JP4296430B2 - Catalyst for water gas shift reaction and process for producing the same - Google Patents
Catalyst for water gas shift reaction and process for producing the same Download PDFInfo
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- JP4296430B2 JP4296430B2 JP2004377729A JP2004377729A JP4296430B2 JP 4296430 B2 JP4296430 B2 JP 4296430B2 JP 2004377729 A JP2004377729 A JP 2004377729A JP 2004377729 A JP2004377729 A JP 2004377729A JP 4296430 B2 JP4296430 B2 JP 4296430B2
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- 239000003054 catalyst Substances 0.000 title claims description 207
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 66
- 238000006243 chemical reaction Methods 0.000 title claims description 58
- 238000000034 method Methods 0.000 title claims description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 76
- 229910052697 platinum Inorganic materials 0.000 claims description 65
- 229910052751 metal Inorganic materials 0.000 claims description 59
- 239000000243 solution Substances 0.000 claims description 47
- 239000002184 metal Substances 0.000 claims description 45
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 40
- 229910052726 zirconium Inorganic materials 0.000 claims description 40
- 229910052742 iron Inorganic materials 0.000 claims description 39
- 229910052727 yttrium Inorganic materials 0.000 claims description 32
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 31
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 31
- 229910052684 Cerium Inorganic materials 0.000 claims description 30
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 21
- 239000006104 solid solution Substances 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 18
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 15
- 229910052703 rhodium Inorganic materials 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 229910052737 gold Inorganic materials 0.000 claims description 9
- 229910052741 iridium Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052762 osmium Inorganic materials 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 229910052779 Neodymium Inorganic materials 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052788 barium Inorganic materials 0.000 claims description 7
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 6
- -1 P d Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 119
- 239000007864 aqueous solution Substances 0.000 description 41
- 239000007789 gas Substances 0.000 description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 23
- 229910000420 cerium oxide Inorganic materials 0.000 description 23
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 23
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 23
- 229910001928 zirconium oxide Inorganic materials 0.000 description 23
- 229910052739 hydrogen Inorganic materials 0.000 description 21
- 238000005470 impregnation Methods 0.000 description 21
- 239000001257 hydrogen Substances 0.000 description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- IXSUHTFXKKBBJP-UHFFFAOYSA-L azanide;platinum(2+);dinitrite Chemical compound [NH2-].[NH2-].[Pt+2].[O-]N=O.[O-]N=O IXSUHTFXKKBBJP-UHFFFAOYSA-L 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 229910017604 nitric acid Inorganic materials 0.000 description 14
- 239000010948 rhodium Substances 0.000 description 14
- 229910052763 palladium Inorganic materials 0.000 description 12
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 11
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 229910052707 ruthenium Inorganic materials 0.000 description 10
- 238000005259 measurement Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 239000010944 silver (metal) Substances 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000010931 gold Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 5
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 150000002506 iron compounds Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
本発明は、水性ガスシフト反応に好適に用いることができる触媒及びその製造方法に関するものである。 The present invention relates to a catalyst that can be suitably used for a water gas shift reaction and a method for producing the same.
水性ガスシフト反応（ＣＯ＋Ｈ２Ｏ→ＣＯ２＋Ｈ２）は、従来より、コークス、天然ガスなどの炭化水素及び水蒸気から得られる水性ガスに含まれるＣＯとＨ２Ｏの比率を変える、あるいはＨ２の製造等のため、化学工業プロセスにおいて利用されている大変重要な反応である。 The water gas shift reaction (CO + H 2 O → CO 2 + H 2 ) has conventionally changed the ratio of CO and H 2 O contained in water gas obtained from hydrocarbons such as coke and natural gas and water vapor, or H 2 It is a very important reaction that is used in chemical industry processes for manufacturing and the like.
また、近年注目を浴びている燃料電池の燃料となる水素を、都市ガス等を改質して得る場合、副生したＣＯが燃料電池電極を被毒して発電効率が低下するため、この副生したＣＯを低減させる反応としてより高活性な水性ガスシフト反応に注目が集まっている。こうした水性ガスシフト反応の触媒は、一般に、１５０〜２３０℃程度の低温においては銅−亜鉛系や白金／アルミナ系が、３５０〜４５０℃程度の高温においては鉄−クロム系が使用される。 In addition, when hydrogen, which is the fuel of fuel cells that has been attracting attention in recent years, is obtained by reforming city gas or the like, the by-produced CO poisons the fuel cell electrode, reducing power generation efficiency. Attention has been focused on a highly active water gas shift reaction as a reaction for reducing the generated CO. As a catalyst for such a water gas shift reaction, a copper-zinc system or a platinum / alumina system is generally used at a low temperature of about 150 to 230 ° C., and an iron-chromium system is used at a high temperature of about 350 to 450 ° C.
しかし、銅−亜鉛系触媒は、酸化やシンタリングによって短時間で失活してしまう問題点がある。またビーズ形状の場合には爆裂することもあり、使用に際して細心を払わなくてはならない。白金／アルミナ系触媒の耐熱性は高いが、高い活性を発現させるためには白金の担持量を多くする必要があるため触媒自体が非常に高価になってしまう問題点がある。さらには稀少な元素を大量に使用することによって枯渇問題やさらなる値段の高騰などの問題が懸念される。 However, the copper-zinc catalyst has a problem that it deactivates in a short time due to oxidation or sintering. In the case of a bead shape, it may explode and must be used with great care. Although the heat resistance of the platinum / alumina catalyst is high, there is a problem that the catalyst itself becomes very expensive because it is necessary to increase the amount of platinum supported in order to exhibit high activity. Furthermore, there are concerns about problems such as depletion and higher prices due to the use of rare elements in large quantities.
また、鉄−クロム系触媒の耐熱性は高いが反応温度が高温であるため、平衡ガス組成のＣＯ濃度がある一定基準より下がらないという問題点がある。また、これらの触媒を成形した触媒体は、高温で焼結させられないために、圧縮成型されることが多いが、この方法では摩擦や衝撃によって表面から徐々に粉体が脱落する粉化現象が起こりやすく、その粉による触媒反応管の閉塞や反応場圧の上昇が起こりやすくなってしまう。 Further, although the heat resistance of the iron-chromium catalyst is high, the reaction temperature is high, so that there is a problem that the CO concentration of the equilibrium gas composition does not fall below a certain standard. In addition, the catalyst bodies that are molded from these catalysts are often compression molded because they cannot be sintered at high temperatures, but in this method, the powdering phenomenon in which the powder gradually falls off the surface due to friction and impact. The catalyst reaction tube is blocked by the powder and the reaction field pressure is likely to increase.
上記問題点を克服した、大量の貴金属を使用しない高活性な触媒が得られれば、一定条件下の化学工業プロセスのみならず、特に変動条件下における種々の利用が期待され、燃料電池に使用される燃料の改質、即ち、電極触媒の触媒毒となるＣＯを燃料電池に有用な燃料の水素に転化させる利用が期待される。 If a highly active catalyst that does not use a large amount of precious metals and that overcomes the above problems is obtained, it can be used not only in chemical industry processes under certain conditions but also in various variable conditions, and is used in fuel cells. Therefore, it is expected that CO, which is a catalyst poison of an electrode catalyst, is converted to hydrogen, a fuel useful for fuel cells.
ジルコニウム及びセリウム若しくはそれらの固溶体にＰｔ，Ｐｄ，Ｒｈ等を担持した触媒は、自動車の排ガス処理触媒などでよく知られており、水性ガスシフト反応用触媒としても活性を示すことが知られている（特許文献１〜３）。 A catalyst in which Pt, Pd, Rh or the like is supported on zirconium and cerium or a solid solution thereof is well known as an exhaust gas treatment catalyst for automobiles, and is also known to exhibit activity as a catalyst for water gas shift reaction ( Patent Documents 1 to 3).
また、通常触媒を使用するときは成型体として使用するので何らかの方法で成型体を作成する必要があり、触媒粉体を型に詰め、圧力をかける方法が広く用いられている。 In addition, since a catalyst is usually used as a molded body, it is necessary to prepare the molded body by some method, and a method in which catalyst powder is packed in a mold and pressure is applied is widely used.
他の成型体の作製方法としてアルミナ等の成型体にセリウム水溶液を浸透させて、触媒成型体を作製する方法も記載されている（特許文献４）。 As another method for producing a molded article, a method for producing a catalyst molded article by infiltrating a cerium aqueous solution into a molded article such as alumina is also described (Patent Document 4).
少量の貴金属でも高い活性を有する触媒は、現在最も要求されているところであるが、この要求を満たすような水性ガスシフト反応用の触媒は未だ提供されていない。 A catalyst having high activity even with a small amount of noble metal is currently most demanded, but a catalyst for a water gas shift reaction that satisfies this requirement has not yet been provided.
即ち、前記特許文献１〜４記載の技術は、触媒活性が低活性であるので、水性ガスシフト反応に用いる触媒として有用とは言い難いものである。 That is, the techniques described in Patent Documents 1 to 4 are hardly useful as a catalyst used in the water gas shift reaction because the catalytic activity is low.
本発明は、前記特許文献１〜４に記載された従来技術の現状に鑑みてなされたものであり、その主な目的は、従来の活性の低い担体に対して、少なくともジルコニウム、セリウム、鉄及び／又はイットリウムを含む酸化物固溶体からなることにより、活性の高い触媒及びその製造方法を提供することである。 The present invention has been made in view of the current state of the prior art described in Patent Documents 1 to 4, and the main object thereof is at least zirconium, cerium, iron, and the like with respect to conventional low activity carriers. It is to provide a highly active catalyst and a method for producing the same by comprising an oxide solid solution containing yttrium.
前記技術的課題は、次の通りの本発明によって達成できる。 The technical problem can be achieved by the present invention as follows.
即ち、本発明は、ジルコニウム及びセリウムとともに鉄及び／又はイットリウムからなる酸化物固溶体に、Ａｕ，Ａｇ，Ｃｕ，Ｐｔ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕの中から選ばれる１種または２種以上の活性金属元素が存在する水性ガスシフト反応用の触媒であって、前記触媒のジルコニウム含有量がＺｒＯ２換算で３０〜９０重量％であり、該触媒のＢＥＴ比表面積が３０〜２００ｍ ２ ／ｇであることを特徴とする水性ガスシフト反応用の触媒である（本発明１）。
る水性ガスシフト反応用の触媒である（本発明１）。
That is, the present invention is selected in the oxide solid solution of iron and / or yttrium with zirconium and cerium, Au, Ag, Cu, Pt , P d, Ni, Ir, Rh, Co, Os, from among Ru 1 a catalyst for the water gas shift reaction to the presence of species or two or more active metal element, wherein the zirconium content of the catalyst Ri 30-90 wt% der in ZrO2 terms, BET specific surface area of the catalyst is 30 a catalyst for the water gas shift reaction, wherein 200 meters 2 / g der Rukoto (present invention 1).
This is a catalyst for water gas shift reaction (Invention 1).
本発明１の触媒を構成する鉄の含有量が、酸化鉄（Ｆｅ３Ｏ４）換算で５．０重量％以下であり、イットリウムの含有量が酸化イットリウム（Ｙ２Ｏ３）換算で１０重量％以下であることを特徴とする水性ガスシフト反応用の触媒である（本発明２）。 The content of iron constituting the catalyst of the present invention 1 is 5.0% by weight or less in terms of iron oxide (Fe 3 O 4 ), and the content of yttrium is 10% in terms of yttrium oxide (Y 2 O 3 ). % Or less, it is a catalyst for water gas shift reaction (Invention 2).
本発明１又は２の触媒において、活性金属元素がジルコニウム及びセリウムとともに鉄及び／又はイットリウムからなる酸化物固溶体に担持されており、該活性金属元素を触媒に対して０．００１〜５．０重量％担持させたことを特徴とする水性ガスシフト反応用の触媒である（本発明３）。 In the catalyst of the present invention 1 or 2, the active metal element is supported on an oxide solid solution composed of iron and / or yttrium together with zirconium and cerium, and the active metal element is 0.001 to 5.0 wt. % Is a catalyst for water gas shift reaction, which is characterized in that it is supported by the catalyst (Invention 3).
本発明１乃至３のいずれかの触媒において、アルミニウム、ジルコニウム、珪素、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、亜鉛、ランタン及びネオジウムの中から選ばれる１種または２種以上の異種金属元素の酸化物を、触媒に対して１〜９００重量％含有させたことを特徴とする水性ガスシフト反応用の触媒である（本発明４）。 Oxidation of one or more different metal elements selected from aluminum, zirconium, silicon, magnesium, calcium, strontium, barium, titanium, zinc, lanthanum and neodymium in any one of the catalysts of the present invention 1 to 3 This is a catalyst for water gas shift reaction characterized in that the product is contained in an amount of 1 to 900% by weight based on the catalyst (Invention 4).
本発明１乃至３のいずれかの触媒において、アルミニウム、ジルコニウム、珪素、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、亜鉛、ランタン及びネオジウムの中から選ばれる１種または２種以上の異種金属元素の酸化物を、触媒に対して１〜９００重量％含有し、さらに、活性金属元素を０．０００１〜５．０重量％担持させたことを特徴とする水性ガスシフト反応用の触媒である（本発明５）。 Oxidation of one or more different metal elements selected from aluminum, zirconium, silicon, magnesium, calcium, strontium, barium, titanium, zinc, lanthanum and neodymium in any one of the catalysts of the present invention 1 to 3 1 to 900% by weight of a catalyst, and further, 0.0001 to 5.0% by weight of an active metal element is supported (invention 5). ).
サポート材に、前記本発明１乃至５のいずれかの触媒を存在させたことを特徴とする水性ガスシフト反応用の触媒体である（本発明６）。 A catalyst body for water gas shift reaction, characterized in that the catalyst according to any one of the present inventions 1 to 5 is present in a support material (invention 6).
サポート材に、前記本発明１乃至５のいずれかの触媒を存在させ、更に、活性金属元素を０．０００１〜５．０重量％担持させたことを特徴とする水性ガスシフト反応用の触媒体である（本発明７）。 A catalyst body for a water gas shift reaction, characterized in that the catalyst according to any one of the first to fifth aspects of the present invention is present in a support material and 0.0001 to 5.0% by weight of an active metal element is supported thereon. There is (Invention 7).
アルカリ性溶液と、ジルコニウム、セリウム、鉄及び／又はイットリウム、活性金属元素を含む溶液とを混合、熟成して得られる粒子を濾別、水洗した後、５００〜８００℃の温度範囲で焼成することを特徴とする前記本発明１の水性ガスシフト反応用の触媒の製造方法である（本発明８）。
Mixing and aging an alkaline solution and a solution containing zirconium, cerium, iron and / or yttrium, and an active metal element, separating the particles obtained by filtration, washing with water , and firing at a temperature range of 500 to 800 ° C. This is a method for producing a catalyst for water gas shift reaction according to the first aspect of the present invention (Invention 8).
アルカリ性溶液と、ジルコニウム、セリウム、鉄及び／又はイットリウムを含む溶液とを混合、熟成して得られる粒子を濾別、水洗した後、活性金属元素を担持させ、５００〜８００℃の温度範囲で焼成することを特徴とする前記本発明１の水性ガスシフト反応用の触媒の製造方法である（本発明９）。
Mixing and aging an alkaline solution and a solution containing zirconium, cerium, iron and / or yttrium, the particles obtained by aging are filtered, washed with water, loaded with an active metal element, and fired at a temperature range of 500 to 800 ° C. This is a method for producing a catalyst for water gas shift reaction according to the first aspect of the invention (Invention 9).
サポート材の表面にセラミックスを含むスラリーを塗布して焼成した後、本発明１乃至５のいずれかの触媒を担持し、更に、活性金属元素を担持させることを特徴とする前記本発明６又は７の水性ガスシフト反応用の触媒体の製造方法である（本発明１０）。 The invention 6 or 7 according to the invention 6 or 7, wherein a slurry containing ceramics is applied to the surface of the support material and fired, then the catalyst according to any one of the inventions 1 to 5 is supported, and further an active metal element is supported. This is a method for producing a catalyst body for the water gas shift reaction (Invention 10).
本発明に係る触媒は、ジルコニウム、セリウム、鉄及び／又はイットリウムを含む酸化物固溶体からなり、更に、活性金属元素を存在させているので、水性ガスシフト反応をより効率よく行えるという優れた効果を奏する。 The catalyst according to the present invention is composed of an oxide solid solution containing zirconium, cerium, iron and / or yttrium, and further has an active metal element, so that the water gas shift reaction can be performed more efficiently. .
また、本発明４又は５に係るアルミニウム酸化物などを含有させた触媒は、水性ガスシフト反応時の粒子成長を抑制することができるので、より効率よく水性ガスシフト反応を行うことができる。 Moreover, since the catalyst containing the aluminum oxide according to the present invention 4 or 5 can suppress the particle growth during the water gas shift reaction, the water gas shift reaction can be performed more efficiently.
また、本発明６又は７に係るサポート材に触媒を存在させた場合には、触媒のほぼ全量が水性ガスシフト反応に寄与することができるので、触媒の機能を十分に発揮することができる。 In addition, when the catalyst is present in the support material according to the sixth or seventh aspect of the invention, almost the entire amount of the catalyst can contribute to the water gas shift reaction, so that the function of the catalyst can be sufficiently exhibited.
本発明の構成をより詳しく説明すれば次の通りである。 The configuration of the present invention will be described in more detail as follows.
本発明に係る触媒は少なくともジルコニウム、セリウム、鉄及び／又はイットリウムからなる固溶体酸化物に、Ａｕ，Ａｇ，Ｃｕ，Ｐｔ，Ｆｅ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕの中から選ばれる１種または２種以上の活性金属元素（以下、「活性金属元素」という。）が存在する触媒からなる。 The catalyst according to the present invention is selected from the group consisting of Au, Ag, Cu, Pt, Fe, Pd, Ni, Ir, Rh, Co, Os, and Ru as a solid solution oxide composed of at least zirconium, cerium, iron and / or yttrium. And a catalyst containing one or more active metal elements (hereinafter referred to as “active metal elements”).
本発明に係る触媒は、セリウム、ジルコニウム、鉄及び／又はイットリウムが固溶体を形成した酸化物である。即ち、Ｃｅ−Ｚｒ−Ｆｅの複合酸化物、Ｃｅ−Ｚｒ−Ｙの複合酸化物又は、Ｃｅ−Ｚｒ−Ｆｅ−Ｙの複合酸化物のいずれかからなるものである。本発明において前記元素が固溶体を形成していない場合、酸素の貯蔵放出能が低下する。また、鉄及び／又はイットリウムが固溶体を形成しない場合は、比表面積が低下し、水性ガスシフト反応用の触媒としての機能が十分でない。 The catalyst according to the present invention is an oxide in which cerium, zirconium, iron and / or yttrium form a solid solution. That is, it is made of either a Ce—Zr—Fe composite oxide, a Ce—Zr—Y composite oxide, or a Ce—Zr—Fe—Y composite oxide. In the present invention, when the element does not form a solid solution, the ability to store and release oxygen decreases. Moreover, when iron and / or yttrium do not form a solid solution, the specific surface area decreases, and the function as a catalyst for the water gas shift reaction is not sufficient.
本発明１〜３の触媒を構成するセリウムの含有量は酸化セリウム（ＣｅＯ２）換算で１０〜７０重量％、ジルコニウムの含有量は酸化ジルコニウム（ＺｒＯ２）換算で３０〜９０重量％、鉄の含有量は酸化鉄（Ｆｅ３Ｏ４）換算で０〜５．０重量％、イットリウムの含有量は酸化イットリウム（Ｙ２Ｏ３）換算で０〜１０重量％の範囲内であることが好ましい。セリウム、ジルコニウム、イットリウム、鉄が前記範囲外の場合には、本発明の目的とする効果が得られない。より好ましくは、セリウムの含有量が２０〜６０重量％、ジルコニウムの含有量が４０〜７５重量％、鉄の含有量が０．０１〜４．５重量％、イットリウムの含有量が０．０１〜９．０重量％の範囲である。更により好ましくは、鉄の含有量が０．１〜４．５重量％、イットリウムの含有量が１．０〜９．０重量％の範囲である。 The content of cerium constituting the catalysts of the present invention 1 to 3 is 10 to 70% by weight in terms of cerium oxide (CeO 2 ), and the content of zirconium is 30 to 90% by weight in terms of zirconium oxide (ZrO 2 ). The content is preferably 0 to 5.0 wt% in terms of iron oxide (Fe 3 O 4 ), and the yttrium content is preferably in the range of 0 to 10 wt% in terms of yttrium oxide (Y 2 O 3 ). When cerium, zirconium, yttrium, and iron are out of the above ranges, the intended effect of the present invention cannot be obtained. More preferably, the cerium content is 20 to 60% by weight, the zirconium content is 40 to 75% by weight, the iron content is 0.01 to 4.5% by weight, and the yttrium content is 0.01 to It is in the range of 9.0% by weight. Even more preferably, the iron content is in the range of 0.1 to 4.5% by weight and the yttrium content is in the range of 1.0 to 9.0% by weight.
本発明に係る触媒の活性金属元素は、前記触媒の表面に担持させる形態又は、触媒中に含有させる形態のいずれの形態でもよく、好ましくは、触媒の表面に担持させる形態である。活性金属元素の存在量は、触媒に対して０．００１〜５．０重量％が好ましく、より好ましくは０．０１〜３．０重量％である。活性金属元素の存在量が前記範囲外の場合には、十分な活性を得ることができない。 The active metal element of the catalyst according to the present invention may be in the form of being supported on the surface of the catalyst or in the form of being contained in the catalyst, and is preferably in the form of being supported on the surface of the catalyst. The amount of the active metal element is preferably 0.001 to 5.0% by weight, more preferably 0.01 to 3.0% by weight, based on the catalyst. If the amount of the active metal element is outside the above range, sufficient activity cannot be obtained.
本発明１〜３に係る触媒のＢＥＴ比表面積は３０ｍ２／ｇ以上が好ましく、より好ましくは５０ｍ２／ｇ以上である。上限は２００ｍ２／ｇ程度である。 The BET specific surface area of the catalysts according to the present invention 1 to 3 is preferably 30 m 2 / g or more, more preferably 50 m 2 / g or more. The upper limit is about 200 m 2 / g.
本発明１〜３に係る触媒のＣＯ転化率は、後述する評価法において、３０％以上が好ましく、より好ましくは５０％以上である。 The CO conversion rate of the catalysts according to the present invention 1 to 3 is preferably 30% or more, more preferably 50% or more, in the evaluation method described later.
本発明４に係る触媒は、前記本発明１乃至３の触媒に、アルミニウム、ジルコニウム、珪素、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、亜鉛、ランタン及びネオジウムの中から選ばれる１種または２種以上の異種金属元素から成る酸化物（以下、「異種金属元素の酸化物」という。）を含有するものである。異種金属元素の酸化物が存在することによって、これらが障壁となり、水性ガスシフト反応時に本発明１乃至３の触媒を構成する粒子の成長を抑制し、触媒活性を高く保持することができる。 The catalyst according to the present invention 4 is the catalyst according to the present invention 1 to 3, wherein one or more selected from aluminum, zirconium, silicon, magnesium, calcium, strontium, barium, titanium, zinc, lanthanum and neodymium. And an oxide composed of a different metal element (hereinafter referred to as “oxide of a different metal element”). By the presence of oxides of different metal elements, these serve as barriers, and during the water gas shift reaction, the growth of particles constituting the catalysts of the present inventions 1 to 3 can be suppressed and the catalytic activity can be kept high.
本発明４に係る触媒において、異種金属元素の酸化物の含有量は、本発明１〜３の触媒に対して、１〜９００重量％含有することが好ましい。異種金属元素の酸化物の含有量が１重量％未満の場合には、障壁としての効果が得られず、９００重量％を越える場合には、本発明１乃至３の触媒成分が少なくなるので、活性が低下してしまうため好ましくない。より好ましくは２０〜８００重量％である。 In the catalyst according to the present invention 4, the content of the oxide of the different metal element is preferably 1 to 900% by weight with respect to the catalyst of the present invention 1 to 3. When the content of the oxide of the dissimilar metal element is less than 1% by weight, the effect as a barrier cannot be obtained, and when it exceeds 900% by weight, the catalyst components of the present invention 1 to 3 are reduced. Since activity falls, it is not preferable. More preferably, it is 20 to 800% by weight.
本発明４に係る触媒のＢＥＴ比表面積は、前記本発明１〜３に係る触媒と同程度である。 The BET specific surface area of the catalyst according to the present invention 4 is about the same as that of the catalyst according to the present invention 1 to 3.
本発明４に係る触媒のＣＯ転化率は、後述する評価法において、７０％以上が好ましく、より好ましくは９０％以上である。 The CO conversion rate of the catalyst according to the present invention 4 is preferably 70% or more, more preferably 90% or more, in the evaluation method described later.
本発明５に係る触媒は、前記本発明４に係る触媒に対して、更に、Ａｕ，Ａｇ，Ｃｕ，Ｐｔ，Ｆｅ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕの中から選ばれる１種または２種以上の活性金属元素を触媒に対し０．０００１〜５．０重量％担持させた触媒であり、担持量はより好ましくは、０．０１〜３．０重量％である。なお、触媒中の活性金属元素の全含有量は０．１〜４．０重量％が好ましい。 The catalyst according to the present invention 5 is further selected from Au, Ag, Cu, Pt, Fe, Pd, Ni, Ir, Rh, Co, Os, and Ru with respect to the catalyst according to the present invention 1 It is a catalyst in which 0.0001 to 5.0% by weight of a seed or two or more active metal elements are supported on the catalyst, and the supported amount is more preferably 0.01 to 3.0% by weight. The total content of active metal elements in the catalyst is preferably 0.1 to 4.0% by weight.
本発明５に係る触媒のＣＯ転化率は、後述する評価法において、７０％以上が好ましく、より好ましくは９０％以上である。 The CO conversion rate of the catalyst according to the present invention 5 is preferably 70% or more, more preferably 90% or more, in the evaluation method described later.
本発明１乃至５に係る触媒は、使用する各用途に合わせて成形しても良い。形状やサイズは特に限定しないが、例えば球状や円柱状、管状、ハニカム体への塗布などの形状でも良い。通常、球状や円柱状、管状の形状を持つ触媒体の場合のサイズは０．１〜３０ｍｍ程度が好適である。条件によっては有機物や無機物などの各種バインダーを添加することで成形体の強度や細孔分布密度を調整しても良い。 You may shape | mold the catalyst which concerns on this invention 1 thru | or 5 according to each use to be used. The shape and size are not particularly limited, but may be, for example, a spherical shape, a cylindrical shape, a tubular shape, or a shape applied to a honeycomb body. In general, the size of a catalyst body having a spherical, cylindrical, or tubular shape is preferably about 0.1 to 30 mm. Depending on conditions, the strength and pore distribution density of the molded body may be adjusted by adding various binders such as organic substances and inorganic substances.
本発明６に係る触媒体は、サポート材に本発明１乃至５に係るいずれかの触媒を付着・被覆したものである。 The catalyst body according to the present invention 6 is obtained by adhering / coating any of the catalysts according to the present invention 1 to 5 to a support material.
本発明におけるサポート材としては、鉄板、ＳＵＳ管、ムライト、アルミナ、シリカ、コージェライト等から成る成型体であり、好ましくはシリカ、アルミナ、コージェライト等である。 The support material in the present invention is a molded body made of iron plate, SUS tube, mullite, alumina, silica, cordierite or the like, preferably silica, alumina, cordierite or the like.
なお、本発明においては、前記サポート材の表面をケイ素、アルミニウム、ジルコニウム等の酸化物又は水酸化物などであらかじめ被覆してもよい。 In the present invention, the surface of the support material may be coated in advance with an oxide or hydroxide of silicon, aluminum, zirconium or the like.
サポート材と本発明に係る触媒の線膨張係数の相違は少ないほど理想であり、好ましくは±１％以下、より好ましくは±０．５％以下が良い。 The smaller the difference in the coefficient of linear expansion between the support material and the catalyst according to the present invention, the more ideal it is, and preferably ± 1% or less, more preferably ± 0.5% or less.
また、前記サポート材に本発明１乃至５の触媒を存在させることによって、高価なジルコニウムやセリウムの使用量を減らすことができ、より安価な触媒を作成できる。 In addition, by using the catalyst of the present invention 1 to 5 in the support material, the amount of expensive zirconium or cerium used can be reduced, and a cheaper catalyst can be produced.
本発明７に係る触媒体は、サポート材に本発明１乃至５に係るいずれかの触媒を被覆し、且つ、Ａｕ，Ａｇ，Ｃｕ，Ｐｔ，Ｆｅ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕの中から選ばれる１種または２種以上の活性金属元素を触媒に対し０．０００１〜５．０重量％担持したものである。より好ましくは、０．０１〜３重量％担持させた触媒である。なお、触媒体中の活性金属元素の全含有量は０．１〜４．０重量％が好ましい。 The catalyst body according to the present invention 7 covers the support material with any one of the catalysts according to the present invention 1 to 5, and Au, Ag, Cu, Pt, Fe, Pd, Ni, Ir, Rh, Co, Os. , One or more active metal elements selected from Ru are supported on the catalyst in an amount of 0.0001 to 5.0% by weight. More preferably, the catalyst is supported by 0.01 to 3% by weight. The total content of active metal elements in the catalyst body is preferably 0.1 to 4.0% by weight.
次に、本発明に係る触媒の製造法について述べる。 Next, a method for producing the catalyst according to the present invention will be described.
まず、本発明１乃至３に係る触媒は、アルカリ性溶液と、ジルコニウム、セリウム、鉄及び／又はイットリウムとを含む溶液とを混合、熟成した後、濾別、水洗、乾燥し、次いで、４００〜１３００℃の温度範囲で加熱して触媒とする製造方法において、Ａｕ，Ａｇ，Ｃｕ，Ｐｔ，Ｆｅ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕから選ばれる一種又は２種以上からなる活性金属元素の溶液をジルコニウムなどと同様に添加・混合する方法、又は、加熱後の酸化物固溶体に前記活性金属元素を担持する方法のいずれによっても得ることができる。 First, the catalyst according to the first to third aspects of the present invention is prepared by mixing and aging an alkaline solution and a solution containing zirconium, cerium, iron and / or yttrium, followed by filtration, washing and drying, and then 400 to 1300. In the manufacturing method to make a catalyst by heating in the temperature range of ° C., active metal consisting of one or more selected from Au, Ag, Cu, Pt, Fe, Pd, Ni, Ir, Rh, Co, Os, Ru It can be obtained by either a method of adding and mixing an elemental solution in the same manner as zirconium or the like, or a method of supporting the active metal element in an oxide solid solution after heating.
熟成時のｐＨは４〜１４が好ましく特に６〜１３が好ましい。 The pH during aging is preferably 4 to 14, and particularly preferably 6 to 13.
加熱温度は、５００〜８００℃がより好ましい。また、加熱雰囲気は、大気中が好ましい。 As for heating temperature, 500-800 degreeC is more preferable. The heating atmosphere is preferably in the air.
ジルコニウム、セリウム、鉄及び／又はイットリウムからなる酸化物固溶体は、ジルコニウム、セリウム、鉄及び／又はイットリウムを含む水溶液を同時に混合し熟成するので、ここで生成した沈澱粒子は、元素の組成が均一な粒子になり、各元素が高分散し、固溶体を形成しやすくなる。 Since the oxide solid solution composed of zirconium, cerium, iron and / or yttrium is simultaneously mixed and aged with an aqueous solution containing zirconium, cerium, iron and / or yttrium, the produced precipitated particles have a uniform elemental composition. It becomes particles and each element is highly dispersed, and a solid solution is easily formed.
本発明においては、活性金属元素の水溶液を、ジルコニウム、セリウム、鉄及び／又はイットリウムを含む水溶液と同時、又はジルコニウムなどの複合化合物がスラリー状態のときに添加するので、活性金属元素が高分散しやすくなり、活性金属元素が高分散することによって活性金属元素の表面積が増加し、触媒活性が向上する。 In the present invention, an active metal element aqueous solution is added simultaneously with an aqueous solution containing zirconium, cerium, iron and / or yttrium, or when a complex compound such as zirconium is in a slurry state, so that the active metal element is highly dispersed. The surface area of the active metal element increases due to high dispersion of the active metal element, and the catalytic activity is improved.
活性金属元素の種類によってはアルカリ性溶液と活性金属元素の溶液を混合しても活性金属元素が沈殿しにくい元素も存在するため、そのような元素は含浸法によって担持させることが好ましい。 Depending on the type of the active metal element, there is an element in which the active metal element is difficult to precipitate even when the alkaline solution and the active metal element solution are mixed. Therefore, it is preferable to support such an element by an impregnation method.
活性金属元素を含浸法によって担持させた場合でも、本発明においては、ジルコニウム及びセリウムとともに、鉄及び／又はイットリウムが固溶した酸化物であるので、高い触媒活性を有するものである。 Even when the active metal element is supported by the impregnation method, in the present invention, since it is an oxide in which iron and / or yttrium is dissolved together with zirconium and cerium, it has high catalytic activity.
本発明４に係る触媒は、前記製造方法で得られた触媒とアルミナなどの異種金属元素の酸化物とを混合して得ることができる。 The catalyst according to the present invention 4 can be obtained by mixing the catalyst obtained by the above production method and an oxide of a different metal element such as alumina.
前記混合は、乾式混合、湿式混合のいずれでもよい。 The mixing may be either dry mixing or wet mixing.
本発明５に係る触媒は、前記製造方法で得られた触媒とアルミナなどの異種金属元素の酸化物とを混合した後、含浸法などにより活性金属元素を担持させることができる。 The catalyst according to the fifth aspect of the present invention can support the active metal element by an impregnation method or the like after mixing the catalyst obtained by the above production method and an oxide of a different metal element such as alumina.
触媒は通常、触媒を成形した触媒体として使用されることが多く、その製造方法も多岐にわたる。一般的な触媒体の製法としては触媒粉体を型に詰めて加圧成型する方法、ケーキ状の触媒を押し出し機によって押し出しその後焼成する方法、若しくは触媒粉体をパンに入れ転動させて造粒する方法等が挙げられる。 Usually, the catalyst is often used as a catalyst body obtained by molding the catalyst, and its production methods are diverse. As a general method for producing a catalyst body, a method in which a catalyst powder is packed in a mold and press-molded, a method in which a cake-like catalyst is extruded by an extruder and then calcined, or a catalyst powder is placed in a pan and rolled. The method of granulating etc. is mentioned.
しかし、実際に触媒を使用する場合、触媒反応に用いられるガスは主に触媒体の表面付近で反応し、触媒体内部にまでは侵入しにくい。よって触媒体内部の触媒成分は触媒反応に十分に寄与することができなくなる。特に、触媒が高価な材料からなる場合、触媒体内部の触媒は無駄になることとなる。
そこで、本発明１０では、セラミックス又はメタル等のサポート材の表面に、前記本発明１〜５のいずれかの触媒を含むスラリーを、必要により、セラミックスを含むスラリーとともに塗布、焼成してコーティングさせることで、サポート材表面に触媒成分の相を形成させ、触媒成分を有効に活用することができる。
However, when a catalyst is actually used, the gas used for the catalytic reaction reacts mainly near the surface of the catalyst body and hardly penetrates into the catalyst body. Therefore, the catalyst component inside the catalyst body cannot sufficiently contribute to the catalytic reaction. In particular, when the catalyst is made of an expensive material, the catalyst inside the catalyst body is wasted.
Therefore, in the present invention 10, a slurry containing the catalyst according to any one of the present inventions 1 to 5 is coated on a surface of a support material such as ceramics or metal, if necessary, together with a slurry containing ceramics, and coated. Thus, a catalyst component phase is formed on the surface of the support material, and the catalyst component can be effectively utilized.
本発明においては、サポート材上にアルミナ等のセラミックスをコーティングさせた後に、前記本発明１〜５のいずれかの触媒をコーティングさせる、若しくは、前記本発明１〜５のいずれかの触媒をコーティングさせた後にセラミックスをごく薄くコーティングさせてもよく、さらに多層にコーティングさせてもよい。サポート材上にセラミックスをコーティングさせた後に前記本発明１〜５のいずれかの触媒をコーティングさせることで、サポート材上に触媒をより強固にコーティングさせることができる。 In the present invention, the support material is coated with a ceramic such as alumina, and then the catalyst according to any one of the present inventions 1 to 5 is coated, or the catalyst according to any one of the present inventions 1 to 5 is coated. After that, the ceramics may be coated very thinly, or may be further coated in multiple layers. The catalyst can be more firmly coated on the support material by coating the catalyst on any one of the present inventions 1 to 5 after coating the ceramic on the support material.
サポート材上に前記本発明１〜５の触媒をコーティングさせた後にごく薄くセラミックスをコーティングする場合は、触媒体同士又は容器などと接触したときの磨耗によって前記触媒が剥離するのを防ぐことができる。この場合、コーティングするセラミックスが多孔質でなければ触媒成分まで反応ガスが届かない。 When coating the ceramics of the present invention 1-5 on the support material very thinly, it is possible to prevent the catalyst from peeling off due to wear when contacting the catalyst bodies or containers. . In this case, the reaction gas does not reach the catalyst component unless the ceramic to be coated is porous.
前出特許文献４記載の方法でもコーティングできるが、金属水溶液に浸しているので触媒層を厚くすることが難しく、触媒層の紛化も起こり易い。担体元素と触媒原料との化学反応により別相の生成も起こり予想以上の活性劣化も起こる。また、触媒層にある程度の厚みがないと十分な触媒活性が得られない。しかし、本発明においてはスラリーを塗布するため、触媒層を容易に厚くでき、粉化も抑制できる。 Although the coating can be performed by the method described in Patent Document 4, it is difficult to increase the thickness of the catalyst layer because it is immersed in a metal aqueous solution, and the catalyst layer is easily pulverized. Due to the chemical reaction between the support element and the catalyst raw material, another phase is generated and the activity is deteriorated more than expected. Further, sufficient catalytic activity cannot be obtained unless the catalyst layer has a certain thickness. However, since the slurry is applied in the present invention, the catalyst layer can be easily thickened and powdering can be suppressed.
次に、本発明に係る触媒を用いた水性ガスシフト反応について述べる。 Next, the water gas shift reaction using the catalyst according to the present invention will be described.
本発明に係る触媒の存在下で、水及び一酸化炭素を５０℃〜８００℃の温度範囲で反応させることで、水素と二酸化炭素が得られる。触媒の存在割合は水と一酸化炭素を合わせたガス空間速度で１００／ｈ以上が好ましい。 Hydrogen and carbon dioxide are obtained by reacting water and carbon monoxide in the temperature range of 50 ° C. to 800 ° C. in the presence of the catalyst according to the present invention. The presence ratio of the catalyst is preferably 100 / h or more in terms of gas space velocity in which water and carbon monoxide are combined.
＜作用＞
本発明において、ジルコニウム、セリウム及び鉄及び／又はイットリウムを含む酸化物固溶体からなる担体に、Ａｕ，Ａｇ，Ｃｕ，Ｐｔ，Ｆｅ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕの中から選ばれる１種または２種以上の活性金属元素を存在させた触媒は、より高い活性を示す。
また、本発明においては、ジルコニアとセリアの固溶体に鉄及び／又はイットリウムを固溶させることによって、鉄又はイットリウムを固溶させずに添加したのみの触媒に対し、比表面積の増加又は触媒の酸素の貯蔵放出能が向上することによって、高い触媒活性が達成される。
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In the present invention, the support made of an oxide solid solution containing zirconium, cerium and iron and / or yttrium is selected from Au, Ag, Cu, Pt, Fe, Pd, Ni, Ir, Rh, Co, Os, and Ru. A catalyst in which one or more active metal elements are present exhibits higher activity.
Further, in the present invention, by dissolving iron and / or yttrium in a solid solution of zirconia and ceria, the specific surface area is increased or the oxygen of the catalyst is increased with respect to the catalyst which is added without dissolving iron or yttrium. High catalytic activity is achieved by improving the storage and release capacity of the catalyst.
ジルコニウムとセリウムが固溶体を形成することで、酸素の貯蔵放出能が向上し、効率よく水性ガスシフト反応が行えると推察される。 It is presumed that when zirconium and cerium form a solid solution, the ability to store and release oxygen is improved, and the water gas shift reaction can be performed efficiently.
なお、比表面積が増大すると担持した活性金属元素が高分散し、活性点が増加しやすくなり、活性が向上しやすくなることは一般的によく知られており、酸素の貯蔵放出能の向上は、酸素原子の移動によって達成されるとされる水性ガスシフト反応において、触媒活性の向上の要因になり得ると推察される。 In addition, it is generally well known that when the specific surface area is increased, the supported active metal element is highly dispersed, the active sites are easily increased, and the activity is easily improved. In the water gas shift reaction that is achieved by the movement of oxygen atoms, it is speculated that it can be a factor for improving the catalytic activity.
ジルコニアなどの固溶体に活性金属元素を担持させる方法として、活性金属元素の塩を含有する水溶液に乾燥させたジルコニアなどの複合体を浸し、蒸発乾固させる含浸法が一般的であり、本発明においても同様に活性金属元素を含浸法によって担持してもよい。 As a method for supporting an active metal element in a solid solution such as zirconia, an impregnation method in which a composite such as zirconia dried in an aqueous solution containing a salt of the active metal element is immersed and evaporated to dryness is common. Similarly, an active metal element may be supported by an impregnation method.
さらに、上記触媒にアルミナなどを添加することによって、アルミナなどが前記本発明１〜３の触媒の障壁となり、製造時やシフト反応時に本発明１〜３の触媒粒子の成長又は焼結を抑制することができる。 Furthermore, by adding alumina or the like to the catalyst, alumina or the like becomes a barrier to the catalyst of the first to third aspects of the invention, and suppresses the growth or sintering of the catalyst particles of the first to third aspects of the invention during the production or shift reaction. be able to.
また、前記特許文献４には、アルミナなどの成型体にセリウム水溶液を浸透させて触媒成型体を作成する方法も記載されているが、水溶液を浸透させるので、アルミナなどの成型体上の触媒層を厚くすることが難しく、粉化がおこりやすい。これに対し、安価なサポート材（シリカなどの成型体）の表面に前記本発明１〜５の触媒をコーティングすることによって、高価なジルコニウムやセリウムの使用量を減らすことができ、より安価な触媒を作成できる。さらに、触媒層を容易に厚くでき、粉化も起こりにくい触媒成型体を得ることができる。 Patent Document 4 also describes a method of making a catalyst molded body by infiltrating a cerium aqueous solution into a molded body such as alumina. However, since the aqueous solution is infiltrated, the catalyst layer on the molded body such as alumina is also described. It is difficult to thicken the powder and pulverization is likely to occur. On the other hand, by coating the catalyst of the present invention 1 to 5 on the surface of an inexpensive support material (molded product such as silica), the amount of expensive zirconium or cerium used can be reduced, and a cheaper catalyst. Can be created. Furthermore, a catalyst molded body can be obtained in which the catalyst layer can be easily thickened and hardly pulverized.
以下、実施例に基づき本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail based on examples.
触媒を構成する金属元素、ジルコニウム、セリウム、イットリウム、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、亜鉛、ランタン、ネオジウム、アルミニウム、鉄、Ａｕ，Ａｇ，Ｃｕ，Ｐｔ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕの含有量は、該触媒を酸で溶解し、「プラズマ発光分光分析装置 ＳＰＳ４０００（セイコー電子工業（株））」で測定して求めた。 Metal elements constituting the catalyst, zirconium, cerium, yttrium, magnesium, calcium, strontium, barium, titanium, zinc, lanthanum, neodymium, aluminum, iron, Au, Ag, Cu, Pt, Pd, Ni, Ir, Rh, Co , Os, Ru content was determined by dissolving the catalyst with an acid and measuring with a “plasma emission spectroscopic analyzer SPS4000 (Seiko Electronics Co., Ltd.)”.
ＢＥＴ比表面積値は、窒素によるＢＥＴ法により測定した。 The BET specific surface area value was measured by the BET method using nitrogen.
相の同定は、Ｘ線回折測定で行った。Ｘ線回折装置は「Ｘ線回折装置ＲＩＮＴ−２５００（理学電機（株）製）」（管球：Ｃｕ、管電圧：４０ｋＶ、管電流：３００ｍＡ、ゴニオメーター：広角ゴニオメーター、サンプリング幅：０．０２０°、走査速度：２°／ｍｉｎ、発散スリット：１°、散乱スリット：１°、受光スリット：０．５０ｍｍ）を使用した。 The phase was identified by X-ray diffraction measurement. The X-ray diffractometer is “X-ray diffractometer RINT-2500 (manufactured by Rigaku Corporation)” (tube: Cu, tube voltage: 40 kV, tube current: 300 mA, goniometer: wide angle goniometer, sampling width: 0. 020 °, scanning speed: 2 ° / min, divergence slit: 1 °, scattering slit: 1 °, light receiving slit: 0.50 mm).
実施例１
塩化セリウム水溶液、オキシ塩化ジルコニウム水溶液及び第二塩化鉄水溶液の混合水溶液に純水を加えて５００ｍｌとしてよく撹拌したものを溶液１−１とし、苛性ソーダを水に溶解し５００ｍｌとしたものを溶液１−２とする。溶液１−２を６０℃に加熱して攪拌しておき、そこに溶液１−１を投入し、８０℃で３時間熟成した。得られた沈殿物を濾過、洗浄し、６００℃で１時間焼成した。
これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。
酸化ジルコニウム、酸化セリウム、酸化鉄の重量比は７２．５：２５：１．０であった。白金の担持量は１．５ｗｔ％とした。
ＸＲＤ測定によって求めた触媒の格子定数のうちａ軸長は、３．６３９７Åであって後出する比較例１より増大しており、鉄化合物に起因するピークもみられないことから、鉄が固溶していることが確認された。
Example 1
A solution obtained by adding pure water to a mixed aqueous solution of a cerium chloride aqueous solution, a zirconium oxychloride aqueous solution and a ferric chloride aqueous solution to make 500 ml is a solution 1-1, and caustic soda is dissolved in water to make 500 ml. 2. The solution 1-2 was heated to 60 ° C. and stirred, and the solution 1-1 was added thereto and aged at 80 ° C. for 3 hours. The resulting precipitate was filtered, washed and baked at 600 ° C. for 1 hour.
A dinitrodiammine platinum nitric acid aqueous solution was used for this, and platinum was supported by an impregnation method. After baking at 400 ° C. for 1 hour, hydrogen reduction was performed at 200 ° C.
The weight ratio of zirconium oxide, cerium oxide, and iron oxide was 72.5: 25: 1.0. The supported amount of platinum was 1.5 wt%.
Among the lattice constants of the catalyst determined by XRD measurement, the a-axis length is 3.697Å, which is larger than that of Comparative Example 1 to be described later, and no peak due to the iron compound is observed. It was confirmed that
実施例２
実施例１と同様に合成し、酸化ジルコニウム、酸化セリウム、酸化鉄の重量比を７１：２５：２．５とした。白金の担持量は１．５ｗｔ％とした。
ＸＲＤ測定によって求めた触媒の格子定数のうちａ軸長は、３．６４２９７Åであって実施例１より増大しており、鉄化合物に起因するピークも見られないことから、鉄が固溶していることが確認された。
Example 2
Synthesis was performed in the same manner as in Example 1, and the weight ratio of zirconium oxide, cerium oxide, and iron oxide was 71: 25: 2.5. The supported amount of platinum was 1.5 wt%.
Of the lattice constants of the catalyst determined by XRD measurement, the a-axis length is 3.64297 mm, which is larger than that in Example 1 and no peak due to the iron compound is observed. It was confirmed that
実施例３
実施例１と同様に合成し、酸化ジルコニウム、酸化セリウム、酸化鉄の重量比を６９．５：２５：４．０とした。白金の担持量は１．５ｗｔ％とした。
ＸＲＤ測定によって求めた触媒の格子定数のうちａ軸長は、３．６５２４１Åであって実施例２より増大しており、鉄化合物に起因するピークも見られないことから、鉄が固溶していることが分かる。
Example 3
The synthesis was performed in the same manner as in Example 1, and the weight ratio of zirconium oxide, cerium oxide, and iron oxide was 69.5: 25: 4.0. The supported amount of platinum was 1.5 wt%.
Of the lattice constants of the catalyst determined by XRD measurement, the a-axis length is 3.65241 mm, which is larger than that of Example 2, and no peak due to the iron compound is observed. I understand that.
実施例４
実施例１と同様に合成し、酸化ジルコニウム、酸化セリウム、酸化鉄の重量比を４８．５：４７．５：２．５とした。白金の担持量は１．５ｗｔ％とした。
Example 4
Synthesis was performed in the same manner as in Example 1, and the weight ratio of zirconium oxide, cerium oxide, and iron oxide was 48.5: 47.5: 2.5. The supported amount of platinum was 1.5 wt%.
実施例５
第二塩化鉄の代わりに硝酸イットリウムを用いて、実施例１と同様に合成した。酸化ジルコニウム、酸化セリウム、酸化イットリウムの重量比を７１．５：２５：２．０とした。白金の担持量は１．５ｗｔ％とした。
ＸＲＤ測定によって求めた触媒の格子定数のうちａ軸長は、３．６４２９９Åであって比較例１より増大しており、イットリウム化合物に起因するピークも見られないことから、イットリウムが固溶していることが確認された。
Example 5
Synthesis was performed in the same manner as in Example 1 except that yttrium nitrate was used instead of ferric chloride. The weight ratio of zirconium oxide, cerium oxide, and yttrium oxide was 71.5: 25: 2.0. The supported amount of platinum was 1.5 wt%.
Of the lattice constants of the catalyst determined by XRD measurement, the a-axis length is 3.64299 mm, which is larger than that of Comparative Example 1, and no peak due to the yttrium compound is observed. It was confirmed that
実施例６
第二塩化鉄の代わりに硝酸イットリウムを用いて、実施例１と同様に合成した。酸化ジルコニウム、酸化セリウム、酸化イットリウムの重量比を６８．５：２５：５．０とした。白金の担持量は１．５ｗｔ％とした。
ＸＲＤ測定によって求めた触媒の格子定数のうちａ軸長は、３．６４９９９Åであって実施例５より増大しており、イットリウム化合物に起因するピークも見られないことから、イットリウムが固溶していることが確認された。
Example 6
Synthesis was performed in the same manner as in Example 1 except that yttrium nitrate was used instead of ferric chloride. The weight ratio of zirconium oxide, cerium oxide, and yttrium oxide was 68.5: 25: 5.0. The supported amount of platinum was 1.5 wt%.
Of the lattice constants of the catalyst determined by XRD measurement, the a-axis length is 3.64999 mm, which is larger than that of Example 5, and no peak due to the yttrium compound is observed. It was confirmed that
実施例７
第二塩化鉄の代わりに硝酸イットリウムを用いて、実施例１と同様に合成した。酸化ジルコニウム、酸化セリウム、酸化イットリウムの重量比を６５．５：２５：８とした。白金の担持量は１．５ｗｔ％とした。
ＸＲＤ測定によって求めた触媒の格子定数のうちａ軸長は、３．６５５９８Åであり、実施例５より増大していることから、イットリウムが固溶していることが分かる。
Example 7
Synthesis was performed in the same manner as in Example 1 except that yttrium nitrate was used instead of ferric chloride. The weight ratio of zirconium oxide, cerium oxide, and yttrium oxide was 65.5: 25: 8. The supported amount of platinum was 1.5 wt%.
Of the lattice constants of the catalyst determined by XRD measurement, the a-axis length is 3.65598 mm, which is larger than Example 5, indicating that yttrium is in solid solution.
実施例８
第二塩化鉄の代わりに硝酸イットリウムを用いて、実施例１と同様に合成した。酸化ジルコニウム、酸化セリウム、酸化イットリウムの重量比を４８．５：４５：５．０とした。白金の担持量は１．５ｗｔ％とした。
Example 8
Synthesis was performed in the same manner as in Example 1 except that yttrium nitrate was used instead of ferric chloride. The weight ratio of zirconium oxide, cerium oxide, and yttrium oxide was 48.5: 45: 5.0. The supported amount of platinum was 1.5 wt%.
実施例９
実施例１と同様に合成し、酸化ジルコニウム、酸化セリウム、酸化鉄の重量比を７１．５：２５：２．５とした。白金の担持量は１．０ｗｔ％とした。
Example 9
Synthesis was performed in the same manner as in Example 1, and the weight ratio of zirconium oxide, cerium oxide, and iron oxide was 71.5: 25: 2.5. The supported amount of platinum was 1.0 wt%.
実施例１０
実施例１と同様に合成し、酸化ジルコニウム、酸化セリウム、酸化鉄の重量比を７１：２５：２．５とした。白金の代わりにルテニウムを担持し、ルテニウムの担持量は１．５ｗｔ％とした。
Example 10
Synthesis was performed in the same manner as in Example 1, and the weight ratio of zirconium oxide, cerium oxide, and iron oxide was 71: 25: 2.5. Ruthenium was supported instead of platinum, and the amount of ruthenium supported was 1.5 wt%.
実施例１１
実施例１と同様に合成し、酸化ジルコニウム、酸化セリウム、酸化鉄の重量比を７１：２５：２．５とした。白金の代わりにロジウムを担持し、ロジウムの担持量は１．５ｗｔ％とした。
Example 11
Synthesis was performed in the same manner as in Example 1, and the weight ratio of zirconium oxide, cerium oxide, and iron oxide was 71: 25: 2.5. Rhodium was supported instead of platinum, and the supported amount of rhodium was 1.5 wt%.
実施例１２
実施例１と同様に合成し、酸化ジルコニウム、酸化セリウム、酸化鉄の重量比を７１：２５：２．５とした。白金の代わりにパラジウムを担持し、パラジウムの担持量は１．５ｗｔ％とした。
Example 12
Synthesis was performed in the same manner as in Example 1, and the weight ratio of zirconium oxide, cerium oxide, and iron oxide was 71: 25: 2.5. Palladium was supported instead of platinum, and the supported amount of palladium was 1.5 wt%.
実施例１３
第二塩化鉄の代わりに硝酸イットリウムを用い、実施例１と同様に合成した。酸化ジルコニウム、酸化セリウム、酸化イットリウムの重量比を６９：２５：５．０とした。白金の担持量は１．０ｗｔ％とした。
Example 13
Synthesis was performed in the same manner as in Example 1 except that yttrium nitrate was used instead of ferric chloride. The weight ratio of zirconium oxide, cerium oxide, and yttrium oxide was 69: 25: 5.0. The supported amount of platinum was 1.0 wt%.
実施例１４
第二塩化鉄の代わりに硝酸イットリウムを用い、実施例１と同様に合成した。酸化ジルコニウム、酸化セリウム、酸化イットリウムの重量比を６８．５：２５：５．０とした。白金の代わりにルテニウムを担持し、ルテニウムの担持量は１．５ｗｔ％とした。
Example 14
Synthesis was performed in the same manner as in Example 1 except that yttrium nitrate was used instead of ferric chloride. The weight ratio of zirconium oxide, cerium oxide, and yttrium oxide was 68.5: 25: 5.0. Ruthenium was supported instead of platinum, and the amount of ruthenium supported was 1.5 wt%.
実施例１５
第二塩化鉄の代わりに硝酸イットリウムを用い、実施例１と同様に合成した。酸化ジルコニウム、酸化セリウム、酸化イットリウムの重量比を６８．５：２５：５．０とした。白金の代わりにロジウムを担持し、ロジウムの担持量は１．５ｗｔ％とした。
Example 15
Synthesis was performed in the same manner as in Example 1 except that yttrium nitrate was used instead of ferric chloride. The weight ratio of zirconium oxide, cerium oxide, and yttrium oxide was 68.5: 25: 5.0. Rhodium was supported instead of platinum, and the supported amount of rhodium was 1.5 wt%.
実施例１６
第二塩化鉄の代わりに硝酸イットリウムを用い、実施例１と同様に合成した。酸化ジルコニウム、酸化セリウム、酸化イットリウムの重量比を６８．５：２５：５．０とした。白金の代わりにパラジウムを担持し、パラジウムの担持量は１．５ｗｔ％とした。
Example 16
Synthesis was performed in the same manner as in Example 1 except that yttrium nitrate was used instead of ferric chloride. The weight ratio of zirconium oxide, cerium oxide, and yttrium oxide was 68.5: 25: 5.0. Palladium was supported instead of platinum, and the supported amount of palladium was 1.5 wt%.
実施例１７
第二塩化鉄及び硝酸イットリウムを用い、実施例１と同様に合成した。酸化ジルコニウム、酸化セリウム、酸化イットリウム及び酸化鉄の重量比を６６：２５：５．０：２．５とした。白金の担持量は１．５ｗｔ％とした。
Example 17
Synthesis was performed in the same manner as in Example 1 using ferric chloride and yttrium nitrate. The weight ratio of zirconium oxide, cerium oxide, yttrium oxide and iron oxide was 66: 25: 5.0: 2.5. The supported amount of platinum was 1.5 wt%.
実施例１８
塩化セリウム水溶液、オキシ塩化ジルコニウム水溶液、硝酸イットリウム及び硝酸ロジウム水溶液の混合水溶液に純水を加えて５００ｍｌとしてよく撹拌したものを溶液１８−１とし、苛性ソーダを水に溶解し５００ｍｌとしたものを溶液１８−２とする。溶液１８−２を６０℃に加熱して攪拌しておき、そこに溶液１８−１を投入し、８０℃で３時間熟成した。得られた沈殿物を濾過、洗浄し、６００℃で１時間焼成した後、２００℃で水素還元を行った。
酸化ジルコニウム、酸化セリウム、酸化イットリウムの重量比を６８．５：２５：５．０とした。ロジウムの担持量は１．５ｗｔ％とした。
Example 18
A solution obtained by adding pure water to a mixed aqueous solution of a cerium chloride aqueous solution, a zirconium oxychloride aqueous solution, a yttrium nitrate and a rhodium nitrate aqueous solution to make 500 ml is made solution 18-1, and caustic soda is dissolved in water to make 500 ml. -2. The solution 18-2 was heated to 60 ° C. and stirred, and the solution 18-1 was added thereto and aged at 80 ° C. for 3 hours. The obtained precipitate was filtered, washed, calcined at 600 ° C. for 1 hour, and then subjected to hydrogen reduction at 200 ° C.
The weight ratio of zirconium oxide, cerium oxide, and yttrium oxide was 68.5: 25: 5.0. The supported amount of rhodium was 1.5 wt%.
比較例１
鉄を添加することなく、酸化ジルコニウム、酸化セリウムの重量比を５１：４７．５とした以外は、実施例１と同様に合成した。白金の担持量は１．５ｗｔ％とした。ＸＲＤ測定によって求めた触媒の格子定数のうちａ軸長は、３．６３７７Åであった。
Comparative Example 1
The synthesis was performed in the same manner as in Example 1 except that the weight ratio of zirconium oxide and cerium oxide was 51: 47.5 without adding iron. The supported amount of platinum was 1.5 wt%. Of the lattice constants of the catalyst determined by XRD measurement, the a-axis length was 3.6377 mm.
比較例２
塩化セリウム水溶液及びオキシ塩化ジルコニウム水溶液の混合水溶液に純水を加えて５００ｍｌとしてよく撹拌したものを溶液２−１とし、苛性ソーダを水に溶解し５００ｍｌとしたものを溶液２−２とする。溶液２−２を６０℃に加熱して攪拌しておき、それに溶液２−１を投入し、８０℃で３時間熟成した。得られた沈殿物を濾過、洗浄し、６００℃で１時間焼成した。これを担体２−１とする。
これとは別に、第二塩化鉄水溶液に純水を加えて５００ｍｌとしてよく撹拌したものを溶液２−３とし、苛性ソーダを水に溶解し５００ｍｌとしたものを溶液２−４とする。溶液２−４を６０℃に加熱して攪拌しておき、それに溶液２−３を投入し、８０℃で３時間熟成した。得られた沈殿物を濾過、洗浄し、６００℃で１時間焼成した。これを担体２−２とする。
前記担体２−１及び前記担体２−２をよく混合し、これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。
酸化ジルコニウム、酸化セリウム、酸化鉄の重量比は７１：２５：２．５であった。白金の担持量は１．５ｗｔ％とした。
ＸＲＤ測定によって求めた触媒の格子定数のうちａ軸長は、３．６３７９Åであり、比較例１とほぼ同じであり鉄が固溶していないことが分かる。
Comparative Example 2
Pure water is added to a mixed aqueous solution of a cerium chloride aqueous solution and a zirconium oxychloride aqueous solution to make 500 ml, and the mixture is thoroughly stirred to make a solution 2-1, and caustic soda dissolved in water to make 500 ml is made a solution 2-2. The solution 2-2 was heated to 60 ° C. and stirred, and the solution 2-1 was added thereto and aged at 80 ° C. for 3 hours. The resulting precipitate was filtered, washed and baked at 600 ° C. for 1 hour. This is designated as Carrier 2-1.
Separately, pure water is added to the ferric chloride aqueous solution to make 500 ml, and the mixture is thoroughly stirred to make solution 2-3, and caustic soda dissolved in water to make 500 ml is made solution 2-4. The solution 2-4 was heated to 60 ° C. and stirred, and the solution 2-3 was added thereto, followed by aging at 80 ° C. for 3 hours. The resulting precipitate was filtered, washed and baked at 600 ° C. for 1 hour. This is designated as Carrier 2-2.
The carrier 2-1 and the carrier 2-2 are mixed well, and platinum is supported thereon by an impregnation method using a dinitrodiammine platinum nitric acid aqueous solution. After baking at 400 ° C. for 1 hour, hydrogen reduction is performed at 200 ° C. went.
The weight ratio of zirconium oxide, cerium oxide, and iron oxide was 71: 25: 2.5. The supported amount of platinum was 1.5 wt%.
Of the lattice constants of the catalyst determined by XRD measurement, the a-axis length is 3.6379 mm, which is almost the same as Comparative Example 1 and it can be seen that iron is not dissolved.
比較例３
塩化セリウム水溶液及びオキシ塩化ジルコニウム水溶液の混合溶液に純水を加えて５００ｍｌとしてよく撹拌したものを溶液３−１とし、苛性ソーダを水に溶解し５００ｍｌとしたものを溶液３−２とする。溶液３−２を６０℃に加熱して攪拌しておき、それに溶液３−１を投入し、８０℃で３時間熟成した。得られた沈殿物を濾過、洗浄し、６００℃で１時間焼成した。これを担体３−１とする。
これとは別に、硝酸イットリウム水溶液に純水を加えて５００ｍｌとしてよく撹拌したものを溶液３−３とし、苛性ソーダを水に溶解し５００ｍｌとしたものを溶液３−４とする。溶液３−４を６０℃に加熱して攪拌しておき、そこに溶液３−３を投入し、８０℃で３時間熟成した。得られた沈殿物を濾過、洗浄し、６００℃で１時間焼成した。これを担体３−２とする。
前記担体３−１及び前記担体３−２をよく混合し、これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。
酸化ジルコニウム、酸化セリウム、酸化イットリウムの重量比を６８．５：２５：５．０とした。白金の担持量は１．５ｗｔ％とした。
ＸＲＤ測定によって求めた触媒の格子定数のうちａ軸長は、３．６３７６Åであり、比較例１とほぼ同じであるので鉄が固溶していないことが分かる。
Comparative Example 3
Pure water is added to a mixed solution of a cerium chloride aqueous solution and a zirconium oxychloride aqueous solution to make 500 ml, and the mixture is thoroughly stirred to make solution 3-1, and caustic soda dissolved in water to make 500 ml is made solution 3-2. The solution 3-2 was heated to 60 ° C. and stirred, and the solution 3-1 was added thereto and aged at 80 ° C. for 3 hours. The resulting precipitate was filtered, washed and baked at 600 ° C. for 1 hour. This is designated as Carrier 3-1.
Separately, pure water was added to an aqueous yttrium nitrate solution to make 500 ml, and the mixture was thoroughly stirred to make solution 3-3. Solution obtained by dissolving caustic soda in water to make 500 ml was made solution 3-4. The solution 3-4 was heated to 60 ° C. and stirred, and the solution 3-3 was added thereto and aged at 80 ° C. for 3 hours. The resulting precipitate was filtered, washed and baked at 600 ° C. for 1 hour. This is designated as Carrier 3-2.
The carrier 3-1 and the carrier 3-2 are mixed well, and a dinitrodiammine platinum nitric acid aqueous solution is used to support platinum by an impregnation method. After baking at 400 ° C. for 1 hour, hydrogen reduction is performed at 200 ° C. went.
The weight ratio of zirconium oxide, cerium oxide, and yttrium oxide was 68.5: 25: 5.0. The supported amount of platinum was 1.5 wt%.
Of the lattice constants of the catalyst determined by XRD measurement, the a-axis length is 3.6376 mm, which is almost the same as in Comparative Example 1, and thus it can be seen that iron is not dissolved.
比較例４
γ−アルミナにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。白金の担持量は１．５ｗｔ％とした。
Comparative Example 4
Using an aqueous solution of dinitrodiammine platinum nitrate on γ-alumina, platinum was supported by an impregnation method, calcined at 400 ° C. for 1 hour, and then subjected to hydrogen reduction at 200 ° C. The supported amount of platinum was 1.5 wt%.
比較例５
オキシ塩化ジルコニウム水溶液に純水を加えて５００ｍｌとしてよく撹拌したものを溶液４−１とし、苛性ソーダを水に溶解し５００ｍｌとしたものを溶液４−２とする。溶液４−２を６０℃に加熱して攪拌しておき、そこに溶液４−１を投入し、８０℃で３時間熟成した。得られた沈殿物を濾過、洗浄し、６００℃で１時間焼成した。これに酸化ジルコニウムにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。白金の担持量は１．５ｗｔ％とした。
Comparative Example 5
A solution obtained by adding pure water to a zirconium oxychloride aqueous solution to 500 ml and stirring well is designated as Solution 4-1, and a solution obtained by dissolving caustic soda in water to obtain 500 ml is designated as Solution 4-2. The solution 4-2 was heated to 60 ° C. and stirred, and the solution 4-1 was added thereto and aged at 80 ° C. for 3 hours. The resulting precipitate was filtered, washed and baked at 600 ° C. for 1 hour. To this, platinum was supported by zirconium impregnation using an aqueous solution of dinitrodiammine platinum nitrate, calcined at 400 ° C. for 1 hour, and then subjected to hydrogen reduction at 200 ° C. The supported amount of platinum was 1.5 wt%.
比較例６
塩化セリウム水溶液に純水を加えて５００ｍｌとしてよく撹拌したものを溶液５−１とし、苛性ソーダを水に溶解し５００ｍｌとしたものを溶液５−２とする。溶液５−２を６０℃に加熱して攪拌しておき、そこに溶液５−１を投入し、８０℃で３時間熟成した。得られた沈殿物を濾過、洗浄し、６００℃で１時間焼成した。これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。白金の担持量は１．５ｗｔ％とした。
Comparative Example 6
A solution obtained by adding pure water to a cerium chloride aqueous solution to 500 ml and stirring well is designated as Solution 5-1, and a solution obtained by dissolving caustic soda in water to obtain 500 ml is designated as Solution 5-2. The solution 5-2 was heated to 60 ° C. and stirred, and the solution 5-1 was added thereto and aged at 80 ° C. for 3 hours. The resulting precipitate was filtered, washed and baked at 600 ° C. for 1 hour. A dinitrodiammine platinum nitric acid aqueous solution was used for this, and platinum was supported by an impregnation method. After baking at 400 ° C. for 1 hour, hydrogen reduction was performed at 200 ° C. The supported amount of platinum was 1.5 wt%.
実施例１９
白金の担持量を１．４ｗｔ％とした以外は、実施例２と同様な方法で製造した触媒と酸化ケイ素とを重量比が５０：５０となるようによく混合した。これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。白金の総担持量は１．５ｗｔ％とした。
Example 19
Except that the amount of platinum supported was 1.4 wt%, the catalyst produced by the same method as in Example 2 and silicon oxide were mixed well so that the weight ratio was 50:50. A dinitrodiammine platinum nitric acid aqueous solution was used for this, and platinum was supported by an impregnation method. After baking at 400 ° C. for 1 hour, hydrogen reduction was performed at 200 ° C. The total supported amount of platinum was 1.5 wt%.
実施例２０
白金の担持量を１．４ｗｔ％とした以外は、実施例２と同様な方法で製造した触媒と酸化チタンとを重量比が５０：５０となるようによく混合した。これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。白金の総担持量は１．５ｗｔ％とした。
Example 20
Except that the amount of platinum supported was 1.4 wt%, the catalyst produced by the same method as in Example 2 and titanium oxide were mixed well so that the weight ratio was 50:50. A dinitrodiammine platinum nitric acid aqueous solution was used for this, and platinum was supported by an impregnation method. After baking at 400 ° C. for 1 hour, hydrogen reduction was performed at 200 ° C. The total supported amount of platinum was 1.5 wt%.
実施例２１
白金の担持量を１．４ｗｔ％とした以外は、実施例２と同様な方法で製造した触媒とγ‐アルミナとを重量比が５０：５０となるようによく混合した。これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。白金の総担持量は１．５ｗｔ％とした。
Example 21
Except that the supported amount of platinum was 1.4 wt%, the catalyst produced by the same method as in Example 2 and γ-alumina were mixed well so that the weight ratio was 50:50. A dinitrodiammine platinum nitric acid aqueous solution was used for this, and platinum was supported by an impregnation method. After baking at 400 ° C. for 1 hour, hydrogen reduction was performed at 200 ° C. The total supported amount of platinum was 1.5 wt%.
実施例２２
白金の担持量を１．４ｗｔ％とした以外は、実施例２と同様な方法で製造した触媒とγ‐アルミナとを重量比が７５：２５となるようによく混合した。これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。白金の総担持量は１．５ｗｔ％とした。
Example 22
Except that the supported amount of platinum was 1.4 wt%, the catalyst produced by the same method as in Example 2 and γ-alumina were mixed well so that the weight ratio was 75:25. A dinitrodiammine platinum nitric acid aqueous solution was used for this, and platinum was supported by an impregnation method. After baking at 400 ° C. for 1 hour, hydrogen reduction was performed at 200 ° C. The total supported amount of platinum was 1.5 wt%.
実施例２３
白金の担持量を１．４ｗｔ％とした以外は、実施例２と同様な方法で製造した触媒とγ‐アルミナとを重量比が２５：７５となるようによく混合した。これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。白金の総担持量は１．５ｗｔ％とした。
Example 23
Except that the supported amount of platinum was 1.4 wt%, the catalyst produced by the same method as in Example 2 and γ-alumina were mixed well so that the weight ratio was 25:75. A dinitrodiammine platinum nitric acid aqueous solution was used for this, and platinum was supported by an impregnation method. After baking at 400 ° C. for 1 hour, hydrogen reduction was performed at 200 ° C. The total supported amount of platinum was 1.5 wt%.
実施例２４
実施例２と同様な方法で製造した触媒と酸化ケイ素とを重量比が５０：５０となるようによく混合した。これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。白金の総担持量は１．５ｗｔ％とした。
Example 24
The catalyst produced in the same manner as in Example 2 and silicon oxide were mixed well so that the weight ratio was 50:50. A dinitrodiammine platinum nitric acid aqueous solution was used for this, and platinum was supported by an impregnation method. After baking at 400 ° C. for 1 hour, hydrogen reduction was performed at 200 ° C. The total supported amount of platinum was 1.5 wt%.
比較例７
白金の担持量を１．４ｗｔ％とした以外は、比較例１と同様な方法で製造した触媒とγ‐アルミナとを重量比５：９５となるように、よく混合した。これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。白金の総担持量は１．５ｗｔ％とした。
Comparative Example 7
Except that the supported amount of platinum was 1.4 wt%, the catalyst produced by the same method as in Comparative Example 1 and γ-alumina were mixed well so that the weight ratio was 5:95. A dinitrodiammine platinum nitric acid aqueous solution was used for this, and platinum was supported by an impregnation method. After baking at 400 ° C. for 1 hour, hydrogen reduction was performed at 200 ° C. The total supported amount of platinum was 1.5 wt%.
これらの触媒を、１から２ｍｍに整粒した。この触媒の触媒層を電気炉で加熱し、所定の温度でＣＯが３３体積％、水蒸気が６７体積％のガスを空間速度（ＧＨＳＶ）２００００および１０００００ｈ−１で流通させた。このときの出口ガス組成をガスクロマトグラフで測定した。
各触媒について、酸化ジルコニウム、酸化セリウム、酸化鉄及び酸化イットリウムの重量比、比表面積、担持金属の種類、担持量、２００℃においてのＣＯ転化率を表１に示した。
また、本発明３の、本発明１又は２の触媒にアルミニウム、ジルコニウム、珪素、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、亜鉛、ランタン及びネオジウムの中から選ばれる１種または２種以上の元素からなる酸化物を前記触媒に対して、０．００１〜９０重量％添加し、Ａｕ，Ａｇ，Ｃｕ，Ｐｔ，Ｆｅ，Ｐｄ，Ｎｉ，Ｉｒ，Ｒｈ，Ｃｏ，Ｏｓ，Ｒｕの中から選ばれる１種または２種以上の金属元素を０．０００１〜５．０重量％担持させた触媒のＣＯ転化率を表２に示した。
These catalysts were sized to 1 to 2 mm. The catalyst layer of this catalyst was heated in an electric furnace, and a gas having a volume of CO of 33% by volume and water vapor of 67% by volume was passed at a predetermined temperature at a space velocity (GHSV) of 20000 and 100,000 h −1 . The outlet gas composition at this time was measured with a gas chromatograph.
Table 1 shows the weight ratio of zirconium oxide, cerium oxide, iron oxide and yttrium oxide, the specific surface area, the type of supported metal, the supported amount, and the CO conversion at 200 ° C. for each catalyst.
In addition, the catalyst of the present invention 3 of the present invention 1 or 2 is made of one or more elements selected from aluminum, zirconium, silicon, magnesium, calcium, strontium, barium, titanium, zinc, lanthanum and neodymium. One type selected from Au, Ag, Cu, Pt, Fe, Pd, Ni, Ir, Rh, Co, Os, and Ru with respect to the catalyst. Alternatively, Table 2 shows the CO conversion of the catalyst in which 0.0001 to 5.0% by weight of two or more metal elements are supported.
なお、ＣＯ転化率が１００％にならないのは、反応平衡に依存するからである。 The reason why the CO conversion rate does not reach 100% is that it depends on the reaction equilibrium.
表１に示すとおり、本発明に係る触媒はいずれも反応温度が２００℃であっても、高いＣＯ転化率を有するものであることが確認された。従って、より高い反応温度でも高いＣＯ転化率を有するものである。 As shown in Table 1, it was confirmed that all the catalysts according to the present invention have a high CO conversion rate even when the reaction temperature is 200 ° C. Therefore, it has a high CO conversion even at a higher reaction temperature.
本発明の触媒と構成元素の重量比が同じであっても、ジルコニウム、セリウム及び鉄若しくはイットリウムを含む固溶体となっていなければ高い活性を示さない。 Even if the weight ratio of the catalyst of the present invention and the constituent elements is the same, high activity is not exhibited unless the solid solution contains zirconium, cerium and iron or yttrium.
表２より、本発明の触媒とアルミナ等を混合した触媒は、高い活性を示す。 From Table 2, a catalyst obtained by mixing the catalyst of the present invention with alumina or the like exhibits high activity.
実施例２５
実施例１９の触媒を、水ガラス及びＰＶＡと共にカイコウして２０％スラリーとした。アルミナの成型体をこのスラリーに浸し、触媒成分を担持後、成型体をスラリーから引き上げ、余分なスラリーを吹き飛ばし、乾燥させ、４００℃にて焼成を行った。これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。
Example 25
The catalyst of Example 19 was silkwormed with water glass and PVA to give a 20% slurry. The alumina molded body was immersed in this slurry, and after supporting the catalyst component, the molded body was pulled up from the slurry, excess slurry was blown off, dried, and fired at 400 ° C. A dinitrodiammine platinum nitric acid aqueous solution was used for this, and platinum was supported by an impregnation method. After baking at 400 ° C. for 1 hour, hydrogen reduction was performed at 200 ° C.
実施例２６
実施例１９の触媒を、シリカ及びＰＶＡと共にニーダー混練しながら水を加え、押し出し成型機を用いてケーキ状のものを押し出し、適度な大きさに切り、形を整え、乾燥させ、１０００℃にて焼成を行った。これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。
Example 26
Add water while kneader kneading the catalyst of Example 19 together with silica and PVA, extrude a cake-like one using an extrusion molding machine, cut into an appropriate size, shape and dry, at 1000 ° C. Firing was performed. A dinitrodiammine platinum nitric acid aqueous solution was used for this, and platinum was supported by an impregnation method. After baking at 400 ° C. for 1 hour, hydrogen reduction was performed at 200 ° C.
比較例８
アルミナの成型体を硝酸セリウム水溶液に浸し、セリウムを担持後、成型体を硝酸セリウム水溶液から引き上げ、乾燥させ、４００℃にて焼成を行った。これにジニトロジアンミン白金硝酸水溶液を用いて、含浸法により白金を担持し、４００℃で１時間焼成した後、２００℃で水素還元を行った。
Comparative Example 8
The molded body of alumina was immersed in an aqueous cerium nitrate solution, and after supporting cerium, the molded body was pulled up from the aqueous cerium nitrate solution, dried, and fired at 400 ° C. A dinitrodiammine platinum nitric acid aqueous solution was used for this, and platinum was supported by an impregnation method. After baking at 400 ° C. for 1 hour, hydrogen reduction was performed at 200 ° C.
比較例８では、水溶液を浸透させるので、アルミナ成型体上の触媒層を厚くすることが難しく、粉化がおこりやすい。これに対し、実施例２５ではアルミナ成型体の表面に触媒スラリーを塗布することで、触媒層を容易に厚くでき、粉化も起こりにくい触媒成型体を得ることができる。 In Comparative Example 8, since the aqueous solution is infiltrated, it is difficult to increase the thickness of the catalyst layer on the alumina molded body, and pulverization is likely to occur. On the other hand, in Example 25, by applying the catalyst slurry to the surface of the alumina molded body, the catalyst layer can be easily thickened and a catalyst molded body that is less likely to be pulverized can be obtained.
一般的な触媒の成型方法である粉体に圧力をかけて成型する方法に比べ、実施例２６では前者ほどの高価な装置や金型を必要とせず、比較的安価な装置で済み、焼結させることで、粉化が起こりにくい触媒を得ることができる。 Compared to the method of forming pressure by applying pressure to the powder, which is a general method of forming a catalyst, Example 26 does not require an expensive device or mold as the former, and a relatively inexpensive device can be used. By making it, the catalyst which does not occur powdering easily can be obtained.
本発明に係る触媒は、ジルコニウム、セリウム、鉄及び／又はイットリウムを含む酸化物の固溶体に活性金属元素を存在させ、必要よりそれにアルミナ等を混合した触媒は、従来の触媒と比べ水性ガスシフト反応をより効率よく行え優れた効果を奏する。また、本発明の触媒成型体の作成方法を用いることでより、実用的な触媒成型体を得ることができる。
In the catalyst according to the present invention, a catalyst in which an active metal element is present in an oxide solid solution containing zirconium, cerium, iron and / or yttrium, and alumina or the like is mixed as necessary, has a water gas shift reaction compared to a conventional catalyst. It is more efficient and has excellent effects. Moreover, a practical catalyst molded body can be obtained by using the method for producing a molded catalyst body of the present invention.
Claims (10)
The oxide solid solution consisting of iron and / or yttrium with zirconium and cerium, Au, Ag, Cu, Pt , P d, Ni, Ir, Rh, Co, Os, 1 or more kinds of selected from among Ru a catalyst for the water gas shift reaction to the presence of active metal element, the zirconium content of the catalyst is Ri 30-90 wt% der in ZrO2 terms, BET specific surface area of the catalyst is at 30 to 200 m 2 / g Catalyst for water gas shift reaction characterized in that
Mixing and aging an alkaline solution and a solution containing iron and / or yttrium, zirconium, cerium, and an active metal element, filtering, washing with water , and firing at a temperature range of 500 to 800 ° C. The method for producing a catalyst for water gas shift reaction according to claim 1, wherein
Mixing and aging an alkaline solution and a solution containing zirconium, cerium, iron and / or yttrium, the particles obtained by aging are filtered, washed with water, loaded with an active metal element, and fired at a temperature range of 500 to 800 ° C. The method for producing a catalyst for water gas shift reaction according to claim 1, wherein:
6. The catalyst according to any one of claims 1 to 5, further comprising an active metal element supported thereon after applying a slurry containing ceramics on the surface of the support material and firing the slurry. Or 7. A process for producing a catalyst body for water gas shift reaction according to 7.
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| EP2608882A4 (en) * | 2010-08-26 | 2014-11-12 | Basf Se | Highly active water gas shift catalyst, preparation process and use thereof |
| US20130288891A1 (en) | 2011-01-14 | 2013-10-31 | Santoku Corporation | Catalysts and process for producing same |
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