CN101402036A - Modified titanium-containing furnace cinder catalyst with visible light catalytic activity and method for producing the same - Google Patents
Modified titanium-containing furnace cinder catalyst with visible light catalytic activity and method for producing the same Download PDFInfo
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- CN101402036A CN101402036A CNA2008102289307A CN200810228930A CN101402036A CN 101402036 A CN101402036 A CN 101402036A CN A2008102289307 A CNA2008102289307 A CN A2008102289307A CN 200810228930 A CN200810228930 A CN 200810228930A CN 101402036 A CN101402036 A CN 101402036A
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Abstract
The invention relates to a modified titanium-bearing blast furnace slag catalyst with visible photocatalytic activity and a preparation method thereof, which belong to the field of material science. The compositions of crystal phase of the catalyst are 33 to 40 weight percent of perovskite, 50 to 59 weight percent of diopside and 7 to 10 weight percent of akermanite-submellite; and the specific surface area is between 9.7 and 20.5 square meters pre gram, and the maximum absorption capacity is between 3.9 and 8.3 milligrams per gram. The preparation method comprises the following steps: firstly, titanium-bearing blast furnace slag is crushed, and titanium-bearing blast furnace slag powder is obtained; secondly, ammonium sulfate is mixed with the titanium-bearing blast furnace slag powder; thirdly, mixture of the titanium-bearing blast furnace slag powder and the ammonium sulfate is grinded; and fourthly, the mixture is roasted for 1 to 4 hours at a temperature of between 300 and 700 DEG C, and is cooled to the room temperature. The STBBFS catalyst prepared by the method has strong photoabsorption and photoresponse when excited by visible light, so that the photocatalyst which is prepared by adoption of the titanium-bearing blast furnace slag as a raw material can utilize visible light sources such as sunlight to effectively photodegrade organic pollutant and inorganic pollutant in the water, and has high energy conversion efficiency.
Description
Technical field
The invention belongs to material science, be specifically related to a kind of modified titanium-containing furnace cinder catalyst and preparation method with visible light catalysis activity.
Background technology
Along with the development of World Economics, it is serious day by day that the energy and environmental problem become, thereby the application of conductor photocatalysis degradation technique in environmental protection is subjected to paying attention to widely.The more conductor photocatalysis material of research has TiO at present
2, ZnO, CdS, WO
3, Fe
2O
3, PBs, SnO
2, In
2O
3, ZnS, SrTiO
3, SiO
2Deng tens kinds.These conductor oxidates all have certain photocatalytic activity, but wherein most of chemistry or photochemical corrosion of easily taking place.Wherein, TiO
2Having characteristics such as good chemical stability and nontoxic, non-secondary pollution, catalytic activity height, is good catalysis material, but pure TiO
2Cost is higher.
Recently, mostly document is that report ammonium sulfate is doped to TiO as a kind of auxiliary agent
2In the conductor oxidate, to strengthen TiO
2Photocatalytic activity etc. the main body oxide.It is generally acknowledged that the doping of ammonium sulfate has suppressed the compound of photohole-light induced electron, thereby strengthened the photocatalytic activity of photochemical catalyst.(see document 1, JiangF, ZhengZ, XuZY.AqueousCr (VI) photo-reductioncatalyzedbyTiO
2AndsulfatedTiO
2.J.Hazard.Mater.B, 2006,134:94-103).
Though titanium resource is a kind of relatively rich in natural resources in China, most titanium resources mainly are and the iron symbiosis that grade is low, does not reach the level of direct development and use.Iron and Steel Enterprises in China extracts iron when developing iron resource in a large number in ilmenite, other element in the mineral is not then made full use of, and not only forms a large amount of titanium-containing blast furnace slags, contaminated environment, and the titanium resource in the waste slag.As everyone knows, ultra-violet radiation energy in the sunlight is lower, only account for about 4% of total solar radiation, if with the semiconductor light-catalyst of ultraviolet excitation be applied to degrade inorganic pollution and complex system thereof, then degrading equipment investment and degraded operating cost all can be very high.How to overcome the dependence of the STBBFS photochemical catalyst of existing preparation method's acquisition to ultraviolet light, the photoresponse range expansion of spectrum is arrived visible light wave range, thereby under radiation of visible light, can excite the photocatalytic degradation activity of STBBFS photochemical catalyst, be an important step of STBBFS photochemical catalyst practicability, have great economic implications and social benefit.
Summary of the invention
The objective of the invention is to overcome the TBBFS photochemical catalyst that has preparation method's acquisition now and depend on the deficiency that ultraviolet light activates, provide a kind of in the wide spectrum scope, stronger light absorption and photoresponse are promptly all arranged, a kind of modified titanium-containing furnace cinder catalyst and preparation method with visible light catalysis activity under ultraviolet light and radiation of visible light.
This method is with titanium-containing blast furnace slag (titanium-bearingblastfurnaceslag, TBBFS) be raw material, processing step is: elder generation is with the TBBFS fragmentation of bulk, then TBBFS particulate after the fragmentation and ammonium sulfate are pressed different doping ratios mixing, ball milling, the gained compound activates through low-temperature bake, acquisition has target STBBFS (sulfate-modifiedtitanium-bearingblastfurnaceslag, the modified titanium-containing furnace cinder) catalyst of visible light catalysis activity.
STBBFS catalyst crystalline phases with visible light catalysis activity of the present invention consists of and contains perovskite (CaTiO
3) 33～40wt%, diopside (Al
0.6Ca
1.0Mg
0.7O
6Si
1.7) 50～59wt%, akermanite-submellite (AlCa
2Mg
0.5O
7Si
1.5) 7～10wt%.
STBBFS catalyst with visible light catalysis activity of the present invention contains undecomposed (NH
4)
2SO
4Be 1～6wt%.
Specific area with STBBFS catalyst of visible light catalysis activity of the present invention is 9.7～20.5m
2/ g, maximum adsorption capacity are 3.9～8.3mg/g.
The present invention adopts and contains TiO
2The titanium-containing blast furnace slag of 16～25wt% is a raw material, and forms through fragmentation, mixing, ball milling and calcination activation.
Preparation method of the present invention may further comprise the steps:
1, fragmentation: with the titanium-containing blast furnace slag fragmentation, obtaining diameter is the titanium-containing blast furnace slag powder of 0.5～1.5mm.
2, mix: with the titanium-containing blast furnace slag powder after ammonium sulfate and the fragmentation, mixed proportion accounts for 2.5～7.5wt% of titanium-containing blast furnace slag powder by ammonium sulfate.
3, ball milling: the mixture of levigate titanium-containing blast furnace slag powder and ammonium sulfate to average grain diameter less than 2 microns, obtain mixed-powder.
4, calcination activation: with the mixed-powder roasting, sintering temperature is under 300～700 ℃, and roasting time is 1～4 hour, and roasting is cooled to room temperature after finishing, and obtains to have STBBFS (modified titanium-containing furnace cinder) catalyst of visible light catalysis activity.
Pack behind the STBBFS with visible light catalysis activity (modified titanium-containing furnace cinder) catalyst seal that obtains.
In the shattering process, when the titanium-containing blast furnace slag block is big, adopt 2～3 grades of fragmentations.
The STBBFS material that cheaply, has a visible light catalysis activity provided by the present invention is a raw material with the titaniferous slag, forms through simple fragmentation, doping, ball milling, the manufacturing of low-temperature bake activating process.Its technology is easy, manufacturing cost is lower, product can be widely used in the waste water that fields such as handling building materials, weaving, medical and health, chemical industry produces, not only solved the pollution problem that the stacking of a large amount of Ti-containing slags brings to environment, and developing and using limited titanium resource more effectively, have good social benefit and economic benefit.
Marked improvement of the present invention is, prepared STBBFS photochemical catalyst excites at visible light (wave-length coverage 400-700nm) just stronger light absorption and photoresponse down, realized absorption in full to visible light, thereby significantly improved the photocatalytic activity of STBBFS, make that titanium-containing blast furnace slag is that the photochemical catalyst of feedstock production can utilize visible light sources such as sunshine, organic and inorganic pollutant in the effective light degradation water, and have higher energy conversion efficiency, for solid theories and practical basis are laid in the practical application of sunlight catalytic degradation of contaminant.
STBBFS photochemical catalyst with this method preparation all has stronger light absorption and photoresponse under ultraviolet light and radiation of visible light, can be under ultraviolet light and radiation of visible light the complex system of the inorganic heavy metal wastewater thereby of catalytic degradation and the coexistence of organic and inorganic pollutant effectively.In addition, replace pure TiO2 as catalysis material with containing titanium blast furnace slag, can make full use of the existing solid waste of China, not only reduce the cost of catalysis material, and find the reasonable use approach for the titanium-containing blast furnace slag of China's bulk deposition, reach the purpose of the treatment of wastes with processes of wastes against one another, have great economic implications and social benefit.
Description of drawings
Fig. 1 is the degradation rate of catalyst prod under mercury lamp and xenon lamp condition of the embodiment of the invention 1,2,3,4,1# is the catalyst of embodiment 1 preparation among the figure, 2# is the catalyst of embodiment 2 preparations, and 3# is the catalyst of embodiment 3 preparations, and 4# is the catalyst of embodiment 4 preparations; A is a mercury lamp, and b is an xenon lamp.
Fig. 2 is the ultraviolet-visible diffuse reflection absorption spectrum of the catalyst prod of the embodiment of the invention 1,2,3,4, as can be seen from Figure, behind the doped sulfuric acid ammonium, spectral response range and the light absorpting ability of STBBFS have been widened, especially the ammonium sulfate doping is 5% o'clock, and STBBFS has stronger light absorpting ability in ultraviolet and visibility region.
Fig. 3 is the degradation rate of catalyst prod under mercury lamp and xenon lamp condition of the embodiment of the invention 5,6,7,8,5# is the catalyst of embodiment 5 preparations among the figure, 6# is the catalyst of embodiment 6 preparations, and 7# is the catalyst of embodiment 7 preparations, and 8# is the catalyst of embodiment 8 preparations; A is a mercury lamp, and b is an xenon lamp.
Fig. 4 is the ultraviolet-visible diffuse reflection absorption spectrum of the embodiment of the invention 5,6,7,8, as can be seen from Figure, compares with 1# sample among Fig. 2, behind the doped sulfuric acid ammonium, has widened spectral response range and the light absorpting ability of STBBFS.
Fig. 5 is the X ray diffracting spectrum of the catalyst prod of the embodiment of the invention 4, among the figure ▲ and perovskite; The ★ diopside; ◆ akermanite-submellite.
The specific embodiment
Below in conjunction with the concrete specific embodiment content of the present invention is described further and replenishes.
The titanium-containing blast furnace slag that the present invention adopts comes from the blast furnace slag of Panzhihua Iron, and its chemical composition is for containing TiO
223.16wt%, Fe 1.85wt%, SiO
224.01wt%, MgO 7.47wt%, Al
2O
313.49wt%, CaO 27.19wt%, V
2O
50.23wt%, mineral composition is perovskite (CaTiO
3) 39wt%, diopside (Ca (Mg, and Al) (Si, Al)
2O
6) 51wt%, akermanite-submellite (Ca
2(Mg
0.5Al
0.5) (Si
1.5Al
0.5O
7)) 10wt%.
The ammonium sulfate that adopts in the embodiment of the invention is general industry ammonium sulfate, and nitrogen content is greater than 21%.
The ball mill that adopts in the embodiment of the invention is Φ 1200 * 2400 type ball mills.
The roasting apparatus that adopts in the embodiment of the invention is a muffle furnace.
Be adopted as UV-2550 type ultraviolet-uisible spectrophotometer in the embodiment of the invention, analyze the UV, visible light diffuse reflection spectrum of variation of Cr VI solution concentration and sample.
Adopt X ' PertHighScorePlus software in the embodiment of the invention, the crystal phase structure of analytic sample also utilizes the crystal content of semi-quantitative analysis method analytic sample, and analytical instrument is a D/max-2550PC type polycrystalline X-ray diffractometer.
Adopt the full-automatic BET specific surface of F-Sorb2400 (amassing) analysis tester, the specific area of analytic sample in the embodiment of the invention.
Adopt SDT2960SimultaneousDSC-TGA in the embodiment of the invention, the mass change of ammonium sulfate in the analytic sample.
Preparation does not add the catalyst of ammonium sulfate.
With the titanium-containing blast furnace slag fragmentation, obtaining diameter is the titanium-containing blast furnace slag powder of 1.0mm.
With levigate its average grain diameter of titanium-containing blast furnace slag powder of ball mill less than (perhaps being 0.5～2 micron) below 2 microns.
Titanium-containing blast furnace slag powder behind the ball milling is put into the muffle furnace roasting, sintering temperature is under 300～700 ℃, and roasting time is 1～4 hour, and roasting finishes the back and be cooled to room temperature in air, obtain the not TBBFS photochemical catalyst of doped sulfuric acid ammonium, its crystalline phase consists of and contains perovskite (CaTiO
3) 32.5wt%, contain diopside (Al
0.6Ca
1.0Mg
0.7O
6Si
1.7) 59wt%, contain akermanite-submellite (AlCa
2Mg
0.5O
7Si
1.5) 8.5wt%.
The method of the photocatalytic activity of evaluate catalysts sample is: the catalyst that takes by weighing 0.5g adds 1000ml and contains in the reservoir of Cr VI solution (mass concentration is 20mg/l), keep catalyst reactor by magnetic agitation and be in suspended state, make reactant liquor in reservoir and reactor, circulate (flow is 25ml/min) by peristaltic pump.Before carrying out light-catalyzed reaction, stirring reaction liquid no longer changes up to solution concentration in the dark, reaches till absorption/desorption balance.In the light-catalyzed reaction process, be radiation source with mercury lamp, xenon lamp respectively, take a sample every 60min.Sample through centrifugal, filter after, (λ max=540nm) locates at chromic maximum absorption wavelength, utilizes its absorbance of diphenylcarbazide colorimetric method for determining, and converts according to calibration curve and to become corresponding concentration.The catalytic activity of catalyst is estimated by measuring Cr VI photocatalytic degradation efficient.Computing formula is:
C in the formula
0' for reaching concentration after the adsorption equilibrium as the initial concentration of light-catalyzed reaction; C
tBe the concentration of hexavalent chromium in the t moment reaction liquid, η is a Cr VI photocatalytic degradation efficient.Cr VI photocatalytic degradation efficient is high more, then explanation, and under mercury lamp or xenon lamp irradiation, the sample of preparation is high more at the photocatalytic activity of ultraviolet or visibility region, is easy to degradation of contaminant more.
The method of evaluate catalysts sample maximum adsorption capacity is: utilize the acquisition Langmuir adsorption isotherm after the linear regression, the inverse of its slope is maximum adsorption capacity.Computing formula is:
C
e/q
e＝1/Q
0K+C
e/Q
0
Q in the formula
e(mg/g) be C for the adsorption equilibrium mass concentration
e(mg/l) adsorbance the time; Q
0Adsorbance when expiring the adsorbate monolayer, i.e. maximum adsorption capacity for every gram adsorbent surface lid; C
eBe balance mass concentration; K is a binding constant.
The method of assess sample light absorpting ability is: the UV, visible light diffuse reflection spectrum of prepared photochemical catalyst is measured on day island proper Tianjin UV-2550 type UV-Vis spectrophotometer, adopts little integrating sphere annex, with standard BaSO
4Powder is as reference, and sweep limits is 240-800nm.In actual applications, absorbance method commonly used characterizes the absorbing properties of photochemical catalyst.Definition reflection absorbance is
Wherein R is the irreflexive reflectivity of sample, and A is the reflection absorbance.
The crystal phase structure of assess sample and the method for crystal content are: adopt the crystal phase structure of X ' PertHighScorePlus software analysis sample and utilize the crystal content of semi-quantitative analysis method analytic sample.
The specific area of the TBBFS photochemical catalyst of doped sulfuric acid ammonium is not 9.4m
2/ g, maximum adsorption capacity are 3.1mg/g.
The absorbance located in ultraviolet (365nm) of the TBBFS of doped sulfuric acid ammonium (titanium-containing blast furnace slag) photochemical catalyst is not 0.58355, and the absorbance of locating at visible (400nm) is 0.50282.
The TBBFS photochemical catalyst of doped sulfuric acid ammonium does not have photocatalytic activity preferably under the radiation of mercury lamp (ultraviolet source), degradation rate 39.8%, and under the radiation of xenon lamp (visible light source), photocatalytic activity is relatively poor, degradation rate 13.2%.
With the titanium-containing blast furnace slag fragmentation, obtaining diameter is the titanium-containing blast furnace slag powder of 0.5mm.
With the titanium-containing blast furnace slag powder after ammonium sulfate and the fragmentation, mixed proportion accounts for the 2.5wt% of titanium-containing blast furnace slag powder by ammonium sulfate.
With the mixture of levigate titanium-containing blast furnace slag powder of ball mill and ammonium sulfate, obtain mixed-powder, its average grain diameter is less than 2 microns.
Mixed-powder is put into the muffle furnace roasting, and sintering temperature is under 300 ℃, and roasting time is 4 hours, and roasting finishes the back and be cooled to room temperature in air, obtains to have the STBBFS catalyst of visible light catalysis activity, and its crystalline phase consists of and contains perovskite (CaTiO
3) 34wt%, contain diopside (Al
0.6Ca
1.0Mg
0.7O
6Si
1.7) 58wt%, contain akermanite-submellite (AlCa
2Mg
0.5O
7Si
1.5) 8wt%.
This has undecomposed (NH in the STBBFS catalyst of visible light catalysis activity
4)
2SO
4Be 1.05wt%.
The specific area of the STBBFS catalyst of preparation is 12.9m
2/ g, maximum adsorption capacity are 5.2mg/g.
The absorbance that the STBBFS catalyst of preparation is located in ultraviolet (365nm) is 0.71829, and the absorbance of locating at visible (400nm) is 0.60771.
The catalyst activity evaluation method is with embodiment 1, and the degradation rate of STBBFS catalyst under the radiation of mercury lamp (ultraviolet source) of preparation is 41.8%, and the degradation rate under the radiation of xenon lamp (visible light source) is 31.3%.
With the titanium-containing blast furnace slag fragmentation, obtaining diameter is the titanium-containing blast furnace slag powder of 0.7mm.
With the titanium-containing blast furnace slag powder after ammonium sulfate and the fragmentation, mixed proportion accounts for the 7.5wt% of titanium-containing blast furnace slag powder by ammonium sulfate.
With the mixture of levigate titanium-containing blast furnace slag powder of ball mill and ammonium sulfate, obtain mixed-powder, its average grain diameter is less than 2 microns.
Mixed-powder is put into the muffle furnace roasting, and sintering temperature is under 300 ℃, and roasting time is 4 hours, and roasting finishes the back and be cooled to room temperature in air, obtains to have the STBBFS catalyst of visible light catalysis activity, and its crystalline phase consists of and contains perovskite (CaTiO
3) 36wt%, contain diopside (Al
0.6Ca
1.0Mg
0.7O
6Si
1.7) 56.1wt%, contain akermanite-submellite (AlCa
2Mg
0.5O
7Si
1.5) 7.9wt%.
This has undecomposed (NH in the STBBFS catalyst of visible light catalysis activity
4)
2SO
4Be 5.75wt%.
The specific area of the STBBFS catalyst of preparation is 17.3m
2/ g, maximum adsorption capacity are 7.0mg/g.
The absorbance that the STBBFS catalyst of preparation is located in ultraviolet (365nm) is 0.7758, and the absorbance of locating at visible (400nm) is 0.64047.
The catalyst activity evaluation method is with embodiment 1, and the degradation rate of STBBFS catalyst under the radiation of mercury lamp (ultraviolet source) of preparation is 56%, and the degradation rate under the radiation of xenon lamp (visible light source) is 44.3%.
With the titanium-containing blast furnace slag fragmentation, obtaining diameter is the titanium-containing blast furnace slag powder of 0.9mm.
With the titanium-containing blast furnace slag powder after ammonium sulfate and the fragmentation, mixed proportion accounts for the 5wt% of titanium-containing blast furnace slag powder by ammonium sulfate.
With the mixture of levigate titanium-containing blast furnace slag powder of ball mill and ammonium sulfate, obtain mixed-powder, its average grain diameter is less than 2 microns.
Mixed-powder is put into the muffle furnace roasting, and sintering temperature is under 300 ℃, and roasting time is 4 hours, roasting finishes the back and be cooled to room temperature in air, acquisition has the STBBFS catalyst of visible light catalysis activity, and its crystalline phase consists of and contains perovskite (CaTiO as shown in Figure 5
3) 38wt%, contain diopside (Al
0.6Ca
1.0Mg
0.7O
6Si
1.7) 53.5wt%, contain akermanite-submellite (AlCa
2Mg
0.5O
7Si
1.5) 8.5wt%.
This has undecomposed (NH in the STBBFS catalyst of visible light catalysis activity
4)
2SO
4Be 3.65wt%.
The specific area of the STBBFS catalyst of preparation is 20.5m
2/ g, maximum adsorption capacity are 8.3mg/g.
The absorbance that the STBBFS catalyst of preparation is located in ultraviolet (365nm) is 0.89059, and the absorbance of locating at visible (400nm) is 0.73528.
The catalyst activity evaluation method is with embodiment 1, and the degradation rate of STBBFS catalyst under the radiation of mercury lamp (ultraviolet source) of preparation is 66.3%, and the degradation rate under the radiation of xenon lamp (visible light source) is 59.3%.
According to X-ray diffraction analysis, behind the doped sulfuric acid ammonium, each crystal content difference of catalyst prod is little, especially crucial mineral composition, and perovskite content is more or less the same; Degradation rate and the ultraviolet-visible diffuse reflection absorption spectrum of catalyst prod under mercury lamp and xenon lamp condition of the contrast embodiment of the invention 1,2,3,4, as can be seen from Figure, behind the doped sulfuric acid ammonium, spectral response range and the light absorpting ability of STBBFS have been widened, especially the ammonium sulfate doping is 5% o'clock, STBBFS has stronger light absorpting ability in ultraviolet and visibility region, thereby has higher photocatalytic degradation efficient.In addition, behind the doped sulfuric acid ammonium, the specific area of catalyst prod, maximum adsorption capacity all increase to some extent.
With the titanium-containing blast furnace slag fragmentation, obtaining diameter is the titanium-containing blast furnace slag powder of 1.1mm.
With the titanium-containing blast furnace slag powder after ammonium sulfate and the fragmentation, mixed proportion accounts for the 5wt% of titanium-containing blast furnace slag powder by ammonium sulfate.
With the mixture of levigate titanium-containing blast furnace slag powder of ball mill and ammonium sulfate, obtain mixed-powder, its average grain diameter is less than 2 microns.
Mixed-powder is put into the muffle furnace roasting, and sintering temperature is under 400 ℃, and roasting time is 3 hours, and roasting finishes the back and be cooled to room temperature in air, obtains to have the STBBFS catalyst of visible light catalysis activity, and its crystalline phase consists of and contains perovskite (CaTiO
3) 38.5wt%, contain diopside (Al
0.6Ca
1.0Mg
0.7O
6Si
1.7) 53.3wt%, contain akermanite-submellite (AlCa
2Mg
0.5O
7Si
1.5) 8.2wt%.
This has undecomposed (NH in the STBBFS catalyst of visible light catalysis activity
4)
2SO
4Be 2.94wt%.
The specific area of the STBBFS catalyst of preparation is 18.7m
2/ g, maximum adsorption capacity are 7.6mg/g.
The absorbance that the STBBFS catalyst of preparation is located in ultraviolet (365nm) is 0.66069, and the absorbance of locating at visible (400nm) is 0.575.
The catalyst activity evaluation method is with embodiment 1, and the degradation rate of STBBFS catalyst under the radiation of mercury lamp (ultraviolet source) of preparation is 55%, and the degradation rate under the radiation of xenon lamp (visible light source) is 46%.
With the titanium-containing blast furnace slag fragmentation, obtaining diameter is the titanium-containing blast furnace slag powder of 1.3mm.
With the titanium-containing blast furnace slag powder after ammonium sulfate and the fragmentation, mixed proportion accounts for the 5wt% of titanium-containing blast furnace slag powder by ammonium sulfate.
With the mixture of levigate titanium-containing blast furnace slag powder of ball mill and ammonium sulfate, obtain mixed-powder, its average grain diameter is less than 2 microns.
Mixed-powder is put into the muffle furnace roasting, and sintering temperature is under 500 ℃, and roasting time is 2 hours, and roasting finishes the back and be cooled to room temperature in air, obtains to have the STBBFS catalyst of visible light catalysis activity, and its crystalline phase consists of and contains perovskite (CaTiO
3) 39wt%, contain diopside (Al
0.6Ca
1.0Mg
0.7O
6Si
1.7) 51.8wt%, contain akermanite-submellite (AlCa
2Mg
0.5O
7Si
1.5) 9.2wt%.
This has undecomposed (NH in the STBBFS catalyst of visible light catalysis activity
4)
2SO
4Be 2.68wt%.
The specific area of the STBBFS catalyst of preparation is 12.7m
2/ g, maximum adsorption capacity are 5.8mg/g.
The absorbance that the STBBFS catalyst of preparation is located in ultraviolet (365nm) is 0.71829, and the absorbance of locating at visible (400nm) is 0.60771.
The catalyst activity evaluation method is with embodiment 1, and the degradation rate of STBBFS catalyst under the radiation of mercury lamp (ultraviolet source) of preparation is 45.8%, and the degradation rate under the radiation of xenon lamp (visible light source) is 38%.
With the titanium-containing blast furnace slag fragmentation, obtaining diameter is the titanium-containing blast furnace slag powder of 1.5mm.
With the titanium-containing blast furnace slag powder after ammonium sulfate and the fragmentation, mixed proportion accounts for 2.5～7.5wt% of titanium-containing blast furnace slag powder by ammonium sulfate.
With the mixture of levigate titanium-containing blast furnace slag powder of ball mill and ammonium sulfate, obtain mixed-powder, its average grain diameter is less than 2 microns.
Mixed-powder is put into the muffle furnace roasting, and sintering temperature is under 600 ℃, and roasting time is 1 hour, and roasting finishes the back and be cooled to room temperature in air, obtains to have the STBBFS catalyst of visible light catalysis activity, and its crystalline phase consists of and contains perovskite (CaTiO
3) 40wt%, contain diopside (Al
0.6Ca
1.0Mg
0.7O
6Si
1.7) 51.5wt%, contain akermanite-submellite (AlCa
2Mg
0.5O
7Si
1.5) 8.5wt%.
This has undecomposed (NH in the STBBFS catalyst of visible light catalysis activity
4)
2SO
4Be 2.65wt%.
The specific area of the STBBFS catalyst of preparation is 10.3m
2/ g, maximum adsorption capacity are 4.3mg/g.
The absorbance that the STBBFS catalyst of preparation is located in ultraviolet (365nm) is 0.7758, and the absorbance of locating at visible (400nm) is 0.64047.
The catalyst activity evaluation method is with embodiment 1, and the degradation rate of STBBFS catalyst under the radiation of mercury lamp (ultraviolet source) of preparation is 41.5%, and the degradation rate under the radiation of xenon lamp (visible light source) is 32%.
With the titanium-containing blast furnace slag fragmentation, obtaining diameter is the titanium-containing blast furnace slag powder of 1.0mm.
With the titanium-containing blast furnace slag powder after ammonium sulfate and the fragmentation, mixed proportion accounts for the 5wt% of titanium-containing blast furnace slag powder by ammonium sulfate.
With the mixture of levigate titanium-containing blast furnace slag powder of ball mill and ammonium sulfate, obtain mixed-powder, its average grain diameter is less than 2 microns.
Mixed-powder is put into the muffle furnace roasting, and sintering temperature is under 700 ℃, and roasting time is 1 hour, and roasting finishes the back and be cooled to room temperature in air, obtains to have the STBBFS catalyst of visible light catalysis activity, and its crystalline phase consists of and contains perovskite (CaTiO
3) 39wt%, contain diopside (Al
0.6Ca
1.0Mg
0.7O
6Si
1.7) 53.1wt%, contain akermanite-submellite (AlCa
2Mg
0.5O
7Si
1.5) 7.9wt%.
This has undecomposed (NH in the STBBFS catalyst of visible light catalysis activity
4)
2SO
4Be 2.57wt%.
The specific area of the STBBFS catalyst of preparation is 9.7m
2/ g, maximum adsorption capacity are 3.9mg/g.
The absorbance that the STBBFS catalyst of preparation is located in ultraviolet (365nm) is 0.8247, and the absorbance of locating at visible (400nm) is 0.69374.
The catalyst activity evaluation method is with embodiment 1, and the degradation rate of STBBFS catalyst under the radiation of mercury lamp (ultraviolet source) of preparation is 39.2%, and the degradation rate under the radiation of xenon lamp (visible light source) is 30%.
Claims (3)
1, a kind of modified titanium-containing furnace cinder catalyst with visible light catalysis activity, it is characterized in that: the crystalline phase of this catalyst consists of and contains perovskite 33～40wt%, diopside 50～59wt%, akermanite-submellite 7～10wt%, and sulfur acid ammonium 1～6wt%, specific area is 9.7～20.5m
2/ g, maximum adsorption capacity are 3.9～8.3mg/g.
2, a kind of preparation method with modified titanium-containing furnace cinder catalyst of visible light catalysis activity is characterized in that may further comprise the steps: (1) with the titanium-containing blast furnace slag fragmentation, obtaining diameter is the titanium-containing blast furnace slag powder of 0.5～1.5mm; (2) with the titanium-containing blast furnace slag powder after ammonium sulfate and the fragmentation, mixed proportion accounts for 2.5～7.5wt% of titanium-containing blast furnace slag powder by ammonium sulfate; (3) mixture of levigate titanium-containing blast furnace slag powder and ammonium sulfate to average grain diameter less than 2 microns, obtain mixed-powder; (4) with the mixed-powder roasting, sintering temperature is under 300～700 ℃, and roasting time is 1～4 hour, and roasting is cooled to room temperature after finishing, and obtains to have the modified titanium-containing furnace cinder catalyst of visible light catalysis activity.
3,, it is characterized in that described titanium-containing blast furnace slag contains TiO according to the described preparation method of claim 2 with modified titanium-containing furnace cinder catalyst of visible light catalysis activity
216～25wt%.
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| CNA2008102289307A CN101402036A (en) | 2008-11-21 | 2008-11-21 | Modified titanium-containing furnace cinder catalyst with visible light catalytic activity and method for producing the same |
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| CN101879433A (en) * | 2010-07-10 | 2010-11-10 | 内蒙古科技大学 | Improved water quenching slag adsorbent and preparation method thereof |
| CN102247894A (en) * | 2011-05-26 | 2011-11-23 | 东北大学 | Rhodamine B-doped modified titanium concentrate photocatalyst and preparation method thereof |
| CN102247893A (en) * | 2011-05-26 | 2011-11-23 | 东北大学 | Rose Bengal-doped modified titanium concentrate photocatalyst and preparation method thereof |
| CN109133651A (en) * | 2018-11-13 | 2019-01-04 | 西南科技大学 | It is a kind of by mentioning the devitrified glass that titanium slag is prepared containing chlorine |
| CN111001376A (en) * | 2019-12-30 | 2020-04-14 | 北京工业大学 | SiO for efficiently adsorbing copper ions2-Al2O3Preparation method of-CaO-MgO quaternary system adsorbent |
| CN112521142A (en) * | 2020-12-08 | 2021-03-19 | 西南科技大学 | Photocatalytic ceramic, preparation method thereof and method for degrading organic dye RhB |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101879433A (en) * | 2010-07-10 | 2010-11-10 | 内蒙古科技大学 | Improved water quenching slag adsorbent and preparation method thereof |
| CN102247894A (en) * | 2011-05-26 | 2011-11-23 | 东北大学 | Rhodamine B-doped modified titanium concentrate photocatalyst and preparation method thereof |
| CN102247893A (en) * | 2011-05-26 | 2011-11-23 | 东北大学 | Rose Bengal-doped modified titanium concentrate photocatalyst and preparation method thereof |
| CN109133651A (en) * | 2018-11-13 | 2019-01-04 | 西南科技大学 | It is a kind of by mentioning the devitrified glass that titanium slag is prepared containing chlorine |
| CN109133651B (en) * | 2018-11-13 | 2022-02-11 | 西南科技大学 | Microcrystalline glass prepared from chlorine-containing titanium extraction slag |
| CN111001376A (en) * | 2019-12-30 | 2020-04-14 | 北京工业大学 | SiO for efficiently adsorbing copper ions2-Al2O3Preparation method of-CaO-MgO quaternary system adsorbent |
| CN111001376B (en) * | 2019-12-30 | 2022-05-17 | 北京工业大学 | SiO for efficiently adsorbing copper ions2-Al2O3Preparation method of-CaO-MgO quaternary system adsorbent |
| CN112521142A (en) * | 2020-12-08 | 2021-03-19 | 西南科技大学 | Photocatalytic ceramic, preparation method thereof and method for degrading organic dye RhB |
| CN112521142B (en) * | 2020-12-08 | 2022-04-26 | 西南科技大学 | Photocatalytic ceramic, preparation method thereof and method for degrading organic dye RhB |
| CN114373918A (en) * | 2022-01-12 | 2022-04-19 | 河北科技大学 | Silicon-carbon negative electrode material and preparation method thereof |
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