JPH02218436A - Catalyst carrier and its manufacture method - Google Patents
Catalyst carrier and its manufacture methodInfo
- Publication number
- JPH02218436A JPH02218436A JP1037795A JP3779589A JPH02218436A JP H02218436 A JPH02218436 A JP H02218436A JP 1037795 A JP1037795 A JP 1037795A JP 3779589 A JP3779589 A JP 3779589A JP H02218436 A JPH02218436 A JP H02218436A
- Authority
- JP
- Japan
- Prior art keywords
- alumina
- specific surface
- surface area
- catalyst
- catalyst carrier
- 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 43
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000000034 method Methods 0.000 title abstract description 9
- 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 51
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 32
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 nitrogen-containing basic compound Chemical class 0.000 claims abstract description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 17
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims description 19
- 229910001593 boehmite Inorganic materials 0.000 claims description 14
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 abstract description 23
- 239000006227 byproduct Substances 0.000 abstract description 7
- QKYBEKAEVQPNIN-UHFFFAOYSA-N barium(2+);oxido(oxo)alumane Chemical compound [Ba+2].[O-][Al]=O.[O-][Al]=O QKYBEKAEVQPNIN-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000010419 fine particle Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 3
- 239000012071 phase Substances 0.000 description 12
- 229910052746 lanthanum Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010304 firing Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 150000001553 barium compounds Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002604 lanthanum compounds Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- TUCNEACPLKLKNU-UHFFFAOYSA-N acetyl Chemical compound C[C]=O TUCNEACPLKLKNU-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、アルミナを主成分とした自動車排ガス浄化用
触媒及び燃焼用触媒に係り、特に高温において、高比表
面積を維持しかつ触媒成分を高分散担持して高活性な触
媒を提供し得る高耐熱性の触媒担体及びその製造方法に
関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a catalyst for purifying automobile exhaust gas and a combustion catalyst containing alumina as a main component, which maintains a high specific surface area and retains the catalytic component, especially at high temperatures. The present invention relates to a highly heat-resistant catalyst carrier capable of providing a highly active catalyst by highly dispersed support, and a method for producing the same.
従来、自動車排ガス浄化用触媒あるいは燃焼用触媒等の
担体に用いられているアルミナは、１０００℃以上の高
温に曝されると、α−アルミナに転移し、これに伴って
比表面積は１０ｍ２／ｇ以下にまで低下する。これによ
って、担持した触媒成分がシンタリング等の変化を起こ
し、触媒が劣化する（触媒の熱劣化）、シたがって、熱
劣化の少ない触媒を得るためには、高温下でも高比表面
積を維持できる安定な触媒担体が望まれている。Alumina, which has conventionally been used as a carrier for automobile exhaust gas purification catalysts or combustion catalysts, transforms into α-alumina when exposed to high temperatures of 1000°C or higher, and the specific surface area decreases to 10 m2/g. It decreases to below. As a result, the supported catalyst components undergo changes such as sintering, and the catalyst deteriorates (thermal deterioration of the catalyst). Therefore, in order to obtain a catalyst with less thermal deterioration, it is necessary to maintain a high specific surface area even at high temperatures. A stable catalyst support is desired.
従来このようなアルミナ担体の熱的安定性を向上させる
方法としては、アルミナにバリウムなどのアルカリ土類
元素の化合物やランタンなどの希土類元素の化合物を添
加すること（特開昭６１−２４５８４４号公報、特開昭
６２−１４５４号公報、特開昭６１−３８６２７号公報
、第５６回触媒討論会（Ａ）講演予稿集４Ｎ１７．１９
２（１９８５）等）が提案されている。これらの方法は
、アルカリ土類元素の化合物あるいは希土類元素の化合
物をアルミナに添加して焼成することによって、アルミ
ナの一部または全部を耐熱性の高いβ−アルミナに転化
するものであり、これによって１２００℃程度の高温で
も物性変化が小さく、比表面積の低下の少ない安定な担
体が得られるというものである。Conventionally, a method for improving the thermal stability of such an alumina support is to add a compound of an alkaline earth element such as barium or a compound of a rare earth element such as lanthanum to alumina (Japanese Patent Laid-Open No. 61-245844). , JP-A-62-1454, JP-A-61-38627, 56th Catalyst Symposium (A) Proceedings 4N17.19
2 (1985) etc.) have been proposed. These methods convert some or all of the alumina into highly heat-resistant β-alumina by adding an alkaline earth element compound or a rare earth element compound to the alumina and firing it. Even at high temperatures of about 1200° C., a stable support with little change in physical properties and little decrease in specific surface area can be obtained.
しかしながら、上記提案の方法によっては高温で安定な
担体は得られるものの、その担体の比表面積が２０ ｒ
ｄ／ ｇ程度と小さく、触媒担体として十分ではなく、
さらに担体中にβ−アルミナ相以外にアルミン酸バリウ
ム（Ｂ ａ Ｏ−Ａ １２０．）やランタンアルミネー
ト（ＬａＡΩ０３）が副生ずるため高価な貴金属等の触
媒成分を高分散担持できず、触媒性能を有効に引きだす
ことができないという問題点があった。However, although a support that is stable at high temperatures can be obtained by the method proposed above, the specific surface area of the support is 20 r
It is small, about d/g, and is not sufficient as a catalyst carrier.
Furthermore, in addition to the β-alumina phase, barium aluminate (B a O-A 120.) and lanthanum aluminate (LaAΩ03) are produced as by-products in the carrier, making it impossible to support catalyst components such as expensive precious metals in a highly dispersed manner, which impairs catalyst performance. There was a problem that it could not be effectively drawn out.
本発明は、上記従来技術の問題点を解決するためになさ
れたものであり、１０００℃以上の高温においても触媒
活性成分を高分散担持するのに十分な比表面積を有しか
つアルミン酸バリウムやランタンアルミネートを含まな
いような高耐熱性の触媒担体及びその製造方法を提供す
ることを目的としている。The present invention has been made to solve the problems of the prior art described above, and has a specific surface area sufficient to support highly dispersed catalytic active components even at high temperatures of 1000°C or higher, and has barium aluminate, etc. The object of the present invention is to provide a highly heat-resistant catalyst carrier that does not contain lanthanum aluminate and a method for producing the same.
（課題を解決するための手段〕
上記目的は、比表面積が１５０ｍ２／ｇ以上のアルミナ
原料をアンモニア、アミン、ピリジンあるいは尿素のい
ずれかの含窒素塩基性化合物で予め浸漬処理した後、酸
化バリウム及び／又は酸化ランタンをアルミナ原料のア
ルミナ分に対して２〜８モル％添加して、焼成した触媒
担体及びその製造方法により、達成される。(Means for Solving the Problem) The above object is to pre-immerse an alumina raw material having a specific surface area of 150 m2/g or more in a nitrogen-containing basic compound such as ammonia, amine, pyridine or urea, and then add barium oxide and This is achieved by adding 2 to 8 mol % of lanthanum oxide to the alumina content of the alumina raw material and firing the catalyst carrier and its manufacturing method.
そして前記アルミナ原料がベーマイト及び／またはベー
マイトゲルであることが好ましい。Preferably, the alumina raw material is boehmite and/or boehmite gel.
β−アルミナは、第１図及び第２図に示すように、酸素
イオンの最密充填からなるスピネルブロックがバリウム
（Ｂａ）やランタン（Ｌａ）などのカチオンを含む鏡映
面によって隔てられた層状アルミネート構造をとってお
り、この鏡映面がスピネルブロックの結晶成長を抑制す
るため耐熱性に優れているとされている。しかし、β−
アルミナは１層状構造をとるために結晶が成長すると積
層して高比表面積が得られない、すなわち、β−アルミ
ナそのものでは耐熱性は高いが高比表面積の担体を得る
ことができない、しかしながら１本発明者らが鋭意研究
した結果、β−アルミナを。As shown in Figures 1 and 2, β-alumina has a layered structure in which spinel blocks consisting of close-packed oxygen ions are separated by mirror planes containing cations such as barium (Ba) and lanthanum (La). It has an aluminate structure, and is said to have excellent heat resistance because this mirrored surface suppresses the crystal growth of the spinel block. However, β−
Alumina has a single-layer structure, so when the crystals grow, they stack up, making it impossible to obtain a high specific surface area.In other words, β-alumina itself has high heat resistance, but it is not possible to obtain a carrier with a high specific surface area. As a result of intensive research by the inventors, β-alumina was discovered.
その優れた耐熱性を生かして焼結抑制剤として比表面積
の大きなアルミナ中に高分散させることができれば高耐
熱性でかつ高比表面積の担体を実現することが可能であ
ることを見い出した。従来の方法は５例えば特開昭６２
−１４５４号公報にみられるように、アルミナ中にバリ
ウム化合物あるいはランタン化合物を適当量添加し、焼
成することによりβ−アルミナ相を生成させるものであ
る。It has been discovered that if it can be highly dispersed in alumina with a large specific surface area as a sintering inhibitor by taking advantage of its excellent heat resistance, it is possible to realize a carrier with high heat resistance and a high specific surface area. The conventional method is 5, for example, JP-A-62
As seen in Japanese Patent No. 1454, a β-alumina phase is produced by adding an appropriate amount of a barium compound or a lanthanum compound to alumina and firing the mixture.
この方法では、比表面積の小さなアルミナ担体しか得ら
れない、これは、β−アルミナ相の生成が結局はアルミ
ナ粒子と酸化バリウムあるいは酸化ランタンの同相反応
によるものであるため、β−アルミナ相の均一な結晶成
長が実現しにくいこと及びβ−アルミナ相を生成させて
担体を十分に安定化させるためには、１１００’Ｃ以上
の高温焼成が必要であり、そのためα−アルミナの生成
が避は難い等の理由によるものと考えられる。さらにま
たアルミナ粒子と酸化バリウムあるいは酸化ランタンの
固相反応でβ−アルミナを生成させる方法ではアルミン
酸バリウムあるいはランタンアルミネートの副生を抑え
ることが困難であり、これら化合物が副生ずると、担体
の塩基性が強くなり過ぎて貴金属等の触媒成分の分散性
が著しく低下してしまう。With this method, only an alumina support with a small specific surface area can be obtained. This is because the formation of the β-alumina phase is ultimately due to the in-phase reaction between alumina particles and barium oxide or lanthanum oxide, and the β-alumina phase is uniform. It is difficult to achieve crystal growth, and in order to generate the β-alumina phase and sufficiently stabilize the support, high-temperature calcination of 1100'C or higher is necessary, so the formation of α-alumina is unavoidable. This is thought to be due to the following reasons. Furthermore, in the method of producing β-alumina through a solid phase reaction between alumina particles and barium oxide or lanthanum oxide, it is difficult to suppress the by-product of barium aluminate or lanthanum aluminate, and when these compounds are produced as by-products, the support If the basicity becomes too strong, the dispersibility of catalyst components such as noble metals will be significantly reduced.
本発明になる担体の製造方法においては、担体の母体と
なるアルミナ原料を予めアンモニア、アミン、ピリジン
あるいは尿素等の含窒素塩基性化合物で予め浸漬処理し
ておくことにより、アルミナ粒子表面にＢａ”、Ｌａ−
オンを引きっけ易くしてよく分散させ、β−アルミナ相
の均一あるいは高分散生成を可能にしているものと思わ
れる。この結果、β−アルミナ相以外の比較的高い比表
面積のアルミナ中に微粒のβ−アルミナ相が高分散した
高耐熱性でかつ高比表面積の担体が得られ。In the method for producing a support according to the present invention, the alumina raw material that is the base of the support is pre-immersed in a nitrogen-containing basic compound such as ammonia, amine, pyridine, or urea, so that the surface of the alumina particles is coated with Ba''. , La-
It is thought that this makes it easier to attract and disperse the ions, making it possible to produce a uniform or highly dispersed β-alumina phase. As a result, a highly heat resistant and high specific surface area support in which fine particles of the β-alumina phase are highly dispersed in alumina other than the β-alumina phase and having a relatively high specific surface area can be obtained.
本発明で得られた担体中にはアルミン酸バリウムやラン
タンアルミネート副生しないため担体の塩基仕度が適度
に保たれ、触媒活性成分を担持しやすいものと考えられ
る。Since no barium aluminate or lanthanum aluminate is produced as a by-product in the carrier obtained in the present invention, the basicity of the carrier is maintained at an appropriate level, and it is considered that the carrier can easily support the catalytically active component.
本発明に係る実施例の触媒担体を製造するにあたって、
使用するアルミナ原料は、比表面積が１５ｏｎｆ／ｇ以
上のものであれば１．ガンマ（γ）デルタ（δ）、シー
タ（θ）、イータ（η）、カイ（χ）等いずれであって
もかまわないが、ベーマイトあるいはベーマイトゲル等
の水和物を用いると特に効果が大きい。アルミナ原料の
比表面積は、高比表面積担体を得るためには１５０ｒｄ
／ｆＫ以上が必要であり、それ以下のものでは効果は小
さい。In manufacturing the catalyst carrier of the example according to the present invention,
If the alumina raw material to be used has a specific surface area of 15 onf/g or more, 1. Any of gamma (γ), delta (δ), theta (θ), eta (η), chi (χ), etc. may be used, but the use of a hydrate such as boehmite or boehmite gel is particularly effective. The specific surface area of the alumina raw material is 150rd in order to obtain a high specific surface area support.
/fK or more is required; anything less than that has little effect.
また、バリウム化合物、ランタン化合物としては、硝酸
バリウム（Ｂ ａ （Ｎｏｗ） ｚ）−酢酸バリウム（
Ｂ ａ （ＣＨａ ＣＯＯ） り 、水酸化バリウム（
Ｂ ａ （ＯＨ） ｉ） 、硝酸ランタン（Ｌａ （Ｎ
Ｏ３） ３） −酢酸ランタン（Ｌ ａ （ＣＨ３ＣＯ
Ｏ） り等を用いることができる。これら化合物の添加
量は、酸化バリウム（Ｂａｄ）あるいは酸化ランタン（
Ｌａ２０、）として、アルミナ原料中のアルミナ分（Ａ
（ｌ ｚ Ｏｚ ）に対して２〜８モル％以内が有効で
あるが、２〜５モル％が特に望ましい、さらに焼成温度
は、担体中にβ−アルミナ相を確実に生成させて担体の
安定化をはかるためには、１１５０℃以上であることが
望ましいが、７００℃以上であれば有効である。１１５
０’Ｃ以下ではβ−アルミナ相は生成しないと考えられ
るが、β−アルミナの前駆体が形成されれば効果が期待
できる。In addition, barium compounds and lanthanum compounds include barium nitrate (B a (Now) z) - barium acetate (
B a (CHA COO) ri, barium hydroxide (
B a (OH) i), lanthanum nitrate (La (N
O3) 3) -Lanthanum acetate (L a (CH3CO
O) ri etc. can be used. The amount of these compounds added is determined by barium oxide (Bad) or lanthanum oxide (
La20,) is the alumina content (A
A range of 2 to 8 mol% based on (l z Oz ) is effective, but a range of 2 to 5 mol % is particularly desirable. Furthermore, the firing temperature must be set to ensure the formation of a β-alumina phase in the carrier and to stabilize the carrier. In order to increase the temperature, it is desirable that the temperature be 1150°C or higher, but it is effective if the temperature is 700°C or higher. 115
Although it is thought that the β-alumina phase is not generated at 0'C or lower, an effect can be expected if a β-alumina precursor is formed.
本発明の実施例なる触媒担体の製造方法において、浸漬
処理に用いる含窒素塩基性化合物の量は、後の製造工程
にて添加されるバリウム化合物あるいはランタン化合物
の量に応じて決まる６添加さラムイオン（ＮＨ４）が生
ずる量以上用いれば効果がある。In the method for manufacturing a catalyst carrier according to an embodiment of the present invention, the amount of the nitrogen-containing basic compound used in the dipping treatment is determined depending on the amount of barium compound or lanthanum compound added in the subsequent manufacturing process. It is effective if used in an amount greater than the amount that (NH4) is produced.
以下本発明の実施例を詳細に説明する。Examples of the present invention will be described in detail below.
実施例１
アルミナ原料として、比表面積が２１０ｎｒ／ｇ（５５
０℃、２時間焼成時）、平均粒径が２．７μｍのベーマ
イトゲル乾燥粉（水分２５．９％）を１３５ｇとり、水
３００ｃｃ中に添加してよく分散させた。それに含窒素
塩基性化合物として２８％のアンモニア水２．７６ｇを
添加してよく混合し、１時間放置した。次いで硝酸ラン
タン（Ｌａ（Ｎｏ□）３）を前記ベーマイト乾燥粉中の
アルミナ分（Ａ Ｑ ｚ Ｏｓ ）に対して、酸化ラン
タン（Ｌａ２０、）として３モル％となるように添加し
、３０分間よく混合した。この混合物を７０℃で１晩乾
燥した後、大気中で１２００℃で２時間焼成して触媒担
体を得た。Example 1 As an alumina raw material, a specific surface area of 210 nr/g (55
135 g of dry boehmite gel powder (moisture 25.9%) with an average particle size of 2.7 μm was taken into 300 cc of water and well dispersed. 2.76 g of 28% aqueous ammonia was added thereto as a nitrogen-containing basic compound, mixed well, and left for 1 hour. Next, lanthanum nitrate (La(No□)3) was added to the alumina content (A Q z Os ) in the dry boehmite powder in an amount of 3 mol % as lanthanum oxide (La20,), and the mixture was stirred for 30 minutes. Mixed. This mixture was dried at 70° C. overnight and then calcined in the air at 1200° C. for 2 hours to obtain a catalyst carrier.
比較例１
実施例１において、アンモニア水を添加しない他には同
様にして触媒担体を得た。Comparative Example 1 A catalyst carrier was obtained in the same manner as in Example 1 except that aqueous ammonia was not added.
実施例２
実施例１において、硝酸ランタンをベーマイト乾燥粉中
のアルミナ分（ＡＱ２ｏ’ｓ）に対して酸化ランタンと
して２モル％となるように添加する他は同様にして触媒
担体を得た。Example 2 A catalyst carrier was obtained in the same manner as in Example 1, except that lanthanum nitrate was added to the alumina content (AQ2o's) in the dry boehmite powder in an amount of 2 mol % as lanthanum oxide.
実施例３．４
実施例１において、アンモニア水の添加量をそれぞれ４
．７９ｇ、７．７６ｇ、硝酸ランタンをベーマイト中の
アルミナ分に対して酸化ランタンとしてそれぞれ５モル
％、８モル％となるように添加する他は同様にして触媒
担体を得た。Example 3.4 In Example 1, the amount of ammonia water added was 4
．． Catalyst carriers were obtained in the same manner except that 79 g and 7.76 g of lanthanum nitrate were added in amounts of 5 mol % and 8 mol % of lanthanum oxide based on the alumina content in the boehmite, respectively.
実施例５
実施例１において、アルミナ原料を、比表面積が１６０
ｍ２／ｇ、平均粒径３μｍのγ−アルミナ粉末１２７ｇ
（水分２１．３％）に替えた他は同様にして触媒担体
を得た。Example 5 In Example 1, the alumina raw material had a specific surface area of 160
m2/g, 127g of γ-alumina powder with an average particle size of 3μm
A catalyst carrier was obtained in the same manner except that the water content was changed to (moisture 21.3%).
実施例６
実施例１において、硝酸ランタンの替わりに水酸化バリ
ウム（Ｂ ａ （ＯＨ） ａ）をベーマイト乾燥粉中の
アルミナ分＜ Ａａ ｍ Ｏ） ）に対して、酸化バリ
ウム（Ｂａｄ）として３モル％となるように添加した他
は同様にして触媒担体を得た。Example 6 In Example 1, barium hydroxide (B a (OH) a) was used instead of lanthanum nitrate in an amount of 3 mol of barium oxide (Bad) based on the alumina content < Aam O) in the dry boehmite powder. A catalyst carrier was obtained in the same manner except that the catalyst carrier was added in such a manner that the amount of
比較例２，３
実施例１において、アンモニア水の添加量をそれぞれ２
．７６ｇ、９．９２ｇ、硝酸ランタンをベーマイト中の
アルミナ分に対して酸化ランタンとしてそれぞれ１モル
％、１０モル％となるように添加する他は同様にして触
媒担体を得た。Comparative Examples 2 and 3 In Example 1, the amount of ammonia water added was 2, respectively.
．． Catalyst carriers were obtained in the same manner except that 76 g and 9.92 g of lanthanum nitrate were added in amounts of 1 mol % and 10 mol % of lanthanum oxide based on the alumina content in the boehmite, respectively.
比較例４．５
実施例５において、アルミナ原料として、それぞれ比表
面積が１２０イ／ｇ、７８ボ／ｇのγ−７／Ｌ／ミナを
１２２ｇ （水分１８．０％）、１１０ｇ（水分９．１
％）用いた他は同様にして触媒担体を得た。Comparative Example 4.5 In Example 5, 122 g (moisture 18.0%) and 110 g (moisture 9.0%) of γ-7/L/mina with specific surface areas of 120 I/g and 78 I/g, respectively, were used as alumina raw materials. 1
A catalyst carrier was obtained in the same manner except that %) was used.
試験例１（比表面積の測定）
触媒担体を大気中で１２００℃、４時間焼成する前後で
ＢＥＴ法（Ｎ２吸着法）により比表面積を測定した。Test Example 1 (Measurement of Specific Surface Area) The specific surface area was measured by the BET method (N2 adsorption method) before and after firing the catalyst carrier in the atmosphere at 1200° C. for 4 hours.
実施例１〜６、及び比較例１〜５の担体について、担体
を得たときの比表面積とそれを１２００℃で４時間大気
中で熱処理した後の比表面積を第１表に示す。For the carriers of Examples 1 to 6 and Comparative Examples 1 to 5, Table 1 shows the specific surface area when the carrier was obtained and the specific surface area after heat treating the carrier at 1200° C. for 4 hours in the air.
発明の実施例の触媒担体は、従来（比較例１）のものに
比べて比表面積が顕著に増大しており、かつさらに１２
００℃で４時間熱処理しても比表面積の低下度が小さく
高耐熱性も兼ね備えていることがわかる。The catalyst carrier of the example of the invention has a significantly increased specific surface area compared to that of the conventional one (comparative example 1), and also has a specific surface area of 12
It can be seen that even after heat treatment at 00°C for 4 hours, the degree of decrease in specific surface area is small and it also has high heat resistance.
第３図、第４図には、比較例１、実施例１のそれぞれで
得た担体のＸ線回折図を示したものである。従来の担体
（比較例１）にはθ−アルミナやランタンβ−アルミナ
（Ｌ ａ、ｏ、 −１１Ａ ｎ、ｏ３）のピークに混じ
って、ランタンアルミネート（Ｌａ、０３・ＡＱ、０３
）のピークが認められるのに対して、本発明になる実施
例１の担体にはランタンアルミネートのピークが全く認
められず、β−アルミナ相が選択的に生成していると考
えられる。FIGS. 3 and 4 show X-ray diffraction patterns of the carriers obtained in Comparative Example 1 and Example 1, respectively. In the conventional carrier (Comparative Example 1), lanthanum aluminate (La, 03, AQ, 03
) peaks were observed, whereas no lanthanum aluminate peaks were observed in the carrier of Example 1 according to the present invention, suggesting that the β-alumina phase was selectively generated.
第５図は、酸化ランタンの添加量に対する担体の１２０
０℃、４時間焼成後の比表面積を示したものである。酸
化ランタン添加量が２〜８モル％で高い比表面積が得ら
れることがわかる。Figure 5 shows the amount of lanthanum oxide added to the support at 120
The figure shows the specific surface area after firing at 0°C for 4 hours. It can be seen that a high specific surface area can be obtained when the amount of lanthanum oxide added is 2 to 8 mol%.
第６図は、アルミナ原料の比表面積に対する担体の１２
００℃、４時間焼成後の比表面積を示したものである。Figure 6 shows the specific surface area of the carrier versus the specific surface area of the alumina raw material.
The figure shows the specific surface area after firing at 00°C for 4 hours.
アルミナ原料の比表面積が１５゜ｎｆ／ｇ以上で著しい
効果が期待できることがわかる。It can be seen that significant effects can be expected when the specific surface area of the alumina raw material is 15°nf/g or more.
なお、実施例１〜６では浸漬処理に用いる含窒素塩基性
化合物としてアンモニアを用いたが、他にアミン、ピリ
ジンあるいは尿素を用いることができる。In Examples 1 to 6, ammonia was used as the nitrogen-containing basic compound used in the dipping treatment, but amine, pyridine, or urea may also be used.
本発明によれば、比表面積が１５０ｍ２／ｇ以上のアル
ミナ原料をアンモニア、アミン、ピリジンあるいは尿素
のいずれかの含窒素塩基性化合物で予め浸漬処理した後
、酸化バリウム及び／又は酸化ランタンをアルミナ原料
のアルミナ分に対して２〜８モル％添加−して、焼成す
ることによりＭ媒担体を製造するので、この触媒担体は
高い比表面積を維持することができ、かつランタンアル
ミネートやアルミン酸バリウムといった、触媒成分の分
散性を著しく低下させる副生物を含有せず、高価な貴金
属等の触媒成分を高分散担持して触媒性能を有効に引き
出すことができる。According to the present invention, an alumina raw material having a specific surface area of 150 m2/g or more is pre-immersed in a nitrogen-containing basic compound such as ammonia, amine, pyridine or urea, and then barium oxide and/or lanthanum oxide is added to the alumina raw material. Since the M medium carrier is produced by adding 2 to 8 mol% to the alumina content and firing, this catalyst carrier can maintain a high specific surface area and is free from lanthanum aluminate and barium aluminate. It does not contain by-products that significantly reduce the dispersibility of catalyst components, and can support catalyst components such as expensive noble metals in a highly dispersed manner, thereby effectively bringing out the catalytic performance.
第１図はバリウムβ−アルミナの構造を示す模式図、第
２図はランタンβ−アルミナの構造を示す模式図、第３
図は実施例１で得られたＸ線回折図、第４図は比較例１
で得られたＸ線回折図、第５図は実施例１〜４及び比較
例２，３で得られた担体について、酸化ランタンの添加
量に対して。
１２００℃、４時間熱処理後の担体の比表面積をプロッ
トした図、第６図は実施例１，５及び比較例４，５で得
られた担体について、アルミナ原料の比表面積に対して
、１２００℃、４時間熱処理後の担体の比表面積をプロ
ットした図である。Figure 1 is a schematic diagram showing the structure of barium β-alumina, Figure 2 is a schematic diagram showing the structure of lanthanum β-alumina, and Figure 3 is a schematic diagram showing the structure of lanthanum β-alumina.
The figure is an X-ray diffraction diagram obtained in Example 1, and Figure 4 is Comparative Example 1.
The X-ray diffraction diagrams obtained in Figure 5 are for the supports obtained in Examples 1 to 4 and Comparative Examples 2 and 3, with respect to the amount of lanthanum oxide added. Figure 6 is a diagram plotting the specific surface area of the carrier after heat treatment at 1200°C for 4 hours. , is a diagram plotting the specific surface area of the carrier after heat treatment for 4 hours.
Claims (4)
をアンモニア、アミン、ピリジンあるいは尿素のいずれ
かの含窒素塩基性化合物で予め浸漬処理した後、酸化バ
リウム及び／又は酸化ランタンをアルミナ原料のアルミ
ナ分に対して２〜８モル％添加して、焼成した触媒担体
。(1) After pre-immersing an alumina raw material with a specific surface area of 150 m^2/g or more in a nitrogen-containing basic compound such as ammonia, amine, pyridine, or urea, barium oxide and/or lanthanum oxide are added to the alumina raw material. A catalyst carrier which is added in an amount of 2 to 8 mol% based on the alumina content and fired.
マイトゲルであることを特徴とする請求項１記載の媒担
体。(2) The medium carrier according to claim 1, wherein the alumina raw material is boehmite and/or boehmite gel.
をアンモニア、アミン、ピリジンあるいは尿素のいずれ
かの含窒素塩基性化合物で予め浸漬処理した後、酸化バ
リウム及び／又は酸化ランタンをアルミナ原料のアルミ
ナ分に対して２〜８モル％添加して、焼成する触媒担体
の製造方法。(3) After pre-immersing an alumina raw material with a specific surface area of 150 m^2/g or more in a nitrogen-containing basic compound such as ammonia, amine, pyridine, or urea, barium oxide and/or lanthanum oxide are added to the alumina raw material. A method for producing a catalyst carrier in which 2 to 8 mol% of alumina is added and fired.
マイトゲルであることを特徴とする請求項３記載の触媒
担体の製造方法。(4) The method for producing a catalyst carrier according to claim 3, wherein the alumina raw material is boehmite and/or boehmite gel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1037795A JPH02218436A (en) | 1989-02-17 | 1989-02-17 | Catalyst carrier and its manufacture method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1037795A JPH02218436A (en) | 1989-02-17 | 1989-02-17 | Catalyst carrier and its manufacture method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02218436A true JPH02218436A (en) | 1990-08-31 |
Family
ID=12507431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1037795A Pending JPH02218436A (en) | 1989-02-17 | 1989-02-17 | Catalyst carrier and its manufacture method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02218436A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10906816B2 (en) | 2016-07-29 | 2021-02-02 | Sumitomo Chemical Company, Limited | Alumina and method for producing automotive catalyst using same |
-
1989
- 1989-02-17 JP JP1037795A patent/JPH02218436A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10906816B2 (en) | 2016-07-29 | 2021-02-02 | Sumitomo Chemical Company, Limited | Alumina and method for producing automotive catalyst using same |
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