JPH0278437A - Method for manufacturing exhaust gas purification catalyst - Google Patents
Method for manufacturing exhaust gas purification catalystInfo
- Publication number
- JPH0278437A JPH0278437A JP63232995A JP23299588A JPH0278437A JP H0278437 A JPH0278437 A JP H0278437A JP 63232995 A JP63232995 A JP 63232995A JP 23299588 A JP23299588 A JP 23299588A JP H0278437 A JPH0278437 A JP H0278437A
- Authority
- JP
- Japan
- Prior art keywords
- carrier
- exhaust gas
- catalyst
- platinum group
- impregnated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 238000000746 purification Methods 0.000 title abstract description 8
- 238000000034 method Methods 0.000 title description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 38
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 13
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 7
- 239000003125 aqueous solvent Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 6
- 230000002378 acidificating effect Effects 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 2
- 230000002542 deteriorative effect Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 16
- 239000010948 rhodium Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910052703 rhodium Inorganic materials 0.000 description 7
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910002090 carbon oxide Inorganic materials 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000010718 Oxidation Activity Effects 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 150000003283 rhodium Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N Nitrogen oxide(NO) Natural products O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005470 impregnation Methods 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
- 239000010410 layer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- -1 platinum group metals Chemical class 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野］
本発明は、排ガス浄化用触媒の製造方法、更に詳しくは
白金族元素を無機質担体に担持させる方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing an exhaust gas purifying catalyst, and more particularly to a method for supporting a platinum group element on an inorganic carrier.
〔従来技術］
従来、無機質担体に白金、パラジウム、ロジウムなどの
白金族元素を担持した触媒は、内燃機関から排出される
一酸化炭素（ＣＯ）、炭化水素（ＨＣ）、窒素酸化物（
ＮＯｘ）等の有害成分を浄化するための触媒として実用
化されている。[Prior Art] Conventionally, catalysts in which platinum group elements such as platinum, palladium, and rhodium are supported on inorganic carriers have been used to reduce carbon monoxide (CO), hydrocarbons (HC), and nitrogen oxides (
It has been put into practical use as a catalyst to purify harmful components such as NOx).
そして、これら触媒の製造方法としては、白金族塩を酸
性水溶液に溶解した溶液を用いて、無機質担体に含浸さ
せる方法が一般的に使用されている。しかし、高価な白
金族を効率良く高活性に働かせるためには、無機質担体
上の表層部にのみこれら触媒成分である白金族元素を高
密度、高分散に担持することが望ましい。A commonly used method for manufacturing these catalysts is to impregnate an inorganic carrier with a solution prepared by dissolving a platinum group salt in an acidic aqueous solution. However, in order to make expensive platinum group metals work efficiently and with high activity, it is desirable to support platinum group elements, which are catalyst components, in a high density and highly dispersed manner only on the surface layer of an inorganic carrier.
このため、従来、含浸溶液を種々工夫した触媒の製造方
法が開示されている。For this reason, conventionally, methods for producing catalysts using various impregnating solutions have been disclosed.
例えば特公昭４７−３５６７０号公報においては、パラ
ジウム塩の酸性水溶液に、炭酸カリウムや炭酸ナトリウ
ムのような炭酸アルカリを加えてｐＨ２，０〜４．８に
調整し、該溶液を担体粒子表面に含浸させ、焼成して、
パラジウムを担持する方法が提案されている。For example, in Japanese Patent Publication No. 47-35670, an alkali carbonate such as potassium carbonate or sodium carbonate is added to an acidic aqueous solution of palladium salt to adjust the pH to 2.0 to 4.8, and the solution is impregnated onto the surface of carrier particles. Let it burn, then bake it.
A method of supporting palladium has been proposed.
また、特公昭５Ｂ−１８１４６号公報においては、水溶
性ロジウム塩の水溶液に苛性ソーダ又は苛性カリを添加
してｐＨ１０以上の水溶液に調整し、該溶液をシリカ系
又はチタニア系の担体表面に含浸させ、焼成して、ロジ
ウムを担持させる方法が開示されている。In addition, in Japanese Patent Publication No. 5B-18146, caustic soda or caustic potassium is added to an aqueous solution of a water-soluble rhodium salt to adjust the pH to 10 or more, and the solution is impregnated onto the surface of a silica-based or titania-based carrier, followed by sintering. A method for supporting rhodium is disclosed.
更に、特公昭６０−５０４９０号公報においては５硝酸
パラジウムにクエン酸アンモニウムを添加した溶液を用
い、該溶液を担体に含浸させ５焼成して、パラジウムを
担体表面に担持する方法が開示されている。Furthermore, Japanese Patent Publication No. 60-50490 discloses a method in which palladium is supported on the surface of a carrier by impregnating a carrier with a solution prepared by adding ammonium citrate to palladium nitrate and firing the solution. .
一方、触媒担体としては、Ｃｏ、ＨＣの浄化活性、即ち
酸化活性の高いべＣブスカイト構造を有するＬａ＋−ｘ
ｓｒｘｃｏｏｚを用いることが望まれている。On the other hand, as a catalyst carrier, La + -
It is desired to use srxcooz.
（解決しようとする課題）
しかしながら、上記ペロプスカイト構造の担体を用いて
、前記従来の製造方法により得た排ガス浄化用触媒は、
パラジウム或いはロジウムの触媒特性が消失し、排ガス
中のＮＯｘの還元活性が低下してしまう、かかる活性低
下の原因は、前記のごとく酸性水溶液を担体に含浸させ
た際に、担体の一部が前記パラジウム塩又はロジウム塩
と反応して、パラジウム、ロジウムの特性を消失させて
いるためと考えられる。(Problem to be Solved) However, the catalyst for exhaust gas purification obtained by the conventional manufacturing method using the carrier having the above-mentioned perovskite structure is
The catalytic properties of palladium or rhodium disappear and the NOx reducing activity in the exhaust gas decreases.The reason for this decrease in activity is that when the carrier is impregnated with the acidic aqueous solution as described above, part of the carrier becomes This is thought to be due to the reaction with palladium salts or rhodium salts, causing the properties of palladium and rhodium to disappear.
即ち、触媒調整用のパラジウム、白金等の責金族溶液は
、安定性等の面から酸性溶液が多く用いられている。こ
のような溶液を、そのまま酸化活性の優れたＬａ＋−ｘ
ｓｒｘｃｏＯ，等のような塩基性物質を含む欠陥ペロプ
スカイト型の複合酸化物担体に担持すると、塩基性物質
である欠陥ペロプスカイト構造の中の■、ａ、Ｓｒが溶
は出し、欠陥ペロプスカイトの一部が分解する。そして
、ペロプスカイト自身の酸化活性が低下し、さらに遊離
生成したＳｒは、Ｐｄと反応して分散性の低い。That is, acidic solutions are often used for catalyst preparation solutions of metals such as palladium and platinum from the viewpoint of stability. Such a solution can be directly converted into La+-x, which has excellent oxidation activity.
When supported on a defective perovskite-type composite oxide support containing a basic substance such as srxcoO, etc., the basic substances (■, a, and Sr in the defective perovskite structure) are eluted, and the defective perovskite is dissolved. Part of it decomposes. Then, the oxidation activity of the perovskite itself decreases, and the liberated Sr reacts with Pd, resulting in poor dispersibility.
Ｐ ｄｘ Ｓ ｒ Ｏａ （Ｘ線回折による平均粒子
は〜１３０人）を形成して、自動車排気ガス中のＣ０１
ＩＣ，ＮＯｘの浄化能に低下をきたす。P dx S r Oa (average particle size by X-ray diffraction is ~130) to form CO1 in automobile exhaust gas
IC, NOx purification ability decreases.
本発明はかかる従来の問題点に鑑み、パラジウム、ロジ
ウム等の白金族元素の浄化特性を低下させることがない
、排ガス浄化用触媒の製造方法を提供しようとするもの
である。In view of these conventional problems, the present invention seeks to provide a method for producing an exhaust gas purifying catalyst that does not reduce the purifying properties of platinum group elements such as palladium and rhodium.
本発明は、白金、パラジウム等の白金族元素の一種又は
二種以上の元素を無機質担体に担持するに際し、白金族
塩を非水溶媒に溶解させた溶液を上記無機質担体に含浸
させ、焼成することを特徴とする排ガス浄化用触媒の製
造方法にある。In the present invention, when supporting one or more platinum group elements such as platinum and palladium on an inorganic carrier, the inorganic carrier is impregnated with a solution in which a platinum group salt is dissolved in a non-aqueous solvent, and then calcined. A method for producing an exhaust gas purifying catalyst is provided.
しかして３本発明において注目すべきことは。However, there are three things to note about the present invention.
上記白金族元素を担体に担持するに当り、上記白金族元
素は塩の状態において、しかも非水溶媒に溶解させてい
ることである。そして、かかる非水溶媒の溶液を、担体
に含浸させ、焼成して排ガス浄化用触媒としていること
である。In supporting the platinum group element on the carrier, the platinum group element is in the form of a salt and is dissolved in a non-aqueous solvent. Then, a carrier is impregnated with the solution of the non-aqueous solvent and fired to produce an exhaust gas purifying catalyst.
本発明において、白金族元素とは、ルテニウム（Ｒｕ）
、ロジウム（Ｒｈ）、パラジウム（Ｐｄ）、オスミウム
（Ｏｓ）、イリジウム（Ｉｒ）。In the present invention, the platinum group element is ruthenium (Ru)
, rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir).
白金（ＰＬ）、Ｒｅ （レニウム）をいう。そして。Platinum (PL) refers to Re (rhenium). and.
これら元素のうち一種又は二種以上を後述する無機質担
体に担持させる。One or more of these elements are supported on the inorganic carrier described below.
白金族塩としては１例えば酢酸パラジウムのごとき酢酸
塩などがある。なお、塩素（ｃｆｆｉ）、カリウム（Ｋ
）、ナトリウム（Ｎａ）を含む塩は。Examples of platinum group salts include acetate salts such as palladium acetate. In addition, chlorine (cffi), potassium (K
), salts containing sodium (Na).
触媒特性を低下させるおそれがある。There is a risk of deteriorating catalyst properties.
無機質担体としては、 ＡＩ！、、Ｏ３などの両性酸化
物、Ｓｉｎｇなどの酸性酸化物、ＣｅＯ，、Ｙｔ Ｏｓ
、 Ｌａｇ Ｃ３、Ｌｕｘ ｏｎ 、 Ｎｄｚ ０３
などの塩基性希土類酸化物、ＭｇＯ，Ｃａｂ、ＳｒＯ，
Ｂ ａ Ｏ，Ｔ ｈ Ｏｔなどの塩基性酸化物などがあ
り、これらの一種又は二種以上からなるものを用いる。As an inorganic carrier, AI! , Amphoteric oxides such as O3, Acidic oxides such as Sing, CeO, YtOs
, Lag C3, Lux on, Ndz 03
Basic rare earth oxides such as MgO, Cab, SrO,
There are basic oxides such as B a O and T h Ot, and one or two or more of these oxides are used.
この中、上記担体として、塩基性物質である塩基性希土
類酸化物、塩基性酸化物を用いた場合には、特にＣｅ、
ＨＣに対する浄化活性に優れた排ガス浄化用触媒を得る
ことができる。かかる塩基性物質の１ｕ体としては、Ｃ
ｅＯ□、ＭｇＯ等の単体物の他、Ｌａ＋−ｘｓｒｘｃｏ
ｏｚ 、Ｌａ＋−ｘｓｒｘＦｅｏ３などの複合酸化物が
ある。Among these, when a basic substance such as a basic rare earth oxide or a basic oxide is used as the carrier, in particular Ce,
It is possible to obtain an exhaust gas purifying catalyst that has excellent purification activity against HC. The 1u form of such a basic substance is C
In addition to simple substances such as eO□ and MgO, La+-xsrxco
There are composite oxides such as oz, La+-xsrxFeo3.
また、上記無機質担体としては、上記担体材料の粉末を
成形したペレット状態、ハニカム状態。Further, the inorganic carrier may be in the form of pellets or honeycomb formed by molding the powder of the carrier material.
或いは上記粉末を金属担体上にコートしたものなどがあ
る。Alternatively, the above powder may be coated on a metal carrier.
また、白金族塩を熔解させる非水溶媒としては。Also, as a non-aqueous solvent for dissolving platinum group salts.
アセトン１ メタノール、エタノール、ベンゼンなどが
ある。Acetone 1 Methanol, ethanol, benzene, etc.
無機質担体への上記溶液の含浸は、溶液中に無機質担体
を浸漬することなどにより行う、含浸後は、乾燥し、高
温に加熱して焼成する。焼成により、酢酸パラジウム等
の白金族塩はＰｄ等の白金族元素又はその酸化物となり
、触媒活性を発渾する。The inorganic carrier is impregnated with the above solution by immersing the inorganic carrier in the solution. After the impregnation, the inorganic carrier is dried, heated to a high temperature, and fired. By calcination, a platinum group salt such as palladium acetate becomes a platinum group element such as Pd or its oxide, and develops catalytic activity.
〔作用及び効果］
本発明においては、白金族元素を無機質担体に担持する
に当り、白金族塩を非水溶媒に溶解し。[Functions and Effects] In the present invention, when supporting a platinum group element on an inorganic carrier, a platinum group salt is dissolved in a nonaqueous solvent.
その溶液を無機質担体に含浸させ１次いで焼成している
。そのため、白金族塩の溶液は、前記従来のごとく酸性
を呈していない、それ故、白金族塩と無機質担体とは反
応することがなく、排ガス中のＣｏ、ＨＣ，ＮＯｘに対
する触媒活性が低下することがない。The solution is impregnated into an inorganic carrier and then fired. Therefore, the platinum group salt solution does not exhibit acidity as in the conventional case, and therefore, the platinum group salt and the inorganic carrier do not react, and the catalytic activity against Co, HC, and NOx in the exhaust gas decreases. Never.
特に１本発明において、無機質担体としてＬａ＋−ｘｓ
ｒχＣｏｏ、のごとき塩基性物質を含む欠陥ペロブスカ
イト型複合酸化物を用いた場合には。In particular, in one aspect of the present invention, La+-xs is used as an inorganic carrier.
When a defective perovskite complex oxide containing a basic substance such as rχCoo is used.
従来では得ることができなかった高活性の排ガス浄化用
触媒を得ることができる。つまり、ＣＯｌ“ＨＣに対す
る酸化活性が大きく、かつＮＯｘの還元活性も高い排ガ
ス浄化用触媒を製造することができる０例えば、欠陥ペ
ロブスカイト構造を有するＬａ６．ａ Ｓｒｏ、ｚ Ｃ
ｏｏｓを用いた場合５その酸化活性はそのまま維持され
、含浸パラジウムは高分散性のＰｄＯ（平均粒径〜５０
人）として爪体上に担持され、Ｃｏ、ＨＣ，ＮＯｘに対
して高い活性を示す。A highly active exhaust gas purifying catalyst that could not be obtained conventionally can be obtained. In other words, it is possible to produce an exhaust gas purifying catalyst that has a high oxidation activity for CO1 and HC and a high reduction activity for NOx.
When using PdO5, its oxidation activity remains intact, and the impregnated palladium contains highly dispersed PdO (average particle size ~50
It is carried on the nail body as a human) and shows high activity against Co, HC, and NOx.
第１実施例
白金族塩としての酢酸パラジウム（Ｐｄ （ＣＨｘ Ｃ
００）ｔ ）５ ｇを、非水溶媒としてのアセトン５０
０−に溶解して非水系溶液を準備した。−方、クエン酸
錯体を前駆体として製作したＬａｏ。First Example Palladium acetate (Pd (CHx C
00)t)5 g of acetone as a non-aqueous solvent
0- to prepare a non-aqueous solution. On the other hand, Lao was produced using a citric acid complex as a precursor.
＠ Ｓｒｏ、ｚ Ｃｏｏｓの粉末を準備した０次いで。@ Sro, z Coos powder was prepared.
該粉末を前記溶液中に浸漬し１次いで取り出し。The powder was immersed in the solution and then taken out.
室温で５時間乾燥後さらに６００°Ｃ，３時間、大気中
で焼成した。これにより、上記粉末担体に対して０．１
５重量（ｗＬ）％のＰｄを担持させた触媒（Ｎα１）を
調整した。After drying at room temperature for 5 hours, it was further fired at 600°C for 3 hours in the air. As a result, 0.1
A catalyst (Nα1) on which 5% by weight (wL) of Pd was supported was prepared.
第２実施例
白金族塩として、２価のロジウム（Ｒｈ）を用いたジア
クア四酢酸二ロジウム（ＩＴ）５ｇを、非水溶媒として
のメタノール５００ｉに溶解して非水系溶液を準備した
。５次いで、第１実施例と同様のＬａｏ、＊ Ｓ ｒｅ
、ｔ Ｃｏ０＝の粉末を上記溶液中に浸漬し、取り出し
、室温で５時間乾燥後さらに６００°Ｃ，３時間、大気
中で焼成した。これにより、上記粉末担体に対して０．
１５ｗｔ％のＲｈを担持させた触媒（階２）を調整した
。Second Example A non-aqueous solution was prepared by dissolving 5 g of dirhodium diaquatetraacetate (IT) using divalent rhodium (Rh) as a platinum group salt in 500 i of methanol as a non-aqueous solvent. 5 Next, Lao, *S re similar to the first example
, tCo0= powder was immersed in the above solution, taken out, dried at room temperature for 5 hours, and then calcined at 600°C for 3 hours in the air. This results in 0.0% for the powder carrier.
A catalyst (floor 2) on which 15 wt% of Rh was supported was prepared.
比較例
白金族塩として硝酸パラジウムを用い５その水溶液（Ｐ
ｄ１度５ｗｔ％）を蒸留水で１０倍に稀釈した水溶液（
ｐｉ−Ｉｔ）を準備した０次いで、該水溶液中に第１実
施例と同様のＬａｏ、ｓ Ｓｒｏ、ｘＣｏｏｓの粉末を
浸漬し、上記溶液を含浸させた。Comparative Example Using palladium nitrate as the platinum group salt, an aqueous solution thereof (P
An aqueous solution (5wt%) diluted 10 times with distilled water (
Next, the same powders of Lao, s Sro, and x Coos as in the first example were immersed in the aqueous solution to impregnate it with the above solution.
その後、１００°Ｃ，１０時間乾燥し、さらに６０Ｑ’
Ｃ，３時間、大気中で焼成した。これにより。After that, it was dried at 100°C for 10 hours, and further dried at 60Q'
C. Sintered in air for 3 hours. Due to this.
０．１５ｗｔ％のＰｄを担持させた比較触媒（漱Ｃ１）
を調整した。Comparative catalyst supporting 0.15wt% Pd (Sob C1)
adjusted.
上記２つの実施例及び比較例により得た触媒について２
次の試験、評価を行った。その結果を下表に示す。Regarding the catalysts obtained in the above two examples and comparative examples 2
The following tests and evaluations were conducted. The results are shown in the table below.
（Ａ）耐久試験
第１及び第２実施例及び比較例で調整した各触媒粉末に
つき、これを加圧成形して、直径１〜４■ノベレフト状
触媒とした０次いで、このベレント状触媒を排気モデル
ガス雰囲気下に置き、９００°Ｃ，５時間の耐久試験を
行った。ガス組成は。(A) Endurance test Each of the catalyst powders prepared in the first and second examples and comparative examples was pressure-molded to form a catalyst in the form of a 1 to 4 cm diameter. A durability test was conducted at 900°C for 5 hours under a model gas atmosphere. What is the gas composition?
内燃機関の排気組成に近い、０．５８％ＣＯ，Ｏ。0.58% CO, O, close to the exhaust composition of an internal combustion engine.
５０％Ｏ，，０，１９％Ｈ！、１１．８１％ＣＯ、，３
，３％Ｈ８０，残部Ｎ２からなるもので。50%O,,0,19%H! , 11.81% CO, ,3
, 3% H80, balance N2.
この基本組成のガスに対してＯ工及びＣＯガスを若干間
欠的に注入して、ガス組成を変動させた。O gas and CO gas were slightly intermittently injected into the gas having this basic composition to vary the gas composition.
（Ｂ）活性評価
上記耐久試験を行った触媒について、４００°Ｃにおけ
る。−酸化炭素（ＣＯ）、プロピレン（Ｃ、Ｈ６）及び
−酸化窒素（ＮＯ）の浄化率を測定した。測定に用いた
ガス組成は、０．１２％Ｎ０１０．７０％Ｃｏ、０．１
６％Ｃ，Ｈ６，３％Ｈ。(B) Activity evaluation The catalysts subjected to the above durability test were evaluated at 400°C. - Purification rates of carbon oxide (CO), propylene (C, H6), and nitrogen oxide (NO) were measured. The gas composition used in the measurement was 0.12%N0, 0.70%Co, 0.1
6% C, H6, 3% H.
０．０．６５％Ｏ，，０，２３％Ｈ，，１０％ＣＯ□、
残部Ｎｔからなるもので、該基本組成のガスに対して４
％の変動を与えるため、２秒間隔でＣＯ及び０２を注入
した。なお、触媒層中への排ガス送入は、空間速度（Ｓ
Ｖ）３００００ｈｒ−’とし、使用したサンプル量は７
−であった。0.0.65%O,,0.23%H,,10%CO□,
The remainder consists of Nt, and 4% for the gas with the basic composition.
CO and 02 were injected at 2 second intervals to give a % variation. Note that the exhaust gas is fed into the catalyst layer at a space velocity (S
V) 30000hr-', the amount of sample used was 7
-It was.
上表より知られるごとく１本発明により得られた触媒（
Ｎｌ１１．２）は、比較例の触媒（Ｃ１）に比べ、耐久
試験後においても高い５浄化活性を維持していることが
分る。As can be seen from the above table, one catalyst obtained according to the present invention (
It can be seen that Nl11.2) maintains a higher 5 purification activity even after the durability test than the catalyst (C1) of the comparative example.
Claims (2)
以上の元素を無機質担体に担持するに際し、白金族塩を
非水溶媒に溶解させた溶液を上記無機質担体に含浸させ
、焼成することを特徴とする排ガス浄化用触媒の製造方
法。(1) When supporting one or more platinum group elements such as platinum and palladium on an inorganic carrier, the inorganic carrier is impregnated with a solution of a platinum group salt dissolved in a non-aqueous solvent and fired. A method for producing an exhaust gas purifying catalyst, characterized by:
体は塩基性物質の一種又は二種以上よりなることを特徴
とする排ガス浄化用触媒の製造方法。(2) The method for producing an exhaust gas purifying catalyst according to claim 1, wherein the inorganic carrier is made of one or more basic substances.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63232995A JPH0278437A (en) | 1988-09-16 | 1988-09-16 | Method for manufacturing exhaust gas purification catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63232995A JPH0278437A (en) | 1988-09-16 | 1988-09-16 | Method for manufacturing exhaust gas purification catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0278437A true JPH0278437A (en) | 1990-03-19 |
Family
ID=16948152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63232995A Pending JPH0278437A (en) | 1988-09-16 | 1988-09-16 | Method for manufacturing exhaust gas purification catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0278437A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009255064A (en) * | 2008-03-21 | 2009-11-05 | Toyota Central R&D Labs Inc | Catalyst for cleaning automobile exhaust gas and manufacturing method of the same |
| JP2011083765A (en) * | 2009-06-30 | 2011-04-28 | Toyota Central R&D Labs Inc | Catalyst for cleaning automobile exhaust gas, and method for manufacturing the same |
| JP2022115969A (en) * | 2016-11-14 | 2022-08-09 | リサーチ トライアングル インスティテュート | Perovskite catalyst and its use |
-
1988
- 1988-09-16 JP JP63232995A patent/JPH0278437A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009255064A (en) * | 2008-03-21 | 2009-11-05 | Toyota Central R&D Labs Inc | Catalyst for cleaning automobile exhaust gas and manufacturing method of the same |
| JP2011083765A (en) * | 2009-06-30 | 2011-04-28 | Toyota Central R&D Labs Inc | Catalyst for cleaning automobile exhaust gas, and method for manufacturing the same |
| JP2022115969A (en) * | 2016-11-14 | 2022-08-09 | リサーチ トライアングル インスティテュート | Perovskite catalyst and its use |
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