JP2008238063A - Catalyst and method for treating organic acid-containing exhaust gas - Google Patents
Catalyst and method for treating organic acid-containing exhaust gas Download PDFInfo
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- JP2008238063A JP2008238063A JP2007082949A JP2007082949A JP2008238063A JP 2008238063 A JP2008238063 A JP 2008238063A JP 2007082949 A JP2007082949 A JP 2007082949A JP 2007082949 A JP2007082949 A JP 2007082949A JP 2008238063 A JP2008238063 A JP 2008238063A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- 150000007524 organic acids Chemical class 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 28
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 34
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 6
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000002131 composite material Substances 0.000 claims description 79
- 229910052684 Cerium Inorganic materials 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 abstract description 24
- 229910052763 palladium Inorganic materials 0.000 abstract description 21
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract 2
- NXGASACSZHOEHS-UHFFFAOYSA-N cerium lanthanum zirconium Chemical compound [Zr].[La].[Ce] NXGASACSZHOEHS-UHFFFAOYSA-N 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 60
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 51
- 239000000843 powder Substances 0.000 description 41
- 229910004625 Ce—Zr Inorganic materials 0.000 description 39
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 36
- 239000007789 gas Substances 0.000 description 29
- 239000000203 mixture Substances 0.000 description 15
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 12
- 229910001930 tungsten oxide Inorganic materials 0.000 description 12
- 239000011812 mixed powder Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 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
- 230000000052 comparative effect Effects 0.000 description 4
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 150000000703 Cerium Chemical class 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 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
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 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
- 238000012824 chemical production Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002603 lanthanum Chemical class 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- Catalysts (AREA)
- Exhaust Gas After Treatment (AREA)
Abstract
Description
本発明は有機酸含有排ガス処理用触媒および処理方法に関し、詳しくは、例えば、炭素数１〜６の有機カルボン酸を含む排ガスを処理するに好適な触媒、およびこの触媒を用いた有機酸含有排ガスの処理方法に関する。 The present invention relates to an organic acid-containing exhaust gas treatment catalyst and a treatment method, and more particularly, for example, a catalyst suitable for treating exhaust gas containing an organic carboxylic acid having 1 to 6 carbon atoms, and an organic acid-containing exhaust gas using the catalyst. It relates to the processing method.
アルミナ、チタニアなどの無機酸化物担体にＰｔ、Ｐｄなどの１種または２種以上の貴金属を担持した触媒を用いて、排ガス中に含まれる有害物質を分解除去することは一般によく知られている。例えば、排ガス中の低濃度炭化水素を酸化分解するのに、アルミナ担体にＰｔとＰｄとを担持した触媒を用いることが提案されている（特許文献１参照）。 It is generally well known to decompose and remove harmful substances contained in exhaust gas by using a catalyst in which one or more kinds of noble metals such as Pt and Pd are supported on an inorganic oxide carrier such as alumina and titania. . For example, in order to oxidatively decompose low-concentration hydrocarbons in exhaust gas, it has been proposed to use a catalyst in which Pt and Pd are supported on an alumina carrier (see Patent Document 1).
一方、内燃機関からの排ガスを処理する触媒として、セリアおよび／またはジルコニアの金属酸化物を含む触媒が提案されている（特許文献２の請求項２参照）。また、セリウムおよびランタンを含むジルコニウム酸化物を含有する触媒が提案されている（特許文献３参照）。 On the other hand, as a catalyst for treating exhaust gas from an internal combustion engine, a catalyst containing a metal oxide of ceria and / or zirconia has been proposed (see claim 2 of Patent Document 2). A catalyst containing a zirconium oxide containing cerium and lanthanum has been proposed (see Patent Document 3).
本発明の目的は、有機酸含有排ガスの処理に好適な触媒、およびこの触媒を用いた有機酸含有排ガスの処理方法を提供することにある。 An object of the present invention is to provide a catalyst suitable for treating an organic acid-containing exhaust gas and a method for treating an organic acid-containing exhaust gas using the catalyst.
セリウム（Ｃｅ）−ジルコニウム（Ｚｒ）酸化物は、上述のとおり、内燃機関からの排ガスを処理するのに助触媒として広く用いられているが、その理由は、この酸化物が酸素吸蔵放出能（ＯＳＣ）を有しており、このＯＳＣ機能により排ガスの雰囲気変動による影響を緩和するためと考えられている。 As described above, cerium (Ce) -zirconium (Zr) oxide is widely used as a co-catalyst for treating exhaust gas from an internal combustion engine because the oxide is capable of storing and releasing oxygen. OSC), and this OSC function is considered to mitigate the influence of atmospheric fluctuation of exhaust gas.
本発明者らは、Ｃｅ−Ｚｒ酸化物を添加した貴金属系触媒について検討したところ、化学プラント排ガスのように雰囲気変動の比較的小さい排ガスの処理においても、Ｃｅ−Ｚｒ酸化物が貴金属系触媒に高い分解活性と耐久性とを付与することを見出し、本発明を完成するに至った。 The present inventors have examined a noble metal catalyst to which a Ce—Zr oxide is added. As a result, Ce—Zr oxide is used as a noble metal catalyst even in the treatment of an exhaust gas having a relatively small atmospheric fluctuation, such as a chemical plant exhaust gas. It has been found that high decomposition activity and durability are imparted, and the present invention has been completed.
本発明は次のとおりである。
（１）貴金属とＣｅ−Ｚｒ複合酸化物とを含有することを特徴とする有機酸含有排ガス処理用触媒。
（２）貴金属と、Ｃｅ−Ｚｒ複合酸化物と、イットリウム（Ｙ）、ランタン（Ｌａ）およびプラセオジム（Ｐｒ）から選ばれる少なくとも１種の元素とを含有することを特徴とする有機酸含有排ガス処理用触媒。
（３）Ｙ、ＬａおよびＰｒから選ばれる少なくとも１種の元素の少なくとも一部がＣｅおよびＺｒとの複合酸化物の形態で含有されている上記（２）の有機酸含有排ガス処理用触媒。
（４）さらにアルミニウム（Ａｌ）および／またはタングステン（Ｗ）を含有する上記（１）、（２）または（３）の有機酸含有排ガス処理用触媒。
（５）有機酸を含有する排ガスを上記（１）ないし（４）のいずれかの有機酸含有排ガス処理用触媒に接触させて排ガス中の有機酸を分解することを特徴とする有機酸含有排ガス処理方法。
（６）有機酸が炭素数１〜６の有機カルボン酸である上記（５）の有機酸含有排ガス処理方法。
The present invention is as follows.
(1) An organic acid-containing exhaust gas treatment catalyst comprising a noble metal and a Ce—Zr composite oxide.
(2) An organic acid-containing exhaust gas treatment containing a noble metal, a Ce—Zr composite oxide, and at least one element selected from yttrium (Y), lanthanum (La), and praseodymium (Pr) Catalyst.
(3) The organic acid-containing exhaust gas treatment catalyst according to (2), wherein at least a part of at least one element selected from Y, La, and Pr is contained in the form of a complex oxide with Ce and Zr.
(4) The organic acid-containing exhaust gas treatment catalyst according to (1), (2) or (3), further containing aluminum (Al) and / or tungsten (W).
(5) An exhaust gas containing an organic acid is brought into contact with the organic acid-containing exhaust gas treatment catalyst according to any one of (1) to (4) above to decompose the organic acid in the exhaust gas, Processing method.
(6) The organic acid-containing exhaust gas treatment method according to (5), wherein the organic acid is an organic carboxylic acid having 1 to 6 carbon atoms.
本発明の触媒は、有機酸含有排ガスの処理において、有機酸分解に係わる高い触媒活性と耐久性とを有する。したがって、本発明の触媒を用いることにより、有機酸含有排ガスを長期にわたり高い有機酸除去率をもって処理することができる。 The catalyst of the present invention has high catalytic activity and durability related to organic acid decomposition in the treatment of organic acid-containing exhaust gas. Therefore, by using the catalyst of the present invention, the organic acid-containing exhaust gas can be treated with a high organic acid removal rate over a long period of time.
本発明の「貴金属」とは、白金（Ｐｔ）、パラジウム（Ｐｄ）、ロジウム（Ｒｈ）、ルテニウム（Ｒｕ）、イリジウム（Ｉｒ）および金（Ａｕ）から選ばれる少なくとも１種の貴金属元素を意味する。なかでも、ＰｔとＰｄとの組合せが好適に用いられる。 The “noble metal” in the present invention means at least one noble metal element selected from platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), iridium (Ir) and gold (Au). . Of these, a combination of Pt and Pd is preferably used.
本発明の「Ｃｅ−Ｚｒ複合酸化物」とは、Ｘ線回折図において、ＣｅＯ２の明らかな固有のピークが認められず、２θ＝２９°付近に回折ピークが認められるものである（図１参照）。このＣｅ−Ｚｒ複合酸化物は一般によく知られており、一般的な方法、例えば、固相法、アルコキシド法、共沈法、気相法などにより容易に調製することができる。具体的には、例えば、酸化ジルコニウムに硝酸セリウムなどのセリウム塩の水溶液を加え、混合し、乾燥した後、４００〜１０００℃で焼成すればよい。 The “Ce—Zr composite oxide” of the present invention is one in which a clear intrinsic peak of CeO 2 is not observed in the X-ray diffraction diagram, and a diffraction peak is observed in the vicinity of 2θ = 29 ° (FIG. 1). reference). This Ce—Zr composite oxide is generally well known, and can be easily prepared by a general method such as a solid phase method, an alkoxide method, a coprecipitation method, a gas phase method and the like. Specifically, for example, an aqueous solution of cerium salt such as cerium nitrate may be added to zirconium oxide, mixed, dried, and then fired at 400 to 1000 ° C.
上記Ｃｅ−Ｚｒ複合酸化物において、ＣｅとＺｒとの割合は、ＣｅＯ２：ＺｒＯ２＝１：８〜１：１、好ましくは１：５〜１：１（質量比）である。Ｃｅ−Ｚｒ複合酸化物のＢＥＴ比表面積は１０ｍ２／ｇ以上であるのが好ましく、より好ましくは３０〜２００ｍ２／ｇである。 In the Ce—Zr composite oxide, the ratio of Ce and Zr is CeO 2 : ZrO 2 = 1: 8 to 1: 1, preferably 1: 5 to 1: 1 (mass ratio). The BET specific surface area of the Ce—Zr composite oxide is preferably 10 m 2 / g or more, more preferably 30 to 200 m 2 / g.
なお、上記のＣｅ−Ｚｒ複合酸化物は市販されており、本発明においては、これら市販品をそのまま使用してもよい。 The Ce-Zr composite oxide is commercially available, and in the present invention, these commercially available products may be used as they are.
本発明の触媒は、上記の貴金属とＣｅ−Ｚｒ複合酸化物とを含むものであり、具体的には、Ｃｅ−Ｚｒ複合酸化物に少なくとも１種の貴金属を担持したものである（以下、この触媒を便宜上「触媒Ａ」という。）。この触媒Ａは、耐火性無機酸化物に貴金属を担持した従来公知の触媒の調製方法に一般に用いられている浸漬法や含浸法などの方法に従って調製することができる。具体的には、例えば、Ｃｅ−Ｚｒ複合酸化物粉体をヘキサアンミン白金水溶液と混合し、乾燥した後、３００〜７００℃で１〜２０時間焼成することにより、白金担持Ｃｅ−Ｚｒ複合酸化物粉体を得ることができる。 The catalyst of the present invention contains the above-described noble metal and Ce—Zr composite oxide, and specifically, is a catalyst in which at least one noble metal is supported on the Ce—Zr composite oxide (hereinafter referred to as “this”). The catalyst is referred to as “catalyst A” for convenience). The catalyst A can be prepared according to a method such as a dipping method or an impregnation method generally used in a conventionally known method for preparing a catalyst in which a noble metal is supported on a refractory inorganic oxide. Specifically, for example, a Ce-Zr composite oxide powder is mixed with a hexaammineplatinum aqueous solution, dried, and then fired at 300 to 700 ° C. for 1 to 20 hours, whereby a platinum-supported Ce—Zr composite oxide is obtained. A powder can be obtained.
上記貴金属供給源としての貴金属含有化合物の具体例としては、例えば、貴金属の硝酸塩、ハロゲン化物、アンモニウム塩、アンミン錯体、ジニトロジアンミン塩、水酸化物などの溶液（例えば、水溶液）またはコロイド溶液（例えば、コロイド水溶液）を挙げることができる。なかでも、貴金属のアンミン錯体、水酸化物などの塩基性水溶液が好適に用いられる。 Specific examples of the noble metal-containing compound as the noble metal source include, for example, solutions (for example, aqueous solutions) or colloidal solutions (for example, aqueous solutions) of nitrates, halides, ammonium salts, ammine complexes, dinitrodiammine salts, and hydroxides of noble metals. , Colloidal aqueous solution). Of these, basic aqueous solutions such as nomine complexes and hydroxides of noble metals are preferably used.
上記触媒Ａにおいて、貴金属の含有量は、触媒の全質量基準（但し、セラミックハニカムに担持する場合は、このセラミックハニカムを除く。）で、０．０２〜５質量％、好ましくは０．０２〜３質量％、より好ましくは０．１〜２．５質量％である。
上記触媒Ａは、貴金属およびＣｅ−Ｚｒ複合酸化物のほかに、その性能を損なわない範囲でＣｅおよびＺｒのそれぞれの単独酸化物を含んでいてもよい。
In the catalyst A, the content of the noble metal is 0.02 to 5% by mass, preferably 0.02 to 5% by mass based on the total mass of the catalyst (however, when supported on a ceramic honeycomb, this ceramic honeycomb is excluded). It is 3 mass%, More preferably, it is 0.1-2.5 mass%.
In addition to the noble metal and the Ce—Zr composite oxide, the catalyst A may contain a single oxide of Ce and Zr as long as the performance is not impaired.
本発明の触媒は、貴金属およびＣｅ−Ｚｒ複合酸化物に加えて、Ｙ、ＬａおよびＰｒから選ばれる少なくとも１種の元素（以下、「Ｌａ等元素」という。）を含有するのが、より高い触媒活性と耐久性とが得られる点において、好ましいものである（以下、この触媒を「触媒Ｂ」という。）。Ｌａ等元素のなかでも、Ｌａが好適に用いられる。 The catalyst of the present invention contains at least one element selected from Y, La and Pr (hereinafter referred to as “La element”) in addition to the noble metal and the Ce—Zr composite oxide. This is preferable in that catalyst activity and durability can be obtained (hereinafter, this catalyst is referred to as “catalyst B”). Of the elements such as La, La is preferably used.
触媒Ｂは、貴金属、Ｃｅ−Ｚｒ複合酸化物およびＬａ等元素を含むものである。具体的には、Ｃｅ−Ｚｒ複合酸化物とＬａ等元素の酸化物とを含む担体に少なくとも１種の貴金属を担持したものである。この触媒Ｂのなかでも、Ｌａ等元素がＣｅおよびＺｒと複合酸化物を形成しているのが好ましい。これら複合酸化物としては、Ｃｅ−Ｚｒ−Ｌａ複合酸化物やＣｅ−Ｚｒ−Ｙ複合酸化物が挙げられる。なかでも、Ｃｅ−Ｚｒ−Ｌａ複合酸化物が好適に用いられる。したがって、触媒Ｂのなかでも、Ｃｅ−Ｚｒ−Ｌａ複合酸化物またはＣｅ−Ｚｒ−Ｙ複合酸化物、特にＣｅ−Ｚｒ−Ｌａ複合酸化物に少なくとも１種の貴金属を担持したものが好ましいものである。 The catalyst B contains a noble metal, a Ce—Zr composite oxide, and an element such as La. Specifically, at least one noble metal is supported on a support containing a Ce—Zr composite oxide and an oxide of an element such as La. Among these catalysts B, elements such as La preferably form a complex oxide with Ce and Zr. Examples of these composite oxides include Ce—Zr—La composite oxide and Ce—Zr—Y composite oxide. Among these, Ce—Zr—La composite oxide is preferably used. Therefore, among the catalysts B, a Ce—Zr—La composite oxide or a Ce—Zr—Y composite oxide, in particular, a catalyst in which at least one noble metal is supported on a Ce—Zr—La composite oxide is preferable. .
上記のＣｅ−Ｚｒ−（Ｌａ等元素）複合酸化物は、Ｃｅ−Ｚｒ複合酸化物と同様に、Ｘ線回折図において、ＣｅＯ２とＬａ等元素の酸化物、例えば、Ｌａ２Ｏ３との明らかな固有のピークが認められず、２θ＝２９°付近に回折ピークが認められるものである。 The Ce—Zr— (La element etc.) composite oxide is similar to the Ce—Zr composite oxide in the X-ray diffraction diagram of the oxide of CeO 2 and La element such as La 2 O 3 . A clear intrinsic peak is not recognized, and a diffraction peak is observed in the vicinity of 2θ = 29 °.
上記のＣｅ−Ｚｒ−（Ｌａ等元素）複合酸化物は、Ｃｅ−Ｚｒ複合酸化物と同様に、一般によく知られており、一般的な方法、例えば、固相法、アルコキシド法、共沈法、気相法などにより容易に調製することができる。具体的には、例えば、酸化ジルコニウムに硝酸セリウムなどのセリウム塩と硝酸ランタンなどのランタン塩などとの水溶液を加え、混合し、乾燥した後、４００〜１０００℃で焼成すればよい。 The Ce—Zr— (elements such as La) composite oxides are generally well known, as are Ce—Zr composite oxides. Common methods such as a solid phase method, an alkoxide method, and a coprecipitation method are known. It can be easily prepared by a vapor phase method or the like. Specifically, for example, an aqueous solution of a cerium salt such as cerium nitrate and a lanthanum salt such as lanthanum nitrate may be added to zirconium oxide, mixed, dried, and then fired at 400 to 1000 ° C.
触媒ＢにおけるＬａ等元素の含有量（Ｃｅ−Ｚｒ−（Ｌａ等元素）複合酸化物のときも含む）は、Ｌａ等酸化物（Ｌａ２Ｏ３、Ｙ２Ｏ３、Ｐｒ２Ｏ３）：ＺｒＯ２＝１：１．５〜１：６０、好ましくは１：１．５〜１：４０（質量比）である。Ｃｅ−Ｚｒ−（Ｌａ等元素）複合酸化物のＢＥＴ比表面積は１０ｍ２／ｇ以上であるのが好ましく、より好ましくは３０〜２００ｍ２／ｇである。 The content of elements such as La in the catalyst B (including the case of Ce-Zr- (La elements) complex oxide) is the oxide of La (La 2 O 3 , Y 2 O 3 , Pr 2 O 3 ): ZrO 2 = 1: 1.5 to 1:60, preferably 1: 1.5 to 1:40 (mass ratio). The BET specific surface area of the Ce—Zr— (La element, etc.) composite oxide is preferably 10 m 2 / g or more, more preferably 30 to 200 m 2 / g.
なお、上記のＣｅ−Ｚｒ−（Ｌａ等元素）複合酸化物、例えば、Ｃｅ−Ｚｒ−Ｌａ複合酸化物やＣｅ−Ｚｒ−Ｙ複合酸化物は市販されており、本発明においては、これら市販品をそのまま使用してもよい。 The Ce-Zr- (La element) composite oxides such as Ce-Zr-La composite oxide and Ce-Zr-Y composite oxide are commercially available. In the present invention, these commercially available products are used. May be used as they are.
触媒Ｂ、例えば、Ｃｅ−Ｚｒ−Ｌａ複合酸化物に少なくとも１種の貴金属を担持した触媒は、上述のＣｅ−Ｚｒ複合酸化物に少なくとも１種の貴金属を担持した触媒と同様に調製することができる。具体的には、例えば、Ｃｅ−Ｚｒ−Ｌａ複合酸化物粉体をヘキサアンミン白金水溶液と混合し、乾燥した後、３００〜７００℃で１〜２０時間焼成することにより、白金担持Ｃｅ−Ｚｒ−Ｌａ複合酸化物粉体を得ることができる。 The catalyst B, for example, a catalyst in which at least one noble metal is supported on a Ce-Zr-La composite oxide can be prepared in the same manner as the catalyst in which at least one noble metal is supported on the above-described Ce-Zr composite oxide. it can. Specifically, for example, the Ce—Zr—La composite oxide powder is mixed with a hexaammineplatinum aqueous solution, dried, and then calcined at 300 to 700 ° C. for 1 to 20 hours, whereby platinum-supported Ce—Zr— La composite oxide powder can be obtained.
触媒Ｂは、貴金属とＣｅ−Ｚｒ−（Ｌａ等元素）複合酸化物とのほかに、その性能を損なわない範囲において、Ｃｅ、ＺｒおよびＬａ等元素それぞれの単独酸化物を含んでいてもよい。 In addition to the noble metal and Ce—Zr— (elements such as La) composite oxide, the catalyst B may contain single oxides of elements such as Ce, Zr and La as long as the performance is not impaired.
上記触媒Ａおよび触媒Ｂは、アルミニウム（Ａｌ）またはタングステン（Ｗ）もしくはＡｌとＷとを含有するのが、触媒性能および耐久性の点で、好ましい。Ａｌおよび／またはＷは、通常、酸化物の形態が含まれので、以下、これらをＡｌ／Ｗ酸化物と表示する。タングステン酸化物としては、ＷＯ、Ｗ２Ｏ３、ＷＯ３などが挙げられる。また、アルミニウム酸化物としては、α−アルミナ、γ−アルミナ、θ−アルミナなどが挙げられる。なかでも、比表面積の大きいγ−アルミナが好適に用いられる。 The catalyst A and the catalyst B preferably contain aluminum (Al) or tungsten (W) or Al and W from the viewpoint of catalyst performance and durability. Since Al and / or W usually include oxide forms, these are hereinafter referred to as Al / W oxides. Examples of the tungsten oxide include WO, W 2 O 3 , WO 3 and the like. Examples of the aluminum oxide include α-alumina, γ-alumina, and θ-alumina. Among these, γ-alumina having a large specific surface area is preferably used.
すなわち、本発明の触媒のなかでも、貴金属とＣｅ−Ｚｒ複合酸化物とＡｌ／Ｗ酸化物とを含む触媒（以下、「触媒Ｃ１」という。）や、貴金属とＣｅ−Ｚｒ複合酸化物とＬａ等元素酸化物、好ましくは貴金属とＣｅ−Ｚｒ−（Ｌａ等元素）複合酸化物とＡｌ／Ｗ酸化物とを含む触媒（以下、「触媒Ｃ２」という。）が好適に用いられる。 That is, among the catalysts of the present invention, a catalyst containing a noble metal, a Ce—Zr composite oxide and an Al / W oxide (hereinafter referred to as “catalyst C1”), a noble metal, a Ce—Zr composite oxide and La A catalyst (hereinafter referred to as “catalyst C2”) containing an equielemental oxide, preferably a noble metal, a Ce—Zr— (La etc.) composite oxide, and an Al / W oxide is suitably used.
触媒Ｃ１は、具体的には、Ｃｅ−Ｚｒ複合酸化物とアルミニウム酸化物（例えば、Ａｌ２Ｏ３）および／またはタングステン酸化物（例えば、ＷＯ３）とを含む担体に少なくとも１種の貴金属を担持したものである。 Specifically, the catalyst C1 contains at least one noble metal on a support containing a Ce—Zr composite oxide and an aluminum oxide (eg, Al 2 O 3 ) and / or a tungsten oxide (eg, WO 3 ). It is supported.
触媒Ｃ１において、Ｃｅ−Ｚｒ複合酸化物とアルミニウム酸化物またはタングステン酸化物とからなる担体を用いる場合、Ｃｅ−Ｚｒ複合酸化物の含有量は、全担体質量基準で、１〜８０質量％、好ましくは５〜８０質量％、より好ましくは５〜４０質量％である（残余はアルミニウム酸化物またはタングステン酸化物であり、合計１００質量％）。Ｃｅ−Ｚｒ複合酸化物の含有量が１質量％未満では、十分なＯＳＣ機能が得られず、一方、８０質量％を超えると逆に活性が低下するおそれがある。 In the catalyst C1, when a support composed of Ce—Zr composite oxide and aluminum oxide or tungsten oxide is used, the content of Ce—Zr composite oxide is 1 to 80% by mass, preferably based on the total support mass. Is 5 to 80% by mass, more preferably 5 to 40% by mass (the balance is aluminum oxide or tungsten oxide, and the total is 100% by mass). When the content of the Ce—Zr composite oxide is less than 1% by mass, a sufficient OSC function cannot be obtained. On the other hand, when the content exceeds 80% by mass, the activity may decrease.
Ｃｅ−Ｚｒ複合酸化物とアルミニウム酸化物とタングステン酸化物との混合物を用いる場合、Ｃｅ−Ｚｒ複合酸化物の含有量は、上記のとおりであり、アルミニウム酸化物の含有量（Ａｌ２Ｏ３換算）は、全担体質量基準で、５〜９４．５質量％であるのが好ましく、より好ましくは１０〜９４．５質量％である。また、タングステン酸化物の含有量（ＷＯ３換算）は、全担体質量基準で、０．５〜４０質量％であるのが好ましく、より好ましくは１〜４０質量％である（３成分合計１００質量％）。アルミニウム酸化物の含有量が２０質量％未満では触媒の比表面積が低下するため好ましくなく、一方８０質量％を超えると触媒活性が低下するおそれがある。また、タングステン酸化物の含有量が０．５質量％未満ではタングステンと貴金属との相互作用が弱まるため十分な効果が得られなくなり、一方４０質量％を超えると比表面積の低下などにより貴金属の分散性が低下して好ましくない。 When a mixture of Ce—Zr composite oxide, aluminum oxide and tungsten oxide is used, the content of Ce—Zr composite oxide is as described above, and the content of aluminum oxide (in terms of Al 2 O 3) ) Is preferably 5 to 94.5% by mass, more preferably 10 to 94.5% by mass based on the total mass of the carrier. Further, the content of tungsten oxide (in terms of WO 3 ) is preferably 0.5 to 40% by mass, more preferably 1 to 40% by mass, based on the total mass of the carrier (the total of the three components is 100% by mass). %). If the aluminum oxide content is less than 20% by mass, the specific surface area of the catalyst decreases, which is not preferable. On the other hand, if it exceeds 80% by mass, the catalyst activity may decrease. If the tungsten oxide content is less than 0.5% by mass, the interaction between tungsten and the noble metal is weakened, so that a sufficient effect cannot be obtained. On the other hand, if the content exceeds 40% by mass, the noble metal is dispersed due to a decrease in the specific surface area. It is not preferable because the properties are lowered.
触媒Ｃ２は、具体的には、Ｃｅ−Ｚｒ複合酸化物とＬａ等元素酸化物とアルミニウム酸化物（例えば、Ａｌ２Ｏ３）および／またはタングステン酸化物（例えば、ＷＯ３）、好ましくはＣｅ−Ｚｒ−（Ｌａ等元素）複合酸化物とＡｌ２Ｏ３および／またはＷＯ３とを含む担体に少なくとも１種の貴金属を担持したものである。 Specifically, the catalyst C2 includes a Ce—Zr composite oxide, an elemental oxide such as La, an aluminum oxide (eg, Al 2 O 3 ) and / or a tungsten oxide (eg, WO 3 ), preferably Ce— At least one kind of noble metal is supported on a support containing a Zr— (element such as La) composite oxide and Al 2 O 3 and / or WO 3 .
触媒Ｃ２において、Ｃｅ−Ｚｒ複合酸化物とＬａ等元素酸化物、好ましくはＣｅ−Ｚｒ−（Ｌａ等元素）複合酸化物とアルミニウム酸化物またはタングステン酸化物とからなる担体を用いる場合、Ｃｅ−Ｚｒ複合酸化物とＬａ等元素酸化物との合計含有量、またはＣｅ−Ｚｒ−（Ｌａ等元素）複合酸化物の含有量は、全担体質量基準で、５〜８０質量％であるのが好ましく、より好ましくは５〜４０質量％である（残余はアルミニウム酸化物またタングステン酸化物であり、合計１００質量％）。上記含有量が５質量％未満では、十分なＯＳＣ機能が得られず、一方、８０質量％を超えると逆に活性が低下するおそれがある。 In the catalyst C2, when using a support made of Ce—Zr composite oxide and La element oxide, preferably Ce—Zr— (La element) composite oxide and aluminum oxide or tungsten oxide, Ce—Zr The total content of the complex oxide and elemental oxide such as La, or the content of Ce-Zr- (element such as La) complex oxide is preferably 5 to 80% by mass based on the total carrier mass, More preferably, it is 5 to 40% by mass (the balance is aluminum oxide or tungsten oxide, and the total is 100% by mass). When the content is less than 5% by mass, a sufficient OSC function cannot be obtained. On the other hand, when the content exceeds 80% by mass, the activity may decrease.
Ｃｅ−Ｚｒ複合酸化物とＬａ等元素酸化物、好ましくはＣｅ−Ｚｒ−（Ｌａ等元素）複合酸化物とアルミニウム酸化物とタングステン酸化物との混合物を用いる場合、Ｃｅ−Ｚｒ複合酸化物またはＣｅ−Ｚｒ−（Ｌａ等元素）複合酸化物の含有量、アルミニウム酸化物の含有量（Ａｌ２Ｏ３換算）、およびタングステン酸化物の含有量（ＷＯ３換算）は、上述の触媒Ｃ１におけると同じである。 When a mixture of Ce-Zr composite oxide and La element oxide, preferably Ce-Zr- (La element) composite oxide, aluminum oxide and tungsten oxide is used, Ce-Zr composite oxide or Ce -Zr- (La, etc. element) content of the composite oxide, the content of aluminum oxide (Al 2 O 3 equivalent), and the content of tungsten oxide (WO 3 equivalent), the same as in the above-mentioned catalyst C1 It is.
上記触媒Ｃ１、Ｃ２は、触媒Ａや触媒Ｂと同様に調製することができる。具体的には、触媒Ｃ１の場合、例えば、Ｃｅ−Ｚｒ複合酸化物粉体とＡｌ２Ｏ３粉体および／またはＷＯ３粉体とをヘキサアンミン白金水溶液と混合し、乾燥した後、３００〜７００℃で１〜２０時間焼成することにより、白金担持（Ｃｅ−Ｚｒ複合酸化物・Ａｌ２Ｏ３および／またはＷＯ３）粉体を得ることができる。触媒Ｃ２の場合、例えば、Ｃｅ−Ｚｒ−Ｌａ複合酸化物粉体とＡｌ２Ｏ３粉体および／またはＷＯ３粉体とをヘキサアンミン白金水溶液と混合し、乾燥した後、３００〜７００℃で１〜２０時間焼成することにより、白金担持（Ｃｅ−Ｚｒ−Ｌａ複合酸化物・Ａｌ２Ｏ３および／またはＷＯ３）粉体を得ることができる。 The catalysts C1 and C2 can be prepared in the same manner as the catalyst A and the catalyst B. Specifically, in the case of the catalyst C1, for example, a Ce—Zr composite oxide powder, an Al 2 O 3 powder and / or a WO 3 powder are mixed with a hexaammineplatinum aqueous solution and dried, and then 300 to By calcination at 700 ° C. for 1 to 20 hours, a platinum-supported (Ce—Zr composite oxide / Al 2 O 3 and / or WO 3 ) powder can be obtained. In the case of the catalyst C2, for example, Ce—Zr—La composite oxide powder, Al 2 O 3 powder and / or WO 3 powder are mixed with a hexaammineplatinum aqueous solution and dried, and then at 300 to 700 ° C. By firing for 1 to 20 hours, a platinum-supported (Ce—Zr—La composite oxide / Al 2 O 3 and / or WO 3 ) powder can be obtained.
発明の触媒を用いて処理する有機酸含有排ガスとは、燃焼排ガス、化学品製造プラントや印刷、塗装などの工程から排出される、有機酸を含有する排ガスである。この有機酸としては、ギ酸、酢酸、アクリル酸、プロピオン酸、酪酸、吉草酸、酒石酸、フタル酸、マレイン酸などが挙げられるが、なかでも、本発明の触媒は、炭素数１〜６のカルボン酸、特に酢酸の分解除去に好適に用いられる。 The organic acid-containing exhaust gas treated using the catalyst of the invention is an exhaust gas containing an organic acid discharged from a process such as combustion exhaust gas, chemical production plant, printing, painting, or the like. Examples of the organic acid include formic acid, acetic acid, acrylic acid, propionic acid, butyric acid, valeric acid, tartaric acid, phthalic acid, maleic acid, and the like. Among these, the catalyst of the present invention is a carboxylic acid having 1 to 6 carbon atoms. It is suitably used for decomposition and removal of acids, particularly acetic acid.
処理対象とする各種排ガスの温度については、１００〜７００℃であることが好ましく、より好ましくは２００〜７００℃、更に好ましくは２５０〜７００℃である。排ガス量は、空間速度で１００〜１０００００Ｈｒ−１、好ましくは１０００〜１０００００Ｈｒ−１である。 About the temperature of the various waste gas made into a process target, it is preferable that it is 100-700 degreeC, More preferably, it is 200-700 degreeC, More preferably, it is 250-700 degreeC. The amount of exhaust gas is 100 to 100,000 Hr −1 , preferably 1000 to 100,000 Hr −1 in space velocity.
本発明の有利な実施態様を示している以下の実施例を挙げて、本発明を更に具体的に説明する。触媒組成の分析は、蛍光Ｘ線分析により、下記条件で行った。
分析装置：リガク製ＲＩＸ２０００
分析時の雰囲気：真空
試料スピン速度：６０ｒｐｍ
Ｘ線源：Ｒｈ管球
（実施例１）
＜工程１＞
Ｃｅ−Ｚｒ複合酸化物６００ｇ（第一稀元素化学工業（株）製、ＣｅＯ２：ＺｒＯ２（質量比）＝１６：８４、比表面積＝３０ｍ２／ｇ）に、白金を１２ｇ含有するヘキサアンミン白金水溶液を加えて混合し、乾燥後、５００℃で１時間焼成することにより、Ｃｅ−Ｚｒ複合酸化物に白金を担持した（Ｐｔ／ＣｅＺｒ）粉体を得た。
＜工程２＞
上記の粉体に、硝酸水溶液を加え、磁性ボールミルに投入し、混合、粉砕してスラリーを得た。このスラリーをコージェライトハニカム（１．０Ｌ、２００セル／平方インチ（ｘ２．５センチ））に付着させ、空気流にてセル内の余剰スラリーを除去した後、１００℃で乾燥し、空気雰囲気下にて５００℃で３時間焼成して、完成触媒を得た。コート量は１００ｇ／Ｌであった。得られた触媒の組成を分析した結果、Ｐｔの含有量は、コージェライトハニカムを除いた全触媒質量の２．０質量％であった。
（実施例２）
＜工程１＞
Ｃｅ−Ｚｒ−Ｌａ複合酸化物６００ｇ（第一稀元素化学工業（株）製、ＣｅＯ２：ＺｒＯ２：Ｌａ２Ｏ３（質量比）＝３０：５０：２０、比表面積＝６０ｍ２／ｇ）に、白金１２ｇを含有するヘキサアンミン白金水溶液およびパラジウム６ｇを含有するテトラアンミンパラジウム水溶液を加えて混合し、乾燥後、５００℃で１時間焼成することにより、Ｃｅ−Ｚｒ−Ｌａ複合酸化物に白金とパラジウムとを担持した（Ｐｔ＋Ｐｄ／ＣｅＺｒＬａ）粉体を得た。なお、Ｃｅ−Ｚｒ−Ｌａ複合酸化物のＸ線回折図を図１に示す。
＜工程２＞
実施例１の工程２において、Ｐｔ／ＣｅＺｒ粉体の代わりに上記Ｐｔ＋Ｐｄ／ＣｅＺｒＬａ粉体を使用したこと以外は実施例１の工程２と同様にして、完成触媒を得た。得られた触媒の組成を分析した結果、ＰｔおよびＰｄの含有量はそれぞれ２．０質量％および１．０質量％であった。
（実施例３）
＜工程１＞
実施例２の工程１において、Ｃｅ−Ｚｒ−Ｌａ複合酸化物６００ｇの代わりに、実施例１で用いたと同じＣｅ−Ｚｒ複合酸化物６０ｇとγ−アルミナ粉体５４０ｇ（比表面積＝１５０ｍ２／ｇ）の混合粉体を使用したこと以外は同様にして、Ｃｅ−Ｚｒ複合酸化物とＡｌ２Ｏ３との混合粉体に白金とパラジウムとを担持した（Ｐｔ＋Ｐｄ／ＣｅＺｒ＋Ａｌ）粉体を得た。
＜工程２＞
実施例２の工程２において、Ｐｔ＋Ｐｄ／ＣｅＺｒＬａ粉体の代わりに上記Ｐｔ＋Ｐｄ／ＣｅＺｒ＋Ａｌ粉体を使用したこと以外は実施例２の工程２と同様にして、完成触媒を得た。得られた触媒の組成を分析した結果、ＰｔおよびＰｄの含有量はそれぞれ２．０質量％および１．０質量％であった。
（実施例４）
＜工程１＞
実施例２の工程１において、Ｃｅ−Ｚｒ−Ｌａ複合酸化物６００ｇの代わりに、実施例２で用いたと同じＣｅ−Ｚｒ−Ｌａ複合酸化物６０ｇとγ−アルミナ粉体５４０ｇ（比表面積＝１５０ｍ２／ｇ）との混合粉体を使用したこと以外は同様にして、Ｃｅ−Ｚｒ−Ｌａ複合酸化物とＡｌ２Ｏ３との混合粉体に白金とパラジウムとを担持した（Ｐｔ＋Ｐｄ／ＣｅＺｒＬａ＋Ａｌ＋Ｗ）粉体を得た。
＜工程２＞
実施例２の工程２において、Ｐｔ＋Ｐｄ／ＣｅＺｒＬａ粉体の代わりに上記Ｐｔ＋Ｐｄ／ＣｅＺｒＬａ＋Ａｌ粉体を使用したこと以外は実施例２の工程２と同様にして、完成触媒を得た。得られた触媒の組成を分析した結果、ＰｔおよびＰｄの含有量はそれぞれ２．０質量％および１．０質量％であった。
（実施例５）
＜工程１＞
実施例２の工程１において、Ｃｅ−Ｚｒ−Ｌａ複合酸化物６００ｇの代わりに、実施例２で用いたと同じＣｅ−Ｚｒ−Ｌａ複合酸化物６０ｇとγ−アルミナ粉体４８０ｇ（比表面積＝１５０ｍ２／ｇ）とＷＯ３粉体６０ｇの混合粉体を使用したこと以外は同様にして、Ｃｅ−Ｚｒ−Ｌａ複合酸化物とＡｌ２Ｏ３とＷＯ３との混合粉体に白金とパラジウムとを担持した（Ｐｔ＋Ｐｄ／ＣｅＺｒＬａ＋Ａｌ＋Ｗ）粉体を得た。
＜工程２＞
実施例２の工程２において、Ｐｔ＋Ｐｄ／ＣｅＺｒＬａ粉体の代わりに上記Ｐｔ＋Ｐｄ／ＣｅＺｒＬａ＋Ａｌ＋Ｗ粉体を使用したこと以外は実施例２の工程２と同様にして、完成触媒を得た。得られた触媒の組成を分析した結果、ＰｔおよびＰｄの含有量はそれぞれ２．０質量％および１．０質量％であった。
（実施例６）
＜工程１＞
実施例４の工程１において、Ｃｅ−Ｚｒ−Ｌａ複合酸化物の代わりに、Ｃｅ−Ｚｒ−Ｙ複合酸化物（第一稀元素化学工業（株）製、ＣｅＯ２：ＺｒＯ２：Ｙ２Ｏ３（質量比）＝３０：５０：２０、比表面積＝６０ｍ２／ｇ）を使用したこと以外は同様にして、Ｃｅ−Ｚｒ−Ｙ複合酸化物とＡｌ２Ｏ３とＷＯ３との混合粉体に白金とパラジウムとを担持した（Ｐｔ＋Ｐｄ／ＣｅＺｒＹ＋Ａｌ＋Ｗ）粉体を得た。＜工程２＞
実施例２の工程２において、Ｐｔ＋Ｐｄ／ＣｅＺｒＬａ粉体の代わりに上記Ｐｔ＋Ｐｄ／ＣｅＺｒＹ＋Ａｌ＋Ｗ粉体を使用したこと以外は実施例２の工程２と同様にして、完成触媒を得た。得られた触媒の組成を分析した結果、ＰｔおよびＰｄの含有量はそれぞれ２．０ｇ／Ｌおよび１．０ｇ／Ｌであった。
（比較例１）
＜工程１＞
実施例２の工程１において、Ｃｅ−Ｚｒ−Ｌａ複合酸化物の代わりにγ−アルミナを使用したこと以外は実施例２の工程１と同様にして、アルミナに白金とパラジウムとを担持した（Ｐｔ＋Ｐｄ／Ａｌ）粉体を得た。
＜工程２＞
実施例２の工程２において、Ｐｔ＋Ｐｄ／ＣｅＺｒＬａ粉体の代わりに上記Ｐｔ＋Ｐｄ／Ａｌ粉体を使用したこと以外は実施例２の工程２と同様にして、完成触媒を得た。得られた触媒の組成を分析した結果、ＰｔおよびＰｄの含有量はそれぞれ２．０質量％および１．０質量％であった。
（比較例２）
＜工程１＞
実施例２の工程１において、Ｃｅ−Ｚｒ−Ｌａ複合酸化物６００ｇの代わりに、ＣｅＯ２粉体９６ｇとＺｒＯ２粉体５０４ｇの混合粉体を使用したこと以外は同様にして、ＣｅＯ２とＺｒＯ２との混合粉体に白金とパラジウムとを担持した（Ｐｔ＋Ｐｄ／Ｃｅ＋Ｚｒ）粉体を得た。
＜工程２＞
実施例２の工程２において、Ｐｔ＋Ｐｄ／ＣｅＺｒＬａの代わりに上記Ｐｔ＋Ｐｄ／Ｃｅ＋Ｚｒ粉体を使用したこと以外は実施例２の工程２と同様にして、完成触媒を得た。得られた触媒の組成を分析した結果、ＰｔおよびＰｄの含有量はそれぞれ２．０質量％および１．０質量％であった。
（実施例７〜１１）
＜工程１＞
実施例５の工程１において、Ｃｅ−Ｚｒ−Ｌａ複合酸化物、アルミナ、ＷＯ３の量を、表２に示す比率となるように量を変更したこと以外は同様にして、Ｐｔ＋Ｐｄ／ＣｅＺｒＬａ＋Ａｌ＋Ｗ粉体を得た。
＜工程２＞
実施例５の工程２と同様にして、完成触媒を得た。得られた触媒の組成を分析した結果、ＰｔおよびＰｄの含有量はそれぞれ２．０質量％および１．０質量％であった。
（実施例１２）
実施例１〜１１および比較例１、２で得られた触媒の性能を評価するために下記の酢酸除去試験を行った。
＜酢酸除去試験＞
試験条件：
排ガス組成＝酢酸：５０００ｐｐｍ、Ｏ２ ：５％、Ｎ２ ：バランス
反応器入口ガス温度＝２８０℃
空間速度（ＳＴＰ）＝３００００Ｈｒ−１
酢酸除去率算出式：
酢酸除去率（％）＝〔（反応器入口酢酸濃度）−（反応器出口酢酸濃度）〕／（反応器入口酢酸濃度）（×１００）
実施例１〜６および比較例１、２の触媒について、その組成と、３時間後と２０００時間後の酢酸除去率を表１に示す。また、実施例７〜１１の触媒について、その組成と、３時間後と２０００時間後の酢酸除去率を表２に示す。
The invention is further illustrated by the following examples, which illustrate advantageous embodiments of the invention. The analysis of the catalyst composition was performed under the following conditions by fluorescent X-ray analysis.
Analyzer: Rigaku RIX2000
Analysis atmosphere: Vacuum sample spin speed: 60 rpm
X-ray source: Rh tube (Example 1)
<Step 1>
Hexammine containing 12 g of platinum in Ce-Zr composite oxide 600 g (Daiichi Rare Element Chemical Co., Ltd., CeO 2 : ZrO 2 (mass ratio) = 16: 84, specific surface area = 30 m 2 / g) An aqueous platinum solution was added, mixed, dried, and then fired at 500 ° C. for 1 hour to obtain (Pt / CeZr) powder carrying platinum on a Ce—Zr composite oxide.
<Process 2>
A nitric acid aqueous solution was added to the above powder, put into a magnetic ball mill, mixed and pulverized to obtain a slurry. This slurry was attached to a cordierite honeycomb (1.0 L, 200 cells / square inch (x2.5 cm)), excess slurry in the cells was removed by air flow, and then dried at 100 ° C. in an air atmosphere. And calcined at 500 ° C. for 3 hours to obtain a finished catalyst. The coating amount was 100 g / L. As a result of analyzing the composition of the obtained catalyst, the Pt content was 2.0% by mass of the total catalyst mass excluding the cordierite honeycomb.
(Example 2)
<Step 1>
Ce-Zr-La composite oxide 600 g (Daiichi Rare Element Chemical Co., Ltd., CeO 2 : ZrO 2 : La 2 O 3 (mass ratio) = 30: 50: 20, specific surface area = 60 m 2 / g) In addition, a hexaammineplatinum aqueous solution containing 12 g of platinum and a tetraamminepalladium aqueous solution containing 6 g of palladium were added, mixed, dried, and calcined at 500 ° C. for 1 hour, whereby platinum was added to the Ce—Zr—La composite oxide. A (Pt + Pd / CeZrLa) powder carrying palladium was obtained. An X-ray diffraction pattern of the Ce—Zr—La composite oxide is shown in FIG.
<Process 2>
A finished catalyst was obtained in the same manner as in Step 2 of Example 1, except that the Pt + Pd / CeZrLa powder was used in place of Pt / CeZr powder in Step 2 of Example 1. As a result of analyzing the composition of the obtained catalyst, the contents of Pt and Pd were 2.0 mass% and 1.0 mass%, respectively.
(Example 3)
<Step 1>
In Step 1 of Example 2, instead of 600 g of Ce—Zr—La composite oxide, 60 g of the same Ce—Zr composite oxide and 540 g of γ-alumina powder used in Example 1 (specific surface area = 150 m 2 / g). (Pt + Pd / CeZr + Al) powder in which platinum and palladium are supported on a mixed powder of Ce—Zr composite oxide and Al 2 O 3 in the same manner except that the mixed powder (1) is used.
<Process 2>
A finished catalyst was obtained in the same manner as in Step 2 of Example 2, except that the Pt + Pd / CeZrLa powder was used instead of the Pt + Pd / CeZrLa powder in Step 2 of Example 2. As a result of analyzing the composition of the obtained catalyst, the contents of Pt and Pd were 2.0 mass% and 1.0 mass%, respectively.
Example 4
<Step 1>
In Step 1 of Example 2, instead of 600 g of Ce—Zr—La composite oxide, 60 g of the same Ce—Zr—La composite oxide and 540 g of γ-alumina powder (specific surface area = 150 m 2) used in Example 2 were used. (Pt + Pd / CeZrLa + Al + W) powder in which platinum and palladium are supported on a mixed powder of Ce—Zr—La composite oxide and Al 2 O 3 in the same manner except that the mixed powder is used. Got the body.
<Process 2>
A finished catalyst was obtained in the same manner as in Step 2 of Example 2, except that the Pt + Pd / CeZrLa + Al powder was used instead of the Pt + Pd / CeZrLa powder in Step 2 of Example 2. As a result of analyzing the composition of the obtained catalyst, the contents of Pt and Pd were 2.0 mass% and 1.0 mass%, respectively.
(Example 5)
<Step 1>
In Step 1 of Example 2, instead of 600 g of Ce—Zr—La composite oxide, 60 g of the same Ce—Zr—La composite oxide and 480 g of γ-alumina powder (specific surface area = 150 m 2) used in Example 2 were used. / G) and WO 3 powder 60 g, except that a mixed powder of Ce-Zr-La composite oxide, Al 2 O 3 and WO 3 is mixed with platinum and palladium. A supported (Pt + Pd / CeZrLa + Al + W) powder was obtained.
<Process 2>
A finished catalyst was obtained in the same manner as in Step 2 of Example 2, except that the Pt + Pd / CeZrLa + Al + W powder was used in place of Pt + Pd / CeZrLa powder in Step 2 of Example 2. As a result of analyzing the composition of the obtained catalyst, the contents of Pt and Pd were 2.0 mass% and 1.0 mass%, respectively.
(Example 6)
<Step 1>
In Step 1 of Example 4, instead of the Ce—Zr—La composite oxide, a Ce—Zr—Y composite oxide (CeO 2 : ZrO 2 : Y 2 O 3 manufactured by Daiichi Rare Element Chemical Industries, Ltd.) (Mass ratio) = 30: 50: 20, specific surface area = 60 m 2 / g), and mixed powder of Ce—Zr—Y composite oxide, Al 2 O 3 and WO 3 (Pt + Pd / CeZrY + Al + W) powder carrying platinum and palladium was obtained. <Process 2>
A finished catalyst was obtained in the same manner as in Step 2 of Example 2, except that the Pt + Pd / CeZrY + Al + W powder was used in place of Pt + Pd / CeZrLa powder in Step 2 of Example 2. As a result of analyzing the composition of the obtained catalyst, the contents of Pt and Pd were 2.0 g / L and 1.0 g / L, respectively.
(Comparative Example 1)
<Step 1>
In Step 1 of Example 2, platinum and palladium were supported on alumina in the same manner as in Step 1 of Example 2 except that γ-alumina was used instead of Ce-Zr-La composite oxide (Pt + Pd / Al) powder was obtained.
<Process 2>
A finished catalyst was obtained in the same manner as in Step 2 of Example 2, except that the Pt + Pd / Al powder was used instead of the Pt + Pd / CeZrLa powder in Step 2 of Example 2. As a result of analyzing the composition of the obtained catalyst, the contents of Pt and Pd were 2.0 mass% and 1.0 mass%, respectively.
(Comparative Example 2)
<Step 1>
In the same manner as in Step 2 of Example 2, except that a mixed powder of 96 g of CeO 2 powder and 504 g of ZrO 2 powder was used instead of 600 g of Ce—Zr—La composite oxide, CeO 2 and ZrO carrying platinum and palladium in a mixed powder and 2 to give the (Pt + Pd / Ce + Zr ) powder.
<Process 2>
In Step 2 of Example 2, a finished catalyst was obtained in the same manner as in Step 2 of Example 2 except that the Pt + Pd / Ce + Zr powder was used instead of Pt + Pd / CeZrLa. As a result of analyzing the composition of the obtained catalyst, the contents of Pt and Pd were 2.0 mass% and 1.0 mass%, respectively.
(Examples 7 to 11)
<Step 1>
Pt + Pd / CeZrLa + Al + W powder in the same manner except that the amounts of Ce—Zr—La composite oxide, alumina, and WO 3 were changed so as to have the ratio shown in Table 2 in Step 1 of Example 5. Got.
<Process 2>
In the same manner as in Step 2 of Example 5, a finished catalyst was obtained. As a result of analyzing the composition of the obtained catalyst, the contents of Pt and Pd were 2.0 mass% and 1.0 mass%, respectively.
(Example 12)
In order to evaluate the performance of the catalysts obtained in Examples 1 to 11 and Comparative Examples 1 and 2, the following acetic acid removal test was performed.
<Acetic acid removal test>
Test conditions:
Exhaust gas composition = acetic acid: 5000 ppm, O 2 : 5%, N 2 : balance reactor inlet gas temperature = 280 ° C.
Space velocity (STP) = 30000Hr −1
Formula for calculating acetic acid removal rate:
Acetic acid removal rate (%) = [(reactor inlet acetic acid concentration) − (reactor outlet acetic acid concentration)] / (reactor inlet acetic acid concentration) (× 100)
Table 1 shows the compositions of Examples 1 to 6 and Comparative Examples 1 and 2 and the acetic acid removal rates after 3 hours and 2000 hours. Moreover, about the catalyst of Examples 7-11, the composition and the acetic acid removal rate after 3 hours and 2000 hours are shown in Table 2.
Claims (6)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007082949A JP4700647B2 (en) | 2007-03-27 | 2007-03-27 | Catalyst for treating exhaust gas containing organic acid and treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007082949A JP4700647B2 (en) | 2007-03-27 | 2007-03-27 | Catalyst for treating exhaust gas containing organic acid and treatment method |
Publications (2)
| Publication Number | Publication Date |
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| JP2008238063A true JP2008238063A (en) | 2008-10-09 |
| JP4700647B2 JP4700647B2 (en) | 2011-06-15 |
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| JP2007082949A Expired - Fee Related JP4700647B2 (en) | 2007-03-27 | 2007-03-27 | Catalyst for treating exhaust gas containing organic acid and treatment method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010032598A1 (en) | 2008-09-17 | 2010-03-25 | 日本電気株式会社 | Input unit, method for controlling same, and electronic device provided with input unit |
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| JPH11333294A (en) * | 1998-05-27 | 1999-12-07 | Johnson Matthey Japan Inc | Exhaust gas cleaning catalyst and exhaust gas cleaning |
| JP2001129400A (en) * | 1999-11-05 | 2001-05-15 | Tokyo Gas Co Ltd | Catalyst for oxidation of hydrocarbon with low concentration in exhaust gas and method for preparing it |
| JP2002079053A (en) * | 2000-06-27 | 2002-03-19 | Ict:Kk | Exhaust gas cleaning catalyst |
| JP2002263449A (en) * | 2001-03-09 | 2002-09-17 | Equos Research Co Ltd | Activated carbon filter |
| JP2003190789A (en) * | 2001-02-22 | 2003-07-08 | Matsushita Electric Ind Co Ltd | Purifying catalyst, its manufacturing method and apparatus for purifying gas |
| JP2004216369A (en) * | 2002-12-26 | 2004-08-05 | Matsushita Electric Ind Co Ltd | Co removal catalyst body, production method of co removal catalyst body, hydrogen purification apparatus, and fuel cell system |
| JP2004330106A (en) * | 2003-05-08 | 2004-11-25 | Mitsubishi Gas Chem Co Inc | Catalyst for modifying carbon monoxide and method for modifying carbon monoxide using it |
| WO2005092493A1 (en) * | 2004-03-25 | 2005-10-06 | Tanaka Kikinzoku Kogyo K.K. | Catalyst and method for producing catalyst |
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11333294A (en) * | 1998-05-27 | 1999-12-07 | Johnson Matthey Japan Inc | Exhaust gas cleaning catalyst and exhaust gas cleaning |
| JP2001129400A (en) * | 1999-11-05 | 2001-05-15 | Tokyo Gas Co Ltd | Catalyst for oxidation of hydrocarbon with low concentration in exhaust gas and method for preparing it |
| JP2002079053A (en) * | 2000-06-27 | 2002-03-19 | Ict:Kk | Exhaust gas cleaning catalyst |
| JP2003190789A (en) * | 2001-02-22 | 2003-07-08 | Matsushita Electric Ind Co Ltd | Purifying catalyst, its manufacturing method and apparatus for purifying gas |
| JP2002263449A (en) * | 2001-03-09 | 2002-09-17 | Equos Research Co Ltd | Activated carbon filter |
| JP2004216369A (en) * | 2002-12-26 | 2004-08-05 | Matsushita Electric Ind Co Ltd | Co removal catalyst body, production method of co removal catalyst body, hydrogen purification apparatus, and fuel cell system |
| JP2004330106A (en) * | 2003-05-08 | 2004-11-25 | Mitsubishi Gas Chem Co Inc | Catalyst for modifying carbon monoxide and method for modifying carbon monoxide using it |
| WO2005092493A1 (en) * | 2004-03-25 | 2005-10-06 | Tanaka Kikinzoku Kogyo K.K. | Catalyst and method for producing catalyst |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2010032598A1 (en) | 2008-09-17 | 2010-03-25 | 日本電気株式会社 | Input unit, method for controlling same, and electronic device provided with input unit |
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| JP4700647B2 (en) | 2011-06-15 |
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