JP2017164671A - Catalyst carrier, manufacturing method therefor, catalyst carrying body and water treatment material - Google Patents
Catalyst carrier, manufacturing method therefor, catalyst carrying body and water treatment material Download PDFInfo
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- JP2017164671A JP2017164671A JP2016050910A JP2016050910A JP2017164671A JP 2017164671 A JP2017164671 A JP 2017164671A JP 2016050910 A JP2016050910 A JP 2016050910A JP 2016050910 A JP2016050910 A JP 2016050910A JP 2017164671 A JP2017164671 A JP 2017164671A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 112
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 title claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 14
- 229910001868 water Inorganic materials 0.000 title claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 60
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 26
- 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 26
- 235000012215 calcium aluminium silicate Nutrition 0.000 claims abstract description 25
- 239000000404 calcium aluminium silicate Substances 0.000 claims abstract description 25
- WNCYAPRTYDMSFP-UHFFFAOYSA-N calcium aluminosilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O WNCYAPRTYDMSFP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229940078583 calcium aluminosilicate Drugs 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 22
- 235000012241 calcium silicate Nutrition 0.000 claims description 27
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 27
- 239000000378 calcium silicate Substances 0.000 claims description 26
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 26
- 230000003197 catalytic effect Effects 0.000 claims description 11
- 238000010304 firing Methods 0.000 claims description 9
- 238000009279 wet oxidation reaction Methods 0.000 claims description 9
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004898 kneading Methods 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 229910001583 allophane Inorganic materials 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229910052661 anorthite Inorganic materials 0.000 claims description 4
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 claims description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 4
- MKTRXTLKNXLULX-UHFFFAOYSA-P pentacalcium;dioxido(oxo)silane;hydron;tetrahydrate Chemical compound [H+].[H+].O.O.O.O.[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O MKTRXTLKNXLULX-UHFFFAOYSA-P 0.000 claims description 4
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052621 halloysite Inorganic materials 0.000 claims description 3
- 229910052903 pyrophyllite Inorganic materials 0.000 claims description 3
- 239000010456 wollastonite Substances 0.000 claims description 3
- 229910052882 wollastonite Inorganic materials 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 52
- 229910021529 ammonia Inorganic materials 0.000 abstract description 26
- 239000002351 wastewater Substances 0.000 abstract description 23
- 239000000203 mixture Substances 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 7
- 238000000465 moulding Methods 0.000 abstract description 6
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- -1 gibbsite Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 6
- 239000000292 calcium oxide Substances 0.000 description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000003991 Rietveld refinement Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- SHPBBNULESVQRH-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].[Zr+4] Chemical compound [O-2].[O-2].[Ti+4].[Zr+4] SHPBBNULESVQRH-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000013379 molasses Nutrition 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten(iv) oxide Chemical compound O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- DUDJJJCZFBPZKW-UHFFFAOYSA-N [Ru]=S Chemical compound [Ru]=S DUDJJJCZFBPZKW-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- JLDKGEDPBONMDR-UHFFFAOYSA-N calcium;dioxido(oxo)silane;hydrate Chemical compound O.[Ca+2].[O-][Si]([O-])=O JLDKGEDPBONMDR-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011381 foam concrete Substances 0.000 description 1
- 229910001678 gehlenite Inorganic materials 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- XBBXDTCPEWHXKL-UHFFFAOYSA-N rhodium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Rh+3].[Rh+3] XBBXDTCPEWHXKL-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BVJAAVMKGRODCT-UHFFFAOYSA-N sulfanylidenerhodium Chemical compound [Rh]=S BVJAAVMKGRODCT-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 235000019976 tricalcium silicate Nutrition 0.000 description 1
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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- Catalysts (AREA)
Abstract
Description
本発明は、触媒担体及びその製造方法、並びに触媒担持体及び水処理材に関する。詳細には、本発明は、触媒湿式酸化法に用いられる触媒担体及びその製造方法、並びに触媒担持体及び水処理材に関する。 The present invention relates to a catalyst carrier, a method for producing the same, a catalyst carrier and a water treatment material. Specifically, the present invention relates to a catalyst carrier used in a catalytic wet oxidation method, a method for producing the same, a catalyst carrier and a water treatment material.
一般に、排水中に存在するアンモニアなどの有機化合物を除去する方法として、低濃度の有機化合物が含まれる場合には標準活性汚泥法などの生物処理法、高濃度の有機化合物が含まれる場合には触媒湿式酸化法などの化学処理法が用いられている。その中でも触媒湿式酸化法は、高温高圧条件下で排水を触媒と接触させることにより、大量の排水を連続的に処理することができるという利点がある。そのため、触媒湿式酸化法は、例えば、半導体洗浄工程で発生するアンモニア含有排水の処理などに用いられている。また、高濃度の糖蜜を含有する排水は、生物処理法を用いると大量のアンモニア含有排水が生成するのに対し、触媒湿式酸化法を用いることにより、糖蜜及びアンモニアを同時に処理することができるという利点もある。 In general, as a method of removing organic compounds such as ammonia present in wastewater, when low concentration organic compounds are included, biological treatment methods such as standard activated sludge method, and when high concentration organic compounds are included. Chemical treatment methods such as catalytic wet oxidation are used. Among them, the catalytic wet oxidation method has an advantage that a large amount of waste water can be treated continuously by contacting the waste water with the catalyst under high temperature and high pressure conditions. Therefore, the catalytic wet oxidation method is used, for example, for the treatment of ammonia-containing wastewater generated in the semiconductor cleaning process. In addition, wastewater containing a high concentration of molasses produces a large amount of ammonia-containing wastewater when using a biological treatment method, whereas molasses and ammonia can be treated simultaneously by using a catalytic wet oxidation method. There are also advantages.
触媒湿式酸化法に用いられる触媒としては、ハニカム状、球状などに成形された触媒担体に活性成分を担持したものが用いられる。活性成分を担持する触媒担体は、高温高圧条件下で高濃度の有機化合物が含まれる排水と連続的に接触するため、高い耐久性が要求される。
従来、触媒担体としては、シリカ、α−アルミナ、γ−アルミナ、酸化鉄、酸化チタンのような金属酸化物、酸化チタン−酸化ジルコニウム複合体のような複合金属酸化物などが一般に用いられている。
As the catalyst used in the catalytic wet oxidation method, a catalyst carrier in which an active component is supported on a catalyst carrier formed into a honeycomb shape or a spherical shape is used. The catalyst carrier carrying the active component is required to have high durability because it continuously contacts wastewater containing a high concentration of organic compound under high temperature and high pressure conditions.
Conventionally, as a catalyst carrier, silica, α-alumina, γ-alumina, metal oxides such as iron oxide and titanium oxide, and composite metal oxides such as a titanium oxide-zirconium oxide composite are generally used. .
触媒担体として用いられているシリカ、α−アルミナ及びγ−アルミナは、成形が容易であり、低濃度のアンモニアを含む排水に対して耐性を有する。しかしながら、高濃度のアンモニアを含む排水と接触すると、シリカは表面が溶解し、α−アルミナ及びγ−アルミナは水和してベーマイト（ＡｌＯＯＨ）が生成する。その結果、触媒担体の比表面積が低下したり、担持された活性成分が脱落して流出したりすることがある。
他方、酸化鉄、酸化チタン及び酸化チタン−酸化ジルコニウム複合体は、高濃度のアンモニアを含む排水に対して耐性を有するものの、成形し難い。そのため、これらの材料を用いて所定の形状の触媒担体を得るためには、加圧成形を行ったり、焼結助剤を使用したり、焼結温度を高くしたり、焼結時間を長くしたりしなければならない。
Silica, α-alumina, and γ-alumina used as a catalyst carrier are easy to mold and have resistance to waste water containing low-concentration ammonia. However, when it comes into contact with wastewater containing a high concentration of ammonia, the surface of silica dissolves, and α-alumina and γ-alumina hydrate to form boehmite (AlOOH). As a result, the specific surface area of the catalyst carrier may decrease, or the supported active component may fall off and flow out.
On the other hand, iron oxide, titanium oxide, and titanium oxide-zirconium oxide composite are resistant to waste water containing high-concentration ammonia, but are difficult to mold. Therefore, in order to obtain a catalyst carrier of a predetermined shape using these materials, pressure molding is performed, a sintering aid is used, the sintering temperature is increased, and the sintering time is lengthened. Have to do.
本発明は、上記のような問題を解決するためになされたものであり、高濃度のアンモニアを含む排水と接触しても比表面積の低下及び活性成分の脱落を抑制することができると共に成形が容易である触媒担体及びその製造方法を提供することを目的とする。
また、本発明は、高濃度のアンモニアを含む排水と接触しても触媒作用が低下し難い触媒担持体及び水処理材を提供することを目的とする。
The present invention has been made to solve the above-described problems, and can reduce the decrease in specific surface area and drop off of active ingredients even when in contact with wastewater containing high-concentration ammonia. It is an object of the present invention to provide an easy catalyst support and a method for producing the same.
Another object of the present invention is to provide a catalyst carrier and a water treatment material in which the catalytic action is unlikely to decrease even when contacted with wastewater containing high-concentration ammonia.
本発明者らは、鋭意研究を続けた結果、γ−アルミナを特定の割合でアルミノシリケート及び／又はカルシウムアルミノシリケートと組み合わせることにより、上記の問題を解決し得る触媒担体が得られ、また、この触媒担体を用いることにより、上記の問題を解決し得る触媒担持体及び水処理材が得られることを見出し、本発明を完成するに至った。
すなわち、本発明は、以下の第（１）項〜第（１１）項である。
（１）γ−アルミナと、アルミノシリケート及び／又はカルシウムアルミノシリケートとを含み、前記γ−アルミナの含有量が１０質量％〜６０質量％であることを特徴とする触媒担体。
（２）ケイ酸カルシウムをさらに含むことを特徴とする第（１）項に記載の触媒担体。
（３）前記触媒担体と２８％のアンモニア水とを固液比が１：１０となるように混合し、１５０℃で１２時間処理した後の比表面積の低下率が５％以下であることを特徴とする第（１）項又は第（２）項に記載の触媒担体。
（４）圧縮強度が２０Ｎ以上であることを特徴とする第（１）項〜第（３）項のいずれか一項に記載の触媒担体。
As a result of continual research, the present inventors have obtained a catalyst support capable of solving the above problems by combining γ-alumina with aluminosilicate and / or calcium aluminosilicate at a specific ratio, and this It has been found that by using a catalyst carrier, a catalyst carrier and a water treatment material capable of solving the above problems can be obtained, and the present invention has been completed.
That is, the present invention includes the following items (1) to (11).
(1) A catalyst carrier comprising γ-alumina and aluminosilicate and / or calcium aluminosilicate, wherein the content of γ-alumina is 10% by mass to 60% by mass.
(2) The catalyst carrier according to item (1), further comprising calcium silicate.
(3) The catalyst carrier and 28% ammonia water are mixed so that the solid-liquid ratio is 1:10, and the reduction rate of the specific surface area after treatment at 150 ° C. for 12 hours is 5% or less. The catalyst carrier according to item (1) or (2), which is characterized.
(4) The catalyst carrier according to any one of (1) to (3), wherein the compressive strength is 20 N or more.
（５）第（１）項〜第（４）項のいずれか一項に記載の触媒担体に活性成分を担持させたことを特徴とする触媒担持体。
（６）触媒湿式酸化法に用いられる水処理材であって、第（５）項に記載の触媒担持体を有することを特徴とする水処理材。
（７）γ−アルミナを与える化合物と、アルミノシリケート及び／又はカルシウムアルミノシリケートを与える化合物とを混練して混練物を得る工程と、
前記混練物を成形した後、８００℃〜１１００℃の温度で焼成する工程と
を含み、
前記混練物中の前記γ−アルミナを与える化合物の含有量が７質量％〜７５質量％である
ことを特徴とする触媒担体の製造方法。
(5) A catalyst carrier comprising an active component supported on the catalyst carrier according to any one of (1) to (4).
(6) A water treatment material used in a catalytic wet oxidation method, comprising the catalyst carrier according to item (5).
(7) a step of kneading a compound giving γ-alumina and a compound giving aluminosilicate and / or calcium aluminosilicate to obtain a kneaded product;
And after baking the kneaded product, firing at a temperature of 800 ° C. to 1100 ° C.,
Content of the compound which provides the said (gamma) -alumina in the said kneaded material is 7 mass%-75 mass%, The manufacturing method of the catalyst support | carrier characterized by the above-mentioned.
（８）前記混練物がケイ酸カルシウムを与える化合物をさらに含むことを特徴とする第（７）項に記載の触媒担体の製造方法。
（９）前記γ−アルミナを与える化合物がγ−アルミナであることを特徴とする第（７）項又は第（８）項に記載の触媒担体の製造方法。
（１０）前記アルミノシリケート及び／又はカルシウムアルミノシリケートを与える化合物が、アノーサイト、カオリン、モンモリロナイト、ハロイサイト、パイロフィライト及びアロフェンからなる群から選択される少なくとも１種であることを特徴とする第（７）項〜第（９）項のいずれか一項に記載の触媒担体の製造方法。
（１１）前記ケイ酸カルシウムを与える化合物が、ワラストナイト、ゾノトライト、トバモライト、ケイ酸カルシウム水和物であることを特徴とする第（８）項〜第（１０）項のいずれか一項に記載の触媒担体の製造方法。
(8) The method for producing a catalyst carrier according to item (7), wherein the kneaded product further contains a compound that gives calcium silicate.
(9) The method for producing a catalyst carrier according to (7) or (8), wherein the compound giving γ-alumina is γ-alumina.
(10) The compound that gives the aluminosilicate and / or calcium aluminosilicate is at least one selected from the group consisting of anorthite, kaolin, montmorillonite, halloysite, pyrophyllite, and allophane. The method for producing a catalyst carrier according to any one of items 7) to (9).
(11) In any one of paragraphs (8) to (10), the compound that provides calcium silicate is wollastonite, zonotlite, tobermorite, or calcium silicate hydrate. A process for producing the catalyst carrier as described.
本発明によれば、高濃度のアンモニアを含む排水と接触しても比表面積の低下及び活性成分の脱落を抑制することができると共に成形が容易である触媒担体及びその製造方法を提供することができる。
また、本発明によれば、高濃度のアンモニアを含む排水と接触しても触媒作用が低下し難い触媒担持体及び水処理材を提供することができる。
According to the present invention, it is possible to provide a catalyst carrier that can suppress a decrease in specific surface area and drop off of an active component even when it comes into contact with wastewater containing high-concentration ammonia and that can be easily molded, and a method for producing the same. it can.
Moreover, according to this invention, even if it contacts with the waste_water | drain containing high concentration ammonia, the catalyst support body and water treatment material which a catalyst action cannot fall easily can be provided.
本発明の触媒担体は、γ−アルミナと、アルミノシリケート及び／又はカルシウムアルミノシリケートとを含む。また、本発明の触媒担体は、上記成分に加えてケイ酸カルシウムをさらに含んでもよい。 The catalyst carrier of the present invention contains γ-alumina and aluminosilicate and / or calcium aluminosilicate. The catalyst carrier of the present invention may further contain calcium silicate in addition to the above components.
γ−アルミナは、触媒担体の比表面積を高めるのに必要な成分である。γ−アルミナは、スピネル型の結晶構造を有しており、高い比表面積を有するため、触媒担体の成分としてγ−アルミナを用いることにより、触媒担体の比表面積を高めることができる。ただし、触媒担体中のγ−アルミナの含有量が少なすぎると、触媒担体の比表面積を十分に高めることができない。一方、触媒担体中のγ−アルミナの含有量が多すぎると、触媒担体の強度が低下する。これらの理由から、本発明の触媒担体におけるγ−アルミナの含有量は、１０質量％〜６０質量％、好ましくは２０質量％〜６０質量％、より好ましくは２５質量％〜６０質量％、さらに好ましくは３０質量％〜６０質量％、最も好ましくは３５質量％〜６０質量％である。 γ-alumina is a component necessary for increasing the specific surface area of the catalyst support. Since γ-alumina has a spinel crystal structure and a high specific surface area, the specific surface area of the catalyst support can be increased by using γ-alumina as a component of the catalyst support. However, if the content of γ-alumina in the catalyst carrier is too small, the specific surface area of the catalyst carrier cannot be sufficiently increased. On the other hand, when the content of γ-alumina in the catalyst carrier is too large, the strength of the catalyst carrier is lowered. For these reasons, the content of γ-alumina in the catalyst carrier of the present invention is 10% by mass to 60% by mass, preferably 20% by mass to 60% by mass, more preferably 25% by mass to 60% by mass, and still more preferably. Is 30% by mass to 60% by mass, most preferably 35% by mass to 60% by mass.
アルミノシリケート及びカルシウムアルミノシリケートは、γ−アルミナの焼結促進及びアンモニアを含む排水によるγ−アルミナの水和を抑制するのに必要な成分である。
アルミノシリケートは、Ａｌ２Ｏ３（アルミナ）とＳｉＯ２（シリカ）とからなる複合酸化物（二元酸化物）である。アルミノシリケートとしては、特に限定されないが、例えば、Ａｌ２Ｏ３・２ＳｉＯ２、Ａｌ２Ｏ３・４ＳｉＯ２などが挙げられる。触媒担体に含有されるアルミノシリケートは、単一の種類であっても、２種以上の混合物であってもよい。
Aluminosilicate and calcium aluminosilicate are components necessary for accelerating sintering of γ-alumina and suppressing hydration of γ-alumina by waste water containing ammonia.
Aluminosilicate is a complex oxide (binary oxide) composed of Al 2 O 3 (alumina) and SiO 2 (silica). The aluminosilicate is not particularly limited, for example, Al 2 O 3 · 2SiO 2, Al 2 O 3 · 4SiO 2 may be mentioned. The aluminosilicate contained in the catalyst support may be a single type or a mixture of two or more types.
カルシウムアルミノシリケートは、ＣａＯ（酸化カルシウム）とＡｌ２Ｏ３とＳｉＯ２とからなる複合酸化物（三元酸化物）である。カルシウムアルミノシリケートの例としては、特に限定されないが、例えば、アノーサイト（ＣａＯ・Ａｌ２Ｏ３・２ＳｉＯ２）、ゲーレナイト（２ＣａＯ・Ａｌ２Ｏ３・ＳｉＯ２）などが挙げられる。触媒担体に含有されるカルシウムアルミノシリケートは、単一の種類であっても、２種以上の混合物であってもよい。
本発明の触媒担体におけるアルミノシリケート及び／又はカルシウムアルミノシリケートの含有量は、特に限定されず、γ−アルミナの量に応じて適宜調整すればよい。例えば、触媒担体中のγ−アルミナの含有量を１０質量％〜６０質量％にする場合、触媒担体中のアルミノシリケート及び／又はカルシウムアルミノシリケートの含有量を４０質量％〜９０質量％にすればよい。
Calcium aluminosilicate is a complex oxide (ternary oxide) composed of CaO (calcium oxide), Al 2 O 3 and SiO 2 . Examples of the calcium aluminosilicate is not particularly limited, for example, anorthite (CaO · Al 2 O 3 · 2SiO 2), gehlenite (2CaO · Al 2 O 3 · SiO 2) , and the like. The calcium aluminosilicate contained in the catalyst support may be a single type or a mixture of two or more types.
The content of aluminosilicate and / or calcium aluminosilicate in the catalyst carrier of the present invention is not particularly limited, and may be appropriately adjusted according to the amount of γ-alumina. For example, when the content of γ-alumina in the catalyst carrier is 10% by mass to 60% by mass, the content of aluminosilicate and / or calcium aluminosilicate in the catalyst carrier is 40% by mass to 90% by mass. Good.
ケイ酸カルシウムは、アンモニアを含む排水によるγ−アルミナの水和を抑制するのに有効な成分である。
ケイ酸カルシウムは、ＣａＯとＳｉＯ２とからなる複合酸化物（二元酸化物）である。ケイ酸カルシウムの例としては、特に限定されないが、ワラストナイト（ＣａＯ・ＳｉＯ２）、ランキナイト（３ＣａＯ・２ＳｉＯ２）、トライカルシウムシリケート（３ＣａＯ・ＳｉＯ２）、ダイカルシウムシリケート（２ＣａＯ・ＳｉＯ２）などが挙げられる。触媒担体に含有されるケイ酸カルシウムは、単一の種類であっても、２種以上の混合物であってもよい。
Calcium silicate is an effective component for suppressing hydration of γ-alumina by wastewater containing ammonia.
Calcium silicate is a complex oxide (binary oxide) composed of CaO and SiO 2 . Examples of calcium silicate is not particularly limited, wollastonite (CaO · SiO 2), rankinite Night (3CaO · 2SiO 2), tri-calcium silicate (3CaO · SiO 2), dicalcium silicate (2CaO · SiO 2 ) And the like. The calcium silicate contained in the catalyst support may be a single type or a mixture of two or more types.
本発明の触媒担体におけるケイ酸カルシウムの含有量は、特に限定されず、γ−アルミナ並びにアルミノシリケート及び／又はカルシウムアルミノシリケートの量に応じて適宜調整すればよい。本発明の触媒担体におけるケイ酸カルシウムの含有量は、一般に５質量％〜２５質量％である。 The content of calcium silicate in the catalyst carrier of the present invention is not particularly limited, and may be appropriately adjusted according to the amount of γ-alumina and aluminosilicate and / or calcium aluminosilicate. The content of calcium silicate in the catalyst carrier of the present invention is generally 5% by mass to 25% by mass.
本発明の触媒担体は、本発明の効果を阻害しない範囲において、当該技術分野で一般に使用される各種成分（例えば、上記成分以外の金属酸化物及び複合金属酸化物）を含むことができる。 The catalyst carrier of the present invention can contain various components generally used in the technical field (for example, metal oxides and composite metal oxides other than the above components) as long as the effects of the present invention are not impaired.
本発明の触媒担体は、当該技術分野において公知の様々な形状とすることができる。触媒担体の形状としては、特に限定されないが、球状、ペレット状、円柱状、直方体状、筒状、破砕片状、ハニカム状、粉末状などが挙げられる。 The catalyst carrier of the present invention can have various shapes known in the art. The shape of the catalyst carrier is not particularly limited, and examples thereof include a spherical shape, a pellet shape, a columnar shape, a rectangular parallelepiped shape, a cylindrical shape, a crushed piece shape, a honeycomb shape, and a powder shape.
本発明の触媒担体は、γ−アルミナを与える化合物と、アルミノシリケート及び／又はカルシウムアルミノシリケートを与える化合物とを混練して混練物を得た後、混練物を成形して焼成することによって製造することができる。なお、本発明の触媒担体がケイ酸カルシウムをさらに含む場合、ケイ酸カルシウムを与える化合物が混練物に加えられる。 The catalyst carrier of the present invention is produced by kneading a compound giving γ-alumina and a compound giving aluminosilicate and / or calcium aluminosilicate to obtain a kneaded product, and then molding and firing the kneaded product. be able to. When the catalyst carrier of the present invention further contains calcium silicate, a compound that gives calcium silicate is added to the kneaded product.
ここで、本明細書において「γ−アルミナを与える化合物」とは、γ−アルミナ、又は焼成によってγ−アルミナを生成する化合物のことを意味する。焼成によってγ−アルミナを生成する化合物としては、特に限定されないが、ギブサイト、ダイアスポア、ベーマイトなどの水酸化物、硝酸アルミニウムなどの硝酸塩、塩化アルミニウムなどの塩化物などが挙げられる。γ−アルミナを与える化合物は、単一又は２種以上を組み合わせて用いることができる。 Here, in this specification, the “compound that gives γ-alumina” means γ-alumina or a compound that forms γ-alumina by firing. Although it does not specifically limit as a compound which produces | generates (gamma) -alumina by baking, Hydrochlorides, such as gibbsite, a diaspore, boehmite, nitrates, such as aluminum nitrate, chlorides, such as aluminum chloride, etc. are mentioned. The compound which gives (gamma) -alumina can be used individually or in combination of 2 or more types.
また、本明細書において「アルミノシリケート及び／又はカルシウムアルミノシリケートを与える化合物」とは、アルミノシリケート及び／又はカルシウムアルミノシリケート、或いは焼成によってアルミノシリケート及び／又はカルシウムアルミノシリケートを生成する化合物のことを意味する。焼成によってアルミノシリケートを生成する化合物としては、特に限定されないが、カオリン（カオリナイト）、ハロイサイト、パイロフィライト、イモゴライト、アロフェンなどのケイ酸塩水和物が挙げられる。また、焼成によってカルシウムアルミノシリケートを与える化合物としては、特に限定されないが、モンモリロナイトなどのケイ酸塩水和物が挙げられる。なお、これらのケイ酸塩水和物を含有する蛙目粘土、木節粘土、信楽土などの陶土を原料として用いてもよい。アルミノシリケート及び／又はカルシウムアルミノシリケートを与える化合物は、単一又は２種以上を組み合わせて用いることができる。 Further, in the present specification, “aluminosilicate and / or calcium aluminosilicate-providing compound” means aluminosilicate and / or calcium aluminosilicate, or a compound that forms aluminosilicate and / or calcium aluminosilicate by firing. To do. Although it does not specifically limit as a compound which produces | generates an aluminosilicate by baking, Silicate hydrates, such as kaolin (kaolinite), halloysite, pyrophyllite, imogolite, allophane, are mentioned. Moreover, it does not specifically limit as a compound which gives a calcium aluminosilicate by baking, However, Silicate hydrates, such as a montmorillonite, are mentioned. In addition, you may use porcelain clay, such as Sasame clay, Kibushi clay, Shigaraki earth, etc. containing these silicate hydrates. The compound which gives aluminosilicate and / or calcium aluminosilicate can be used singly or in combination of two or more.
また、本明細書において「ケイ酸カルシウムを与える化合物」とは、ケイ酸カルシウム、又は焼成によってケイ酸カルシウムを生成する化合物のことを意味する。焼成によってケイ酸カルシウムを生成する化合物としては、特に限定されないが、トバモライト、ゾノトライト、ケイ酸カルシウム水和物（Ｃ−Ｓ−Ｈ）などが挙げられる。なお、これらの成分を含有する建設材料（例えば、軽量気泡コンクリートの端材、生コンのスラッジなど）を原料として用いてもよい。ケイ酸カルシウムを与える化合物は、単一又は２種以上を組み合わせて用いることができる。 In the present specification, the “compound that provides calcium silicate” means calcium silicate or a compound that generates calcium silicate by firing. Although it does not specifically limit as a compound which produces | generates a calcium silicate by baking, Tobermorite, a zonotolite, a calcium silicate hydrate (C-S-H), etc. are mentioned. In addition, you may use the construction material (For example, the end material of lightweight cellular concrete, sludge of ready-mixed concrete, etc.) containing these components as a raw material. The compound which gives calcium silicate can be used individually or in combination of 2 or more types.
上記の原料を混練して混練物を得る場合、混練性及びその後の成形性を確保する観点から、水、１，３−ブタンジオールなどの溶剤を混練物に配合してもよい。混練方法としては、特に限定されず、当該技術分野において公知の混練機などを用いて行なえばよい。
原料の配合割合としては、触媒担体中のγ−アルミナの含有量を１０質量％〜６０質量％とするために、混練物中のγ−アルミナを与える化合物の含有量を７質量％〜７５質量％、好ましくは１０質量％〜７０質量％、より好ましくは１５質量％〜６５質量％、さらに好ましくは２０質量％〜６０質量％、最も好ましくは２５質量％〜５５質量％に設定する。
In the case of obtaining a kneaded product by kneading the above raw materials, a solvent such as water or 1,3-butanediol may be added to the kneaded product from the viewpoint of ensuring kneadability and subsequent moldability. The kneading method is not particularly limited, and may be performed using a kneader known in the technical field.
As a mixing ratio of the raw material, in order to make the content of γ-alumina in the catalyst carrier 10 mass% to 60 mass%, the content of the compound giving γ-alumina in the kneaded product is 7 mass% to 75 mass%. %, Preferably 10 mass% to 70 mass%, more preferably 15 mass% to 65 mass%, still more preferably 20 mass% to 60 mass%, and most preferably 25 mass% to 55 mass%.
また、それ以外の原料の配合割合としては、特に限定されず、γ−アルミナを与える化合物の量に応じて適宜調整すればよい。例えば、混練物中のアルミノシリケート及び／又はカルシウムアルミノシリケートを与える化合物の含有量は、一般に２５質量％〜９３質量％、好ましくは３０質量％〜９０質量％である。また、ケイ酸カルシウムを与える化合物を配合する場合、混練物中のケイ酸カルシウムの含有量は、一般に１質量％〜２５質量％、好ましくは５質量％〜２３質量％である。 Further, the blending ratio of the other raw materials is not particularly limited, and may be appropriately adjusted according to the amount of the compound giving γ-alumina. For example, the content of the compound giving aluminosilicate and / or calcium aluminosilicate in the kneaded material is generally 25% by mass to 93% by mass, preferably 30% by mass to 90% by mass. Moreover, when mix | blending the compound which gives a calcium silicate, content of the calcium silicate in a kneaded material is generally 1 mass%-25 mass%, Preferably it is 5 mass%-23 mass%.
混練物の成形方法としては、特に限定されず、作製する触媒担体の形状に応じて適切な方法を選択すればよい。例えば、混練物を球状の成形体に成形する場合、造粒機などを用いて成形すればよい。また、混練物を円柱状、直方体状、筒状、ハニカム状などの成形体に成形する場合、押出成形機などを用いて成形すればよい。 The method for forming the kneaded product is not particularly limited, and an appropriate method may be selected according to the shape of the catalyst carrier to be produced. For example, when the kneaded product is molded into a spherical molded body, it may be molded using a granulator or the like. Moreover, what is necessary is just to shape | mold using an extrusion molding machine etc., when shape | molding kneaded material into molded objects, such as a column shape, a rectangular parallelepiped shape, a cylinder shape, and honeycomb shape.
混練物を成形した後、成形体を直ぐに焼成してもよいが、クラックなどの発生を防止する観点から、必要に応じて焼成前に乾燥を行ってもよい。
成形体の焼成は、８００℃〜１１００℃の温度で行われる。この温度範囲で焼成を行うことにより、強度を確保しつつ、γ−アルミナによる高い比表面積を維持した触媒担体を得ることが可能になる。焼成温度が８００℃未満であると、触媒担体の強度が低下し、触媒担体が崩壊し易くなる。一方、焼成温度が１１００℃を超えると、γ−アルミナが転移してコランダム構造のα−アルミナとなり、アルミナの焼結も進行するため、触媒担体の比表面積が低下してしまう。
焼成方法としては、特に限定されず、当該技術分野において公知の焼成装置を用いて行うことができる。焼成装置としては、バッチ炉、トンネル窯、ロータリーキルンなどを用いることができる。
After molding the kneaded product, the molded body may be fired immediately, but from the viewpoint of preventing the occurrence of cracks and the like, drying may be performed before firing as necessary.
Firing of the molded body is performed at a temperature of 800 ° C to 1100 ° C. By performing the calcination in this temperature range, it is possible to obtain a catalyst carrier that maintains a high specific surface area with γ-alumina while ensuring strength. When the calcination temperature is less than 800 ° C., the strength of the catalyst carrier is lowered, and the catalyst carrier is easily collapsed. On the other hand, when the calcination temperature exceeds 1100 ° C., γ-alumina is transformed to α-alumina having a corundum structure, and the alumina is also sintered, so that the specific surface area of the catalyst carrier is reduced.
The baking method is not particularly limited, and can be performed using a baking apparatus known in the technical field. As a baking apparatus, a batch furnace, a tunnel kiln, a rotary kiln, etc. can be used.
上記のようにして製造される本発明の触媒担体は、一般に２０Ｎ以上、好ましくは２５Ｎ以上、さらに好ましくは３０Ｎ以上の圧縮強度を有する。２０Ｎ以上の圧縮強度を有する触媒担体であれば、使用時に崩壊し難い。
ここで、本明細書において「圧縮強度」とは、株式会社島津製作所製のオートグラフなどの試験機を用いて測定されるものを意味する。
The catalyst carrier of the present invention produced as described above generally has a compressive strength of 20 N or more, preferably 25 N or more, more preferably 30 N or more. If the catalyst carrier has a compressive strength of 20 N or more, it is difficult to disintegrate during use.
Here, “compressive strength” in this specification means that measured using a tester such as an autograph manufactured by Shimadzu Corporation.
また、本発明の触媒担体は、高濃度のアンモニアを含む排水と接触しても比表面積の低下が起こり難く、一般に、触媒担体と２８％のアンモニア水とを固液比（質量比）が１：１０となるように混合して、１５０℃で１２時間処理した後の比表面積の低下率が５％以下である。この比表面積の低下率が５％以下であれば、担持された活性成分が脱落して流出することを抑制することができる。 Further, the catalyst carrier of the present invention is unlikely to decrease in specific surface area even when it comes into contact with wastewater containing a high concentration of ammonia. In general, the solid-liquid ratio (mass ratio) of the catalyst carrier and 28% ammonia water is 1. : The ratio of decrease in specific surface area after mixing at 10 ° C. and treating at 150 ° C. for 12 hours is 5% or less. If the reduction rate of the specific surface area is 5% or less, it is possible to suppress the supported active ingredient from falling off and flowing out.
本発明の触媒担体は、高濃度のアンモニアを含む排水と接触しても比表面積の低下及び活性成分の脱落を抑制することができるため、高濃度のアンモニアを含む排水と接触しても触媒作用が低下し難い触媒担持体を作製することができる。
本発明の触媒担持体は、触媒担体に活性成分を担持させることによって得ることができる。担持させる活性成分としては、特に限定されず、当該技術分野において公知のものを用いることができる。活性成分の例としては、白金、パラジウム、ルテニウム、ロジウム、インジウム、イリジウム、金、銀、コバルト、銅、ニッケル、タングステン、及びこれらの金属の水不溶性又は水難溶性の化合物が挙げられる。具体的には、一酸化コバルト、一酸化ニッケル、二酸化ルテニウム、三酸化二ロジウム、一酸化パラジウム、二酸化イリジウム、酸化第二銅、二酸化タングステンなどの酸化物；二塩化ルテニウム、二塩化白金などの塩化物；硫化ルテニウム、硫化ロジウムなどの硫化物などを用いることができる。
活性成分の担持量としては、特に限定されないが、一般に、触媒担体の重量の０．０５質量％〜２５質量％である。
The catalyst carrier of the present invention can suppress a decrease in specific surface area and drop off of active components even when it comes into contact with wastewater containing high concentration of ammonia. It is possible to produce a catalyst carrier that is difficult to decrease.
The catalyst carrier of the present invention can be obtained by loading an active component on a catalyst carrier. The active ingredient to be supported is not particularly limited, and those known in the technical field can be used. Examples of the active ingredient include platinum, palladium, ruthenium, rhodium, indium, iridium, gold, silver, cobalt, copper, nickel, tungsten, and water-insoluble or poorly water-soluble compounds of these metals. Specifically, oxides such as cobalt monoxide, nickel monoxide, ruthenium dioxide, dirhodium trioxide, palladium monoxide, iridium dioxide, cupric oxide, tungsten dioxide; chlorides such as ruthenium dichloride and platinum dichloride Materials: Sulfides such as ruthenium sulfide and rhodium sulfide can be used.
The amount of the active component supported is not particularly limited, but is generally 0.05% by mass to 25% by mass of the weight of the catalyst carrier.
本発明の触媒担持体は、高濃度のアンモニアを含む排水と接触しても触媒作用が低下し難いため、高温高圧条件下で排水を活性成分と接触させることが要求される触媒湿式酸化法に用いられる水処理材に用いるのに特に適している。 Since the catalyst carrier of the present invention is unlikely to deteriorate in catalytic activity even when it comes into contact with wastewater containing a high concentration of ammonia, it is suitable for a catalytic wet oxidation method in which wastewater is required to be contacted with an active component under high temperature and high pressure conditions. It is particularly suitable for use in the water treatment material used.
以下、実施例及び比較例によって本発明を詳細に説明するが、これらによって本発明が限定されるものではない。
（１）原料
原料として下記のものを準備した。
・γ−アルミナを与える化合物：γ−アルミナ（水澤化学工業株式会社製）
・カルシウムアルミノシリケートを与える化合物：モンモリロナイト（カネサン工業株式会社製）
・カルシウムアルミノシリケートを与える化合物：アノーサイト（水酸化カルシウムと酸化アルミニウムと二酸化ケイ素とを混合してペレット成型し、１１００℃の条件下で１時間焼成を行った後、粉砕することによって製造した。）
・アルミノシリケートを与える化合物：カオリン（ハットリ株式会社製）
・アルミノシリケートを与える化合物：アロフェン（品川化成株式会社製）
・ケイ酸カルシウムを与える化合物：トバモライト（酸化カルシウムと珪石と水とを混合したスラリーを１８０℃、１００００ｈＰａの条件下で１０時間水和反応を行った後、濾過して乾燥させることによって製造した。）
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited by these.
(1) Raw materials The following were prepared as raw materials.
Compound giving γ-alumina: γ-alumina (manufactured by Mizusawa Chemical Co., Ltd.)
・ Compound giving calcium aluminosilicate: Montmorillonite (manufactured by Kanesan Industry Co., Ltd.)
Compound that gives calcium aluminosilicate: Anorthite (produced by mixing calcium hydroxide, aluminum oxide and silicon dioxide, pellet-molding, firing at 1100 ° C. for 1 hour, and then pulverizing. )
・ Compound giving aluminosilicate: Kaolin (manufactured by Hattori Co., Ltd.)
・ Compound giving aluminosilicate: Allophane (manufactured by Shinagawa Kasei Co., Ltd.)
Compound that gives calcium silicate: Tobermorite (produced by subjecting a slurry obtained by mixing calcium oxide, silica, and water to a hydration reaction at 180 ° C. and 10,000 hPa for 10 hours, followed by filtration and drying. )
（２）製造方法
上記の原料を用い、表１に示す割合で原料を混合し、水及び１，３−ブタンジオールを加えて混練した。次に、混練物を直径約５ｍｍとなるように造粒した後、１５０℃で乾燥させ、表１に示す温度で５時間焼成することによって球状の触媒担体を得た。なお、サンプル中、Ｎｏ．６〜７及び１０〜１１は、成形性が悪く、成形することができなかった。
(2) Production method Using the above raw materials, the raw materials were mixed in the proportions shown in Table 1, and water and 1,3-butanediol were added and kneaded. Next, the kneaded product was granulated to have a diameter of about 5 mm, dried at 150 ° C., and calcined at the temperature shown in Table 1 for 5 hours to obtain a spherical catalyst carrier. In the sample, no. 6 to 7 and 10 to 11 had poor moldability and could not be molded.
（３）評価
上記で得られた触媒担体について、γ−アルミナ含有量、圧縮強度、並びにアンモニア耐久性試験前後の鉱物組成及び比表面積の低下率の評価を行った。
触媒担体のγ−アルミナ含有量は、リートベルト法によって算出した。
圧縮強度は、株式会社島津製作所製のオートグラフを用いて測定した。測定は１０個のサンプルで行い、その測定値の平均を評価結果とした。
(3) Evaluation The catalyst carrier obtained above was evaluated for the γ-alumina content, the compressive strength, the mineral composition before and after the ammonia durability test, and the reduction rate of the specific surface area.
The γ-alumina content of the catalyst support was calculated by the Rietveld method.
The compressive strength was measured using an autograph manufactured by Shimadzu Corporation. Measurement was performed on 10 samples, and the average of the measured values was used as the evaluation result.
アンモニア耐久性試験は、三愛科学株式会社製の高圧分解反応容器１００ｍＬ中で触媒担体２ｇ及び関東化学株式会社製アンモニア水（特級、濃度２８％）２０ｇを混合（固液比は１：１０である）して密閉した後、該反応容器を乾燥機に入れて１５０℃で１２時間放置することによって行った。アンモニア耐久性試験の終了後は、該反応容器を乾燥機から取り出して２０℃になるまで放冷した。そして、該反応容器から触媒担体を取り出した後、触媒担体を蒸留水で洗浄して１０５℃で乾燥させた。 In the ammonia durability test, 2 g of the catalyst carrier and 20 g of ammonia water (special grade, concentration 28%) manufactured by Kanto Chemical Co., Ltd. were mixed in 100 mL of a high-pressure decomposition reaction vessel manufactured by Sanai Kagaku Co., Ltd. (solid-liquid ratio is 1:10). ) And sealed, the reaction vessel was placed in a dryer and allowed to stand at 150 ° C. for 12 hours. After completion of the ammonia durability test, the reaction vessel was taken out of the dryer and allowed to cool to 20 ° C. Then, after removing the catalyst carrier from the reaction vessel, the catalyst carrier was washed with distilled water and dried at 105 ° C.
触媒担体の鉱物組成は、アルミナの種類を特定することとし、粉末Ｘ線回折装置（ブルカー・エイエックスエス株式会社製Ｄ８ａｄｖａｎｃｅ）を用いて同定した。γ−アルミナの含有量は、粉末Ｘ線回折を利用したリートベルト解析法によって求めた。
比表面積は、日本ベル株式会社製ＢＥＬＳＯＲＰｍａｘを用い、窒素吸着ＢＥＴ法によって測定した。比表面積の低下率は、（アンモニア耐久性試験前の触媒担体の比表面積−アンモニア耐久性試験後の触媒担体の比表面積）／アンモニア耐久性試験前の触媒担体の比表面積×１００によって算出した。
上記の各評価結果を表２に示す。
The mineral composition of the catalyst carrier was determined by specifying the type of alumina and using a powder X-ray diffractometer (D8 advance manufactured by Bruker AXS Co., Ltd.). The content of γ-alumina was determined by a Rietveld analysis method using powder X-ray diffraction.
The specific surface area was measured by a nitrogen adsorption BET method using BELSORPmax manufactured by Nippon Bell Co., Ltd. The reduction rate of the specific surface area was calculated by (specific surface area of catalyst support before ammonia durability test−specific surface area of catalyst support after ammonia durability test) / specific surface area of catalyst support before ammonia durability test × 100.
Each evaluation result is shown in Table 2.
表２に示されるように、サンプルＮｏ．２〜４、８〜９、１３〜１５及び１７〜１９の触媒担体（本発明例）は、強度が高いと共に比表面積の低下率が小さかった。
これに対してサンプルＮｏ．１の触媒担体（比較例）は、γ−アルミナを含有していないために比表面積が小さく、触媒担体としての使用に適していなかった。サンプルＮｏ．５の触媒担体（比較例）は、γ−アルミナの含有量が高すぎたため、強度が低く、比表面積の低下率も大きくなった。サンプルＮｏ．１６の触媒担体（比較例）は、焼成温度が高すぎたため、γ−アルミナがα−アルミナに転移し、比表面積が小さくなった。サンプルＮｏ．６〜７及び１０〜１１は、成形性が悪く、触媒担体を得ることができなかったため、評価を行うことができなかった。サンプルＮｏ．１２は、アンモニア耐久試験によって割れ、粉状化が生じ、触媒担体としての形状を維持できなかったため、評価を行わなかった。
As shown in Table 2, sample no. The catalyst carriers 2 to 4, 8 to 9, 13 to 15, and 17 to 19 (examples of the present invention) were high in strength and had a small decrease in specific surface area.
In contrast, sample no. No. 1 catalyst carrier (Comparative Example) did not contain γ-alumina, so the specific surface area was small, and it was not suitable for use as a catalyst carrier. Sample No. The catalyst carrier (Comparative Example) No. 5 had a too low content of γ-alumina, so the strength was low and the rate of decrease in specific surface area was also large. Sample No. In No. 16 catalyst carrier (comparative example), the calcination temperature was too high, so that γ-alumina was transferred to α-alumina and the specific surface area was reduced. Sample No. 6 to 7 and 10 to 11 could not be evaluated because the moldability was poor and a catalyst carrier could not be obtained. Sample No. No. 12 was not evaluated because cracking and powdering occurred in the ammonia endurance test and the shape as a catalyst carrier could not be maintained.
以上の結果からわかるように、本発明によれば、高濃度のアンモニアを含む排水と接触しても比表面積の低下及び活性成分の脱落を抑制することができると共に成形が容易である触媒担体及びその製造方法を提供することができる。また、本発明によれば、高濃度のアンモニアを含む排水と接触しても触媒作用が低下し難い触媒担持体及び水処理材を提供することができる。 As can be seen from the above results, according to the present invention, a catalyst carrier that can suppress a decrease in specific surface area and drop off of an active component even when contacted with wastewater containing high-concentration ammonia, and can be easily molded, and A manufacturing method thereof can be provided. Moreover, according to this invention, even if it contacts with the waste_water | drain containing high concentration ammonia, the catalyst support body and water treatment material which a catalyst action cannot fall easily can be provided.
Claims (11)
前記混練物を成形した後、８００℃〜１１００℃の温度で焼成する工程と
を含み、
前記混練物中の前記γ−アルミナを与える化合物の含有量が７質量％〜７５質量％である
ことを特徴とする触媒担体の製造方法。 kneading a compound giving γ-alumina and a compound giving aluminosilicate and / or calcium aluminosilicate to obtain a kneaded product;
And after baking the kneaded product, firing at a temperature of 800 ° C. to 1100 ° C.,
Content of the compound which provides the said (gamma) -alumina in the said kneaded material is 7 mass%-75 mass%, The manufacturing method of the catalyst support | carrier characterized by the above-mentioned.
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