JP4267403B2 - Fuel treatment agent - Google Patents
Fuel treatment agent Download PDFInfo
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- JP4267403B2 JP4267403B2 JP2003293931A JP2003293931A JP4267403B2 JP 4267403 B2 JP4267403 B2 JP 4267403B2 JP 2003293931 A JP2003293931 A JP 2003293931A JP 2003293931 A JP2003293931 A JP 2003293931A JP 4267403 B2 JP4267403 B2 JP 4267403B2
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- 239000000446 fuel Substances 0.000 title claims description 75
- 239000003795 chemical substances by application Substances 0.000 title claims description 67
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 83
- 239000002245 particle Substances 0.000 claims description 80
- 239000008188 pellet Substances 0.000 claims description 67
- 238000000465 moulding Methods 0.000 claims description 45
- 239000002131 composite material Substances 0.000 claims description 37
- 239000011148 porous material Substances 0.000 claims description 35
- 230000005484 gravity Effects 0.000 claims description 27
- 238000012545 processing Methods 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 239000010419 fine particle Substances 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 15
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000010304 firing Methods 0.000 claims description 11
- 239000001913 cellulose Substances 0.000 claims description 8
- 229920002678 cellulose Polymers 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 7
- 229920002472 Starch Polymers 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 229920002101 Chitin Polymers 0.000 claims description 4
- 229920002558 Curdlan Polymers 0.000 claims description 4
- 239000001879 Curdlan Substances 0.000 claims description 4
- 229920001353 Dextrin Polymers 0.000 claims description 4
- 239000004375 Dextrin Substances 0.000 claims description 4
- 229920002527 Glycogen Polymers 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 229940078035 curdlan Drugs 0.000 claims description 4
- 235000019316 curdlan Nutrition 0.000 claims description 4
- 235000019425 dextrin Nutrition 0.000 claims description 4
- 150000004676 glycans Chemical class 0.000 claims description 4
- 229940096919 glycogen Drugs 0.000 claims description 4
- 229920001282 polysaccharide Polymers 0.000 claims description 4
- 239000005017 polysaccharide Substances 0.000 claims description 4
- 229940032147 starch Drugs 0.000 claims description 4
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 49
- 239000007787 solid Substances 0.000 description 31
- 238000001125 extrusion Methods 0.000 description 30
- 239000002002 slurry Substances 0.000 description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- 238000011156 evaluation Methods 0.000 description 23
- 239000000047 product Substances 0.000 description 21
- 238000005299 abrasion Methods 0.000 description 20
- 239000011230 binding agent Substances 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 20
- 239000000017 hydrogel Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 14
- 235000010724 Wisteria floribunda Nutrition 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000000377 silicon dioxide Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 239000012798 spherical particle Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000010298 pulverizing process Methods 0.000 description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 239000002734 clay mineral Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000003825 pressing Methods 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 238000011049 filling Methods 0.000 description 8
- 238000009775 high-speed stirring Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 235000010980 cellulose Nutrition 0.000 description 7
- 238000001694 spray drying Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910000480 nickel oxide Inorganic materials 0.000 description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 5
- 235000019353 potassium silicate Nutrition 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 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 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000440 bentonite Substances 0.000 description 3
- 229910000278 bentonite Inorganic materials 0.000 description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 239000002737 fuel gas Substances 0.000 description 3
- -1 hydrogen ions Chemical class 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000004113 Sepiolite Substances 0.000 description 2
- 229910001583 allophane Inorganic materials 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 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 2
- 239000003350 kerosene Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 229910052624 sepiolite Inorganic materials 0.000 description 2
- 235000019355 sepiolite Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-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
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910005533 GaO Inorganic materials 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000003869 coulometry Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
本発明は、細孔容積が大きくても、あるいは粒子径が小さくても高い圧縮強度を有し、流動性、耐摩耗性等に優れたガス、ガソリン、灯油などの硫黄を含有する燃料の処理剤に関する。 The present invention has a high compressive strength even when the pore volume is large or the particle diameter is small, and it is excellent in fluidity and wear resistance. It relates to the agent.
近年、クリーンな水素をエネルギー源とする高効率、無公害でＣＯ2等温暖化ガスを発生しない発電システムとして燃料電池が注目されている。このような燃料電池は、家庭や事業所など固定設備、自動車などの移動設備などでの使用を目的に本格的な開発研究が行われている。 In recent years, fuel cells have attracted attention as power generation systems that use clean hydrogen as an energy source and do not generate greenhouse gases such as CO 2 with no pollution. Such fuel cells have been fully developed and researched for use in fixed facilities such as homes and offices, and mobile facilities such as automobiles.
この燃料電池に用いる燃料としては、天然ガス、ＬＰガス、都市ガス、アルコール、ガソリン、灯油、軽油等の他バイオマスなどの炭化水素系燃料が挙げられる。 Examples of the fuel used in the fuel cell include hydrocarbon fuels such as natural gas, LP gas, city gas, alcohol, gasoline, kerosene, light oil, and other biomass.
このような炭化水素系燃料を、まず水蒸気改質、部分酸化などの反応により水素ガス、ＣＯガスに変換し、後述するアノードを被毒して発電性能を低下させるＣＯガスを除去して水素ガスを得る。この水素は、アノードに供給され、アノードの金属触媒によって水素イオンと電子に解離し、電子は外部回路を通じて仕事をしながらカソードに流れ、水素イオンは電解質膜を拡散してカソードに流れ、カソードにてこの電子、水素イオンとカソードに供給される酸素とから水となって電解質膜に拡散する。すなわち、酸素と燃料ガスに由来する水素とを供給して水を生成する過程で電流を取り出すメカニズムになっている。 Such hydrocarbon fuel is first converted into hydrogen gas and CO gas by reactions such as steam reforming and partial oxidation, and the hydrogen gas is removed by poisoning the anode described later to remove the CO gas that lowers the power generation performance. Get. This hydrogen is supplied to the anode, dissociated into hydrogen ions and electrons by the metal catalyst of the anode, the electrons flow to the cathode while working through an external circuit, and the hydrogen ions diffuse to the cathode and flow to the cathode. The electrons, hydrogen ions, and oxygen supplied to the cathode are converted into water and diffused into the electrolyte membrane. That is, it is a mechanism for taking out an electric current in the process of supplying water with oxygen and hydrogen derived from fuel gas.
しかしながら、前記ＣＯガス除去工程では通常Ｒu、Ｐt、Ｎi、Ｆe等の貴金属あるいは金属触媒が用いられるが、燃料中に硫黄成分がｐｐｍオーダーでも存在するとＣＯ除去触媒が被毒されて活性が低下し、燃料電池の性能が低下する問題がある。 However, noble metals or metal catalysts such as Ru, Pt, Ni, and Fe are usually used in the CO gas removal step. However, if the sulfur component is present even in the order of ppm, the CO removal catalyst is poisoned and its activity decreases. There is a problem that the performance of the fuel cell deteriorates.
このため、燃料電池に用いられる燃料に硫黄成分が含まれている場合は、水素化脱硫法（通常、高温・水素加圧下）によって硫黄を除去して用いることが検討されている。しかしながら、この方法では副製する硫化水素を別途除去する工程が必要であり、さらに燃料油中の硫黄成分の少ない場合は硫黄除去量に対する水素化脱硫費用（設備、ランニングコスト等）が高く経済性に問題がある。 For this reason, when the sulfur component is contained in the fuel used for a fuel cell, using after removing sulfur by hydrodesulfurization method (usually under high temperature and hydrogen pressurization) is examined. However, this method requires a separate step of removing by-produced hydrogen sulfide, and if the sulfur component in the fuel oil is small, the hydrodesulfurization cost (equipment, running cost, etc.) relative to the amount of sulfur removal is high and economical. There is a problem.
また、燃料電池にＬＰガス、都市ガス等を用いる場合においては、通常の燃料としての使用における安全性の観点から所定量（１〜５０ｐｐｍ）のベンゾチオフェン、ジベンゾチオフェンなどの硫黄化合物を添加し、着臭して用いることが法律で義務づけられている。従って、ＬＰガス、都市ガス等を燃料電池に用いる場合も、使用時にこの硫黄化合物を除去して用いる必要がある。 In addition, when using LP gas, city gas or the like for the fuel cell, a predetermined amount (1 to 50 ppm) of a sulfur compound such as benzothiophene or dibenzothiophene is added from the viewpoint of safety in use as a normal fuel, It is required by law to use with odor. Therefore, when using LP gas, city gas or the like for the fuel cell, it is necessary to remove this sulfur compound before use.
しかしながら、活性、耐久性が不充分であったり、触媒の充填時に破損・摩耗して粉化したり、均一に充填することが困難で充填効率が低いなどの問題がある場合があった。 However, there are cases where there are problems such as insufficient activity and durability, breakage and abrasion when the catalyst is filled, and pulverization, and difficulty in uniformly filling and low filling efficiency.
一方、吸着剤、触媒、触媒担体等として無機酸化物粒子が用いられている。 On the other hand, inorganic oxide particles are used as adsorbents, catalysts, catalyst carriers and the like.
無機酸化物粒子は微粉末で用いられることは少なく、多くの場合ペレット状、球状、ハニカム状等に成形して用いられている。しかしながら、成形体の大きさや形状は、使用目的、条件等によって適宜選択して用いられているが、ペレットではエッジが破損・摩耗して粉化することがあり、また均一に充填することが困難であったり、充填効率が低いなどの問題がある場合があった。 Inorganic oxide particles are rarely used in the form of fine powder, and are often used after being formed into pellets, spheres, honeycombs or the like. However, the size and shape of the molded body are appropriately selected depending on the purpose of use, conditions, etc., but the pellets may be crushed due to breakage or wear of the pellets, and it is difficult to uniformly fill them. In some cases, the charging efficiency is low.
このため、球状の成形体の使用が望まれているが、高い嵩比重、充分な強度、摩耗性等を有する成形体を得ることが困難であった。特に、粒子径が５ｍｍ以下の微小な球状成形体を得ることが困難であったり、得られたとしても収率や生産効率が低い等、経済性に問題があった。 For this reason, use of a spherical molded body is desired, but it has been difficult to obtain a molded body having high bulk specific gravity, sufficient strength, wearability, and the like. In particular, it was difficult to obtain a fine spherical molded body having a particle diameter of 5 mm or less, and even if it was obtained, there was a problem in economic efficiency such as low yield and production efficiency.
本発明者等は、燃料ガス等を処理するための処理剤について鋭意検討した結果、特定の製造方法で成形体を作成すれば、高嵩比重で、圧縮強度、耐摩耗性に優れた微小球状成形体が得られ、かかる成形体を使用することで、高嵩比重で、圧縮強度、耐摩耗性等に優れ、活性、耐久性に優れた燃料処理剤が得られることを見出した。 As a result of intensive studies on the treatment agent for treating fuel gas and the like, the present inventors have found that a microsphere having a high bulk specific gravity, excellent compressive strength, and wear resistance can be obtained by creating a molded body by a specific production method. It has been found that a molded article is obtained, and by using such a molded article, a fuel treatment agent having a high bulk specific gravity, excellent compressive strength, wear resistance, etc., and excellent activity and durability can be obtained.
すなわち、本発明に係る燃料処理剤は、平均粒子径(D)が０.３〜５ｍｍの範囲にあり、細孔径が３０〜５００ｎｍの範囲の細孔容積(PV)が０.１〜０.６ｍｌ／ｇの範囲にあり、平均圧縮強度(N)が１〜３０Ｎ（ニュートン）の範囲にあり、下記式で表される平均圧縮強度指数(C)が０.５〜５の範囲にある無機酸化物を含み、前記無機酸化物が活性成分とマトリックス成分とを含んでなり、活性成分がＩ-Ｂ、II-ＢおよびVIII族から選ばれる１種以上の元素の酸化物または複合酸化物であり、Ｂ成分がII-Ａ、III-Ａ、III-Ｂ、IV-Ａ、IV-Ｂ、V-Ａ、V-Ｂ、VI-ＡおよびVII-Ａから選ばれる１種以上の元素の酸化物または複合酸化物である微小球状成形体からなることを特徴としている。 That is, the fuel treatment agent according to the present invention has an average particle diameter (D) in the range of 0.3 to 5 mm, and a pore volume (PV) in the range of the pore diameter of 30 to 500 nm of 0.1 to 0.00. It is in the range of 6 ml / g, the average compressive strength (N) is in the range of 1-30 N (Newton), and the average compressive strength index (C) represented by the following formula is in the range of 0.5-5. Comprising an oxide, wherein the inorganic oxide comprises an active component and a matrix component, and the active component is an oxide or composite oxide of one or more elements selected from the group IB, II-B and VIII Yes, oxidation of one or more elements selected from II-A, III-A, III-B, IV-A, IV-B, VA, V-B, VI-A and VII-A It is characterized by comprising a fine spherical molded body which is a product or a complex oxide.
Ｃ＝Ｎ×PV／Ｄ
前記成形体の嵩比重（ＣＢＤ）が０.８〜２.０ｇ／ｍｌの範囲にあることが好ましい。
C = N x PV / D
The molded body preferably has a bulk specific gravity (CBD) in the range of 0.8 to 2.0 g / ml.
本発明に係る燃料処理剤は、前記無機酸化物が周期律表のI-Ｂ、II-Ａ、II-Ｂ、III-Ａ、III-Ｂ、IV-Ａ、IV-Ｂ、V-Ａ、V-Ｂ、VI-Ａ、VII-Ａ、VIII族から選ばれる１種以上の元素の酸化物または複合酸化物であることが好ましい。 The fuel treatment agent according to the present invention is characterized in that the inorganic oxide is IB, II-A, II-B, III-A, III-B, IV-A, IV-B, VA of the periodic table. An oxide or composite oxide of one or more elements selected from the group V-B, VI-A, VII-A, and VIII is preferable.
さらに、成形助剤または成形助剤に由来する炭素を炭素換算で５重量％以下の範囲で含有することが望ましい。 Furthermore, it is desirable to contain the molding aid or carbon derived from the molding aid in a range of 5% by weight or less in terms of carbon.
前記成形助剤がセルロース、デンプン、グリコーゲン、カードラン、デキストリン、キチンから選ばれる１種以上の多糖類であることを特徴とする請求項１〜７のいずれかに記載の燃料処理剤。 The fuel processing agent according to any one of claims 1 to 7, wherein the molding aid is one or more polysaccharides selected from cellulose, starch, glycogen, curdlan, dextrin, and chitin.
前記無機酸化物微小球状成形体の長径(DL)と短径(DS)との比（球状係数(DL)/(DS)）が１〜１.５の範囲にあることが好ましい。 The ratio of the major axis (D L ) to the minor axis (D S ) (spherical coefficient (D L ) / (D S )) of the inorganic oxide microspherical molded body is preferably in the range of 1 to 1.5. .
平均粒子径(D)×(１±０.３)の範囲にある無機酸化物微小球状成形体の割合が８０重量％以上であることが好ましい。 It is preferable that the ratio of the inorganic oxide microspherical molded body in the range of average particle diameter (D) × (1 ± 0.3) is 80% by weight or more.
本発明によれば、嵩比重が高く、細孔容積が大きくてもあるいは粒子径が小さくても圧縮強度が高く耐摩耗性にすぐれ、かつ、球状係数が１に近く、粒子径分布が均一で、このため粉化が抑制され、流動性に優れ、均一にかつ多量の処理剤を充填することができ、処理能力に優れた燃料処理剤を提供することができる。 According to the present invention, even if the bulk specific gravity is high, the pore volume is large or the particle size is small, the compression strength is high and the wear resistance is excellent, the spherical coefficient is close to 1, and the particle size distribution is uniform. For this reason, pulverization is suppressed, it is excellent in fluidity | liquidity, it can be filled with a large amount of processing agents uniformly, and the fuel processing agent excellent in processing capacity can be provided.
以下、本発明に係る燃料処理剤について具体的に説明する。 Hereinafter, the fuel processing agent according to the present invention will be specifically described.
燃料処理剤
本発明に係る燃料処理剤は、平均粒子径(D)が０.３〜５ｍｍの範囲にあり、細孔径が３０〜５００ｎｍの範囲の細孔容積(PV)が０.１〜０.６ｍｌ／ｇの範囲にあり、平均圧縮強度(N)が１〜３０Ｎ（ニュートン）の範囲にあり、下記式で表される平均圧縮強度指数(C)が０.５〜５の範囲にある無機酸化物微小球状成形体からなることを特徴としている。
Fuel treatment agent The fuel treatment agent according to the present invention has an average particle diameter (D) in the range of 0.3 to 5 mm and a pore volume (PV) in the range of pore diameter of 30 to 500 nm of 0. The average compressive strength (N) is in the range of 1-30 N (Newton), and the average compressive strength index (C) represented by the following formula is 0.5-5. It is characterized by comprising an inorganic oxide microspherical molded body in the range of.
Ｃ＝Ｎ×PV／Ｄ
球状成形体は、平均粒子径(D)が０.３〜５ｍｍ、さらには０.５〜３ｍｍの範囲にあることが好ましい。
C = N x PV / D
The spherical molded body preferably has an average particle diameter (D) of 0.3 to 5 mm, more preferably 0.5 to 3 mm.
球状成形体の平均粒子径(D)が０.３ｍｍ未満のものは、ダイスの孔径が小さいために押し出し成形することができず、このため得ることが困難である。 A spherical molded body having an average particle diameter (D) of less than 0.3 mm cannot be extruded because the hole diameter of the die is small, and is thus difficult to obtain.
球状成形体の平均粒子径(D)が５ｍｍを越える場合は、このような大きな球状触媒は他の方法で容易に製造可能である。 When the average particle diameter (D) of the spherical molded body exceeds 5 mm, such a large spherical catalyst can be easily produced by other methods.
また、球状成形体は、細孔径が３０〜５００ｎｍの範囲の細孔容積(PV)が０.１〜０.６ｍｌ／ｇ、さらには０.２〜０.５ｍｌ／ｇの範囲にあることが好ましい。 The spherical molded body may have a pore volume (PV) in the range of 30 to 500 nm in the range of 0.1 to 0.6 ml / g, and further in the range of 0.2 to 0.5 ml / g. preferable.
球状成形体の細孔径が３０〜５００ｎｍの範囲の細孔容積(PV)が前記下限未満の場合は、活性や吸着性能が低下し燃料処理能力が不充分となる。球状成形体の細孔径が３０〜５００ｎｍの範囲の細孔容積(PV)が前記上限を越えると、無機酸化物微小球状成形体の圧縮強度および嵩比重が低下し、耐摩耗性も低下することがある。 When the pore volume (PV) in the range where the pore diameter of the spherical molded body is in the range of 30 to 500 nm is less than the lower limit, the activity and the adsorption performance are lowered and the fuel processing capacity becomes insufficient. If the pore volume (PV) in the range where the pore diameter of the spherical molded body is in the range of 30 to 500 nm exceeds the above upper limit, the compressive strength and bulk specific gravity of the inorganic oxide microspherical molded body will decrease, and the wear resistance will also decrease. There is.
本発明における上記した細孔容積は水銀圧入法による細孔分布測定装置（QUANTA CHROME 社製：AUTOSCAN-60 POROSOMETER、水銀接触角１３０℃、水銀表面張力４７３Dyn/cm2、測定レンジ「高圧」）により測定することができる。 The above pore volume in the present invention is measured by a pore distribution measuring device (manufactured by QUANTA CHROME: AUTOSCAN-60 POROSOMETER, mercury contact angle 130 ° C., mercury surface tension 473 Dyn / cm 2 , measurement range “high pressure”). Can be measured.
つぎに、球状成形体の平均圧縮強度(N)が１〜３０Ｎ（ニュートン）、さらには１.５〜２０Ｎの範囲にあることが好ましい。無機酸化物微小球状成形体の平均圧縮強度(N)が前記下限未満の場合は、使用に際して充填したり、これを抜き出したりする際に壊れ、使用条件によっては差圧が生じて燃料処理能力が低下したり、繰り返し使用することが困難となる。 Next, the average compression strength (N) of the spherical molded body is preferably in the range of 1 to 30 N (Newton), more preferably 1.5 to 20 N. When the average compressive strength (N) of the inorganic oxide microspherical molded body is less than the lower limit, it is broken when filled or pulled out during use, and depending on the use conditions, a differential pressure is generated, resulting in a fuel processing capacity. It becomes difficult to use repeatedly.
無機酸化物微小球状成形体の平均圧縮強度(N)が３０Ｎを越えて高い圧縮強度の無機酸化物微小球状成形体を得ることは困難である。 It is difficult to obtain an inorganic oxide microspherical molded article having a high compressive strength when the average compressive strength (N) of the inorganic oxide microspherical molded article exceeds 30N.
本発明で用いる平均圧縮強度(N)は、２０個の無機酸化物微小球状成形体について圧縮強度を木屋式硬度計（藤原製作所製）で測定し、この平均値とした。 The average compressive strength (N) used in the present invention was determined by measuring the compressive strength of 20 inorganic oxide microspherical molded bodies with a Kiyama hardness tester (manufactured by Fujiwara Seisakusho).
つぎに、本発明に係る無機酸化物微小球状成形体は、下記式で表される圧縮強度指数(C)が０.５〜５、好ましくは１.０〜５の範囲にある。 Next, the inorganic oxide microspherical molded body according to the present invention has a compressive strength index (C) represented by the following formula in the range of 0.5 to 5, preferably 1.0 to 5.
Ｃ＝Ｎ×PV／Ｄ
この圧縮強度指数(C)は、無機酸化物微小球状成形体の平均圧縮強度(N)を求め、これに細孔容積(PV)を乗じ、平均粒子径(D)で除して得られる。
C = N x PV / D
The compressive strength index (C) is obtained by calculating the average compressive strength (N) of the inorganic oxide microspherical shaped product, multiplying this by the pore volume (PV), and dividing by the average particle size (D).
通常、圧縮強度は粒子径に比例し、細孔容積に反比例することから、上記圧縮強度指数(C)は粒子径、細孔容積に依存しない圧縮強度を意味している。 Usually, since the compressive strength is proportional to the particle diameter and inversely proportional to the pore volume, the compressive strength index (C) means a compressive strength independent of the particle diameter and pore volume.
無機酸化物微小球状成形体の圧縮強度指数(C)が０.５未満の場合は、粒子径にかかわらず、使用に際して充填したり、これを抜き出したりする際に壊れ、使用条件によっては差圧が生じて反応成績が低下したり、繰り返し使用することが困難となる。 If the compressive strength index (C) of the inorganic oxide microspherical molded body is less than 0.5, it will break when used or withdrawn regardless of the particle size, and depending on the usage conditions, the differential pressure Will occur, resulting in poor reaction results and difficulty in repeated use.
無機酸化物微小球状触成形体の圧縮強度指数(C)が５を越えて高い圧縮強度指数の無機酸化物微小球状成形体を得ることは困難である。 It is difficult to obtain an inorganic oxide microspherical molded article having a high compressive strength index when the compressive strength index (C) of the inorganic oxide microspherical molded article exceeds 5.
前記無機酸化物微小球状成形体の長径(DL)と短径(DS)との比（球状係数：(DL)／(DS)）が１〜２、さらには１〜１.５、特に１〜１.２の範囲にあることが好ましい。この範囲にあれば球に近い形状を有しており、充填密度を高めることが可能であり、流動性にすぐれている。 The ratio (spherical coefficient: (D L ) / (D S )) of the major axis (D L ) and the minor axis (D S ) of the inorganic oxide microspherical molded body is 1 to 2, and further 1 to 1.5. In particular, it is preferably in the range of 1 to 1.2. If it is in this range, it has a shape close to a sphere, it is possible to increase the packing density, and it has excellent fluidity.
この球状係数が２を越えると、充填密度が低下するとともに充填の再現性に劣ることがあり、このため性能が充分発揮されなかったり再現性に劣ることがあり、また流動性が低下し、球状触媒とする効果が充分得られないことがある。 When this spherical coefficient exceeds 2, the packing density is lowered and the reproducibility of the filling may be inferior. For this reason, the performance may not be sufficiently exhibited or the reproducibility may be inferior. The effect as a catalyst may not be sufficiently obtained.
本発明における平均粒子径および球状係数は、粒子の光学写真を撮影し、ノギスにて粒子の長径と短径をもとめ、その平均値を粒子径とし、これを１００個の粒子についてもとめ、その平均値を平均粒子径(D)とし、また、長径と短径との比の平均値を球状係数(DL)／(DS)とした。 The average particle diameter and spherical coefficient in the present invention are obtained by taking an optical photograph of particles, obtaining the long and short diameters of the particles with a caliper, and determining the average value as the particle diameter. The value was defined as the average particle diameter (D), and the average value of the ratio between the long diameter and the short diameter was defined as the spherical coefficient (D L ) / (D S ).
微小球状成形体は、粒子径が(D)×（１±０.３）の範囲にある粒子の割合が８０重量％以上、さらには９０重量％以上であることが好ましい。(D)×（１±０.３）の範囲にある粒子の割合が８０重量％未満の場合は、反応の種類によっては粒子径の違いによる活性や選択性の違いがあるため最適な性能を得ることが困難となったり、反応条件によっては差圧が生じる原因となることがある。 The proportion of particles having a particle diameter in the range of (D) × (1 ± 0.3) is preferably 80% by weight or more, more preferably 90% by weight or more. When the proportion of particles in the range of (D) × (1 ± 0.3) is less than 80% by weight, depending on the type of reaction, there are differences in activity and selectivity due to differences in particle size, so optimal performance is achieved. It may be difficult to obtain or may cause a differential pressure depending on reaction conditions.
微小球状成形体の嵩比重（ＣＢＤ）は０.８〜２.０ｇ／ｍｌ、好ましくは0.9〜1.5ｇ／ｍｌの範囲にあることが望ましい。 The bulk specific gravity (CBD) of the microspherical molded body is in the range of 0.8 to 2.0 g / ml, preferably 0.9 to 1.5 g / ml.
このような範囲にあると、触媒の単位重量あたりの活性を損なうことなく一定容積の反応塔に高重量の触媒を充填できるので高い処理能力を発揮することができる。 Within such a range, a high capacity catalyst can be packed in a constant volume reaction tower without impairing the activity per unit weight of the catalyst, so that high throughput can be exhibited.
無機酸化物
本発明に用いる無機酸化物は、周期律表のＩ-Ｂ、II-Ａ、II-Ｂ、III-Ａ、III-Ｂ、IV-Ａ、IV-Ｂ、V-Ａ、V-Ｂ、VI-Ａ、VII-ＡおよびVIII族から選ばれる１種以上の元素の酸化物または複合酸化物である。
Inorganic oxides The inorganic oxides used in the present invention are IB, II-A, II-B, III-A, III-B, IV-A, IV-B, VA, V- It is an oxide or composite oxide of one or more elements selected from group B, VI-A, VII-A and VIII.
このような酸化物、複合酸化物としてはＣuＯ、ＡgＯ、ＭgＯ、ＣaＯ、ＢaＯ、ＺnＯ、Ｌa2Ｏ3、ＣeＯ2、Ａl2Ｏ3、ＧaＯ、ＴiＯ2、ＺrＯ2、ＳiＯ2、ＧeＯ2、ＳnＯ2、Ｖ2Ｏ5、Ｖ2Ｏ5、Ｎb2Ｏ5、Ｐ2Ｏ5、Ｓb2Ｏ3、Ｓb2Ｏ5、Ｂi2Ｏ3、ＣrＯ3、ＭoＯ3、ＷＯ3、ＭnＯ2、Ｆe2Ｏ3、ＣoＯ、ＮiＯ等の酸化物、ＳiＯ2-Ａl2Ｏ3、ＳiＯ2-ＴiＯ2、ＳiＯ2-ＺrＯ2、Ａl2Ｏ3-ＭgＯ、Ａl2Ｏ3-ＣuＯ、Ａl2Ｏ3-ＺnＯ、Ａl2Ｏ3-ＮiＯ等の複合酸化物が挙げられる。 Such oxides, CuO is a composite oxide, AgO, MgO, CaO, BaO , ZnO, La 2 O 3, CeO 2, Al 2 O 3, GaO, TiO 2, ZrO 2, SiO 2, GeO 2, SnO 2, V 2 O 5, V 2 O 5, Nb 2 O 5, P 2 O 5, Sb 2 O 3, Sb 2 O 5, Bi 2 O 3, CrO 3, MoO 3, WO 3, MnO 2, Oxides such as Fe 2 O 3 , CoO, NiO, SiO 2 —Al 2 O 3 , SiO 2 —TiO 2 , SiO 2 —ZrO 2 , Al 2 O 3 —MgO, Al 2 O 3 —CuO, Al 2 O Complex oxides such as 3 -ZnO and Al 2 O 3 -NiO are mentioned.
本発明に係る燃料処理剤では、無機酸化物が活性成分とマトリックス成分とを含んでなる。 In the fuel treatment agent according to the present invention, the inorganic oxide includes an active component and a matrix component.
活性成分としては、Ｉ-Ｂ、II-ＢおよびVIIIから選ばれる１種以上の元素の酸化物または複合酸化物であり、マトリックス成分がII-Ａ、III-Ａ、III-Ｂ、IV-Ａ、IV-Ｂ、V-Ａ、V-Ｂ、VI-Ａ、VI-ＢおよびVII-Ｂから選ばれる１種以上の元素の酸化物または複合酸化物であることが好ましい。 The active component is an oxide or composite oxide of one or more elements selected from IB, II-B and VIII, and the matrix component is II-A, III-A, III-B, IV-A. IV-B, VA, VB, VI-A, VI-B and VII-B are preferably oxides or composite oxides of one or more elements selected from the group consisting of
活性成分としては、ＣuＯ、ＡgＯ、ＺnＯ、Ｆe2Ｏ3、ＣoＯ、ＮiＯ等の酸化物、複合酸化物、これらの混合物が挙げられる。これらの酸化物、複合酸化物を含んでいると反応の種類によっても異なるが、活性、選択性、耐久性等に優れた触媒を得ることができる。また、吸着剤として用いた場合に吸着性能に優れた吸着材を得ることができる。 Examples of the active component include oxides such as CuO, AgO, ZnO, Fe 2 O 3 , CoO, and NiO, composite oxides, and mixtures thereof. When these oxides and composite oxides are contained, a catalyst excellent in activity, selectivity, durability and the like can be obtained, although it varies depending on the type of reaction. Moreover, when used as an adsorbent, an adsorbent excellent in adsorption performance can be obtained.
また、マトリックス成分としては、前記活性成分を除く前記酸化物、複合酸化物等が挙げられ、なかでも、ＳiＯ2、Ａl2Ｏ3、ＴiＯ2、ＺrＯ2から選ばれる１種以上の酸化物ま
たは複合酸化物であることが好ましい。
Examples of the matrix component include the oxides and composite oxides excluding the active component. Among them, one or more oxides selected from SiO 2 , Al 2 O 3 , TiO 2 , and ZrO 2 or A composite oxide is preferable.
このような酸化物、複合酸化物をマトリックス成分として含んでいると、細孔容積、比表面積等の大きな吸着剤、触媒、触媒担体を得ることができ、加えて、圧縮強度、耐摩耗性、流動性等に優れた微小球状の燃料処理剤を得ることができる。 When such an oxide or composite oxide is included as a matrix component, a large adsorbent such as pore volume and specific surface area, a catalyst, and a catalyst support can be obtained, and in addition, compressive strength, abrasion resistance, A fine spherical fuel treatment agent having excellent fluidity and the like can be obtained.
このような酸化物、複合酸化物は、例えば、前記元素の化合物の水溶液に酸またはアルカリ等を加えて中和することによって、あるいは前記元素の化合物の水溶液を混合するか、混合水溶液に酸またはアルカリ等を加えて中和することによって得られる沈殿を、洗浄、乾燥、焼成等することによって得ることができる。 Such oxides and composite oxides are, for example, neutralized by adding an acid or alkali to an aqueous solution of the element compound, or mixed with an aqueous solution of the element compound, A precipitate obtained by neutralization by adding an alkali or the like can be obtained by washing, drying, firing or the like.
バインダー
本発明の燃料処理剤は、前記無機酸化物に加えてバインダーを含んでいることが好ましい。
Binder The fuel treatment agent of the present invention preferably contains a binder in addition to the inorganic oxide.
バインダーとしては、前記無機酸化物と結合することができれば特に制限はなく、従来公知のバインダーを用いることができる。具体的には、微粒子状のアルミナ、シリカ、ジルコニア、チタニア、シリカ・アルミナ、シリカ・ジルコニアなどが例示され、これらはアルミナゾル、シリカゾル、ジルコニアゾル、チタニアゾル、シリカ・アルミナゾル、シリカ・ジルコニアゾル等のゾルとして使用することも可能である。微粒子は、平均粒子径が概ね５〜１００ｎｍの範囲にあることが好ましい。 The binder is not particularly limited as long as it can be bonded to the inorganic oxide, and a conventionally known binder can be used. Specifically, particulate alumina, silica, zirconia, titania, silica / alumina, silica / zirconia, etc. are exemplified, and these are sols such as alumina sol, silica sol, zirconia sol, titania sol, silica / alumina sol, silica / zirconia sol, etc. It can also be used. The fine particles preferably have an average particle diameter in the range of about 5 to 100 nm.
また、カオリン、モンモリロナイト、ベントナイト、アロフェン、セピオライト等の粘土鉱物もバインダーとして使用することが可能である。 In addition, clay minerals such as kaolin, montmorillonite, bentonite, allophane and sepiolite can also be used as a binder.
粘土鉱物は、粒子径が概ね０.１〜１０μｍの範囲にあることが好ましく、その形状は特に制限されるものではなく、球状、繊維状、不定形等のいずれであってもよい。 The clay mineral preferably has a particle diameter in the range of about 0.1 to 10 μm, and the shape is not particularly limited, and may be any of spherical, fibrous, amorphous, and the like.
さらに、必要に応じて前記ゾルと粘土鉱物を併用することもできる。 Furthermore, the sol and clay mineral can be used in combination as necessary.
このようなバインダーの含有量は、無機酸化物微小球状成形体中に固形分として２〜６０重量％、さらには５〜５０重量％の範囲にあることが好ましい。 The content of such a binder is preferably in the range of 2 to 60% by weight, more preferably 5 to 50% by weight as a solid content in the inorganic oxide microspherical molded body.
バインダーの含有量が無機酸化物微小球状成形体中に固形分として２重量％未満の場合は、無機酸化物の種類によっては成形性に劣ることがある。 When the content of the binder is less than 2% by weight as the solid content in the inorganic oxide microspherical molded body, the moldability may be inferior depending on the type of the inorganic oxide.
バインダーの含有量が無機酸化物微小球状成形体中に固形分として６０重量％を越えると、触媒、触媒単体、吸着材等として用いる場合に無機酸化物の特性が充分発揮されないことがある。 When the content of the binder exceeds 60% by weight as the solid content in the inorganic oxide microspherical molded article, the characteristics of the inorganic oxide may not be sufficiently exhibited when used as a catalyst, a catalyst simple substance, an adsorbent or the like.
上記において、バインダーとして前記微粒子が含まれていると、無機酸化物を結合し、成型時の可塑性を増して成形性を良くし、また得られる無機酸化物微小球状成形体の圧縮強度および耐摩耗性を高めることができる。 In the above, when the fine particles are contained as a binder, the inorganic oxide is bound, the plasticity at the time of molding is increased and the moldability is improved, and the compression strength and abrasion resistance of the resulting inorganic oxide microspherical molded body Can increase the sex.
また、粘土鉱物が含まれていると、成形性を向上させたり、強度、耐摩耗性が向上するとともに、細孔容積、細孔径、粒子密度、嵩比重等を調節することができる。 Moreover, when a clay mineral is contained, moldability can be improved, strength and wear resistance can be improved, and pore volume, pore diameter, particle density, bulk specific gravity and the like can be adjusted.
本発明で用いる粘土鉱物としては、中でもベントナイト等の繊維状のフィラーは成形性に優れ、このため均一な粒径分布を有し、球状で、圧縮強度、摩耗性に優れた無機酸化物微小球状成形体を得ることができる。 Among the clay minerals used in the present invention, among others, fibrous fillers such as bentonite are excellent in moldability, and thus have a uniform particle size distribution, are spherical, and are inorganic oxide microspheres that are excellent in compressive strength and wear resistance. A molded body can be obtained.
粉砕粉体
さらに、上記無機酸化物微粒子成形体は、後述する工程（ｄ）で得られた無機酸化物微小球状成形体を粉砕して（または粉砕したのち焼成して）得た平均粒子径が１０〜１００μｍ、さらには２０〜８０μｍの範囲にある粉体を、全固形分中の含有量が２〜４０重量％、さらには５〜３０重量％の範囲となるように含んでいることが好ましい。すなわち(a)〜(d)工程を経て得られた無機酸化物微小球状成形体の粉砕物を含んでいると、その理由は明確ではないものの、成形性の向上、無機酸化物微小球状成形体の圧縮強度、耐摩耗性の向上を発現することができる。
Milling powder addition, the inorganic oxide fine particle compacts, (by firing After or ground) ground to the inorganic oxide fine spherical green body obtained in later-described step (d) the average particle size obtained It is preferable that the powder in the range of 10 to 100 μm, more preferably 20 to 80 μm, is contained so that the content in the total solid content is 2 to 40% by weight, more preferably 5 to 30% by weight. . That is, when the inorganic oxide microspherical molded product obtained through the steps (a) to (d) is included, the reason is not clear, but the improvement in moldability, inorganic oxide microspherical molded product Compressive strength and wear resistance can be improved.
このような、工程（ｄ）で得られた無機酸化物微小球状成形体を粉砕して得た粉体の全固形分中の含有量が２重量％未満の場合は、粉砕して得た粉体を混合する効果が充分得られないことがある。 When the content in the total solid content of the powder obtained by pulverizing the inorganic oxide microspherical molded body obtained in step (d) is less than 2% by weight, the powder obtained by pulverization The effect of mixing the body may not be sufficiently obtained.
無機酸化物微小球状成形体を粉砕して得た粉体の全固形分中の含有量が４０重量％を越えると、押し出し成形が困難となったり、球状化する際に粉化したり球状成形体が得られないことがある。 When the content in the total solid content of the powder obtained by pulverizing the inorganic oxide microspherical molded body exceeds 40% by weight, extrusion molding becomes difficult, or powdered when spheroidized or spherical molded body May not be obtained.
また、無機酸化物微小球状成形体を粉砕して得た粉体の平均粒子径が１０μｍ未満の場合は、粉砕して得た粉体を混合する効果、すなわち成形性の向上、無機酸化物微小球状成形体の圧縮強度、耐摩耗性の向上が充分得られないことがある。 In addition, when the average particle size of the powder obtained by pulverizing the inorganic oxide microspherical molded body is less than 10 μm, the effect of mixing the powder obtained by pulverization, that is, improvement of moldability, In some cases, the compression strength and wear resistance of the spherical molded body cannot be sufficiently improved.
無機酸化物微小球状成形体を粉砕して得た粉体の平均粒子径が１００μｍを越えると、含有量にもよるが押し出し成形が困難となったり、球状化する際に粉化する傾向がある。 When the average particle size of the powder obtained by pulverizing the inorganic oxide microspherical molded body exceeds 100 μm, although it depends on the content, extrusion molding becomes difficult or the powder tends to be pulverized when spheroidized. .
成形助剤
さらに、本発明の燃料処理剤は、成形助剤（可塑剤ということがある）または成形助剤に由来する炭素を、全固形分（無機酸化物、バインダー、粉砕粉体等の合計）中に炭素換算で５重量％以下、さらには０.２〜３重量％の範囲で含有することが好ましい。
Molding aid Further, the fuel treatment agent of the present invention comprises a molding aid (sometimes referred to as a plasticizer) or carbon derived from the molding aid in a total solid content (inorganic oxide, binder, pulverized powder, etc.). ) Is preferably 5% by weight or less, more preferably 0.2 to 3% by weight in terms of carbon.
前記成形助剤としては、成形性を向上できれば特に制限はなく従来公知の成形助剤を用いることができる。 The molding aid is not particularly limited as long as the moldability can be improved, and a conventionally known molding aid can be used.
例えば、結晶セルローズ、メチルセルローズ、カルボキシメチルセルローズ、ヒドロキシエチルセルローズなどのセルローズ系助剤、デンプン、グリコーゲン、カードラン、デキストリン、キチン等の多糖類、ポリビニルアルコール、澱粉、リグニン等が挙げられる。 For example, cellulose auxiliary such as crystalline cellulose, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, polysaccharides such as starch, glycogen, curdlan, dextrin, chitin, polyvinyl alcohol, starch, lignin and the like.
なかでも、セルローズ系助剤、デンプン、グリコーゲン、カードラン、デキストリン、キチンから選ばれる１種以上の多糖類であることが好ましい。 Of these, one or more polysaccharides selected from cellulose auxiliary, starch, glycogen, curdlan, dextrin, and chitin are preferable.
成形助剤の含有量が炭素換算で５重量％を越えると、成形助剤が多すぎて後に球形化する際に粉化したり、得られる無機酸化物微小球状成形体の嵩比重、圧縮強度や耐摩耗性が低下する傾向にある。 When the content of the molding aid exceeds 5% by weight in terms of carbon, there are too many molding aids and powdered when spheroidizing later, or the bulk specific gravity, compressive strength, Abrasion resistance tends to decrease.
成形助剤を前記範囲で含んでいると、後述する押し出し成型時の水分含有量の範囲を広くすることができる。例えば、成形助剤を添加しない場合の成形可能な水分含有量の範囲は４０〜５２重量％であるが、成形助剤として結晶セルローズを固形分の３重量％使用すると水分含有量の範囲は３８〜５５重量％であっても成形性が良く、造粒時に付着することがなく、充分な圧縮強度と耐摩耗性を有する無機酸化物微小球状成形体を得ることができる。さらに、理由は明らかではないが、後述する押し出し成形した際にペレットは、ペレットの長さ（Ｌ）と径（Ｄ）の比Ｌ／Ｄが概ね１〜２の範囲となるように折れるので、人為的にカットすることなく造粒することができる。 If the molding aid is contained in the above range, the moisture content range during extrusion molding described later can be widened. For example, the range of water content that can be molded without the addition of a molding aid is 40 to 52% by weight, but when 3% by weight of crystalline cellulose is used as a molding aid, the range of water content is 38%. Even if it is ˜55% by weight, the formability is good, it does not adhere at the time of granulation, and an inorganic oxide microspherical shaped article having sufficient compressive strength and wear resistance can be obtained. Furthermore, although the reason is not clear, when the extrusion molding described later, the pellet is folded so that the ratio L / D of the length (L) and the diameter (D) of the pellet is approximately in the range of 1-2. Granulate without artificially cutting.
さらに、高嵩比重で圧縮強度、耐摩耗性および流動性に優れた無機酸化物微小球状触媒を得ることができる。ここで、嵩比重が高いと燃料処理剤の充填量が多くなり、このため処理能力を向上させることができる。 Furthermore, an inorganic oxide microspherical catalyst having a high bulk specific gravity and excellent compressive strength, abrasion resistance and fluidity can be obtained. Here, when the bulk specific gravity is high, the filling amount of the fuel processing agent increases, and thus the processing capacity can be improved.
無機酸化物微小球状成形体の製造方法
上記した燃料処理剤である無機酸化物微小球状成形体の製造方法は、前記した無機酸化物微小球状成形体が得られれば特に制限はないが、下記の工程（ａ）〜工程（ｄ）からなる無機酸化物微小球状成形体の製造方法は好適に採用することができる。
（ａ）水分含有量が３０〜６０重量％の範囲にある無機酸化物微粒子成形前駆体を調製する工程
（ｂ）下押し成形機にて成形し、径（Ｄ）が０.３〜５ｍｍの範囲にあるペレット状成形体とする工程
（ｃ）ついで、球形機にて球状成形体とする工程
（ｄ）ついで、乾燥および／または焼成する工程
工程（ａ）
無機酸化物
無機酸化物としては前記したと同様のものを用いることができる。
Manufacturing method of inorganic oxide microspherical molded body The manufacturing method of the inorganic oxide microspherical molded body, which is the fuel treatment agent described above, is not particularly limited as long as the above-described inorganic oxide microspherical molded body is obtained. The manufacturing method of the inorganic oxide microspherical molded object which consists of a process (a)-a process (d) is employable suitably.
(A) Step of preparing an inorganic oxide fine particle molding precursor having a moisture content in the range of 30 to 60% by weight (b) Molding with a down-press molding machine and a diameter (D) in the range of 0.3 to 5 mm Step (c) for forming a pellet-shaped molded body in step (b), Step (d) for forming a spherical molded body with a spheroid machine, and then drying and / or firing
Step (a)
The same inorganic oxide as described above can be used.
具体的には、例えば、前記元素の化合物の水溶液に酸またはアルカリ等を加えて中和することによって、あるいは前記元素の化合物の水溶液の混合水溶液を互いに混合するか酸またはアルカリ等を加えて中和することによって得られる沈殿を、洗浄し、必要に応じて熟成して得られる酸化物（水酸化物）、複合酸化物（複合水酸化物）等の無機酸化物ヒドロゲルスラリーを好適に用いることができる。ヒドロゲルスラリーの固形分濃度は、固形分濃度は２〜４０重量％、好適には５〜３０重量％のものが望ましい。 Specifically, for example, by adding an acid or alkali to an aqueous solution of the elemental compound to neutralize, or by mixing an aqueous mixed solution of the elemental compound with each other or adding an acid or alkali or the like Preferably, an inorganic oxide hydrogel slurry such as oxide (hydroxide) or composite oxide (composite hydroxide) obtained by washing and aging as necessary is obtained by washing the precipitate. Can do. The solid content concentration of the hydrogel slurry is desirably 2 to 40% by weight, preferably 5 to 30% by weight.
バインダー
バインダーとしては前記したと同様の微粒子・ゾルおよび／または粘土鉱物を用いることができる。
As the binder, the same fine particles / sol and / or clay mineral as described above can be used.
ゾルとしては、アルミナゾル、シリカゾル、ジルコニアゾル、チタニアゾル、シリカ・アルミナゾル、シリカ・ジルコニアゾル等のゾルは好適に用いることができる。ゾルを使用する場合、固形分濃度は１〜５０重量％、好適には２〜４０重量％のものが望ましい。 As the sol, sols such as alumina sol, silica sol, zirconia sol, titania sol, silica / alumina sol and silica / zirconia sol can be preferably used. When a sol is used, the solid concentration is preferably 1 to 50% by weight, preferably 2 to 40% by weight.
このときのゾルは、平均粒子径が概ね５〜１００ｎｍの範囲にあることが好ましい。 The sol at this time preferably has an average particle diameter in the range of about 5 to 100 nm.
また、カオリン、モンモリロナイト、ベントナイト、アロフェン、セピオライト等の粘土鉱物も好適に用いることができる。 In addition, clay minerals such as kaolin, montmorillonite, bentonite, allophane, and sepiolite can also be suitably used.
粘土鉱物は、粒子径が概ね０.１〜５μｍの範囲にあることが好ましく、その形状は特に制限されるものではなく、球状、繊維状、不定形等のいずれであってもよい。 The clay mineral preferably has a particle diameter in the range of about 0.1 to 5 μm, and the shape is not particularly limited, and may be any of spherical, fibrous, amorphous, and the like.
さらに、必要に応じて前記ゾルと粘土鉱物を併用することもできる。 Furthermore, the sol and clay mineral can be used in combination as necessary.
本発明の無機酸化物微小球状成形体の製造方法では、上記した無機酸化物ヒドロゲルスラリーに、必要に応じてバインダー、粉砕粉体、成形助剤を混合し、えられた無機酸化物微粒子成形前駆体の水分量を、無機酸化物の種類によって異なるが３５〜６０重量％、好ましくは３７〜５８重量％の範囲のとなるように調整する。 In the method for producing an inorganic oxide microspherical molded body of the present invention, the inorganic oxide hydrogel slurry is mixed with a binder, a pulverized powder, and a molding aid as necessary, and the resulting inorganic oxide fine particle molding precursor is mixed. The moisture content of the body is adjusted to be in the range of 35 to 60% by weight, preferably 37 to 58% by weight, although it varies depending on the type of inorganic oxide.
成形前駆体の水分含有量が３５重量％未満の場合は、押し出し成形が困難となり、混合物粉体の水分含有量が６０重量％を越えると、押し出し成形されたペレットの長さが不均一であったり、長くなる傾向にあり、造粒工程で球状の粒子とすることが困難となり、このため後述するペレットの長さ（Ｌ）に切断する必要が生じる。また、ペレットが互いに付着して凝集した成形体となることがある。 When the moisture content of the molding precursor is less than 35% by weight, extrusion molding becomes difficult. When the moisture content of the mixture powder exceeds 60% by weight, the length of the extruded pellets is not uniform. It becomes difficult to obtain spherical particles in the granulation process, and it is necessary to cut the pellet to the length (L) described later. In addition, pellets may adhere to each other and form a molded body.
水分を調整する方法としては、上記した水分量になれば特に制限はなく、従来公知の方法を採用することができ、例えば無機酸化物ヒドロゲルスラリーとバインダー、さらには、粉砕粉体等の混合物に所定量の水を加えるか、あるいは脱水・乾燥することによって調整することができる。 The method for adjusting the moisture is not particularly limited as long as the amount of moisture described above is reached, and a conventionally known method can be adopted. For example, the mixture can be a mixture of an inorganic oxide hydrogel slurry and a binder, and further a pulverized powder. It can be adjusted by adding a predetermined amount of water or by dehydrating and drying.
噴霧乾燥
本発明では、工程（ａ）において、無機酸化物ヒドロゲルスラリーを、必要に応じてバインダーを混合した混合スラリーを、噴霧乾燥して得られた噴霧乾燥粉体を用いることが好ましい。
Spray Drying In the present invention, in the step (a), it is preferable to use a spray-dried powder obtained by spray-drying a mixed slurry in which an inorganic oxide hydrogel slurry is mixed with a binder as necessary.
このときのスラリーの濃度は固形分として１〜４０重量％、さらには２〜３５重量％の範囲にあることが好ましい。 The concentration of the slurry at this time is preferably in the range of 1 to 40% by weight, more preferably 2 to 35% by weight as the solid content.
スラリーの濃度が固形分として１重量％未満の場合は、噴霧乾燥熱効率が低いだけでなく、後述する所望の粒子径の噴霧乾燥粉体が得られないことがある。 When the concentration of the slurry is less than 1% by weight as the solid content, not only the spray drying thermal efficiency is low, but also a spray dried powder having a desired particle size described later may not be obtained.
スラリーの濃度が固形分として４０重量％を越えると、スラリーの粘度が高くなり安定的に噴霧乾燥できないことがある。 When the concentration of the slurry exceeds 40% by weight as the solid content, the viscosity of the slurry becomes high and stable spray drying may not be possible.
また、無機酸化物ヒドロゲルスラリーとバインダーとを混合して用いる場合の混合割合は、無機酸化物およびバインダーの種類や粒子径によっても異なるが、混合物中のバインダーの含有量が固形分として２〜４０重量％、さらには５〜３０重量％の範囲にあることが好ましい。 In addition, the mixing ratio when the inorganic oxide hydrogel slurry and the binder are mixed and used varies depending on the type and particle size of the inorganic oxide and the binder, but the binder content in the mixture is 2 to 40 as the solid content. It is preferable to be in the range of wt%, more preferably 5 to 30 wt%.
混合物中のバインダーの含有量が固形分として２重量％未満の場合は、可塑性が不充分なために成形性が低下し、また最終的に得られる無機酸化物微小球状成形体の圧縮強度や耐摩耗性が不充分となることがある。 When the content of the binder in the mixture is less than 2% by weight as a solid content, the moldability is lowered due to insufficient plasticity, and the compression strength and resistance of the finally obtained inorganic oxide microspherical molded body are reduced. Abrasion may be insufficient.
混合物中のバインダーの含有量が固形分として４０重量％を越えると、最終的に得られる燃料処理剤の処理能力が不充分となることがある。 When the content of the binder in the mixture exceeds 40% by weight as the solid content, the processing ability of the finally obtained fuel processing agent may be insufficient.
噴霧乾燥方法としては、平均粒子径が２０〜１５０μｍ、好ましくは３０〜１２０μｍの範囲にあり、水分含有量が３〜４０重量％、好ましくは５〜３０重量％の範囲にある噴霧乾燥粉体が得られれば特に制限はなく、従来公知の噴霧乾燥方法を採用することができる。 As the spray drying method, a spray-dried powder having an average particle size in the range of 20 to 150 μm, preferably 30 to 120 μm, and a moisture content in the range of 3 to 40% by weight, preferably 5 to 30% by weight. If it is obtained, there is no particular limitation, and a conventionally known spray drying method can be employed.
例えば、スラリーの固形分濃度によってもことなるが、通常７０〜５００℃の熱風気流中に、前記スラリーをディスクあるいはノズルを用いて噴霧する方法は好適に採用することができる。 For example, although it depends on the solid content concentration of the slurry, a method of spraying the slurry using a disk or a nozzle in a hot air stream usually at 70 to 500 ° C. can be suitably employed.
噴霧乾燥粉体の平均粒子径が２０μｍ未満の場合は、押し出し成形するために水分を加えて水分調整する際に噴霧乾燥して得た粒子が凝集し、均一な水分調整ができないためか押し出し成形が困難であったり、ついで造粒する際にペレットが互いに付着して凝集することがあり、均一な粒子径の無機酸化物微小球状成形体が得られないことがある。 When the average particle size of the spray-dried powder is less than 20 μm, the particles obtained by spray-drying are aggregated when adding water to adjust the moisture content for extrusion molding. In some cases, the pellets adhere to each other and agglomerate during granulation, and an inorganic oxide microspherical molded product having a uniform particle size may not be obtained.
噴霧乾燥粉体の平均粒子径が１５０μｍを越えると、押し出し成型時の圧力を高くする必要があり、前記範囲の平均粒子径の粒子の場合と同程度の圧力で押し出し成形すると、得られる無機酸化物微小球状成形体の圧縮強度や耐摩耗性が不充分となることがある。 When the average particle size of the spray-dried powder exceeds 150 μm, it is necessary to increase the pressure at the time of extrusion molding, and when the extrusion molding is performed at a pressure comparable to that of particles having an average particle size in the above range, the resulting inorganic oxidation Compressive strength and wear resistance of the product microsphere shaped product may be insufficient.
また、噴霧乾燥粉体の水分含有量が３重量％未満の場合は、得られる無機酸化物微粒子成形前駆体の水分含有量を前記範囲に調整しても、ついで押し出し成形する際の成形性が低下したり、ペレットの長さが不均一となり、球状粒子の収率が低下したり、球状粒子の粒子径が不均一となる傾向がある。 In addition, when the moisture content of the spray-dried powder is less than 3% by weight, the moldability during extrusion molding can be improved even if the moisture content of the resulting inorganic oxide fine particle molding precursor is adjusted to the above range. It tends to decrease, the length of the pellets becomes non-uniform, the yield of spherical particles decreases, and the particle size of the spherical particles tends to become non-uniform.
噴霧乾燥粉体の水分含有量が４０重量％を越えると、噴霧乾燥粉体を用いる効果、すなわち、成形性が向上し、ペレットの長さが押し出し径に近くかつ均一となり、球状係数が１に近い真球状の微小球状成形体が得られる効果が不充分となる。 When the moisture content of the spray-dried powder exceeds 40% by weight, the effect of using the spray-dried powder, that is, the moldability is improved, the length of the pellet is close to the extrusion diameter and uniform, and the spherical coefficient is 1. The effect of obtaining a near-spherical microspherical molded body is insufficient.
さらに、上記無機酸化物微粒子成形前駆体は、前記したように、後述する工程（ｄ）で得られた無機酸化物微小球状成形体を粉砕して（または粉砕したのち焼成して）得た平均粒子径が１０〜１００μｍ、さらには２０〜８０μｍの範囲にある粉体（前記した粉砕粉体）を、全固形分中の含有量が２〜４０重量％、さらには５〜３０重量％の範囲となるように含ませてもよい。 Further, as described above, the inorganic oxide fine particle molding precursor is an average obtained by pulverizing (or pulverizing and firing) the inorganic oxide microspherical molded body obtained in the step (d) described later. A powder having a particle diameter of 10 to 100 μm, more preferably 20 to 80 μm (the above-mentioned pulverized powder) has a total solid content of 2 to 40% by weight, more preferably 5 to 30% by weight. It may be included so that
さらに、上記無機酸化物微粒子成形前駆体には、必要に応じて成形助剤（可塑剤ということがある）を、全固形分（無機酸化物、バインダー、粉砕粉体等の合計）中に炭素換算で５重量％以下、さらには０.２〜３重量％の範囲となるように添加させてもよい。 Furthermore, the inorganic oxide fine particle molding precursor may contain a molding aid (sometimes referred to as a plasticizer), if necessary, in a total solid content (total of inorganic oxide, binder, pulverized powder, etc.). You may make it add so that it may become 5 weight% or less in conversion, and also the range of 0.2 to 3 weight%.
このような成形助剤を含んでいると、高嵩比重で圧縮強度、耐摩耗性および流動性に優れた無機酸化物微小球状触媒を得ることができる。ここで、嵩比重が高いと燃料処理剤の充填量が多くなり、このため処理能力を向上させることができる。
工程（ｂ）
ついで、前記工程（ａ）で得られた無機酸化物微粒子成形前駆体を成形機にて押し出し成形し、径（Ｄ）が０.３〜５ｍｍφ、好ましくは０.５〜３ｍｍφの範囲にあるペレットとする。成形機としては、下押しロール型の押し出し機で、ペレット吐出用ダイスを有するものが使用される。このダイスの口径により成形体の径が制御される。
When such a molding aid is included, an inorganic oxide microspherical catalyst having a high bulk specific gravity and excellent compressive strength, abrasion resistance and fluidity can be obtained. Here, when the bulk specific gravity is high, the filling amount of the fuel processing agent increases, and thus the processing capacity can be improved.
Step (b)
Next, the inorganic oxide fine particle molding precursor obtained in the step (a) is extruded using a molding machine, and the diameter (D) is in the range of 0.3 to 5 mmφ, preferably 0.5 to 3 mmφ. And As the molding machine, a bottom push roll type extruder having a pellet discharging die is used. The diameter of the formed body is controlled by the diameter of the die.
ペレットの径（Ｄ）が０.３ｍｍφ未満のものは、ダイスの孔径が小さいために押し出し成形することが困難で、ペレットの径（Ｄ）が５ｍｍφを越えるものは得られる成形体の粒子径が５ｍｍφを越え、このような大きな球状成形体は本願発明の方法によらずとも他の方法で可能であったり、触媒として用いる場合は有効係数が低下する場合があり、前記範囲の径を有するペレットから得られる無機酸化物微小球状成形体より活性が劣ることがある。 When the diameter (D) of the pellet is less than 0.3 mmφ, it is difficult to extrude because the hole diameter of the die is small, and when the diameter (D) of the pellet exceeds 5 mmφ, the resulting molded article has a particle size of Pellets having a diameter in the above range may exceed 5 mmφ, and such a large spherical shaped body may be produced by other methods without using the method of the present invention, or when used as a catalyst, the effectiveness factor may decrease. The activity may be inferior to that of the inorganic oxide microspherical molded body obtained from the above.
このとき、あらかじめ所望の径よりも大きな径のダイスで少なくとも１回押し出しを行った後、所望の径のダイスにて押し出しを行うことが好ましい。理由は必ずしも明らかではないが、所望の径のダイスでの押し出しが容易になるとともに、最終的に得られる無機酸化物微小球状成形体の圧縮強度が向上する傾向がある。 At this time, it is preferable to extrude at least once with a die having a diameter larger than the desired diameter, and then extrude with a die having a desired diameter. The reason is not necessarily clear, but it tends to be easy to extrude with a die having a desired diameter and to improve the compressive strength of the finally obtained inorganic oxide microspherical molded body.
押し出し成形機としては、例えば、前押しスクリュウ型、横押しスクリュウ型、前押しラム型、横押しロール型、下押しロール型、横押しバスケット型、下押しスクリーン型等の成形機があるが、なかでも、前記した下押しロール型は、他の成形機に比べて水分の少ない混合物粉体を押し出し成形することができ、このため球状化する際にペレットが互いに付着することなく、高収率で均一な粒子径分布の無機酸化物微小球状成形体を得ることができる。 Examples of the extrusion molding machine include a front pressing screw type, a side pressing screw type, a front pressing ram type, a horizontal pressing roll type, a lower pressing roll type, a horizontal pressing basket type, and a lower pressing screen type. The above-described lower pressing roll mold can extrude a mixture powder with less moisture compared to other molding machines, so that the pellets do not adhere to each other when spheroidizing, and it is uniform in high yield. An inorganic oxide microspherical shaped product having a particle size distribution can be obtained.
また、ペレットの長さ（Ｌ）は、押し出し成形機のダイスの孔径（あるいは得られるペレットの径（Ｄ））によって異なるが、０.３〜１０ｍｍ、好ましくは０.４〜７.５ｍｍの範囲にあり、ペレットの径（Ｄ）は概ね所望の無機酸化物微小球状成形体の粒子径とすることが好ましい。このとき、ペレットの長さ（Ｌ）とペレットの径（Ｄ）との比Ｌ／Ｄは１〜２、さらには１〜１.５の範囲にあることが好ましい。前記Ｌ／Ｄが１未満とすることは困難であり、できたとしても球状になりにくい傾向がある。前記Ｌ／Ｄが２を越えると、得られる粒子が球状となりにくく、できたとしても球状化に長時間を要するので生産効率が低下することがある。このためＬ／Ｄを２以下にカットすることもできるが、やはり生産効率が低下する問題がある。 The length (L) of the pellet varies depending on the hole diameter of the die of the extrusion molding machine (or the diameter (D) of the obtained pellet), but is in the range of 0.3 to 10 mm, preferably 0.4 to 7.5 mm. Therefore, it is preferable that the diameter (D) of the pellet is approximately the particle diameter of the desired inorganic oxide microspherical shaped body. At this time, the ratio L / D between the length (L) of the pellet and the diameter (D) of the pellet is preferably in the range of 1 to 2, more preferably 1 to 1.5. It is difficult for L / D to be less than 1, and even if it is possible, it tends to be difficult to be spherical. When the L / D exceeds 2, the resulting particles are unlikely to be spherical, and even if it can be produced, it takes a long time to spheroidize, and production efficiency may be reduced. For this reason, L / D can be cut to 2 or less, but there is still a problem that the production efficiency is lowered.
上記したように、本発明の方法で得られる無機酸化物微小球状成形体の粒子径は押し出し成形機のダイスの孔径に依存するので、極めて均一な粒子径分布を有している。
工程（ｃ）
ついで、上記工程（ｂ）で調製したペレットを、高速転動式球形成形機にて球状成形体とする。
As described above, since the particle diameter of the inorganic oxide microspherical molded body obtained by the method of the present invention depends on the hole diameter of the die of the extrusion molding machine, it has a very uniform particle size distribution.
Step (c)
Next, the pellet prepared in the above step (b) is formed into a spherical molded body with a high-speed rolling sphere forming machine.
高速転動式球形成形機としては、従来公知の転動造粒機（マルメライザーと言うことがある。）等を用いることができる。転動造粒機を用いる場合、工程（ｂ）で得たペレットを充填して造粒機を回転させ、あるいは回転させた転動造粒機にペレットを充填することによって球状とする。このときの球形化条件、例えば、回転速度、周速、造粒時間等は、球形機の大きさ、充填するペレットのサイズ、球状の度合い等によって異なり、適宜選択して設定することが好ましい。なお、本発明では、工程（ａ）で所定の水分含有量に調整し、工程（ｂ）で所定のサイズに押し出し成形されているのでペレット同士が付着して凝集することがなく、このため球形化前、あるいは球形化時に凝集を防ぐためのペレットの乾燥等を行う必要がなく、また乾燥することによる成形性の悪化もない。
工程（ｄ）
得られた球状成形体は、ついで、乾燥および／または焼成する。
A conventionally known rolling granulator (sometimes referred to as a Malmerizer) or the like can be used as the high-speed rolling sphere forming machine. When using a rolling granulator, it is made spherical by filling the pellets obtained in step (b) and rotating the granulator, or filling the rotated rolling granulator with pellets. The spheroidizing conditions at this time, for example, the rotational speed, the peripheral speed, the granulation time, and the like vary depending on the size of the spheroid machine, the size of the pellets to be filled, the degree of sphericalness, etc., and are preferably selected and set as appropriate. In the present invention, the water content is adjusted to a predetermined value in the step (a) and is extruded to a predetermined size in the step (b), so that the pellets do not adhere to each other and agglomerate. It is not necessary to dry the pellets to prevent aggregation before spheroidization or at the time of spheroidization, and there is no deterioration in moldability due to drying.
Step (d)
The resulting spherical shaped body is then dried and / or fired.
球状成形体を乾燥する場合、用途によって乾燥程度を適宜設定すればよいが、粒子径の小さい粒子は乾燥速度を比較的早めに設定できるが、粒子径の大きな粒子はゆっくり乾燥することが好ましい。乾燥温度は、５０〜２００℃、さらには８０〜１５０℃の範囲にあることが好ましい。また乾燥時間は、乾燥温度によっても異なるが、１０分〜４８時間、さらには３０分〜２４時間の範囲にあることが好ましい。 When the spherical molded body is dried, the degree of drying may be appropriately set depending on the application. However, it is preferable to dry the particles having a large particle diameter slowly, although the drying speed can be set relatively early for the particles having a small particle diameter. The drying temperature is preferably 50 to 200 ° C, more preferably 80 to 150 ° C. Moreover, although drying time changes also with drying temperature, it is preferable that it exists in the range of 10 minutes-48 hours, Furthermore, 30 minutes-24 hours.
焼成する場合、温度は２００〜１０００℃、さらには３００〜８００℃の範囲にあることが好ましい。焼成温度が２００℃未満の場合は、得られる粒子の強度が不充分であったり、摩耗による粉化が顕著になることがある。焼成温度が１０００℃を越えても、粒子の強度がさらに向上することもなく、無機酸化物の種類によっては結晶化したり、比表面積が低下し、燃料ガス処理能力が不充分となることがある。なお、ホン発明では、焼成を窒素ガス等の不活性ガス雰囲気下で行うことが好ましい。この場合、得られる燃料処理剤には成形助剤に由来する炭素成分が残存し、必ずしもその理由は明確ではないものの、処理能力が向上する効果が発現することがある。 When firing, the temperature is preferably in the range of 200 to 1000 ° C, more preferably 300 to 800 ° C. When the firing temperature is less than 200 ° C., the strength of the obtained particles may be insufficient, or powdering due to wear may be remarkable. Even if the firing temperature exceeds 1000 ° C., the strength of the particles does not further improve, and depending on the type of inorganic oxide, it may crystallize, the specific surface area may decrease, and the fuel gas processing capacity may be insufficient. . In the present invention, the firing is preferably performed in an inert gas atmosphere such as nitrogen gas. In this case, the carbon component derived from the molding aid remains in the obtained fuel treatment agent, and although the reason is not necessarily clear, an effect of improving the treatment capability may be exhibited.
本発明では、乾燥および焼成はいずれか一方を行えばよく、また双方とも行ってもよい。 In the present invention, either drying or firing may be performed, or both may be performed.
以上のような製造方法によれば、本発明に係る燃料処理剤を効率よく製造することができる。 According to the manufacturing method as described above, the fuel treatment agent according to the present invention can be efficiently manufactured.
［実施例］
以下、本発明を実施例により説明するが、本発明はこれらに実施例により限定されるものではない。
［実施例１］
硝酸銅（Cu(NO3)2・3H2O）６３５ｇ、硝酸ニッケル（Ni(NO3)2・6H2O）９４５ｇ、硝酸亜鉛（Zn（NO3）2・6H2O）１５５７ｇ、硝酸アルミニウム（Al(NO)3・9H2O）４４９ｇを水１０Lに溶解した。これを撹拌しながら、濃度５.４４重量％の炭酸ソーダ水溶液を徐々にｐＨが７.２になるまで加え、そのまま２時間攪拌を続けた。沈殿を濾過し、さらに水１００Lをかけて洗浄した。得られた洗浄ケーキを再度水に分散し、複合酸化物ヒドロゲルスラリーを調製した。このとき、固形分濃度は２０.５重量で、固形分の組成は、ＮｉＯ：２５.１重量％、ＣｕＯ：２１.７重量％、ＺnＯ：４４.３重量％、Ａｌ2Ｏ3：８.９重量％であった。
[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to an Example by these.
[Example 1]
635 g of copper nitrate (Cu (NO 3 ) 2 .3H 2 O), 945 g of nickel nitrate (Ni (NO 3 ) 2 .6H 2 O), 1557 g of zinc nitrate (Zn (NO 3 ) 2 .6H 2 O), aluminum nitrate 449 g of (Al (NO) 3 .9H 2 O) was dissolved in 10 L of water. While stirring this, an aqueous sodium carbonate solution having a concentration of 5.44% by weight was gradually added until the pH reached 7.2, and stirring was continued for 2 hours. The precipitate was filtered and washed with 100 L of water. The obtained washed cake was dispersed again in water to prepare a composite oxide hydrogel slurry. At this time, the solid concentration is 20.5 wt, the composition of the solids, NiO: 25.1 wt%, CuO: 21.7 wt%, ZnO: 44.3 wt%, Al 2 O 3: 8 . It was 9% by weight.
この複合酸化物ヒドロゲルスラリーを、スプレードライヤーにて噴霧乾燥（熱風の入口温度２８０〜３１０℃、出口温度１１８〜１２８℃）した。得られた噴霧乾燥粉体の平均粒子径は５４μｍ、固形分濃度は８１.７重量％、水分含有量は１８.３重量％であった。 This composite oxide hydrogel slurry was spray-dried with a spray dryer (hot air inlet temperature 280 to 310 ° C., outlet temperature 118 to 128 ° C.). The resulting spray-dried powder had an average particle size of 54 μm, a solid content concentration of 81.7% by weight, and a water content of 18.3% by weight.
複合酸化物の噴霧乾燥粉体１０００ｇを高速攪拌粉体混合機（三井鉱山（株）製：ヘンシェルミキサー、FM-20C型）に入れ、ついで、水５７０ｇを徐々に加え、充分混合し、水分含有量４１.２重量％の無機酸化物微粒子成形前駆体(1)を調製した。 Place 1000g of spray-dried powder of complex oxide into a high-speed stirring powder mixer (Mitsui Mining Co., Ltd .: Henschel mixer, FM-20C type), then gradually add 570g of water, mix well, and contain water An inorganic oxide fine particle molding precursor (1) having an amount of 41.2% by weight was prepared.
この無機酸化物微粒子成形前駆体(1)を、下押しロール型押出し機（不二パウダル（株）製：デイスクペレッター、F-5(PV-S)/11-175型)にてペレットに成形した。このとき、先ず、押出し機のノズル径２ｍｍφで２回押し出しを行い、ついでノズル径０.７ｍｍφで１回押出しを行いペレットに成形した。このときのペレットの長さは比較的均一で、平均長さは１.１ｍｍであった。 This inorganic oxide fine particle molding precursor (1) is molded into pellets using a down roll type extruder (manufactured by Fuji Powder Co., Ltd .: disk pelleter, F-5 (PV-S) / 11-175 type). did. At this time, first, extrusion was performed twice with a nozzle diameter of 2 mmφ of the extruder, and then extrusion was performed once with a nozzle diameter of 0.7 mmφ to form pellets. The length of the pellet at this time was relatively uniform, and the average length was 1.1 mm.
得られた径０.７ｍｍφのペレットを球形機（不二パウダル（株）製：マルメライザー、QJ-400）で球状粒子とした。この時の球形機の回転数は６００ｒｐｍ、外熱温度は６０℃、処理時間は６分であった。 The obtained pellets having a diameter of 0.7 mmφ were formed into spherical particles using a spherical machine (Fuji Paudal Co., Ltd .: Malmerizer, QJ-400). The rotational speed of the spherical machine at this time was 600 rpm, the external heat temperature was 60 ° C., and the treatment time was 6 minutes.
得られた球状成形物を１３０℃で２４時間乾燥し、ついて、窒素気流中、６７０℃で３時間焼成して燃料処理剤(1)を得た。 The obtained spherical molded product was dried at 130 ° C. for 24 hours and then calcined in a nitrogen stream at 670 ° C. for 3 hours to obtain a fuel treatment agent (1).
得られた燃料処理剤(1)の嵩比重（ＣＢＤ）平均短径、平均長径、平均粒子径、球状係数、細孔容積、圧縮強度を測定し、平均圧縮強度指数を求め、結果を表１に示した。また耐摩耗性を測定し、結果を表１に示した。 The bulk specific gravity (CBD) average short diameter, average long diameter, average particle diameter, spherical coefficient, pore volume, and compressive strength of the obtained fuel treatment agent (1) were measured to obtain an average compressive strength index. It was shown to. The abrasion resistance was measured and the results are shown in Table 1.
なお、圧縮強度は圧縮強度計（(株)藤原製作所製：木屋式硬度計、ｍａｘ５Ｋｇ）により測定し、耐摩強度は磨耗強度測定法（ＪＩＳ ＮＯ, Ｋ１４６４）に基づき測定した。細孔容積は、水銀圧入法により求め、細孔径５０〜５００ｎｍの範囲の細孔容積として示した。 The compressive strength was measured with a compressive strength meter (manufactured by Fujiwara Seisakusho Co., Ltd .: Kiyama-type hardness meter, max 5 kg), and the abrasion resistance was measured based on the wear strength measuring method (JIS NO, K1464). The pore volume was determined by a mercury intrusion method and indicated as a pore volume in a pore diameter range of 50 to 500 nm.
平均短径、平均長径は光学顕微鏡写真を撮影し、１００個の粒子について測定し、平均粒子径は（平均短径＋平均長径）／２として示した。 The average minor axis and the average major axis were measured with respect to 100 particles by taking an optical micrograph, and the average particle diameter was expressed as (average minor axis + average major axis) / 2.
かさ比重は、100ccのメスシリンダーに約100ccの微小球状ゼオライト燃料処理剤を充填し、適度に振動を加えた後の処理剤の容積を測定し、充填した処理剤の重量(g)を処理剤の容積で除して求めることができる。 The bulk specific gravity is measured by filling the 100cc graduated cylinder with about 100cc of fine spherical zeolite fuel treatment agent, measuring the volume of the treatment agent after applying moderate vibration, and using the weight (g) of the filled treatment agent as the treatment agent. It can be obtained by dividing by the volume of.
性能能評価
内径１７ｍｍのステンレス鋼製反応管に燃料処理剤(1)１０ｍｌ（１３.８ｇ）を充填した。ついで常圧下、水素気流中にて１２０℃に昇温し、１時間保持したのち、さらに４００℃に昇温後、１時間保持し触媒の還元処理を行なった。その後、反応温度の１８０℃まで降温した。ついで、硫黄分濃度６０重量ｐｐｍのＪＩＳ１号灯油を、常圧下、ＬＨＳＶ２０ｈ-1で反応管に供給を行ない、生成油中の硫黄分濃度をイオウ電量滴定装置（三菱化学製）によって分析し、生成油中のイオウ濃度が１ｐｐｍとなるまでの処理時間を表１に示した。
［実施例２］
８０℃の純水８０Ｌに硫酸ニッケル（酸化ニッケル濃度２８．４重量％）７．１ｋｇを溶解し、次いで硫酸銅（酸化銅濃度３１.８重量％）１．６ｋｇを溶解しさらに硫酸アルミニウム（アルミナ濃度６４．１重量％）を０.１ｋｇ混合し、ｐＨ４の（Ａ）液を調製した。一方、８０℃の純水８０Ｌに炭酸ナトリウム５．２ｋｇを溶解し、これに水ガラス（シリカ濃度２４．０重量％）１．７ｋｇを加え、ｐＨ１０．６の（Ｂ）液を調製した。次いでラインミキサーを用い（Ａ）液４．０ｋｇ／ｍｉｎ、（Ｂ）液４．０ｋｇ／ｍｉｎの速度で混合した。
Performance capability evaluation A stainless steel reaction tube having an inner diameter of 17 mm was filled with 10 ml (13.8 g) of the fuel treatment agent (1). Next, under normal pressure, the temperature was raised to 120 ° C. in a hydrogen stream, held for 1 hour, further heated to 400 ° C. and then held for 1 hour to reduce the catalyst. Thereafter, the temperature was lowered to the reaction temperature of 180 ° C. Next, JIS No. 1 kerosene with a sulfur content of 60 ppm by weight is supplied to the reaction tube under normal pressure with LHSV20h- 1 , and the sulfur content in the product oil is analyzed by a sulfur coulometric titrator (Mitsubishi Chemical). The treatment time until the sulfur concentration in the oil reaches 1 ppm is shown in Table 1.
[Example 2]
In 80 L of pure water at 80 ° C., 7.1 kg of nickel sulfate (nickel oxide concentration 28.4% by weight) is dissolved, then 1.6 kg of copper sulfate (copper oxide concentration 31.8% by weight) is dissolved, and aluminum sulfate (alumina) 0.1 kg of 64.1% by weight) was mixed to prepare a solution (A) having a pH of 4. On the other hand, 5.2 kg of sodium carbonate was dissolved in 80 L of pure water at 80 ° C., and 1.7 kg of water glass (silica concentration 24.0 wt%) was added thereto to prepare a solution (B) having a pH of 10.6. Subsequently, it mixed at the speed | rate of (A) liquid 4.0kg / min and (B) liquid 4.0kg / min using the line mixer.
生成した沈殿を濾過し、さらに水１５０Lをかけて洗浄した。得られた洗浄ケーキを再度水に分散し、複合酸化物ヒドロゲルスラリーを調製した。このとき、固形分濃度は７.０重量、固形分の組成はＮｉＯ：６７．０重量％、ＣｕＯ：１７．０重量％、ＳｉＯ2：１３．７重量％、Ａｌ2Ｏ3：２．３重量％であった。 The formed precipitate was filtered and further washed with 150 L of water. The obtained washed cake was dispersed again in water to prepare a composite oxide hydrogel slurry. At this time, the solid concentration is 7.0 wt, the composition of the solids NiO: 67.0 wt%, CuO: 17.0 wt%, SiO 2: 13.7 wt%, Al 2 O 3: 2.3 % By weight.
この複合酸化物ヒドロゲルスラリーを入口温度３００℃、出口温度１０５℃、アトマイザー回転１００００ｒｐｍ、スラリー供給速度４００ｇ／ｍｉｎの条件下で噴霧乾燥した。得られた複合酸化物粉末の平均粒子径は６５μｍ、固形分濃度は７５.５重量％、水分含有量は２４.５重量％であった。 This composite oxide hydrogel slurry was spray-dried under conditions of an inlet temperature of 300 ° C., an outlet temperature of 105 ° C., an atomizer rotation of 10,000 rpm, and a slurry supply rate of 400 g / min. The obtained composite oxide powder had an average particle size of 65 μm, a solid content concentration of 75.5% by weight, and a water content of 24.5% by weight.
複合酸化物粉末１.３２Ｋｇを高速攪拌粉体混合機（三井鉱山（株）製：ヘンシェルミキサー、FM-20C/Ｉ型）に入れ、ついで、成形助剤（旭化成工業(株)製：アビセルＲＣ−５９１）３０ｇを予め溶解懸濁した水溶液０.４７Ｋｇとを入れ充分混合し、水分を４４.２重量％に調整た。 1.32 kg of complex oxide powder is put into a high-speed stirring powder mixer (Mitsui Mine Co., Ltd .: Henschel mixer, FM-20C / I type), and then a molding aid (Asahi Kasei Co., Ltd .: Avicel RC) -591) 0.47 Kg of an aqueous solution in which 30 g was dissolved and suspended in advance was added and mixed well to adjust the water content to 44.2% by weight.
この水分調整した粉末を、下押しロール型押出し機（不二パウダル（株）製：デイスクペレッター、F-5(PV-S)/11-175型)にてペレットに成形した。このとき、まず、押出し機のノズル径３ｍｍφで１回押し出しを行い、ついでノズル径１.５ｍｍφで１回押出しを行いペレットに成形した。このときのペレットの長さは比較的均一で、平均長さは２.１ｍｍであった。 The moisture-adjusted powder was formed into pellets using a down roll type extruder (Fuji Paudal Co., Ltd .: Disc pelleter, F-5 (PV-S) / 11-175 type). At this time, first, extrusion was performed once with a nozzle diameter of 3 mmφ of the extruder, and then extrusion was performed once with a nozzle diameter of 1.5 mmφ to form pellets. At this time, the length of the pellets was relatively uniform, and the average length was 2.1 mm.
得られた径１.５ｍｍφのペレットを球形機（不二パウダル（株）製：マルメライザー、QJ-400）で球状粒子とした。この時の球形機の回転数は６００ｒｐｍ、外熱温度は６０℃、処理時間は３.５分であった。 The obtained pellets having a diameter of 1.5 mmφ were formed into spherical particles using a spherical machine (Fuji Paudal Co., Ltd .: Malmerizer, QJ-400). The rotational speed of the spherical machine at this time was 600 rpm, the external heat temperature was 60 ° C., and the treatment time was 3.5 minutes.
得られた球状成形物を１３０℃で２４時間乾燥し、ついて、窒素気流中、４５０℃で３時間焼成して燃料処理剤(2)を得た。 The obtained spherical molded product was dried at 130 ° C. for 24 hours and then calcined at 450 ° C. for 3 hours in a nitrogen stream to obtain a fuel treatment agent (2).
得られた燃料処理剤(2)の嵩比重（ＣＢＤ）、炭素含有量、平均短径、平均長径、平均粒子径、球状係数、細孔容積、圧縮強度を測定し、平均圧縮強度指数を求め、結果を表１に示した。また耐摩耗性を測定し、結果を表１に示した。 The bulk specific gravity (CBD), carbon content, average short diameter, average long diameter, average particle diameter, spherical coefficient, pore volume, and compressive strength of the obtained fuel treatment agent (2) are measured to obtain an average compressive strength index. The results are shown in Table 1. The abrasion resistance was measured and the results are shown in Table 1.
性能評価
燃料処理剤(2)１０ｍｌ（１２.９ｇ）を用いた以外は実施例１と同様にして性能評価を行い、結果を表１に示した。
［実施例３］
８０℃の純水８０Ｌに硫酸ニッケル（酸化ニッケル濃度２８．４重量％）６．５ｋｇを溶解し、次いで硫酸銅（酸化銅濃度３１，８重量％）２．１ｋｇを溶解しさらに硫酸アルミニウム溶液（アルミナ濃度６４．１重量％）を０．１ｋｇ混合し、ｐＨ４の（Ａ）液を調製した。一方、８０℃の純水８０Ｌに炭酸ナトリウム５．２ｋｇを溶解し、これに水ガラス（シリカ濃度２４．０重量％）１．７ｋｇを加え、ｐＨ１０．６の（Ｂ）液を調製した。次いでラインミキサーを用い（Ａ）液４．０ｋｇ／ｍｉｎ、（Ｂ）液４．０ｋｇ／ｍｉｎの速度で混合した。
Performance Evaluation Performance evaluation was performed in the same manner as in Example 1 except that 10 ml (12.9 g) of the fuel processing agent (2) was used, and the results are shown in Table 1.
[Example 3]
In 80 L of pure water at 80 ° C., 6.5 kg of nickel sulfate (nickel oxide concentration 28.4% by weight) is dissolved, then 2.1 kg of copper sulfate (copper oxide concentration 31.8% by weight) is dissolved, and an aluminum sulfate solution ( 0.1 kg of alumina concentration (64.1% by weight) was mixed to prepare a liquid (A) having a pH of 4. On the other hand, 5.2 kg of sodium carbonate was dissolved in 80 L of pure water at 80 ° C., and 1.7 kg of water glass (silica concentration 24.0 wt%) was added thereto to prepare a solution (B) having a pH of 10.6. Subsequently, it mixed at the speed | rate of (A) liquid 4.0kg / min and (B) liquid 4.0kg / min using the line mixer.
生成した沈殿を濾過し、さらに水１５０Lをかけて洗浄した。得られた洗浄ケーキを再度水に分散し、複合酸化物ヒドロゲルスラリーを調製した。このとき、固形分濃度は１２.０重量であった。（ＮｉＯ：６２．０重量％、ＣｕＯ：２２．０重量％、ＳｉＯ2：１３．７重量％、Ａｌ2Ｏ3：２．３重量％、）
この複合酸化物ヒドロゲルスラリーを入口温度３００℃、出口温度１０５℃、アトマイザー回転１００００ｒｐｍ、スラリー供給速度４００ｇ／ｍｉｎの条件下で噴霧乾燥した。得られた複合酸化物粉末の平均粒子径は６５μｍ、水分含有量は２４.５重量％であった。
The formed precipitate was filtered and further washed with 150 L of water. The obtained washed cake was dispersed again in water to prepare a composite oxide hydrogel slurry. At this time, the solid content concentration was 12.0 wt. (NiO: 62.0 wt%, CuO: 22.0 wt%, SiO 2: 13.7 wt%, Al 2 O 3: 2.3 wt%)
This composite oxide hydrogel slurry was spray-dried under conditions of an inlet temperature of 300 ° C., an outlet temperature of 105 ° C., an atomizer rotation of 10,000 rpm, and a slurry supply rate of 400 g / min. The obtained composite oxide powder had an average particle size of 65 μm and a water content of 24.5% by weight.
複合酸化物粉末１.３２Ｋｇを高速攪拌粉体混合機（三井鉱山（株）製：ヘンシェルミキサー、FM-20C/Ｉ型）に入れ、ついで、成形助剤（武田製薬(株)製：ビーオポリー）３１.９ｇを予め溶解懸濁した水溶液０.４５Ｋｇとを入れ充分混合し、水分を３８.６重量％に調整した。 1.32 kg of composite oxide powder is put into a high-speed stirring powder mixer (Mitsui Mine Co., Ltd .: Henschel mixer, FM-20C / I type), and then a molding aid (Takeda Pharmaceutical Co., Ltd .: Biopoly). An aqueous solution of 0.45 kg in which 31.9 g was dissolved and suspended in advance was added and mixed well to adjust the water content to 38.6% by weight.
この水分調整した粉末を、下押しロール型押出し機（不二パウダル（株）製：デイスクペレッター、F-5(PV-S)/11-175型)にてペレットに成形した。このとき、まず、押出し機のノズル径３ｍｍφで１回押し出しを行い、ついでノズル径０.７ｍｍφで１回押出しを行いペレットに成形した。このときのペレットの長さは比較的均一で、平均長さは１.２ｍｍであった。 The moisture-adjusted powder was formed into pellets using a down roll type extruder (Fuji Paudal Co., Ltd .: Disc pelleter, F-5 (PV-S) / 11-175 type). At this time, first, extrusion was performed once with an extruder nozzle diameter of 3 mmφ, and then extrusion was performed once with a nozzle diameter of 0.7 mmφ to form pellets. The length of the pellet at this time was relatively uniform, and the average length was 1.2 mm.
得られた径０.７ｍｍφのペレットを球形機（不二パウダル（株）製：マルメライザー、QJ-400）で球状粒子とした。この時の球形機の回転数は６００ｒｐｍ、外熱温度は６０℃、処理時間は３.５分であった。 The obtained pellets having a diameter of 0.7 mmφ were formed into spherical particles using a spherical machine (Fuji Paudal Co., Ltd .: Malmerizer, QJ-400). The rotational speed of the spherical machine at this time was 600 rpm, the external heat temperature was 60 ° C., and the treatment time was 3.5 minutes.
得られた球状成形物を１３０℃で２４時間乾燥し、ついて、窒素気流中、４５０℃で３時間焼成して燃料処理剤(3)を得た。 The obtained spherical molded product was dried at 130 ° C. for 24 hours and then calcined at 450 ° C. for 3 hours in a nitrogen stream to obtain a fuel treatment agent (3).
得られた燃料処理剤(3)の嵩比重（ＣＢＤ）、炭素含有量、平均短径、平均長径、平均粒子径、球状係数、細孔容積、圧縮強度を測定し、平均圧縮強度指数を求め、結果を表１に示した。また耐摩耗性を測定し、結果を表１に示した。 The bulk specific gravity (CBD), carbon content, average short diameter, average long diameter, average particle diameter, spherical coefficient, pore volume, and compressive strength of the obtained fuel treatment agent (3) are measured to obtain an average compressive strength index. The results are shown in Table 1. The abrasion resistance was measured and the results are shown in Table 1.
性能評価
燃料処理剤(3)１０ｍｌ（１３.１ｇ）を用いた以外は実施例１と同様にして性能評価を行い、結果を表１に示した。
［実施例４］
８０℃の純水８０Ｌに硫酸ニッケル（酸化ニッケル濃度２８．４重量％）８．９ｋｇを溶解し、さらに硫酸アルミニウム溶液（アルミナ濃度６４．１重量％）を０．１ｋｇ混合し、ｐＨ３．８の（Ａ）液を調製した。一方、８０℃の純水８０Ｌに炭酸ナトリウム５．２ｋｇを溶解し、これに水ガラス１．７ｋｇ（シリカ濃度２４．０重量％）を加え、ｐＨ１０．６の（Ｂ）液を調製した。次いでラインミキサーを用い（Ａ）液４．０ｋｇ／ｍｉｎ、（Ｂ）液４．０ｋｇ／ｍｉｎの速度で混合した。
Performance Evaluation Performance evaluation was performed in the same manner as in Example 1 except that 10 ml (13.1 g) of the fuel processing agent (3) was used, and the results are shown in Table 1.
[Example 4]
In 80 L of pure water at 80 ° C., 8.9 kg of nickel sulfate (nickel oxide concentration 28.4% by weight) is dissolved, and 0.1 kg of aluminum sulfate solution (alumina concentration 64.1% by weight) is further mixed to a pH of 3.8. (A) A solution was prepared. On the other hand, 5.2 kg of sodium carbonate was dissolved in 80 L of pure water at 80 ° C., and 1.7 kg of water glass (silica concentration 24.0% by weight) was added thereto to prepare a solution (B) having a pH of 10.6. Subsequently, it mixed at the speed | rate of (A) liquid 4.0kg / min and (B) liquid 4.0kg / min using the line mixer.
生成した沈殿を濾過し、さらに水１５０Lをかけて洗浄した。得られた洗浄ケーキを再度水に分散し、複合酸化物ヒドロゲルスラリーを調製した。このとき、固形分濃度は１２.０重量であった。（ＮｉＯ：８４．０重量％、ＳｉＯ2：１３．７重量％、Ａｌ2Ｏ3：２．３重量％）
この複合酸化物ヒドロゲルスラリーを入口温度３００℃、出口温度１０５℃、アトマイザー回転１００００ｒｐｍ、スラリー供給速度４００ｇ／ｍｉｎの条件下で噴霧乾燥した。得られた複合酸化物粉末の平均粒子径は６０μｍ、水分含有量は２４.０重量％であった。
The formed precipitate was filtered and further washed with 150 L of water. The obtained washed cake was dispersed again in water to prepare a composite oxide hydrogel slurry. At this time, the solid content concentration was 12.0 wt. (NiO: 84.0 wt%, SiO 2: 13.7 wt%, Al 2 O 3: 2.3 wt%)
This composite oxide hydrogel slurry was spray-dried under conditions of an inlet temperature of 300 ° C., an outlet temperature of 105 ° C., an atomizer rotation of 10,000 rpm, and a slurry supply rate of 400 g / min. The obtained composite oxide powder had an average particle size of 60 μm and a water content of 24.0% by weight.
複合酸化物粉末１.３２Ｋｇを高速攪拌粉体混合機（三井鉱山（株）製：ヘンシェルミキサー、FM-20C/Ｉ型）に入れ、ついで、成形助剤（武田製薬(株)製：ビーオポリー）３１.９ｇを予め溶解懸濁した水溶液０.４５Ｋｇとを入れ充分混合し、水分を３８.６重量％に調整した。 1.32 kg of composite oxide powder is put into a high-speed stirring powder mixer (Mitsui Mine Co., Ltd .: Henschel mixer, FM-20C / I type), and then a molding aid (Takeda Pharmaceutical Co., Ltd .: Biopoly). An aqueous solution of 0.45 kg in which 31.9 g was dissolved and suspended in advance was added and mixed well to adjust the water content to 38.6% by weight.
この水分調整した粉末を、下押しロール型押出し機（不二パウダル（株）製：デイスクペレッター、F-5(PV-S)/11-175型)にてペレットに成形した。このとき、まず、押出し機のノズル径３ｍｍφで１回押し出しを行い、ついでノズル径０.７ｍｍφで１回押出しを行いペレットに成形した。このときのペレットの長さは比較的均一で、平均長さは１.２ｍｍであった。 The moisture-adjusted powder was formed into pellets using a down roll type extruder (Fuji Paudal Co., Ltd .: Disc pelleter, F-5 (PV-S) / 11-175 type). At this time, first, extrusion was performed once with an extruder nozzle diameter of 3 mmφ, and then extrusion was performed once with a nozzle diameter of 0.7 mmφ to form pellets. The length of the pellet at this time was relatively uniform, and the average length was 1.2 mm.
得られた径０.７ｍｍφのペレットを球形機（不二パウダル（株）製：マルメライザー、QJ-400）で球状粒子とした。この時の球形機の回転数は６００ｒｐｍ、外熱温度は６０℃、処理時間は３.５分であった。 The obtained pellets having a diameter of 0.7 mmφ were formed into spherical particles using a spherical machine (Fuji Paudal Co., Ltd .: Malmerizer, QJ-400). The rotational speed of the spherical machine at this time was 600 rpm, the external heat temperature was 60 ° C., and the treatment time was 3.5 minutes.
得られた球状成形物を１３０℃で２４時間乾燥し、ついて、窒素気流中、４５０℃で３時間焼成して燃料処理剤(4)を得た。 The obtained spherical molded product was dried at 130 ° C. for 24 hours and then calcined at 450 ° C. for 3 hours in a nitrogen stream to obtain a fuel treatment agent (4).
得られた燃料処理剤(4)の嵩比重（ＣＢＤ）、炭素含有量、平均短径、平均長径、平均粒子径、球状係数、細孔容積、圧縮強度を測定し、平均圧縮強度指数を求め、結果を表１に示した。また耐摩耗性を測定し、結果を表１に示した。 The bulk specific gravity (CBD), carbon content, average short diameter, average long diameter, average particle diameter, spherical coefficient, pore volume, and compressive strength of the obtained fuel treatment agent (4) are measured to obtain an average compressive strength index. The results are shown in Table 1. The abrasion resistance was measured and the results are shown in Table 1.
性能評価
燃料処理剤(4)１０ｍｌ（１１.９ｇ）を用いた以外は実施例１と同様にして性能評価を行い、結果を表１に示した。
［実施例５］
８０℃の純水８０Ｌに硫酸ニッケル５．７（酸化ニッケル濃度２８．４重量％）ｋｇを溶解し、次いで硫酸銅（酸化銅濃度３１，８重量％）１．３ｋｇを溶解しさらに硫酸アルミニウム溶液（アルミナ濃度６４．１重量％）を０．２ｋｇ混合し、ｐＨ４．２の（Ａ）液を調製した。一方、８０℃の純水８０Ｌに炭酸ナトリウム５．２ｋｇを溶解し、これに水ガラス３．４ｋｇ（シリカ濃度２４．０重量％）を加え、ｐＨ１０．８の（Ｂ）液を調製した。次いでラインミキサーを用い（Ａ）液４．０ｋｇ／ｍｉｎ、（Ｂ）液４．０ｋｇ／ｍｉｎの速度で混合した。
Performance Evaluation Performance evaluation was carried out in the same manner as in Example 1 except that 10 ml (11.9 g) of the fuel processing agent (4) was used, and the results are shown in Table 1.
[Example 5]
Dissolve 5.7 kg of nickel sulfate (nickel oxide concentration: 28.4 wt%) in 80 L of pure water at 80 ° C., then dissolve 1.3 kg of copper sulfate (copper oxide concentration: 31.8 wt%), and further add an aluminum sulfate solution (Alumina concentration 64.1% by weight) 0.2 kg was mixed to prepare a solution (A) having a pH of 4.2. On the other hand, 5.2 kg of sodium carbonate was dissolved in 80 L of pure water at 80 ° C., and 3.4 kg of water glass (silica concentration 24.0% by weight) was added thereto to prepare a solution (B) having a pH of 10.8. Subsequently, it mixed at the speed | rate of (A) liquid 4.0kg / min and (B) liquid 4.0kg / min using the line mixer.
生成した沈殿を濾過し、さらに水１５０Lをかけて洗浄した。得られた洗浄ケーキを再度水に分散し、複合酸化物ヒドロゲルスラリーを調製した。このとき、固形分濃度は１２.０重量であった。（ＮｉＯ：５４．２重量％、ＣｕＯ：１３．８重量％、ＳｉＯ2：２７．４重量％、Ａｌ2Ｏ3：４．６重量％）
この複合酸化物ヒドロゲルスラリーを入口温度３００℃、出口温度１０５℃、アトマイザー回転１００００ｒｐｍ、スラリー供給速度４００ｇ／ｍｉｎの条件下で噴霧乾燥した。得られた複合酸化物粉末の平均粒子径は６０μｍ、水分含有量は２６.５重量％であった。
The formed precipitate was filtered and further washed with 150 L of water. The obtained washed cake was dispersed again in water to prepare a composite oxide hydrogel slurry. At this time, the solid content concentration was 12.0 wt. (NiO: 54.2 wt%, CuO: 13.8 wt%, SiO 2: 27.4 wt%, Al 2 O 3: 4.6 wt%)
This composite oxide hydrogel slurry was spray-dried under conditions of an inlet temperature of 300 ° C., an outlet temperature of 105 ° C., an atomizer rotation of 10,000 rpm, and a slurry supply rate of 400 g / min. The obtained composite oxide powder had an average particle size of 60 μm and a water content of 26.5% by weight.
複合酸化物粉末１.３２Ｋｇを高速攪拌粉体混合機（三井鉱山（株）製：ヘンシェルミキサー、FM-20C/Ｉ型）に入れ、ついで、成形助剤（武田製薬(株)製：ビーオポリー）３１.９ｇを予め溶解懸濁した水溶液０.４５Ｋｇとを入れ充分混合し、水分を３８.６重量％に調整た。 1.32 kg of composite oxide powder is put into a high-speed stirring powder mixer (Mitsui Mine Co., Ltd .: Henschel mixer, FM-20C / I type), and then a molding aid (Takeda Pharmaceutical Co., Ltd .: Biopoly). An aqueous solution of 0.45 kg in which 31.9 g was dissolved and suspended in advance was added and mixed well to adjust the water content to 38.6 wt%.
この水分調整した粉末を、下押しロール型押出し機（不二パウダル（株）製：デイスクペレッター、F-5(PV-S)/11-175型)にてペレットに成形した。このとき、まず、押出し機のノズル径３ｍｍφで１回押し出しを行い、ついでノズル径０.７ｍｍφで１回押出しを行いペレットに成形した。このときのペレットの長さは比較的均一で、平均長さは１.２ｍｍであった。 The moisture-adjusted powder was formed into pellets using a down roll type extruder (Fuji Paudal Co., Ltd .: Disc pelleter, F-5 (PV-S) / 11-175 type). At this time, first, extrusion was performed once with an extruder nozzle diameter of 3 mmφ, and then extrusion was performed once with a nozzle diameter of 0.7 mmφ to form pellets. The length of the pellet at this time was relatively uniform, and the average length was 1.2 mm.
得られた径０.７ｍｍφのペレットを球形機（不二パウダル（株）製：マルメライザー、QJ-400）で球状粒子とした。この時の球形機の回転数は６００ｒｐｍ、外熱温度は６０℃、処理時間は３.５分であった。 The obtained pellets having a diameter of 0.7 mmφ were formed into spherical particles using a spherical machine (Fuji Paudal Co., Ltd .: Malmerizer, QJ-400). The rotational speed of the spherical machine at this time was 600 rpm, the external heat temperature was 60 ° C., and the treatment time was 3.5 minutes.
得られた球状成形物を１３０℃で２４時間乾燥し、ついて、窒素気流中、４５０℃で３時間焼成して燃料処理剤(5)を得た。 The obtained spherical molded product was dried at 130 ° C. for 24 hours and then calcined at 450 ° C. for 3 hours in a nitrogen stream to obtain a fuel treatment agent (5).
得られた燃料処理剤(5)の嵩比重（ＣＢＤ）、炭素含有量、平均短径、平均長径、平均粒子径、球状係数、細孔容積、圧縮強度を測定し、平均圧縮強度指数を求め、結果を表１に示した。また耐摩耗性を測定し、結果を表１に示した。 The bulk specific gravity (CBD), carbon content, average short diameter, average long diameter, average particle diameter, spherical coefficient, pore volume, and compressive strength of the obtained fuel treatment agent (5) are measured to obtain an average compressive strength index. The results are shown in Table 1. The abrasion resistance was measured and the results are shown in Table 1.
性能評価
燃料処理剤(5)１０ｍｌ（１１.０ｇ）を用いた以外は実施例１と同様にして性能評価を行い、結果を表１に示した。
［実施例６］
８０℃の純水８０Ｌに硫酸ニッケル（酸化ニッケル濃度２８．４重量％）７．１ｋｇを溶解し、次いで硫酸亜鉛（酸化亜鉛濃度２８．３重量％）１．８ｋｇを溶解しさらに硫酸アルミニウム溶液（アルミナ濃度６４．１重量％）を０．１ｋｇ混合し、ｐＨ４の（Ａ）液を調製した。一方、８０℃の純水８０Ｌに炭酸ナトリウム５．２ｋｇを溶解し、これに水ガラス（シリカ濃度２４．０重量％）１．７ｋｇを加え、ｐＨ１０．６の（Ｂ）液を調製した。次いでラインミキサーを用い（Ａ）液４．０ｋｇ／ｍｉｎ、（Ｂ）液４．０ｋｇ／ｍｉｎの速度で混合した。生成した沈殿を濾過し、さらに水１５０Lをかけて洗浄した。このとき、固形分濃度は１２.０重量であった。
Performance Evaluation Performance evaluation was performed in the same manner as in Example 1 except that 10 ml (11.0 g) of the fuel processing agent (5) was used. The results are shown in Table 1.
[Example 6]
In 80 L of pure water at 80 ° C., 7.1 kg of nickel sulfate (nickel oxide concentration 28.4% by weight) is dissolved, and then 1.8 kg of zinc sulfate (zinc oxide concentration 28.3% by weight) is dissolved. 0.1 kg of alumina concentration (64.1% by weight) was mixed to prepare a liquid (A) having a pH of 4. On the other hand, 5.2 kg of sodium carbonate was dissolved in 80 L of pure water at 80 ° C., and 1.7 kg of water glass (silica concentration 24.0 wt%) was added thereto to prepare a solution (B) having a pH of 10.6. Subsequently, it mixed at the speed | rate of (A) liquid 4.0kg / min and (B) liquid 4.0kg / min using the line mixer. The formed precipitate was filtered and further washed with 150 L of water. At this time, the solid content concentration was 12.0 wt.
（ＮｉＯ：６７．０重量％、ＺｎＯ：１７．０重量％、ＳｉＯ2：１３．７重量％、Ａｌ2Ｏ3：２．３重量％）
この複合酸化物ヒドロゲルスラリーを入口温度３００℃、出口温度１０５℃、アトマイザー回転１００００ｒｐｍ、スラリー供給速度４００ｇ／ｍｉｎの条件下で噴霧乾燥した。得られた複合酸化物粉末の平均粒子径は６５μｍ、水分含有量は２４.５重量％であった。
(NiO: 67.0 wt%, ZnO: 17.0 wt%, SiO 2: 13.7 wt%, Al 2 O 3: 2.3 wt%)
This composite oxide hydrogel slurry was spray-dried under conditions of an inlet temperature of 300 ° C., an outlet temperature of 105 ° C., an atomizer rotation of 10,000 rpm, and a slurry supply rate of 400 g / min. The obtained composite oxide powder had an average particle size of 65 μm and a water content of 24.5% by weight.
複合酸化物粉末１.３２Ｋｇを高速攪拌粉体混合機（三井鉱山（株）製：ヘンシェルミキサー、FM-20C/Ｉ型）に入れ、ついで、成形助剤（武田製薬(株)製：ビーオポリー）３１.９ｇを予め溶解懸濁した水溶液０.４５Ｋｇとを入れ充分混合し、水分を３８.６重量％に調整した。 1.32 kg of composite oxide powder is put into a high-speed stirring powder mixer (Mitsui Mine Co., Ltd .: Henschel mixer, FM-20C / I type), and then a molding aid (Takeda Pharmaceutical Co., Ltd .: Biopoly). An aqueous solution of 0.45 kg in which 31.9 g was dissolved and suspended in advance was added and mixed well to adjust the water content to 38.6% by weight.
この水分調整した粉末を、下押しロール型押出し機（不二パウダル（株）製：デイスクペレッター、F-5(PV-S)/11-175型)にてペレットに成形した。このとき、まず、押出し機のノズル径３ｍｍφで１回押し出しを行い、ついでノズル径０.７ｍｍφで１回押出しを行いペレットに成形した。このときのペレットの長さは比較的均一で、平均長さは１.２ｍｍであった。 The moisture-adjusted powder was formed into pellets using a down roll type extruder (Fuji Paudal Co., Ltd .: Disc pelleter, F-5 (PV-S) / 11-175 type). At this time, first, extrusion was performed once with an extruder nozzle diameter of 3 mmφ, and then extrusion was performed once with a nozzle diameter of 0.7 mmφ to form pellets. The length of the pellet at this time was relatively uniform, and the average length was 1.2 mm.
得られた径０.７ｍｍφのペレットを球形機（不二パウダル（株）製：マルメライザー、QJ-400）で球状粒子とした。この時の球形機の回転数は６００ｒｐｍ、外熱温度は６０℃、処理時間は３.５分であった。 The obtained pellets having a diameter of 0.7 mmφ were formed into spherical particles using a spherical machine (Fuji Paudal Co., Ltd .: Malmerizer, QJ-400). The rotational speed of the spherical machine at this time was 600 rpm, the external heat temperature was 60 ° C., and the treatment time was 3.5 minutes.
得られた球状成形物を１３０℃で２４時間乾燥し、ついて、窒素気流中、４５０℃で３時間焼成して燃料処理剤(6)を得た。 The obtained spherical molded product was dried at 130 ° C. for 24 hours and then calcined at 450 ° C. for 3 hours in a nitrogen stream to obtain a fuel treatment agent (6).
得られた燃料処理剤(6)の嵩比重（ＣＢＤ）、炭素含有量、平均短径、平均長径、平均粒子径、球状係数、細孔容積、圧縮強度を測定し、平均圧縮強度指数を求め、結果を表１に示した。また耐摩耗性を測定し、結果を表１に示した。 The bulk specific gravity (CBD), carbon content, average short diameter, average long diameter, average particle diameter, spherical coefficient, pore volume, and compressive strength of the obtained fuel treatment agent (6) are measured to obtain an average compressive strength index. The results are shown in Table 1. The abrasion resistance was measured and the results are shown in Table 1.
性能評価
燃料処理剤(6)１０ｍｌ（１２.８ｇ）を用いた以外は実施例１と同様にして性能評価を行い、結果を表１に示した。
［実施例７］
実施例１と同様にして平均粒子径は５４μｍ、水分含有量は１８.３重量％の噴霧乾燥粉体を調製した。
Performance Evaluation Performance evaluation was performed in the same manner as in Example 1 except that 10 ml (12.8 g) of the fuel treatment agent (6) was used. The results are shown in Table 1.
[Example 7]
In the same manner as in Example 1, a spray-dried powder having an average particle size of 54 μm and a water content of 18.3% by weight was prepared.
噴霧乾燥粉体１０００ｇを高速攪拌粉体混合機（三井鉱山（株）製：ヘンシェルミキサー、FM-20C型）に入れ、ついで、シリカゾル（触媒化成(株)製：ＳＩ-３５０、ＳiＯ２濃度２０重量％、平均粒子径８.５ｎｍ）１００ｇと水４００ｇと結晶セルロース３０ｇを予め溶解懸濁した水溶液１２１２ｇとを徐々に加え、充分混合し、水分含有量４４.２重量％の無機酸化物微粒子成形前駆体(7)を調製した。 1000g of spray-dried powder is put into a high-speed stirring powder mixer (Mitsui Mining Co., Ltd .: Henschel mixer, FM-20C type), and then silica sol (Catalyst Kasei Co., Ltd .: SI-350, SiO2 concentration 20 weight) %, Average particle diameter 8.5 nm) 100 g , 400 g of water and 1212 g of an aqueous solution in which 30 g of crystalline cellulose are dissolved and suspended in advance are gradually added and mixed thoroughly to form inorganic oxide fine particles having a water content of 44.2% by weight. Precursor (7) was prepared.
この無機酸化物微粒子成形前駆体(7)を、下押しロール型押出し機（不二パウダル（株）製：デイスクペレッター、F-5(PV-S)/11-175型)にてペレットに成形した。このとき、先ず、押出し機のノズル径２ｍｍφで２回押し出しを行い、ついでノズル径０.７ｍｍφで１回押出しを行いペレットに成形した。このときのペレットの長さは比較的均一で、平均長さは１.２ｍｍであった。 This inorganic oxide fine particle molding precursor (7) is molded into pellets with a down roll type extruder (manufactured by Fuji Powder Co., Ltd .: disk pelleter, F-5 (PV-S) / 11-175 type). did. At this time, first, extrusion was performed twice with a nozzle diameter of 2 mmφ of the extruder, and then extrusion was performed once with a nozzle diameter of 0.7 mmφ to form pellets. The length of the pellet at this time was relatively uniform, and the average length was 1.2 mm.
得られた径０.７ｍｍφのペレットを球形機（不二パウダル（株）製：マルメライザー、QJ-400）で球状粒子とした。この時の球形機の回転数は６００ｒｐｍ、外熱温度は６０℃、処理時間は６分であった。 The obtained pellets having a diameter of 0.7 mmφ were formed into spherical particles using a spherical machine (Fuji Paudal Co., Ltd .: Malmerizer, QJ-400). The rotational speed of the spherical machine at this time was 600 rpm, the external heat temperature was 60 ° C., and the treatment time was 6 minutes.
得られた球状成形物を１３０℃で２４時間乾燥し、ついて、窒素気流中、６７０℃で３時間焼成して燃料処理剤(7)を得た。 The obtained spherical molded product was dried at 130 ° C. for 24 hours and then calcined in a nitrogen stream at 670 ° C. for 3 hours to obtain a fuel treatment agent (7).
得られた燃料処理剤(7)の嵩比重（ＣＢＤ）、炭素含有量、平均短径、平均長径、平均粒子径、球状係数、細孔容積、圧縮強度を測定し、平均圧縮強度指数を求め、結果を表１に示した。また耐摩耗性を測定し、結果を表１に示した。 The bulk specific gravity (CBD), carbon content, average short diameter, average long diameter, average particle diameter, spherical coefficient, pore volume, and compressive strength of the obtained fuel treatment agent (7) are measured to obtain an average compressive strength index. The results are shown in Table 1. The abrasion resistance was measured and the results are shown in Table 1.
性能評価
燃料処理剤(7)１０ｍｌ（１２.１ｇ）を用いた以外は実施例１と同様にして性能評価を行い、結果を表１に示した。
［実施例８］
実施例１で得られた燃料処理剤(1)を粉砕して、平均粒子径が１２μｍの粉砕粉体（固形分９６重量％）を調製した。
Performance Evaluation Performance evaluation was performed in the same manner as in Example 1 except that 10 ml (12.1 g) of the fuel processing agent (7) was used. The results are shown in Table 1.
[Example 8]
The fuel treatment agent (1) obtained in Example 1 was pulverized to prepare a pulverized powder (solid content 96 wt%) having an average particle size of 12 μm.
また、実施例１と同様にして平均粒子径は５４μｍ、水分含有量は１８.３重量％の噴霧乾燥粉体を調製した。 Further, in the same manner as in Example 1, a spray-dried powder having an average particle size of 54 μm and a water content of 18.3% by weight was prepared.
噴霧乾燥粉体１０００ｇを高速攪拌粉体混合機（三井鉱山（株）製：ヘンシェルミキサー、FM-20C型）に入れ、ついで、粉砕粉体８５.１ｇと水１９８ｇと結晶セルロース３０ｇを予め溶解懸濁した水溶液２７０ｇとを徐々に加え、充分混合し、水分含有量４１.１重量％の無機酸化物微粒子成形前駆体(8)を調製した。 1000g of spray-dried powder is put into a high-speed stirring powder mixer (Mitsui Mining Co., Ltd .: Henschel mixer, FM-20C type), then 85.1g of pulverized powder, 198g of water and 30g of crystalline cellulose are dissolved beforehand. 270 g of a turbid aqueous solution was gradually added and mixed well to prepare an inorganic oxide fine particle molding precursor (8) having a water content of 41.1% by weight.
この無機酸化物微粒子成形前駆体(8)を、下押しロール型押出し機（不二パウダル（株）製：デイスクペレッター、F-5(PV-S)/11-175型)にてペレットに成形した。このとき、先ず、押出し機のノズル径２ｍｍφで２回押し出しを行い、ついでノズル径０.７ｍｍφで１回押出しを行いペレットに成形した。このときのペレットの長さは比較的均一で、平均長さは１.２ｍｍであった。 This inorganic oxide fine particle molding precursor (8) is molded into pellets using a down roll type extruder (manufactured by Fuji Powder Co., Ltd .: disk pelleter, F-5 (PV-S) / 11-175 type). did. At this time, first, extrusion was performed twice with a nozzle diameter of 2 mmφ of the extruder, and then extrusion was performed once with a nozzle diameter of 0.7 mmφ to form pellets. The length of the pellet at this time was relatively uniform, and the average length was 1.2 mm.
得られた径０.７ｍｍφのペレットを球形機（不二パウダル（株）製：マルメライザー、QJ-400）で球状粒子とした。この時の球形機の回転数は６００ｒｐｍ、外熱温度は６０℃、処理時間は６分であった。 The obtained pellets having a diameter of 0.7 mmφ were formed into spherical particles using a spherical machine (Fuji Paudal Co., Ltd .: Malmerizer, QJ-400). The rotational speed of the spherical machine at this time was 600 rpm, the external heat temperature was 60 ° C., and the treatment time was 6 minutes.
得られた球状成形物を１３０℃で２４時間乾燥し、ついて、窒素気流中、６７０℃で３時間焼成して燃料処理剤(7)を得た。 The obtained spherical molded product was dried at 130 ° C. for 24 hours and then calcined in a nitrogen stream at 670 ° C. for 3 hours to obtain a fuel treatment agent (7).
得られた燃料処理剤(8)の嵩比重（ＣＢＤ）、炭素含有量、平均短径、平均長径、平均粒子径、球状係数、細孔容積、圧縮強度を測定し、平均圧縮強度指数を求め、結果を表１に示した。また耐摩耗性を測定し、結果を表１に示した。 The bulk specific gravity (CBD), carbon content, average short diameter, average long diameter, average particle diameter, spherical coefficient, pore volume, and compressive strength of the obtained fuel treatment agent (8) are measured to obtain an average compressive strength index. The results are shown in Table 1. The abrasion resistance was measured and the results are shown in Table 1.
性能評価
燃料処理剤(7)１０ｍｌ（１２.５ｇ）を用いた以外は実施例１と同様にして性能評価を行い、結果を表１に示した。
［比較例１］
実施例１と同様にして調製した複合酸化物ヒドロゲルスラリー（固形分濃度２０.５重量％）２５００ｇをスチーム加熱濃縮機に入れ、これにアビセル（旭化成製）７５ｇ入れて充分混合した後、ジャケットにスチームを通じ加熱しながら水分が約４５重量％になるまで濃縮し、ついで、冷却した。この濃縮品の水分は４６.５重量％であった。
Performance Evaluation Performance evaluation was performed in the same manner as in Example 1 except that 10 ml (12.5 g) of the fuel processing agent (7) was used, and the results are shown in Table 1.
[Comparative Example 1]
2500 g of composite oxide hydrogel slurry (solid content concentration 20.5% by weight) prepared in the same manner as in Example 1 was placed in a steam-heated concentrator, and 75 g of Avicel (Asahi Kasei) was added and mixed well. While heating through steam, the solution was concentrated to about 45% by weight, and then cooled. The water content of this concentrated product was 46.5% by weight.
この水分調整品を押出し機（本田鉄工(株)製：DE-75型、前押しスクリュー型）で、０.７ｍｍφのダイスを用いてペレットの成型を試みたがダイスが目詰まりし、押し出すことが困難であった。
［比較例２］
実施例２と同様にして固形分濃度は７.０重量の複合酸化物ヒドロゲルスラリー１７.８６Ｋｇを調製した。ついで、スチーム加熱濃縮機に入れ、アビセル（旭化成製）３７.５ｇを加え、１１０℃で混合、捏和し、水分含有量５７重量％の捏和物を調製した。
I tried to mold this moisture-adjusted product with an extruder (Honda Tekko Co., Ltd .: DE-75 type, front screw type) using a 0.7mmφ die, but the die was clogged and extruded. It was difficult.
[Comparative Example 2]
In the same manner as in Example 2, 17.86 kg of a complex oxide hydrogel slurry having a solid content concentration of 7.0 weight was prepared. Next, the mixture was placed in a steam heat concentrator, 37.5 g of Avicel (manufactured by Asahi Kasei) was added, and the mixture was mixed and kneaded at 110 ° C. to prepare a kneaded product having a moisture content of 57% by weight.
ついで、この捏和物を押出し機（本田鉄工(株)製：DE-75型、前押しスクリュー型）で、１.１ｍｍφのダイスを用いてペレットに成型した。このときのペレットの長さは比較的不均一で、平均長さは２.２ｍｍであった。 Next, this kneaded product was molded into pellets using a 1.1 mmφ die with an extruder (Honda Iron Works Co., Ltd .: DE-75 type, front-pressing screw type). At this time, the length of the pellet was relatively non-uniform, and the average length was 2.2 mm.
得られたペレットを１２０℃で１２時間乾燥し、ついて、窒素気流中、４５０℃で３時間焼成して燃料処理剤(R-2)を得た。 The obtained pellets were dried at 120 ° C. for 12 hours and then calcined at 450 ° C. for 3 hours in a nitrogen stream to obtain a fuel treatment agent (R-2).
得られた燃料処理剤(R-2)の嵩比重（ＣＢＤ）、炭素含有量、平均径、平均長、細孔容積、圧縮強度を測定し、結果を表１に示した。また耐摩耗性を測定し、結果を表１に示した。 The bulk specific gravity (CBD), carbon content, average diameter, average length, pore volume, and compressive strength of the obtained fuel treatment agent (R-2) were measured, and the results are shown in Table 1. The abrasion resistance was measured and the results are shown in Table 1.
性能評価
燃料処理剤(R-2)１０ｍｌ（９.８ｇ）を用いた以外は実施例１と同様にして性能評価を行い、結果を表１に示した。
［比較例３］
押し出し成形機のダイス径１.５ｍｍφを用いた以外は実施例１と同様にして径１.５ｍｍφ、長さ２.１ｍｍのペレットを成形し、ついで、１３０℃で２４時間乾燥し、ついて、窒素気流中、４５０℃で３時間焼成して燃料処理剤(R-3)を得た。
Performance Evaluation Performance evaluation was performed in the same manner as in Example 1 except that 10 ml (9.8 g) of the fuel processing agent (R-2) was used, and the results are shown in Table 1.
[Comparative Example 3]
A pellet having a diameter of 1.5 mmφ and a length of 2.1 mm was formed in the same manner as in Example 1 except that a die diameter of 1.5 mmφ of the extrusion molding machine was used, and then dried at 130 ° C. for 24 hours, and then nitrogen. The fuel treatment agent (R-3) was obtained by firing at 450 ° C. for 3 hours in an air stream.
得られた燃料処理剤(R-3)の嵩比重（ＣＢＤ）、炭素含有量、平均径、平均長、細孔容積、圧縮強度を測定し、結果を表１に示した。また耐摩耗性を測定し、結果を表１に示した。 The bulk specific gravity (CBD), carbon content, average diameter, average length, pore volume, and compressive strength of the obtained fuel treatment agent (R-3) were measured, and the results are shown in Table 1. The abrasion resistance was measured and the results are shown in Table 1.
性能評価
燃料処理剤(R-3)１０ｍｌ（９.９ｇ）を用いた以外は実施例１と同様にして性能評価を行い、結果を表１に示した。
［比較例４］
実施例７と同様にして径０.７ｍｍφ、長さ１.２ｍｍのペレットを成形し、ついで、１３０℃で２４時間乾燥し、ついて、窒素気流中、４５０℃で３時間焼成して燃料処理剤(R-4)を得た。
Performance Evaluation Performance evaluation was performed in the same manner as in Example 1 except that 10 ml (9.9 g) of the fuel treatment agent (R-3) was used. The results are shown in Table 1.
[Comparative Example 4]
A pellet with a diameter of 0.7 mmφ and a length of 1.2 mm was formed in the same manner as in Example 7, then dried at 130 ° C. for 24 hours, and then calcined at 450 ° C. for 3 hours in a nitrogen stream. (R-4) was obtained.
得られた燃料処理剤(R-4)の嵩比重（ＣＢＤ）、炭素含有量、平均径、平均長、細孔容積、圧縮強度を測定し、結果を表１に示した。また耐摩耗性を測定し、結果を表１に示した。 The bulk specific gravity (CBD), carbon content, average diameter, average length, pore volume, and compressive strength of the obtained fuel treatment agent (R-4) were measured, and the results are shown in Table 1. The abrasion resistance was measured and the results are shown in Table 1.
性能評価
燃料処理剤(R-4)１０ｍｌ（９.７ｇ）を用いた以外は実施例１と同様にして性能評価を行い、結果を表１に示した。
［比較例５］
実施例８と同様にして径０.７ｍｍφ、長さ１.２ｍｍのペレットを成形し、ついで、１３０℃で２４時間乾燥し、ついて、窒素気流中、６７０℃で３時間焼成して燃料処理剤(R-5)を得た。
Performance Evaluation Performance evaluation was performed in the same manner as in Example 1 except that 10 ml (9.7 g) of the fuel processing agent (R-4) was used, and the results are shown in Table 1.
[Comparative Example 5]
A pellet having a diameter of 0.7 mmφ and a length of 1.2 mm was formed in the same manner as in Example 8, then dried at 130 ° C. for 24 hours, and then calcined at 670 ° C. for 3 hours in a nitrogen stream. (R-5) was obtained.
得られた燃料処理剤(R-5)の嵩比重（ＣＢＤ）、炭素含有量、平均径、平均長、細孔容積、圧縮強度を測定し、結果を表１に示した。また耐摩耗性を測定し、結果を表１に示した。 The bulk specific gravity (CBD), carbon content, average diameter, average length, pore volume, and compressive strength of the obtained fuel treatment agent (R-5) were measured, and the results are shown in Table 1. The abrasion resistance was measured and the results are shown in Table 1.
性能評価
燃料処理剤(R-5)１０ｍｌ（９.６ｇ）を用いた以外は実施例１と同様にして性能評価を行い、結果を表１に示した。
Performance Evaluation Performance evaluation was performed in the same manner as in Example 1 except that 10 ml (9.6 g) of the fuel processing agent (R-5) was used, and the results are shown in Table 1.
Claims (6)
トン）の範囲にあり、長径(D L )と短径(D S )との比（球状係数(D L )/(D S )）が１〜１.５の範囲にあり、下記式で表される平均圧縮強度指数(C)が０.５〜５の範囲にある無機酸化物を含む微小球状成形体からなり、
前記無機酸化物が活性成分とマトリックス成分とを含んでなり、活性成分がＣuＯ、ＡgＯ、ＺnＯ、Ｆe2Ｏ3、ＣoＯ、ＮiＯから選ばれる1種以上の酸化物または複合酸化物であ
り、マトリックス成分が、ＳiＯ2、Ａl2Ｏ3、ＴiＯ2、ＺrＯ2から選ばれる１種以上の酸
化物または複合酸化物であり、
該微小球状成形体が、下記工程(a)〜(d)により製造された成形体であることを特徴とする燃料処理剤：
(a)水分含有量が30〜60重量%の範囲の無機酸化物微粒子成形前駆体を調製する工程、
(b)無機酸化物微粒子成形前駆体を、押出成形機にてペレット径が0.3〜5mmの範囲のペレ
ット状成形体とする工程、
(ｃ)得られたペレット状成形体を、球形成形機にて球状成形体とする工程、
(d)得られた球状成形体を、乾燥および/または焼成する工程。
Ｃ＝Ｎ×PV／Ｄ The average particle size (D) is in the range of 0.3 to 5 mm, the pore size (PV) in the range of 30 to 500 nm is in the range of 0.1 to 0.6 ml / g, and the average compressive strength is (N) is in the range of 1 to 30 N (Newton), and the ratio of the major axis (D L ) to the minor axis (D S ) (spherical coefficient (D L ) / (D S )) is 1 to 1.5. It consists of a microspherical molded body containing an inorganic oxide having a range and an average compressive strength index (C) represented by the following formula in a range of 0.5 to 5,
The inorganic oxide comprises an active component and a matrix component, and the active component is one or more oxides or composite oxides selected from CuO, AgO, ZnO, Fe 2 O 3 , CoO, and NiO. The component is one or more oxides or composite oxides selected from SiO 2 , Al 2 O 3 , TiO 2 , and ZrO 2 ;
The fuel processing agent, wherein the microspherical molded body is a molded body produced by the following steps (a) to (d) :
(a) a step of preparing an inorganic oxide fine particle molding precursor having a moisture content in the range of 30 to 60% by weight;
(b) An inorganic oxide fine particle molding precursor is applied to a pellet having a pellet diameter in the range of 0.3 to 5 mm using an extruder.
A step of forming a cup-shaped body,
(c) a step of converting the obtained pellet-shaped molded body into a spherical molded body with a sphere forming machine,
(d) A step of drying and / or firing the obtained spherical molded body.
C = N x PV / D
たはSi02からなることを特徴とする請求項１に記載の燃料処理剤。 The active ingredient is comprised NiO and / or CuO, fuel processing agent according to claim 1, characterized in that the matrix component consists of Al 2 0 3 and / or Si0 2.
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