JPH07108771B2 - L-type zeolite and catalyst for aromatic hydrocarbon production - Google Patents

L-type zeolite and catalyst for aromatic hydrocarbon production

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Publication number
JPH07108771B2
JPH07108771B2 JP4198194A JP19819492A JPH07108771B2 JP H07108771 B2 JPH07108771 B2 JP H07108771B2 JP 4198194 A JP4198194 A JP 4198194A JP 19819492 A JP19819492 A JP 19819492A JP H07108771 B2 JPH07108771 B2 JP H07108771B2
Authority
JP
Japan
Prior art keywords
catalyst
type zeolite
hydrocarbons
platinum
aromatic hydrocarbon
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 - Lifetime
Application number
JP4198194A
Other languages
Japanese (ja)
Other versions
JPH0639291A (en
Inventor
洋 大橋
尚 勝野
道雄 杉本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Idemitsu Kosan Co Ltd
Original Assignee
Idemitsu Kosan Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Idemitsu Kosan Co Ltd filed Critical Idemitsu Kosan Co Ltd
Priority to JP4198194A priority Critical patent/JPH07108771B2/en
Priority to TW081106166A priority patent/TW315366B/zh
Priority to CA002075364A priority patent/CA2075364C/en
Priority claimed from CA002075364A external-priority patent/CA2075364C/en
Priority to US07/966,262 priority patent/US5294579A/en
Priority to US08/183,124 priority patent/US5354933A/en
Publication of JPH0639291A publication Critical patent/JPH0639291A/en
Publication of JPH07108771B2 publication Critical patent/JPH07108771B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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

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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、Ｌ型ゼオライト及び芳
香族炭化水素製造用触媒に関し、詳しくは、白金及びハ
ロゲン成分を担持させてなる新規なＬ型ゼオライト、該
Ｌ型ゼオライトからなる芳香族化反応に適した触媒、お
よび該触媒を用いてパラフィン系炭化水素などの非芳香
族炭化水素から芳香族炭化水素を効率よく製造する方法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an L-type zeolite and a catalyst for producing an aromatic hydrocarbon, and more specifically, a novel L-type zeolite carrying platinum and a halogen component, and an aromatic compound comprising the L-type zeolite. The present invention relates to a catalyst suitable for a chemical reaction, and a method for efficiently producing an aromatic hydrocarbon from a non-aromatic hydrocarbon such as paraffinic hydrocarbon using the catalyst.

【０００２】[0002]

【従来の技術及び発明が解決しようとする課題】従来か
ら、脂肪族炭化水素などの非芳香族炭化水素を芳香族化
して芳香族炭化水素を製造する触媒としては、白金・ア
ルミナ系触媒が用いられていたが、近年転化率の向上し
た白金担持Ｌ型ゼオライト触媒を使用する方法が提案さ
れた（特公昭５８−５７４０８号公報，特開昭５８−２
２３６１４号公報，特開昭５９−８０３３３号公報）。2. Description of the Related Art Conventionally, platinum-alumina-based catalysts have been used as catalysts for aromatizing non-aromatic hydrocarbons such as aliphatic hydrocarbons to produce aromatic hydrocarbons. However, in recent years, a method of using a platinum-supported L-type zeolite catalyst having an improved conversion rate has been proposed (Japanese Patent Publication No. 58-57408, Sho 58-2).
23614, Japanese Patent Laid-Open No. 59-80333).

【０００３】しかしながら、これらの方法で使用する白
金担持Ｌ型ゼオライト触媒は、いずれも芳香族選択率が
低く、触媒寿命も短く満足しうるものではなかった。ま
た、これを改良したものとして、アルカリ土類金属（Ｂ
ａ，Ｓｒ，Ｃａ）を導入した白金担持Ｌ型ゼオライト触
媒が提案されている（特開昭５８−１３３８３５号公
報）が、本発明者らの追試検討によれば、この触媒も芳
香族選択率および触媒寿命が充分改良されておらず、ま
た触媒安定性も低く、実用的でない。However, none of the platinum-supported L-type zeolite catalysts used in these methods has a low aromatic selectivity and a short catalyst life, which is unsatisfactory. As an improved version of this, alkaline earth metals (B
Although a platinum-supported L-type zeolite catalyst into which (a, Sr, Ca) has been introduced has been proposed (Japanese Patent Laid-Open No. 58-133835), according to the follow-up examination by the present inventors, this catalyst also has an aromatic selectivity. Moreover, the catalyst life is not sufficiently improved, and the catalyst stability is low, which is not practical.

【０００４】さらに、VIII族金属を担持したＬ型ゼオ
ライトをオキシ塩素化処理することにより、触媒活性及
び触媒寿命を改善した触媒（特開昭６０−１６８５３９
号公報）、白金を均一に分散担持するために白金溶液
と非白金金属塩からなる溶液で処理を行う触媒（特開昭
６１−１３８５３９号公報）、ハロゲン含有化合物で
処理されたＬ型ゼオライトに白金を担持してなる触媒
（特開昭６２−５７６５３号公報）、白金を担持した
Ｌ型ゼオライトをハロゲン含有化合物で処理した触媒
（特開昭６３−９１３３４号公報）等が提案されてい
る。Further, by subjecting the L-type zeolite carrying a Group VIII metal to oxychlorination treatment, a catalyst having improved catalytic activity and catalyst life (Japanese Patent Laid-Open No. 60-168539).
(JP-A-61-138539), a catalyst which is treated with a solution consisting of a platinum solution and a non-platinum metal salt in order to uniformly disperse and support platinum (JP-A-61-138539), and an L-type zeolite treated with a halogen-containing compound. A catalyst supporting platinum (Japanese Unexamined Patent Publication No. 62-57653), a catalyst obtained by treating an L-type zeolite supporting platinum with a halogen-containing compound (Japanese Unexamined Patent Publication No. 63-91334), and the like have been proposed.

【０００５】しかし、の触媒の調製工程においてはオ
キシ塩素化処理を高温で行うため、処理装置が高価とな
り経済性が極めて低く、またの触媒では触媒活性が不
充分なものである。さらに及びでは、触媒活性は改
善されるものの、触媒寿命が充分でなく、またハロゲン
処理のための特別の設備が必要となる。その上、ハロゲ
ン含有化合物として、通常は最近環境への影響が問題に
なっているフロンガスが使用されており、その使用は環
境上望ましくない。このように、従来の触媒は、調製工
程，触媒活性，触媒寿命等に問題があり、実用上満足で
きる触媒は未だ提案されていないのが現状である。However, since the oxychlorination treatment is carried out at a high temperature in the step of preparing the catalyst, the processing equipment is expensive and the economy is extremely low, and the catalyst has insufficient catalytic activity. Further, in the cases of and, although the catalyst activity is improved, the catalyst life is not sufficient, and special equipment for halogen treatment is required. In addition, as the halogen-containing compound, chlorofluorocarbon, which has recently become a problem in terms of environmental impact, has been used, and its use is not environmentally desirable. As described above, the conventional catalysts have problems in preparation process, catalyst activity, catalyst life, and the like, and the present situation is that a catalyst that is practically satisfactory has not yet been proposed.

【０００６】[0006]

【課題を解決するための手段】そこで、本発明者らは、
上記の従来の触媒の問題点を解消し、芳香族製造用の触
媒として、調製に特別な装置を必要とせず簡易な工程で
得られ、かつ活性が高く、寿命の長い触媒を開発すべく
鋭意研究を重ねた。その結果、白金成分とハロゲン成分
とを担持するとともに、担持されている白金の電子密度
を高くし、かつ脱アルミニウム量を極力抑制したＬ型ゼ
オライトからなる触媒が、上記目的に適うものであるこ
とを見出した。本発明はかかる知見に基いて完成したも
のである。Therefore, the present inventors have
As a catalyst for aromatic production, the above-mentioned problems of conventional catalysts are solved, and a catalyst having a high activity and a long life, which can be obtained in a simple process without requiring a special apparatus for preparation, is earnestly developed. Repeated research. As a result, a catalyst composed of an L-type zeolite that supports a platinum component and a halogen component, increases the electron density of the supported platinum, and suppresses the dealumination amount as much as possible is suitable for the above purpose. Found. The present invention has been completed based on such findings.

【０００７】すなわち、本発明は、ハロゲン含有化合物
を含むと共に白金含有化合物を担持してなるＬ型ゼオラ
イトであって、担持されている白金のＸ線近吸収端構造
（X-ray Absorption Near Edge Structure；ＸＡＮＥ
Ｓ) 測定におけるピーク強度が0.４以下であり、かつ該
ゼオライト中の脱アルミニウム量が全アルミニウム量の
３％以下であることを特徴とするＬ型ゼオライトを提供
し、またこのＬ型ゼオライトからなる芳香族製造用触媒
を提供するものである。更に、本発明は、パラフィン系
炭化水素，オレフィン系炭化水素，アセチレン系炭化水
素，環状パラフィン系炭化水素及び環状オレフィン系炭
化水素からなる群から選ばれた一種または二種以上の炭
化水素を上記の触媒と接触させることを特徴とする芳香
族炭化水素の製造方法をも提供するものである。That is, the present invention relates to an L-type zeolite containing a halogen-containing compound and carrying a platinum-containing compound, wherein the supported X-ray absorption near edge structure of platinum. XANE
S) Provided is an L-type zeolite characterized in that the peak intensity in the measurement is 0.4 or less and the dealumination amount in the zeolite is 3% or less of the total aluminum amount. The present invention provides a catalyst for aromatic production. Furthermore, the present invention provides one or more hydrocarbons selected from the group consisting of paraffinic hydrocarbons, olefinic hydrocarbons, acetylene hydrocarbons, cyclic paraffinic hydrocarbons and cyclic olefinic hydrocarbons as described above. The present invention also provides a method for producing an aromatic hydrocarbon, which is characterized by contacting with a catalyst.

【０００８】本発明の新規なＬ型ゼオライトを調製する
には従来のＬ型ゼオライトを原料として使用する。ここ
で原料Ｌ型ゼオライトは、組成式0.９〜1.３Ｍ2/n Ｏ・
Ａｌ 2 Ｏ3 ・5.０〜7.０ＳｉＯ2 ・０〜９Ｈ2 Ｏ（式
中、Ｍはアルカリ金属あるいはアルカリ土類金属を示
し、ｎはＭの原子価を示す。）で表わされるものであ
り、具体的には特開昭５８−１３３８３５号公報第９〜
１０頁及び特開昭５９−８０３３３号公報第５頁に開示
されているものである。Preparation of the novel L-type zeolite of the present invention
Conventional L-type zeolite is used as a raw material. here
The raw material L-type zeolite has a composition formula of 0.9 to 1.3M.2 / nO
Al 2O3・ 5.0-7.0SiO2・ 0-9H2O (expression
Inside, M is an alkali metal or alkaline earth metal
However, n shows the valence of M. )
Specifically, specifically, JP-A No. 58-133835, No. 9 to
Disclosed on page 10 and page 5 of JP-A-59-80333.
It has been done.

【０００９】本発明の新規なＬ型ゼオライトは、この上
記原料Ｌ型ゼオライトに白金含有化合物及びハロゲン含
有化合物を担持処理して調製される。このように、白金
成分とハロゲン成分を担持させることにより、従来にな
い優れた触媒活性及び触媒寿命を付与することができ
る。The novel L-type zeolite of the present invention is prepared by supporting the above-mentioned starting L-type zeolite with a platinum-containing compound and a halogen-containing compound. Thus, by supporting the platinum component and the halogen component, it is possible to impart unprecedentedly excellent catalytic activity and catalyst life.

【００１０】ここで、白金含有化合物としては、白金源
となるものであれば特に制限されないが、通常白金塩が
用いられる。具体的には塩化テトラアンミン白金，塩化
白金酸，塩化白金酸塩，水酸化テトラアンミン白金，ジ
ニトロジアミノ白金等を挙げることができる。Here, the platinum-containing compound is not particularly limited as long as it serves as a platinum source, but a platinum salt is usually used. Specific examples thereof include tetraammineplatinum chloride, chloroplatinic acid, chloroplatinate, tetraammineplatinum hydroxide, and dinitrodiaminoplatinum.

【００１１】また、ハロゲン含有化合物としては種々の
ものが挙げられる。具体的には塩化水素，塩化アンモニ
ウム等の塩素含有化合物、フッ化水素，フッ化アンモニ
ウム等のフッ素含有化合物、沃化水素，沃化アンモニウ
ム等の沃素含有化合物、臭化水素，臭化アンモニウム等
の臭素含有化合物等が挙げられる。ハロゲン含有化合物
は、上記の化合物を一種あるいは二種類以上を混合して
使用してもよい。As the halogen-containing compound, various compounds can be mentioned. Specifically, chlorine-containing compounds such as hydrogen chloride and ammonium chloride, fluorine-containing compounds such as hydrogen fluoride and ammonium fluoride, iodine-containing compounds such as hydrogen iodide and ammonium iodide, hydrogen bromide and ammonium bromide, etc. Examples thereof include bromine-containing compounds. As the halogen-containing compound, one kind or a mixture of two or more kinds of the above compounds may be used.

【００１２】本発明の新規なＬ型ゼオライトを調製する
にあたって、その方法は、白金成分とハロゲン成分が原
料Ｌ型ゼオライトに担持される方法であれば特に制限は
なく、通常行われている常圧含浸法，真空含浸法，浸透
法，イオン交換法等により行うことができる。白金含有
化合物及びハロゲン含有化合物を原料Ｌ型ゼオライトに
担持する際、同時でもあるいは予め白金を担持した後ハ
ロゲンを担持あるいはその逆でも可能である。担持処理
における担持量は特に制限はないが、白金含有化合物の
担持量は、通常触媒の全重量基準で白金として0.１〜5.
０重量％が好ましく、特に0.３〜1.５重量％の範囲が最
適である。また、ハロゲン含有化合物の担持量は、通常
触媒の全重量基準でハロゲンとして0.１〜５重量％が好
ましい。また、本発明のＬ型ゼオライト中の脱アルミニ
ウム量は少ない方がよく、通常は原料Ｌ型ゼオライトの
骨格中のアルミニウム量基準で０〜3.０重量％、好まし
くは０〜2.０重量％、より好ましくは０〜1.０重量％で
ある。ここでＬ型ゼオライト中の脱アルミニウム量の測
定は、29Ｓｉ−ＮＭＲの測定によりＳｉ原子の周りのア
ルミニウム原子の配位の割合を求め、それにより骨格中
のアルミニウム量を算出することにより行われる。更
に、本発明のＬ型ゼオライトに担持されている白金のＸ
ＡＮＥＳ測定によるピーク強度が0.４以下である。ここ
でＸＡＮＥＳ、即ちＸ線近吸収端構造は、測定元素の電
子状態を反映するものである。上記ＸＡＮＥＳ測定は、
Ｌ型ゼオライト中の白金のＬ３吸収端の測定を行い、得
られたＸ線吸収スペクトルは共存原子によるバックグラ
ウンド吸収などを含んでいるため、これを差し引いて
（通常、吸収端より低エネルギー部分をVictoreen 式で
近似したものをバックグラウンド吸収とする）図２に示
すようなＸＡＮＥＳスペクトルを得る。このＸＡＮＥＳ
スペクトルはｄバンドの空孔の数と関係があり、白金の
電子密度を表すと考えられている。得られたＸＡＮＥＳ
スペクトルから以下のパラメーターを測定した。 ｈ：（最初のピークトップ強度）−（最初の谷の強度） Ｈ： １2.７ｋｅＶでの強度 このようにして得られたパラメーター（ｈ／Ｈ）が、Ｘ
ＡＮＥＳ測定によるピーク強度を意味する。本発明のＬ
型ゼオライトにおいて、ｈ／Ｈは0.４以下、好ましくは
0.３以下、より好ましくは0.２５以下である。本発明に
おいて、担持処理の条件は、特に制限はなく各種状況に
応じて適宜選定すればよいが、室温〜９０℃にて１分〜
１０時間、Ｌ型ゼオライトを白金含有化合物及びハロゲ
ン含有化合物と接触させればよい。The method for preparing the novel L-type zeolite of the present invention is not particularly limited as long as it is a method in which the platinum component and the halogen component are supported on the starting material L-type zeolite, and the usual atmospheric pressure is used. It can be performed by an impregnation method, a vacuum impregnation method, an infiltration method, an ion exchange method, or the like. When the platinum-containing compound and the halogen-containing compound are loaded on the starting material L-type zeolite, they can be loaded simultaneously, or they can be loaded with platinum and then loaded with halogen, or vice versa. The supported amount in the supporting treatment is not particularly limited, but the supported amount of the platinum-containing compound is usually 0.1 to 5 as platinum based on the total weight of the catalyst.
0 wt% is preferable, and the range of 0.3 to 1.5 wt% is most suitable. Further, the supported amount of the halogen-containing compound is preferably 0.1 to 5% by weight in terms of halogen based on the total weight of the catalyst. Further, the dealumination amount in the L-type zeolite of the present invention is preferably as small as possible, usually 0 to 3.0% by weight, preferably 0 to 2.0% by weight based on the amount of aluminum in the skeleton of the starting L-type zeolite. , And more preferably 0 to 1.0% by weight. Here, the amount of dealumination in the L-type zeolite is measured by determining the proportion of the coordination of aluminum atoms around the Si atom by 29 Si-NMR measurement, and thereby calculating the amount of aluminum in the skeleton. . Furthermore, the platinum X supported on the L-type zeolite of the present invention
The peak intensity measured by ANES is 0.4 or less. Here, XANES, that is, the X-ray near absorption edge structure reflects the electronic state of the measurement element. The above XANES measurement is
The L3 absorption edge of platinum in L-type zeolite was measured, and the obtained X-ray absorption spectrum includes background absorption due to coexisting atoms. The XANES spectrum as shown in FIG. 2 is obtained by approximating the Victoreen equation as the background absorption. This XANES
The spectrum is related to the number of v-band holes and is considered to represent the electron density of platinum. The obtained XANES
The following parameters were measured from the spectrum. h: (Initial peak top intensity)-(Initial valley intensity) H: Intensity at 12.7 keV The parameter (h / H) thus obtained is X
It means the peak intensity measured by ANES. L of the present invention
Type zeolite, h / H is 0.4 or less, preferably
It is 0.3 or less, and more preferably 0.25 or less. In the present invention, the conditions of the supporting treatment are not particularly limited and may be appropriately selected depending on various situations, but are from room temperature to 90 ° C. for 1 minute to
The L-type zeolite may be contacted with the platinum-containing compound and the halogen-containing compound for 10 hours.

【００１３】本発明の触媒は、上記Ｌ型ゼオライトから
なるものであるが、更に必要に応じて、天然又は合成無
機酸化物、例えばアルミナ，シリカ，アルミノケイ酸塩
などをバインダーとして添加することができる。これら
バインダーの使用量は、触媒の全重量基準で５〜９０重
量％とするのが好ましい。The catalyst of the present invention comprises the above-mentioned L-type zeolite, but if necessary, a natural or synthetic inorganic oxide such as alumina, silica, aluminosilicate, etc. can be added as a binder. . The amount of these binders used is preferably 5 to 90% by weight based on the total weight of the catalyst.

【００１４】このように、本発明の触媒は特別な装置，
工程を必要とせずに調製することができる。得られた触
媒は、様々な炭化水素から適当な反応条件下で芳香族炭
化水素を高収率で製造する、いわゆる芳香族化触媒とし
て利用されるが、本発明の方法によれば、極めて効率よ
く芳香族炭化水素を製造することができる。As described above, the catalyst of the present invention has a special device,
It can be prepared without any steps. The obtained catalyst is used as a so-called aromatization catalyst for producing aromatic hydrocarbons in high yield from various hydrocarbons under appropriate reaction conditions, but according to the method of the present invention, it is extremely efficient. Aromatic hydrocarbons can be produced well.

【００１５】本発明の芳香族炭化水素の製造方法におい
ては、原料の炭化水素としてパラフィン系炭化水素，オ
レフィン系炭化水素，アセチレン系炭化水素，環状パラ
フィン系炭化水素及び環状オレフィン系炭化水素からな
る群から選ばれた一種または二種以上の炭化水素を使用
し、上記本発明の触媒に接触させて芳香族炭化水素を製
造する。In the method for producing an aromatic hydrocarbon of the present invention, the group consisting of paraffinic hydrocarbons, olefinic hydrocarbons, acetylene hydrocarbons, cyclic paraffinic hydrocarbons and cyclic olefinic hydrocarbons as the starting hydrocarbons. One or two or more kinds of hydrocarbons selected from the above are used in contact with the catalyst of the present invention to produce an aromatic hydrocarbon.

【００１６】上記パラフィン系炭化水素としては、炭化
数６〜１０のものが好ましく、具体的にはｎ−ヘキサ
ン，メチルペンタン，ｎ−ヘプタン，メチルヘキサン，
ジメチルペンタン，ｎ−オクタンなどを挙げることがで
きる。The paraffinic hydrocarbon preferably has 6 to 10 carbon atoms, specifically, n-hexane, methylpentane, n-heptane, methylhexane,
Examples thereof include dimethyl pentane and n-octane.

【００１７】また、オレフィン系炭化水素としては、炭
化数６〜１０のオレフィン、具体的にはヘキセン，メチ
ルペンテン，ヘプテン，メチルヘキセン，ジメチルペン
テン，オクテンなどを挙げることができる。アセチレン
系炭化水素としては、炭化数６〜１０のもの、具体的に
はヘキシン，ヘプチン，オクチンなどを挙げることがで
きる。Examples of the olefinic hydrocarbons include olefins having 6 to 10 carbon atoms, specifically hexene, methylpentene, heptene, methylhexene, dimethylpentene, octene and the like. As the acetylene-based hydrocarbon, those having a carbon number of 6 to 10, specifically, hexyne, heptin, octyne and the like can be mentioned.

【００１８】環状パラフィン系炭化水素としては、炭化
数６〜１０のもの、具体的にはメチルシクロペンタン，
シクロヘキサン，メチルシクロヘキサン，ジメチルシク
ロヘキサンなどを挙げることができる。さらに、環状オ
レフィン系炭化水素としては、炭化数６〜１０のもの、
具体的にはメチルシクロペンテン，シクロヘキセン，メ
チルシクロヘキセン，ジメチルシクロヘキセンなどを挙
げることができる。The cyclic paraffin hydrocarbon has a carbon number of 6 to 10, specifically, methylcyclopentane,
Examples thereof include cyclohexane, methylcyclohexane and dimethylcyclohexane. Further, the cyclic olefin hydrocarbon has a carbon number of 6 to 10,
Specific examples include methylcyclopentene, cyclohexene, methylcyclohexene, dimethylcyclohexene and the like.

【００１９】本発明の方法は、上記原料炭化水素を前記
触媒と接触させることによって進行し、その際の条件な
どについては特に制限はない。しかし、良好な結果を得
るためには、温度３５０〜６００℃、好ましくは４００
〜５５０℃、圧力０〜４０ｋｇ／ｃｍ2 Ｇ、好ましくは
０〜１０ｋｇ／ｃｍ2 Ｇ、液時空間速度（ＬＨＳＶ）0.
１〜２０ｈｒ-1、好ましくは１〜１０ｈｒ-1とすべきで
ある。さらに、水素ガス／原料炭化水素の供給比は0.１
〜５０モル／モルの範囲に選定すると、一層好結果が期
待できる。The method of the present invention proceeds by bringing the above-mentioned raw material hydrocarbon into contact with the above-mentioned catalyst, and there are no particular restrictions on the conditions at that time. However, in order to obtain good results, a temperature of 350-600 ° C, preferably 400
˜550 ° C., pressure 0-40 kg / cm 2 G, preferably 0-10 kg / cm 2 G, liquid hourly space velocity (LHSV) 0.
It should be 1 to 20 hr -1 , preferably 1 to 10 hr -1 . In addition, the hydrogen gas / feedstock hydrocarbon feed ratio is 0.1.
If it is selected in the range of ˜50 mol / mol, even better results can be expected.

【００２０】[0020]

【実施例】次に本発明を、実施例及び比較例により更に
詳しく説明する。 実施例１ （１）触媒の調製 Ｌ型ゼオライト（東ソー（株）製；ＴＳＺ−５００ＫＯ
Ａ）１００重量部にシリカバインダー（日産化学（株）
製；スノーテックス）２０重量部を添加し、混練成型し
た。その後、５００℃にて２時間空気焼成を行ってシリ
カバインダー成型Ｌ型ゼオライトを得た。次いで3.６重
量％の塩化水素溶液1.３９ｇ，フッ化アンモニウム0.０
９７ｇ，塩化テトラアンミン白金0.１７１ｇ及びイオン
交換水3.６ｇを混合し、含浸液を調製した。このように
して調製した含浸液を、上記のシリカバインダー成型Ｌ
型ゼオライト１０ｇに攪拌しながら徐々に滴下し、白金
及びハロゲンの担持処理を同時に行った。次いで、室温
で一晩乾燥させた後、空気中３００℃で３０分間処理し
て、触媒を調製した。EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. Example 1 (1) Preparation of catalyst L-type zeolite (manufactured by Tosoh Corporation; TSZ-500KO)
A) 100 parts by weight of silica binder (Nissan Chemical Co., Ltd.)
(Manufactured by Snowtex) 20 parts by weight was added and kneaded and molded. Then, air baking was performed at 500 ° C. for 2 hours to obtain a silica binder-molded L-type zeolite. Then 1.39 g of 3.6% by weight hydrogen chloride solution, ammonium fluoride 0.0
97 g, tetraammineplatinum chloride 0.171 g and ion-exchanged water 3.6 g were mixed to prepare an impregnating solution. The impregnating solution prepared in this manner was used as the above silica binder molding L.
The mixture was gradually added dropwise to 10 g of type zeolite while stirring, and platinum and halogen loading treatments were simultaneously performed. Then, after drying at room temperature overnight, the catalyst was prepared by treating in air at 300 ° C. for 30 minutes.

【００２１】（２）芳香族炭化水素の製造 実施例（１）で調製された触媒0.５ｇを、石英反応管に
充填した後、水素気流中、５４０℃で２４時間処理し
た。次いで、ｎ−ヘキサン／イソヘキサン／メチルシク
ロペンタン＝４９／４３／８の重量組成比を有する軽質
ナフサ及び水素を、それぞれ重量空間速度２ｈｒ-1，水
素／軽質ナフサ＝５モル／モルで供給し、圧力５ｋｇ／
ｃｍ2 Ｇ，温度５００℃に調節し、芳香族への転化反応
を行った。この際の芳香族収率の経時変化を図１に示
す。(2) Production of Aromatic Hydrocarbon 0.5 g of the catalyst prepared in Example (1) was charged into a quartz reaction tube and treated in a hydrogen stream at 540 ° C. for 24 hours. Then, light naphtha and hydrogen having a weight composition ratio of n-hexane / isohexane / methylcyclopentane = 49/43/8 are supplied at a weight hourly space velocity of 2 hr −1 and hydrogen / light naphtha = 5 mol / mol, respectively. Pressure 5kg /
It was adjusted to cm 2 G and temperature of 500 ° C., and the conversion reaction to aromatic was carried out. The change with time in the aromatic yield at this time is shown in FIG.

【００２２】比較例１ （１）触媒の調製 上記実施例１（１）で得られたシリカバインダー成型Ｌ
型ゼオライト２０ｇを、石英反応管に充填し、窒素を流
しながら２００℃で３０分間保持し、その後ガスを窒素
をモノクロロトリフルオロメタンに切替え、５００℃に
昇温した。５００℃に昇温後、２時間処理した後、ガス
を再び窒素に切替えて降温し、ハロゲン処理Ｌ型ゼオラ
イトを得た。次に、このハロゲン処理Ｌ型ゼトライト１
０ｇに対し、塩化テトラアンミン白金0.１７１ｇ及びイ
オン交換水4.０ｇからなる含浸液を攪拌しながら徐々に
滴下して、担持を行った。担持後、乾燥器で８０℃にて
３時間乾燥して、触媒を調製した。Comparative Example 1 (1) Preparation of Catalyst L Silica binder molding L obtained in Example 1 (1) above
20 g of type zeolite was filled in a quartz reaction tube and maintained at 200 ° C. for 30 minutes while flowing nitrogen, and then the gas was switched to monochlorotrifluoromethane and the temperature was raised to 500 ° C. After heating to 500 ° C. and treating for 2 hours, the gas was switched to nitrogen again and the temperature was lowered to obtain a halogen-treated L-type zeolite. Next, this halogen-treated L-type zeolite
An impregnating solution consisting of 0.171 g of tetraammineplatinum chloride and 4.0 g of ion-exchanged water was gradually added dropwise to 0 g of the solution while stirring to carry it. After loading, the catalyst was prepared by drying in a dryer at 80 ° C. for 3 hours.

【００２３】（２）芳香族炭化水素の製造 上記実施例１（２）において、触媒として比較例１
（１）で得られた触媒を使用したこと以外は、実施例１
（２）と同様にして転化反応を行った。芳香族収率の経
時変化を図１に示す。(2) Production of Aromatic Hydrocarbon In Comparative Example 1 as the catalyst in the above Example 1 (2)
Example 1 except that the catalyst obtained in (1) was used
The conversion reaction was carried out in the same manner as in (2). The time-dependent change in aromatic yield is shown in FIG.

【００２４】比較例２ （１）触媒の調製 上記実施例１（１）で得られたシリカバインダー成型Ｌ
型ゼオライト１０ｇに対し、塩化テトラアンミン白金0.
１７１ｇ及びイオン交換水4.８ｇからなる含浸液を攪拌
しながら徐々に滴下して、室温で２時間乾燥し、さらに
空気中８０℃で３時間処理して触媒を得た。得られた触
媒を石英反応管に充填し、窒素を流しながら２００℃で
１時間保持した後４８０℃まで昇温した。４８０℃にて
フロン１１２／窒素＝0.１／９9.９（体積％）のガスに
切替えて、１０時間処理した。その後、再びガスを窒素
に切替えて降温し、触媒を調製した。Comparative Example 2 (1) Preparation of catalyst Silica binder molded L obtained in Example 1 (1) above
Tetraammineplatinum chloride 0.
An impregnating solution consisting of 171 g and ion-exchanged water 4.8 g was gradually added dropwise with stirring, dried at room temperature for 2 hours, and further treated in air at 80 ° C. for 3 hours to obtain a catalyst. The obtained catalyst was filled in a quartz reaction tube, kept at 200 ° C. for 1 hour while flowing nitrogen, and then heated to 480 ° C. At 480 ° C., the gas was changed to Freon 112 / nitrogen = 0.1 / 99.9 (volume%) and treated for 10 hours. Then, the gas was switched to nitrogen again and the temperature was lowered to prepare a catalyst.

【００２５】（２）芳香族炭化水素の製造 上記実施例１（２）において、触媒として比較例２
（１）で得られた触媒を使用したこと以外は、実施例１
（２）と同様にして転化反応を行った。芳香族収率の経
時変化を図１に示す。(2) Production of Aromatic Hydrocarbon In Comparative Example 2 as the catalyst in Example 1 (2) above.
Example 1 except that the catalyst obtained in (1) was used
The conversion reaction was carried out in the same manner as in (2). The time-dependent change in aromatic yield is shown in FIG.

【００２６】実施例２ （１）触媒の調製 上記実施例１（１）と同様である。Example 2 (1) Preparation of catalyst The same as in Example 1 (1) above.

【００２７】（２）芳香族炭化水素の製造 実施例２（１）で得られた触媒0.０５ｇを採取し、パル
ス反応器に充填した。次いで水素気流中で５００℃まで
１時間かけて昇温し、５００℃にて１時間保持した。反
応温度を４７０℃に調節し、水素気流中（2.２リットル
／時）でｎ−ヘキサンを３マイクロリットルパルスし、
転化反応を行った。この際のベンゼンの収率は５5.７％
であった。(2) Production of aromatic hydrocarbons 0.05 g of the catalyst obtained in Example 2 (1) was sampled and charged in a pulse reactor. Then, the temperature was raised to 500 ° C. over 1 hour in a hydrogen stream, and the temperature was kept at 500 ° C. for 1 hour. The reaction temperature was adjusted to 470 ° C., and 3 microliters of n-hexane was pulsed in a hydrogen stream (2.2 liter / hour),
The conversion reaction was carried out. The yield of benzene in this case is 55.7%
Met.

【００２８】比較例３ （１）触媒の調製 上記実施例１（１）で得られたシリカバインダー成型Ｌ
型ゼオライト１０ｇに塩化テトラアンミン白金0.１７１
ｇ及びイオン交換水4.８ｇからなる含浸液を攪拌しなが
ら徐々に滴下し、室温で一晩乾燥させた後、空気中３０
０℃で３０分間処理し、触媒を調製した。Comparative Example 3 (1) Preparation of catalyst Silica binder molding L obtained in Example 1 (1) above
Tetraammineplatinum chloride 0.171 on 10g type zeolite
g and ion-exchanged water 4.8 g were added dropwise with stirring, and the mixture was dried overnight at room temperature and then in air 30
The catalyst was prepared by treating at 0 ° C. for 30 minutes.

【００２９】（２）芳香族炭化水素の製造 上記実施例２（２）において、触媒として上記比較例３
（１）で得られた触媒を使用したこと以外は、実施例２
（２）と同様にして転化反応を行った。この際のベンゼ
ンの収率は３2.１％であった。(2) Production of aromatic hydrocarbon In the above Example 2 (2), the above Comparative Example 3 was used as a catalyst.
Example 2 except that the catalyst obtained in (1) was used.
The conversion reaction was carried out in the same manner as in (2). The yield of benzene at this time was 32.1%.

【００３０】実施例３ （１）触媒の調製 Ｌ型ゼオライト（東ソー（株）製；ＴＳＺ−５００ＫＯ
Ａ）１００重量部にシリカバインダー（日産化学（株）
製；スノーテックス）２０重量部を添加し、混練成型し
た。その後、５００℃にて２時間空気焼成を行ってシリ
カバインダー成型Ｌ型ゼオライトを得た。次いで、フッ
化アンモニウム0.０９７ｇ，塩化テトラアンミン白金0.
１７１ｇ及びイオン交換水4.８ｇを混合し、含浸液を調
製した。このようにして調製した含浸液を、上記のシリ
カバインダー成型Ｌ型ゼオライト１０ｇに攪拌しながら
徐々に滴下し、白金及びハロゲンの担持処理を同時に行
った。次いで、室温で一晩乾燥させた後、空気中３００
℃で３時間処理して、触媒を調製した。Example 3 (1) Preparation of catalyst L-type zeolite (manufactured by Tosoh Corporation; TSZ-500KO)
A) 100 parts by weight of silica binder (Nissan Chemical Co., Ltd.)
(Manufactured by Snowtex) 20 parts by weight was added and kneaded and molded. Then, air baking was performed at 500 ° C. for 2 hours to obtain a silica binder-molded L-type zeolite. Next, 0.097 g of ammonium fluoride and tetraammineplatinum chloride.
171 g and ion-exchanged water 4.8 g were mixed to prepare an impregnation liquid. The impregnating solution thus prepared was gradually added dropwise to 10 g of the above-mentioned silica binder-molded L-type zeolite while stirring to simultaneously carry out platinum and halogen loading treatment. Then, after drying overnight at room temperature, 300 in air
The catalyst was prepared by treating at 3 ° C. for 3 hours.

【００３１】（２）芳香族炭化水素の製造 実施例３（１）で調製された触媒0.５ｇを、石英反応管
に充填した後、水素気流中、５４０℃で２４時間処理し
た。次いで、ｎ−ヘキサン／イソヘキサン／メチルシク
ロペンタン＝４９／４３／８の重量組成比を有する軽質
ナフサを、それぞれ重量空間速度１６ｈｒ-1，水素／軽
質ナフサ＝５モル／モルで供給し、圧力５ｋｇ／ｃｍ2
Ｇ，温度５１７℃に調節した後、２０時間保持し、芳香
族への転化反応を行った。この際の芳香族の収率は５2.
９％であった。(2) Production of Aromatic Hydrocarbon 0.5 g of the catalyst prepared in Example 3 (1) was charged into a quartz reaction tube and treated in a hydrogen stream at 540 ° C. for 24 hours. Next, light naphtha having a weight composition ratio of n-hexane / isohexane / methylcyclopentane = 49/43/8 was supplied at a weight hourly space velocity of 16 hr −1 and hydrogen / light naphtha = 5 mol / mol, and a pressure of 5 kg. / Cm 2
After adjusting G and temperature to 517 ° C., the temperature was maintained for 20 hours to carry out a conversion reaction to an aromatic compound. The yield of aromatics in this case is 52.
It was 9%.

【００３２】実施例４ （１）触媒の調製 上記実施例３（１）で得られたシリカバインダー成型Ｌ
型ゼオライト１０ｇにフッ化アンモニウム0.０９７ｇ，
塩化アンモニウム0.０７５ｇ，塩化テトラアンミン白金
0.１７１ｇ及びイオン交換水4.８ｇからなる含浸液を攪
拌しながら徐々に滴下し、室温で一晩乾燥し、さらに空
気中３００℃で３時間処理して触媒を調製した。Example 4 (1) Preparation of catalyst Silica binder molding L obtained in the above Example 3 (1)
Type zeolite 10g to ammonium fluoride 0.097g,
Ammonium chloride 0.075 g, tetraammine platinum chloride
An impregnation liquid consisting of 0.171 g and 4.8 g of ion-exchanged water was gradually added dropwise with stirring, dried overnight at room temperature, and further treated in air at 300 ° C. for 3 hours to prepare a catalyst.

【００３３】（２）芳香族炭化水素の製造 実施例３（２）において、触媒として上記実施例４
（１）で得られた触媒を使用したこと以外は、実施例３
（２）と同様にして転化反応を行った。この際の芳香族
の収率は６3.８％であった。(2) Production of Aromatic Hydrocarbon In Example 3 (2), the above-mentioned Example 4 was used as a catalyst.
Example 3 except that the catalyst obtained in (1) was used.
The conversion reaction was carried out in the same manner as in (2). At this time, the yield of aromatics was 63.8%.

【００３４】実施例５ （１）触媒の調製 上記実施例３（１）で得られたシリカバインダー成型Ｌ
型ゼオライト１０ｇにフッ化アンモニウム0.０９７ｇ，
臭化アンモニウム0.０６１ｇ，塩化テトラアンミン白金
0.１７１ｇ及びイオン交換水4.８ｇからなる含浸液を攪
拌しながら徐々に滴下し、室温で一晩乾燥し、さらに空
気中３００℃で３時間処理して触媒を調製した。Example 5 (1) Preparation of catalyst Silica binder molding L obtained in the above Example 3 (1)
Type zeolite 10g to ammonium fluoride 0.097g,
Ammonium bromide 0.061 g, tetraammine platinum chloride
An impregnation liquid consisting of 0.171 g and 4.8 g of ion-exchanged water was gradually added dropwise with stirring, dried overnight at room temperature, and further treated in air at 300 ° C. for 3 hours to prepare a catalyst.

【００３５】（２）芳香族炭化水素の製造 実施例３（２）において、触媒として上記実施例５
（１）で得られた触媒を使用したこと以外は、実施例３
（２）と同様にして転化反応を行った。この際の芳香族
の収率は６0.９％であった。(2) Production of aromatic hydrocarbon In Example 3 (2), the above-mentioned Example 5 was used as a catalyst.
Example 3 except that the catalyst obtained in (1) was used.
The conversion reaction was carried out in the same manner as in (2). At this time, the yield of aromatics was 60.9%.

【００３６】比較例４ （１）触媒の調製 上記実施例３（１）で得られたシリカバインダー成型Ｌ
型ゼオライト１０ｇに塩化テトラアンミン白金0.１７１
ｇ及びイオン交換水4.８ｇからなる含浸液を攪拌しなが
ら徐々に滴下し、室温で２時間乾燥し、さらに空気中１
２０℃で３時間処理して白金担持触媒を得た。Comparative Example 4 (1) Preparation of Catalyst Silica Binder Molded L Obtained in Example 3 (1) Above
Tetraammineplatinum chloride 0.171 on 10g type zeolite
g and ion-exchanged water (4.8 g) are slowly added dropwise with stirring, dried at room temperature for 2 hours, and further in air 1
It was treated at 20 ° C. for 3 hours to obtain a platinum-supported catalyst.

【００３７】（２）芳香族炭化水素の製造 実施例３（２）において、触媒として上記比較例４
（１）で得られた触媒を使用したこと以外は、実施例３
（２）と同様にして転化反応を行った。この際の芳香族
の収率は３5.２％であった。(2) Production of aromatic hydrocarbon In Example 3 (2), the catalyst of Comparative Example 4 was used as the catalyst.
Example 3 except that the catalyst obtained in (1) was used.
The conversion reaction was carried out in the same manner as in (2). At this time, the yield of aromatics was 35.2%.

【００３８】実施例６ （１）触媒の調製 Ｌ型ゼオライト（東ソー（株）製：ＴＳＺ−５００ＫＯ
Ａ）１００重量部にシリカバインダー（日産化学（株）
製：スノーテックス）２０重量部を添加し、混練成型し
た。その後、５００℃にて２時間空気焼成を行ってシリ
カバインダー成型Ｌ型ゼオライトを得た。次いで塩化テ
トラアンミン白金0.１７１ｇ，フッ化アンモニウム0.１
６７ｇ，塩化アンモニウム0.０７５ｇ及びイオン交換水
4.５ｇを混合し、含浸液を調製した。このようにして調
製した含浸液を、上記のシリカバインダー成型Ｌ型ゼオ
ライト１０ｇに攪拌しながら徐々に滴下し、白金及びハ
ロゲンの担持処理を行った。次いで、乾燥後、空気中３
００℃で３時間処理して触媒を調製した。Example 6 (1) Preparation of catalyst L-type zeolite (manufactured by Tosoh Corp .: TSZ-500KO)
A) 100 parts by weight of silica binder (Nissan Chemical Co., Ltd.)
(Manufactured by: Snowtex) 20 parts by weight was added and kneaded and molded. Then, air baking was performed at 500 ° C. for 2 hours to obtain a silica binder-molded L-type zeolite. Next, tetraammineplatinum chloride 0.171 g, ammonium fluoride 0.1
67 g, ammonium chloride 0.075 g and deionized water
An impregnation liquid was prepared by mixing 4.5 g. The impregnating liquid thus prepared was gradually added dropwise to 10 g of the above silica binder-molded L-type zeolite with stirring to carry out a platinum and halogen supporting treatment. Then, after drying, 3 in air
The catalyst was prepared by treating at 00 ° C. for 3 hours.

【００３９】（２）触媒物性の評価脱アルミニウム量 上記実施例６（１）の触媒の29Ｓｉ−ＮＭＲ測定を行
い、その測定結果を波形分離し骨格中のアルミニウム量
を計算し、原料Ｌ型ゼオライトと比較し脱アルミニウム
量を求めた。この値を第１表に示す。ＸＡＮＥＳ測定 上記実施例６（１）の触媒を５４０℃，２４時間水素還
元（水素流量6.５リットル／ｈｒ）を行い、試料を粉砕
成型して in situ測定装置に入れ、再度５４０℃，１時
間水素還元（水素流量１０cc／ｍｉｎ）を行った。その
後、同じ温度で真空排気し、室温まで冷却後、窒素を導
入して系を封じた。このようにして調製した試料を用い
てＸＡＮＥＳ測定を行った。得られた結果は前述した定
義により計算した。この値を第１表に示す。(2) Evaluation of physical properties of catalyst Amount of dealumination The catalyst of Example 6 (1) was subjected to 29 Si-NMR measurement, the measurement result was separated into waveforms, and the amount of aluminum in the skeleton was calculated. The dealumination amount was determined in comparison with zeolite. This value is shown in Table 1. XANES measurement The catalyst of Example 6 (1) above was subjected to hydrogen reduction (hydrogen flow rate 6.5 liter / hr) at 540 ° C. for 24 hours, the sample was crushed and molded, and put into an in situ measurement device, and again at 540 ° C., 1 Hydrogen reduction (hydrogen flow rate 10 cc / min) was performed for an hour. Then, the system was evacuated at the same temperature, cooled to room temperature, and then nitrogen was introduced to seal the system. XANES measurement was performed using the sample thus prepared. The results obtained were calculated according to the definitions given above. This value is shown in Table 1.

【００４０】（３）芳香族炭化水素の製造反応 上記実施例６（１）の触媒0.２５ｇを、石英反応管に充
填した後、５４０℃，２４時間水素還元（水素流量6.５
リットル／ｈｒ）を行った。次いで、ｎ−ヘキサン／イ
ソヘキサン／メチルシクロペンタン＝４９／４３／８の
重量組成比を有する軽質ナフサ及び水素を、それぞれ重
量空間速度３２ｈ-1，水素／炭化水素＝５モル／モルで
供給し、圧力５ｋｇ／ｃｍ2 Ｇ，外温５１７℃に調節
し、芳香族炭化水素への転化反応を行った。この時の反
応開始５時間後の芳香族収率を第１表に示す。(3) Aromatic hydrocarbon production reaction After charging 0.25 g of the catalyst of Example 6 (1) above into a quartz reaction tube, hydrogen reduction was performed at 540 ° C. for 24 hours (hydrogen flow rate 6.5).
Liter / hr). Then, light naphtha having a weight composition ratio of n-hexane / isohexane / methylcyclopentane = 49/43/8 and hydrogen are supplied at a weight hourly space velocity of 32 h −1 and hydrogen / hydrocarbon = 5 mol / mol, respectively. The pressure was adjusted to 5 kg / cm 2 G and the external temperature was adjusted to 517 ° C., and the conversion reaction to aromatic hydrocarbon was performed. The aromatic yield after 5 hours from the start of the reaction is shown in Table 1.

【００４１】比較例５ （１）触媒の調製 上記実施例６（１）で得られたシリカバインダー成型Ｌ
型ゼオライト２０ｇを、石英反応管に充填し、窒素を流
しながら２００℃で３０分間保持し、その後ガスをモノ
クロロトリフルオロメタンに切替え、５００℃に昇温し
た。５００℃に昇温後、２時間処理した後、ガスを再び
窒素に切替えて室温まで降温して、実施例６とほぼ同量
のハロゲン量となるハロゲン処理Ｌ型ゼオライトを得
た。次に、このハロゲン処理Ｌ型ゼトライト１０ｇに対
し、塩化テトラアンミン白金0.１７１ｇ及びイオン交換
水4.５ｇからなる含浸液を攪拌しながら徐々に滴下し
て、担持を行った。担持後、乾燥機で１２０℃にて３時
間乾燥して、触媒を調製した。Comparative Example 5 (1) Preparation of catalyst Silica binder molded L obtained in Example 6 (1) above
20 g of type zeolite was filled in a quartz reaction tube and kept at 200 ° C. for 30 minutes while flowing nitrogen, after which the gas was switched to monochlorotrifluoromethane and the temperature was raised to 500 ° C. After the temperature was raised to 500 ° C. and treated for 2 hours, the gas was switched to nitrogen again and the temperature was lowered to room temperature to obtain a halogen-treated L-type zeolite having the same halogen amount as in Example 6. Next, to 10 g of this halogen-treated L-type zeolite, an impregnating solution consisting of 0.171 g of tetraammineplatinum chloride and 4.5 g of ion-exchanged water was gradually added dropwise with stirring to carry the particles. After the supporting, the catalyst was prepared by drying in a dryer at 120 ° C. for 3 hours.

【００４２】（２）触媒物性の評価 上記実施例６（２）において、触媒として比較例５
（１）で得られた触媒を使用したこと以外は、実施例６
（２）と同様にして行った。その時の値を第１表に示
す。(2) Evaluation of physical properties of catalyst In Comparative Example 5 as a catalyst in the above Example 6 (2)
Example 6 except that the catalyst obtained in (1) was used.
It carried out like (2). The values at that time are shown in Table 1.

【００４３】（３）芳香族炭化水素の製造反応 上記実施例６（３）において、触媒として比較例５
（１）で得られた触媒を使用したこと以外は、実施例６
（３）と同様にして行った。その時の値を第１表に示
す。(3) Production Reaction of Aromatic Hydrocarbon In Comparative Example 5 as the catalyst in Example 6 (3) above.
Example 6 except that the catalyst obtained in (1) was used.
It carried out like (3). The values at that time are shown in Table 1.

【００４４】比較例６ （１）触媒の調製 上記実施例６（１）で得られたシリカバインダー成型Ｌ
型ゼオライト１０ｇに対し、塩化テトラアンミン白金0.
１７１ｇ及びイオン交換水4.５ｇからなる含浸液を攪拌
しながら徐々に滴下して、担持を行った。担持後、乾燥
機で１２０℃にして３時間乾燥して触媒を調製した。Comparative Example 6 (1) Preparation of Catalyst L Silica binder molding L obtained in Example 6 (1) above
Tetraammineplatinum chloride 0.
An impregnating solution consisting of 171 g and ion-exchanged water 4.5 g was gradually added dropwise with stirring to carry the particles. After the supporting, the catalyst was prepared by drying at 120 ° C. for 3 hours with a dryer.

【００４５】（２）触媒物性の評価 上記実施例６（２）において、触媒として上記比較例６
（１）で得られた触媒を使用したこと以外は実施例６
（２）と同様にして行った。その時の値を第１表に示
す。(2) Evaluation of physical properties of catalyst In the above-mentioned Example 6 (2), the catalyst of Comparative Example 6 was used as a catalyst.
Example 6 except that the catalyst obtained in (1) was used.
It carried out like (2). The values at that time are shown in Table 1.

【００４６】（３）芳香族炭化水素の製造反応 上記実施例６（３）において、触媒として上記比較例６
（１）で得られた触媒を使用したこと以外は実施例６
（３）と同様にして行った。その時の値を第１表に示
す。(3) Aromatic Hydrocarbon Production Reaction In the above Example 6 (3), the above Comparative Example 6 was used as a catalyst.
Example 6 except that the catalyst obtained in (1) was used.
It carried out like (3). The values at that time are shown in Table 1.

【００４７】比較例７ （１）触媒の調製 フッ化カリウム0.１０７ｇ，塩化カリウム0.０７３５
ｇ，塩化テトラアンミン白金0.１２０ｇ及びイオン交換
水3.５０ｇを混合し、含浸液を調製した。このようにし
て調製した含浸液を、上記実施例６（１）で得られたシ
リカバインダー成型Ｌ型ゼオライト７ｇに攪拌しながら
徐々に滴下した。その後、室温で一晩乾燥させた後、空
気中３００℃で３０分間処理して、触媒を調製した。Comparative Example 7 (1) Preparation of catalyst 0.107 g of potassium fluoride, 0.0735 of potassium chloride
g, tetraammineplatinum chloride 0.120 g and ion-exchanged water 3.50 g were mixed to prepare an impregnating solution. The impregnating liquid thus prepared was gradually added dropwise to 7 g of the silica binder-molded L-type zeolite obtained in Example 6 (1) while stirring. Then, it was dried at room temperature overnight and then treated in air at 300 ° C. for 30 minutes to prepare a catalyst.

【００４８】（２）触媒物性の評価 上記実施例６（２）において、触媒として上記比較例７
（１）で得られた触媒を使用したこと以外は、実施例６
（２）と同様にして行った。その時の値を第１表に示
す。(2) Evaluation of physical properties of catalyst In the above-mentioned Example 6 (2), the above-mentioned Comparative Example 7 was used as a catalyst.
Example 6 except that the catalyst obtained in (1) was used.
It carried out like (2). The values at that time are shown in Table 1.

【００４９】（３）芳香族炭化水素の製造反応 上記実施例６（３）において、触媒として上記比較例７
（１）で得られた触媒を使用したこと以外は、実施例６
（３）と同様にして行った。その時の値を第１表に示
す。(3) Aromatic Hydrocarbon Production Reaction In the above Example 6 (3), the above Comparative Example 7 was used as a catalyst.
Example 6 except that the catalyst obtained in (1) was used.
It carried out like (3). The values at that time are shown in Table 1.

【００５０】[0050]

【表１】 [Table 1]

【００５１】以上の結果から、無機ハロゲン化合物で処
理を行うことにより、脱アルミニウムの生成が抑制さ
れ、さらに白金の電子密度が高い触媒の調製が可能とな
った。また、そのような触媒は、炭化水素の芳香族化反
応においても高い活性を示した。From the above results, the treatment with the inorganic halogen compound suppressed the production of dealumination and made it possible to prepare a catalyst having a high electron density of platinum. Moreover, such a catalyst also showed high activity in the aromatization reaction of hydrocarbons.

【００５２】[0052]

【発明の効果】以上の如く、本発明の触媒は、特別の装
置等を必要とせず従来行われている簡易な工程で調製す
ることができるとともに、様々な炭化水素から芳香族炭
化水素を高活性，高収率にて、しかも長期にわたって安
定して製造できるものであり、芳香族炭化水素製造用の
触媒として有効に使用することができる。また、本発明
の芳香族炭化水素の製造方法によれば、高い収率で芳香
族炭化水素を製造することができ、しかも触媒は長時間
高活性を維持できるため、長期にわたる連続運転を行っ
ても芳香族炭化水素の収率は非常に高い。さらにまた本
発明の触媒は、触媒寿命が著しく改善されているため、
触媒の再生の頻度が減り、生産性が向上し、製造コスト
の低減という工業的利点を有し、その利用価値は非常に
高いものである。従って、本発明は、芳香族炭化水素を
製造する石油化学工業あるいは高オクタン価燃料を製造
する石油産業などの分野において幅広くかつ有効に利用
される。INDUSTRIAL APPLICABILITY As described above, the catalyst of the present invention can be prepared by a simple process which has been conventionally carried out without the need for a special device and the like, and can enhance aromatic hydrocarbons from various hydrocarbons. It can be produced with high activity and high yield and stably for a long period of time, and can be effectively used as a catalyst for producing aromatic hydrocarbons. Further, according to the method for producing an aromatic hydrocarbon of the present invention, it is possible to produce an aromatic hydrocarbon in a high yield, and since the catalyst can maintain high activity for a long time, continuous operation over a long period of time is performed. Also, the yield of aromatic hydrocarbons is very high. Furthermore, the catalyst of the present invention has a significantly improved catalyst life,
The catalyst has an industrial advantage that the frequency of regeneration is reduced, the productivity is improved, and the manufacturing cost is reduced, and its utility value is very high. Therefore, the present invention can be widely and effectively utilized in the fields such as the petrochemical industry for producing aromatic hydrocarbons and the petroleum industry for producing high octane fuel.

【図面の簡単な説明】[Brief description of drawings]

【図１】図１は、実施例１，比較例１及び比較例２にお
ける芳香族収率の経時変化を示すグラフである。FIG. 1 is a graph showing changes with time in aromatic yield in Example 1, Comparative Example 1 and Comparative Example 2.

【図２】図２は、Ｌ型ゼオライトにおける白金含有化合
物のＸＡＮＥＳスペクトルである。FIG. 2 is an XANES spectrum of a platinum-containing compound in L-type zeolite.

───────────────────────────────────────────────────── 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 // Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location // C07B 61/00 300

Claims (4)

【特許請求の範囲】[Claims] 【請求項１】 ハロゲン含有化合物を含むと共に白金含
有化合物を担持してなるＬ型ゼオライトであって、担持
されている白金のＸ線近吸収端構造測定におけるピーク
強度が0.４以下であり、かつ該ゼオライト中の脱アルミ
ニウム量が全アルミニウム量の３％以下であることを特
徴とするＬ型ゼオライト。1. An L-type zeolite containing a halogen-containing compound and supporting a platinum-containing compound, wherein the supported platinum has a peak intensity of 0.4 or less in the X-ray near-absorption edge structure measurement. Further, the amount of dealumination in the zeolite is 3% or less of the total amount of aluminum, L-type zeolite. 【請求項２】 請求項１記載のＬ型ゼオライトからなる
芳香族炭化水素製造用触媒。2. A catalyst for producing an aromatic hydrocarbon, which comprises the L-type zeolite according to claim 1. 【請求項３】 パラフィン系炭化水素，オレフィン系炭
化水素，アセチレン系炭化水素，環状パラフィン系炭化
水素及び環状オレフィン系炭化水素からなる群から選ば
れた一種または二種以上の炭化水素を、請求項２の触媒
と接触させることを特徴とする芳香族炭化水素の製造方
法。3. One or more hydrocarbons selected from the group consisting of paraffinic hydrocarbons, olefinic hydrocarbons, acetylene hydrocarbons, cyclic paraffinic hydrocarbons and cyclic olefinic hydrocarbons. A method for producing an aromatic hydrocarbon, which comprises bringing the catalyst into contact with the catalyst of 2. 【請求項４】 炭化水素を、温度３５０〜６００℃，圧
力０〜４０ｋｇ／ｃｍ2 Ｇ，液時空間速度0.１〜２０ｈ
ｒ-1および水素ガス／炭化水素の供給比０〜５０（モル
比）の条件下で、触媒と接触させる請求項３記載の芳香
族炭化水素の製造方法。4. Hydrocarbons at a temperature of 350 to 600 ° C., a pressure of 0 to 40 kg / cm 2 G, and a liquid hourly space velocity of 0.1 to 20 h.
The method for producing an aromatic hydrocarbon according to claim 3, wherein the catalyst is brought into contact with r -1 and the hydrogen gas / hydrocarbon feed ratio of 0 to 50 (molar ratio).
JP4198194A 1991-02-05 1992-07-24 L-type zeolite and catalyst for aromatic hydrocarbon production Expired - Lifetime JPH07108771B2 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP4198194A JPH07108771B2 (en) 1992-07-24 1992-07-24 L-type zeolite and catalyst for aromatic hydrocarbon production
TW081106166A TW315366B (en) 1991-02-05 1992-08-04
CA002075364A CA2075364C (en) 1991-02-05 1992-08-05 L-type zeolite and catalyst for the production of aromatic hydrocarbons
US07/966,262 US5294579A (en) 1991-02-05 1992-10-26 L-type zeolite and catalyst for the production of aromatic hydrocarbons
US08/183,124 US5354933A (en) 1991-02-05 1994-01-18 Process for producing aromatic hydrocarbons

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP4198194A JPH07108771B2 (en) 1992-07-24 1992-07-24 L-type zeolite and catalyst for aromatic hydrocarbon production
CA002075364A CA2075364C (en) 1991-02-05 1992-08-05 L-type zeolite and catalyst for the production of aromatic hydrocarbons

Publications (2)

Publication Number Publication Date
JPH0639291A JPH0639291A (en) 1994-02-15
JPH07108771B2 true JPH07108771B2 (en) 1995-11-22

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Country Link
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998056502A1 (en) * 1997-06-12 1998-12-17 Idemitsu Kosan Co., Ltd. Halogen-containing catalyst and process for the preparation thereof

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11169729A (en) * 1997-12-10 1999-06-29 Idemitsu Kosan Co Ltd Catalyst production
US6812180B2 (en) 1997-12-10 2004-11-02 Idemitsu Kosan Co., Ltd. Method for preparing catalyst
JP4812149B2 (en) * 1999-11-11 2011-11-09 株式会社日本触媒 Beta-type binderless zeolite molding and method for producing the same
JP4812148B2 (en) * 1999-10-14 2011-11-09 株式会社日本触媒 MTW type binderless zeolite molding and method for producing the same
JP4567129B2 (en) * 1999-11-11 2010-10-20 株式会社日本触媒 NU-1 type binderless zeolite molding and method for producing the same
JP4214183B2 (en) * 2003-04-10 2009-01-28 川口精機株式会社 Screw type dehydrator

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998056502A1 (en) * 1997-06-12 1998-12-17 Idemitsu Kosan Co., Ltd. Halogen-containing catalyst and process for the preparation thereof

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