JPS6214942A - Production method of catalyst for hydrogenation reaction of aromatic carboxylic acids - Google Patents
Production method of catalyst for hydrogenation reaction of aromatic carboxylic acidsInfo
- Publication number
- JPS6214942A JPS6214942A JP60153584A JP15358485A JPS6214942A JP S6214942 A JPS6214942 A JP S6214942A JP 60153584 A JP60153584 A JP 60153584A JP 15358485 A JP15358485 A JP 15358485A JP S6214942 A JPS6214942 A JP S6214942A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- hydrogenation reaction
- carboxylic acids
- aromatic carboxylic
- production method
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims description 14
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- -1 aromatic carboxylic acids Chemical class 0.000 title claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 6
- 150000002484 inorganic compounds Chemical class 0.000 claims description 4
- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000464 lead oxide Inorganic materials 0.000 claims 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 8
- 239000005711 Benzoic acid Substances 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 2
- KGBUQHGXOAESDX-UHFFFAOYSA-N [Zr].OOO Chemical compound [Zr].OOO KGBUQHGXOAESDX-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
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
。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a catalyst effective for producing aromatic aldehydes by hydrogenation reaction of aromatic carboxylic acids.
〈つかたされｆいふが一最近クロム、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。Recently, a method using a zirconium oxide catalyst containing as an essential component one or more elements selected from chromium, indium, and lead has been 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
ものであシ、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
行なったものである。The present invention relates to the production of the above-mentioned zirconium oxide catalyst, and is the result of extensive research aimed at developing a method for producing a catalyst that has 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
として用いるととＫよシ、飛摩的に触媒活性が増大する
ことを見出したものである。The present invention proposes that water-soluble inorganic compounds of chromium, indium, and lead (hereinafter simply referred to as essential elements), which are one of the constituent components of the catalyst, are used as a starting material to supply them. It was discovered that the catalytic activity dramatically increased.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
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 shaped by conventional methods. For example, a method in which an aqueous solution of an inorganic compound of an essential element and a powder of zirconium oxyhydroxide are mixed in the presence of a binder component if necessary, dried after extrusion molding, and fired at a predetermined temperature; Methods include a method of pulverizing the product to an appropriate particle size and tablet-forming, or a method of making an aqueous slurry of the above-mentioned necessary ingredients, granulating it by an appropriate method such as spray drying, and then tablet-forming, but is 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, and inorganic salts such as chromic anhydride, dichromic acid, or their ammonium salts and alkali salts. Salts that decompose at relatively low temperatures and do not contain other poisonous elements, such as nitrates, chromic anhydride, and ammonium dichromate, are preferred from the viewpoint of not containing impurities that exhibit poisoning effects.
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、ｏ、ｏｏｉ Ｎｏ、ｚｌ
よシ好ましくは０．０ ／ ＮＯ，／程度が適当である
。In addition, as for the addition amount of these essential elements, when expressed in atomic ratio to zirconium, o, ooi No, zl
A suitable value is preferably about 0.0/NO.
又、必要によって添加するバインダーとじては、前述と
同様な理由から焼成にょシ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。In addition, as for the binder to be added if necessary, it is preferable to use an organic compound that disappears during baking for the same reason as mentioned above, such as polyvinyl alcohol starch paste, crystalline cellulose, various surfactants, low melting point wax, stearic acid, etc. Any binder used for normal 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ａＯＯ〜？ ０
０℃、好ましくはｇｏｏ 〜ｔｏｏ”Ｃが適当である。Furthermore, when firing the granules, the firing temperature is aOO~? 0
0°C, preferably goo-too''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
脱しない限シ、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 with reference to examples, but the present invention is not limited to the following examples unless it deviates 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ｆ ｊ、４４％）コ３ｅｏｇに、硝１よシなる水
溶液を加え、ニーダ−で混練後押出し成形様で３眉φの
ヒモ状に成形乾燥した。Example 1 An aqueous solution of nitric acid was added to commercially available zirconium oxyhydroxide (zirconium oxide equivalent purity fj, 44%), and after kneading it in a kneader, it was formed into a string shape with a diameter of 3 mm by extrusion molding. Dry.
続いて！ｒｇｏ℃で３時間焼成した後１０−２０メツシ
ユに粗砕して触媒を調製し、次の反応条件で安息香酸の
水素化反応を行なった。反応成績及び調製した触媒のＮ
２吸着法による比表面積を表−７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
。continue! After calcining at rgo° C. for 3 hours, the catalyst was crushed into 10-20 mesh to prepare a catalyst, and hydrogenation reaction of benzoic acid was carried out under the following reaction conditions. Reaction results and N of the prepared catalyst
Table 7 shows the specific surface area determined by the 2-adsorption method. The amount of essential elements added was set at an atomic ratio of 0.05 to zirconium.
安息香酸の水素化反応条件
触ｍ景 ／３−
反応温度 ３３０℃
反応圧力 常 圧
空間速度 安息香ＨＬＨ８Ｖ： ｏ、／ｅｋｇ／ｌ −
Ｎｒ媒Ｈｒ水 素 ＧＨ８Ｖ＝７ｘｓｏｔ／を一触媒
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−７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詩製し、同一
条件で安息香酸の水素化反応を行なった。結果を表−ノ
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ｏ、ｏｒとした。Hydrogenation reaction conditions for benzoic acid /3- Reaction temperature 330°C Reaction pressure Normal pressure Space velocity Benzoic acid HLH8V: o, /ekg/l -
Nr medium Hr hydrogen GH8V=7xsot/monocatalyst Hr Examples 2 to 3, Comparative Example 1-2 Same as Example 1 except that the compound shown in Table 7 was used instead of chromium nitrate nonahydrate. A catalyst was prepared using the same method, and the hydrogenation reaction of benzoic acid was carried out under the same conditions. The results are shown in Table No. The amount of essential elements added was set to o and or in atomic ratio to zirconium.
表 −ｌ
実施例グ〜５、比較例Ｊ
硝酸クロム９水和物Ｋかえて表−λに示す化合物を用い
たこと以外は実施例７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った。結果を表−一
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Ｏ，ＯＳとした。Table-1 Examples G to 5, Comparative Example J Chromium nitrate nonahydrate A hydrogenation reaction was carried out. The results are shown in Table 1. The amounts of essential elements added were O and OS in atomic ratio to zirconium.
表 −−
〔発明の効果〕
本発明方法によシ裳遺した触媒は、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Ｎ。Table -- [Effects of the Invention] Compared to the case where organic acid salts are used as starting materials for essential elements, the catalyst obtained by the method of the present invention has a lower N content even when calcined at the same temperature.
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（、必須元素の出発物質の差によシ、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。The specific surface area obtained by the adsorption method is large, and the catalytic activity is also extremely high. This shows that it is being brought about.
Claims (1)
の元素と酸化ジルコニウムよりなる芳香族カルボン酸の
水素化反応用触媒の製法に於て、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) In the production process of a catalyst for the hydrogenation reaction of aromatic carboxylic acids consisting of one or more elements selected from chromium, indium and lead and zirconium oxide, water-soluble A method for producing a catalyst characterized by using an inorganic compound.
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 true JPS6214942A (en) | 1987-01-23 |
| JPH0615039B2 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) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5239108A (en) * | 1990-01-22 | 1993-08-24 | Mitsubishi Kasei Corporation | Process for producing aliphatic or alicyclic aldehyde |
| US6541662B2 (en) * | 2000-12-26 | 2003-04-01 | Mitsubishi Gas Chemical Company, Inc. | Process for producing a hydrogenation product of an aromatic carboxylic acid |
-
1985
- 1985-07-12 JP JP60153584A patent/JPH0615039B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5239108A (en) * | 1990-01-22 | 1993-08-24 | Mitsubishi Kasei Corporation | Process for producing aliphatic or alicyclic aldehyde |
| US6541662B2 (en) * | 2000-12-26 | 2003-04-01 | Mitsubishi Gas Chemical Company, Inc. | Process for producing a hydrogenation product of an aromatic carboxylic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0615039B2 (en) | 1994-03-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |