CN103055840B - Method and device for preparing rare earth doping nano-titania photocatalyst with supercritical carbon dioxide process - Google Patents
Method and device for preparing rare earth doping nano-titania photocatalyst with supercritical carbon dioxide process Download PDFInfo
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Abstract
The invention relates to a method and a device for preparing rare earth doping nano-titania photocatalyst with supercritical carbon dioxide process. The method comprises the following specific steps: adding titanium alkoxide, absolute ethyl alcohol and rare earth element nitrate hydrate in a reaction kettle for stirring and dissolving; pumping high purity CO2 in the reaction kettle at the temperature of 110-150 DEG C under the pressure of 80-500 bar; adding deionized water in a deionized water dissolving kettle and raising the temperature till 110-150 DEG C; then pumping high purity CO2 in the deionized water dissolving kettle under the pressure of 80-500 bar, and causing the pressure difference between the deionized water dissolving kettle and the reaction kettle to be kept at 10-30 bar; flowing supercritical CO2 fluid doped with deionized water in the reaction kettle at the temperature of 110-150 DEG C and under the pressure of 80-500 bar, stirring for 4-24h for reaction; and after the reaction is finished, drying obtained products after being washed, and grinding the products so as to obtain the rare earth doping nano-titania photocatalyst.
Description
Technical field
The present invention relates to a kind of preparation method and device of rare earth mixing with nano titanium dioxide optical catalyst, particularly a kind of supercritical carbon dioxide process and prepare method and the device of rare earth mixing with nano titanium dioxide optical catalyst.
Background technology
In recent years, we are also being faced with energy shortage and problem of environmental pollution largest on Chinese history, that involvement aspect is the widest, consequence is the most serious when enjoying fast increasing economy.To the processing of incident discarded object, emission and circular regeneration, reduce consumption and the environmental pollution of resource, be more and more subject to everybody attention.Development in recent years is got up take the photocatalysis technology that metal oxide semiconductor is catalyst, a kind of method that desirable using energy source is provided and has curbed environmental pollution for us, especially it can utilize inexhaustible, nexhaustible solar energy to process poisonous and harmful substance, improve environment, reach the object of utilization of resources ecology.
The semiconductor light-catalyst great majority of broad research and application all belong to the N-shaped semiconducting compound of broad stopband, wherein TiO at present
2catalysis material is the most potential, and its advantage is: photoetch does not occur after illumination, and resistance to acids and bases is good, and stable chemical nature, to biological nontoxic; Source is abundant, and world's year consumption figure is 5,000,000 tons of left and right; Energy gap is larger, and the electromotive force current potential that produces light induced electron and hole is high, has very strong oxidisability and reproducibility.But meanwhile, simple TiO
2semiconductor is during as photochemical catalyst, and because quantum efficiency is lower, its photocatalytic activity is limited, especially low compared with long-wave band utilization rate to solar energy.In order to improve TiO
2photocatalysis performance, researchers adopt the whole bag of tricks, comprise noble-metal-supported titanium dioxide, prepare composite semiconductor, nonmetal doping and metal-doped etc.In patent: La rear earth ion doped TiO
2200310112184.2), patent the preparation method of spherical photochemical catalyst (number of patent application:: for the organic TiO of natural photodegradation
2200410041039.4), patent: rare earth modified carbon nanotube-TiO based photocatalyst and preparation method thereof (number of patent application:
2200910054603.9) and patent the preparation method of photochemical catalyst (number of patent application:: a kind of rare earth doping titanium dioxide nano luminescent material and preparation method thereof (number of patent application: 200610135394.7), researchers incorporate TiO by deposition, mode compound or doping by rare earth element respectively with liquid phase method
2in system, in the hope of improving its photocatalysis or other performances, all obtained different effects.But making a general survey of their preparation condition, is all to adopt traditional hydro-thermal method, sol-gel process or the precipitation method etc., and liquid flux reaction environment is to its gained TiO
2crystal formation, crystallite dimension and rare earth element doping level all to some extent restriction, photocatalysis performance also can not better be broken through.
Overcritical (Supecritical, SC-CO
2) carbon dioxide progressively replacing organic solvent some routines, that environment is had to harm as the cleaning solvent of " Green Chemistry "; in extract and separate, analytical technology, food industry, Chinese medicine extraction, biomaterial, environmental protection etc., be all applied aspect many, there is prospect widely.SC-CO
2easily reach critical condition (Tc=31 ℃, Pc=7.2MPa), and there is high diffusibility, low viscosity, density is adjustable (and then solubility is adjustable), polarity is little, be difficult for causing the chemical agglomeration of particulate and the product purity advantages of higher of preparation, can show supercritical fluid technique at superfine powder the advantage aspect preparing.The domestic researcher's supercritical CO that has more
2dry technology (list of references: Zhou Yasong, Fan little Hu, " preparation and the character of nano TiO 2-SiO2 composite oxides " SCI, 2003,24 (7), 1266-1270; Jia Jining, Sun Qin, Cheng Rong, Yang Asan, Zheng Yanping, the Liu Tifeng, " supercritical CO of oxide silica aerogel catalyst
2seasoning preparation and application thereof " modern chemical industry; 2006; 26 (S1); 316-320) remove the liquid phase in gel; by effectively eliminating the surface tension that causes that colloidal particle is reunited, that in the situation that keeping wet gel original structure, realizes liquid phase removes to make low reunion high pure and ultra-fine particulate.
Summary of the invention
One of object of the present invention is to provide a kind of supercritical CO
2legal system is for the method for rare earth-doped titanium dioxide photocatalysis performance.
Two of object of the present invention is to provide the device that uses the method.
Supercritical carbon dioxide process is prepared a method for rare earth mixing with nano titanium dioxide optical catalyst, it is characterized in that the concrete steps of the method are:
A.. the mixed in molar ratio with 1:1 ~ 50:0.002 ~ 0.05 by titanium alkoxide, absolute ethyl alcohol and rare earth element nitrate hydrate, the solution that obtains mixing, and join in reactor, under stirring, temperature of reaction kettle is risen to 110 ℃ ~ 150 ℃; Then by high-purity CO
2pump in this reactor, make the pressure of reactor reach 80bar ~ 500bar;
B. deionized water is joined in deionized water dissolving still, and be warming up to 110 ℃ ~ 150 ℃; By high-purity CO
2pump in this deionized water dissolving still, and make the pressure difference of the reactor of described deionized water dissolving still and step a remain on 10 ~ 30bar;
C. by the supercritical CO of the deionized water of carrying under one's arms in deionized water dissolving still
2fluid flows in the reactor of step a, under stirring, deionized water is fully mixed with step a gained solution, and the mol ratio of controlling deionized water and titanium alkoxide is 4 ~ 10:1; 110 ℃ ~ 150 ℃ temperature, react 4 ~ 24 hours; After reaction finishes, products therefrom is washed to post-drying, after grinding, obtain rare earth mixing with nano titanium dioxide optical catalyst.
Above-mentioned titanium alkoxide can be: butyl titanate or tetraisopropyl titanate.
Above-mentioned rare earth element can be: lanthanum, yttrium, neodymium, gadolinium or europium.
A kind of for realizing the device of above-mentioned method, comprise dioxide bottle, force (forcing) pump, valve, deionized water dissolving still and reactor, it is characterized in that filling deionized water in described deionized water dissolving still, in described reactor, fill the ethanol solution of titanium alkoxide and rare earth element nitrate hydrate; Carbon dioxide in described dioxide bottle is divided into two-way through described force (forcing) pump and the first valve, and the first via enters described deionized water dissolving still through the second valve, and the second tunnel the 3rd valve enters in described reactor; Carbon dioxide with deionized water in described deionized water dissolving still enters in described reactor through the 4th valve; In described reactor, products therefrom is discharged by the 5th valve.
Above-mentioned deionized water dissolving still is less than described reactor, and both pressure differences before being communicated with reaction are 10 ~ 30bar
For by supercritical CO
2fluid is successfully incorporated in reaction system, and the present invention has done some improvement on the basis of original supercritical extracting equipment, between pump and reactor, has increased control valve.Wherein deionized water dissolving still and reactor are used for respectively splendid attire deionized water and medicine, keep pressure difference, thermometer and the heated for controlling temperature system of 10-30bar between deionized water dissolving still and reactor.Pressurized equipment B, is used for to two reactors, providing pressure source simultaneously.Specifically as shown in Figure 1.
The present invention is incorporated into hydrolysis in supercritical environment, and friendly, the unique chemical reaction environment that utilizes the strong solubility energy of supercritical fluid, the performance of carrying under one's arms and supercritical fluid to provide, prepares rare earth doped nano-TiO
2photochemical catalyst.Supercritical CO
2low surface tension can reduce or substitution tables surface-active agent adds, clean green, the TiO making
2sample is anatase, and particle diameter is in 30nm left and right, better dispersed.Products therefrom approaches 50% to salicylic degradation rate in 6 hours under visible ray, is much better than commercialization photochemical catalyst P25; Under ultraviolet lighting in 30 minutes to the degradation rate of methyl orange higher than 95%, photocatalysis performance is desirable.
Accompanying drawing explanation
Fig. 1 is the structural representation of device of the present invention;
Fig. 2 mixes lanthanum 4% in the embodiment of the present invention 1, under 450bar, 120 ℃ of conditions, utilize supercritical CO
2the TiO of preparation
2xRD figure;
Fig. 3 is the TiO obtaining in the embodiment of the present invention 1
2photochemical catalyst under visible ray condition to organic degradation effect figure.Light source is 500 watts of xenon lamps, the salicylic acid 100ml that organic matter is 100mg/L, TiO
2powder 100mg, 6 hours reaction time; The TiO that as we can see from the figure prepared by overcritical doping
2utilization rate to visible ray is remarkable, and the commercial P25 performance of visible light catalytic Performance Ratio will be got well;
Fig. 4 is the TiO obtaining in the embodiment of the present invention 1
2photochemical catalyst under ultraviolet light conditions to organic degradation effect figure.Light source is 300 watts of mercury lamps, the methyl orange 100ml that organic matter is 20mg/L, TiO
2powder 100mg, 30 minutes reaction time; The TiO that as we can see from the figure prepared by overcritical doping
2excellent in the performance of ultraviolet light wave band photocatalysis performance;
Fig. 5 is the nano-TiO that the embodiment of the present invention 1 obtains
2, the granule-morphology of seeing under the S4800 of Hitachi ESEM, 100,000 times of multiplication factors.TiO as seen from the figure
2particle diameter is even, most of in 30nm left and right; Good dispersion, reunites not obvious.
The specific embodiment
Embodiment 1, referring to Fig. 1
(1) get butyl titanate 17ml, La (NO
3)
3nHO
2take 0.6498g, be dissolved in together in 150ml absolute ethyl alcohol, be stirred well to nitrate hydrate and dissolve completely, obtain homogeneous solution, and join in reactor A41, with suitable speed, stir; A41 is heated to 120 ℃; By high-purity CO
2pump in A41, pressure is raised to 430bar, closes k3;
(2) 6ml deionized water is added in preheating container A31, be warmed up to 120 ℃; By high-purity CO
2pump in reactor A31, the power of boosting is to 450bar;
(3) open k4, the deionized water in A31 can be by supercritical CO
2fluid is swept along and is brought in A41, and under the effect of stirring, deionized water is fully mixed and reacts with liquid.Continuation pumps into CO to A31
2to reach pressurize value 450bar, constant voltage constant temperature 24 hours;
(4) reaction finishes, and from the rewinding of k5 outlet valve, to putting into 60 ℃ of oven dry of convection oven after products therefrom washing, obtains TiO after grinding
2powder, then carries out characterization test.
Embodiment 2: referring to Fig. 1,
(1) get butyl titanate 8ml, Y (NO
3)
36HO
2take 0.0479g, be dissolved in together in 70ml absolute ethyl alcohol, be stirred well to nitrate hydrate and dissolve completely, obtain homogeneous solution, and join in reactor A41, with suitable speed, stir; A41 is heated to 140 ℃; By high-purity CO
2pump in A41, pressure is raised to 320bar, closes k3;
(2) 3ml deionized water is added in preheating container A31, be warmed up to 140 ℃; By high-purity CO
2pump in reactor A31, the power of boosting is to 350bar;
(3) open k4, the deionized water in A31 can be by supercritical CO
2fluid is swept along and is brought in A41, and under the effect of stirring, deionized water is fully mixed and reacts with liquid.Continuation pumps into CO to A31
2to reach pressurize value 350bar, constant voltage constant temperature 16 hours;
(4) reaction finishes, and from the rewinding of k5 outlet valve, to putting into 60 ℃ of oven dry of convection oven after products therefrom washing, obtains TiO after grinding
2powder, then carries out characterization test.
Embodiment 3, referring to Fig. 1
(1) get tetraisopropyl titanate 15ml, Gd (NO
3)
36HO
2take 0.0925g, be dissolved in together in 140ml absolute ethyl alcohol, be stirred well to nitrate hydrate and dissolve completely, obtain homogeneous solution, and join in reactor A41, with suitable speed, stir; A41 is heated to 140 ℃; By high-purity CO
2pump in A41, pressure is raised to 220bar, closes k3;
(2) 6ml deionized water is added in preheating container A31, be warmed up to 140 ℃; By high-purity CO
2pump in reactor A31, the power of boosting is to 250bar;
(3) open k4, the deionized water in A31 can be by supercritical CO
2fluid is swept along and is brought in A41, and under the effect of stirring, deionized water is fully mixed and reacts with liquid.Continuation pumps into CO to A31
2to reach pressurize value 250bar, constant voltage constant temperature 8 hours;
(4) reaction finishes, and from the rewinding of k5 outlet valve, to putting into 60 ℃ of oven dry of convection oven after products therefrom washing, obtains TiO after grinding
2powder, then carries out characterization test.
Embodiment 4: referring to Fig. 1
(1) get tetraisopropyl titanate 15ml, La (NO
3)
3nHO
2take 0.3249g, be dissolved in together in 140ml absolute ethyl alcohol, be stirred well to nitrate hydrate and dissolve completely, obtain homogeneous solution, and join in reactor A41, with suitable speed, stir; A41 is heated to 150 ℃; By high-purity CO
2pump in A41, pressure is raised to 120bar, closes k3;
(2) 6ml deionized water is added in preheating container A31, be warmed up to 150 ℃; By high-purity CO
2pump in reactor A31, the power of boosting is to 150bar;
(3) open k4, the deionized water in A31 can be by supercritical CO
2fluid is swept along and is brought in A41, and under the effect of stirring, deionized water is fully mixed and reacts with liquid.Continuation pumps into CO to A31
2to reach pressurize value 150bar, constant voltage constant temperature 4 hours;
(4) reaction finishes, and from the rewinding of k5 outlet valve, to putting into 60 ℃ of oven dry of convection oven after products therefrom washing, obtains TiO after grinding
2powder, then carries out characterization test.
Embodiment 5: referring to Fig. 1
(1) get butyl titanate 8ml, Nd (NO
3)
36HO
2take 0.3288g, be dissolved in together in 70ml absolute ethyl alcohol, be stirred well to nitrate hydrate and dissolve completely, obtain homogeneous solution, and join in reactor A41, with suitable speed, stir; A41 is heated to 110 ℃; By high-purity CO
2pump in A41, pressure is raised to 220bar, closes k3;
(2) 3ml deionized water is added in preheating container A31, be warmed up to 110 ℃; By high-purity CO
2pump in reactor A31, the power of boosting is to 250bar;
(3) open k4, the deionized water in A31 can be by supercritical CO
2fluid is swept along and is brought in A41, and under the effect of stirring, deionized water is fully mixed and reacts with liquid.Continuation pumps into CO to A31
2to reach pressurize value 250bar, constant voltage constant temperature 8 hours;
(4) reaction finishes, and from the rewinding of k5 outlet valve, to putting into 60 ℃ of oven dry of convection oven after products therefrom washing, obtains TiO after grinding
2powder, then carries out characterization test.
Embodiment 6: referring to Fig. 1
(1) get tetraisopropyl titanate 15ml, Eu (NO
3)
36HO
2take 0.2286g, be dissolved in together in 140ml absolute ethyl alcohol, be stirred well to nitrate hydrate and dissolve completely, obtain homogeneous solution, and join in reactor A41, with suitable speed, stir; A41 is heated to 120 ℃; By high-purity CO
2pump in A41, pressure is raised to 120bar, closes k3;
(2) 6ml deionized water is added in preheating container A31, be warmed up to 120 ℃; By high-purity CO
2pump in reactor A31, the power of boosting is to 150bar;
(3) open k4, the deionized water in A31 can be by supercritical CO
2fluid is swept along and is brought in A41, and under the effect of stirring, deionized water is fully mixed and reacts with liquid.Continuation pumps into CO2 to reach pressurize value 150bar, constant voltage constant temperature 24 hours to A31;
(4) reaction finishes, and from the rewinding of k5 outlet valve, to putting into 60 ℃ of oven dry of convection oven after products therefrom washing, obtains TiO after grinding
2powder, then carries out characterization test.
Participate in Fig. 2-Fig. 5, from the characterization result of embodiment gained sample, supercritical CO
2the rear-earth-doped TiO preparing
2belong to dispersed nano particle preferably, crystal formation is anatase, under its visible ray to organic degradation efficiency far above commercial P25, illustrate at supercritical CO
2tiO has significantly been expanded in the doping of lower rare earth element
2the utilization of photochemical catalyst to visible ray reached more than 95% organic degradation rate simultaneously under ultraviolet lighting, is a kind of efficient photochemical catalyst.
Claims (5)
1. supercritical carbon dioxide process is prepared a method for rare earth mixing with nano titanium dioxide optical catalyst, it is characterized in that the concrete steps of the method are:
A.. the mixed in molar ratio with 1:1 ~ 50:0.002 ~ 0.05 by titanium alkoxide, absolute ethyl alcohol and rare earth element nitrate hydrate, the solution that obtains mixing, and join in reactor, under stirring, temperature of reaction kettle is risen to 110 ℃ ~ 150 ℃; Then by high-purity CO
2pump in this reactor, make the pressure of reactor reach 80bar ~ 500bar;
B. deionized water is joined in deionized water dissolving still, and be warming up to 110 ℃ ~ 150 ℃; By high-purity CO
2pump in this deionized water dissolving still, and make the pressure difference of the reactor of described deionized water dissolving still and step a remain on 10 ~ 30bar;
C. by the supercritical CO of the deionized water of carrying under one's arms in deionized water dissolving still
2fluid flows in the reactor of step a, under stirring, deionized water is fully mixed with step a gained solution, and the mol ratio of controlling deionized water and titanium alkoxide is 4 ~ 10:1; 110 ℃ ~ 150 ℃ temperature, react 4 ~ 24 hours; After reaction finishes, products therefrom is washed to post-drying, after grinding, obtain rare earth mixing with nano titanium dioxide optical catalyst.
2. according to the supercritical carbon dioxide process described in claim 1, prepare the method for rare earth mixing with nano titanium dioxide optical catalyst, it is characterized in that described titanium alkoxide is: butyl titanate or tetraisopropyl titanate.
3. according to the supercritical carbon dioxide process described in claim 1, prepare the method for rare earth mixing with nano titanium dioxide optical catalyst, it is characterized in that described rare earth element is: lanthanum, yttrium, neodymium, gadolinium or europium.
4. one kind for realizing the device of method according to claim 1, comprise dioxide bottle (C), force (forcing) pump (B), valve (k1, k2, k3, k4, k5), deionized water dissolving still (A31) and reactor (A41), it is characterized in that filling deionized water in described deionized water dissolving still (A31), in described reactor (A41), fill the ethanol solution of titanium alkoxide and rare earth element nitrate hydrate; Carbon dioxide in described dioxide bottle (C) is divided into two-way through described force (forcing) pump (B) and the first valve (k1), the first via enters described deionized water dissolving still through the second valve (k2), and the second tunnel the 3rd valve (k3) enters in described reactor (A41); Carbon dioxide with deionized water in described deionized water dissolving still (A31) enters in described reactor (A41) through the 4th valve (k4); In described reactor (A41), products therefrom is discharged by the 5th valve (k5).
5. device according to claim 4, is characterized in that described deionized water dissolving still (A31) is less than described reactor (A41), and both pressure differences before being communicated with reaction are 10 ~ 30bar.
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| CN103623746B (en) * | 2013-12-02 | 2016-04-06 | 上海纳米技术及应用国家工程研究中心有限公司 | Overcritical-solvent heat combines and prepares the device and method of nano material |
| CN104974557B (en) * | 2015-07-10 | 2017-07-18 | 上海纳米技术及应用国家工程研究中心有限公司 | Utilize the method for supercritical carbon dioxide modified superfine oxide powder |
| CN104945660B (en) * | 2015-07-10 | 2017-11-10 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of method being modified to mineral filler |
| CN105126609A (en) * | 2015-08-18 | 2015-12-09 | 广西大学 | Method used for photocatalytic reduction of carbon dioxide |
| CN106422996B (en) * | 2015-12-31 | 2023-06-02 | 罗道友 | Supercritical CO 2 Preparation of nano TiO by fluid method 2 Method and device for functionalizing micro-nano dispersion |
| CN107583461A (en) * | 2017-10-18 | 2018-01-16 | 上海纳旭实业有限公司 | Preparation method of the manganese codoped nano zine oxide of titanium and products thereof and application |
| WO2019126994A1 (en) * | 2017-12-26 | 2019-07-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Multi-functional supercritical micro-particle preparation system |
| CN109174072A (en) * | 2018-10-13 | 2019-01-11 | 吴亚良 | A kind of supercritical preparation process of the uniform nano-titanium dioxide of particle diameter distribution |
| CN110237833A (en) * | 2019-05-13 | 2019-09-17 | 杭州电子科技大学 | A method of the loaded composite photo-catalyst of nano metal is prepared using ultraviolet light supercritical fluid |
| CN114054013A (en) * | 2021-12-03 | 2022-02-18 | 南京工业大学 | For CO2Photocatalytic reduced CeO2-TiO2Preparation method of composite aerogel |
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