JP2000233134A - Photocatalyst supporting composition - Google Patents
Photocatalyst supporting compositionInfo
- Publication number
- JP2000233134A JP2000233134A JP11033699A JP3369999A JP2000233134A JP 2000233134 A JP2000233134 A JP 2000233134A JP 11033699 A JP11033699 A JP 11033699A JP 3369999 A JP3369999 A JP 3369999A JP 2000233134 A JP2000233134 A JP 2000233134A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- cement
- supporting
- composition
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 31
- 239000004568 cement Substances 0.000 claims abstract description 53
- 239000000463 material Substances 0.000 claims abstract description 47
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 22
- 239000011575 calcium Substances 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 230000001699 photocatalysis Effects 0.000 claims description 22
- 239000002562 thickening agent Substances 0.000 claims description 8
- 239000003623 enhancer Substances 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 229940043430 calcium compound Drugs 0.000 claims description 6
- 150000001674 calcium compounds Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 2
- 230000007423 decrease Effects 0.000 abstract description 5
- 238000006253 efflorescence Methods 0.000 abstract description 3
- 206010037844 rash Diseases 0.000 abstract description 3
- 238000006303 photolysis reaction Methods 0.000 abstract description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 53
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 15
- 229910000019 calcium carbonate Inorganic materials 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 9
- 239000003112 inhibitor Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- -1 platinum is present Chemical class 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 238000004061 bleaching Methods 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000002087 whitening effect Effects 0.000 description 4
- 239000011398 Portland cement Substances 0.000 description 3
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光触媒を含有した
光触媒担持組成物について、その分解性能を高めながら
分解性能の経時的な低下を抑止し、長期間安定して窒素
酸化物(NOx)等を光分解できる光触媒担持組成物に関す
る。BACKGROUND OF THE INVENTION The present invention relates to a photocatalyst-containing composition containing a photocatalyst, which suppresses deterioration of decomposition performance over time while increasing its decomposition performance, and stabilizes nitrogen oxides (NOx) and the like for a long period of time. The present invention relates to a photocatalyst-supporting composition that can photodecompose the compound.
【０００２】[0002]
【従来技術】最近、光触媒活性を利用した光触媒材料が
各種分野で用いられている。通常、光触媒材料は普通ポ
ルトランドセメント等を担持材料とし、この担持材料に
混合して使用されているが、光触媒材料を含有したこの
ようなセメント系光触媒担持組成物は製造直後の光触媒
活性による分解効果が低い場合があり、また長期間経過
すると窒素酸化物に対する分解性能が次第に低下する場
合がある。2. Description of the Related Art Recently, photocatalytic materials utilizing photocatalytic activity have been used in various fields. Usually, the photocatalyst material is normally used as a supporting material such as Portland cement, and is used by mixing with the supporting material. However, such a cement-based photocatalyst supporting composition containing the photocatalytic material has a decomposition effect due to the photocatalytic activity immediately after production. May be low, and after a long period of time, the decomposition performance for nitrogen oxides may gradually decrease.
【０００３】この原因は次のように考えられる。光触媒
担持組成物に配合される光触媒材料はその光触媒活性を
高めるために微粉末で比表面積の大きいものが用いられ
ている。このため、組成物を混練する際の混練水が過剰
になり易く、セメントと水との反応から生成される水酸
化カルシウム量が多くなり、この水酸化カルシウムが大
気中の二酸化炭素と反応し、光触媒担持組成物表面に炭
酸カルシウム結晶層を形成するため、窒素酸化物(ＮＯ
x)等が光触媒粒子と接触し難くなり、分解性能が低下す
ると考えられる。この対策として、表面に形成された炭
酸カルシウム等の結晶層を弱酸などで定期的に洗浄除去
するメンテナンスによる対策が考えられるが、これには
洗浄後の排水処理、作業者の安全対策、組成物の厚さが
次第に減少するなどの実用上の問題がある。The cause is considered as follows. As the photocatalyst material to be mixed with the photocatalyst-supporting composition, a fine powder having a large specific surface area is used in order to enhance the photocatalytic activity. For this reason, kneading water at the time of kneading the composition is likely to be excessive, the amount of calcium hydroxide generated from the reaction between cement and water increases, and this calcium hydroxide reacts with carbon dioxide in the atmosphere, In order to form a calcium carbonate crystal layer on the surface of the photocatalyst supporting composition, nitrogen oxide (NO
It is considered that x) and the like hardly come into contact with the photocatalyst particles, and the decomposition performance is reduced. As a countermeasure, maintenance by periodically cleaning and removing the crystal layer such as calcium carbonate formed on the surface with a weak acid can be considered.This includes wastewater treatment after cleaning, worker safety measures, and composition. There is a practical problem such as a gradual decrease in the thickness of the film.
【０００４】[0004]
【発明の解決課題】本発明は、従来の光触媒担持組成物
における上記問題を解決したものであり、窒素酸化物等
に対する分解性能の経時的な低下が少なく、長期間使用
しても安定に窒素酸化物等を光分解できる光触媒担持組
成物を提供するものである。DISCLOSURE OF THE INVENTION The present invention has solved the above-mentioned problems in the conventional photocatalyst-supporting composition, and has a small deterioration with time with respect to the decomposition performance of nitrogen oxides and the like. An object of the present invention is to provide a photocatalyst-supporting composition capable of photodecomposing oxides and the like.
【０００５】[0005]
【課題の解決手段】すなわち、本発明は以下の構成から
なる光触媒担持組成物に関する。 （１）セメントを主体とする担持材料に光触媒材料を配
合してなる光触媒担持組成物において、カルシウム量が
酸化物換算で５５wt％以下のセメントを用いてなること
を特徴とする光触媒担持組成物。 （２）セメント重量に対して光触媒材料を５〜２００wt
％配合した上記(１)に記載する光触媒担持組成物。 （３）カルシウム化合物、骨材、増粘剤、保水剤および
接着強度増強剤の１種以上を含有する上記(１)又は(２)
に記載する光触媒担持組成物。 （４）セメントを主体とする担持材料に光触媒材料と白
華防止剤を配合してなる光触媒担持組成物において、白
華防止剤をセメント重量の０.１〜５wt％配合したこと
を特徴とする光触媒担持組成物。 （５）セメント重量に対して光触媒材料を５〜２００wt
％配合した上記(４)に記載する光触媒担持組成物。 （６）カルシウム化合物、骨材、増粘剤、保水剤および
接着強度増強剤の１種以上を含有する上記(４)又は(５)
に記載する光触媒担持組成物。That is, the present invention relates to a photocatalyst carrying composition having the following constitution. (1) A photocatalyst supporting composition comprising a photocatalyst material mixed with a supporting material mainly composed of cement, wherein calcium having an amount of calcium of 55% by weight or less in terms of oxide is used. (2) 5 to 200 wt% of photocatalytic material based on cement weight
%. The photocatalyst-carrying composition according to (1) above, wherein (3) The above (1) or (2) containing one or more of a calcium compound, an aggregate, a thickener, a water retention agent, and an adhesive strength enhancer.
The photocatalyst-supporting composition described in 1. (4) A photocatalyst supporting composition comprising a photocatalytic material and an anti-whitening agent mixed with a supporting material mainly composed of cement, wherein the whitening preventing agent is compounded in an amount of 0.1 to 5 wt% of the cement weight. Photocatalyst supporting composition. (5) 5 to 200 wt% photocatalytic material based on cement weight
%. The photocatalyst-carrying composition according to (4) above, wherein (6) The above (4) or (5) containing one or more of a calcium compound, an aggregate, a thickener, a water retention agent and an adhesive strength enhancer.
The photocatalyst-supporting composition described in 1.
【０００６】[0006]
【発明の実施の形態】以下、本発明を実施形態に即して
具体的に説明する。本発明の光触媒担持組成物の一つ
は、セメントを主体とする担持材料に光触媒材料を配合
してなる光触媒担持組成物において、カルシウム量が酸
化物換算で５５wt％以下のセメントを担持材料としたこ
とを特徴とする光触媒担持組成物である。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically with reference to embodiments. One of the photocatalyst support compositions of the present invention is a photocatalyst support composition obtained by mixing a photocatalyst material with a support material mainly composed of cement, wherein calcium having a calcium content of 55 wt% or less in terms of oxide is used as the support material. A photocatalyst-supporting composition characterized by the above-mentioned.
【０００７】本発明の光触媒担持組成物に用いるセメン
トはカルシウム含有量が少ないものが望ましく、具体的
には、カルシウム量が酸化物(ＣａＯ)換算で５５wt％以
下のセメントである。好ましくは５０wt％以下のセメン
トが良い。セメント中のカルシウム量が５５wt％より多
いと、長期の使用期間中に担持組成物の表面に炭酸カル
シウム結晶層が形成されやすく、窒素酸化物等に対する
光分解能が次第に低下する。光触媒材料の配合量にもよ
るが、上記カルシウム量のセメントを用いることによ
り、光触媒担持組成物中のカルシウム量を概ね１５wt％
以下に抑えれば、炭酸カルシウム結晶層の生成を十分に
抑制することができる。[0007] The cement used in the photocatalyst-supporting composition of the present invention desirably has a low calcium content, specifically, a cement having a calcium content of 55 wt% or less in terms of oxide (CaO). Preferably, 50% by weight or less of cement is good. If the calcium content in the cement is more than 55% by weight, a calcium carbonate crystal layer is likely to be formed on the surface of the support composition during a long use period, and the optical resolution for nitrogen oxides and the like gradually decreases. The amount of calcium in the photocatalyst-supporting composition can be reduced to about 15% by weight by using a cement having the above-mentioned calcium content, depending on the amount of the photocatalyst material.
When the content is controlled to be below, the formation of the calcium carbonate crystal layer can be sufficiently suppressed.
【０００８】通常の普通ポルトランドセメントに含有さ
れるカルシウム量は、酸化物(ＣａＯ)に換算して６５wt
％前後であるので、上記低カルシウムセメントには適さ
ない。一方、高炉セメントやシリカセメントないしフラ
イアッシュセメントなどの混合セメント、およびＧＲＣ
セメントやアルミナセメントの一部はカルシウム量が本
発明の上記範囲に適するので、これらを上記光触媒担持
組成物の低カルシウムセメントとして用いることができ
る。[0008] The amount of calcium contained in ordinary ordinary Portland cement is 65 wt% in terms of oxide (CaO).
%, It is not suitable for the low calcium cement. On the other hand, mixed cement such as blast furnace cement, silica cement or fly ash cement, and GRC
Some of the cement and the alumina cement have a calcium content suitable for the above-mentioned range of the present invention, and thus can be used as the low calcium cement of the photocatalyst-supporting composition.
【０００９】本発明における他の光触媒担持組成物は、
セメントを主体とする担持材料に光触媒材料と共に白華
防止剤を配合し、白華防止剤をセメント重量の０.１〜
５wt％含有することを特徴とするものであり、好ましく
は、担持材料であるセメントとセメント成分以外に含ま
れる炭酸カルシウム及び／又は炭酸カルシウムを反応生
成し得るカルシウム化合物との合計量に対して白華防止
剤を０.１〜５wt％含有させたものである。Another photocatalyst-supporting composition according to the present invention comprises:
An anti-whitening agent is compounded together with a photocatalyst material in a carrier material mainly composed of cement, and the anti-whitening agent is added in an amount of 0.1 to 0.1% by weight of cement.
It is characterized by containing 5 wt%, and is preferably white based on the total amount of cement as a supporting material and calcium carbonate and / or a calcium compound capable of reacting and producing calcium carbonate contained in addition to the cement component. It contains 0.1 to 5% by weight of an anti-flowering agent.
【００１０】白華防止剤はセメント中のカルシウムと錯
体を形成するので、白華防止剤を光触媒材料と共に配合
することにより、炭酸カルシウム層の生成をさらに抑制
することができる。白華防止剤は一般にセメントコンク
リート組成物の白華防止剤として知られているものなら
特に限定されず、例えば界面活性剤やシリコーン系の市
販品を使用することができる。白華防止剤の使用量が上
記範囲より少ないと、白華防止の効果が現れない場合が
あり、また、これより過剰に使用すると窒素酸化物等の
分解性能が低下する場合があるので何れも好ましくな
い。Since the bleaching inhibitor forms a complex with calcium in cement, the formation of the calcium carbonate layer can be further suppressed by blending the bleaching inhibitor with the photocatalytic material. The bleaching inhibitor is not particularly limited as long as it is generally known as a bleaching inhibitor of a cement concrete composition. For example, a surfactant or a silicone-based commercial product can be used. If the amount of the anti-whitening agent is less than the above range, the effect of anti-whitening may not be exhibited, and if it is used in excess, the decomposition performance of nitrogen oxides and the like may be reduced. Not preferred.
【００１１】白華防止剤を含有する光触媒担持組成物に
おいては、担持材料の主体であるセメントは特に限定さ
れず、何れのセメントであっても用いることができる
が、カルシウム量が５５wt％を超えるセメントを用いた
場合は白華防止剤未含有のものと比較しＮＯx除去率に
顕著な改善効果が見られ、またカルシウム量が５５wt％
以下のセメントを用いると、炭酸カルシウムの生成をよ
り効果的に抑制することができる。[0011] In the photocatalyst-supporting composition containing an anti-whitening agent, the cement which is the main component of the support material is not particularly limited, and any cement can be used, but the calcium content exceeds 55 wt%. In the case of using cement, a remarkable improvement effect on NOx removal rate was observed as compared with the case where no anti-whitening agent was contained, and the calcium content was 55 wt%.
When the following cement is used, generation of calcium carbonate can be more effectively suppressed.
【００１２】光触媒材料としては光触媒作用を有する金
属酸化物粉末、具体的には、二酸化チタン、二酸化ス
ズ、酸化亜鉛、三酸化タングステン、酸化セリウム、チ
タン酸バリウム、酸化第二鉄などを用いることができ
る。このうち二酸化チタンは優れた光触媒活性を有し、
なかでもアナターゼ型二酸化チタンは光触媒活性が高い
ので好ましい。二酸化チタンは比表面積(BET値)が２０
〜３５０m2/g程度の粉末が適当である。光触媒材料の配
合量はセメント重量に対して５〜２００wt％が適当であ
る。この配合量が５wt％未満では光触媒効果が乏しく、
２００wt％を上回ると組成物の流動性が大幅に低下し、
施工が難しくなる場合がある。As the photocatalyst material, a metal oxide powder having a photocatalytic action, specifically, titanium dioxide, tin dioxide, zinc oxide, tungsten trioxide, cerium oxide, barium titanate, ferric oxide, or the like can be used. it can. Among them, titanium dioxide has excellent photocatalytic activity,
Among them, anatase type titanium dioxide is preferable because of its high photocatalytic activity. Titanium dioxide has a specific surface area (BET value) of 20
A powder of about 350 m 2 / g is suitable. The amount of the photocatalyst material is suitably from 5 to 200% by weight based on the weight of the cement. If the amount is less than 5% by weight, the photocatalytic effect is poor.
If it exceeds 200 wt%, the fluidity of the composition will be greatly reduced,
Construction may be difficult.
【００１３】光触媒材料の粒子表面及び／又は粒子内部
に、銅、銀、金、ランタン、セリウム、亜鉛、バナジウ
ム、鉄、コバルト、ニッケル、ルテニウム、ロジウム、
パラジウム、白金などの金属や金属化合物の少なくとも
１種を存在させると、優れた光触媒活性を有するため好
ましい。より好ましい光触媒材料は、二酸化チタンの粒
子表面及び／又は粒子内部に、銅、銀、金、ランタン、
セリウム、亜鉛、バナジウム、鉄、コバルト、ニッケ
ル、ルテニウム、ロジウム、パラジウム、白金などの金
属や金属化合物の少なくとも１種を存在させた光触媒材
料であり、最も好ましい光触媒材料は、二酸化チタンの
粒子表面及び／又は粒子内部に、ランタンの酸化物、水
酸化物を存在させた光触媒材料である。ランタンの酸化
物、水酸化物を存在させると、大気中のＮＯx除去に特
に有効である。[0013] Copper, silver, gold, lanthanum, cerium, zinc, vanadium, iron, cobalt, nickel, ruthenium, rhodium, on the surface and / or inside the particles of the photocatalytic material.
The presence of at least one kind of metal or metal compound such as palladium or platinum is preferable because of having excellent photocatalytic activity. More preferred photocatalytic materials include copper, silver, gold, lanthanum, on the surface and / or inside the particles of titanium dioxide.
Cerium, zinc, vanadium, iron, cobalt, nickel, ruthenium, rhodium, palladium, a photocatalytic material in which at least one kind of metal or metal compound such as platinum is present, the most preferred photocatalytic material is a titanium dioxide particle surface and And / or a photocatalyst material in which lanthanum oxide or hydroxide is present inside the particles. The presence of lanthanum oxides and hydroxides is particularly effective for removing NOx from the atmosphere.
【００１４】本発明の光触媒担持組成物は、上記カルシ
ウム量の範囲内で、流動性を高めるために炭酸カルシウ
ム及び／又は水酸化カルシウムを添加することができ
る。これらのカルシウム化合物を添加することにより、
カルシウムイオンがセメント中のアルミネート相に水と
共に取り込まれ、アルミネート相の急速な水和を抑制し
て流動性を長時間高く維持することができる。In the photocatalyst-supporting composition of the present invention, calcium carbonate and / or calcium hydroxide can be added to increase the fluidity within the above-mentioned range of the amount of calcium. By adding these calcium compounds,
Calcium ions are taken into the aluminate phase in the cement together with the water, thereby suppressing rapid hydration of the aluminate phase and maintaining a high fluidity for a long time.
【００１５】また、本発明の光触媒担持組成物には、ア
ルカリ金属硫酸塩及び／又はアルカリ土類金属硫酸塩を
配合しても良い。アルカリ金属硫酸塩及び／又はアルカ
リ土類金属硫酸塩を配合させることにより光触媒材料の
光分解性能をより高めることができる場合がある。アル
カリ金属硫酸塩及び／又はアルカリ土類金属硫酸塩とし
ては、硫酸ナトリウム、硫酸カリウム、硫酸マグネシウ
ムなどを用いることができ、それらは水和物であっても
良い。アルカリ金属硫酸塩及び／又はアルカリ土類金属
硫酸塩の配合量は、光触媒材料に対して、０.０１〜１
０wt％が適当であり、０.０５〜５wt％が好ましい。The photocatalyst-supporting composition of the present invention may contain an alkali metal sulfate and / or an alkaline earth metal sulfate. The photodecomposition performance of the photocatalyst material can be further enhanced by blending an alkali metal sulfate and / or an alkaline earth metal sulfate. As the alkali metal sulfate and / or alkaline earth metal sulfate, sodium sulfate, potassium sulfate, magnesium sulfate and the like can be used, and they may be hydrates. The compounding amount of the alkali metal sulfate and / or the alkaline earth metal sulfate is 0.01 to 1 with respect to the photocatalyst material.
0 wt% is appropriate, and 0.05 to 5 wt% is preferable.
【００１６】さらに、本発明の光触媒担持組成物は強度
を高めるために骨材を含有することができ、また、増粘
剤や保水剤あるいは接着強度増強剤の１種または２種以
上を含有することができる。骨材は一般のモルタルやコ
ンクリートに配合されるものを用いることができる。増
粘剤や保水剤あるいは接着強度増強剤などの作用を有す
る添加剤としては、セルロース系化合物、アクリル系化
合物、ビニル系化合物、アクリル酸系増粘剤、植物性増
粘剤、エマルジョン・ラテックス系化合物などを用いる
ことができる。これら添加剤の使用量はセメント重量に
対して０.０５〜２wt％が適当である。使用量がこれよ
り少ないと、例えば保水性が不足して硬化後にヒビ割れ
を生じやすくなる。一方、使用量が上記範囲より多いと
流動性が低下して取り扱い難くなる。また、本発明の光
触媒担持組成物は、必要に応じ、市販の分散剤、消泡
剤、減水剤、高性能減水剤等を適量添加することができ
る。セメントに光触媒材料などの各材料を適量配合し、
適量の水を加えて混練し、水和凝結させることにより本
発明の光触媒担持組成物が得られる。Further, the photocatalyst-carrying composition of the present invention can contain an aggregate for increasing the strength, and contains one or more of a thickener, a water retention agent and an adhesive strength enhancer. be able to. Aggregate can be used in general mortar or concrete. Additives having an action such as a thickener, a water retention agent, or an adhesive strength enhancer include a cellulose compound, an acrylic compound, a vinyl compound, an acrylic acid thickener, a vegetable thickener, an emulsion / latex type. Compounds and the like can be used. The amount of these additives used is suitably 0.05 to 2% by weight based on the weight of cement. If the amount is less than this, cracking is likely to occur after curing due to, for example, insufficient water retention. On the other hand, if the used amount is more than the above range, the fluidity is lowered and it becomes difficult to handle. In addition, the photocatalyst-supporting composition of the present invention can be added with an appropriate amount of a commercially available dispersant, defoaming agent, water reducing agent, high-performance water reducing agent, and the like, if necessary. Mix appropriate amount of each material such as photocatalyst material with cement,
The photocatalyst-supporting composition of the present invention can be obtained by adding an appropriate amount of water, kneading and hydrating and condensing.
【００１７】[0017]
【実施例】以下、本発明を実施例によって具体的に示
す。実施例・比較例 表１に示す各種セメントを用い、各材料を以下の単位配
合量に従って配合し、ミキサーで混練した後に、この混
練物をスレート板(5×10cm)に厚さ０.５mm程度に塗布
し、24時間自然乾燥させて光触媒担持組成物を調製し
た。この各組成物試料について、次の試験条件下でＮＯ
x浄化性能の評価試験を行った。この結果を表１に示し
た。 [単位配合量(重量部)] (Ａ) セメント:100部、骨材:174部、増粘保水剤:0.66
部、接着増強剤:33.2部、炭酸カルシウム:5.5部、水酸
化カルシウム:5.5部、分散剤:4.41部、光触媒材料:46.5
部、水:88.5部 (Ｂ) 白華防止剤を用いた試料：上記配合比のセメント1
00重量部に対して白華防止剤を１重量部添加 [材料]普通ポルトランドセメント(太平洋セメント社製)、ア
ルミナセメント(ラファーシ゛ュ社製)、混合セメント(高炉スラ
グ60wt％含有)、ＧＲＣセメント(太平洋セメント社製)、白
華防止剤(竹本油脂社製:商品名エフロクリーン、宇部興産社製:
商品名ハッカノン)、光触媒材料(石原産業社製品:HP-01、水
酸化ランタン８wt％を粒子表面に担持した二酸化チタン粉末、
比表面積250m2/g、平均粒径７nm) [試験条件] 対象ガス:一酸化窒素(NO)約15ppm、光源・光量:ブラック
ライト1.0mW/cm2、反応容量:４リットル、ガス循環:６リットル/
min、温度:24〜26℃、湿度:43〜50％、測定時間20分、
暴露前のＮＯx分解性能を測定後、屋外で２週間の自然
暴露を実施後、２週間後のＮＯx分解性能(除去率)を測
定した。なお、各試料のＮＯx除去率(％)は濃度１５ppm
の一酸化窒素ガスを対象とした浄化試験後の濃度減少値
から算出した。EXAMPLES The present invention will be specifically described below with reference to examples. Examples and Comparative Examples Using the various cements shown in Table 1, the respective materials were mixed according to the following unit compounding amounts, and after kneading with a mixer, the kneaded material was placed on a slate plate (5 × 10 cm) with a thickness of about 0.5 mm. And dried naturally for 24 hours to prepare a photocatalyst-supporting composition. For each composition sample, NO
x An evaluation test of purification performance was performed. The results are shown in Table 1. [Unit blending amount (parts by weight)] (A) Cement: 100 parts, aggregate: 174 parts, thickening water retention agent: 0.66
Parts, adhesion enhancer: 33.2 parts, calcium carbonate: 5.5 parts, calcium hydroxide: 5.5 parts, dispersant: 4.41 parts, photocatalytic material: 46.5
Part, water: 88.5 parts (B) Sample using a whitening inhibitor: Cement 1 with the above compounding ratio
1 part by weight of a whitening inhibitor to 00 parts by weight [Materials] Ordinary Portland cement (manufactured by Taiheiyo Cement), alumina cement (manufactured by Rafah Shu), mixed cement (containing 60 wt% blast furnace slag), GRC cement (pacific Cement Co., Ltd.), Efflorescence inhibitor (Takemoto Yushi Co., Ltd .: Efloclean, Ube Industries, Ltd.)
Product name: Hackanone), photocatalyst material (product of Ishihara Sangyo Co., Ltd .: HP-01, titanium dioxide powder carrying 8 wt% of lanthanum hydroxide on the particle surface,
(Specific surface area: 250 m 2 / g, average particle size: 7 nm) [Test conditions] Target gas: Nitric oxide (NO) about 15 ppm, light source / light amount: black light 1.0 mW / cm 2 , reaction capacity: 4 liters, gas circulation: 6 liter/
min, temperature: 24-26 ° C, humidity: 43-50%, measurement time 20 minutes,
After measuring NOx decomposition performance before exposure, natural exposure was performed outdoors for 2 weeks, and then NOx decomposition performance (removal rate) after 2 weeks was measured. The NOx removal rate (%) of each sample was 15 ppm
It was calculated from the concentration decrease value after the purification test for nitrogen monoxide gas.
【００１８】表１に示すように、カルシウム量(JIS R 5
202に準拠した方法で測定)が５５wt％を超えるセメント
を用いた比較試料(No.6)は暴露２週間後のＮＯx除去率
が３３％と大幅に低下するが、カルシウム量が５５wt％
以下のセメントを用いた本発明試料(No.1〜3)は暴露２
週間後のＮＯx除去率が何れも高く、試料No.1及び３で
は暴露前のＮＯx除去率に匹敵する９５％以上の除去率
であった。また、比較試料(No.6)と同様の高いカルシウ
ム含有量のセメントを用いた場合であっても、白華防止
剤を添加した本発明試料(No.4、5)はＮＯx除去率が高い
値となった。As shown in Table 1, the amount of calcium (JIS R 5
The comparative sample (No. 6) using a cement having a concentration of more than 55 wt% (measured by a method in accordance with 202) has a greatly reduced NOx removal rate of 33% after two weeks of exposure, but has a calcium content of 55 wt%.
The sample of the present invention (No. 1 to 3) using the following cement was exposed 2
Both the NOx removal rates after one week were high, and samples Nos. 1 and 3 had a removal rate of 95% or more, which was comparable to the NOx removal rate before exposure. In addition, even when a cement having a high calcium content similar to that of the comparative sample (No. 6) was used, the samples of the present invention (Nos. 4 and 5) to which the whitening inhibitor was added had a high NOx removal rate. Value.
【００１９】[0019]
【表１】 [Table 1]
【００２０】[0020]
【発明の効果】本発明の光触媒担持組成物は、光触媒の
分解性能の経時的な低下が少なく、長期間安定して窒素
酸化物(NOx)等を光分解することができる。According to the photocatalyst-supporting composition of the present invention, the degradation performance of the photocatalyst over time is small, and nitrogen oxides (NOx) can be photodecomposed stably for a long period of time.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 松久 真人 千葉県佐倉市大作２丁目４番２号 太平洋 セメント株式会社佐倉研究所内 (72)発明者 副田 孝一 千葉県佐倉市大作２丁目４番２号 太平洋 セメント株式会社佐倉研究所内 (72)発明者 新井 範彦 千葉県佐倉市大作２丁目４番２号 太平洋 セメント株式会社佐倉研究所内 (72)発明者 渡辺 満 三重県四日市市石原町１番地 石原産業株 式会社四日市事業所内 Ｆターム(参考） 4D048 AA06 AB01 AB03 BA02X BA06X BA07X BA15Y BA16Y BA19Y BA27Y BA36Y BA41X BA41Y BA42Y BB03 EA01 4G012 PB03 PC01 4G069 AA03 BA04A BA04B BA48A BB04A BB04B BC09A BC09B BD08A BD08B CA01 CA07 CA10 CA13 DA06 EA14 EC03Y ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masato Matsuhisa 2-4-2, Daisaku, Sakura-shi, Chiba Pref. Inside the Sakura Research Laboratories of Pacific Cement Co., Ltd. (72) Koichi Soeda 2-4-2, Daisaku, Sakura-shi, Chiba Pacific Cement Co., Ltd. Sakura Laboratory (72) Inventor Norihiko Arai 2-4-2, Daisaku, Sakura City, Chiba Prefecture Pacific Cement Co., Ltd. Sakura Laboratory (72) Inventor Mitsuru Watanabe 1 Ishiharacho, Yokkaichi-shi, Mie Ishihara Sangyo Co., Ltd. F-term (reference) at Yokkaichi Plant of Shikisha 4D048 AA06 AB01 AB03 BA02X BA06X BA07X BA15Y BA16Y BA19Y BA27Y BA36Y BA41X BA41Y BA42Y BB03 EA01 4G012 PB03 PC01 4G069 AA03 BA04A BA04B BA48A BB04A03CA08
Claims (6)
材料を配合してなる光触媒担持組成物において、カルシ
ウム量が酸化物換算で５５wt％以下のセメントを用いて
なることを特徴とする光触媒担持組成物。1. A photocatalyst supporting composition comprising a photocatalytic material mixed with a supporting material mainly composed of cement, characterized in that the amount of calcium is 55% by weight or less in terms of oxides of cement. object.
２００wt％配合した請求項１に記載する光触媒担持組成
物。2. A photocatalytic material of 5 to 5% by weight of cement.
2. The photocatalyst-carrying composition according to claim 1, which is blended at 200% by weight.
剤および接着強度増強剤の１種以上を含有する請求項１
又は２に記載する光触媒担持組成物。3. The method according to claim 1, further comprising one or more of a calcium compound, an aggregate, a thickener, a water retention agent and an adhesive strength enhancer.
Or the photocatalyst-supporting composition according to 2.
材料と白華防止剤を配合してなる光触媒担持組成物にお
いて、白華防止剤をセメント重量の０.１〜５wt％配合
したことを特徴とする光触媒担持組成物。4. A photocatalyst-supporting composition comprising a photocatalytic material and an anti-whitening agent mixed with a supporting material mainly composed of cement, characterized in that the anti-whitening agent is added in an amount of 0.1 to 5% by weight of the cement. A photocatalyst-supporting composition to be used.
２００wt％配合した請求項４に記載する光触媒担持組成
物。5. A photocatalyst material of 5 to 5% by weight of cement.
The photocatalyst-supporting composition according to claim 4, which is blended at 200 wt%.
剤および接着強度増強剤の１種以上を含有する請求項４
又は５に記載する光触媒担持組成物。6. The composition according to claim 4, which comprises at least one of a calcium compound, an aggregate, a thickener, a water retention agent and an adhesive strength enhancer.
Or the photocatalyst-supporting composition according to 5.
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| JP (1) | JP3483244B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100361924C (en) * | 2005-07-28 | 2008-01-16 | 上海三瑞化学有限公司 | Nano-photo catalytic cement base ground material |
| EP2275391A1 (en) | 2009-07-16 | 2011-01-19 | Redco S.A. | Air-purifying fiber reinforced cementitious building material. |
| JP2011518657A (en) * | 2008-03-31 | 2011-06-30 | ロックウッド イタリア スパ | Use of photocatalyst-coated particles for the degradation of air pollutants. |
| CN114904553A (en) * | 2022-05-26 | 2022-08-16 | 福建工程学院 | Carbon nitride-loaded photocatalytic cement-based material and preparation method thereof |
-
1999
- 1999-02-12 JP JP03369999A patent/JP3483244B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100361924C (en) * | 2005-07-28 | 2008-01-16 | 上海三瑞化学有限公司 | Nano-photo catalytic cement base ground material |
| JP2011518657A (en) * | 2008-03-31 | 2011-06-30 | ロックウッド イタリア スパ | Use of photocatalyst-coated particles for the degradation of air pollutants. |
| EP2275391A1 (en) | 2009-07-16 | 2011-01-19 | Redco S.A. | Air-purifying fiber reinforced cementitious building material. |
| CN114904553A (en) * | 2022-05-26 | 2022-08-16 | 福建工程学院 | Carbon nitride-loaded photocatalytic cement-based material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3483244B2 (en) | 2004-01-06 |
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