JP3137200B2 - Phenol production catalyst and phenol production method - Google Patents
Phenol production catalyst and phenol production methodInfo
- Publication number
- JP3137200B2 JP3137200B2 JP02401303A JP40130390A JP3137200B2 JP 3137200 B2 JP3137200 B2 JP 3137200B2 JP 02401303 A JP02401303 A JP 02401303A JP 40130390 A JP40130390 A JP 40130390A JP 3137200 B2 JP3137200 B2 JP 3137200B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- phenol
- benzoic acid
- phenol production
- selectivity
- 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
【０００１】[0001]
【産業上の利用分野】本発明は、フェノールを製造する
ための触媒、およびその触媒の存在下で安息香酸を気相
酸化してフェノールを製造する方法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for producing phenol and a method for producing phenol by subjecting benzoic acid to gas phase oxidation in the presence of the catalyst.
【０００２】[0002]
【従来の技術】従来、安息香酸を気相接触酸化してフェ
ノールを製造する方法およびこれに使用される触媒とし
ては、種々の方法および触媒が知られている。2. Description of the Related Art Conventionally, various methods and catalysts have been known as a method for producing phenol by gas phase catalytic oxidation of benzoic acid and a catalyst used therefor.
【０００３】例えば、特開昭57-11932号公報には、銅化
合物、バラジウム化合物、銀化合物、リチウム化合物、
ナトリウム化合物およびマグネシウム化合物の１種また
は２種以上からなる触媒と、この触媒を使用する製造方
法が開示されている。For example, JP-A-57-11932 discloses copper compounds, palladium compounds, silver compounds, lithium compounds,
A catalyst comprising one or more of a sodium compound and a magnesium compound and a production method using the catalyst are disclosed.
【０００４】また、特公昭59-20384号公報には、酸化さ
れた銅、ジルコニウムおよびアルカリ金属を含み、これ
らがα−アルミナ上に支持された触媒を使用する製造方
法が開示されている。Further, Japanese Patent Publication No. 59-20384 discloses a production method using a catalyst containing oxidized copper, zirconium and an alkali metal, which are supported on α-alumina.
【０００５】さらに、特公昭64-934号公報には、モリブ
デンを必須の成分とし、その他にバナジウム、ニオブ、
タンタルの少なくとも１種と、銅、銀、マンガン、鉄、
コバルト、ニッケル、ロジウム、パラジウム、白金の少
なくとも１種と、タリウム、アルカリ金属、アルカリ土
類金属の少なくとも１種とを含む、非常に多種類にわた
る金属元素からなる酸化物触媒を使用する製造方法が開
示されている。Further, Japanese Patent Publication No. 64-934 discloses that molybdenum is an essential component, and vanadium, niobium,
At least one of tantalum and copper, silver, manganese, iron,
A production method using an oxide catalyst composed of a very wide variety of metal elements including at least one of cobalt, nickel, rhodium, palladium, and platinum and at least one of thallium, an alkali metal, and an alkaline earth metal is disclosed. It has been disclosed.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、特開昭
57-11932号公報に開示された触媒は、活性および選択性
がいずれも充分でなく、この触媒を使用した製造方法で
も、安息香酸転化率50.5％、フェノール選択率88.6％が
それぞれ最高値であった。また、銅化合物を含有する触
媒を使用して安息香酸の酸化反応のような発熱反応を実
施した場合、触媒層にホットスポットが生じやすく、か
つそれによる触媒のシンタリングが進行し、活性の劣化
が著しいという問題点があった。SUMMARY OF THE INVENTION However, Japanese Patent Application Laid-Open
The catalyst disclosed in JP-A-57-11932 has insufficient activity and selectivity, and the production method using this catalyst has the highest values of benzoic acid conversion of 50.5% and phenol selectivity of 88.6%. Was. In addition, when an exothermic reaction such as an oxidation reaction of benzoic acid is performed using a catalyst containing a copper compound, hot spots are easily generated in the catalyst layer, and the sintering of the catalyst proceeds, thereby deteriorating the activity. However, there was a problem that it was remarkable.
【０００７】また、特公昭59-20384号公報に開示された
製造方法も、転化率、選択率がともに充分でなく、最高
でも安息香酸転化率が63.7％、フェノール選択率が82.2
％であった。また、ジフェニルオキサイド等の副成生物
が多く生成するため、生成フェノールの精製工程が必要
であり、経済的に不利であった。Further, the production method disclosed in Japanese Patent Publication No. 59-20384 is also insufficient in conversion and selectivity, and at the maximum, benzoic acid conversion is 63.7% and phenol selectivity is 82.2%.
%Met. In addition, since many by-products such as diphenyl oxide are produced, a purification step of the produced phenol is required, which is economically disadvantageous.
【０００８】特公昭64-934号公報に開示された製造方法
においても、安息香酸転化率75％、フェノール選択率89
％が最高であり、工業的にみて充分なものではなかっ
た。In the production method disclosed in Japanese Patent Publication No. 64-934, benzoic acid conversion is 75% and phenol selectivity is 89.
% Was the highest and was not industrially sufficient.
【０００９】さらに、上述した製造方法はいずれもフェ
ノールの空時収率（触媒単位容積あたり、単位時間あた
りのフェノールの製造量）が低いため、生産生が悪く、
工業的に到来採用し難いものであった。Furthermore, the above-mentioned production methods all have low space-time yields of phenol (the amount of phenol produced per unit volume of catalyst per unit time), so that the production is poor.
It was difficult to adopt industrially.
【００１０】本発明は、以上の問題点を解決し、安息香
安酸転化率およびフェノール選択率がいずれも高いフェ
ノール製造用触媒および空時収率の高いフェノールの製
造方法を提供することを目的とする。An object of the present invention is to solve the above problems and to provide a phenol production catalyst having a high conversion rate of benzoic acid and a high phenol selectivity, and a method of producing phenol having a high space-time yield. I do.
【００１１】[0011]
【課題を解決するための手段】本発明者らは、上記目的
を達成するために鋭意研究したところ、安息香酸を気相
接触酸化してフェノールを製造するための触媒として、
金属酸化物担体上にニッケル化合物が担持された触媒
が、高活性、高選択性を有することを見出し、またこの
触媒を用いることによりフェノールを高い空時収率で製
造し得ることを見出し、本発明を完成させた。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a catalyst for producing phenol by subjecting benzoic acid to gas phase catalytic oxidation.
The present inventors have found that a catalyst in which a nickel compound is supported on a metal oxide carrier has high activity and high selectivity, and that it is possible to produce phenol with a high space-time yield by using this catalyst. Completed the invention.
【００１２】すなわち、本発明のフェノール製造用触媒
は、金属酸化物担体上にニッケル化合物が担持されてい
ることを特徴として構成されている。That is, the catalyst for producing phenol of the present invention is characterized in that a nickel compound is supported on a metal oxide carrier.
【００１３】また、本発明のフェノール製造方法は、安
息香酸を気相接触酸化してフェノールを製造する方法に
おいて、金属酸化物担体上にニッケル化合物が担持され
ているフェノール製造用触媒の存在下で行うことを特徴
として構成されている。The phenol production method of the present invention is a method for producing phenol by subjecting benzoic acid to gas phase catalytic oxidation, wherein the phenol is produced in the presence of a phenol production catalyst in which a nickel compound is supported on a metal oxide carrier. It is characterized by performing.
【００１４】本発明で使用される金属酸化物担体として
は、チタニア、マグネシア、α−アルミナ、シリカゲ
ル、ジルコニア、酸化スズ、酸化ランタンなどの酸化物
があるが、なかでもチタニア、マグネシアまたはα−ア
ルミナが、転化率及び選択率が高いので好ましい。The metal oxide carrier used in the present invention includes oxides such as titania, magnesia, α-alumina, silica gel, zirconia, tin oxide and lanthanum oxide. Among them, titania, magnesia or α-alumina Is preferred because of high conversion and selectivity.
【００１５】金属酸化物担体上に担持されるニッケル化
合物としては、ニッケルの酸化物、水酸化物、炭酸塩、
硝酸塩、塩化物、炭化物、窒化物、硫化物などがある
が、なかでも酸化物が初期から安定した活性が得られる
ので好ましい。The nickel compound supported on the metal oxide carrier includes nickel oxide, hydroxide, carbonate, and the like.
There are nitrates, chlorides, carbides, nitrides, sulfides and the like, among which oxides are preferred because a stable activity can be obtained from the beginning.
【００１６】金属酸化物担体上へのニッケル化合物の担
持には、通常の含浸技術が利用できる。For supporting the nickel compound on the metal oxide carrier, a usual impregnation technique can be used.
【００１７】触媒中のニッケル化合物の含有率は、約0.
5〜50重量％の範囲が好ましい。ニッケル化合物の含有
率が約0.5重量％よりも小さい場合は、安息香酸の転化
率が低く、また、ニッケル化合物の含有率が約50重量％
よりも大きい場合は、完全燃焼によるＣＯ、ＣＯ2の生
成が増大し、フェノールの選択率が低下する。The content of the nickel compound in the catalyst is about 0.
A range of 5 to 50% by weight is preferred. When the content of the nickel compound is less than about 0.5% by weight, the conversion of benzoic acid is low, and the content of the nickel compound is about 50% by weight.
If it is larger than this, the production of CO and CO 2 by complete combustion increases, and the selectivity of phenol decreases.
【００１８】ニッケル化合物は、安息香酸の転化率が向
上するので、塩基性化合物が添加されるのが好ましい。The nickel compound improves the conversion of benzoic acid, so that a basic compound is preferably added.
【００１９】塩基性化合物としては、Ｌi2Ｏ、Ｎa2、Ｋ
2Ｏ、Ｒb2Ｏ、Ｃs2Ｏ等のアルカリ金属の酸化物、もし
くはアルカリ金属の炭酸塩、水酸化物、硝酸塩等、また
はＭgＯ、ＣaＯ、ＳrＯ、ＢaＯ等のアルカリ土類金属の
酸化物、もしくはアルカリ土類金属の炭酸塩、水酸化
物、硝酸塩等がある。As the basic compound, Li 2 O, Na 2 , K
Oxides of alkali metals such as 2 O, Rb 2 O and Cs 2 O, or carbonates, hydroxides and nitrates of alkali metals; oxides of alkaline earth metals such as MgO, CaO, SrO and BaO; Alternatively, there are alkaline earth metal carbonates, hydroxides, nitrates and the like.
【００２０】塩基性化合物を添加する時期は、ニッケル
化合物を金属酸化物担体上に担持する前後、もしくはニ
ッケル化合物担持時のいずれの時期でもよい。The timing of adding the basic compound may be before or after the nickel compound is supported on the metal oxide carrier, or at the time of loading the nickel compound.
【００２１】触媒中の塩基性化合物の含有率は、0.1〜3
0重量％が好ましい。The content of the basic compound in the catalyst is 0.1 to 3
0% by weight is preferred.
【００２２】含浸操作により調製された触媒組成物は空
気中90〜150℃で12〜36時間乾燥され、このあと必要が
あれば常法により焼成してもよい。焼成は、窒素中また
は空気中において、400℃〜1000℃の温度で１〜10時間
加熱して行うのが好ましい。The catalyst composition prepared by the impregnation operation is dried in air at 90 to 150 ° C. for 12 to 36 hours, and if necessary, calcined by a conventional method. The calcination is preferably performed by heating at a temperature of 400 ° C. to 1000 ° C. for 1 to 10 hours in nitrogen or air.
【００２３】次に、本発明のフェノールの製造方法につ
いて説明する。Next, the method for producing phenol of the present invention will be described.
【００２４】本発明の方法では、原料の安息香酸と共に
酸素を供給するが、供給する酸素は原料の安息香酸に対
して理論量以上あればよく、約0.5〜50倍モルの範囲が
好ましい。酸素の供給が約50倍モルより多い場合は、原
料安息香酸の完全酸化が起こりやすくなる。また、酸素
の供給量が約0.5倍モルより少ない場合は、充分な安息
香酸転化率を得られない。In the method of the present invention, oxygen is supplied together with benzoic acid as a raw material. The amount of oxygen to be supplied may be at least a theoretical amount based on benzoic acid as a raw material, and is preferably in a range of about 0.5 to 50 times mol. When the supply of oxygen is more than about 50 times mol, complete oxidation of the starting benzoic acid is likely to occur. On the other hand, if the supply amount of oxygen is less than about 0.5 mol, a sufficient benzoic acid conversion cannot be obtained.
【００２５】また、供給する酸素は、分子状酸素でもよ
いが、一般的には空気が使用され、さらにこれを不活性
ガスで希釈したものでもよい。The oxygen to be supplied may be molecular oxygen, but air is generally used, and may be diluted with an inert gas.
【００２６】反応は、一般に水蒸気の存在下において行
うが、供給する水蒸気は原料の安息香酸に対して約１倍
モルから100倍モルの範囲が好ましい。水蒸気の供給量
が約100倍モルより多いと経済的でなく、また約１倍モ
ルより少ないと一般にフェノールの選択率が低下する。The reaction is generally carried out in the presence of steam. The amount of steam supplied is preferably in the range of about 1 to 100 moles per mole of benzoic acid as a raw material. If the supply of water vapor is more than about 100 moles, it is not economical, and if it is less than about 1 mole, the phenol selectivity generally decreases.
【００２７】空間速度は、約100〜5000h-1の範囲が好ま
しい。空間速度が約100h-1より小さい場合は、充分な空
時収率が得られず、また、約50000h-1より大きい場合
は、安息香酸転化率が低くなる。The space velocity preferably ranges from about 100 to 5000 h -1 . If the space velocity is about 100h -1 less not sufficient space time yield can be obtained and, if greater than about 50000h -1 are benzoic acid conversion rate decreases.
【００２８】反応温度は、約200〜600℃の範囲が好まし
く、特に約300〜500℃の範囲が好ましい。反応温度が約
600℃より高いとフェノールの選択率が低下し、また、
反応温度が約200℃より低いと安息香酸転化率が低くな
る。[0028] The reaction temperature is preferably in the range of about 200 to 600 ° C, particularly preferably in the range of about 300 to 500 ° C. Reaction temperature is about
If the temperature is higher than 600 ° C, the selectivity of phenol decreases, and
If the reaction temperature is lower than about 200 ° C., the conversion of benzoic acid will decrease.
【００２９】反応圧力は、反応条件下で供給原料が気体
状態を保つ範囲であれば特に制限はないが、通常は常圧
または若干の加圧状態である。The reaction pressure is not particularly limited as long as the feedstock is kept in a gaseous state under the reaction conditions, but is usually at normal pressure or slightly pressurized.
【００３０】なお、本発明方法においては、固定床、流
動床のいずれの装置を用いてもよい。In the method of the present invention, either a fixed bed or a fluidized bed may be used.
【００３１】[0031]
【作用】本発明のフェノール製造用触媒は、安息香酸の
気相接触酸化によるフェノールの合成に対して、高い安
息香酸転化率および高いフェノール選択率を示す。ま
た、本発明のフェノールの製造方法は、高い空時収率で
フェノールを生成させる。The phenol production catalyst of the present invention exhibits a high benzoic acid conversion and a high phenol selectivity with respect to the synthesis of phenol by gas phase catalytic oxidation of benzoic acid. In addition, the method for producing phenol of the present invention produces phenol with a high space-time yield.
【００３２】[0032]
【実施例】I．触媒の調製 実施例１、２ 硝酸ニッケル（Ｎi（ＮＯ3）2・６Ｈ2Ｏ）38.9ｇを300c
cのイオン交換水に溶解させ、さらに二酸化チタン188ｇ
を攪拌しながら加えた。120℃で乾燥後、空気中500℃で
３時間焼成した。所定のメッシュに粉砕した後、2.4ｇ
の水酸化カリウムを溶解させたイオン交換水中にこの触
媒を加え120℃で再び乾燥させた。さらに空気中500℃で
３間焼成した。得られた触媒は、ＮiＯとＫ2ＯとＴiＯ2
の重量比が５：１：94であった。Embodiment I. Preparation of catalyst Examples 1 and 2 38.9 g of nickel nitrate (Ni (NO 3 ) 2 .6H 2 O) was added to 300 c
Dissolve in ion-exchanged water of c and add 188 g of titanium dioxide
Was added with stirring. After drying at 120 ° C., it was fired in air at 500 ° C. for 3 hours. 2.4g after crushing to the specified mesh
This catalyst was added to ion-exchanged water in which potassium hydroxide was dissolved, and dried at 120 ° C. again. Further, firing was performed at 500 ° C. for 3 minutes in the air. The resulting catalyst was composed of NiO, K 2 O and TiO 2
Was 5: 1: 94.
【００３３】実施例３〜５ 硝酸ニッケル（Ｎi（ＮＯ3）2・６Ｈ2Ｏ）77.8ｇをイオ
ン交換水300ccに溶解させ、さらに二酸化チタン180ｇを
攪拌しながら加えた。そして、120℃で乾燥後、空気中5
00℃で３時間焼成した。Examples 3 to 5 77.8 g of nickel nitrate (Ni (NO 3 ) 2 .6H 2 O) was dissolved in 300 cc of ion-exchanged water, and 180 g of titanium dioxide was added with stirring. And after drying at 120 ° C, 5
Baking was performed at 00 ° C. for 3 hours.
【００３４】得られた触媒は、ＮiＯとＴiＯ2の重量比
が10：90であった。The resulting catalyst had a weight ratio of NiO to TiO 2 of 10:90.
【００３５】実施例６、７ 硫酸ニッケル3.9ｇと硝酸鉄5.1ｇとをイオン交換水30cc
に溶解させ、さらに二酸化チタン18ｇを攪拌しながら加
えた。そして、120℃で乾燥後、空気中500℃で３時間焼
成した。Examples 6 and 7 3.9 g of nickel sulfate and 5.1 g of iron nitrate were mixed with 30 cc of ion-exchanged water.
And 18 g of titanium dioxide was further added with stirring. Then, after drying at 120 ° C., it was fired in air at 500 ° C. for 3 hours.
【００３６】得られた触媒は、ＮiＯとＦe2Ｏ３とＴiＯ
２の重量比が５：５：90であった。The obtained catalyst is composed of NiO, Fe 2 O 3 and TiO.
The weight ratio of 2 was 5: 5: 90.
【００３７】比較例１ 硝酸ニッケル200ｇをイオン交換水500mlに溶解させたも
のと、水酸化ナトリウム約100ｇをイオン交換水500mlに
溶解させたものとを、イオン交換水２１に、pHを７〜８
に保ちながら滴下した。滴下終了後、約１時間攪拌を続
け、生成した沈澱の濾過および洗浄を行った。そして、
ケーキ状物質を乾燥し、これを空気中、800℃で４時間
焼成した。Comparative Example 1 A solution in which 200 g of nickel nitrate was dissolved in 500 ml of ion-exchanged water and a solution in which about 100 g of sodium hydroxide were dissolved in 500 ml of ion-exchanged water were added to ion-exchanged water 21 at a pH of 7 to 8.
The solution was dropped. After completion of the dropwise addition, stirring was continued for about 1 hour, and the formed precipitate was filtered and washed. And
The cake was dried and calcined in air at 800 ° C. for 4 hours.
【００３８】比較例２ 特公昭64-934号公報に記載された実施例１に従って触媒
を調製した。Comparative Example 2 A catalyst was prepared according to Example 1 described in Japanese Patent Publication No. 64-934.
【００３９】比較例３ 特公昭59-20384号公報に記載された参考例１に従って触
媒を調製した。Comparative Example 3 A catalyst was prepared according to Reference Example 1 described in JP-B-59-20384.
【００４０】比較例４ 硝酸鉄200ｇをイオン交換水500mlに溶解させたものと、
水酸化ナトリウム約100ｇをイオン交換水500mlに溶解さ
せたものとを、イオン交換水２１に、pHを７〜８に保ち
ながら滴下した。滴下終了後、約１時間攪拌を続け、生
成した沈澱の濾過および洗浄を行った。そして、ケーキ
状物質を乾燥し、これを空気中、800℃で４時間焼成し
た。Comparative Example 4 200 g of iron nitrate was dissolved in 500 ml of ion-exchanged water.
A solution prepared by dissolving about 100 g of sodium hydroxide in 500 ml of ion-exchanged water was dropped into ion-exchanged water 21 while maintaining the pH at 7 to 8. After completion of the dropwise addition, stirring was continued for about 1 hour, and the formed precipitate was filtered and washed. Then, the cake-like substance was dried and calcined at 800 ° C. for 4 hours in the air.
【００４１】II．実験方法 触媒を所定のメッシュに粉砕し、内径20mmの石英管に所
定量充填した。そして、この反応管に安息香酸、水蒸
気、空気および窒素を所定量供給し、所定の温度で反応
させた。II. Experimental Method The catalyst was pulverized into a predetermined mesh and filled in a predetermined amount in a quartz tube having an inner diameter of 20 mm. Then, a predetermined amount of benzoic acid, steam, air and nitrogen were supplied to the reaction tube and reacted at a predetermined temperature.
【００４２】III．実験条件および実験結果 実施例１〜７の実験条件および実験結果を表１に示す。III. Experimental conditions and experimental results Table 1 shows experimental conditions and experimental results of Examples 1 to 7.
【００４３】比較例１〜４の実験条件および実験結果を
表２に示す。Table 2 shows the experimental conditions and experimental results of Comparative Examples 1 to 4.
【００４４】[0044]
【表１】 [Table 1]
【００４５】[0045]
【表２】 [Table 2]
【００４６】[0046]
【発明の効果】本発明は、金属酸化物担体上にニッケル
化合物が担持されている触媒を使用することにより、安
息香酸からフェノールを高い空時収率で製造できる効果
を有する。The present invention has an effect that phenol can be produced from benzoic acid with a high space-time yield by using a catalyst in which a nickel compound is supported on a metal oxide carrier.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 舘 和彦 東京都千代田区丸の内一丁目１番２号 日本鋼管株式会社内 (72)発明者 橘 躍動 東京都千代田区丸の内一丁目１番２号 日本鋼管株式会社内 (56)参考文献 特開 平２−188542（ＪＰ，Ａ) 特開 昭58−62126（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 21/00 - 38/74 C07B 61/00 300 ＪＩＣＳＴファイル（ＪＯＩＳ) ＷＰＩ／Ｌ（ＱＵＥＳＴＥＬ)────────────────────────────────────────────────── ─── Continuing on the front page (72) Kazuhiko Tachi, 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Nippon Kokan Co., Ltd. (72) Jiku Tachibana 1-1-2, Marunouchi, Chiyoda-ku, Tokyo Nippon Kokan (56) References JP-A-2-188542 (JP, A) JP-A-58-62126 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) B01J 21/00 -38/74 C07B 61/00 300 JICST file (JOIS) WPI / L (QUESTEL)
Claims (3)
持されていることを特徴とするフェノール製造用触媒1. A catalyst for producing phenol, wherein a nickel compound is supported on a metal oxide carrier.
シア又はα−アルミナである請求項１に記載のフェノー
ル製造用触媒2. The catalyst for producing phenol according to claim 1, wherein the metal oxide carrier is titania, magnesia or α-alumina.
を製造する方法において、該酸化を請求項１又は２に記
載の触媒の存在下で行なうフェノールの製造方法3. A method for producing phenol by subjecting benzoic acid to gas phase catalytic oxidation, wherein the oxidation is carried out in the presence of the catalyst according to claim 1 or 2.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02401303A JP3137200B2 (en) | 1990-04-17 | 1990-12-11 | Phenol production catalyst and phenol production method |
| EP92121979A EP0538912B1 (en) | 1990-04-17 | 1991-03-21 | Use of a catalyst for producing phenol |
| DE69103191T DE69103191T2 (en) | 1990-04-17 | 1991-03-21 | Production of a catalyst and its use for the production of phenol. |
| DE69120075T DE69120075T2 (en) | 1990-04-17 | 1991-03-21 | Use of a catalyst for the production of phenol |
| EP91104471A EP0452695B1 (en) | 1990-04-17 | 1991-03-21 | Production of a catalyst and its use for producing phenol |
| CA002039193A CA2039193C (en) | 1990-04-17 | 1991-03-27 | Catalyst and process for producing |
| KR1019910006043A KR910018079A (en) | 1990-04-17 | 1991-04-16 | Phenol production catalyst and phenol production method |
| US07/954,794 US5268512A (en) | 1990-04-17 | 1992-07-10 | Catalyst and process for producing phenol |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2-99333 | 1990-04-17 | ||
| JP9933390 | 1990-04-17 | ||
| JP19916190 | 1990-07-30 | ||
| JP2-199161 | 1990-07-30 | ||
| JP02401303A JP3137200B2 (en) | 1990-04-17 | 1990-12-11 | Phenol production catalyst and phenol production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH045250A JPH045250A (en) | 1992-01-09 |
| JP3137200B2 true JP3137200B2 (en) | 2001-02-19 |
Family
ID=27308925
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02401303A Expired - Fee Related JP3137200B2 (en) | 1990-04-17 | 1990-12-11 | Phenol production catalyst and phenol production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3137200B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0639553B1 (en) * | 1993-08-20 | 1998-01-14 | Nkk Corporation | Catalyst and method for producing phenols |
-
1990
- 1990-12-11 JP JP02401303A patent/JP3137200B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH045250A (en) | 1992-01-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0336571B2 (en) | ||
| JP2934222B2 (en) | Method for producing acrolein from propylene by redox reaction and use of solid mixed oxide composition as redox system in the reaction | |
| JPH07116070B2 (en) | Process for producing methacrolein and methacrylic acid from methyl tert-butyl ether | |
| JPH089556B2 (en) | Dehydrogenation catalysts, their production and non-oxidative dehydrogenation | |
| EP1025069A1 (en) | USE OF Ce/Zr MIXED OXIDE PHASE FOR THE MANUFACTURE OF STYRENE BY DEHYDROGENATION OF ETHYLBENZENE | |
| JP3137200B2 (en) | Phenol production catalyst and phenol production method | |
| US5268512A (en) | Catalyst and process for producing phenol | |
| JPS58219944A (en) | Supported catalyst containing cobalt and production thereof | |
| EP0452695B1 (en) | Production of a catalyst and its use for producing phenol | |
| JP3221447B2 (en) | Catalyst for producing phenol, method for producing the same, and method for producing phenol | |
| JP2697441B2 (en) | Phenol production catalyst and phenol production method | |
| JP3221446B2 (en) | Catalyst for producing phenol, method for producing the same, and method for producing phenol | |
| JP3221445B2 (en) | Catalyst for producing phenol, method for producing the same, and method for producing phenol | |
| JP3268648B2 (en) | Catalyst for producing phenol, method for producing the same, and method for producing phenol | |
| JP2874017B2 (en) | Method for producing gamma-butyrolactone | |
| JP2969960B2 (en) | Method for producing phenol | |
| JP2874016B2 (en) | Production method of γ-butyrolactone | |
| JPH0456015B2 (en) | ||
| JP3230243B2 (en) | Phenol production catalyst and phenol production method | |
| JP3124347B2 (en) | Method for producing .GAMMA.-butyrolactone | |
| JP2979675B2 (en) | Method for producing phenol and apparatus for producing phenol | |
| JP3221448B2 (en) | Catalyst for producing phenols and method for producing phenols | |
| JP3734403B2 (en) | Catalyst for producing methacrylic acid and method for producing methacrylic acid | |
| JP2988210B2 (en) | Catalyst and method for producing phenol and alkylphenol | |
| JPH0525151A (en) | Production of gamma-butyrolactone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |