JPH0615039B2 - Process for producing catalyst for hydrogenation reaction of aromatic carboxylic acid - Google Patents
Process for producing catalyst for hydrogenation reaction of aromatic carboxylic acidInfo
- Publication number
- JPH0615039B2 JPH0615039B2 JP60153584A JP15358485A JPH0615039B2 JP H0615039 B2 JPH0615039 B2 JP H0615039B2 JP 60153584 A JP60153584 A JP 60153584A JP 15358485 A JP15358485 A JP 15358485A JP H0615039 B2 JPH0615039 B2 JP H0615039B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- carboxylic acid
- hydrogenation reaction
- aromatic carboxylic
- producing
- 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
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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、芳香族カルボン酸類の水素化反応による芳香
族アルデヒド類の製造に有効な触媒の製造方法に関す
る。TECHNICAL FIELD The present invention relates to a method for producing a catalyst effective for producing aromatic aldehydes by a hydrogenation reaction of aromatic carboxylic acids.
従来より芳香族カルボン酸類を水素化し、芳香族アルデ
ヒド類を製造しようとする試みはいくつかなされている
が、最近クロム、インジウム及び鉛から選ばれた一種以
上の元素を必須成分として含む酸化ジルコニウム触媒を
用いる方法が提案された。There have been some attempts to produce aromatic aldehydes by hydrogenating aromatic carboxylic acids, but recently, a zirconium oxide catalyst containing one or more elements selected from chromium, indium and lead as essential components. A method using is proposed.
本発明は、上述の酸化ジルコニウム触媒の製造に関する
ものであり、なかんづく、高い比表面積を有し、且つ高
い活性を有する触媒の製造方法を開発すべく鋭意検討を
行なつたものである。The present invention relates to the production of the above-mentioned zirconium oxide catalyst, and has been earnestly studied to develop a method for producing a catalyst having a high specific surface area and high activity.
本発明は、触媒の構成成分の一方であるクロム、インジ
ウム及び鉛の各元素（以下単に必須元素という）の供給
源として、これらの元素の水溶性無機化合物を出発原料
として用いることにより、飛躍的に触媒活性が増大する
ことを見出したものである。INDUSTRIAL APPLICABILITY The present invention is dramatically improved by using a water-soluble inorganic compound of these elements as a starting material as a supply source for each element of chromium, indium and lead (hereinafter simply referred to as essential elements), which is one of the constituent components of the catalyst. It was found that the catalytic activity increases.
以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
本発明において、触媒は通常の方法で成形される。例え
ば必須元素の無機化合物水溶液と、オキシ水酸化ジルコ
ニウムの粉末とを、必要に応じてバインダー成分の存在
下混合し、押出し成形後乾燥し、所定の温度で焼成する
方法、この乾燥品もしくは焼成品を適当な粒度に粉砕
し、打錠成形する方法、或いは前述の必要成分を水性ス
ラリーとし、噴霧乾燥等の適当な方法で顆粒化し、打錠
成形する方法等があるが、特に限定されない。In the present invention, the catalyst is formed by a usual method. For example, an inorganic compound aqueous solution of essential elements and zirconium oxyhydroxide powder are mixed, if necessary, in the presence of a binder component, followed by extrusion molding, drying, and firing at a predetermined temperature. This dried or fired product There is a method of crushing to a suitable particle size and tableting, or a method of making the above-mentioned necessary components into an aqueous slurry and granulating by an appropriate method such as spray drying and tableting, but not particularly limited.
又必須元素の水溶性無機化合物としては、硫酸塩、硝酸
塩、ハロゲン化物、或は、無水クロム酸、重クロム酸も
しくはそのアンモニウム塩、アルカリ塩等の無機塩が挙
げられるが、触媒に対する一般的な被毒作用を呈する不
純物を含まないという点から、硝酸塩類、無水クロム
酸、重クロム酸アンモニウム等比較的低温で分解し、且
つ他の被毒元素を含まない塩が好ましい。Examples of water-soluble inorganic compounds of essential elements include sulfates, nitrates, halides, or inorganic salts such as chromic anhydride, dichromic acid or its ammonium salt, and alkali salt. Salts that decompose at relatively low temperatures, such as nitrates, chromic anhydride, and ammonium dichromate, and do not contain other poisoning elements are preferred because they do not contain impurities that exhibit poisoning action.
尚、これらの必須元素の添加量としては、ジルコニウム
に対する原子比で示した場合、０．００１〜0.5、より
好ましくは０．０１〜0.1程度が適当である。The addition amount of these essential elements is appropriately 0.001 to 0.5, and more preferably 0.01 to 0.1, in terms of atomic ratio to zirconium.
又、必要によつて添加するバインダーとしては、前述と
同様な理由から焼成により消失する有機化合物が好まし
く、ポリビニルアルコールでんぷん糊、結晶性セルロー
ス、各種の界面活性剤、低融点ワックス、ステアリン酸
等の通常の造粒に用いられるバインダーを使うことがで
きる。Further, as the binder to be added if necessary, an organic compound which disappears by firing for the same reason as described above is preferable, and polyvinyl alcohol starch paste, crystalline cellulose, various surfactants, low melting point wax, stearic acid, etc. The binder used for usual granulation can be used.
又酸化ジルコニウム源としては、市販のジルコニウム水
酸化物（水酸化ジルコニル、水酸化ジルコニウム）或い
は、酸化ジルコニウムが適当である。As the zirconium oxide source, commercially available zirconium hydroxide (zirconyl hydroxide, zirconium hydroxide) or zirconium oxide is suitable.
更に造粒物を焼成する場合、焼成温度は400〜９００
℃、好ましくは４００〜７００℃が適当である。When firing the granulated material, the firing temperature is 400 to 900.
C., preferably 400 to 700.degree. C. is suitable.
次に本発明を実施例を挙げて説明するが、その要旨を逸
脱しない限り、以下の実施例に限定されるものではな
い。Next, the present invention will be described by way of examples, but the present invention is not limited to the following examples without departing from the gist thereof.
実施例１ 市販のオキシ水酸化ジルコニウム（酸化ジルコニウム換
算純度８５．４％）２３４０ｇに、硝酸クロム９水和物
３２５ｇ、ポリビニルアルコール（日本合成(株)ＥＧ０
５）４０ｇ及び水 940ｇよりなる水溶液を加え、ニーダ
ーで混練後押出し成形機で３mmφのヒモ状に成形乾燥し
た。続いて５８０℃で３時間焼成した後１０〜２０メツ
シュに粗枠して触媒を調製し、次の反応条件で安息香酸
の水素化反応を行なつた。反応成績及び調製した触媒の
N2吸着法による比表面積を表−１に示した。必須元素の
添加量はジルコニウムに対して原子比で０．０５とし
た。Example 1 2340 g of commercially available zirconium oxyhydroxide (purity equivalent to zirconium oxide: 85.4%), 325 g of chromium nitrate nonahydrate, polyvinyl alcohol (Nippon Gosei Co., Ltd. EG0
5) An aqueous solution containing 40 g and 940 g of water was added, and the mixture was kneaded with a kneader and then extruded into a string of 3 mmφ and dried. Subsequently, the mixture was calcined at 580 ° C. for 3 hours and then roughly framed in 10 to 20 mesh to prepare a catalyst, and a benzoic acid hydrogenation reaction was carried out under the following reaction conditions. Reaction results and prepared catalyst
The specific surface area by N 2 adsorption method is shown in Table 1. The amount of the essential element added was 0.05 in terms of atomic ratio with respect to zirconium.
安息香酸の水素化反応条件 触媒量 １３m 反応温度 ３３０℃ 反応圧力 常 圧 空間速度 安息香酸 LHSV＝0.14kg／-触媒Hr 水 素 GHSV＝1250／-触媒Hr 実施例２〜３、比較例１〜２ 硝酸クロム９水和物にかえて表−１に示す化合物を用い
たこと以外は実施例１と同様にして触媒を調製し、同一
条件で安息香酸の水素化反応を行なつた。結果を表−１
に示す。必須元素の添加量はジルコニウムに対して原子
比で0.05とした。Hydrogenation reaction conditions of benzoic acid Catalyst amount 13 m Reaction temperature 330 ° C. Reaction pressure Normal pressure Space velocity Benzoic acid LHSV = 0.14 kg / -catalyst Hr Hydrogen GHSV = 1250 / -catalyst Hr Examples 2-3, Comparative Examples 1-2 A catalyst was prepared in the same manner as in Example 1 except that the compound shown in Table 1 was used instead of chromium nitrate nonahydrate, and the hydrogenation reaction of benzoic acid was carried out under the same conditions. The results are shown in Table-1
Shown in. The amount of the essential element added was 0.05 in terms of atomic ratio with respect to zirconium.
実施例４〜５、比較例３ 硝酸クロム９水和物にかえて表−２に示す化合物を用い
たこと以外は実施例１と同様にして触媒を調製し、同一
条件で安息香酸の水素化反応を行なつた。結果を表−２
に示す。必須元素の添加量はジルコニウムに対して原子
比で0.05とした。 Examples 4-5, Comparative Example 3 A catalyst was prepared in the same manner as in Example 1 except that the compounds shown in Table 2 were used instead of chromium nitrate nonahydrate, and hydrogenation of benzoic acid was conducted under the same conditions. The reaction was carried out. The results are shown in Table-2.
Shown in. The amount of the essential element added was 0.05 in terms of atomic ratio with respect to zirconium.
〔発明の効果〕 本発明方法により製造した触媒は、必須元素の出発原料
として有機酸塩類を用いた場合に比べて、同一温度で焼
成して場合でも、触媒のN2吸着法による比表面積が大き
く、ひいては触媒活性も著しく高く、必須元素の出発物
質の差により、該元素の触媒中での分散状態もしくは、
該元素と酸化ジルコニウムとの結合状態に大きな違いが
もたらされていることを示している。 (Effects of the invention) The catalyst produced by the method of the present invention has a specific surface area by the N 2 adsorption method of the catalyst, even when calcined at the same temperature, as compared with the case where an organic acid salt is used as a starting material of an essential element. It is large and, by extension, also has a significantly high catalytic activity.
It is shown that a large difference is brought about in the bonding state between the element and zirconium oxide.
フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｃ０７Ｂ 61/00 ３００ (72)発明者 横山 寿治 神奈川県横浜市緑区鴨志田町1000番地 三 菱化成工業株式会社総合研究所内 (72)発明者 瀬戸山 亨 神奈川県横浜市緑区鴨志田町1000番地 三 菱化成工業株式会社総合研究所内Continuation of the front page (51) Int.Cl. 5 Identification number Reference number within the agency FI Technical display location // C07B 61/00 300 (72) Inventor Toshiharu Yokoyama 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Kasei Kogyo Inside Research Institute, Inc. (72) Inventor Toru Toyoyama 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Kasei Co., Ltd.
Claims (1)
種以上の元素と酸化ジルコニウムよりなる芳香族カルボ
ン酸を水素化して芳香族アルデヒドを製造する反応に使
用される触媒の製法に於て、クロム、インジウム及び鉛
の出発原料として、水溶性の無機化合物を使用すること
を特徴とする触媒の製法。1. A method for producing a catalyst used in a reaction for producing an aromatic aldehyde by hydrogenating an aromatic carboxylic acid composed of zirconium oxide and one or more elements selected from chromium, indium and lead, and chromium. A method for producing a catalyst, which comprises using a water-soluble inorganic compound as a starting material for indium and lead.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60153584A JPH0615039B2 (en) | 1985-07-12 | 1985-07-12 | Process for producing catalyst for hydrogenation reaction of aromatic carboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60153584A JPH0615039B2 (en) | 1985-07-12 | 1985-07-12 | Process for producing catalyst for hydrogenation reaction of aromatic carboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6214942A JPS6214942A (en) | 1987-01-23 |
| JPH0615039B2 true JPH0615039B2 (en) | 1994-03-02 |
Family
ID=15565682
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60153584A Expired - Fee Related JPH0615039B2 (en) | 1985-07-12 | 1985-07-12 | Process for producing catalyst for hydrogenation reaction of aromatic carboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0615039B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0439115B1 (en) * | 1990-01-22 | 1995-10-18 | Mitsubishi Chemical Corporation | Process for producing aliphatic or alicyclic aldehydes |
| US5239108A (en) * | 1990-01-22 | 1993-08-24 | Mitsubishi Kasei Corporation | Process for producing aliphatic or alicyclic aldehyde |
| DE60118510T2 (en) * | 2000-12-26 | 2006-08-24 | Mitsubishi Gas Chemical Co., Inc. | Process for the preparation of a hydrogenation product of an aromatic carboxylic acid |
-
1985
- 1985-07-12 JP JP60153584A patent/JPH0615039B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6214942A (en) | 1987-01-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |