JP3314301B2 - Method for producing palladium (Pd) three-way catalyst - Google Patents
Method for producing palladium (Pd) three-way catalystInfo
- Publication number
- JP3314301B2 JP3314301B2 JP36868797A JP36868797A JP3314301B2 JP 3314301 B2 JP3314301 B2 JP 3314301B2 JP 36868797 A JP36868797 A JP 36868797A JP 36868797 A JP36868797 A JP 36868797A JP 3314301 B2 JP3314301 B2 JP 3314301B2
- Authority
- JP
- Japan
- Prior art keywords
- palladium
- way catalyst
- catalyst
- producing
- solution
- 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.)
- Expired - Fee Related
Links
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims description 63
- 239000003054 catalyst Substances 0.000 title claims description 54
- 229910052763 palladium Inorganic materials 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000000919 ceramic Substances 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910001868 water Inorganic materials 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000000306 component Substances 0.000 description 14
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 239000010948 rhodium Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 229910052703 rhodium Inorganic materials 0.000 description 8
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 7
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000003801 milling Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012533 medium component Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000725 suspension Substances 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、パラジウム（Ｐ
ｄ）三元触媒の製造方法に関するものであり、より具体
的にはパラジウム溶液をアルミナに含浸して還元させた
後、これに第三の触媒成分と酸化バリウム等からなる混
合溶液を添加し、ｐＨを調節して反応させた後にミリン
グし、得られた触媒物組成物スラリ−中にセラミックモ
ノリス(monolith)担体を浸してコーティングした後に乾
燥、焼成するパラジウム三元触媒の製造方法に関する。
したがって、従来の白金、ロジウム及びパラジウムから
なる三元触媒の代りに触媒主要成分がパラジウムだけで
構成し、その製造費用を節減し、自動車排気ガスの有害
物質を浄化させる効果がすぐれるパラジウム三元触媒の
製造方法に関するものである。[0001] The present invention relates to palladium (P)
d) a method for producing a three-way catalyst. More specifically, after reducing a palladium solution by impregnating the same with alumina, a mixed solution including a third catalyst component and barium oxide is added thereto, The present invention relates to a method for producing a palladium three-way catalyst in which a reaction is performed by adjusting the pH, milling is performed, a ceramic monolith carrier is immersed in the obtained slurry of the catalyst composition, coated, dried and calcined.
Therefore, instead of the conventional three-way catalyst consisting of platinum, rhodium and palladium, the main component of the catalyst is composed only of palladium, which reduces production costs and has an excellent effect of purifying harmful substances in automobile exhaust gas. The present invention relates to a method for producing a catalyst.
【０００２】[0002]
【従来の技術】従来、三元触媒(three way catalyst)と
しては、自動車等の排気ガスの主要な三つの有害成分で
ある炭化水素系化合物、一酸化炭素及び窒素酸化物（Ｎ
Ｏｘ）と反応してこれらの化合物を排ガス中から同時に
除去する触媒として、Ｐｔ／ＲｈやＰｄ／Ｒｈ、Ｐｔ／
Ｐｄ／Ｒｈ等からなる三元触媒を使用してきた。2. Description of the Related Art Conventionally, three-way catalysts include hydrocarbon compounds, carbon monoxide and nitrogen oxides (N 2), which are three main harmful components of exhaust gas from automobiles and the like.
Pt / Rh, Pd / Rh, Pt / Rh
A three-way catalyst such as Pd / Rh has been used.
【０００３】[0003]
【発明が解決しようとする課題】 しかしながら、前記触
媒は、排気ガスの中に窒素酸化物を還元させる元素とし
てロジウム（Ｒｈ）を使用しているが、ロジウム（Ｒ
ｈ）は高価であり、また耐熱性の面でも問題があった。 [SUMMARY OF THE INVENTION However, the catalyst, the use of the rhodium (Rh) as an element for reducing nitrogen oxides in the exhaust gas, rhodium (R
h) is expensive and has a problem in terms of heat resistance.
【０００４】本発明は、三元三機能パラジウム触媒の製
造において、高価なロジウムを使用せず、また主要触媒
成分としてはパラジウムだけであって経済的であり、か
つ自動車等の排気ガスの有害物質の浄化効果が優れてい
る三元触媒の製造方法を提供することをその目的とす
る。即ち、本発明者は前記のような従来の三元触媒にか
かわる問題点を解決するために、鋭意研究、努力した結
果、高価なロジウムを使用せずパラジウムだけを主要触
媒成分として使用し、これをアルミナに含浸させて更
に、第二、第三の触媒作用を有する元素を含む基材金属
酸化物（ｂａｓｅ ｍｅｔａｌ ｏｘｉｄｅ）と反応さ
せた後、ミリングし、担体にコーティング乾燥、焼成し
て本発明を完成する。 The present invention is economical in the production of a three-way trifunctional palladium catalyst without using expensive rhodium, and is only palladium as a main catalyst component, and is harmful to exhaust gas from automobiles and the like. It is an object of the present invention to provide a method for producing a three-way catalyst having an excellent purification effect. That is, the present inventor has proposed a conventional three-way catalyst as described above.
Intensive research and efforts have been made to resolve
As a result, only palladium is used without using expensive rhodium.
Used as a medium component, impregnated with alumina and
A base metal containing an element having a second or third catalytic action
Reacts with oxides (base metal oxide)
After milling, milling, coating the carrier, drying and firing
To complete the present invention.
【０００５】[0005]
【課題を解決するための手段】本発明は、パラジウム溶
液をアルミナに含浸して還元させた後、酸化セリウム
（ＣｅＯ２）及び第三触媒成分含有溶液を添加し、これ
に硝酸を添加してｐＨを４．５以下に調節した後、粒度
が７〜９μｍであるものが９０％以上となるように粉砕
し、当該粉砕物をセラミックモノリス（ｍｏｎｏｌｉｔ
ｈ）担体にコーティングした後に、乾燥、焼成する製造
方法であって、前記第三触媒成分含有溶液が、全体担体
の見かけ体積１リットル当り５〜６ｇの酸化バリウム、
１〜２ｇの酸化ランタン（Ｌａ ２ Ｏ ３ ）、２３．５〜３
３．５ｇの硝酸を水に溶解したものであることを特徴と
するパラジウム三元触媒の製造方法である。セラミック
モノリス担体は、主として、浄化器の形状に合わせて一
体成形した中空状構造のセラミックス担体であるが、本
発明のコーティング方法はその他の種々の形状の中空セ
ラミックス担体の集合体にも応用できる。このような本
発明を更に具体的に説明すれば次の通りである。According to the present invention, a palladium solution is impregnated with alumina and reduced, and then cerium oxide (CeO 2 ) and a solution containing a third catalyst component are added, and nitric acid is added thereto. After adjusting the pH to 4.5 or less, the particles having a particle size of 7 to 9 μm are pulverized so as to be 90% or more, and the pulverized material is ceramic monolith (monolit).
h) Manufacturing after coating and drying and firing
The method, wherein the third catalyst component-containing solution comprises an entire carrier
5-6 g of barium oxide per liter of apparent volume of
Lanthanum oxide 1~2g (La 2 O 3), 23.5~3
A method for producing a palladium three-way catalyst, characterized by dissolving 3.5 g of nitric acid in water . The ceramic monolith carrier is mainly a ceramic carrier having a hollow structure integrally formed in accordance with the shape of the purifier, but the coating method of the present invention can be applied to an aggregate of hollow ceramic carriers of various other shapes. The present invention will be described more specifically below.
【０００６】[0006]
【発明の実施の形態】本発明は、主要触媒成分としてパ
ラジウムだけからなる三元触媒の製造方法に関するもの
で、本発明の製造方法の概略を示すと添附図面の通りで
ある。 先ず、パラジウム溶液をアルミナに含浸し、こ
れを還元させる。パラジウム溶液としては、通常塩化パ
ラジウムから成るパラジウム化合物を、水、エチルアル
コール、含水アルコール等の可溶性溶媒に溶解させたも
のを使う。パラジウムの使用量は、通常、最終的触媒表
面のＰｄ濃度として、０．１〜５重量％の範囲内の適当
な濃度となるような量（例えば０．５〜３重量％）が使
用される。還元方法は、ヒドラジン水和物をパラジウム
１ｇ当り１．６６ｍｌになるように添加して反応させ
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a three-way catalyst comprising only palladium as a main catalyst component, and the outline of the production method of the present invention is as shown in the accompanying drawings. First, alumina is impregnated with a palladium solution and reduced. As the palladium solution, a solution in which a palladium compound composed of palladium chloride is dissolved in a soluble solvent such as water, ethyl alcohol, or hydrous alcohol is used. The amount of palladium to be used is usually such that the Pd concentration on the final catalyst surface is an appropriate concentration within the range of 0.1 to 5% by weight (for example, 0.5 to 3% by weight). . In the reduction method, hydrazine hydrate is added and reacted so as to be 1.66 ml per 1 g of palladium.
【０００７】酸化セリウムとしては、バルクのＣｅＯ2
と溶解性のＣｅＯ2 で構成された酸化セリウム（ＣｅＯ
2 ）を使用する。この時に酸化セリウムは、パラジウム
とともにアルミナとの化合物形成を抑制して耐熱性を向
上させる役割をはたし、パラジウムの触媒能の長期安定
化に寄与する。その添加量は全体担体の見かけ体積１リ
ットル当り３０〜４０ｇを使用することが望しい。[0007] As cerium oxide, bulk CeO 2
And configured cerium oxide solubility CeO 2 (CeO
2 ) Use. At this time, cerium oxide, together with palladium, plays a role of suppressing the formation of a compound with alumina and improving heat resistance, and contributes to long-term stabilization of palladium's catalytic ability. It is desirable to use 30 to 40 g per liter of apparent volume of the whole carrier.
【０００８】また、これに第三の触媒成分を含有する溶
液を添加するが、該溶液の組成は酸化ランタン（Ｌａ2
Ｏ3 ）、酸化バリウム、硝酸及び水を混合することから
なる。この時に添加される酸化バリウムの含量は、全体
担体の見かけ体積１リットル当り５〜６ｇであり、アル
ミナの耐熱性を好ましく向上させる。酸化ランタンの添
加量は、全体担体の見かけ体積１リットル当り１〜２ｇ
であることがアルミナの耐熱性並びにＣｅＯ2 の触媒効
果であるＰｄ触媒の耐熱性並びにの持続性向上作用並び
に触媒の特性向上のために望しい。また、別途に添加さ
れる硝酸は、第三の触媒成分含有溶液中に添加される
が、その添加量は全体担体の見かけ体積１リットル当り
２３．５〜３３．５ｇであり、所定の水素イオン濃度
（ｐＨ）に調節することが望しい。本発明の反応におい
て、水素イオン濃度は４．５以下であることがコーティ
ングスラリ(coating slurry)製造において、粘度調節そ
の他のために望しい。A solution containing a third catalyst component is added thereto, and the composition of the solution is lanthanum oxide (La 2
O 3 ), barium oxide, nitric acid and water. The content of barium oxide added at this time is 5 to 6 g per liter of apparent volume of the whole carrier, and preferably improves the heat resistance of alumina. The added amount of lanthanum oxide is 1-2 g per liter of apparent volume of the whole carrier.
Is desirable for improving the heat resistance of alumina and the catalytic effect of CeO 2 for improving the heat resistance and sustainability of the Pd catalyst and improving the properties of the catalyst. The separately added nitric acid is added to the third catalyst component-containing solution, and the amount added is 23.5 to 33.5 g per liter of the apparent volume of the whole carrier. It is desirable to adjust the concentration (pH). In the reaction of the present invention, it is desirable that the hydrogen ion concentration be 4.5 or less in order to control the viscosity and the like in the production of a coating slurry.
【０００９】前記酸化バリウムと酸化ランタンのような
金属酸化物は、前記酸化セリウムと同様にパラジウムと
アルミナとの化合を抑制して耐熱性を向上させる役割を
果たしている。このように、第三の触媒成分を含有する
溶液を添加してボールミル(ballmill)によってスラリー
化し、固形分の粒度を調節する。ミリングによって得ら
れる粒子の大きさは、粒子全体の中で７〜９μｍである
ものが９０％以上になるようにすればよい。粒子の大き
さを前記範囲から超過するようにミリングすると、触媒
の初期活性や耐久性に問題を生じる。The metal oxides such as barium oxide and lanthanum oxide, like the cerium oxide, play a role in suppressing the compounding of palladium and alumina and improving the heat resistance. Thus, the solution containing the third catalyst component is added and slurried by a ball mill to control the particle size of the solids. The size of the particles obtained by milling may be such that 90% or more of particles having a size of 7 to 9 μm in the whole particles. If the particle size is milled so as to exceed the above range, a problem occurs in the initial activity and durability of the catalyst.
【００１０】ミリング過程を通じて微粉化された触媒用
組成物を懸濁液（スラリー）状ないし薄いペースト状と
してコーティングするが、本発明では焼成前触媒組成物
のスラリーにセラミックmonolith担体（一体成型の大型
成形セラミック担体から小形の各種形状の中空筒状また
はペレット状の組立または集合セラミック担体までを含
む）を浸してコーティングする。本発明におけるコーテ
ィングは、segregation 効果（微粉の分離吸着効果）を
利用した一回コーティングとしているが、更に、該組成
物の適宜の量を担体の所望部位に充分に付着させるため
に２回コーティングをする場合もある。何れにせよ、前
記触媒組成物の微粉は触媒担体表面へ付着性が良いの
で、必要部分に充分に塗布することが可能であるので、
単一コーティングで充分なる塗布効果をあげ、塗布作業
の効率を極大化させることができ、製品触媒の触媒性能
を充分に向上させることができる。即ち、本発明におけ
るコーティングでは、所望の触媒成分組成物スラリーへ
のモノリス担体の投入またはディッピングという方法に
よって、スラリーを担体表面に充分広範囲に拡散させる
事ができ、所望成分を含有する触媒成分組成物を触媒担
体の所望の位置に比較的均一にコーティングすることが
できる。[0010] The catalyst composition finely divided through the milling process is coated as a suspension (slurry) or a thin paste. According to the present invention, the slurry of the catalyst composition before calcining is coated on a ceramic monolithic carrier (a large monolithic molding). From the molded ceramic carrier to the small-sized hollow cylindrical or pellet-shaped assembled or assembled ceramic carrier (including ceramic carriers), it is dipped and coated. The coating in the present invention is a one-time coating utilizing the segregation effect (the effect of separating and adsorbing fine powder), and is further applied twice in order to sufficiently attach an appropriate amount of the composition to a desired site of the carrier. In some cases. In any case, since the fine powder of the catalyst composition has good adhesion to the surface of the catalyst carrier, it can be sufficiently applied to necessary portions,
A single coating can provide a sufficient coating effect, maximize the efficiency of the coating operation, and sufficiently improve the catalytic performance of the product catalyst. That is, in the coating in the present invention, the slurry can be sufficiently diffused to the surface of the carrier by a method of adding or dipping the monolith carrier into the slurry of the desired catalyst component composition, and the catalyst component composition containing the desired component Can be relatively uniformly coated on desired positions of the catalyst carrier.
【００１１】前記のような本発明の方法によってコーテ
ィングされた触媒成分組成物を乾燥、焼成する。乾燥
は、乾燥炉で約１５０℃の温度で２時間にわたって行な
われる。焼成する時には電気炉で４５０〜５５０℃の温
度で４２時間にわたって焼成させる。この時に乾燥條件
及び焼成時間が前記範囲を超過すると、コーティング層
の亀裂発生及び有害な化合物が形成される問題がある。
本発明の乾焼並びに焼成には、不活性（例えば、窒素ま
たはアルゴン）雰囲気または、還元性（例えば、一酸化
炭素または水素含有不活性気体）雰囲気が好ましく用い
られる。The catalyst component composition coated by the method of the present invention as described above is dried and calcined. Drying is performed in a drying oven at a temperature of about 150 ° C. for 2 hours. When firing, firing is performed in an electric furnace at a temperature of 450 to 550 ° C. for 42 hours. At this time, if the drying conditions and the baking time exceed the above ranges, there is a problem that cracks are generated in the coating layer and harmful compounds are formed.
An inert (eg, nitrogen or argon) atmosphere or a reducing (eg, carbon monoxide or hydrogen-containing inert gas) atmosphere is preferably used for the drying and baking of the present invention.
【００１２】[0012]
【発明の効果】前記方法により製造されたパラジウム三
元触媒は、自動車排気ガスの有害物質である炭化水素系
物質、一酸化炭素及び窒素酸化物を同時に浄化する三元
触媒としてその浄化効率は従来の三元触媒と比較して、
炭化水素と一酸化炭素の浄化率は、同等以上の水準であ
り、かつ窒素酸化物の浄化効率は７０％以上であった。
また、本発明の三元酸機能触媒は、従来の三元触媒のよ
うにロジウムを添加しないので、その製造コストを節減
することができる。The palladium three-way catalyst produced by the above-described method is a three-way catalyst for simultaneously purifying hydrocarbon-based substances, carbon monoxide and nitrogen oxides, which are harmful substances of automobile exhaust gas, and has a purification efficiency of conventional. Compared to the three-way catalyst,
The purification rates of hydrocarbons and carbon monoxide were equivalent or higher, and the purification efficiency of nitrogen oxides was 70% or more.
Further, the ternary acid functional catalyst of the present invention does not add rhodium unlike the conventional three-way catalyst, so that the production cost can be reduced.
【００１３】したがって、本発明の方法により製造され
たパラジウム三元触媒は、自動車排気ガスの浄化、ディ
ーゼルエンジン排ガス浄化用触媒及び産業用の排気ガス
浄化用触媒として幅広く使用することができる極めて優
秀かつ有用な自動車並びに産業用の公害防止用触媒であ
る。Therefore, the three-way palladium catalyst produced by the method of the present invention is extremely excellent and can be widely used as a catalyst for purifying automobile exhaust gas, a catalyst for purifying exhaust gas of diesel engines and a catalyst for purifying industrial exhaust gas. It is a useful anti-pollution catalyst for automobiles and industries.
【図１】図１は、本発明によるパラジウム三元触媒の製
造方法を概略的に示す工程図である。FIG. 1 is a process diagram schematically showing a method for producing a palladium three-way catalyst according to the present invention.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 21/00 - 38/74 B01D 53/94 F01N 3/28 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 7 , DB name) B01J 21/00-38/74 B01D 53/94 F01N 3/28
Claims (5)
元させた後、酸化セリウム（ＣｅＯ２）及び第三触媒成
分含有溶液を添加し、これに硝酸を添加してｐＨを４．
５以下に調節した後、粒度が７〜９μｍであるものが９
０％以上となるように粉砕し、当該粉砕物をセラミック
モノリス（ｍｏｎｏｌｉｔｈ）担体にコーティングした
後に、乾燥、焼成する製造方法であって、 前記第三触媒成分含有溶液が、全体担体の見かけ体積１
リットル当り５〜６ｇの酸化バリウム、１〜２ｇの酸化
ランタン（Ｌａ ２ Ｏ ３ ）、２３．５〜３３．５ｇの硝酸
を水に溶解したものである ことを特徴とするパラジウム
三元触媒の製造方法。After reducing a palladium solution by impregnating the same with alumina, a solution containing cerium oxide (CeO 2 ) and a third catalyst component is added, and nitric acid is added to the solution to adjust the pH to 4.
After adjustment to 5 or less, 9 particles having a particle size of 7 to 9 μm
0% or more, a pulverized material is coated on a ceramic monolith (monolith) carrier, and then dried and calcined , wherein the third catalyst component-containing solution has an apparent volume of 1
5-6 g of barium oxide, 1-2 g of oxidation per liter
Lanthanum (La 2 O 3), nitric acid of 23.5~33.5g
A method for producing a palladium three-way catalyst, characterized in that is dissolved in water .
ｒａｚｉｎｅ ｈｙｄｒａｔｅ）をパラジウム１ｇ当り
１．５〜２．０ｍｌになるように添加して行なわれるこ
とを特徴とする請求項１記載のパラジウム三元触媒の製
造方法。2. The method according to claim 1, wherein the reduction is carried out using hydrazine hydrate (hyd
2. The method for producing a palladium three-way catalyst according to claim 1, wherein the hydration is carried out by adding 1.5 to 2.0 ml per 1 g of palladium.
記酸化セリウム２０〜４０ｇを添加することを特徴とす
る請求項１記載のパラジウム三元触媒の製造方法。3. The method for producing a palladium three-way catalyst according to claim 1, wherein 20 to 40 g of the cerium oxide is added per 1 liter of apparent volume of the whole carrier.
時間にわたって行なわれることを特徴とする請求項１記
載のパラジウム三元触媒の製造方法。 4. The method according to claim 1, wherein the drying is performed at 100 to 200 ° C. for 1 to 2 hours.
The method for producing a palladium three-way catalyst according to claim 1, wherein the method is performed over a period of time .
時間にわたって行なわれることを特徴とする請求項１記
載のパラジウム三元触媒の製造方法。 5. The method according to claim 1, wherein the firing is performed at 450 to 600 ° C. for 2 to 5 hours.
The method for producing a palladium three-way catalyst according to claim 1, wherein the method is performed over a period of time .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36868797A JP3314301B2 (en) | 1997-12-26 | 1997-12-26 | Method for producing palladium (Pd) three-way catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36868797A JP3314301B2 (en) | 1997-12-26 | 1997-12-26 | Method for producing palladium (Pd) three-way catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11207180A JPH11207180A (en) | 1999-08-03 |
| JP3314301B2 true JP3314301B2 (en) | 2002-08-12 |
Family
ID=18492479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP36868797A Expired - Fee Related JP3314301B2 (en) | 1997-12-26 | 1997-12-26 | Method for producing palladium (Pd) three-way catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3314301B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4556716B2 (en) * | 2004-03-22 | 2010-10-06 | パナソニック株式会社 | Exhaust gas purification catalyst, production method thereof, exhaust gas purification material, and exhaust gas purification system |
| EP1916029B1 (en) * | 2006-10-23 | 2014-06-04 | Haldor Topsoe A/S | Method and apparatus for the purifiction of exhaust gas from a compression ignition engine |
| CN104661746B (en) | 2012-09-18 | 2017-07-04 | 国立研究开发法人科学技术振兴机构 | Use the catalyst of PdRu based solid solution alloys particulates |
-
1997
- 1997-12-26 JP JP36868797A patent/JP3314301B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11207180A (en) | 1999-08-03 |
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