JPH07155614A - Production of exhaust gas purifying catalyst - Google Patents
Production of exhaust gas purifying catalystInfo
- Publication number
- JPH07155614A JPH07155614A JP5306587A JP30658793A JPH07155614A JP H07155614 A JPH07155614 A JP H07155614A JP 5306587 A JP5306587 A JP 5306587A JP 30658793 A JP30658793 A JP 30658793A JP H07155614 A JPH07155614 A JP H07155614A
- Authority
- JP
- Japan
- Prior art keywords
- sapo
- catalytic metal
- catalyst
- ion exchange
- type
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、排気ガスの浄化用触媒
の製造方法に関し、さらに詳細に述べるならば、触媒金
属の担持量が高い排気ガス浄化用触媒の製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a catalyst for purifying exhaust gas, and more specifically, it relates to a method for producing a catalyst for purifying exhaust gas having a high catalytic metal loading.
【０００２】[0002]
【従来の技術】従来、自動車の排気ガス浄化用触媒とし
て、排気ガス中の一酸化炭素（ＣＯ）及び炭化水素（Ｈ
Ｃ）の酸化と窒素酸化物（ＮＯx ) の還元とを同時に行
って排気ガスを浄化する排気ガス浄化用三元触媒が数多
く知られている。このような触媒としては、例えばコー
ジェライトなどの耐火性担体にγ−アルミナスラリーを
塗布し、焼成し、パラジウム、白金、ロジウムなどの貴
金属を担持させたものが典型的である（例えば、特公昭
56−27295 号公報など参照）。2. Description of the Related Art Conventionally, carbon monoxide (CO) and hydrocarbon (H) in exhaust gas have been used as catalysts for purifying exhaust gas of automobiles.
There are many known three-way catalysts for purifying exhaust gas that simultaneously purify C) and reduce nitrogen oxides (NO x ) to purify exhaust gas. A typical example of such a catalyst is one in which a γ-alumina slurry is applied to a refractory carrier such as cordierite and baked to carry a noble metal such as palladium, platinum or rhodium (for example, Japanese Patent Publication No.
56-27295, etc.).
【０００３】ところで、前記排気ガス浄化用触媒の性能
はエンジンの設定空燃比によって大きく左右され、希薄
混合比、すなわち空燃比の大きなリーン側では燃焼後の
排気ガス中の酸素量が大きくなり、酸化作用が活発に、
還元作用が不活発になる。逆に、空燃比の小さなリッチ
側では燃焼後の排気ガス中の酸素量が少なくなり、酸化
作用が不活発に、還元作用が活発になる。By the way, the performance of the exhaust gas purifying catalyst is greatly influenced by the set air-fuel ratio of the engine. On the lean side where the lean mixture ratio, that is, the air-fuel ratio is large, the amount of oxygen in the exhaust gas after combustion becomes large, and oxidation occurs. Active action,
The reducing action becomes inactive. On the other hand, on the rich side where the air-fuel ratio is small, the amount of oxygen in the exhaust gas after combustion becomes small, the oxidizing action becomes inactive, and the reducing action becomes active.
【０００４】近年、自動車等の内燃機関において、省エ
ネルギーの見地から低燃費化が要請されており、この低
燃費化の一つの手段として走行時に酸素過剰の混合気で
燃焼させることが従来より行われている。このような空
燃比がリーン側の酸素過剰雰囲気では、排気ガス中の有
害成分のうちＨＣ及びＣＯは酸化除去可能であるが、Ｎ
Ｏx は触媒床に吸着したＯ2 により触媒金属との接触が
大幅に妨げられるため還元除去が困難であり、たとえ触
媒金属と接触でき、還元することができた場合であって
も、窒素は触媒床に吸着した酸素とただちに結合するた
め、浄化効率が著しく低くなるとうい問題があった。In recent years, in an internal combustion engine of an automobile or the like, there has been a demand for low fuel consumption from the viewpoint of energy saving. As one of the means for reducing the fuel consumption, it has been conventionally performed to burn an air-fuel mixture with excess oxygen during traveling. ing. In such an oxygen excess atmosphere where the air-fuel ratio is lean, HC and CO, which are harmful components in the exhaust gas, can be removed by oxidation.
O x is difficult to reduce and remove because the O 2 adsorbed on the catalyst bed is contacted with the catalyst metal significantly inhibit, if possible contact with the catalyst metal, even if it is possible to be reduced, nitrogen Since it immediately binds to oxygen adsorbed on the catalyst bed, there is a problem that the purification efficiency becomes extremely low.
【０００５】こうした問題を解決するため、ゼオライト
の表面に多数存在する細孔内に銅を担持させた触媒が開
発された（米国特許第 4297328号）。この触媒は酸化雰
囲気下においてＮＯx の還元除去が可能であるが、耐熱
性及び耐久性が劣っていた。In order to solve these problems, a catalyst was developed in which copper was supported in the large number of pores present on the surface of zeolite (US Pat. No. 4,297,328). Although this catalyst is capable of reducing and removing NO x in an oxidizing atmosphere, it has poor heat resistance and durability.
【０００６】このような問題を解決するため、結晶質シ
リコアルミノフォスフェート多孔質担体に触媒金属を担
持させた触媒が提案された（特開平２−251246）。この
触媒は、触媒金属を常法のイオン交換法により担持させ
たものであり、触媒金属の付着力が強く、かつ耐熱性及
び耐久性に優れている。しかし、常法のイオン交換では
担持させる触媒金属の量に限界があり、イオン交換を多
数回繰り返し行ってもある程度（２重量％）以上担持さ
せることができなかった。In order to solve such a problem, a catalyst in which a catalytic metal is supported on a crystalline silicoaluminophosphate porous carrier has been proposed (JP-A-2-251246). This catalyst has a catalytic metal supported by a conventional ion exchange method, and has a strong catalytic metal adhesion and excellent heat resistance and durability. However, the amount of catalyst metal to be supported by the conventional ion exchange is limited, and even if ion exchange is repeated many times, it cannot be supported to a certain extent (2% by weight).
【０００７】[0007]
【発明が解決しようとする課題】本発明は、自動車排気
ガス浄化用触媒の製造方法の有する前記の如き欠点を解
消し、金属触媒の担持量の高い触媒を提供することを目
的とする。SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned drawbacks of the method for producing a catalyst for purifying automobile exhaust gas and to provide a catalyst having a high metal catalyst loading.
【０００８】[0008]
【課題を解決するための手段】本発明者は、上記の自動
車排気ガス浄化用触媒の上記問題点を解決すべく鋭意研
究を重ねた結果、ＳＡＰＯの固体酸点に存在するＨ+ イ
オンをアンモニウムイオンとイオン交換させ、その後触
媒金属イオンとアンモニウムイオンとをイオン交換させ
ることにより、触媒金属の担持量を高くすることができ
ることを見出し、本発明を完成した。As a result of intensive studies to solve the above problems of the above-mentioned catalyst for purifying automobile exhaust gas, the present inventor has found that H + ions existing at solid acid points of SAPO are ammonium. The present invention has been completed by finding that it is possible to increase the supported amount of the catalytic metal by performing ion exchange with the ions and then exchanging the catalytic metal ions with the ammonium ions.
【０００９】すなわち、本発明の自動車排気ガス浄化用
触媒の製造方法は、(i) アンモニア水溶液にシリコアル
ミノフォスフェート（ＳＡＰＯ）を混合することによっ
てアンモニウムイオン（ＮＨ4 + ) によりイオン交換
し、ＮＨ4 型ＳＡＰＯを形成すること、次いで(ii)前記
ＮＨ4 型ＳＡＰＯを触媒金属を含む水溶液に添加するこ
とによって触媒金属イオンによりイオン交換し、ＳＡＰ
Ｏに触媒金属を担持させること、を特徴とするものであ
る。That is, according to the method for producing a catalyst for purifying automobile exhaust gas of the present invention, (i) ion exchange is performed with ammonium ions (NH 4 + ) by mixing silicoaluminophosphate (SAPO) with an aqueous ammonia solution, Forming type 4 SAPO, and then (ii) adding the NH 4 type SAPO to an aqueous solution containing the catalytic metal to ion-exchange with catalytic metal ions to form SAP
The catalytic metal is supported on O.
【００１０】また、上記方法において、触媒金属を均一
なアンミン錯体の形状で用いイオン交換することによ
り、触媒金属の担持量をさらに高めることが可能である
ことを見出した。すなわち、本発明の自動車排気ガス浄
化用触媒の製造方法は、(i) アンモニア水溶液にシリコ
アルミノフォスフェート（ＳＡＰＯ）を混合することに
よってアンモニウムイオン（ＮＨ4 + ) によりイオン交
換し、ＮＨ4 型ＳＡＰＯを形成すること、(ii)触媒金属
を含む水溶液にアンモニア水を添加することによってア
ンミン錯体均一分散液を形成し、この分散液に酸を添加
しｐＨ６〜８の範囲に調整した分散液を形成すること、
次いで(iii) 前記ＮＨ4 型ＳＡＰＯと前記分散液を混合
し、触媒金属をイオン交換によりＳＡＰＯに担持させる
こと、を特徴とするものである。Further, in the above method, it was found that it is possible to further increase the supported amount of the catalytic metal by using the catalytic metal in the form of a uniform ammine complex and performing ion exchange. That is, the method for producing a catalyst for purifying automobile exhaust gas according to the present invention comprises: (i) mixing an aqueous ammonia solution with silicoaluminophosphate (SAPO) for ion exchange with ammonium ions (NH 4 + ), and NH 4 -type SAPO And (ii) adding ammonia water to an aqueous solution containing a catalytic metal to form an ammine complex uniform dispersion liquid, and adding an acid to this dispersion liquid to form a dispersion liquid adjusted to a pH range of 6 to 8. What to do,
Then, (iii) the NH 4 type SAPO is mixed with the dispersion, and the catalytic metal is supported on the SAPO by ion exchange.
【００１１】本発明の方法において触媒の担体として用
いられるＳＡＰＯとしては、細孔が均一であり、約３Å
より大きな直径を有し、無水型であって、化学組成が下
式 （Ｓｉx Ａｌy Ｐz ）Ｏ2 （上式中、ｘ＋ｙ＋ｚ＝１）で表されるものである。The SAPO used as a catalyst carrier in the method of the present invention has uniform pores and has a pore size of about 3 Å.
Has a larger diameter, a anhydrous form, in which chemical composition is represented by the following formula (Si x Al y P z) O 2 ( In the above formula, x + y + z = 1 ).
【００１２】前記ＳＡＰＯの細孔径としては、ＮＯx 分
子径よりもわずかに大きい約５〜10Åが好ましい。ＳＡ
ＰＯ中のＳｉの割合は、0.01≦ｘ＜0.8 、好ましくは0.
05〜0.25である。この割合が0.05以下では担体の固体酸
性が低く、活性金属の担持能が低下してしまう。一方、
この割合が0.25以上になると、耐熱性が低下するため望
ましくない。The pore diameter of the SAPO is preferably about 5 to 10 Å, which is slightly larger than the NO x molecular diameter. SA
The proportion of Si in PO is 0.01 ≦ x <0.8, preferably 0.
It is from 05 to 0.25. When this ratio is 0.05 or less, the solid acidity of the carrier is low, and the ability to support the active metal is reduced. on the other hand,
If this ratio is 0.25 or more, the heat resistance decreases, which is not desirable.
【００１３】ＳＡＰＯは通常の方法、例えば特公平３−
72010 号公報に記載の方法によって合成してよい。すな
わち、リン酸塩、水和アルミナ及びシリカゾル等を出発
原料として用い、これらを均一に混合し、該混合物に細
孔構造を規定するために有機テンプレート化剤を混入
し、均一になるように攪拌後、水熱合成によりＳＡＰＯ
粉末を得る。ＳＡＰＯとしては、特公平３−72010 号公
報に記載されているＳＡＰＯ−３４が、得られる触媒と
しての機能の点から好ましい。SAPO is an ordinary method, for example, Japanese Patent Publication No.
It may be synthesized by the method described in 72010. That is, phosphate, hydrated alumina, silica sol, etc. are used as starting materials, these are uniformly mixed, and an organic templating agent is mixed into the mixture to define the pore structure, and the mixture is stirred to be uniform. Later, SAPO by hydrothermal synthesis
Get a powder. As SAPO, SAPO-34 described in Japanese Patent Publication No. 3-72010 is preferable from the viewpoint of the function as the obtained catalyst.
【００１４】本発明の方法において、まず上記のＳＡＰ
Ｏ粉末をアンモニウム水溶液に混合することにより、Ｓ
ＡＰＯに結合しているプロトンをアンモニウムイオンと
イオン交換させ、ＮＨ4 型ＳＡＰＯを得る。この際、ｐ
Ｈが４以上８未満の範囲内にあることが好ましい。ｐＨ
４未満ではＨ+ 濃度が高すぎ、イオン交換が進行しにく
く、ｐＨ８以上ではＳＡＰＯの結晶構造が破壊してしま
うことがあるからである。In the method of the present invention, first, the above SAP
By mixing O powder with an aqueous ammonium solution, S
The proton bound to APO is ion-exchanged with ammonium ion to obtain NH 4 type SAPO. At this time, p
It is preferable that H is in the range of 4 or more and less than 8. pH
If it is less than 4, the H + concentration is too high, and ion exchange is difficult to proceed, and if the pH is 8 or more, the crystal structure of SAPO may be destroyed.
【００１５】次いで、上記のＳＡＰＯ粉末に通常のイオ
ン交換法により触媒金属を担持させる。すなわち、触媒
金属の塩の水溶液中に上記ＮＨ4 型ＳＡＰＯを加え、触
媒金属とアンモニウムイオンをイオン交換させる。この
際もｐＨは上記と同様の理由により、４以上８未満の範
囲内にあることが好ましく、ｐＨ６であることが特に好
ましい。触媒金属の塩の濃度は0.01〜0.2 規定であるこ
とが好ましい。0.01規定未満では薄すぎてイオン交換の
反応が進みにくく、0.2 規定より高いと塩が完全に溶解
せず、イオン交換ではなく触媒金属の凝集物が吸着して
しまうことがあるからである。触媒金属としては、イオ
ン半径がＳＡＰＯの細孔より小さく、好ましくは４オン
グストローム未満であるものであり、例えば１Ａ〜７Ａ
族、８族、１Ｂ〜２Ｂ族の元素であり、好ましくはこれ
らの族の第４及び第５周期の元素である。銅、コバル
ト、ニッケル及びマンガンが特に好ましい。また、塩と
しては酢酸塩が好ましい。それは弱酸であるためｐＨ調
整が容易であるからである。Then, a catalytic metal is supported on the above SAPO powder by a usual ion exchange method. That is, the above-mentioned NH 4 type SAPO is added to the aqueous solution of the salt of the catalytic metal to ion-exchange the catalytic metal with ammonium ions. In this case also, the pH is preferably in the range of 4 or more and less than 8 for the same reason as above, and particularly preferably pH 6. The concentration of the salt of the catalytic metal is preferably 0.01 to 0.2 N. If it is less than 0.01 N, the ion exchange reaction is difficult to proceed because it is too thin, and if it is more than 0.2 N, the salt may not be completely dissolved and the aggregate of the catalyst metal may be adsorbed instead of ion exchange. The catalyst metal has an ionic radius smaller than that of the pores of SAPO, and preferably less than 4 angstrom, for example, 1A to 7A.
It is an element of Group 8, Group 1B to 2B, and is preferably an element of the 4th and 5th periods of these groups. Copper, cobalt, nickel and manganese are particularly preferred. In addition, acetate is preferable as the salt. This is because the pH is easy to adjust because it is a weak acid.
【００１６】また、本発明の他の態様において、触媒金
属の塩の水溶液にアンモニア水を添加することによりｐ
Ｈを10以上に調整して均一に分散したアンミン錯体を形
成させる。このアンミン錯体分散液に酸、例えば酢酸も
しくは硝酸を加えｐＨを６〜７に調整し、この分散液を
前記ＮＨ4 型ＳＡＰＯと混合することにより、触媒金属
とアンモニウムイオンをイオン交換させる。In another embodiment of the present invention, by adding aqueous ammonia to the aqueous solution of the salt of the catalytic metal, p
The H is adjusted to 10 or more to form a uniformly dispersed ammine complex. An acid, for example, acetic acid or nitric acid is added to the ammine complex dispersion liquid to adjust the pH to 6 to 7, and the dispersion liquid is mixed with the NH 4 type SAPO to ion-exchange the catalyst metal and ammonium ions.
【００１７】以上のようにして得られた粉末状の触媒
は、そのまま用いてよく、又は該触媒粉末にアルミナゾ
ルやシリカゾル等のバインダーを添加し、所定の形状に
成形したり、水を加えてスラリー状として、ハニカム等
の形状の耐火性基体上に塗布して用いてもよい。The powdery catalyst obtained as described above may be used as it is, or a binder such as alumina sol or silica sol may be added to the catalyst powder to form a desired shape, or water may be added to form a slurry. As a shape, it may be applied on a refractory substrate in the shape of a honeycomb or the like and used.
【００１８】[0018]
【作用】ＳＡＰＯはＳｉ、Ａｌ、Ｐ及びＯから構成さ
れ、孔径４Åの３次元構造を有する人造のマイクロポア
クリスタルである。これはＺＳＭ−５のゼオライトと同
様に固体酸点を有しており、この固体酸点にＨ+ 、Ｎａ
+ 等のイオンが存在している。このプロトンは直に触媒
金属とイオン交換することが困難であるため、本発明で
はこのプロトンをまずアンモニウムイオンとイオン交換
させ、次いでこのアンモニウムイオンを触媒金属とイオ
ン交換させることにより、触媒金属の担持量を高くする
ことができるのである。触媒金属をイオン交換させる際
に、触媒金属の塩溶液にアンモニア水を加えてｐＨを10
以上にすることにより、触媒金属は均一なアンミン錯体
の形状をとり、この錯体を用いることによりさらに触媒
金属の担持量を高めることが可能になる。FUNCTION SAPO is an artificial micropore crystal composed of Si, Al, P and O and having a three-dimensional structure with a pore diameter of 4Å. Like ZSM-5 zeolite, it has a solid acid point, and H + and Na are added to this solid acid point.
Ions such as + are present. Since it is difficult to directly ion-exchange this proton with the catalyst metal, in the present invention, this proton is first ion-exchanged with ammonium ion, and then this ammonium ion is ion-exchanged with the catalyst metal to support the catalyst metal. The quantity can be increased. When ion-exchanging the catalytic metal, pH is adjusted to 10 by adding aqueous ammonia to the catalytic metal salt solution.
By the above, the catalytic metal takes the form of a uniform ammine complex, and by using this complex, the supported amount of the catalytic metal can be further increased.
【００１９】触媒金属イオンとアンモニウムイオンと
は、アンミン錯体を形成しやすいため、ＳＡＰＯの細孔
の固体酸点にイオン交換させることができる。その際、
アンモニウムイオンが消費され、イオン交換液のｐＨが
酸性側となるので、ｐＨ６〜８に調整し、アンモニウム
イオンを補給させ、イオン交換を促進する。これによ
り、触媒金属を細孔内の固体酸点に吸引でき、イオン交
換反応が促進される。Since the catalytic metal ion and the ammonium ion easily form an ammine complex, they can be ion-exchanged with the solid acid sites in the pores of SAPO. that time,
Since the ammonium ions are consumed and the pH of the ion exchange solution is on the acidic side, the pH is adjusted to 6 to 8 to replenish the ammonium ions and promote the ion exchange. As a result, the catalytic metal can be attracted to the solid acid points in the pores, and the ion exchange reaction is promoted.
【００２０】[0020]
【実施例】本発明を下記実施例により更に詳細に説明す
るが、本発明はこれらに制限されるものではない。The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the invention.
【００２１】実施例１ 200 ℃×７日間で水熱合成し、600 ℃×６時間の仮焼に
より得たＳＡＰＯ−34の粉末10g を、アンモニア水を添
加することによりｐＨ６に調整した水溶液200ml に加
え、攪拌機により均一に混合した。均一になった後、ア
ンモニア水を加えｐＨ６に調整し、室温において24時間
攪拌した。その後3000rpm ×５分の遠心分離により固形
物を回収し、室温において乾燥し、ＮＨ4 型ＳＡＰＯ−
34粉末を得た。 Example 1 10 g of SAPO-34 powder hydrothermally synthesized at 200 ° C. for 7 days and calcined at 600 ° C. for 6 hours was added to 200 ml of an aqueous solution adjusted to pH 6 by adding aqueous ammonia. In addition, the mixture was uniformly mixed with a stirrer. After the mixture became homogeneous, aqueous ammonia was added to adjust the pH to 6, and the mixture was stirred at room temperature for 24 hours. Then, the solid matter was recovered by centrifugation at 3000 rpm for 5 minutes, dried at room temperature, and NH 4 type SAPO-
34 powders were obtained.
【００２２】次に、酢酸銅を水に溶解し、0.03規定の酢
酸銅水溶液を製造し、これにアンモニア水を添加しｐＨ
６に調整した。この溶液に上記ＮＨ4 型ＳＡＰＯ−34粉
末を10g 加え、混合し、再びｐＨを６に調整した。この
状態で室温において24時間攪拌し、遠心分離を行い、次
いで真空乾燥し、最後に500 ℃×３時間の仮焼を行い、
Ｃｕ型ＳＡＰＯ−34を得た。Next, copper acetate is dissolved in water to prepare a 0.03N copper acetate aqueous solution, to which aqueous ammonia is added to adjust the pH.
Adjusted to 6. To this solution, 10 g of the above NH 4 type SAPO-34 powder was added, mixed, and the pH was adjusted to 6 again. In this state, the mixture is stirred at room temperature for 24 hours, centrifuged, dried in vacuum, and finally calcined at 500 ° C for 3 hours.
Cu type SAPO-34 was obtained.
【００２３】こうして得られたＣｕ型ＳＡＰＯ−34の組
成をＩＰＣの定量分析により調べ、Ｃｕの担持量を測定
した。また、このＣｕ型ＳＡＰＯ−34粉末を直径１mmの
ペレットに圧縮成形し、このペレット触媒を石英管にセ
ットし、以下の表１に示すモデルガスを、図１に示すモ
デルガス評価装置において、７リットル／分、ＳＶ＝10
万/hで流し、触媒入口と出口のＮＯ濃度を測定すること
によりＮＯ浄化率を求めた。結果を表２に示す。なお、
ＮＯ浄化率は下式より計算した。 ＮＯ浄化率（％）＝100 ×（入りガス濃度−出ガス濃
度）／入りガス濃度The composition of the Cu-type SAPO-34 thus obtained was investigated by quantitative analysis of IPC, and the amount of Cu supported was measured. Further, this Cu-type SAPO-34 powder was compression-molded into pellets having a diameter of 1 mm, the pellet catalyst was set in a quartz tube, and the model gas shown in Table 1 below was used in the model gas evaluation apparatus shown in FIG. L / min, SV = 10
The NO purification rate was determined by measuring the NO concentration at the catalyst inlet and outlet at a flow rate of 10,000 / h. The results are shown in Table 2. In addition,
The NO purification rate was calculated by the following formula. NO purification rate (%) = 100 x (inlet gas concentration-outlet gas concentration) / inlet gas concentration
【００２４】[0024]
【表１】 [Table 1]
【００２５】実施例２ 実施例１と同様にしてＳＡＰＯ−34にアンモニア水を加
え、ｐＨを６に調整し室温において24時間攪拌し、これ
を遠心分離せず引き続いて酢酸銅を0.03規定となるよう
に加え、実施例１と同様にしてＣｕ型ＳＡＰＯ−34を得
た。このＣｕ型ＳＡＰＯ−34について、実施例１と同様
にしてＣｕ担持量及びＮＯ浄化率を測定した。結果を表
２に示す。 Example 2 In the same manner as in Example 1, aqueous ammonia was added to SAPO-34 to adjust the pH to 6, and the mixture was stirred at room temperature for 24 hours, which was subsequently not centrifuged and copper acetate was adjusted to 0.03N. In the same manner as above, Cu-type SAPO-34 was obtained in the same manner as in Example 1. For this Cu-type SAPO-34, the amount of supported Cu and the NO purification rate were measured in the same manner as in Example 1. The results are shown in Table 2.
【００２６】実施例３ 実施例１と同様にして真空乾燥後のＮＨ4 型ＳＡＰＯ−
34粉末を製造した。次に酢酸銅を0.02規定及び酢酸コバ
ルトを0.02規定の濃度となるように酢酸銅及び酢酸コバ
ルトの水溶液を調製し、これにアンモニア水を添加しｐ
Ｈを６に調整し、この溶液に前記ＮＨ4 型ＳＡＰＯ−34
粉末を10g 加え、実施例１と同様にしてＣｕ、Ｃｏ型Ｓ
ＡＰＯ−34を得た。これについて実施例１と同様にして
Ｃｕ及びＣｏ担持量及びＮＯ浄化率を測定した。結果を
表２に示す。 Example 3 NH 4 SAPO-after vacuum drying in the same manner as in Example 1
34 powders were produced. Next, an aqueous solution of copper acetate and cobalt acetate is prepared so that the concentration of copper acetate is 0.02 N and the concentration of cobalt acetate is 0.02 N.
H was adjusted to 6 and the NH 4 type SAPO-34 was added to this solution.
Add 10 g of the powder, and in the same manner as in Example 1, Cu, Co type S
APO-34 was obtained. For this, the amounts of Cu and Co carried and the NO purification rate were measured in the same manner as in Example 1. The results are shown in Table 2.
【００２７】比較例１〜６ 実施例において使用したＳＡＰＯ−34の粉末を用い、表
２に示す条件においてあるいは直接酢酸銅溶液にＳＡＰ
Ｏ−34の粉末を加えｐＨ調整することなくイオン交換を
行った。得られた触媒について実施例１と同様にして評
価し、結果を表２に示す。 Comparative Examples 1 to 6 Using the powder of SAPO-34 used in Examples, SAP was directly added to the copper acetate solution under the conditions shown in Table 2.
O-34 powder was added to carry out ion exchange without adjusting the pH. The obtained catalyst was evaluated in the same manner as in Example 1, and the results are shown in Table 2.
【００２８】[0028]
【表２】 [Table 2]
【００２９】実施例１〜３ではＣｕ及びＣｏの担持量が
２重量％以上であり、Ｘ線回折、ＦＥ−ＳＥＭによる観
察によってもすべてイオン交換されていた。担持量が増
加するに従いＮＯ浄化率が向上した。これに対し比較例
では担持量が２重量％未満であり、又は比較例４のよう
にイオン交換ではなく凝集した金属元素の吸着が13.5重
量％と多くなり、触媒表面が覆われ、ＮＯ浄化率が低下
した。In Examples 1 to 3, the supported amounts of Cu and Co were 2% by weight or more, and all were ion-exchanged by observation with X-ray diffraction and FE-SEM. The NO purification rate improved as the supported amount increased. On the other hand, in Comparative Example, the supported amount is less than 2% by weight, or as in Comparative Example 4, adsorption of aggregated metal elements instead of ion exchange increases to 13.5% by weight, the catalyst surface is covered, and the NO purification rate is increased. Has dropped.
【００３０】実施例４ 実施例１と同様にしてＮＨ4 型ＳＡＰＯ−34粉末を製造
した。次に、酢酸銅を水に溶解し、0.03規定の酢酸銅水
溶液を製造し、これにアンモニア水を添加しｐＨを10.5
にし、銅アンミン錯体を生成させた。これに酢酸を添加
し、ｐＨを７に調整した後、この溶液に上記ＮＨ4 型Ｓ
ＡＰＯ−34粉末を10g 加え、混合し、再びｐＨを７に調
整した。この状態で室温において24時間攪拌し、遠心分
離を行い、次いで真空乾燥し、最後に500 ℃×３時間の
仮焼を行い、Ｃｕ型ＳＡＰＯ−34を得た。 Example 4 NH 4 type SAPO-34 powder was produced in the same manner as in Example 1. Next, copper acetate is dissolved in water to produce a 0.03N copper acetate aqueous solution, and ammonia water is added to adjust the pH to 10.5.
To produce a copper ammine complex. Acetic acid was added to this to adjust the pH to 7, and then the above NH 4 type S was added to this solution.
10 g of APO-34 powder was added, mixed and the pH was adjusted to 7 again. In this state, the mixture was stirred at room temperature for 24 hours, centrifuged, dried in vacuum, and finally calcined at 500 ° C. for 3 hours to obtain Cu-type SAPO-34.
【００３１】このＣｕ型ＳＡＰＯ−34について、実施例
１と同様にしてＣｕ担持量及びＮＯ浄化能を測定した。
結果を表３に示す。With respect to this Cu-type SAPO-34, the amount of supported Cu and the NO purifying ability were measured in the same manner as in Example 1.
The results are shown in Table 3.
【００３２】実施例５ 酢酸銅の0.03規定水溶液を製造し、これにアンモニアを
添加し、ｐＨを10に調整し、これに硝酸を加えてｐＨを
6.5 に調整した。これを、実施例１と同様にしてＳＡＰ
Ｏ−34にアンモニア水を加え、ｐＨを６に調整し室温に
おいて24時間攪拌し、遠心分離しない混合液に加え、実
施例４と同様にしてＣｕ型ＳＡＰＯ−34を得た。そして
実施例１と同様にしてＣｕ担持量及びＮＯ浄化能を測定
した。結果を表３に示す。 Example 5 A 0.03N aqueous solution of copper acetate was prepared, ammonia was added to this to adjust the pH to 10, and nitric acid was added to this to adjust the pH.
Adjusted to 6.5. This is the same as in the first embodiment, SAP
Aqueous ammonia was added to O-34 to adjust the pH to 6, and the mixture was stirred at room temperature for 24 hours, added to the mixed solution without centrifugation, and Cu-type SAPO-34 was obtained in the same manner as in Example 4. Then, the amount of supported Cu and the NO purifying ability were measured in the same manner as in Example 1. The results are shown in Table 3.
【００３３】実施例６ 実施例１と同様にしてＮＨ4 型ＳＡＰＯ−34粉末を製造
した。次いで0.02規定酢酸銅及び0.02規定酢酸コバルト
の水溶液を製造し、これにアンモニア水を添加しｐＨを
11に調整し、実施例4 と同様にしてＣｕ、Ｃｏ型ＳＡＰ
Ｏ−34を製造し、実施例４と同様にして評価した。結果
を表３に示す。 Example 6 In the same manner as in Example 1, an NH 4 type SAPO-34 powder was produced. Next, an aqueous solution of 0.02N copper acetate and 0.02N cobalt acetate is produced, and ammonia water is added to this to adjust the pH.
Adjusted to 11, and in the same manner as in Example 4, Cu, Co type SAP
O-34 was produced and evaluated in the same manner as in Example 4. The results are shown in Table 3.
【００３４】比較例７〜12 実施例において使用したＳＡＰＯ−34の粉末を用い、表
３に示す条件においてあるいは直接酢酸銅溶液にＳＡＰ
Ｏ−34の粉末を加えｐＨ調整することなくイオン交換を
行った。得られた触媒について実施例４と同様にして評
価し、結果を表３に示す。 Comparative Examples 7 to 12 Using the powder of SAPO-34 used in Examples, SAP was directly added to the copper acetate solution under the conditions shown in Table 3.
O-34 powder was added to carry out ion exchange without adjusting the pH. The obtained catalyst was evaluated in the same manner as in Example 4, and the results are shown in Table 3.
【００３５】[0035]
【表３】 [Table 3]
【００３６】実施例１〜３と同様に、実施例４〜６では
Ｃｕ及びＣｏの担持量が２重量％以上であり、Ｘ線回
折、ＦＥ−ＳＥＭによる観察によってもすべてイオン交
換されていた。担持量が増加するに従いＮＯ浄化率が向
上した。これに対し比較例では担持量が２重量％未満で
あり、又は比較例10のようにイオン交換ではなく凝集し
た金属元素の吸着が14.3重量％と多くなり、触媒表面が
覆われ、ＮＯ浄化率が低下した。Similar to Examples 1 to 3, in Examples 4 to 6, the supported amounts of Cu and Co were 2% by weight or more, and all were ion-exchanged by observation with X-ray diffraction and FE-SEM. The NO purification rate improved as the supported amount increased. On the other hand, in Comparative Example, the supported amount is less than 2% by weight, or as in Comparative Example 10, adsorption of aggregated metal elements instead of ion exchange increases to 14.3% by weight, the catalyst surface is covered, and the NO purification rate is increased. Has dropped.
【００３７】[0037]
【発明の効果】本発明の方法は、触媒担体であるＳＡＰ
Ｏをまずアンモニアでイオン交換し、次いでこのアンモ
ニアを触媒金属でイオン交換し、２段階でイオン交換を
行うことにより触媒金属の担持量を高めることが可能と
なった。また触媒金属をアンミン錯体形状で用いてイオ
ン交換することにより、さらに担持量を高めることが可
能となった。INDUSTRIAL APPLICABILITY The method of the present invention uses SAP as a catalyst carrier
By carrying out ion exchange of O with ammonia first, then ion exchange of this ammonia with catalyst metal, and performing ion exchange in two stages, it became possible to increase the amount of catalyst metal supported. In addition, by carrying out ion exchange using a catalytic metal in the form of an ammine complex, it became possible to further increase the supported amount.
【図１】本発明の触媒の評価に用いる装置の略図であ
る。FIG. 1 is a schematic diagram of an apparatus used to evaluate the catalyst of the present invention.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｄ 53/36 １０２ Ｄ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location B01D 53/36 102 D
Claims (2)
フォスフェート（ＳＡＰＯ）を混合することによってア
ンモニウムイオン（ＮＨ4 + ) によりイオン交換し、Ｎ
Ｈ4 型ＳＡＰＯを形成すること、次いで (ii)前記ＮＨ4 型ＳＡＰＯを触媒金属を含む水溶液に添
加することによって触媒金属イオンによりイオン交換
し、ＳＡＰＯに触媒金属を担持させること、を特徴とす
る排気ガス浄化用触媒の製造方法。1. (i) A mixture of silicoaluminophosphate (SAPO) is mixed with an aqueous ammonia solution to carry out ion exchange with ammonium ions (NH 4 + ).
Forming H 4 type SAPO, and then (ii) adding the NH 4 type SAPO to an aqueous solution containing the catalytic metal to cause ion exchange with catalytic metal ions and to support the catalytic metal on SAPO. Exhaust gas purification catalyst manufacturing method.
フォスフェート（ＳＡＰＯ）を混合することによってア
ンモニウムイオン（ＮＨ4 + ) によりイオン交換し、Ｎ
Ｈ4 型ＳＡＰＯを形成すること、 (ii)触媒金属を含む水溶液にアンモニア水を添加するこ
とによってアンミン錯体均一分散液を形成し、この分散
液に酸を添加しｐＨ６〜８の範囲に調整した分散液を形
成すること、次いで (iii) 前記ＮＨ4 型ＳＡＰＯと前記分散液を混合し、触
媒金属をイオン交換によりＳＡＰＯに担持させること、 を特徴とする排気ガス浄化用触媒の製造方法。2. (i) Ion-exchange with ammonium ion (NH 4 + ) by mixing silicoaluminophosphate (SAPO) with an aqueous ammonia solution,
Forming H 4 type SAPO, and (ii) adding ammonia water to an aqueous solution containing a catalytic metal to form an ammine complex uniform dispersion liquid, and adding an acid to this dispersion liquid to adjust the pH to a range of 6 to 8. A method for producing an exhaust gas purifying catalyst, comprising forming a dispersion liquid, and then (iii) mixing the NH 4 -type SAPO and the dispersion liquid and supporting the catalytic metal on the SAPO by ion exchange.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5306587A JPH07155614A (en) | 1993-12-07 | 1993-12-07 | Production of exhaust gas purifying catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5306587A JPH07155614A (en) | 1993-12-07 | 1993-12-07 | Production of exhaust gas purifying catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07155614A true JPH07155614A (en) | 1995-06-20 |
Family
ID=17958867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5306587A Pending JPH07155614A (en) | 1993-12-07 | 1993-12-07 | Production of exhaust gas purifying catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07155614A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003059849A1 (en) * | 2002-01-03 | 2003-07-24 | Exxonmobil Chemical Patents Inc. | Stabilisation of acid catalysts |
| JP2006247460A (en) * | 2005-03-08 | 2006-09-21 | Catalysts & Chem Ind Co Ltd | Manufacturing method of adsorbent |
| WO2010084930A1 (en) * | 2009-01-22 | 2010-07-29 | 三菱化学株式会社 | Catalyst for removing nitrogen oxides and method for producing same |
| JP2011510899A (en) * | 2008-01-31 | 2011-04-07 | ビー・エイ・エス・エフ、コーポレーション | Catalysts, systems and methods utilizing non-zeolitic metals comprising molecular sieves having a CHA crystal structure |
| WO2011061841A1 (en) * | 2009-11-19 | 2011-05-26 | イビデン株式会社 | Honeycomb structure and exhaust gas purification apparatus |
| JP2011125852A (en) * | 2009-11-19 | 2011-06-30 | Ibiden Co Ltd | Honeycomb structure and exhaust gas cleaning apparatus |
| JP2011125793A (en) * | 2009-12-18 | 2011-06-30 | Jgc Catalysts & Chemicals Ltd | Method for manufacturing metal-bearing crystalline silica aluminophosphate catalyst, and metal-bearing crystalline silica aluminophosphate catalyst |
| WO2012029159A1 (en) * | 2010-09-02 | 2012-03-08 | イビデン株式会社 | Silicoalumina phosphate salt, honeycomb structure, and exhaust gas purification device |
| WO2012158239A1 (en) * | 2011-02-28 | 2012-11-22 | Johnson Matthey Public Limited Company | High-temperature scr catalyst |
| JP2014504255A (en) * | 2010-12-22 | 2014-02-20 | クラリアント プロダクツ （ドイチェランド） ゲーエムベーハー | Method for producing titano- (silico) -alumino-phosphate |
| JP2015062874A (en) * | 2013-09-26 | 2015-04-09 | 株式会社豊田中央研究所 | NOx SELECTIVE REDUCTION CATALYST, METHOD FOR PRODUCING THE SAME AND NOx PURIFICATION METHOD USING THE SAME |
| US9138732B2 (en) | 2007-02-27 | 2015-09-22 | Basf Corporation | Copper CHA zeolite catalysts |
| US9802182B2 (en) | 2013-03-13 | 2017-10-31 | Basf Corporation | Stabilized metal-exchanged SAPO material |
| US10583424B2 (en) | 2008-11-06 | 2020-03-10 | Basf Corporation | Chabazite zeolite catalysts having low silica to alumina ratios |
-
1993
- 1993-12-07 JP JP5306587A patent/JPH07155614A/en active Pending
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003059849A1 (en) * | 2002-01-03 | 2003-07-24 | Exxonmobil Chemical Patents Inc. | Stabilisation of acid catalysts |
| US6897180B2 (en) | 2002-01-03 | 2005-05-24 | Exxonmobil Chemical Patents Inc. | Stabilization of acid catalysts |
| US7193122B2 (en) | 2002-01-03 | 2007-03-20 | Exxonmobil Chemical Patents Inc. | Stabilization of acid catalysts |
| JP2006247460A (en) * | 2005-03-08 | 2006-09-21 | Catalysts & Chem Ind Co Ltd | Manufacturing method of adsorbent |
| US9839905B2 (en) | 2007-02-27 | 2017-12-12 | Basf Corporation | Copper CHA zeolite catalysts |
| US11845067B2 (en) | 2007-02-27 | 2023-12-19 | Basf Corporation | Copper CHA zeolite catalysts |
| US11529619B2 (en) | 2007-02-27 | 2022-12-20 | Basf Corporation | Copper CHA zeolite catalysts |
| US10654031B2 (en) | 2007-02-27 | 2020-05-19 | Basf Corporation | Copper CHA zeolite catalysts |
| US9138732B2 (en) | 2007-02-27 | 2015-09-22 | Basf Corporation | Copper CHA zeolite catalysts |
| US9656254B2 (en) | 2007-02-27 | 2017-05-23 | Basf Corporation | Copper CHA zeolite catalysts |
| US9162218B2 (en) | 2007-02-27 | 2015-10-20 | Basf Corporation | Copper CHA zeolite catalysts |
| JP2011510899A (en) * | 2008-01-31 | 2011-04-07 | ビー・エイ・エス・エフ、コーポレーション | Catalysts, systems and methods utilizing non-zeolitic metals comprising molecular sieves having a CHA crystal structure |
| US10105649B2 (en) | 2008-01-31 | 2018-10-23 | Basf Corporation | Methods utilizing non-zeolitic metal-containing molecular sieves having the CHA crystal structure |
| US11660585B2 (en) | 2008-11-06 | 2023-05-30 | Basf Corporation | Chabazite zeolite catalysts having low silica to alumina ratios |
| US10583424B2 (en) | 2008-11-06 | 2020-03-10 | Basf Corporation | Chabazite zeolite catalysts having low silica to alumina ratios |
| WO2010084930A1 (en) * | 2009-01-22 | 2010-07-29 | 三菱化学株式会社 | Catalyst for removing nitrogen oxides and method for producing same |
| US8961886B2 (en) | 2009-11-19 | 2015-02-24 | Ibiden Co., Ltd. | Honeycomb structure |
| US8691157B2 (en) | 2009-11-19 | 2014-04-08 | Ibiden Co., Ltd. | Honeycomb structure and exhaust gas converter |
| JP2011125852A (en) * | 2009-11-19 | 2011-06-30 | Ibiden Co Ltd | Honeycomb structure and exhaust gas cleaning apparatus |
| WO2011061841A1 (en) * | 2009-11-19 | 2011-05-26 | イビデン株式会社 | Honeycomb structure and exhaust gas purification apparatus |
| JP2011125793A (en) * | 2009-12-18 | 2011-06-30 | Jgc Catalysts & Chemicals Ltd | Method for manufacturing metal-bearing crystalline silica aluminophosphate catalyst, and metal-bearing crystalline silica aluminophosphate catalyst |
| US8808633B2 (en) | 2010-09-02 | 2014-08-19 | Ibiden Co., Ltd. | Silico-alumino phosphate, honeycomb structural body and exhaust gas conversion apparatus |
| WO2012029159A1 (en) * | 2010-09-02 | 2012-03-08 | イビデン株式会社 | Silicoalumina phosphate salt, honeycomb structure, and exhaust gas purification device |
| JP2014504255A (en) * | 2010-12-22 | 2014-02-20 | クラリアント プロダクツ （ドイチェランド） ゲーエムベーハー | Method for producing titano- (silico) -alumino-phosphate |
| WO2012158239A1 (en) * | 2011-02-28 | 2012-11-22 | Johnson Matthey Public Limited Company | High-temperature scr catalyst |
| US9802182B2 (en) | 2013-03-13 | 2017-10-31 | Basf Corporation | Stabilized metal-exchanged SAPO material |
| US9931620B2 (en) | 2013-03-13 | 2018-04-03 | Basf Corporation | Stabilized metal-exchanged SAPO material |
| JP2015062874A (en) * | 2013-09-26 | 2015-04-09 | 株式会社豊田中央研究所 | NOx SELECTIVE REDUCTION CATALYST, METHOD FOR PRODUCING THE SAME AND NOx PURIFICATION METHOD USING THE SAME |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2032799C (en) | Catalyst for and method of purifying oxygen-excess exhaust gas | |
| JP3086015B2 (en) | Exhaust gas purification catalyst | |
| US5270024A (en) | Process for reducing nitrogen oxides from exhaust gas | |
| JP2660411B2 (en) | Method for reducing and removing nitrogen oxides in exhaust gas | |
| EP0396085B1 (en) | Catalyst for purification of exhaust gases | |
| JPH0763631B2 (en) | Exhaust gas purification catalyst manufacturing method | |
| JPH07155614A (en) | Production of exhaust gas purifying catalyst | |
| JPH01135541A (en) | Catalyst for purifying exhaust gas | |
| JP2529739B2 (en) | Exhaust gas purification catalyst and method | |
| JP2000024505A (en) | Catalyst for selective nitrogen oxide reduction having wide active temperature range | |
| JPH04219141A (en) | Exhaust gas purification catalyst | |
| JPH07100386A (en) | Catalyst for purification of exhaust gas | |
| JPH0640964B2 (en) | Exhaust gas purification catalyst manufacturing method | |
| JP2851444B2 (en) | Exhaust gas purification method | |
| JP3114982B2 (en) | Exhaust gas purification catalyst and method of using the same | |
| JP3362401B2 (en) | Exhaust gas purification catalyst | |
| JP2939484B2 (en) | Exhaust gas purification method | |
| JP3221706B2 (en) | Nitrogen oxide removal catalyst and exhaust gas purification method using the same | |
| JP2921130B2 (en) | Exhaust gas purification catalyst | |
| JP3482661B2 (en) | Nitrogen oxide removal method | |
| JPH0557196A (en) | Production of catalyst for purifying exhaust gas | |
| JP2901295B2 (en) | Exhaust gas purification catalyst and method of using the same | |
| JP2802335B2 (en) | Method for producing exhaust purification catalyst | |
| JP3026355B2 (en) | Exhaust gas purification catalyst | |
| JPH05103949A (en) | Catalyst for removal of nitrogen oxide and method for removing nitrogen oxide with the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |