JPH0784394B2 - Method for producing acenaphthylene - Google Patents
Method for producing acenaphthyleneInfo
- Publication number
- JPH0784394B2 JPH0784394B2 JP62151083A JP15108387A JPH0784394B2 JP H0784394 B2 JPH0784394 B2 JP H0784394B2 JP 62151083 A JP62151083 A JP 62151083A JP 15108387 A JP15108387 A JP 15108387A JP H0784394 B2 JPH0784394 B2 JP H0784394B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- acenaphthene
- acenaphthylene
- weight
- parts
- 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〕 本発明はアセナフチレンの製造方法に関するものであ
る。TECHNICAL FIELD The present invention relates to a method for producing acenaphthylene.
アセナフチレンの製造方法としてはアセナフテンを脱水
素する方法が知られている。例えば、特開昭47−25,165
号公報には、アセナフテンを気体状態で酸化チタン又は
酸化チタンとアルカリ金属化合物、アルカリ土類金属化
合物もしくはクロム化合物からなる触媒と接触させて脱
水素する方法が記載されている。As a method for producing acenaphthylene, a method of dehydrogenating acenaphthene is known. For example, JP-A-47-25,165
The publication describes a method of dehydrogenating acenaphthene in the gaseous state by contacting it with a catalyst composed of titanium oxide or titanium oxide and an alkali metal compound, an alkaline earth metal compound or a chromium compound.
しかしながら、この種の触媒を使用する方法は収率又は
長期触媒活性の点で工業的に十分とは言い難い。工業的
な脱水素触媒としてFe−Cr−Ｋ系の触媒がエチルベンゼ
ンの脱水素等に使用され、良好な収率又は長期触媒活性
を示している。そこで、この種の触媒を使用することが
できれば、工業的に有利なことである。しかしながら、
本発明者らの実験によればアセナフチレンの製造にこの
種の触媒を用いると収率の点で不満足なものであった。However, the method using this type of catalyst is not industrially sufficient in terms of yield or long-term catalytic activity. As an industrial dehydrogenation catalyst, an Fe-Cr-K-based catalyst is used for dehydrogenation of ethylbenzene and the like, and shows good yield or long-term catalytic activity. Therefore, it would be industrially advantageous if this type of catalyst could be used. However,
According to the experiments conducted by the present inventors, the use of this type of catalyst for producing acenaphthylene was unsatisfactory in terms of yield.
本発明の目的は、長期触媒活性、触媒強度等の点で優れ
る鉄系脱水素触媒を用いてアセナフテンを脱水素して高
収率でアセナフチレンを得ることにある。An object of the present invention is to dehydrogenate acenaphthene using an iron-based dehydrogenation catalyst which is excellent in terms of long-term catalytic activity, catalyst strength, etc., to obtain acenaphthylene in high yield.
本発明者らは上記のような問題点を解決するため研究を
行い、酸化鉄、酸化チタンおよびカリウム化合物を含有
する触媒をアセナフテンの脱水素触媒として使用すれ
ば、アセナフチレンを長時間にわたって高い収率で得ら
れることを見出し、本発明を完成した。すなわち、本発
明はFe2O3に換算して５〜85重量部の酸化鉄、TiO2に換
算して１〜75重量部の酸化チタンおよびK2Oに換算して
５〜30重量部のカリウム化合物を含有する触媒にアセナ
フテンを温度500〜750℃、気体状態で接触させて脱水素
するアセナフチレンの製造方法である。The present inventors have conducted research to solve the above problems, and if a catalyst containing iron oxide, titanium oxide and a potassium compound is used as a dehydrogenation catalyst of acenaphthene, acenaphthylene can be produced at a high yield over a long period of time. The present invention has been completed by finding out that it can be obtained by. That is, the present invention uses 5 to 85 parts by weight of Fe 2 O 3 in terms of iron oxide, 1 to 75 parts by weight in terms of TiO 2 and 5 to 30 parts by weight in terms of K 2 O. This is a method for producing acenaphthylene, in which acenaphthene is brought into contact with a catalyst containing a potassium compound at a temperature of 500 to 750 ° C in a gaseous state to dehydrogenate.
以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
本発明で使用する触媒は、Fe2O3に換算して５〜85重量
部の酸化鉄、TiO2に換算して１〜75重量部の酸化チタン
およびK2Oに換算して５〜30重量部のカリウム化合物を
含有する。各成分の含有量の好ましい範囲は、酸化鉄25
〜65重量部、酸化チタン15〜50重量部である。The catalyst used in the present invention is 5 to 85 parts by weight of iron oxide in terms of Fe 2 O 3 , 1 to 75 parts by weight of titanium oxide in terms of TiO 2 and 5 to 30 in terms of K 2 O. It contains parts by weight of potassium compounds. The preferred range of the content of each component is iron oxide 25
~ 65 parts by weight, titanium oxide 15 to 50 parts by weight.
酸化鉄としてはα型Fe2O3が好ましく、BET表面積が１〜
10m2/gのα型Fe2O3を原料とするのがよい。この酸化鉄
は水酸化第二鉄を400〜1000℃程度で焼成することによ
り得られる。酸化鉄の含有量が５重量部未満では長期触
媒活性が悪く、85重量部を越えるとアセナフチレンの選
択性が悪くなる。As the iron oxide, α-type Fe 2 O 3 is preferable, and the BET surface area is 1 to
It is recommended to use 10 m 2 / g of α-type Fe 2 O 3 as a raw material. This iron oxide is obtained by firing ferric hydroxide at about 400 to 1000 ° C. If the iron oxide content is less than 5 parts by weight, the long-term catalytic activity is poor, and if it exceeds 85 parts by weight, the acenaphthylene selectivity is poor.
酸化チタンとしてはルチル型、アナターゼ型等がある
が、後者の方が好ましい。またTiOSO4を含有する酸化チ
タンを含有する酸化チタンを原料とすると、アセナフチ
レンの収率が向上する。酸化チタンの含有量が１重量部
未満であっても、また75重量部を越えても、アナフチレ
ンの収率は低下する。Titanium oxide includes rutile type and anatase type, but the latter is preferable. When titanium oxide containing titanium oxide containing TiOSO 4 is used as a raw material, the yield of acenaphthylene improves. Even if the content of titanium oxide is less than 1 part by weight or exceeds 75 parts by weight, the yield of naphthylene decreases.
カリウム化合物としては、酸化カリウム、炭酸カリウ
ム、硫酸カリウム、塩化カリウム等の酸化物や塩などが
あるが、炭酸カリウムや硫酸カリウム等の酸素を含有す
るカリウム塩を原料とするのが良い。Examples of the potassium compound include oxides and salts of potassium oxide, potassium carbonate, potassium sulfate, potassium chloride and the like, but it is preferable to use a potassium salt containing oxygen such as potassium carbonate and potassium sulfate as a raw material.
本発明で使用する触媒は、酸化鉄、酸化チタンおよびカ
リウム化合物以外の化合物、すなわち、酸化バナジウ
ム、酸化ビスマス、酸化クロム、酸化コバルト、酸化リ
ン等の酸化物や金属塩等を20重量％以下含有してしても
よい。なお、本発明でいう酸化鉄、酸化チタンは計算上
のものであり、使用状態においては、他の化合物になっ
ていてもよい。The catalyst used in the present invention contains iron oxide, compounds other than titanium oxide and potassium compounds, that is, vanadium oxide, bismuth oxide, chromium oxide, cobalt oxide, 20 wt% or less of oxides and metal salts such as phosphorus oxide. You may do it. The iron oxide and titanium oxide referred to in the present invention are calculated ones, and may be other compounds in the usage state.
本発明で使用する触媒は、例えば以下のような方法で製
造することができる。α型Fe2O3、アナターゼ型酸化チ
タン、炭酸カリウムおよび必要により添加される硝酸コ
バルトに水を加えて混合し、適当な形状、例えば、円筒
形に成形する。これを600〜1000℃の温度で焼成して触
媒とする。The catalyst used in the present invention can be produced, for example, by the following method. Water is added to and mixed with α-type Fe 2 O 3 , anatase-type titanium oxide, potassium carbonate, and cobalt nitrate added as necessary, and formed into a suitable shape, for example, a cylindrical shape. This is calcined at a temperature of 600 to 1000 ° C to obtain a catalyst.
反応は、例えば、アセナフテンを気体状態に保ちなが
ら、触媒層に導入することによって行う。この際には、
気体状態のアセナフテンのみを、触媒層に導入してもよ
いが、アセナフテンを水蒸気等で希釈したのち、触媒層
に導入することがよい。水蒸気には、触媒層から炭素質
残渣を除去する作用があるので、アセナフテンを水蒸気
で希釈することは有効である。アセナフテン１モルに対
して、１〜30モル、好ましくは６〜18モルの水蒸気を使
用することがよい。The reaction is carried out, for example, by introducing acenaphthene into the catalyst layer while keeping it in a gaseous state. In this case,
Only acenaphthene in a gas state may be introduced into the catalyst layer, but it is preferable to introduce acenaphthene into the catalyst layer after diluting acenaphthene with steam or the like. Since steam has a function of removing carbonaceous residues from the catalyst layer, it is effective to dilute acenaphthene with steam. It is preferable to use 1 to 30 mol, and preferably 6 to 18 mol of water vapor with respect to 1 mol of acenaphthene.
反応温度は500〜750℃が好ましく、より好ましくは560
〜680℃である。温度が低すぎるとアセナフテンの転化
率が低下し、高すぎるとアセナフチレン選択率が低下す
る。また、アセナフテンや水蒸気を触媒層に導入する際
には、アセナフテンや水蒸気を事前に触媒と同程度の温
度に加熱しておくのが好ましい。反応圧力はアセナフテ
ンが気体状態である圧力ならば任意であるが、常圧ある
いは、減圧下で反応することが好ましい。The reaction temperature is preferably 500 to 750 ° C, more preferably 560
It is ~ 680 ° C. If the temperature is too low, the conversion of acenaphthene will decrease, and if it is too high, the acenaphthylene selectivity will decrease. Further, when introducing acenaphthene or steam into the catalyst layer, it is preferable to previously heat acenaphthene or steam to a temperature similar to that of the catalyst. The reaction pressure is arbitrary as long as acenaphthene is in a gaseous state, but it is preferable to carry out the reaction under normal pressure or reduced pressure.
アセナフテンと触媒の触媒時間は、SV（１時間当たり、
触媒単位容積当たりのアセナフテンの供給質量）で表す
と、0.1〜1.0g/cc・ｈ、好ましくは0.2〜0.6g/cc・ｈが
よい。SVを変化させることにより、転化率を調節するこ
とも可能である。The catalyst time of acenaphthene and catalyst is SV (per hour,
In terms of the amount of acenaphthene supplied per unit volume of the catalyst), it is 0.1 to 1.0 g / cc · h, preferably 0.2 to 0.6 g / cc · h. It is also possible to adjust the conversion rate by changing the SV.
本発明の方法は、連続法、バッチ法等で行い得るが、連
続法が好ましい。反応は、固定床、流動床あるいは懸濁
床等で行うことができるが、固定床が有利である。ま
た、多段階反応器であってもよい。The method of the present invention can be performed by a continuous method, a batch method or the like, but the continuous method is preferable. The reaction can be carried out in a fixed bed, a fluidized bed, a suspension bed or the like, but a fixed bed is advantageous. It may also be a multi-stage reactor.
以下本発明の実施例を示す。 Examples of the present invention will be shown below.
水酸化第二鉄を温度800℃で10時間焼成して得られたα
型Fe2O3（BET表面積1.68m2/g）、ルチル型酸化チタン、
アナターゼ型酸化チタンおよび炭酸カリウム又はこれら
と酸化バナジウム、硝酸ビスマス、硝酸クロム、リン酸
第二アンモニウム若しくは硝酸コバルトを原料として触
媒を製造した。約320gになるように各原料を採取し、自
動らいかい機をつかて、乾式で５分間、湿式で30分間ら
いかいした。加えて水の量は、約100〜130ccである。こ
れを5mm×5mmの円筒形に成型した後、110℃の乾燥器で
約４時間乾燥した。次いで、これを300℃×１時間、800
℃×10時間焼成し触媒とした。各触媒の組成を第１表に
示す。これらの触媒を充填した固定床常圧流通反応装置
に、水蒸気で希釈したアセナフテンを、SV＝0.2g/cc・
ｈで供給した。反応条件および反応開始後10日目又は90
日目の反応結果を第２表に示す。Α obtained by firing ferric hydroxide at 800 ℃ for 10 hours
Type Fe 2 O 3 (BET surface area 1.68 m 2 / g), rutile type titanium oxide,
Anatase type titanium oxide and potassium carbonate, or vanadium oxide, bismuth nitrate, chromium nitrate, diammonium phosphate or cobalt nitrate were used as raw materials to produce a catalyst. Each raw material was sampled so that it weighs about 320 g, and was dried for 5 minutes in a dry system and 30 minutes in a wet system by using an automatic squeeze machine. In addition, the amount of water is about 100-130cc. This was molded into a 5 mm × 5 mm cylindrical shape and then dried in a dryer at 110 ° C. for about 4 hours. Then, this is 300 ℃ × 1 hour, 800
The mixture was calcined at ℃ × 10 hours to obtain a catalyst. The composition of each catalyst is shown in Table 1. A fixed bed atmospheric pressure reactor filled with these catalysts was charged with acenaphthene diluted with steam at an SV of 0.2 g / cc.
h. Reaction conditions and 10 days after the start of the reaction or 90
Table 2 shows the reaction results on the day.
〔発明の効果〕 本発明によれば長期間、高収率でアセナフチレンを得る
ことができる。 EFFECTS OF THE INVENTION According to the present invention, acenaphthylene can be obtained in a high yield for a long period of time.
───────────────────────────────────────────────────── 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 Ｂ０１Ｊ 23/847 23/86 Ｘ 27/185 Ｘ Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical indication location B01J 23/847 23/86 X 27/185 X C07B 61/00 300
Claims (1)
iO2に換算して１〜75重量部の酸化チタンおよびK2Oに換
算して５〜30重量部のカリウム化合物を含有する触媒に
アセナフテンを温度500〜750℃、気体状態で接触させて
脱水素することを特徴とするアセナフチレンの製造方
法。1. Iron oxide, T of 5 to 85 parts by weight in terms of Fe 2 O 3.
Dehydrated by bringing acenaphthene into contact with a catalyst containing 1 to 75 parts by weight of titanium oxide converted to iO 2 and 5 to 30 parts by weight of potassium compound converted to K 2 O in a gas state at a temperature of 500 to 750 ° C. A method for producing acenaphthylene, which is characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62151083A JPH0784394B2 (en) | 1987-06-19 | 1987-06-19 | Method for producing acenaphthylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62151083A JPH0784394B2 (en) | 1987-06-19 | 1987-06-19 | Method for producing acenaphthylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63316746A JPS63316746A (en) | 1988-12-26 |
| JPH0784394B2 true JPH0784394B2 (en) | 1995-09-13 |
Family
ID=15510948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62151083A Expired - Fee Related JPH0784394B2 (en) | 1987-06-19 | 1987-06-19 | Method for producing acenaphthylene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0784394B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2596020B2 (en) * | 1987-11-27 | 1997-04-02 | 日本鋼管株式会社 | Method for producing acenaphthylene |
| JPH04277030A (en) * | 1991-03-05 | 1992-10-02 | Nissan Gaadoraa Shokubai Kk | Ethylbenzene dehydrogenation catalyst |
| CN115501896B (en) * | 2021-06-23 | 2024-06-25 | 鞍山小巨人生物科技有限公司 | A catalyst for preparing acenaphthylene |
-
1987
- 1987-06-19 JP JP62151083A patent/JPH0784394B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63316746A (en) | 1988-12-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |