CN105032174A - Application of photo-catalytic coating particles in decomposition of air pollutants - Google Patents
Application of photo-catalytic coating particles in decomposition of air pollutants Download PDFInfo
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- CN105032174A CN105032174A CN201510208409.7A CN201510208409A CN105032174A CN 105032174 A CN105032174 A CN 105032174A CN 201510208409 A CN201510208409 A CN 201510208409A CN 105032174 A CN105032174 A CN 105032174A
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- cement
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- ferric oxide
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 62
- 239000002245 particle Substances 0.000 title claims abstract description 52
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 27
- 239000000809 air pollutant Substances 0.000 title claims abstract description 23
- 231100001243 air pollutant Toxicity 0.000 title claims abstract description 23
- 239000011248 coating agent Substances 0.000 title abstract description 4
- 238000000576 coating method Methods 0.000 title abstract description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 255
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 77
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 69
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 32
- 239000004568 cement Substances 0.000 claims description 75
- 238000007146 photocatalysis Methods 0.000 claims description 33
- 239000004567 concrete Substances 0.000 claims description 19
- 239000003973 paint Substances 0.000 claims description 19
- 239000004035 construction material Substances 0.000 claims description 15
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 6
- 235000019738 Limestone Nutrition 0.000 claims description 3
- 239000010440 gypsum Substances 0.000 claims description 3
- 229910052602 gypsum Inorganic materials 0.000 claims description 3
- 239000006028 limestone Substances 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 239000012855 volatile organic compound Substances 0.000 abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 45
- 239000000049 pigment Substances 0.000 description 36
- 230000003647 oxidation Effects 0.000 description 30
- 238000007254 oxidation reaction Methods 0.000 description 30
- 230000003197 catalytic effect Effects 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 24
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 22
- 229910052742 iron Inorganic materials 0.000 description 19
- 239000000463 material Substances 0.000 description 17
- 239000007789 gas Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 230000032683 aging Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000004576 sand Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000002186 photoactivation Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000002079 cooperative effect Effects 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000001034 iron oxide pigment Substances 0.000 description 3
- VGQXTTSVLMQFHM-UHFFFAOYSA-N peroxyacetyl nitrate Chemical compound CC(=O)OO[N+]([O-])=O VGQXTTSVLMQFHM-UHFFFAOYSA-N 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000000306 recurrent effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- NJVOHKFLBKQLIZ-UHFFFAOYSA-N (2-ethenylphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1C=C NJVOHKFLBKQLIZ-UHFFFAOYSA-N 0.000 description 1
- CNSKBOOEAKAYDJ-UHFFFAOYSA-N C1=CC=CC=C1.CC1=CC=CC=C1.CCC1=CC=CC=C1.CC1=CC=CC=C1C Chemical group C1=CC=CC=C1.CC1=CC=CC=C1.CCC1=CC=CC=C1.CC1=CC=CC=C1C CNSKBOOEAKAYDJ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 208000004852 Lung Injury Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N Nitrogen oxide(NO) Natural products O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 206010069363 Traumatic lung injury Diseases 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 238000011481 absorbance measurement Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 231100000515 lung injury Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009325 pulmonary function Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 201000008827 tuberculosis Diseases 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
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Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to an application of photo-catalytic coating particles in decomposition of air pollutants and particularly, relates to the application that ferric oxide particles at least partially coated with titanium dioxide is used for photo-catalytically decomposing air pollutants, selected from nitrogen oxide (NOx) and volatile organic compounds (VOC), which are contacted with the particles.
Description
The divisional application that the application is the applying date is on March 31st, 2008, application number is 200880128190.8, denomination of invention is the application of " photocatalysis coated particle is for decomposing the purposes of air pollutants " (PCT/EP2008/053854, enter State Period date on March 31st, 2008).
Technical field
The present invention relates to the purposes of the ferric oxide particles being coated with titanium dioxide, in particular to the purposes of its photocatalysis Decomposition air pollutants.
Background technology
In recent years, the pollution of air, water and soil becomes hot issue, especially in urban area.Air pollutants mainly through production process as industrial activity or combustion process such as heating, generating and motor vehicles are discharged in environment.These pollutants can encourage urban air-quality problem such as photochemical fog, and adversely affect the health of human health and other biology.
Two overall situation polluters comprise nitrogen oxide (NO
x) and VOC (VOC).Especially, these compounds are dangerous, because they cause the formation of secondary pollution material.NO is worked as in formation due to most of Tropospheric ozone
xoccur when reacting in an atmosphere under the existence of daylight and carbon monoxide with VOC, therefore NO
xwith VOC also referred to as ozone precursors.In addition, NO
xcause with the reaction of VOC under the existence of daylight the photochemical fog containing especially peroxyacetyl nitrate (PAN) (PAN), this is a kind of air pollution of important form, especially in summer.Children, tuberculosis is as asthmatic patient and work out of doors or the people that takes exercise is easy to be subject to the adverse effect of photochemical fog, such as lung injury and decline in pulmonary function.
Various solution is proposed to reduce the concentration of environmental air polluter.
WO02/38272 discloses a kind of photocatalysis film, and described film has oxidisability to toluene and the deodorizing being suitable for indoor environment and the purification of air-flow of being polluted by VOC.
WO2006/000565 describes one to air pollutants as NO
xhave the construction material of photocatalytic activity, wherein photocatalytic activity comes from the TiO with cement physical mixed
2the existence of nano particle.
US6136186 describes a kind of photo catalysis reactor for being oxidized the organic pollution from gas or water, and photochemical catalyst is wherein the final TiO doped with another metallic catalyst be formed on porous surface
2or binary TiO
2the porous layer of oxide or surface.
WO2006/008434 describes a kind of coating of titanium dioxide with VOC degraded and automatically cleaning and anti-microbial properties.
EP1559753 relates to a kind of TiO containing anatase form
2photocatalysis potassium silicate paint.Described paint is designed in inhabitation and public building to give the automatically cleaning character of antipollution thing.
Still to need to have in the decomposition environment of raising polluter as nitrogen oxide (NO
x) and the material of ability of VOC (VOC).
Summary of the invention
An object of the present invention is to provide a kind of photocatalytic activity material of effective decomposition air pollutants.The present invention relates to provides and uses suitable material to carry out photocatalysis Decomposition to be selected from nitrogen oxide (NO
x) and the air pollutants of VOC (VOC).Another object of the present invention in construction material, uses this material decompose to be selected from NO
xwith the air pollutants of VOC.Another object of the present invention in paint, uses this material decompose to be selected from NO
xwith the air pollutants of VOC.
Another object of the present invention is to provide and uses suitable material to be selected from nitrogen oxide (NO to reduce photocatalysis Decomposition
x) and VOC (VOC) air pollutants process in photoetch.
In addition, the present invention relates to use and be coated with the ferric oxide particles of titanium dioxide at least partly to reduce NO
2the mode photocatalysis Decomposition NO generated.
In addition, the present invention relates to ferric oxide particles that use is coated with titanium dioxide at least partly to carry out photocatalysis Decomposition and be selected from nitrogen oxide (NO
x) and the air pollutants of VOC (VOC).
In addition, the present invention relates to use and be coated with the ferric oxide particles of titanium dioxide photocatalysis Decomposition NO under UV and/or visible ray at least partly.
In addition, the present invention relates to use and be coated with the ferric oxide particles of titanium dioxide photocatalysis Decomposition VOC under UV and/or visible ray at least partly.
These and other object of the present invention is resolved by the purposes described in claim.Preferred embodiment derives from the combination of the feature of dependent claims and the feature of independent claims.
Accompanying drawing explanation
Fig. 1 shows the schematic diagram of the experimental provision (10) being applicable to nitrogen conversion test.Sample (40) is placed in the cell (50) of 3.6l, the test gas obtained from cylinder (20) with the flow of 1.5l/ minute by cell (50).The selected light (30) that utilization is arranged on cell (50) top irradiates sample by glass cover (60).Gas chromatograph (70) is used to analyze the concentration of NO in gas continuously.
Fig. 2 shows NO, NO of the sample a of embodiment 1
2, NO
xand O
3transform the relation with irradiation time, sample a is containing the photochemical catalytic oxidation iron of 6% and the concrete segment of standard cement.
Fig. 3 and Fig. 4 to respectively illustrate described in embodiment 34 samples before ageing, NO and NO that record after 96 hours and after 192 hours
2photocatalytic conversion.Sample 1 is not containing the photo catalytic cement of pigment; Sample 2 is the photo catalytic cement containing standard oxidation iron oxide yellow (3.8wt% for total cement weight); Sample 3 for content be that the photochemical catalytic oxidation iron 1 of the 6.8wt% of total cement weight is (containing the TiO of the 45wt% of total pigment weight
2) standard cement; Sample 4 for content be that the photochemical catalytic oxidation iron 2 of the 6.8wt% of total cement weight is (containing the TiO of the 45wt% of total pigment weight
2) standard cement.
Fig. 5 and Fig. 6 respectively illustrates the sample 2 of embodiment 2 and NO, NO of sample 3
2, NO
xand O
3transform the relation with UV irradiation time.Sample 2 is the colored block that photoactivation cement and standard iron oxide are made, and sample 3 is the colored block that photoactivation pigment and standard cement are made.
Fig. 7 shows Fe (II) the light dissolution data of three kinds of different samples of embodiment 3.Fe (II) concentration in the water extract that the concrete sample that curve shows different duration under being exposed to NO and UV light as described in example 3 above obtains.Sample a is the cement containing Ferroxide48 (3wt%); Sample b is content is that the photochemical catalytic oxidation iron of the 5wt% of total cement weight is (containing the TiO of the 21wt% of total pigment weight
2); Sample c is the photo catalytic cement containing Ferroxide48 (3%).
Fig. 8 and Fig. 9 respectively illustrates the conversion under w light of VOC in four kinds of different sample situations of embodiment 4 and average transformation.Fig. 8 shows VOC conversion under w light as described in example 4 above.Sample a is not containing the photo catalytic cement of pigment; Sample b is the photo catalytic cement containing standard oxidation iron oxide yellow (3.8wt% for total cement weight); Sample c is content is that the photochemical catalytic oxidation iron oxide yellow A of the 6.8wt% of total cement weight is (containing the TiO of the 45wt% of total pigment weight
2) standard cement; Sample d is content is that the photochemical catalytic oxidation iron oxide yellow B of the 6.8wt% of total cement weight is (containing the TiO of the 45wt% of total pigment weight
2) standard cement.Fig. 9 shows the cinnamic mixture of benzene, ethylbenzene, toluene and neighbour total conversion under w light as described in example 4 above.Sample a is not containing the photo catalytic cement of pigment; Sample b is the photo catalytic cement containing standard oxidation iron oxide yellow (3.8wt% for total cement weight); Sample c is content is that the photochemical catalytic oxidation iron oxide yellow A of the 6.8wt% of total cement weight is (containing the TiO of the 45wt% of total pigment weight
2) standard cement; Sample d is content is that the photochemical catalytic oxidation iron oxide yellow B of the 6.8wt% of total cement weight is (containing the TiO of the 45wt% of total pigment weight
2) standard cement.
Figure 10 shows and uses the photochemical catalytic oxidation iron of 5% (containing the TiO of the 23wt% of total pigment weight as described in example 6 above
2) NO, NO of painted silicate paint
2, NO
xand O
3transform the relation with irradiation time.
Detailed description of the invention
Surprisingly, find a kind of catalysis material of particular type, be coated with the ferric oxide particles of titanium dioxide, be particularly suited for air pollutants particularly NO
xdecompose with the high efficiency photocatalysis of VOC.
Be coated with the ferric oxide particles of titanium dioxide for photocatalysis Decomposition NO
xand/or the purposes of VOC is highly favourable, because it can be in the painted use of such as construction material, paint and paint field or in paper industry, the conventional pigment for painted application provides photocatalysis property.
In addition observe, only reducing in time based on the photocatalytic activity of the photochemical catalyst of titanium dioxide of conventional use.Use when being coated with the iron particle of titanium dioxide, photocatalysis titanium dioxide and pigment more stable under UV and radiation of visible light, thus make the life-span of pigment and photochemical catalyst longer.In addition, use the ferric oxide particles being coated with titanium dioxide as degraded NO
xand/or during the photochemical catalyst of VOC, the wider illumination spectra from UV to visible ray can be used.This is presumably because caused by the cooperative effect between iron oxide and titanium dioxide.
In addition, use the ferric oxide particles being coated with titanium dioxide as degraded NO
xand/or during the photochemical catalyst of VOC, recurrent NO in the degradation process of NO
2generate and significantly reduce.Use and to record during these catalysis materials and observe at NO
xexistence under in UV and radiation of visible light process contingent ozone generate and will be restricted.
In one embodiment of the invention, nitrogen oxide (NO is selected from for photocatalysis Decomposition
x) and the ferric oxide particles of air pollutants of VOC (VOC) be coated with titanium dioxide at least partly.In another embodiment of the present invention, nitrogen oxide (NO is selected from for photocatalysis Decomposition
x) and the ferric oxide particles of air pollutants of VOC (VOC) be coated with titanium dioxide completely.
Titanium dioxide can be randomly distributed on the surface of particulate inorganic material, such as, with the form of denser or more not densely distributed crystalline temperature, and the nanoscale crystallite of preferred titanium dioxide.As an alternative, under higher carrying capacity, titanium dioxide also can form the crystalline material of larger area in carrier particle surface, until cover substantially completely.
In an exemplary of purposes of the present invention, the ferric oxide particles being coated with titanium dioxide is at least partly introduced in construction material.Such as, described particle can be mixed with construction material.In another exemplary of purposes of the present invention, the ferric oxide particles being coated with titanium dioxide is at least partly coated on construction material.Such as, can with the form of water based paint or paint by described particle coating on construction material.Construction material of the present invention can comprise inorganic material as concrete, cement, mortar, lime stone or gypsum.
In another exemplary of purposes of the present invention, the ferric oxide particles being coated with titanium dioxide is at least partly introduced in paint.Such as, described particle can be mixed with paint or is dispersed in paint.Described paint can comprise such as based on the paint of silicate, acrylic paint, paint or water-based paints.
Particle for purposes described in the present invention applies for the method preparation described in PCT/EP2006/068245 by such as applicant is co-pending, wherein such as by the aqueous solution of inorganic oxide iron dispersion and at least one titanyl salt (as titanyl sulfate, titanium chloride or titanium oxyoxalate) and by add alkali and as described in precipitated titania on ferric oxide particles, wherein titanium oxide precipitates at least partly.Finally by such as filtering ferric oxide particles also washing and the low temperature drying subsequently of isolating from reactant mixture and being coated with photocatalytic activity compound.The particle diameter being applicable to the particle of purposes of the present invention can within the scope of 0.01-100 μm, and surface area can at about 5-200m
2within the scope of/g.For purposes of the present invention, described particle can provide with the form be shaped, such as particle, spherolite or sheet.
Do not wish to be bound by any theory, think and be exposed to the DT, polluter nitrogen oxide (NO
x) and VOC (VOC) can disintegration under the existence of ferric oxide particles being coated with titanium dioxide, produce and the interactional free radical of pollutant and/or other active material.This causes degraded or the decomposition reaction of these molecules, and such as oxides of nitrogen gas can be oxidized to nitrate, and significantly can reduce the concentration of this pollutant.Therefore, such as, on construction material, the concentration of these materials will reduce, thus keep the brightness of color for a long time, make the concentration of environmental pollutants in environment reduce in addition.In addition, air quality can improve, and produces anti-fogging effect.
The present inventor finds, and the ferric oxide particles being coated with titanium dioxide replaces the use of convention pigment in painted application to cause the long-time color fastness improved.In addition, the present inventor finds, the photoetch that the ferric oxide particles being coated with titanium dioxide goes out to reduce than regular oxidation iron pigment displays.Fig. 7 illustrates that the light of Fe (II) dissolves only for being obvious containing the cement block of standard iron oxide pigment, and is unconspicuous for the cement block containing the ferric oxide particles being coated with titanium dioxide.Therefore, the present invention also makes iron oxide pigment have long-time stability by reducing photoetch effect.
In addition, the present inventor finds, with the conventional photocatalysis Compound Phase ratio of use, uses the ferric oxide particles being coated with titanium dioxide can obtain the stability of higher conversion of nitric oxide gas with open-assembly time.As shown in Figures 5 and 6, in the process being exposed to UV, for the painted cement block made with the ferric oxide particles being coated with titanium dioxide, the painted cement block that the minimizing of conversion of nitric oxide gas does not comprise conventional photo catalytic cement and iron oxide pigment is obvious.In addition, Fig. 3 shows that the cement block made with the ferric oxide particles being coated with titanium is than showing higher conversion of nitric oxide gas stability with the cement block that painted photo catalytic cement is made.
In addition find, when use is coated with the ferric oxide particles of titanium dioxide, recurrent NO in photocatalytic process
2formed and significantly reduce than using during conventional photocatalysis compound.Do not wish to be bound by any theory, the present inventor thinks, at least some foregoing observations indicates the cooperative effect of iron oxide and titanium oxide when close contact.
Embodiment
conversion of nitrogen oxides is tested
The experimental provision (10) for nitrogen oxide (NO) conversion test is schematically shown in Fig. 1.Sample (40) is placed in the cell (50) of 3.6l, the test gas obtained from cylinder (20) with the flow of 1.5l/ minute by cell (50).The selected light (30) that utilization is arranged on cell (50) top irradiates sample by glass cover (60).
Use traffic is the synthesis humid air (79%N of 1.5l/ minute
2, 21%O
2, 50% relative humidity) with the mixture of the NO of 0.5ppmv as inlet gas.For testing under uv illumination, (within the scope of 290-400nm, radiant power is 40Wm to be used in the HgHP125 of UV district luminescence
-2) light irradiation sample.The concentration of NO in gas is analyzed continuously by gas chromatograph (70).
For testing under visible ray or UV-visible ray, irradiation source uses PhilipsPAR30S lamp respectively, and (100W, within the scope of 400-700nm, radiant power is 178Wm
-2) or XenonLOTOriel lamp (150W, runs under 140W, power is 25% of Philips lamp, 36% of Hg lamp).
Be converted into NO
2the percentage of NO be defined as:
NO transforms %=(C
nO entrance-C
nO exports)/C
nO entrance* 100
NO
2transform %=C
nO2 exports/ C
nO entrance* 100
NO
xfor NO non-in NO converted product
2part, be defined as:
NO
xtransform %=NO and transform %-NO
2transform %
vOC conversion test
Experimental provision is similar to above-mentioned NO conversion test, is collecting after in Cryo Equipment exit gas by (the every 30-40 minute) analysis in a non-continuous manner of gas QMS.Inlet gas is with the BTEX mixture (toluene of 13.5ppbv, the ethylbenzene of 23ppbv, the ortho-xylene of 20ppbv, the benzene of 20ppbv) of the total dividing potential drop of 76.5ppbv of flowing in 1.5l/ minute.
colorimetric measurement
Colorimetric measurement is carried out on concrete sample, uses the MinoltaKonicaDP301 be coupled with the illuminator CR310 with D65 lamp.Data CieLab scale represents.
For tinctorial strength, use Gardner-BYK colorimeter (45/0 measured angular).Tinctorial strength value is based on the difference under the reflectivity curve of given the test agent and standard sample between area.
concrete sample preparation method
Method 1: by mixing each pigment and white Portland cement (AquilaBiancaCEMII/B-LL32,5R), sand (Sibelco2, Sibelco5/RD) and water prepare concrete sample.Relative amount provides in the following table:
| Weight (g) | Based on ... wt% | |
| Sibelco 2 | 289 | 72.3 of total sand weight |
| Sibelco 5/RD | 111 | 27.7 of total sand weight |
| Water | 46.2 | 35 of total cement weight |
| Cement | 132 | 33 of total sand weight |
Sand, pigment and the water motor hybrids (BifinetKH203,230W, 5 speed) with a metal pulping device, speed 2 times mixing 30 seconds, then adds cement, mixes 30 seconds again 2 times in speed.Then scraper hand mix resulting materials is used, subsequently in speed 3 times electronic mixing 60 seconds again.This concrete mix is poured in the circular die of diameter 7cm.Sample in the baking oven of 110 DEG C in polybag inner drying two hours, then with dry 15 minutes of atmosphere.
In some tests, use photo catalytic cement (TXAriawhite) to replace Portland cement.Pigment as standard yellow iron oxide is the Ferroxide48 that RockwoodPigment produces.In ventilated drying oven after drying, by sample 90 DEG C and 95% relative humidity under aging 192 hours with the passivation of accelerated ageing.
Method 2: be mixed with sample to measure as follows with normal sand DINEN196-1 (Normensand)
| Weight (g) | Based on ... wt% | |
| Normal sand | 400 | 77 of total mixture weight |
| Water | 27 | 30 of total cement weight |
| Cement | 90 | 22.5 of total sand weight |
Mixing and drying program are as described in method 1.
After outdoor aging in 3 months, sample is tested.
embodiment 1
Measure (pigment is the 6wt% of cement weight) when UV irradiates lower pigment self and introduces in concrete substrate (sample a) photochemical catalytic oxidation iron sample (containing the TiO of the 23wt% of total pigment weight
2) NO under w light transforms.In addition, photoactivation cement (TXAriawhite) and 6% Ferroxide48 make concrete sample (sample b).All concrete samples are all prepared by method 2 above and are tested after aging 3 months out of doors.
Result provides in the following table:
| The NO% transformed when 180 minutes | The NO transformed when 180 minutes 2％ | The NO produced 2％ | |
| Pigment | 66.4 | 45.4 | 68.4 |
| Sample a | 31.5 | 1 | 3.2 |
| Sample b | 30 | 7 | 23.3 |
Data show, the cement containing photochemical catalytic oxidation iron produces less NO than the reference photo catalytic cement of current industrial use
2.
Fig. 2 shows the conversion of sample a and the relation of irradiation time.From curve, transform and increase in several minutes from 0 and after turning on light, reach equilibrium valve, then keep stable under irradiation.
Should point out, to provide in embodiment 2 and the inversion cuver of sample 2 (photo catalytic cement/iron oxide) shown in Figure 5 shows different characteristics, prove that the transformation mechanism of two kinds of catalysis materials is different.
Catalysis material of the present invention shows the stability of higher conversion of nitric oxide gas with open-assembly time than reference photo catalytic cement.In addition, the reaction on photochemical catalytic oxidation iron produces less NO
2.Although the present inventor is not wishing to be bound by theory, these two results indicate the cooperative effect of the two oxides (iron and titanium) when close contact.
embodiment 2
By described in method 1 prepare four kinds of concrete samples and be placed in T=95 DEG C and humidity be 90% humidity chamber (accelerated ageing) different duration.Be prepared as follows sample:
Sample 1: photo catalytic cement, without pigment
Sample 2: photo catalytic cement, standard oxidation iron oxide yellow (3.8wt% for total cement weight)
Sample 3: standard cement, photochemical catalytic oxidation iron 1 is (containing the TiO of total pigment weight 45wt%
2), be the 6.8wt% of total cement weight
Sample 4: standard cement, photochemical catalytic oxidation iron 2 is (containing the TiO of total pigment weight 45wt%
2), be the 6.8wt% of total cement weight
Photochemical catalytic oxidation iron 1 and 2 for such as described in patent application PCT/EP2006/068245 by material prepared by two kinds of different preparation processes.
Before aging, after 96 hours and after 192 hours, measure photocatalytic conversion under w light.Data provide in figures 3 and 4 and in following table:
| Sample | The Δ (NO% of conversion) of aging 196 hours-0 hour |
| 1 | -65％ |
| 2 | -84％ |
| 3 | -66％ |
| 4 | -74％ |
In addition, the colored block that NO transforms and prepared by photoactivation cement of two kinds of photocatalytic oxides is suitable.
Fig. 5 and 6 shows, it is obvious that the NO of colored block prepared by photoactivation pigment transforms the colored block that the minimizing with UV open-assembly time do not have photoactivation cement to prepare, and shows that these materials have higher NO transition temperature.Inversion cuver also shows, under NO exists, conversion does not under w light produce ozone.
For sample 3 and 4, also determine colourimetric number and provide in the following table, indicating the tinctorial property that described photocatalysis pigment is good.
Be that standard (equal iron oxide content) under the 3.8wt% for total cement weight measures tinctorial strength with Ferroxide48.
| L | a | b | TS％ | |
| Sample 3 | 74.76 | 2.96 | 36.04 | 83.9 |
| Sample 4 | 73.94 | 3.77 | 35.94 | 81.8 |
Embodiment 3
By preparing two kinds of concrete samples described in method 1 and irradiating under w light:
Sample a: containing the cement of Ferroxide48 (3%)
Sample b: containing the photochemical catalytic oxidation iron of the 5wt% of total cement weight (containing the TiO of total pigment weight 21wt%
2)
As in NO conversion test, under NO exists, sample is exposed to UV light.After different duration, measure Fe (II) to extract, wherein extraction procedure is performed as follows: by the 2mMH of concrete segment previously through deoxidation
2sO
4infiltration also exposes 10 minutes in the microwave of 375W.Filtering solution by the absorbance measurement Fe (II) under wavelength 510nm after adding Phen.Data are shown in Figure 7, and Fig. 7 shows, it is only obvious for standard iron oxide (Ferroxide48) that the light of Fe (II) is dissolved under UV-NO condition, and is unconspicuous for photochemical catalytic oxidation iron of the present invention.
The value (it is also shown in Figure 7) of the concrete segment (sample c) these data can made with the Ferroxide by photo catalytic cement and 3% is compared.After 250 minutes, the Fe (II) existed in extract is 4.2310
-3, higher than photocatalytic oxide used according to the invention.
embodiment 4
By prepare four kinds of concrete samples described in embodiment 1 and be placed in T=95 DEG C and humidity be 90% humidity chamber (accelerated ageing) 192 hours.Be prepared as follows sample:
Sample a: photo catalytic cement, without pigment
Sample b: photo catalytic cement, standard oxidation iron oxide yellow is the 3.8wt% of total cement weight
Sample c: standard cement, photochemical catalytic oxidation iron oxide yellow A is (containing the TiO of total pigment weight 45wt%
2), be the 6.8wt% of total cement weight
Sample d: standard cement, photochemical catalytic oxidation iron oxide yellow B is (containing the TiO of total pigment weight 45wt%
2), be the 6.8wt% of total cement weight
Photochemical catalytic oxidation iron oxide yellow A and B is all prepared by PCT/EP2006/068245, TiO
2carrying capacity is the 45wt% of total pigment weight.
By the conversion of VOC under described mensuration UV light above.Percentage conversion provides in the following table:
| Transform % | Benzene | Toluene | Ethylbenzene | Ortho-xylene | Average BTEX transforms % |
| a | 0 | 3.6 | 1.1 | 1 | 1.4 |
| b | 1.5 | 3.3 | 4.6 | 4 | 3.4 |
| c | 2.7 | 5.1 | 4.3 | 4.5 | 4.2 |
| d | 4.3 | 5.9 | 5.9 | 6.2 | 5.6 |
The result of drawing in Fig. 8 and 9 shows, photochemical catalytic oxidation iron of the present invention has the higher ability removing VOC than the conventional catalysis material used at present.
embodiment 5
By prepare two kinds of concrete samples described in embodiment 1 and be placed in T=95 DEG C and humidity be 90% humidity chamber (accelerated ageing) 192 hours.Be prepared as follows sample:
Sample 1: standard cement, for the photochemical catalytic oxidation iron oxide yellow (sample A) of total cement weight 6.8wt% is (containing the TiO of total pigment weight 45wt%
2, sample a)
Sample 2: standard cement, for the photochemical catalytic oxidation iron oxide yellow (sample B) of total cement weight 6.8wt% is (containing the TiO of total pigment weight 45wt%
2, sample b)
From the data shown in following table, when utilizing the illumination in visible spectral range to penetrate, two kinds of photocatalytic oxides all can transform NO.As irradiated with UV in embodiment 4, between the stage of reaction, do not produce ozone.
| Sample | The NO% transformed | The NO transformed 2％ | The O transformed 3％ |
| A | 7.9 | 2.2 | 0 |
| B | 6.2 | 3.1 | 0 |
embodiment 6
To the photochemical catalytic oxidation iron based on introducing 5% in the paint (water based on 28.25%, the ConsolrefK of 23%, the inert material of 38%, the styrene-acrylate of 9%) of silicate (containing the TiO of the 23wt% of total pigment weight
2) and be applied on concrete surface.Measure the conversion of NO with standard method, inversion cuver is shown in Figure 10.
Following content corresponds to the original claims in parent application, and an existing part as description is incorporated to herein:
1. the ferric oxide particles being coated with titanium dioxide is at least partly selected from nitrogen oxide (NO for photocatalysis Decomposition and described particle contacts
x) and the purposes of air pollutants of VOC (VOC).
2., according to the purposes of item 1, wherein said ferric oxide particles is introduced in construction material.
3., according to the purposes of item 1, wherein said ferric oxide particles is applied on construction material.
4., according to the purposes of item 2 or 3, wherein said construction material is selected from concrete, cement, mortar, lime stone or gypsum.
5., according to the purposes of item 1, wherein said ferric oxide particles is introduced in paint.
6. according to the purposes of item 1, for reduce NO
2the mode generated carrys out photocatalysis Decomposition NO.
7. according to the purposes of item 1, for being selected from nitrogen oxide (NO in photocatalysis Decomposition
x) and VOC (VOC) air pollutants during avoid the generation of ozone.
8. according to the purposes of item 1, for photocatalysis Decomposition NO under UV and/or visible ray.
9. according to the purposes of item 1, for photocatalysis Decomposition VOC under UV and/or visible ray.
10. according to the purposes of item 1, for being selected from NO in photocatalysis Decomposition
xwith the photoetch effect reducing described ferric oxide particles during the air pollutants of VOC.
Claims (10)
1. the ferric oxide particles being coated with titanium dioxide is at least partly selected from nitrogen oxide (NO for photocatalysis Decomposition and described particle contacts
x) and the purposes of air pollutants of VOC (VOC).
2. purposes according to claim 1, wherein said ferric oxide particles is introduced in construction material.
3. purposes according to claim 1, wherein said ferric oxide particles is applied on construction material.
4., according to the purposes of Claims 2 or 3, wherein said construction material is selected from concrete, cement, mortar, lime stone or gypsum.
5. purposes according to claim 1, wherein said ferric oxide particles is introduced in paint.
6. purposes according to claim 1, for reduce NO
2the mode generated carrys out photocatalysis Decomposition NO.
7. purposes according to claim 1, for being selected from nitrogen oxide (NO in photocatalysis Decomposition
x) and VOC (VOC) air pollutants during avoid the generation of ozone.
8. purposes according to claim 1, for photocatalysis Decomposition NO under UV and/or visible ray.
9. purposes according to claim 1, for photocatalysis Decomposition VOC under UV and/or visible ray.
10. purposes according to claim 1, for being selected from NO in photocatalysis Decomposition
xwith the photoetch effect reducing described ferric oxide particles during the air pollutants of VOC.
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|---|---|---|---|
| CN2008801281908A CN101980988A (en) | 2008-03-31 | 2008-03-31 | Use of photocatalytically coated particles for decomposition of air pollutants |
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|---|---|---|---|
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001071121A1 (en) * | 2000-03-21 | 2001-09-27 | 3M Innovative Properties Company | Photocatalytic composition and method for preventing algae growth on building materials |
| EP1413607A2 (en) * | 2002-10-24 | 2004-04-28 | Toda Kogyo Corporation | Black iron-based particles and black toner containing the same |
| JP2004161978A (en) * | 2002-09-24 | 2004-06-10 | Yoshiyuki Nagae | Photocatalyst-coated pigment, paint, method for manufacturing photocatalyst-coated pigment and method for manufacturing paint |
| CN1513040A (en) * | 2001-04-25 | 2004-07-14 | 南欧派克有限公司 | Photocatalytic coating material having photocatalytic activity and adsorption property and method for preparating same |
| CN1876417A (en) * | 2005-06-09 | 2006-12-13 | 仁亿集团有限公司 | A photocatalyst processor for eliminating organic volatiles in automobiles |
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2008
- 2008-03-31 CN CN201510208409.7A patent/CN105032174A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001071121A1 (en) * | 2000-03-21 | 2001-09-27 | 3M Innovative Properties Company | Photocatalytic composition and method for preventing algae growth on building materials |
| CN1513040A (en) * | 2001-04-25 | 2004-07-14 | 南欧派克有限公司 | Photocatalytic coating material having photocatalytic activity and adsorption property and method for preparating same |
| JP2004161978A (en) * | 2002-09-24 | 2004-06-10 | Yoshiyuki Nagae | Photocatalyst-coated pigment, paint, method for manufacturing photocatalyst-coated pigment and method for manufacturing paint |
| EP1413607A2 (en) * | 2002-10-24 | 2004-04-28 | Toda Kogyo Corporation | Black iron-based particles and black toner containing the same |
| CN1876417A (en) * | 2005-06-09 | 2006-12-13 | 仁亿集团有限公司 | A photocatalyst processor for eliminating organic volatiles in automobiles |
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