion is respectively 95.3%, 97.1% and 99.1%, and decolorizing effect is good.
Two, the decoloration performance of sial iron carbonyl composite catalyst to anionic dye
Take 2 parts of 0.05g sial iron carbonyl composite catalyst powder in the 100mL beaker, then adding respectively 50mL concentration in 2 beakers is in the anionic dye solution (being acid orange 7) of 20mg/L, regulate respectively pH to 2.7 and 4.95 with the salpeter solution of 0.1M and the NaOH solution of 0.1M, then add respectively 1mL H
2O
2Carry out the adsoption catalysis oxidation reaction, interval certain hour sampling through measuring its absorbance at 483nm place after 0.45 μ m membrane filtration, is studied sial iron carbonyl composite catalyst catalysis H
2O
2Degraded to anionic dye (acid orange 7).Be 2.7 and 4.95 at pH, reaction 1h, sial iron carbonyl composite catalyst catalysis H
2O
2It is 99% and 96.7% that the anionic dye percent of decolourization that is acid orange 7 is respectively.
Three, the decoloration performance of sial iron carbonyl composite catalyst to zwitterionic dyestuff
Take 3 parts of 0.05g sial iron carbonyl composite catalyst powder in 3 beakers, adding respectively 50mL concentration in 3 beakers is the zwitterionic dyestuff rhodamine B solution of 20mg/L, regulate respectively pH to 4.71,6.29 and 9.15 with the salpeter solution of 0.1M and the NaOH solution of 0.1M again, then add respectively 1mL H
2O
2Carry out the adsoption catalysis oxidation reaction, interval certain hour sampling, after 0.45 μ m membrane filtration in 552nm place its absorbance of mensuration.Research sial iron carbonyl composite catalyst catalysis H
2O
2To absorption and the oxidation of anionic dye rhodamine B under acidity, neutrality and alkali condition.Under acidity, neutrality and alkali condition, reaction 1h, sial iron carbonyl composite catalyst catalysis H
2O
2Adsoption catalysis degradation to rhodamine B is close, all less than 50%.
Four, the removal capacity of sial iron carbonyl composite catalyst Endocrine chaff interference
Take three parts of 0.2g sial iron carbonyl composite catalyst powder in the 250mL conical flask, add respectively 200mL concentration to be about the phthalic acid ester solution of 10mg/L, after regulating respectively pH to 4.71,6.29 and 9.15 with the NaOH solution of the salpeter solution of 0.1M and 0.1M, add 4mL H
2O
2Carry out Fenton's reaction, at regular intervals sampling after the micropore filtering film with water sample by 0.22 μ m filters, is injected and is contained appropriate sodium thiosulfate (Na
2S
2O
3) (Na in the sample bottle of solution
2S
2O
3Solution is used for the excessive H of quencher sample
2O
2), to analyze with high performance liquid chromatography (HPLC), (XB C185um * 4.6mm * 250mm), use the L-2455 PDAD, the place carries out the detection of phenol to anti-phase C18 liquid-phase chromatographic column at the 224nm wavelength.The testing conditions of HPLC: mobile phase ratio is 60% acetonitrile: 40% ultra-pure water, flow velocity 1mL/min, column temperature: 30 ℃.Under acidity, neutrality and alkali condition, sial iron carbonyl composite catalyst catalysis H
2O
2Can the slow degradation phthalic acid ester, through 12h, degradation rate is all in 90% left and right.
Recycling iron-contained waste material of the present invention is turned waste into wealth it, prepare a kind ofly novel have high adsorption capacity, applicable pH range is wide, recycling capable of circulation and can efficient catalytic H
2O
2The composite catalyst of degradation of dye waste water and incretion interferent, thus economize on resources, protection of the environment.
Claims (7)
1. method of utilizing iron-contained waste material to prepare sial iron carbonyl composite catalyst is characterized in that: comprise the following steps:
(1) emery wheel ash iron filings are placed in beaker, add dilute nitric acid solution, be placed in the isothermal vibration device, isothermal vibration;
(2) the pH value with reaction system is adjusted to 12, continues isothermal vibration 30min, then sample is aging; Then centrifugation goes out solid, is washed with distilled water to neutrality, and oven dry is ground, and obtains sial iron carbonyl composite catalyst.
2. the method for utilizing iron-contained waste material to prepare sial iron carbonyl composite catalyst as claimed in claim 1, it is characterized in that: the iron-holder of described emery wheel ash iron filings is greater than 10%, and emery wheel ash iron filings derive from the iron-contained waste material of auto parts machinery factory, blast furnace dedusting ash, steel-smelting sewage sludge, slag.
3. the method for utilizing iron-contained waste material to prepare sial iron carbonyl composite catalyst as claimed in claim 1, it is characterized in that: the concentration of described rare nitric acid is 1.0mol/L.
4. the method for utilizing iron-contained waste material to prepare sial iron carbonyl composite catalyst as claimed in claim 1, it is characterized in that: the temperature of the isothermal vibration in described step (1) is 55 ℃, the concussion time is 2h.
5. the method for utilizing iron-contained waste material to prepare sial iron carbonyl composite catalyst as claimed in claim 1, it is characterized in that: the pH value with reaction system in described step (2) is adjusted to 12, is the pH value that adopts the sodium hydroxide solution conditioned reaction system of 2.5mol/L.
6. the method for utilizing iron-contained waste material to prepare sial iron carbonyl composite catalyst as claimed in claim 1, it is characterized in that: the aging temperature in described step (2) is 55 ℃, ageing time is 2 days.
7. the method for utilizing iron-contained waste material to prepare sial iron carbonyl composite catalyst as claimed in claim 1, it is characterized in that: the temperature of the oven dry in described step (2) is 90 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104178240A (en) * | 2014-08-11 | 2014-12-03 | 江苏省镔鑫钢铁集团有限公司 | Method for preparing fire coal catalyst by using high-iron waste solid |
| CN104772153A (en) * | 2014-01-12 | 2015-07-15 | 中国科学院过程工程研究所 | Preparation method and applications of steel slag-based metal oxide solid base catalyst |
| CN108117274A (en) * | 2017-12-28 | 2018-06-05 | 许昌学院 | A kind of method that liquid phase transmission prepares alpha-ferric oxide film |
-
2013
- 2013-02-05 CN CN201310047405.6A patent/CN103127938B/en not_active Expired - Fee Related
Non-Patent Citations (3)
| Title |
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| 吴吉权等: "自然光下羟基氧化铁处理水溶液中甲基橙的研究", 《矿物岩石地球化学通报》 * |
| 巩志坚等: "不同原料制备羟基氧化铁的晶型及脱硫活性研究", 《煤炭学报》 * |
| 林继辉等: "羟基氧化铁催化臭氧氧化降解苯胺废水", 《宁德师范学院学报(自然科学版)》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104772153A (en) * | 2014-01-12 | 2015-07-15 | 中国科学院过程工程研究所 | Preparation method and applications of steel slag-based metal oxide solid base catalyst |
| CN104178240A (en) * | 2014-08-11 | 2014-12-03 | 江苏省镔鑫钢铁集团有限公司 | Method for preparing fire coal catalyst by using high-iron waste solid |
| CN104178240B (en) * | 2014-08-11 | 2015-08-12 | 江苏省镔鑫钢铁集团有限公司 | Utilize high ferro to give up and admittedly prepare the method for coal combustion catalyst |
| CN108117274A (en) * | 2017-12-28 | 2018-06-05 | 许昌学院 | A kind of method that liquid phase transmission prepares alpha-ferric oxide film |
| CN108117274B (en) * | 2017-12-28 | 2020-12-01 | 许昌学院 | Method for preparing alpha-ferric oxide film by liquid phase transmission |
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