CN104841431A - Iron ion and TiO2 supported powdery active carbon composite photocatalyst and preparation method thereof - Google Patents

Iron ion and TiO2 supported powdery active carbon composite photocatalyst and preparation method thereof Download PDF

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CN104841431A
CN104841431A CN201510160010.6A CN201510160010A CN104841431A CN 104841431 A CN104841431 A CN 104841431A CN 201510160010 A CN201510160010 A CN 201510160010A CN 104841431 A CN104841431 A CN 104841431A
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activated carbon
tio
powdered activated
solution
catalyst
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毕东苏
臧鹏
李隽�
王鹏
何慧红
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Shanghai Institute of Technology
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Shanghai Institute of Technology
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Abstract

The invention discloses an iron ion and TiO2 supported powdery active carbon composite photocatalyst and a preparation method thereof. The method comprises the following steps: uniformly mixing tetrabutyl titanate, anhydrous ethanol and glacial acetic acid at room temperature, adjusting the pH value to 2-3, stirring, and carrying out ultrasonic treatment to obtain a solution A; mixing anhydrous ethanol with deionized water to obtain a solution B, adding Fe(NO3).9H2O and TiO2 into the solution B, stirring for dissolving to obtain a solution C, adding the solution C to the solution A, stirring, carrying out ultrasonic treatment to obtain iron doped TiO2 sol, adding pretreated powdery active carbon passing through a 400-500 mesh sieve into the iron doped TiO2 sol, stirring, carrying out ultrasonic treatment, standing for ageing, drying, grinding, carrying out atmosphere heat treatment at 300DEG C for 2-3h, carrying out heat treatment at 500DEG C under air isolation conditions for 2-3h, and cooling in a furnace to obtain the iron ion and TiO2 supported powdery active carbon composite photocatalyst. The composite photocatalyst has the advantages of low cost and high catalysis efficiency.

Description

A kind of load iron ion and TiO 2powdered Activated Carbon composite photo-catalyst and preparation method thereof
Technical field
The present invention relates to a kind of load iron ion and TiO 2powdered Activated Carbon composite photo-catalyst and preparation method thereof.
Background technology
The Processing tecchnics of current water factory to Taste and odor compounds dimethyl isocamphol different in drinking water mostly is traditional handicraft, comprise aeration, coagulation, precipitation, sand filtration etc., researcher has carried out a large amount of lab scale to traditional handicraft, (Lalezary S., Pirbazari M., McGuire M.J.and Krasner S.W.Air stripping of taste and oder compounds from water.Jour. aWWA, 1984, (3): 83-87) finding that initial concentration affects aeration to remove the leading factor of smelling taste effect, clearance raises with concentration and concentration is worked as in rising, and when 100ng/L, dimethyl isocamphol clearance only has 48%; (Wang Junyu; woods wealth; the research of Fengshan and Gang Xi water treatment plant bad-smell problem; 17 running water collection of thesis; 2000; 49-65) study the dimethyl isocamphol clearance of coagulation, precipitation, sand filtration removal Fengshan water treatment plant, find that clearance only has 45%, residual concentration is still up to 47ng/L; Researcher has also carried out deep exploration to treatment process such as charcoal absorption, chemical oxidation and advanced oxidations, (Kim Y., Lcc Y., Gcc C.S.and Choi E.Treatment of taste and oder causing substances in drinking water. wat.Sci.Tech.., 1997,35 (8): 29-36.) and carry out the research of ozone and activated carbon Adsorption Model, after finding traditional handicraft process, then through ozone oxidation, dimethyl isocamphol clearance only has 28.1%,, and directly activated-carbon filter bed process only has 20.7% to its clearance.But with carrying the TiO of iron 2the Powdered Activated Carbon loading to fine grain is used it for the photocatalytic degradation removing different Taste and odor compounds dimethyl isocamphol and there is not yet relevant report before.
Photocatalysis technology have nontoxic, reaction temperature and, advantage become in recent years the study hotspot such as mineralization rate is high, cost-saving, obtain the extensive high praise of insider, more and more manifest its application prospect widely simultaneously.
TiO 2be typical catalysis material, chemical stability be high, nontoxic, can the thorough advantage such as mineralising, non-secondary pollution to organic degraded, be the fabulous photochemical catalyst of generally acknowledging in recent years.But due to TiO 2forbidden band wider (about 3.2eV), the ultraviolet light of 387nm can only be less than by response wave length, to illumination or solar energy utilization ratio very low (lower than 5%) not in this wave-length coverage, photo-generate electron-hole is short to the life-span, phosphorescent quantum yields is low thus reduce photocatalysis efficiency, constrains business-like application development.
But mix iron/TiO through metal-doped 2there is again reunion inactivation, be separated and difficult recovery problem in particle, the cost high investment caused thus and the low problem of degradation rate propose new requirement, therefore TiO to research personage in photocatalytic process 2load immobilization be to realize commercialization, scale, practical critical problem.For the appearance of this problem, have before and utilize activated carbon supported relevant report.But active carbon, due to problems such as particle are comparatively large, particle diameter is uneven, avtive spot is limited, microcellular structure is abundant not, constrains the photocatalysis efficiency of composite catalyst equally, not yet finds that there is and mix iron/TiO through metal-doped in currently available technology 2particle is as the application of Taste and odor compounds dimethyl isocamphol different in catalyst degradation water.
Summary of the invention
An object of the present invention is the above-mentioned TiO in order to solve 2photoresponse narrow range, easily reunite inactivation, be separated and the technical problem such as reclaim with difficulty and a kind of load iron ion and TiO are provided 2powdered Activated Carbon composite photo-catalyst, this load iron ion and TiO 2powdered Activated Carbon composite photo-catalyst realize Fe ion and be successfully doped to TiO 2in, replace traditional granular activated carbon with Powdered Activated Carbon simultaneously.Therefore load iron ion of the present invention and TiO 2powdered Activated Carbon composite photo-catalyst substantially increase TiO 2degradation efficiency, and due to load iron ion, be therefore convenient to load iron ion and TiO 2the recycling and reclaiming of Powdered Activated Carbon composite photo-catalyst.
Two of object of the present invention is to provide above-mentioned a kind of load iron ion and TiO 2the preparation method of Powdered Activated Carbon composite photo-catalyst.
Three of object of the present invention utilizes above-mentioned load iron ion and TiO 2powdered Activated Carbon composite photo-catalyst as Taste and odor compounds dimethyl isocamphol different in catalyst degradation water.
Know-why of the present invention
TiO 2as its band gap of semi-conducting material Eg=3.2eV, maximum absorption wavelength is confined to the ultraviolet region that wavelength is less than 387nm, low to target contaminant photodegradation rate under bringing its other illumination conditions outside this wavelength or visible ray thus, introduce transition metal iron ion and greatly can widen TiO 2photoresponse scope, improve the photocatalysis efficiency of this catalyst.
Powdered Activated Carbon is the carbon granule that a kind of particle diameter is very tiny, uniform particle sizes after pretreatment screening.Have that very large surface area, avtive spot are abundant, microcellular structure and central hole structure quantity many.And also have more tiny pore tubule in carbon granule.This capillary has very strong adsorption capacity.Because the surface area of carbon granule is very large, so fully can contact with water body.Organic matters in water etc. are adsorbed when encountering capillary, aseptic.Powdered Activated Carbon has a large amount of binding sites as carrier, to load iron ion and TiO 2powdered Activated Carbon provide the structure in effective specific area and hole, the fabulous deficiency improving commercially available various active carbon.
Technical scheme of the present invention
A kind of load iron ion and TiO 2powdered Activated Carbon composite photo-catalyst, be prepared by a method comprising the following steps and form:
(1), the pretreatment of Powdered Activated Carbon:
Be that to join mass percent concentration be after stirring 30min in the aqueous hydrochloric acid solution of 10% for the Powdered Activated Carbon of 28-38 μm by particle diameter, static soak 48 ~ 60h, the filter cake of suction filtration, gained spends deionized water to efflux for neutral, then control temperature is 80 ~ 120 DEG C of vacuum drying 4 ~ 8h, pulverize, cross 400-500 mesh sieve, lower part of screen divides sealing stand-by;
(2), under room temperature, by butyl titanate, absolute ethyl alcohol and glacial acetic acid, in butyl titanate: absolute ethyl alcohol: the volume ratio of glacial acetic acid is that the ratio of 1:4:0.66 carries out mixing mixing, then regulates pH to be 2 ~ 3 with concentrated hydrochloric acid, after magnetic agitation 30min, ultrasonic 10 ~ 20min, obtains solution A;
(3), by absolute ethyl alcohol and deionized water in absolute ethyl alcohol: the volume ratio of deionized water is that the ratio of 2:0.94 mixes, after magnetic agitation 30 ~ 60min, by Fe(NO 3) 9H 2o adds and wherein continues stirring and dissolving, obtains solution B;
Fe(NO in solution B 3) 9H 2the concentration of O is 0.0048-0.0966mol/L;
(4), control drop rate is 4-6ml/min, solution B joined in step (2) gained solution A, continues stirring 30 ~ 60min after adding, ultrasonic 10 ~ 20min, forms the TiO mixing iron 2colloidal sol;
The consumption of solution B, calculates in molar ratio, Fe(NO in solution B 3) 9H 2o: in step (2) solution A, butyl titanate is 0.005 ~ 0.1:1;
(5), step (1) is crossed the TiO mixing iron that the Powdered Activated Carbon divided 400-500 mesh sieve lower part of screen joins step (4) gained 2in colloidal sol, stir 30 ~ 60min, ultrasonic vibration 1 ~ 3h again, then still aging 24 ~ 48h, and then control temperature is 80 ~ 120 DEG C dries 1 ~ 4h, then fully grinds, then first at 300 DEG C of atmospheric heat process 2 ~ 3h, in high-temperature roasting furnace, control temperature is carry out roasting 2 ~ 3h under 500 DEG C of isolated air conditionses again, then with stove cooling, obtains load iron ion and TiO 2powdered Activated Carbon composite photo-catalyst;
Step (1) crosses the consumption of the Powdered Activated Carbon that 400-500 mesh sieve lower part of screen is divided, and calculates in mass ratio, and step (1) crosses the Powdered Activated Carbon that 400-500 mesh sieve lower part of screen is divided: the TiO mixing iron 2ti in colloidal sol 4+for 1:0.01-0.1.
The load iron ion of above-mentioned gained and TiO 2powdered Activated Carbon composite photo-catalyst, due to it, to combine powder electroless plating ability strong and mix iron TiO 2photocatalysis efficiency is high, product cost input is low, be easy to the advantages such as preparation, therefore this composite photo-catalyst has good catalytic degradation ability to trace organic pollutant in water dimethyl isocamphol, its consumption calculates in mass ratio, dimethyl isocamphol: load iron ion and TiO 2powdered Activated Carbon composite photo-catalyst be 1:50000.
The load iron ion of above-mentioned gained and TiO 2powdered Activated Carbon composite photo-catalyst use after, its regeneration method, step is as follows:
By the load iron ion after the use in above-mentioned reactant liquor and TiO 2powdered Activated Carbon composite photo-catalyst adopt centrifugal mode to isolate, then wash by deionized water, then filter, after the filter cake of gained is dried at 60-80 DEG C, under 28-32 DEG C of sunshine, namely illumination 4-10h completes load iron ion and TiO 2powdered Activated Carbon composite photo-catalyst regeneration.
Load iron ion after above-mentioned regeneration and TiO 2powdered Activated Carbon composite photo-catalyst, can be recycled 3-4 time, it still can arrive 54.87-88.75% to the degradation rate of dimethyl isocamphol.
Beneficial effect of the present invention
A kind of load iron ion of the present invention and TiO 2powdered Activated Carbon composite photo-catalyst, successfully utilize sol-gel process first by iron ion doping to TiO 2on, then by them by dip loading on Powdered Activated Carbon, therefore, the load iron ion of final gained and TiO 2powdered Activated Carbon composite photo-catalyst in, the TiO of transition metal iron ion doping 2single TiO can be made up 2the deficiency partially narrow to the responsive bandwidth of illumination, thus photoresponse scope also from being extended, improves TiO 2to effective utilization of light.
Further, a kind of load iron ion of the present invention and TiO 2powdered Activated Carbon composite photo-catalyst, because its preparation process carrier selects the Powdered Activated Carbon of particle diameter 28-38 μm to instead of the larger active carbon of common particle, under this situation, particle diameter diminishes, specific area becomes large, increase Powdered Activated Carbon and water body contact area, abundant micropore and the mesoporous avtive spot that also brings become many, absorption property grow.Meanwhile, the photochemical catalyst that meets that provide not only final gained that adds of support powder active carbon recycles the new way with secondary recovery, and greatly reduces processing cost and improve photocatalysis efficiency, simple to operate, equipment requirement is low, high-efficiency environment friendly.
Accompanying drawing explanation
Fig. 1 a, embodiment 1 gained load iron ion and TiO 2the scanning electron microscope (SEM) photograph of Powdered Activated Carbon composite photo-catalyst under 7.00K multiplying power;
Fig. 1 b, embodiment 1 gained load iron ion and TiO 2the scanning electron microscope (SEM) photograph of Powdered Activated Carbon composite photo-catalyst under 17.0K multiplying power;
Fig. 2, embodiment 1 gained load iron ion and TiO 2the infrared spectrogram of Powdered Activated Carbon composite photo-catalyst;
Fig. 3, embodiment 1 gained load iron ion and TiO 2the Raman spectrogram of Powdered Activated Carbon composite photo-catalyst.
Detailed description of the invention
Also by reference to the accompanying drawings the present invention is set forth further below by specific embodiment, but do not limit the present invention.
The instrument that in Application Example 1 of the present invention, the mensuration of dimethyl isocamphol is used is Shimadzu QP2010SE gas chromatograph-mass spectrometer (GC-MS), measure method used with reference to (He little Yan, Liu Qing, Li Qingsong, Deng. NACF, chlorine dioxide and coupling technique thereof remove 2-MIB, Central South University's journal (natural science edition), 2014,973-978).
embodiment 1
A kind of load iron ion and TiO 2powdered Activated Carbon composite photo-catalyst, be prepared by a method comprising the following steps and form:
(1), the pretreatment of Powdered Activated Carbon:
Be that to join mass percent concentration be after stirring 30min in the aqueous hydrochloric acid solution of 10% for the Powdered Activated Carbon of 28-38 μm by particle diameter, leave standstill and soak 48h, then the filter cake of suction filtration, gained spends deionized water to efflux for neutral, then control temperature is 80 DEG C of vacuum drying 4h, pulverize, cross 400 mesh sieves, lower part of screen divides sealing stand-by;
(2), under room temperature, 10ml butyl titanate, 40ml absolute ethyl alcohol and 6.6ml glacial acetic acid are mixed, then regulate pH to be 2 with concentrated hydrochloric acid, then magnetic agitation 30min, and then ultrasonic 20min, obtain solution A;
The consumption of above-mentioned butyl titanate, absolute ethyl alcohol and glacial acetic acid, calculates by volume, i.e. butyl titanate: absolute ethyl alcohol: glacial acetic acid is 1:4:0.66;
(3), by 20ml absolute ethyl alcohol and the mixing of 9.4ml deionized water, after magnetic agitation 30 ~ 60min, by 0.0573g Fe(NO 3) 9H 2o adds and wherein continues stirring and dissolving, obtains solution B;
The consumption of absolute ethyl alcohol and deionized water, calculates by volume, i.e. absolute ethyl alcohol: deionized water is 1:0.47;
Fe(NO in solution B 3) 9H 2the concentration of O is 0.0048mol/L;
(4), control drop rate is 4ml/min, the solution B of step (3) gained joined in step (2) gained solution A, continues to stir 30min, then ultrasonic 10min, form the TiO mixing iron after adding 2colloidal sol;
The consumption of solution B, calculates in molar ratio, Fe(NO in solution B 3) 9H 2o: in step (2) solution A, butyl titanate is 0.005:1;
(5), 134.0957g step (1) is crossed the TiO mixing iron that the Powdered Activated Carbon divided 400-500 mesh sieve lower part of screen joins step (4) gained 2in colloidal sol, stir 30min, ultrasonic vibration 3h again, then still aging 24h, and then control temperature is 80 DEG C dries 4h, then fully grinds, then first at 300 DEG C of atmospheric heat process 2h, in high-temperature roasting furnace, control temperature is carry out roasting 2h under 500 DEG C of isolated air conditionses again, then naturally cools with stove, obtains load iron ion and TiO 2powdered Activated Carbon composite photo-catalyst;
Step (1) crosses the consumption of the Powdered Activated Carbon that 400-500 mesh sieve lower part of screen is divided, and calculates in mass ratio, and step (1) crosses the Powdered Activated Carbon that 400-500 mesh sieve lower part of screen is divided: the TiO mixing iron of step (4) gained 2ti in colloidal sol 4+for 1:0.01.
Adopt the S-3400N ESEM of FDAC (Hitachi) Co., Ltd. under 7.00K and 17.0K multiplying power respectively to load iron ion and the TiO of above-mentioned gained 2powdered Activated Carbon composite photo-catalyst scan, respectively as shown in Figure 1 a, 1 b, as can be seen from Fig. 1 a, Fig. 1 b, Powdered Activated Carbon has abundant micropore and meso-hole structure for the scanning electron microscope (SEM) photograph of gained, simultaneously TiO 2be evenly distributed on powder activity carbon surface, especially at inner surface that is mesoporous, micropore.
Adopt the iZ10 Fourier trasfonn infrared microscope imaging spectrometer of Thermo Fischer Scient Inc. of the U.S. (Themo Fisher Scientific) to the load iron ion of above-mentioned gained and TiO 2the infrared spectrum of Powdered Activated Carbon composite photo-catalyst measure, the infrared spectrogram of gained as shown in Figure 2, as can be seen from Figure 2,3365cm -1with 1557 cm -1place is load iron ion and TiO respectively 2powdered Activated Carbon composite photo-catalyst surface O-H stretching vibration peak and flexural vibrations peak; 1053 cm -1for C-O-Ti absworption peak, this may be because TiO 2with the generation of Powdered Activated Carbon contact surface place C-O-Ti key; 777cm -1, 571cm -1and 468cm -1neighbouring is Fe-O, Ti-O stretching vibration peak, may be because adding of Powdered Activated Carbon causes Fe-O, Ti-O stretching vibration peak to offset to low ripple.
Adopt the DXR laser capture microdissection Raman spectrometer of Thermo Fischer Scient Inc. of the U.S. (Themo Fisher Scientific) to the load iron ion of above-mentioned gained and TiO 2the Raman spectrum of Powdered Activated Carbon composite photo-catalyst measure, the Raman spectrogram of gained as shown in Figure 3, as can be seen from Figure 3,2908cm -1, 2572cm -1, 2113cm -1, 1600cm -1, 1353cm -1, 621cm -1all may due to Fe and Ti 4+load effect, at 1600cm -1, 1353cm -1peak strength reaches maximum, and as 150cm -1very weak shoulder seam may be that lattice vibrations cause.
embodiment 2
A kind of load iron ion and TiO 2powdered Activated Carbon composite photo-catalyst, be prepared by a method comprising the following steps and form:
(1), the pretreatment of Powdered Activated Carbon:
Be that to join mass percent concentration be after stirring 30min in the aqueous hydrochloric acid solution of 10% for the Powdered Activated Carbon of 28-38 μm by particle diameter, leave standstill and soak 52h, then the filter cake of suction filtration, gained spends deionized water to efflux for neutral, then control temperature is 100 DEG C of vacuum drying 7h, pulverize, cross 400 mesh sieves, lower part of screen divides sealing stand-by;
(2), under room temperature, 10ml butyl titanate, 40ml absolute ethyl alcohol and 6.6ml glacial acetic acid are mixed, then regulate pH to be 2 with concentrated hydrochloric acid, then magnetic agitation 30min, and then ultrasonic 20min, obtain solution A;
The consumption of above-mentioned butyl titanate, absolute ethyl alcohol and glacial acetic acid, calculates by volume, i.e. butyl titanate: absolute ethyl alcohol: glacial acetic acid is 1:4:0.66;
(3), by 20ml absolute ethyl alcohol and the mixing of 9.4ml deionized water, after magnetic agitation 30 ~ 60min, by 0.1146g Fe(NO 3) 9H 2o adds and wherein continues stirring and dissolving, obtains solution B;
The consumption of absolute ethyl alcohol and deionized water, calculates by volume, i.e. absolute ethyl alcohol: deionized water is 1:0.47;
Fe(NO in solution B 3) 9H 2the concentration of O is 0.0096mol/L;
(4), control drop rate is 4.5ml/min, the solution B of step (3) gained joined in step (2) gained solution A, continues to stir 40min, then ultrasonic 10min, form the TiO mixing iron after adding 2colloidal sol;
The consumption of solution B, calculates in molar ratio, Fe(NO in solution B 3) 9H 2o: in step (2) solution A, butyl titanate is 0.01:1;
(5), 43.1712g step (1) is crossed the TiO mixing iron that the Powdered Activated Carbon divided 400-500 mesh sieve lower part of screen joins step (4) gained 2in colloidal sol, stir 40min, ultrasonic vibration 2h again, then still aging 30h, and then control temperature is 90 DEG C dries 4h, then fully grinds, then first at 300 DEG C of atmospheric heat process 2h, in high-temperature roasting furnace, control temperature is carry out roasting 2h under 500 DEG C of isolated air conditionses again, then naturally cools with stove, obtains load iron ion and TiO 2powdered Activated Carbon composite photo-catalyst;
Step (1) crosses the consumption of the Powdered Activated Carbon that 400-500 mesh sieve lower part of screen is divided, and calculates in mass ratio, and step (1) crosses the Powdered Activated Carbon that 400-500 mesh sieve lower part of screen is divided: the TiO mixing iron of step (4) gained 2ti in colloidal sol 4+for 1:0.03.
embodiment 3
A kind of load iron ion and TiO 2powdered Activated Carbon composite photo-catalyst, be prepared by a method comprising the following steps and form:
(1), the pretreatment of Powdered Activated Carbon:
Namely be first that to join mass percent concentration be after stirring 30min in the aqueous hydrochloric acid solution of 10% for the Powdered Activated Carbon of 28-38 μm by particle diameter, leave standstill and soak 56h, then the filter cake of suction filtration, gained spends deionized water to efflux for neutral, then control temperature is 110 DEG C of vacuum drying 6h, pulverize, cross 500 mesh sieves, lower part of screen divides sealing stand-by;
(2), under room temperature, 10ml butyl titanate, 40ml absolute ethyl alcohol and 6.6ml glacial acetic acid are mixed, then regulate pH to be 3 with concentrated hydrochloric acid, then magnetic agitation 30min, and then ultrasonic 10min, obtain solution A;
The consumption of above-mentioned butyl titanate, absolute ethyl alcohol and glacial acetic acid, calculates by volume, i.e. butyl titanate: absolute ethyl alcohol: glacial acetic acid is 1:4:0.66;
(3), by 20ml absolute ethyl alcohol and the mixing of 9.4ml deionized water, after magnetic agitation 50min, by 0.5734 gfe(NO 3) 9H 2o adds and wherein continues stirring and dissolving, obtains solution B;
The consumption of absolute ethyl alcohol and deionized water, calculates by volume, i.e. absolute ethyl alcohol: deionized water is 1:0.47;
Fe(NO in solution B 3) 9H 2the concentration of O is 0.0483mol/L;
(4), control drop rate is 4.8ml/min, the solution B of step (3) gained joined in step (2) gained solution A, continues to stir 50min, then ultrasonic 20min, form the TiO mixing iron after adding 2colloidal sol;
The consumption of solution B, calculates in molar ratio, Fe(NO in solution B 3) 9H 2o: in step (2) solution A, butyl titanate is 0.05:1;
(5), 24.9236g step (1) is crossed the TiO mixing iron that the Powdered Activated Carbon divided 400-500 mesh sieve lower part of screen joins step (4) gained 2in colloidal sol, stir 50min, ultrasonic vibration 3h again, then still aging 36h, and then control temperature is 100 DEG C dries 3h, then fully grinds, then first at 300 DEG C of atmospheric heat process 3h, in high-temperature roasting furnace, control temperature is carry out roasting 3h under 500 DEG C of isolated air conditionses again, then naturally cools with stove, obtains load iron ion and TiO 2powdered Activated Carbon composite photo-catalyst;
Step (1) crosses the consumption of the Powdered Activated Carbon that 400-500 mesh sieve lower part of screen is divided, and calculates in mass ratio, and step (1) crosses the Powdered Activated Carbon that 400-500 mesh sieve lower part of screen is divided: the TiO mixing iron of step (4) gained 2ti in colloidal sol 4+for 1:0.05.
embodiment 4
A kind of load iron ion and TiO 2powdered Activated Carbon composite photo-catalyst, be prepared by a method comprising the following steps and form:
(1), the pretreatment of Powdered Activated Carbon:
Namely be first that to join mass percent concentration be after stirring 30min in the aqueous hydrochloric acid solution of 10% for the Powdered Activated Carbon of 28-38 μm by particle diameter, leave standstill and soak 60h, then the filter cake of suction filtration, gained spends deionized water to efflux for neutral, then control temperature is 120 DEG C of vacuum drying 4h, pulverize, cross 500 mesh sieves, lower part of screen divides sealing stand-by;
(2), under room temperature, 10ml butyl titanate, 40ml absolute ethyl alcohol and 6.6ml glacial acetic acid are mixed, then regulate pH to be 3 with concentrated hydrochloric acid, then magnetic agitation 30min, and then ultrasonic 10min, obtain solution A;
The consumption of above-mentioned butyl titanate, absolute ethyl alcohol and glacial acetic acid, calculates by volume, i.e. butyl titanate: absolute ethyl alcohol: glacial acetic acid is 1:4:0.66;
(3), by 20ml absolute ethyl alcohol and the mixing of 9.4ml deionized water, after magnetic agitation 60min, by 1.1468g Fe(NO 3) 9H 2o adds and wherein continues stirring and dissolving, obtains solution B;
The consumption of absolute ethyl alcohol and deionized water, calculates by volume, i.e. absolute ethyl alcohol: deionized water is 1:0.47;
Fe(NO in solution B 3) 9H 2the concentration of O is 0.0966mol/L;
(4), control drop rate is 6ml/min, the solution B of step (3) gained joined in step (2) gained solution A, continues to stir 60min, then ultrasonic 20min, form the TiO mixing iron after adding 2colloidal sol;
The consumption of solution B, calculates in molar ratio, Fe(NO in solution B 3) 9H 2o: in step (2) solution A, butyl titanate is 0.1:1;
(5), 10.0726g step (1) is crossed the TiO mixing iron that the Powdered Activated Carbon divided 400-500 mesh sieve lower part of screen joins step (4) gained 2in colloidal sol, stir 60min, ultrasonic vibration 3h again, then still aging 48h, and then control temperature is 120 DEG C dries 1h, then fully grinds, then first at 300 DEG C of atmospheric heat process 3h, in high-temperature roasting furnace, control temperature is carry out roasting 3h under 500 DEG C of isolated air conditionses again, then naturally cools with stove, obtains load iron ion and TiO 2powdered Activated Carbon composite photo-catalyst;
Step (1) crosses the consumption of the Powdered Activated Carbon that 400-500 mesh sieve lower part of screen is divided, and calculates in mass ratio, and step (1) crosses the Powdered Activated Carbon that 400-500 mesh sieve lower part of screen is divided: the TiO mixing iron of step (4) gained 2ti in colloidal sol 4+for 1:0.1.
application Example 1
By the load iron ion of embodiment 1-4 gained and TiO 2powdered Activated Carbon composite photo-catalyst be respectively used to the reaction that catalysis dimethyl isocamphol carries out degrading, step is as follows:
Compound concentration is the dimethyl isocamphol aqueous solution 4 parts of 200ng/L, adds load iron ion and the TiO of embodiment 1-4 gained respectively 2powdered Activated Carbon composite photo-catalyst, its addition, by load iron ion and TiO 2powdered Activated Carbon composite photo-catalyst: the ratio of concentration to be the dimethyl isocamphol aqueous solution of 200ng/L be 10mg:1L calculates, after adding, after under room temperature, first dark reaction reaches adsorption equilibrium, again under ultraviolet lighting, control reaction temperature is 25 ± 2 DEG C and carries out degradation reaction 4h, the reactant liquor sampling obtained detects the content of wherein dimethyl isocamphol, thus the degradation rate obtaining dimethyl isocamphol is as following table:
In upper table, the computing formula of the degradation rate of dimethyl isocamphol= (wherein C t, C 0be respectively the concentration of dimethyl isocamphol solution degradation in t reactant liquor and the initial concentration of dimethyl isocamphol solution, in this application embodiment, the initial concentration of dimethyl isocamphol is 200ng/L).
As can be seen from the above table, the load iron ion of gained of the present invention and TiO 2powdered Activated Carbon composite photo-catalyst, the dimethyl isocamphol degradation rate after ultraviolet lighting 4h in dimethyl isocamphol solution can reach 63.81-96.47%.
By the load iron ion of above-described embodiment 1-4 gained and TiO 2powdered Activated Carbon composite photo-catalyst use once regenerate afterwards, its regeneration method step as follows:
By the load iron ion after the use in the reactant liquor of gained after reaction 4h and TiO 2powdered Activated Carbon composite photo-catalyst adopt centrifugal mode to separate; Then by the load iron ion after use and TiO 2powdered Activated Carbon composite photo-catalyst deionized water wash, then filter, after the filter cake of gained is dried at 60-80 DEG C, illumination 4-10h under 28-32 DEG C of sunshine, namely completes load iron ion and TiO 2powdered Activated Carbon composite photo-catalyst regeneration.
Load iron ion after above-mentioned regeneration 1 time and TiO 2powdered Activated Carbon composite photo-catalyst, mode identical with Application Example 1 is respectively carried out the 1st time and is reused, and it sees the above table the degradation rate of dimethyl isocamphol, is up to 95.43%;
According to above-mentioned identical mode, regenerate, carry out the 2nd time and reuse, it sees the above table the degradation rate of dimethyl isocamphol, the highlyest also can reach 94.70%;
According to above-mentioned identical mode, regenerate, carry out the 3rd time and reuse, it sees the above table the degradation rate of dimethyl isocamphol, the highlyest also can reach 90.41%.
According to above-mentioned identical mode, regenerate, carry out the 3rd time and reuse, it sees the above table the degradation rate of dimethyl isocamphol, the highlyest still can reach 88.75%.
As can be seen from the above table, a kind of load iron ion of the present invention and TiO 2powdered Activated Carbon composite photo-catalyst, under ultraviolet light, degrade for catalysis dimethyl isocamphol, degradation rate can reach 63.81-96.47%, particularly the load iron ion of embodiments of the invention 3 gained and TiO 2powdered Activated Carbon composite photo-catalyst, degrade for catalysis dimethyl isocamphol, its degradation rate can reach 96.47%.
In sum, load iron ion of the present invention and TiO 2powdered Activated Carbon composite photo-catalyst, breach the treatment process such as traditional aeration, coagulation, precipitation, sand filtration and charcoal absorption, chemical oxidation and advanced oxidation, providing new approach for solving different taste organic matter dimethyl isocamphol removal problem of smelling in water, before the method, there is not yet relevant report.Especially as described in Example 3, as load iron ion and TiO 2powdered Activated Carbon composite photo-catalyst with molal weight than the iron of mixing being 5%, when mass ratio is 5% year titanium amount, best to the degradation effect of dimethyl isocamphol in water, reach 96.47%, and after reusing 4 times, degradation effect is still fine, reaches 88.75%.In addition, composite photo-catalyst renovation process involved in the present invention is from embodiment 1-4 experimental result, and after reusing 4 times, dimethyl isocamphol degradation rate reduces all about 10%.
The above is only the citing of embodiments of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; also can make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.

Claims (7)

1. a load iron ion and TiO 2the preparation method of Powdered Activated Carbon composite photo-catalyst, it is characterized in that specifically comprising the steps:
(1), the pretreatment of Powdered Activated Carbon:
Be that to join mass percent concentration be after stirring 30min in the aqueous hydrochloric acid solution of 10% for the Powdered Activated Carbon of 28-38 μm by particle diameter, static soak 48 ~ 60h, the filter cake of suction filtration, gained spends deionized water to efflux for neutral, then control temperature is 80 ~ 120 DEG C of vacuum drying 4 ~ 8h, pulverize, cross 400-500 mesh sieve, lower part of screen divides sealing stand-by;
(2), under room temperature, butyl titanate, absolute ethyl alcohol and glacial acetic acid are mixed, then regulate pH to be 2 ~ 3 with concentrated hydrochloric acid, then magnetic agitation 30min, then ultrasonic 10 ~ 20min, obtains solution A;
The consumption of above-mentioned butyl titanate, absolute ethyl alcohol and glacial acetic acid, calculates by volume, i.e. butyl titanate: absolute ethyl alcohol: glacial acetic acid is 1:4:0.66;
(3), by absolute ethyl alcohol and deionized water mixing, after magnetic agitation 30 ~ 60min, by Fe(NO 3) 9H 2o adds and wherein continues stirring and dissolving, obtains solution B;
The consumption of absolute ethyl alcohol and deionized water, calculates by volume, i.e. absolute ethyl alcohol: deionized water is 1:0.47;
Fe(NO in solution B 3) 9H 2the concentration of O is 0.0048-0.0966mol/L;
(4), control drop rate is 4-6ml/min, solution B joined in step (2) gained solution A, continues stirring 30 ~ 60min after adding, then ultrasonic 10 ~ 20min, forms the TiO mixing iron 2colloidal sol;
The consumption of solution B, calculates in molar ratio, Fe(NO in solution B 3) 9H 2o: in step (2) solution A, butyl titanate is 0.005 ~ 0.1:1;
(5), step (1) is crossed the TiO mixing iron that the Powdered Activated Carbon divided 400-500 mesh sieve lower part of screen joins step (4) gained 2in colloidal sol, stir 30 ~ 60min, ultrasonic vibration 1 ~ 3h again, then still aging 24 ~ 48h, and then control temperature is 80 ~ 120 DEG C dries 1 ~ 4h, then fully grinds, then first at 300 DEG C of atmospheric heat process 2 ~ 3h, in high-temperature roasting furnace, control temperature is carry out roasting 2 ~ 3h under 500 DEG C of isolated air conditionses again, then naturally cools with stove, obtains load iron ion and TiO 2powdered Activated Carbon composite photo-catalyst;
Step (1) crosses the consumption of the Powdered Activated Carbon that 400-500 mesh sieve lower part of screen is divided, and calculates in mass ratio, and step (1) crosses the Powdered Activated Carbon that 400-500 mesh sieve lower part of screen is divided: the TiO mixing iron of step (4) gained 2ti in colloidal sol 4+for 1:0.01-0.1.
2. a kind of load iron ion as claimed in claim 1 and TiO 2the preparation method of Powdered Activated Carbon composite photo-catalyst, it is characterized in that Fe(NO in solution B described in step (3) 3) 9H 2the concentration of O is 0.0048mol/L;
Described in step (4), drop rate is 4ml/min;
Calculating in mass ratio described in step (5), step (1) crosses the Powdered Activated Carbon that 400-500 mesh sieve lower part of screen is divided: the TiO mixing iron of step (4) gained 2ti in colloidal sol 4+for 1:0.01.
3. a kind of load iron ion as claimed in claim 1 and TiO 2the preparation method of Powdered Activated Carbon composite photo-catalyst, it is characterized in that Fe(NO in solution B described in step (3) 3) 9H 2the concentration of O is 0.0096mol/L;
Described in step (4), drop rate is 4.5ml/min;
Calculating in mass ratio described in step (5), step (1) crosses the Powdered Activated Carbon that 400-500 mesh sieve lower part of screen is divided: the TiO mixing iron of step (4) gained 2ti in colloidal sol 4+for 1:0.03.
4. a kind of load iron ion as claimed in claim 1 and TiO 2the preparation method of Powdered Activated Carbon composite photo-catalyst, it is characterized in that Fe(NO in solution B described in step (3) 3) 9H 2the concentration of O is 0.0483mol/L;
Described in step (4), drop rate is 4.8ml/min;
Calculating in mass ratio described in step (5), step (1) crosses the Powdered Activated Carbon that 400-500 mesh sieve lower part of screen is divided: the TiO mixing iron of step (4) gained 2ti in colloidal sol 4+for 1:0.05.
5. a kind of load iron ion as claimed in claim 1 and TiO 2the preparation method of Powdered Activated Carbon composite photo-catalyst, it is characterized in that Fe(NO in solution B described in step (3) 3) 9H 2the concentration of O is 0.0966mol/L;
Described in step (4), drop rate is 6ml/min;
Calculating in mass ratio described in step (5), step (1) crosses the Powdered Activated Carbon that 400-500 mesh sieve lower part of screen is divided: the TiO mixing iron of step (4) gained 2ti in colloidal sol 4+for 1:0.1.
6. the load iron ion of the preparation method's gained as described in as arbitrary in claim 1-5 and TiO 2powdered Activated Carbon composite photo-catalyst.
7. load iron ion and TiO as claimed in claim 6 2powdered Activated Carbon composite photo-catalyst be used under ultraviolet light catalytic degradation is carried out to the dimethyl isocamphol in the aqueous solution containing dimethyl isocamphol, its consumption calculates in mass ratio, dimethyl isocamphol: load iron ion and TiO 2powdered Activated Carbon composite photo-catalyst be 1:50000.
CN201510160010.6A 2015-04-07 2015-04-07 Iron ion and TiO2 supported powdery active carbon composite photocatalyst and preparation method thereof Pending CN104841431A (en)

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Application publication date: 20150819