CN101909750A - Silver-(titanium oxide)-zeolite adsorbent/decomposing material and process for production thereof - Google Patents
Silver-(titanium oxide)-zeolite adsorbent/decomposing material and process for production thereof Download PDFInfo
- Publication number
- CN101909750A CN101909750A CN2009801015938A CN200980101593A CN101909750A CN 101909750 A CN101909750 A CN 101909750A CN 2009801015938 A CN2009801015938 A CN 2009801015938A CN 200980101593 A CN200980101593 A CN 200980101593A CN 101909750 A CN101909750 A CN 101909750A
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- CN
- China
- Prior art keywords
- titanium oxide
- zeolite
- complex
- decomposing material
- absorption
- 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.)
- Pending
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- 239000010457 zeolite Substances 0.000 title claims abstract description 142
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 141
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000003463 adsorbent Substances 0.000 title abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000000203 mixture Substances 0.000 claims abstract description 45
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 42
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 8
- 238000005342 ion exchange Methods 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims description 89
- 229910052719 titanium Inorganic materials 0.000 claims description 89
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 53
- 238000010521 absorption reaction Methods 0.000 claims description 41
- 229920001131 Pulp (paper) Polymers 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 239000004411 aluminium Substances 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 6
- 239000011941 photocatalyst Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000004615 ingredient Substances 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 119
- 230000000052 comparative effect Effects 0.000 description 21
- 238000000354 decomposition reaction Methods 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 150000002894 organic compounds Chemical class 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 239000004115 Sodium Silicate Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 6
- 229910052622 kaolinite Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 235000019795 sodium metasilicate Nutrition 0.000 description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 6
- 229910052911 sodium silicate Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 235000012222 talc Nutrition 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- MZFIXCCGFYSQSS-UHFFFAOYSA-N silver titanium Chemical compound [Ti].[Ag] MZFIXCCGFYSQSS-UHFFFAOYSA-N 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
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- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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Abstract
An adsorbent/decomposing material having a (titanium oxide)-zeolite complex skeleton can be produced through the following steps (A) and (B): (A) treating a mixture containing an aluminum component and a silicon component and having a chemical composition from which titanium oxide and zeolite can be formed with an alkali containing an alkali metal ion to produce a (titanium oxide)-zeolite complex having a photocatalytic activity; and (B) immersing the (titanium oxide)-zeolite complex produced in step (A) in a solution containing a silver ion to cause the substitution of the alkali metal ion in the (titanium oxide)-zeolite complex by the silver ion through ion exchange.
Description
Technical field
The present invention relates to a kind of absorption decomposing material, its titanium oxide-zeolite complex or titanium oxide-zeolite mixture that will disperse titanium oxide to form in the crystal of zeolite is made skeleton structure.
Background technology
All the time, the exploitation of relevant organic absorption decomposing material has been carried out repeatedly catalyst metals being loaded on the carrier that is formed by adsorbents such as active carbon, silica gel, zeolites, the test of absorption decomposing organic matter.In these present technology, because catalyst metals is loaded on adsorbent surface as carrier, so the adsorption function that exists sorbent material to have is affected or do not decompose and the following degradation problem of the oxidation Decomposition function that causes at the catalyst metals surface reaction thing that does not contact with adsorbent.
In order to solve the problem of such supported catalyst, present inventors have carried out following test, promptly, be not to be that carrier makes titania oxide supported method thereon with the zeolite, but so that titanium oxide is present in the state synthetic zeolite (with reference to patent documentation 1) of the feedstock composition that is used for the artificial synthetic zeolite., repeatedly improve this synthetic method, up to having obtained titanium oxide-zeolite complex that titanium oxide and zeolite carry out compound thereafter.This complex is except that all characteristics that possess zeolite, also have the photocatalytic activity of titanium oxide concurrently, therefore for example organic matter (aldehydes or amine etc.) as malodorant is adsorbed in the pore of zeolite, it is good that utilization has the function that the titanium oxide of photocatalyst activity efficiently decomposes etc., and it is the various fields of representative that expectation is applied to the environmental area.
Patent documentation 1:(Japan) No. 3994096 communique of special permission
Because titanium oxide-zeolite complex is a hydrophily, so, be difficult to bring into play its absorption decomposition function with respect to toluene or the low organic compound of dimethylbenzene isopolarity.
As with the zeolite being the structure that carrier and its are gone up the centre of the structure of loading titanium oxide and titanium oxide-zeolite complex, the mixture of consideration zeolite and titanium oxide.Because this mixture is possess hydrophilic property still, thus the same with titanium oxide-zeolite complex, can not expect the organic compound performance absorption decomposition function low with respect to polarity.
So,, consider to make zeolite have hydrophobicity as its solution.The silica-rich zeolite that the silicon ratio in the synthetic zeolite is high (silica alumina ratio (Si/Al atomic ratio number) is more than 10) for example.Though can the synthesizing high-silicon zeolite, exist synthetic extremely difficult, combined coefficient is extremely low so that output synthetic is problems such as about 1/10.
Summary of the invention
The objective of the invention is to make the skeleton structure that contains titanium oxide-zeolite complex and zeolite-titania mixture,, but can adsorb the low organic compound of polarity by other method not by making the zeolite that is contained in wherein have hydrophobic method.
So, bonding has the mode of the state of alkali metal ion to synthesize titanium oxide-zeolite complex in titanium oxide-zeolite complex to become, be impregnated in various metal ion solutions then, metal ion and alkali metal ion are exchanged, obtain thus can adsorbing the opinion of decomposing the low organic compound of polarity, and finished the present invention according to the kind of metal ion.With respect to zeolite-titania mixture, also obtained identical opinion.
That is, the present invention has the absorption decomposing material of silver (Ag) ion for bonding in the skeleton structure that is formed by titanium oxide and zeolite.
Titanium oxide-zeolite the complex of preferred skeleton structure in the crystal of zeolite, disperseing titanium oxide to form.
As skeleton structure, in addition, also comprise the mixture of zeolite and titanium oxide.
Manufacture method of the present invention comprises that for making the method as the absorption decomposing material with titanium oxide-zeolite complex skeleton of the best mode in the absorption decomposing material following operation (A) reaches (B).
(A) aluminium component and the silicon mixture of ingredients that contain titanium oxide and be modulated to the composition that constitutes zeolite are handled with alkali, made the operation of titanium oxide-zeolite complex with photocatalyst activity;
(B) will impregnated in the solution that contains silver ion by titanium oxide-zeolite complex that described operation (A) obtains,, replace the operation of the alkali metal ion in titanium oxide-zeolite complex by silver ion by ion-exchange.
As the alkali that is used for making titanium oxide-zeolite complex, preferred alkali metal hydroxide in operation (A).If the use alkali metal hydroxide, then alkali metal ion is implanted in synthetic titanium oxide-zeolite complex.This is because if alkali metal ion then carries out the ion-exchange reactions with silver ion easily in operation (B).
In addition, as zeolite, it is desirable to porous matter or silica alumina ratio (Si/Al atomicity than) less than 10.This is owing to the low zeolite hydrophily height of silica alumina ratio, the processing of acceptant liquid phase.
The material of making titanium oxide-zeolite complex in operation (A) also can use the pure reagent modulation to become the composition of regulation, but, also can access the cost efficiency in the practicality thus owing to used the discarded object or the accurate kaolinite of sintering of inorganic constituents such as containing system paper pulp or system paper pulp burning ash in this mixture.
Among the present invention, comprise the operation of the method for the invention of using patent documentation 1 record as operation (A).Under this situation, the aluminium component and the silicon mixture of ingredients that contain titanium oxide and be modulated into the composition that constitutes zeolite can be used as: (a) burn the mixture that adds the silicon composition in the ash and obtain at the system paper pulp that contains titanium oxide and aluminium component or its, (b) burn the mixture that adds silicon composition and titanium oxide in the ash and obtain at the system paper pulp that contains aluminium component or its, (c) burn the mixture that adds silicon composition and aluminium component in the ash and obtain at the system paper pulp that contains titanium oxide or its, or (d) in the burning ash of the discarded object that contains aluminium component and silicon composition or this discarded object, add titanium oxide and the mixture that obtains is modulated.
According to the present invention, can obtain to adsorb and decompose the low organic compound of polarity and can stablize synthetic absorption decomposing material.
Description of drawings
Fig. 1 is the scanning electron microscope picture of titanium oxide-zeolite complex of embodiment 1;
Fig. 2 is the scanning electron microscope picture of zeolite;
Fig. 3 is the ESCA spectrum before and after the silver-colored load of titanium oxide-zeolite complex of embodiment 1, be load down before, on be load after;
Fig. 4 is the X-ray diffraction spectrum before and after the silver-colored load of titanium oxide-zeolite complex of embodiment 1, on be load before, be load down after;
Fig. 5 is the scanning electron microscope of titanium oxide-zeolite mixture of embodiment 3;
Fig. 6 is that the toluene of Ag-titanium oxide-zeolite complex of expression embodiment 1 adsorbs decomposition run result's figure;
Fig. 7 is the silver-colored load capacity in Ag-titanium oxide-zeolite complex of expression embodiment 1 and the figure of the relation of toluene absorption property;
Fig. 8 is toluene absorption decomposition run result's the figure of Ag-titanium oxide-zeolite mixture of the expression Ag-titanium oxide-zeolite complex of embodiment 1 and embodiment 3, is embodiment 1 down, on be embodiment 3;
Fig. 9 is that the toluene of the Na-titanium oxide-zeolite complex of expression comparative example 1 adsorbs decomposition run result's figure;
Figure 10 is that the toluene of the Ca displacement-titanium oxide-zeolite complex of expression comparative example 2 adsorbs decomposition run result's figure;
Figure 11 is that the toluene of the Fe displacement-titanium oxide-zeolite complex of expression comparative example 3 adsorbs decomposition run result's figure;
Figure 12 is that the toluene of the Cu displacement-titanium oxide-zeolite complex of expression comparative example 4 adsorbs decomposition run result's figure.
The specific embodiment
(embodiment 1)
As embodiment 1, the manufacture method of using the synthetic Ag-titanium oxide of pure reagent-zeolite complex is described.
Below, represent concrete raw material composition and reaction condition, but the present invention not only is defined in concrete like this scope.
In the solution that contains sodium metasilicate 40～400mg/ml and sodium aluminate 30～300mg/ml, the scope adding titanium dioxide powder with 1～90 weight % is modulated into NaOH 3N, and has carried out ageing.
As the silicic acid source, except that sodium metasilicate, also can use reagent such as cataloid or in the aqueous solution such as the accurate kaolinite of sintering, generate the material that contains the silicon source of silicic acid.In addition, as the aluminium source, also can replace sodium aluminate and use reagent such as aluminium hydroxide or in the aqueous solution such as aluminium bits, generate aluminum ions aluminium source.In a word, modulation silicic acid source and aluminium source in the aqueous solution are to become the composition of zeolite.
Ageing is carried out under any condition that leaves standstill, vibrates, stirs, and it is desirable to carry out in the temperature range of room temperature～100 ℃.Preferred ageing was carried out more than 1 hour.At this, carry out with the condition that left standstill under the room temperature 24 hours.
Solution after the ageing that will obtain by above-mentioned method heats under the temperature more than 70 ℃, has obtained zeolite-titanium oxide complex.
Ag-titanium oxide-zeolite complex is made by the sodium ion in titanium oxide-zeolite complex and silver ion are carried out ion-exchange.That is, will be by the AgNO of the titanium oxide that obtains in the above-mentioned operation-zeolite complex 1g and 0.1M
3The aqueous solution 30ml 50ml centrifuge tube of packing into, vibrate back 1 minute after, carry out three centrifugations more repeatedly, thereby carried out ion-exchange reactions.Thereafter, the distilled water of usefulness 30ml cleans about three times, descends dry 12 hours at 105 ℃ then, has obtained Ag-titanium oxide-zeolite complex.At this moment, in order not destroy the crystal structure of zeolite and titanium oxide-zeolite complex, the solution of preferred impregnation is more than the pH4, at this embodiment and in embodiment 2,3, all is modulated into pH5.
Fig. 1 is illustrated in the image of the SEM of titanium oxide-zeolite complex of obtaining in the process of manufacture method of embodiment 1 (silver replace before).Fig. 2 is used to compare and the scanning electron microscope photo of the only zeolite that shows.The plane of crystal of zeolite is level and smooth, cannot see spherical nano particle.According to the shape of crystal as can be known, the big crystal among Fig. 1 is a zeolite, and the crystal of micro mist shape is a titanium oxide.
Image according to Fig. 1 can be confirmed, in titanium oxide-zeolite complex, at the surperficial ubiquity titanium oxide of zeolite crystal.Also there is Titanium particles in affirmation in the crack of zeolite crystal face, therefore the inside of zeolite crystal has also entered titanium oxide as can be known.
Fig. 3 is illustrated in the result of the elementary analysis of the titanium oxide-zeolite complex that carries out silver-colored load front and back among the embodiment 1.Fig. 3 is the analysis result of ESCA (Electron Spectroscopy for Chemical Analysis).The spectrum of downside is before the silver-colored load, after the spectrum of upside is silver-colored load.Near two peak values 350～380eV are the peak values from the 3d track of silver.Can confirm to exist really in Ag-titanium oxide-zeolite complex after silver-colored load silver according to this esca analysis result.
Then, utilized X-ray diffraction studies with respect to titanium oxide-zeolite complex, whether the skeleton structure of crystal variation has taken place before and after silver-colored load.Fig. 4 is the X-ray diffraction spectrum of titanium oxide-zeolite complex of embodiment 1, and the spectrum of upside is before the silver-colored load, after the spectrum of downside is silver-colored load.These two spectrum are compared, find that several peak values change, but at the position that can adsorb large-scale molecule promptly near the peak value 2 θ=6 ° big variation does not take place, and the crystal structure of titanium oxide and zeolite does not almost change before and after silver-colored load.
Silver ion is implanted in the complex by the sodium ion that is replaced in titanium oxide-zeolite complex by silver ion.But, consider by the reaction silver ion outside replacing and also implant possibility in the complex.In a word, according to the esca analysis result, confirm that silver is present in the surface of titanium oxide-zeolite complex, this silver helps adsorbing decomposition reaction.
(embodiment 2)
As the embodiment 2 of manufacture method, to being that the method that the zeolite raw material are made Ag-titanium oxide-zeolite complex describes with system paper pulp (PS:Paper Sludge).
System paper pulp is system paper factory discarded part as sediment or suspension generation in the manufacture process of paper, perhaps sediment or the suspension that produces from the draining of system paper factory.System paper pulp burns ash and forms for burning system paper pulp.
The main component of the burning ash of system paper pulp is silicic acid (SiO
2), aluminium oxide (Al
2O
3), magnesia (MgO) etc.These compositions derive from the filler in the paper materials such as making an addition to paper pulp in the papermaking operation.As filler, except that carclazytes such as kaolinite, earth (clay) or clay, can also use talcum, calcium carbonate, titanium dioxide, aluminium hydroxide etc.These components in proportions ratio whole with respect to inorganic constituents that system paper pulp or system paper pulp burn in the ash is respectively, about silicic acid 10～40 weight %, aluminium oxide 15～75 weight %, magnesia 7～20 weight %.
In system paper operation, use under the situation of titanium oxide, contain titanium oxide in its system paper pulp as Chinese white.The content that contains the titanium oxide in the system paper pulp of titanium oxide is whole with respect to inorganic constituents, is generally 1～35 weight %.In system paper operation, do not use under the few situation of the situation of titanium oxide or its use amount, when synthetic titanium oxide-zeolite complex, burn the desirable titanium oxide of interpolation in the ash at system paper pulp or its.As the titanium oxide that uses, also can be to be contained in almost not having photocatalyst activity or having the titanium oxide of photocatalyst activity in the system paper pulp as Chinese white.
As raw material, the system paper pulp that has used burning system paper pulp to obtain burns the burning ash that contains the about 20 weight % of anatase type titanium oxide in the ash (PS ash).Its raw material system paper pulp burns shown in ash composed as follows:
Sintering kaolinite (2SiO
2-Al
2O
3) ... 50.6 weight %,
Anatase type titanium oxide (TiO
2) ... 21.5 weight %,
Talcum (4SiO
2-3MgO) ... 15.6 weight %,
Noncrystalline aluminium oxide (Al
2O
3) ... 12.2 weight %.
Wherein be considered to, sintering kaolinite, anatase type titanium oxide and talcum are discharged from as the conduct system paper pulp that the system filler for paper uses, the aluminum sulfate (Al of the agglutinant use of noncrystalline aluminium oxide by will handle as draining the time
2(SO
4)
3) sintering and generating.Mineral as the expectation of zeolite raw material are to contain the accurate kaolinite of sintering of Si, Al and the noncrystalline material of noncrystalline aluminium oxide.
In order to modulate above-mentioned synthesis material, in the 300ml conical flask, add this system paper pulp and burn ash, sodium metasilicate, NaOH and water.Shown in it is composed as follows.
System paper pulp burns ash ... 5.0g,
Sodium metasilicate ... 5.9g,
NaOH……6.3g、
Water ... 55g.
As sodium metasilicate, No. 3 (SiO of goods sodium metasilicate of three Lose chemical industry Co., Ltd. have been used
2: 28.5 weight %, Na O
2: 9.30 weight %, H
2O:62.2 weight %).
This titanium oxide-zeolite complex raw material at room temperature placed 24 hours before reaction after, make it under normal pressure, to keep boiling point and reacted in 4 hours with 95～100 ℃.In reaction, in order to prevent the evaporation of moisture, cooling tube is installed in conical flask, and is not stirred.Reactant carries out Separation of Solid and Liquid by centrifugal separation, and after the distilled water of the about 30ml of usefulness cleaned three times, drying was 12 hours under 105 ℃, thereby has obtained the titanium oxide-zeolite complex of off-white powder.
The same with embodiment 1, the titanium oxide-zeolite complex that obtains is contained the solution that is dipped in the silver ion that contains sodium ion and will replace, obtained the Ag-titanium oxide-zeolite complex of purpose.
(embodiment 3)
As embodiment 3, make Ag-titanium oxide-zeolite mixture.
As the raw material of titanium oxide-zeolite mixture, in mortar be 1: 4 mode mixed oxidization titanium powder (anatase titanium dioxide, particle diameter 20nm) and zeolite crystal powder (Na type faujasite-type, particle diameter 3 μ m) with weight ratio.
The same with embodiment 1, the titanium oxide-zeolite mixture that is modulated into is like this contained the solution that is dipped in the silver ion that contains sodium ion and will replace, obtained the Ag-titanium oxide-zeolite mixture of purpose.
Fig. 5 represents the image of the scanning electron microscope of titanium oxide-zeolite mixture that the silver-colored load of embodiment 3 is preceding.According to the image of Fig. 5 as can be known, the particulate of titanium oxide is the solid shape, is connected unevenly with the periphery of zeolite crystal.
The absorption decomposability of the nonpolar molecule of the absorption decomposing material that forms for Ag-titanium oxide-zeolite complex and the Ag-titanium oxide-zeolite mixture of determining by these embodiment, prepared not carry out titanium oxide-zeolite complex that silver replaces, with other the metal-oxide titanium-zeolite complex of metal replacement, as a comparative example.
(comparative example 1)
If the titanium oxide-zeolite complex before the metal of being made by the manufacturing process as the titanium oxide-zeolite complex of embodiment 1 record replaces is a comparative example 1.This test portion note is made Na-titanium oxide-zeolite complex.
(comparative example 2)
Comparative example 2 is Ca-titanium oxide-zeolite complexs.As its manufacture method, will be at the AgNO of the manufacturing process of the Ag-of embodiment 1 titanium oxide-zeolite complex
3The aqueous solution is replaced as the CaCl of 0.5M
2The aqueous solution, the method by identical with embodiment 1 has obtained Ca-titanium oxide-zeolite complex.
(comparative example 3)
Comparative example 3 is Fe-titanium oxide-zeolite complexs.As its manufacture method, Ca-titanium oxide-zeolite complex 1g that will obtain by comparative example 2 and the Fe of 0.01M
2(NO
3)
3Aqueous solution 30ml adds the 50ml centrifuge tube, and the method by identical with embodiment 1 has obtained Fe-titanium oxide-zeolite complex.
(comparative example 4)
Comparative example 4 is Cu-titanium oxide-zeolite complexs.As its manufacture method, will be at the AgNO in the manufacturing process of the Ag-of embodiment 1 titanium oxide-zeolite complex
3The aqueous solution is replaced as the CuCl of 0.5M
2The aqueous solution, the method by identical with embodiment 1 has obtained Cu-titanium oxide-zeolite complex.
(toluene absorption decomposition run)
Select toluene as nonpolar molecule, the absorption decomposing material of embodiment 1,3 and the titanium oxide of comparative example 1～4-zeolite complex have been carried out toluene absorption decomposition run.
Will be in agate mortar the 0.10g of the fine various titanium oxide-zeolite complex that grinds or titanium oxide-zeolite mixture be deployed into 25mm * 77mm respectively microscope with on the sample, adding distil water is made suspension, and full dose is applied as area 19.25cm separately
2After dry 2 hours, in drier, cooled off 30 minutes again under 105 ℃, made test portion.After each test portion being statically placed in the polyethylene system airbag of volume 1000ml, with the airbag sealing and outgas.After the degassing, the 500ml room air is imported airbag., 900ppm toluene calibrating gas with syringe injected airbag, make the toluene initial stage concentration in the airbag become 80ppm from about 15, measured the toluene gas concentration in the airbag of process in time thereafter.The mensuration of toluene gas concentration is gathered gas from airbag and is undertaken by gas chromatograph.For the photocatalyst activity energy of the titanium oxide confirming to contain in the test portion, from toluene concentration change reduce the time light, utilize to be arranged at, from airbag outside illumination wavelength 365nm, intensity 4.0mW/cm apart from the ultraviolet lamp of the position of test portion height 5cm
2Ultraviolet ray.
Fig. 6～Figure 12 represents measurement result.Fig. 6 is the toluene absorption decomposition run result of Ag-titanium oxide-zeolite complex of embodiment 1.
Fig. 7 is the figure of the toluene absorption property when being illustrated in the load capacity that makes silver ion among the embodiment 1 and changing.As can be known the absorption property of toluene along with silver-colored load capacity with respect to 2%, 8% and 15% the increase of the weight % of complex integral body and increase.The existence that can confirm silver ion thus improves the absorption property to the low molecule of polarity.
Fig. 8 is the figure that the toluene absorption property of Ag-titanium oxide-zeolite mixture of embodiment 3 and embodiment 1 are compared.The curve of downside is embodiment 1, and the curve of upside is embodiment 3.Toluene absorption property before the irradiation ultraviolet radiation as can be known, the complex of embodiment 1 is better than the mixture of embodiment 3.Thus, the absorption property of toluene not only helps the existence of silver ion, and helps the interaction of silver ion and crystalline framework, but detailed mechanism is not clear.Embodiment 3 compares with the complex of embodiment 1, though the performance that self adsorbs toluene is little, possesses the ability of decomposing toluene equally after the ultraviolet ray irradiation.Even this is to think that the performance of self adsorbing toluene shown in embodiment 3 is little, but when decomposing by the adsorbed toluene of ultraviolet ray irradiation and when adsorption site is removed, at the new toluene molecule of this position absorption, again by ultraviolet light degradation, therefore aspect decomposability, bring into play sufficient ability.
Fig. 9 is the toluene absorption decomposition run result of the Na-titanium oxide-zeolite complex of comparative example 1.
Figure 10 is the toluene absorption decomposition run result of the Ca-titanium oxide-zeolite complex of comparative example 2.
Figure 11 is the toluene absorption decomposition run result of the Fe-titanium oxide-zeolite complex of comparative example 3.
Figure 12 is the toluene absorption decomposition run result of the Cu-titanium oxide-zeolite complex of comparative example 4.
According to these measurement results, find Ag-titanium oxide-zeolite complex of embodiment 1 and Ag-titanium oxide-zeolite mixture of embodiment 3, when irradiation ultraviolet radiation not, after in case the decline of the concentration of toluene slows down, shine by ultraviolet ray, the concentration of toluene further reduces, thereby can confirm that Ag-titanium oxide-zeolite complex and Ag-titanium oxide-zeolite mixture have the function that toluene is decomposed in absorption.Thus, can infer Ag-titanium oxide-zeolite complex of embodiment 2,, have the function that toluene is decomposed in absorption similarly to Example 1 though manufacture method is different with embodiment 1.
Relative therewith, the titanium oxide-zeolite complex by Ca, Fe or Cu replacement of the titanium oxide-zeolite complex that does not carry out the metal replacement of comparative example 1 and comparative example 2～4, under the non-irradiation of ultraviolet ray and under the ultraviolet ray irradiation, do not find that all toluene concentration significantly reduces, therefore these titanium oxide-zeolite complex does not have the function that toluene is decomposed in absorption as can be known.
Absorption decomposition function to toluene is measured, but an example of the toluene organic compound that only polarity is low also can be brought into play the absorption decomposition function but can be easy to infer absorption decomposing material of the present invention with respect to other low polar organic compound.
The possibility of utilizing on the industry
Ag-titanium oxide of the present invention-zeolite complex and mixture can be used as adsorption-decomposition function and is present in device, factory's exhaust or the atmosphere or the catalyst of the low polarity such as the toluene in the water of rivers and creeks or lakes and marhshes or nonpolar organic compound and utilizing.
Claims (8)
1. one kind adsorbs decomposing material, and wherein, bonding has silver ion in the skeleton structure that is formed by titanium oxide and zeolite.
2. absorption decomposing material according to claim 1, wherein, described skeleton structure is for being dispersed with titanium oxide-zeolite complex that titanium oxide forms in the crystal of zeolite.
3. absorption decomposing material according to claim 1, wherein, described skeleton structure is the mixture of zeolite and titanium oxide.
4. according to each described absorption decomposing material in the claim 1～3, wherein, the silica alumina ratio less than 10 of described zeolite.
5. manufacture method, it is a method of making the absorption decomposing material with titanium oxide-zeolite complex skeleton, has following operation (A) and (B):
(A) with alkali the aluminium component and the silicon mixture of ingredients that contain titanium oxide and be modulated to the composition that constitutes zeolite are handled, made the operation of titanium oxide-zeolite complex with photocatalyst activity;
(B) will impregnated in the solution that contains silver ion by titanium oxide-zeolite complex that described operation (A) obtains,, replace the operation of the alkali metal ion in titanium oxide-zeolite complex by silver ion by ion-exchange.
6. the manufacture method of absorption decomposing material according to claim 5, wherein, described alkali is alkali metal hydroxide.
7. according to the manufacture method of claim 5 or 6 described absorption decomposing materials, wherein, described mixture contains system paper pulp or system paper pulp burns ash.
8. according to the manufacture method of each described absorption decomposing material in the claim 5～7, wherein,, contain aluminium component and silicon mixture of ingredients in the preparation section (A) in the mode of the silica alumina ratio less than 10 of gained zeolite.
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| JP2008022526 | 2008-02-01 | ||
| JP2008-022526 | 2008-09-02 | ||
| PCT/JP2009/051629 WO2009096548A1 (en) | 2008-02-01 | 2009-01-30 | Silver-(titanium oxide)-zeolite adsorbent/decomposing material and process for production thereof |
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| CN101909750A true CN101909750A (en) | 2010-12-08 |
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| JP (1) | JP4943516B2 (en) |
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| ITFI20130049A1 (en) * | 2013-03-07 | 2014-09-08 | Onofrio Daniele D | GRANULAR COMPOSITION AND ITS USES |
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2009
- 2009-01-30 JP JP2009551616A patent/JP4943516B2/en not_active Expired - Fee Related
- 2009-01-30 CN CN2009801015938A patent/CN101909750A/en active Pending
- 2009-01-30 WO PCT/JP2009/051629 patent/WO2009096548A1/en active Application Filing
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| US11904306B2 (en) | 2017-05-31 | 2024-02-20 | Furukawa Electric Co., Ltd. | Catalyst structure and method for producing the catalyst structure |
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| CN114522500A (en) * | 2020-11-23 | 2022-05-24 | 中国科学院城市环境研究所 | Deodorization and sterilization equipment and method and application for purifying gas by using same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2009096548A1 (en) | 2011-05-26 |
| WO2009096548A1 (en) | 2009-08-06 |
| JP4943516B2 (en) | 2012-05-30 |
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