JPH0716461A - Catalyst for purification of exhaust gas from alcohol fuel engine - Google Patents
Catalyst for purification of exhaust gas from alcohol fuel engineInfo
- Publication number
- JPH0716461A JPH0716461A JP5157257A JP15725793A JPH0716461A JP H0716461 A JPH0716461 A JP H0716461A JP 5157257 A JP5157257 A JP 5157257A JP 15725793 A JP15725793 A JP 15725793A JP H0716461 A JPH0716461 A JP H0716461A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- zirconium oxide
- exhaust gas
- aldehyde
- alcohol
- 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 53
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000000446 fuel Substances 0.000 title claims abstract description 12
- 238000000746 purification Methods 0.000 title abstract description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 5
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 239000010948 rhodium Substances 0.000 claims description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract description 30
- 239000011247 coating layer Substances 0.000 abstract description 7
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 6
- 238000002485 combustion reaction Methods 0.000 abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 2
- 230000001476 alcoholic effect Effects 0.000 abstract 1
- 230000001473 noxious effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000002002 slurry Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910052878 cordierite Inorganic materials 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
- 238000010304 firing Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- -1 platinum group metals Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はアルコール及び含アルコ
ール燃料を用いた自動車等の内燃機関から排出される排
ガス中の有害成分である炭化水素（ＨＣ）、一酸化炭素
（ＣＯ）、窒素酸化物（ＮＯｘ）、アルデヒドを効率よ
くかつ同時に浄化するアルコール燃料機関の排ガス浄化
用触媒に関する。FIELD OF THE INVENTION The present invention relates to hydrocarbon (HC), carbon monoxide (CO), and nitrogen oxide which are harmful components in exhaust gas discharged from internal combustion engines such as automobiles using alcohol and alcohol-containing fuel. The present invention relates to an exhaust gas purifying catalyst for an alcohol fuel engine, which purifies (NOx) and aldehyde efficiently and simultaneously.
【０００２】[0002]
【従来の技術】従来、内燃機関から排出される排ガス中
のＨＣ、ＣＯ、ＮＯｘを浄化する排ガス浄化用触媒は種
々提案され、白金（Ｐｔ）、パラジウム（Ｐｄ）および
ロジウム（Ｒｈ）等の白金族金属により三成分同時に除
去する三元触媒などが知られている。さらにアルコール
燃料の場合、それに加えて内燃機関でのアルコールの部
分酸化によるアルデヒド類も並行して浄化することが必
要となる。2. Description of the Related Art Conventionally, various exhaust gas purifying catalysts for purifying HC, CO, and NOx in exhaust gas discharged from an internal combustion engine have been proposed, and platinum such as platinum (Pt), palladium (Pd) and rhodium (Rh) has been proposed. A three-way catalyst that removes three components at the same time by a group metal is known. Further, in the case of alcohol fuel, in addition to that, it is necessary to concurrently purify aldehydes due to partial oxidation of alcohol in the internal combustion engine.
【０００３】しかしながら従来の白金族金属による触媒
では、内燃機関で未燃となったアルコールの部分酸化反
応が起りアルデヒドが触媒内で生成し、触媒通過後には
アルデヒドにとってむしろ逆効果になり、従来の触媒を
そのまま適用することはできなかった。However, in the conventional catalysts using platinum group metals, partial oxidation reaction of alcohol which has not been burnt in the internal combustion engine occurs and aldehydes are produced in the catalyst, and after passing through the catalyst, it has a rather adverse effect on the aldehydes. The catalyst could not be applied as is.
【０００４】上記問題点を解決する目的で、例えば特開
昭６２−１２９１２９号公報に開示されているように、
貴金属であるＰｄに銀（Ａｇ）等を添加し、アルデヒド
を同時に除去する触媒が提案されている。これは、Ｐｄ
とＡｇの共存効果により触媒性能向上を図ったものであ
る。For the purpose of solving the above problems, for example, as disclosed in JP-A-62-129129,
A catalyst has been proposed in which silver (Ag) or the like is added to Pd which is a noble metal to simultaneously remove aldehyde. This is Pd
The catalyst performance is improved by the coexistence effect of Ag and Ag.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、上記提
案された触媒にあっては、 １）基本的に貴金属と銀を共存させてアルデヒドを除去
するために担持の仕方、分散性により活性が大きく異な
る。 ２）完全にはアルコールの部分酸化によるアルデヒドの
生成が抑制されない。 ３）活性成分の分散性が重要であるので使用を続けるに
つれ、性能の劣化があり、また貴金属と銀の合金化によ
り貴金属本来の浄化能が阻害される。 等の問題があった。However, in the above-proposed catalyst, 1) basically, the activity largely varies depending on the loading method and dispersibility in order to remove aldehyde by coexisting noble metal and silver. . 2) Generation of aldehyde due to partial oxidation of alcohol is not completely suppressed. 3) Since the dispersibility of the active ingredient is important, the performance deteriorates with continued use, and the alloying of the noble metal and silver impairs the original purifying ability of the noble metal. There was a problem such as.
【０００６】[0006]
【課題を解決するための手段】本発明者らは上記問題点
に鑑み鋭意研究の結果、酸化ジルコニウムはアルデヒド
の酸化活性が高く、メタノールの部分酸化にくらべ優先
的にアルデヒドと反応することを知見した。この知見に
基づき以下に述べる新規な触媒を開発するに至った。 １）一体構造型担体上に白金族金属とともにジルコニウ
ム酸化物粉末を含有し、必要に応じてアルミナを混合し
たコート層を備えること。 ２）該ジルコニウム酸化物粉末は触媒１リットル当り２
５ｇ〜３００ｇ担持されていること。 ３）白金族金属は触媒１リットル当り０．２４〜１０．
６ｇ担持されていること。 ４）好ましくは、排ガス流に近い側に多くジルコニウム
酸化物を配置することを特徴とする。DISCLOSURE OF THE INVENTION As a result of intensive studies in view of the above problems, the present inventors have found that zirconium oxide has a high aldehyde oxidation activity and reacts preferentially with aldehyde as compared with partial oxidation of methanol. did. Based on this finding, we have developed the following novel catalyst. 1) To provide a coat layer containing a zirconium oxide powder together with a platinum group metal on a monolithic structure type carrier, and optionally mixing alumina. 2) The zirconium oxide powder is 2 per liter of catalyst.
Carry 5g to 300g. 3) Platinum group metal is 0.24-10.
Must carry 6g. 4) Preferably, more zirconium oxide is arranged on the side closer to the exhaust gas flow.
【０００７】以下、この発明について説明する。本発明
の触媒はアルコールを燃料とする自動車の排ガス浄化に
関し、酸化ジルコニウムと白金族金属を同一の触媒コー
ト層内に配置することにより、１個の触媒でＨＣ、Ｃ
Ｏ、ＮＯｘ及びアルデヒド除去能に富んだ触媒が実現で
きる。これは、酸化ジルコニウムは、アルコールとアル
デヒドが共存するガス中でアルデヒドを優先的に酸化
し、無害なＣＯ2 と水を生成でき、また貴金属によるア
ルコールの部分酸化で生成したアルデヒドも酸化ジルコ
ニウムを同時に配置することにより効率よく除去できる
という、本発明者の知見に基づくものである。また、コ
ート層中に含有させる酸化ジルコニウムをコート層中の
浄化ガス側に近い部分に遍在させて配置することが好ま
しい。これはコート層内部で生成したアルデヒドがコー
ト層中を拡散して排ガス流中に放出されることを最小限
に抑えるためである。The present invention will be described below. The catalyst of the present invention relates to the purification of automobile exhaust gas using alcohol as a fuel. By arranging zirconium oxide and a platinum group metal in the same catalyst coating layer, HC and C can be obtained by one catalyst.
A catalyst rich in the ability to remove O, NOx and aldehyde can be realized. This is because zirconium oxide preferentially oxidizes an aldehyde in a gas in which an alcohol and an aldehyde coexist, and can produce harmless CO 2 and water. Also, an aldehyde produced by partial oxidation of an alcohol by a noble metal simultaneously produces zirconium oxide. This is based on the knowledge of the present inventor that it can be efficiently removed by disposing it. Further, it is preferable that the zirconium oxide contained in the coat layer is ubiquitously arranged in a portion near the purified gas side in the coat layer. This is to minimize the diffusion of the aldehyde generated inside the coating layer into the exhaust gas flow by diffusing in the coating layer.
【０００８】また、コート層中のジルコニウム酸化物の
含有量は多い程良いが、１リットル当り２５ｇから３０
０ｇ含有することが望ましい。２５ｇ未満では効果が得
られず、３００ｇより多く加えても効果はあがらない。Further, the higher the content of zirconium oxide in the coat layer, the better, but it is 25 g to 30 per liter.
It is desirable to contain 0 g. If the amount is less than 25 g, no effect is obtained, and if the amount is more than 300 g, the effect is not obtained.
【０００９】[0009]
【作用】次に作用を説明する。本発明のアルデヒド浄化
用触媒は、一体構造型担体上のコート層に酸化ジルコニ
ウムを含んでなる。例えばメタノールを燃料とした内燃
機関の場合、排ガス中の有害成分としてＣＯ、ＮＯｘ、
メタノール、アルデヒドを含む。[Operation] Next, the operation will be described. The aldehyde-purifying catalyst of the present invention comprises zirconium oxide in the coating layer on the monolithic structure type carrier. For example, in the case of an internal combustion engine that uses methanol as fuel, CO, NOx,
Including methanol and aldehyde.
【００１０】メタノールの酸化とアルデヒドの生成、酸
化は以下の反応により進行する。The oxidation of methanol and the formation and oxidation of aldehyde proceed by the following reactions.
【数１】 ＣＨ3 ＯＨ＋1/2 Ｏ2 →ＣＨ2 Ｏ＋Ｈ2 Ｏ （反応１） ＣＨ2 Ｏ＋Ｏ2 →Ｈ2 Ｏ＋ＣＯ2 （反応２） アルデヒド除去用触媒としては（反応１）より（反応
２）の反応が優先することが望ましい。一般の貴金属等
の活性物質は反応：（反応１）と（反応２）を並行して
進行させるが、触媒の使用条件により（反応１）がより
速く進行し、アルデヒドが多く生成することがある。こ
れは触媒の活性点上にアルコールとアルデヒドが競争吸
着し反応が進行するためでそれを触媒で制御することは
できない。[Equation 1] CH 3 OH + 1/2 O 2 → CH 2 O + H 2 O (Reaction 1) CH 2 O + O 2 → H 2 O + CO 2 (Reaction 2) The reaction of (Reaction 2) takes precedence over (Reaction 1) as a catalyst for aldehyde removal. Is desirable. Generally, an active substance such as a noble metal progresses the reaction: (Reaction 1) and (Reaction 2) in parallel, but (Reaction 1) may proceed faster and a large amount of aldehyde may be produced depending on the use conditions of the catalyst. . This is because the alcohol and the aldehyde are competitively adsorbed on the active site of the catalyst and the reaction proceeds, so that it cannot be controlled by the catalyst.
【００１１】ところが酸化ジルコニウムはアルデヒドの
吸着のみ、或いは圧倒的に多く優先的にアルデヒドの吸
着が起り易い化学状態を有すると考えられ、（反応１）
の反応に比べ（反応２）が圧倒的に速くなる。その結果
メタノールの酸化よりもアルデヒドの酸化が優先的に実
現されアルデヒドの選択的酸化となる。従ってアルデヒ
ド除去用として優れるものとなる。しかし同一触媒で三
元成分に加えアルデヒドも同時に除去するためには酸化
ジルコニウムと白金族金属を同一触媒内に配置すること
により、部分酸化によりアルコールからと白金族金属上
でアルデヒドが生成したとしても近傍に配置したジルコ
ニアにより浄化され、触媒全体としてアルデヒドを排出
しなくなり有効になる。However, zirconium oxide is considered to have a chemical state in which only aldehyde is adsorbed, or overwhelmingly many aldehydes are preferentially adsorbed (reaction 1).
(Reaction 2) is overwhelmingly faster than the reaction (1). As a result, the oxidation of the aldehyde is preferentially realized over the oxidation of methanol, resulting in the selective oxidation of the aldehyde. Therefore, it is excellent for removing aldehyde. However, in order to remove the aldehyde as well as the ternary component at the same time with the same catalyst, by placing zirconium oxide and the platinum group metal in the same catalyst, even if the aldehyde is produced from alcohol and on the platinum group metal by partial oxidation. Purified by zirconia arranged in the vicinity, the catalyst as a whole becomes effective without discharging aldehyde.
【００１２】[0012]
【実施例】以下、この発明を実施例、比較例および試験
例により説明する。 実施例１ 市販の酸化ジルコニウム粉末１１２．５ｇ、Ｐｄを担持
した活性アルミナ粉末を空気中４００℃で焼成した粉末
７８７．５ｇ、硝酸水溶液９００ｇを磁性ボールミルに
投入し、混合攪拌してスラリーを得た。このスラリーを
コーディライト質モノリス担体（１．３Ｌ、４００セ
ル）に浸し、空気流にてセル内の余剰のスラリーを取り
除いて乾燥し、４００℃で１時間焼成してコート層重量
２００ｇ／Ｌ（酸化ジルコニウム量；２５ｇ／Ｌ）の触
媒（ａ）を得た。この時触媒１Ｌ当りのＰｄ量は１．１
８ｇとした。EXAMPLES The present invention will be described below with reference to Examples, Comparative Examples and Test Examples. Example 1 112.5 g of commercially available zirconium oxide powder, 787.5 g of powder obtained by firing activated alumina powder carrying Pd at 400 ° C. in air, and 900 g of nitric acid aqueous solution were put into a magnetic ball mill, and mixed and stirred to obtain a slurry. . This slurry was dipped in a cordierite monolith carrier (1.3 L, 400 cells), excess slurry in the cells was removed by an air stream, dried, and baked at 400 ° C. for 1 hour to give a coat layer weight of 200 g / L ( A catalyst (a) having a zirconium oxide amount of 25 g / L was obtained. At this time, the amount of Pd per liter of catalyst was 1.1.
It was 8 g.
【００１３】実施例２ 実施例１におけるジルコニウム酸化物粉末を４５０ｇ、
Ｐｄ担持アルミナ粉末を４５０ｇにした以外は実施例１
と同様の方法で触媒（ｂ）を得た。（酸化ジルコニウム
量；１００ｇ／Ｌ）Example 2 450 g of the zirconium oxide powder in Example 1,
Example 1 except that the Pd-supported alumina powder was changed to 450 g.
A catalyst (b) was obtained in the same manner as in. (Zirconium oxide amount; 100 g / L)
【００１４】実施例３ 実施例２においてＰｄ担持ジルコニウム酸化物粉末を４
５０ｇ、活性アルミナ粉末を４５０ｇにした以外は実施
例２と同様の方法で触媒（ｃ）を得た。（酸化ジルコニ
ウム量；１００ｇ／Ｌ）Example 3 In Example 2, 4 parts of Pd-supported zirconium oxide powder was used.
A catalyst (c) was obtained in the same manner as in Example 2 except that 50 g and activated alumina powder were changed to 450 g. (Zirconium oxide amount; 100 g / L)
【００１５】実施例４ 酸化ジルコニウム粉末にＰｄを担持した後、４００℃で
焼成したＰｄ担持酸化ジルコニウム粉末９００ｇと硝酸
水溶液９００ｇだけでスラリーを調製した以外は実施例
１と同様の方法で触媒（ｄ）を得た。（酸化ジルコニウ
ム量；２００ｇ／Ｌ）Example 4 A catalyst (d) was prepared in the same manner as in Example 1 except that a slurry was prepared only from 900 g of Pd-supported zirconium oxide powder calcined at 400 ° C. after supporting zirconium oxide powder with Pd. ) Got. (Zirconium oxide amount; 200 g / L)
【００１６】実施例５ 活性アルミナ粉末に硝酸ジルコニウム水溶液を含浸した
後乾燥し、６００℃で１時間空気中で焼成し、アルミナ
に対しジルコニウムを金属換算８重量％含むジルコニア
含有活性アルミナを得た。ジルコニア含有活性アルミナ
粉末にＰｄを担持した後焼成した粉末９００ｇ、硝酸水
溶液９００ｇを磁性ボールミルに投入し、混合攪拌して
スラリーを得た。このスラリーをコーディライト質モノ
リス担体に浸し、空気流にてセル内の余剰のスラリーを
取り除いて乾燥し、４００℃で１時間焼成してコート層
重量２５０ｇ／Ｌ（酸化ジルコニウム量；２５ｇ／Ｌ）
の触媒（ｅ）を得た。この時触媒１Ｌ当りのＰｄ担持量
は１．１８ｇとした。Example 5 Activated alumina powder was impregnated with an aqueous zirconium nitrate solution, dried and calcined in air at 600 ° C. for 1 hour to obtain activated alumina containing zirconia containing 8% by weight of zirconium in terms of metal based on alumina. 900 g of a powder obtained by supporting Pd on a zirconia-containing activated alumina powder and baked, and 900 g of a nitric acid aqueous solution were put into a magnetic ball mill, and mixed and stirred to obtain a slurry. The slurry is dipped in a cordierite monolithic carrier, excess slurry in the cell is removed by an air stream, dried, and baked at 400 ° C. for 1 hour to give a coat layer weight of 250 g / L (zirconium oxide amount; 25 g / L).
The catalyst (e) of was obtained. At this time, the amount of Pd supported on 1 L of the catalyst was 1.18 g.
【００１７】実施例６ 実施例２においてＰｄを担持する代わりにＰｔを担持し
た以外は全く同様にして触媒（ｆ）を得た。Example 6 A catalyst (f) was obtained in exactly the same manner as in Example 2 except that Pt was loaded instead of Pd.
【００１８】実施例７ 実施例２においてＰｄを担持する代わりにＲｈを担持
し、Ｒｈの担持量は触媒１Ｌ当り０．２４ｇにした以外
は全く同様にして触媒（ｇ）を得た。Example 7 A catalyst (g) was obtained in exactly the same manner as in Example 2 except that Rh was loaded instead of Pd and the loading amount of Rh was 0.24 g per 1 L of the catalyst.
【００１９】実施例８ Ｐｄを担持した活性アルミナからなるスラリーを調製
し、このスラリーをモノリス担体に浸し、余剰のスラリ
ーを取り除いて乾燥し、４００℃で１時間焼成してコー
ト層重量１００ｇ／Ｌとした触媒にさらに酸化ジルコニ
ウムからなるスラリーを浸し、乾燥、焼成して酸化ジル
コニアの重量を１００ｇ／Ｌとし、全体のコート量を２
００ｇ／Ｌの触媒（ｈ）を得た。またこの時のＰｄ担持
量も１．１８ｇ／Ｌとした。Example 8 A slurry of activated alumina carrying Pd was prepared, and the slurry was dipped in a monolith carrier, excess slurry was removed and dried, followed by firing at 400 ° C. for 1 hour to give a coat layer weight of 100 g / L. A slurry of zirconium oxide was further dipped in the above catalyst, dried and calcined to make the weight of zirconia oxide 100 g / L, and the total coating amount was 2
00 g / L of catalyst (h) was obtained. The amount of Pd supported at this time was also set to 1.18 g / L.
【００２０】実施例９ 実施例１で用いたＰｄ担持ジルコニウム酸化物粉末を４
５０ｇ、実施例７で用いたＲｈ担持ジルコニウム酸化物
粉末を４５０ｇ、硝酸水溶液９００ｇを混合攪拌した以
外は実施例１と同様の方法で触媒（ｉ）を得た。Example 9 The Pd-supported zirconium oxide powder used in Example 1 was mixed with 4 parts.
A catalyst (i) was obtained in the same manner as in Example 1, except that 50 g, 450 g of the Rh-supported zirconium oxide powder used in Example 7 and 900 g of a nitric acid aqueous solution were mixed and stirred.
【００２１】実施例１０ 実施例６で用いたＰｔ担持ジルコニウム酸化物粉末を４
５０ｇ、実施例７で用いたＲｈ担持ジルコニウム酸化物
粉末を４５０ｇ、硝酸水溶液９００ｇを混合攪拌した以
外は実施例１と同様の方法で触媒（ｊ）を得た。Example 10 Pt-supported zirconium oxide powder used in Example 6
A catalyst (j) was obtained in the same manner as in Example 1 except that 50 g, 450 g of the Rh-supported zirconium oxide powder used in Example 7 and 900 g of a nitric acid aqueous solution were mixed and stirred.
【００２２】比較例１ 実施例４においてジルコニウム酸化物粉だけでスラリー
化した以外は実施例４と同様の方法で触媒（ア）を得
た。Comparative Example 1 A catalyst (A) was obtained in the same manner as in Example 4, except that the slurry was prepared from only zirconium oxide powder.
【００２３】比較例２ 酸化アルミニウム粉末にＰｄを担持した後、４００℃で
焼成したＰｄ担持酸化アルミニウム粉末９００ｇと硝酸
水溶液９００ｇだけでスラリーを調製した以外は実施例
１と同様の方法で触媒（イ）を得た。（酸化ジルコニウ
ム量；０ｇ／Ｌ）Comparative Example 2 A catalyst (a) was prepared in the same manner as in Example 1 except that a slurry was prepared by using 900 g of Pd-supported aluminum oxide powder calcined at 400 ° C. and 900 g of an aqueous nitric acid solution after supporting Pd on the aluminum oxide powder. ) Got. (Zirconium oxide amount; 0 g / L)
【００２４】試験例 実施例１〜１０、比較例１〜２の各触媒（触媒ａ〜ｊお
よびア、イ）につき、下記条件で空気耐久を行った後の
性能評価を行い、耐久劣化触媒のアルデヒド、メタノー
ル浄化率を測定した。性能評価結果を表１に示す。Test Example For each of the catalysts of Examples 1 to 10 and Comparative Examples 1 to 2 (catalysts a to j and a and b), performance evaluation was performed after air durability under the following conditions, and the durability deteriorated catalysts were evaluated. Aldehyde and methanol purification rates were measured. The performance evaluation results are shown in Table 1.
【００２５】 ＜空気耐久条件＞ 耐久温度 １０００℃ 耐久時間 ４時間 ＜性能評価条件＞ エンジン 排気量 １８００ｃｃ 燃料 Ｍ８５（メタノール８５％含有ガソリン） 空気過剰率 ０．９ 試験方法 ２５℃ソーク後、ガスを昇温させ、触媒前後の排ガ スを連続的に分析し昇温後、６００秒までの平均浄 化率を測定、最終排ガス到達温度は４００℃〜５０ ０℃<Air endurance conditions> Endurance temperature 1000 ° C Endurance time 4 hours <Performance evaluation conditions> Engine displacement 1800cc Fuel M85 (gasoline containing 85% methanol) Excess air ratio 0.9 Test method 25 ° C After soaking, gas rise After heating and continuously analyzing the exhaust gas before and after the catalyst and raising the temperature, the average purification rate up to 600 seconds is measured.
【００２６】[0026]
【表１】[Table 1]
【００２７】[0027]
【発明の効果】以上説明してきたように、本発明のアル
コール燃料機関の排ガス浄化用触媒は、一体構造型担体
上にジルコニウム酸化物と白金、ロジウムおよびパラジ
ウムからなる群から選ばれた少なくとも１種の白金族元
素とを必須成分として規定量含有するコート層を備えた
ことにより、ＨＣ、ＣＯ、ＮＯｘ及びアルデヒドの除去
能に優れる。As described above, the catalyst for purifying exhaust gas of an alcohol fuel engine of the present invention is at least one selected from the group consisting of zirconium oxide, platinum, rhodium and palladium on a monolithic structure type carrier. By providing the coating layer containing the platinum group element of (1) and (2) as the essential components in specified amounts, the ability to remove HC, CO, NOx and aldehyde is excellent.
Claims (2)
粉末と、白金、ロジウムおよびパラジウムからなる群か
ら選ばれた少なくとも１種の白金族元素を含有し、アル
ミナを混合してまたは混合することなく形成したコート
層を備え、該コート層中に該ジルコニウム酸化物は触媒
１Ｌ当り２５ｇ〜３００ｇであり、白金族元素は触媒１
Ｌ当り０．２４ｇ〜１０．６ｇであることを特徴とする
アルコール燃料機関の排ガス浄化用触媒。1. A zirconium oxide powder and at least one platinum group element selected from the group consisting of platinum, rhodium and palladium on a monolithic structure type carrier, mixed with or without alumina. The coated layer is formed, and the zirconium oxide in the coated layer is 25 g to 300 g per 1 L of the catalyst, and the platinum group element is the catalyst 1
An exhaust gas purifying catalyst for an alcohol fuel engine, characterized in that it is 0.24 g to 10.6 g per L.
化物をコート層中の浄化ガス側に近い部分に遍在させ配
置したことを特徴とする請求項１記載のアルコール燃料
機関の排ガス浄化用触媒。2. The catalyst for purifying exhaust gas of an alcohol fuel engine according to claim 1, wherein the zirconium oxide contained in the coat layer is arranged ubiquitously in a portion of the coat layer near the purified gas side.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5157257A JPH0716461A (en) | 1993-06-28 | 1993-06-28 | Catalyst for purification of exhaust gas from alcohol fuel engine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5157257A JPH0716461A (en) | 1993-06-28 | 1993-06-28 | Catalyst for purification of exhaust gas from alcohol fuel engine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0716461A true JPH0716461A (en) | 1995-01-20 |
Family
ID=15645702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5157257A Pending JPH0716461A (en) | 1993-06-28 | 1993-06-28 | Catalyst for purification of exhaust gas from alcohol fuel engine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0716461A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017148764A (en) * | 2016-02-26 | 2017-08-31 | 東洋紡株式会社 | Aldehyde removing catalyst composition, manufacturing method therefor and a removing method of aldehyde gas |
-
1993
- 1993-06-28 JP JP5157257A patent/JPH0716461A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017148764A (en) * | 2016-02-26 | 2017-08-31 | 東洋紡株式会社 | Aldehyde removing catalyst composition, manufacturing method therefor and a removing method of aldehyde gas |
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