JPS59225130A - Preparation of aromatic hydrocarbon - Google Patents
Preparation of aromatic hydrocarbonInfo
- Publication number
- JPS59225130A JPS59225130A JP58099570A JP9957083A JPS59225130A JP S59225130 A JPS59225130 A JP S59225130A JP 58099570 A JP58099570 A JP 58099570A JP 9957083 A JP9957083 A JP 9957083A JP S59225130 A JPS59225130 A JP S59225130A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- zinc oxide
- weight
- alumina
- carrier
- 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.)
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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
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（１」的）
本発明は炭素数６以−にの非芳香族炭化水素から芳香族
炭化水素を製造する方法に関するものであり、特に特定
の担体に酸化亜鉛を担持させた触媒を使用することを特
徴とする。Detailed Description of the Invention (1) The present invention relates to a method for producing aromatic hydrocarbons from non-aromatic hydrocarbons having 6 or more carbon atoms, and particularly relates to a method for producing aromatic hydrocarbons from non-aromatic hydrocarbons having 6 or more carbon atoms. It is characterized by using a catalyst that has been
（先行技術）
オレフィン糸物質から芳香族炭化水素を製造するのに酸
化亜鉛を触媒として使用すること【こつＩ７為では特公
昭４６−１８０２０号に記載かある力）、その実施例に
おける芳香族の全収量は供給原料番と対し５．１重量％
（同公報実施例２０）に過きす工業触媒としての実用性
に乏しい。(Prior Art) The use of zinc oxide as a catalyst for the production of aromatic hydrocarbons from olefin thread materials (as described in Japanese Patent Publication No. 46-18020), Total yield is 5.1% by weight based on feedstock number
(Example 20 of the same publication) has poor practicality as an industrial catalyst.
また特公昭５６−４２６３９号はＺＳＭ−５類のゼオラ
イトを触媒としてバラフインン、オレフィン及び／又は
ナフテンからなる原料から芳香族化合物を製造する方法
に関するものであるか、そのなかに助触媒として亜鉛を
添加することにより芳香族の収率が向上することが述べ
られている。Furthermore, Japanese Patent Publication No. 56-42639 relates to a method for producing aromatic compounds from raw materials consisting of paraffin, olefin and/or naphthene using ZSM-5 class zeolite as a catalyst, or to a method in which zinc is added as a co-catalyst. It is stated that the yield of aromatics is improved by doing so.
しかしながら回公報には同時に比較例としてモルデナイ
ト、エリオナイトのような通常のセピライト類に亜鉛を
添加した触媒によっては殆ど芳香族が得られず、Ｚ ｎ
−工’）オナイトの場合（同公報実施例４６）原刺１
００ｇ当りに得られた芳香族は僅か０．８重量％である
というようなデータか示されており、亜鉛を主要な活性
成分とする触媒が工業的に有用であることを示唆しては
いなＱ）。However, the publication also states as a comparative example that almost no aromatic compounds can be obtained using a catalyst in which zinc is added to ordinary sepilites such as mordenite and erionite;
-In the case of onite (Example 46 of the same publication) Original stab 1
The data shows that the amount of aromatics obtained per 00g is only 0.8% by weight, which does not suggest that catalysts containing zinc as the main active component are industrially useful. Q).
このほか一般に芳香族化合物を製造するための触媒とし
てはＰｔのような貴金属とかＣｒ２Ｏ３のような重金属
醇化物とかが用いられているが、高価であるとか、健康
上有害な物質なので取り扱いや廃触媒の処理に特別の注
意を払わなければならない等の欠点を有する。In addition, noble metals such as Pt and heavy metal liquefied materials such as Cr2O3 are generally used as catalysts for producing aromatic compounds, but they are expensive and harmful to health, so they are difficult to handle and discard. It has disadvantages such as the need to pay special attention to its treatment.
水元明治らは安価でしかも安全性が高く取り扱い易い酪
化亜鉛を触媒として芳香族炭化水素を製造する方法につ
いて鋭意研究を行った結果、特定の担体に担持させた酸
化亜鉛触媒が原料炭化水素の転化率及び芳香族選択率と
もに酸化亜鉛単独の場合に比べて著しく向−１ニするこ
とを見出し本発明を完成するに至った。Meiji Mizumoto and his colleagues conducted extensive research into a method for producing aromatic hydrocarbons using zinc butyride, which is inexpensive, safe, and easy to handle, as a catalyst, and found that zinc oxide catalysts supported on a specific carrier can be used as feedstock hydrocarbons. The present inventors have discovered that both the conversion rate and the aromatic selectivity are significantly improved by -1 compared to the case of using zinc oxide alone, and have completed the present invention.
（発明の構成）
すなわち本発明はアルミナ、活性炭、シリカライト、チ
タニア、ナタニアΦシリカ、アルミナ・ボリア、Ｙ型ゼ
オライト、モンモリロナイト、及びセピオライトよりな
る群から選ばれる少なくとも１種の担体に酸化亜鉛を担
持した触媒に、炭素数６以上のパラフィン、オレフィン
またはナフテンよりなる非芳香族炭化水素の少なくとも
１種を接触させることよりなる芳香族炭化水素の製造法
である。(Structure of the Invention) That is, the present invention provides zinc oxide supported on at least one carrier selected from the group consisting of alumina, activated carbon, silicalite, titania, natania Φ silica, alumina boria, Y-type zeolite, montmorillonite, and sepiolite. This is a method for producing aromatic hydrocarbons, which comprises contacting the prepared catalyst with at least one non-aromatic hydrocarbon consisting of paraffin, olefin or naphthene having 6 or more carbon atoms.
ＺＳＭ−５による芳香族化反応では、Ｊｏｕｒｎａｌｏ
ｆ Ｃａｔａｌｙｓｉｓ ６３，３３１（１９８０）
にも記載されている如く、１２０〜１３０Ｋｊ１モル以
上の強い酸点（ＮＨ３−熱計量法で測定した酸性度）を
必要条件とするが、本発明において使用する担体は必ず
しもそのような強い酸点は必要としない。アルミナ・ボ
リアのように１２０Ｋｊ１モル以りの強い酸点があって
も芳香族化反応を抑制することはしないが、あまり強い
酸点があると炭素析出を促進し触媒寿命が短くなる可能
性も′あるので、この点からは酸強度の弱い、あるいは
酸点が全くない担体か望ましい。上記の担体の中ではア
ルミナ、活性炭、シリカライトが特に好ましい。In the aromatization reaction using ZSM-5, Journalo
f Catalysis 63, 331 (1980)
As described in the above, a strong acid site of 120 to 130 Kj 1 mol or more (acidity measured by NH3-calorimetric method) is a necessary condition, but the carrier used in the present invention does not necessarily have such a strong acid site. is not required. Even if there is a strong acid site of 120 Kj 1 mole or more, such as in alumina/boria, it will not inhibit the aromatization reaction, but if there is too strong an acid site, it may promote carbon precipitation and shorten the catalyst life. From this point of view, it is desirable to use a carrier with low acid strength or no acid sites at all. Among the above carriers, alumina, activated carbon, and silicalite are particularly preferred.
酸化亜鉛（ＺｎＯ）の含有量は約０．５〜７５重量％−
の範囲で可能であるが通常０．５〜５０重量％、好まし
くは１．０〜３０重量％である。The content of zinc oxide (ZnO) is approximately 0.5 to 75% by weight.
The amount is usually 0.5 to 50% by weight, preferably 1.0 to 30% by weight.
触媒の調製方法は亜鉛の可溶性塩の水溶液に担体を浸漬
するか真空含浸した後焼成拳酸化する方法、あるいは酸
化亜鉛と担体とを機械的に混合する方法等がある。真空
含浸の場合は担体をあらかじめ１時間程真空説気した後
に飽和含水量に相当する硝酸亜鉛水溶液を含浸させる。The catalyst can be prepared by immersing or vacuum impregnating a carrier in an aqueous solution of a soluble salt of zinc, followed by oxidation by firing, or by mechanically mixing zinc oxide and the carrier. In the case of vacuum impregnation, the carrier is previously vacuum aerated for about one hour and then impregnated with an aqueous zinc nitrate solution corresponding to the saturated water content.
前処理は酸化雰囲気あるいは不活性ガス気流中で行う。Pretreatment is performed in an oxidizing atmosphere or an inert gas stream.
反応条件は温度か４５０〜６５０°Ｃ１圧力は常圧−２
０Ｋｇ／ｃｍ’Ｇ、ＬＨ３Ｖは０．１−１０／時が適当
である。The reaction conditions are temperature: 450 to 650°C, pressure: normal pressure -2
0Kg/cm'G, LH3V is suitably 0.1-10/hour.
以下実施例により更に詳細に説明するが、本発明は下記
実施例のみに限定されるものではない。The present invention will be explained in more detail with reference to examples below, but the present invention is not limited to the following examples.
（実施例）
Ａ 触媒調製
触媒１〜３
市販の試薬特級硝酸亜鉛を水に溶解して担体の飽和含水
量に見合う硝酸亜鉛水溶液を調製する。(Example) A Catalyst Preparation Catalysts 1 to 3 A commercially available reagent special grade zinc nitrate is dissolved in water to prepare an aqueous zinc nitrate solution suitable for the saturated water content of the carrier.
この水溶液を予め１時間真空脱気した球状（３ｍｍφ）
のγ−アルミナ８０ｇにスプレーにより均一に真空含浸
せしめ、さらに１時間真空脱気し水分を法発させた。こ
れを１２０°Ｃで１昼夜乾燥した後、５００°Ｃで３時
間焼成することにより、ＺｎＯ含有量がそれぞれ２，５
．１０重量％のアルミナ担持酸化亜鉛を得、これらをそ
れぞれ８〜１６メンシユの大きさに粉砕したものを触媒
とした。This aqueous solution was vacuum-degassed for 1 hour beforehand into a spherical shape (3 mmφ).
80 g of γ-alumina was uniformly impregnated in a vacuum by spraying, and further vacuum degassed for 1 hour to allow water to evaporate. After drying this at 120°C for 1 day and night, it was fired at 500°C for 3 hours to reduce the ZnO content to 2 and 5, respectively.
．． Zinc oxide supported on alumina of 10% by weight was obtained, and each of these was pulverized to a size of 8 to 16 meshes and used as a catalyst.
触媒Ｉ ＺｎＯ含有量２重量％。Catalyst I ZnO content 2% by weight.
比表面積２２３ 、５ ｒｎ’ ／ ｇ 。Specific surface area 223, 5 rn'/g.
細孔容積０ 、９８５ ｃ ｃ ／ ｇ触媒２ Ｚｎ
Ｏ含有量５重量％。Pore volume 0, 985 c c / g catalyst 2 Zn
O content 5% by weight.
比表面積２２２ 、６ ｍ’ ／ ｇ 。Specific surface area 222, 6 m'/g.
細孔容積０．７９９ｃｃ／ｇ 触媒３ ＺｎＯ含有量１０重量％。Pore volume 0.799cc/g Catalyst 3 ZnO content 10% by weight.
比表面積２４３．４ｍ’／ｇ。Specific surface area 243.4 m'/g.
細孔容積０ 、９６３ ｃ ｃ ／ ｇ触媒４
前記と同様な方法で１時間真空脱気した活性炭担体５０
ｇに、所要量の硝酸亜鉛水溶液を真空含浸せしめた。さ
らに触媒１〜３と同様に処理してＺｎＯ含有量が２重量
％の活性炭１５」持酸化亜鉛触媒を得た。Pore volume 0, 963 c c / g Catalyst 4 Activated carbon carrier 50 vacuum degassed for 1 hour in the same manner as above
g was vacuum impregnated with the required amount of zinc nitrate aqueous solution. Further, the catalyst was treated in the same manner as Catalysts 1 to 3 to obtain an activated carbon 15'' zinc oxide catalyst having a ZnO content of 2% by weight.
比表面積７５６ 、１ ｍ’ ／ ｇ 。Specific surface area 756, 1 m'/g.
細孔容積０．３７３ｃｃ／ｇ 触媒５ シリカライＩ・を以下のような方法で調製した。Pore volume 0.373cc/g catalyst 5 Silicalite I was prepared in the following manner.
塩化すｌ・リウム水溶液１１８２ｇ （ＮａＣｉ２０重
量％）に水ガラス６２１ｇ （Ｓｉ０２３０重量％）と
テトラプロピルアンモニウムプロマイト溶液（（Ｃ３Ｈ
７）４ ・ＮＩＩＢｒ４０．５ｇ，濃流酸５２．５ｇ，
水５４０ｃｃ）を加え２時間攪拌した。このゲルをオー
トクレーブに入れ、攪拌しながら１７０℃、５ Ｋ ｇ
／ ｃ ｒｎ’ Ｇで４８時間保持して結晶化した。1182 g of sulfur/lium chloride aqueous solution (20 wt.% NaCi), 621 g of water glass (30 wt.% Si0) and tetrapropylammonium puromite solution ((C3H
7) 4 ・NIIBr40.5g, concentrated acid 52.5g,
540 cc of water was added and stirred for 2 hours. This gel was placed in an autoclave and heated at 170°C with stirring for 5 Kg.
/ crn' G for 48 hours to crystallize.
生成物はａ過・洗浄後、乾燥Φ焼成（５３０°Ｃ、５時
間）した。かくして得られたシリカライトはＮＨ３−熱
量計法による酸性質測定の結果酸点はほとんどなど、ま
た本反応条件下ではｎ−Ｃ６ＨＩ４の転化反応活性は無
視できた。このようなシリカライトを打錠成型した後、
触媒１〜３と同様な方法でＺｎＯ含有量が５重量％にな
るように硝酸亜鉛水溶液で真空含浸した後乾燥・焼成し
た。The product was filtered and washed, then dried and calcined (530°C, 5 hours). The silicalite thus obtained was found to have almost no acid sites when measured by the NH3 calorimetry method, and the conversion reaction activity of n-C6HI4 was negligible under the present reaction conditions. After forming such silicalite into tablets,
In the same manner as Catalysts 1 to 3, the catalysts were vacuum impregnated with an aqueous zinc nitrate solution so that the ZnO content was 5% by weight, and then dried and calcined.
比表面積２４０ 、２ｇ 。Specific surface area 240, 2g.
細孔容積０．３０７ｃｃ／ｇ
触媒６
触媒１〜３と同様な方法にてＺｎＯ含有量か２重量％の
チタニア（アナターゼ型）担持酸化亜鉛触媒を得た。Pore volume: 0.307 cc/g Catalyst 6 A titania (anatase type) supported zinc oxide catalyst having a ZnO content of 2% by weight was obtained in the same manner as in Catalysts 1 to 3.
比表面積６０．４ｔｎ’／ｇ。Specific surface area 60.4tn'/g.
細孔容積０ 、 ２ ４ ２ ｃ ｃ ／ ｇ触媒７
チタニア・シリカを以下のような方法で調製した。（Ｃ
２ Ｈｓ ）４ ・ＳｉＯ４ （２２．６ｃｃ）を溶解
した冷水（１１３ｃｃ）中に、Ｔｉｃ交４（１０２．２
ｃｃ）を溶解した冷水（５１１ｃｃ）を添加し、さらに
これに濃塩酸２００ｃｃを加え、９５°Ｃで１時間、加
温・攪拌する。白濁が生した後２８％アンモニア水を４
５０ｃｃ添加してｐＨ＝８ 、５とした。さらにこれを
９５℃、１時間加熱攪拌した後濾過・洗浄し、その後乾
燥・焼成（５００°Ｃ、空気中、３時間）した。これを
触媒１〜３と同様な方法にて硝酸亜鉛水溶液で真空含浸
した後乾燥・焼成してＺｎＯ含有量２重量％のチタニア
・シリカ担持酸化亜鉛触媒を得た。Pore volume 0, 2 4 2 cc/g Catalyst 7 Titania silica was prepared in the following manner. (C
2 Hs )4 ・SiO4 (22.6 cc) was dissolved in cold water (113 cc).
Add cold water (511 cc) in which cc) was dissolved, and further add 200 cc of concentrated hydrochloric acid, and heat and stir at 95°C for 1 hour. After it becomes cloudy, add 28% ammonia water for 4 hours.
50 cc was added to adjust the pH to 8.5. This was further heated and stirred at 95°C for 1 hour, filtered and washed, and then dried and calcined (500°C, in air, for 3 hours). This was vacuum impregnated with an aqueous zinc nitrate solution in the same manner as Catalysts 1 to 3, and then dried and calcined to obtain a titania-silica supported zinc oxide catalyst having a ZnO content of 2% by weight.
比表面積１３２．２ｍ’／ｇ。Specific surface area 132.2 m'/g.
細孔容積０ 、 ２ ８ ５ ｃ ｃ ／ ｇ触りＸ８
アルミナ・ボリアを以下のような方法で調製した。硝酸
アルミニウム水溶液（硝酸アルミニウム２８０ｇ十水８
０ ０ ｃ ｃ）に攪拌しながらホウ酸水溶液（ホウ
酸４０ｇ十水３００ｃｃ＋３３％アンモニア水６０ｃｃ
）を滴下した。これに３３％アンモニア水８０ｃｃを添
加しｐＨ＝８．０とし、同−条件下で更に２時間熟成し
た。濾過・洗浄後、乾燥・焼成（ ５ ０ ０ ’Ｃ、
空気中、３時間）した。これを触媒ｌ〜３と同様な方法
にて処理してＺｎＯ含有量２重量％のアルミナ・ボリア
担持酸化亜鉛触媒を得た。Pore volume 0, 285 cc/g touch X8 Alumina boria was prepared by the following method. Aluminum nitrate aqueous solution (aluminum nitrate 280 g 10 water 8
0 0 c c) While stirring, add a boric acid aqueous solution (40 g of boric acid, 300 cc of water + 60 cc of 33% aqueous ammonia)
) was added dropwise. 80 cc of 33% aqueous ammonia was added to this to adjust the pH to 8.0, and the mixture was further aged for 2 hours under the same conditions. After filtration and washing, drying and baking (500'C,
in air for 3 hours). This was treated in the same manner as Catalysts 1 to 3 to obtain an alumina/boria supported zinc oxide catalyst having a ZnO content of 2% by weight.
比表面積３ ０ ０ 、 ７ｍ’／ｇ 。Specific surface area 300, 7m'/g.
細孔容積０ 、 ４ ４ ２ ｃ ｃ ／ ｇ触媒９
触媒１〜３と同様にしてＺｎＯ含有量２重量％のＹ型ゼ
オライト担持酸化亜鉛触媒を得た。Pore volume: 0, 442 cc/g Catalyst 9 A Y-type zeolite-supported zinc oxide catalyst having a ZnO content of 2% by weight was obtained in the same manner as Catalysts 1 to 3.
比表面積４８４．２ｍ’／ｇ。Specific surface area 484.2 m'/g.
細孔容積０ 、３２ ｃ ｃ ／ ｇ
触媒ｌＯ
触媒１〜３と同様にしてＺｎＯ含有量２重量％のモンモ
リロナイ） １１４持酸化亜鉛触媒を得た。Pore volume: 0, 32 cc/g Catalyst lO A Montmorillonium 114-bearing zinc oxide catalyst having a ZnO content of 2% by weight was obtained in the same manner as Catalysts 1 to 3.
触媒１１
触媒１〜３と同様にしてＺｎＯ含有量５重量％のセピオ
ライト担持酸化亜鉛触媒を得た。Catalyst 11 A sepiolite-supported zinc oxide catalyst having a ZnO content of 5% by weight was obtained in the same manner as Catalysts 1 to 3.
比較例１の触媒
触媒１〜３で用いたγーアルミナ
比較例２の触媒
硝酸斬鉛４００ｇを純水２文に溶解し、８０″Ｃで加熱
攪拌しながらこれに炭酸ソーダ水溶液（炭酸ソータ２０
０ｇ＋純水１父）をｐＨ＝７．５になるまで添加し沈殿
せしめた。同一条件で５時間熟成後、濾過・洗浄し、そ
の後乾燥・焼成（５０ｏ ’ｃ、空気中、３時間）した
。400 g of γ-alumina used in catalysts 1 to 3 of Comparative Example 1 400 g of the catalyst of Comparative Example 2 was dissolved in two volumes of pure water, and while heating and stirring at 80"C, a sodium carbonate aqueous solution (carbonate sorter 20
0 g + 1 part of pure water) was added until pH = 7.5 to cause precipitation. After aging for 5 hours under the same conditions, it was filtered and washed, and then dried and fired (50 o'c in air for 3 hours).
Ｂ 実施例１〜１１、比較例１、２
固定床型の反応器（内容積３５ｃｃ）に、触媒４ｃｃを
充填後、不活性ガスを通して約１時間１１Ｊ処理し、反
応温度５７０ ’Ｃ（実施例８のみ５００°Ｃ）、圧力
＝常圧、ＬＨ３Ｖ＝０．３／Ｈｒ、原料炭化水素：ヘリ
ウム＝ｌ：５の組成のガスを通して芳香族化反応を行っ
た。１０時間経過後の原料炭化水素の転化率、芳香族選
択率（重量％）を第１表に示す。各実施例で用いた触媒
は実施例と同番号の前記触媒である。B Examples 1 to 11, Comparative Examples 1 and 2 After filling a fixed bed reactor (inner volume 35 cc) with 4 cc of catalyst, inert gas was passed through the reactor for about 1 hour at 11 J, and the reaction temperature was 570'C (Example The aromatization reaction was carried out by passing a gas having a composition of raw material hydrocarbon: helium = 1:5 at 500°C), pressure = normal pressure, LH3V = 0.3/Hr. Table 1 shows the conversion rate of the raw material hydrocarbon and the aromatic selectivity (wt%) after 10 hours. The catalyst used in each example is the same numbered catalyst as in the example.
なお である。In addition It is.
実施例の１部について生成芳香族中ベンセン、）・ルエ
ン、キシレンの分布を示すと次の如くである。但し、収
率＝転化率×選択率 である。The distribution of benzene, ).luene, and xylene in the produced aromatics for a part of the example is as follows. However, yield=conversion rate×selectivity.
実施例Ｉ ＺｎＯ−Ａｌ２’０３触媒（ＺｎＯ含有率
２重量％）
（１）原料：ｎ−ヘキサン
生成全芳香族（収−ｖ、１９．２重間％）のうちヘンセ
ン １００％
（２）原料：１−ヘキセン
生成全芳香族（収率４７．７重量％）のうちヘンセン
１００ ％
実施例２ ＺｎＯ−Ａｌ２Ｏ３触媒
（ＺｎＯ含有率５重量％）
原料：ｎ−へブタン
生成全芳香族（収率３３．５重量％）のうちヘンセン
３．９％
トルエン ９６．１％
実施例３ ＺｎＯ−、Ａｌ２Ｏ３触媒（ＺｎＯ含有率
１０重量％）
原料：メチルシクロヘキサン
生成全芳香族（収率７３．２重量％）のうちベンゼン
３．５％
トルエン ９３．１％
キシレン ３．４％
実施例４Ｚｎ−０−活性炭触媒
（ＺｎＯ含有率２重量％）
（１）原料：ｎ−へキサン
生成全芳香族（収率６２．９重量％）のうちベンゼン
９９ ％
トルエン中キシレン １ ％
（２）原料１．ｎ−＝ブタン
生成全芳香族（収率、７３ 、７重量％）のうちベンセ
ン ４．１％
トルエン ９４．６％
キシレン １・３％
（３）原料：１−ヘキセン
生成全芳香族（収率７８．６重量％）のうちベンゼン
９８．７％
トルエン・キシレン １．３％
（４）原Ｎ ：メチルシクロヘキサン
生成全芳香族（収率９５８重量％）のうちベンゼン
３．６％
トルエン ９３．２％
キシレン ３．２％
実施例５ ＺｎＯ−シリカライト触媒（ＺｎＯ含有率
５重量％）
（１）原料：ｎ−へキサン
生成全芳香族（収率２８．７重量％）のうちベンセン
８９．７％
トルエン ５．９％
キシレン ４．４％
（２）原料：ｎ−へブタン
生成全芳香族（収率６ｏ、３重量％）のうちベンゼン
７．１％
トルエン ８９．３％
キシレン ３．６％
（３）原料：１−ヘキセン
生成全芳香族（収率６２．４重量％）のうちヘンセン
８７．１％
トルエン ７．１％
キシレン ５，８％
（４）原料：メチルシクロヘキサン
生成全芳香族（収：ｉＳ９４ 、５玉量％）のうちヘン
セン ４川％
トルエン ９２．７％
キシレン ３２％
またＺｎＯ含イ４量２重量％のアルミナ担持酸化亜鉛触
媒を用いたｎ−ヘキサン、ｎ−ヘプタン及、ひメチルシ
クロヘキサンの各芳香族化反応における経過時間と転化
率、芳香族選択率との関係を第１図及び第２図に示した
。Example I ZnO-Al2'03 catalyst (ZnO content 2% by weight) (1) Raw material: Hensen 100% of all aromatics produced in n-hexane (yield -v, 19.2% by weight) (2) Raw material :1-hexene among all aromatics produced (yield 47.7% by weight)
100% Example 2 ZnO-Al2O3 catalyst (ZnO content 5% by weight) Raw material: Hensen of all aromatics produced in n-hebutane (yield 33.5% by weight)
3.9% Toluene 96.1% Example 3 ZnO-, Al2O3 catalyst (ZnO content 10% by weight) Raw material: Benzene among all aromatics produced in methylcyclohexane (yield 73.2% by weight)
3.5% Toluene 93.1% Xylene 3.4% Example 4 Zn-0-activated carbon catalyst (ZnO content 2% by weight) (1) Raw material: n-hexane produced wholly aromatic (yield 62.9% by weight) %) of which benzene
99% xylene in toluene 1% (2) Raw materials 1. n-=benzene 4.1% toluene 94.6% xylene 1.3% of the total aromatics produced in butane (yield, 73, 7% by weight) (3) Raw materials: total aromatics produced in 1-hexene (yield 78.6% by weight) of which benzene
98.7% Toluene/xylene 1.3% (4) Raw N: Benzene among all aromatics produced in methylcyclohexane (yield 958% by weight)
3.6% Toluene 93.2% Xylene 3.2% Example 5 ZnO-silicalite catalyst (ZnO content 5% by weight) (1) Raw material: n-hexane producing wholly aromatic (yield 28.7% by weight) %) of which benzene
89.7% Toluene 5.9% Xylene 4.4% (2) Raw materials: Benzene among all aromatics produced in n-hebutane (yield 6o, 3% by weight)
7.1% Toluene 89.3% Xylene 3.6% (3) Raw materials: 1-hexene of all aromatics produced (yield 62.4% by weight)
87.1% Toluene 7.1% Xylene 5.8% (4) Raw materials: Methyl cyclohexane produced completely aromatic (yield: iS94, 5 mass%) Hensen 4% Toluene 92.7% Xylene 32% Relationship between elapsed time, conversion rate, and aromatic selectivity in each aromatization reaction of n-hexane, n-heptane, and dimethylcyclohexane using an alumina-supported zinc oxide catalyst containing 4% by weight of ZnO. It is shown in FIGS. 1 and 2.
（効果）
−１−６記の実施例及び添旧図面から明らかなように本
発明の方法は、ａ、芳香族炭化水素への追択率が比較的
高く、かつ安定している。ｂ、用いる触媒が安価である
。Ｃ，Ｍ媒製造における再現性がよい。ｄ、失活した触
媒は空気再生により容易に活性が戻る。(Effects) As is clear from the Examples and the attached drawings in -1-6, the method of the present invention has a relatively high addition rate to aromatic hydrocarbons and is stable. b. The catalyst used is inexpensive. Good reproducibility in producing C and M media. d. The deactivated catalyst is easily reactivated by air regeneration.
第１図はＺ’ｎＯ含有量２重Ｍ％のアルミナ担持酸化亜
鉛触媒を用いた場合のｎ−ヘキサン、■−ヘプタン及び
メチルシクロヘキサンの各芳香族化反応における経過時
間と転化率、第２図は同じく経過時間と芳香族選択率と
の関係を示すものである。
出願人 日 揮 株 式 会 社代理人
弁理士 青 麻 昌 二
２Figure 1 shows the elapsed time and conversion rate in each aromatization reaction of n-hexane, ■-heptane, and methylcyclohexane using an alumina-supported zinc oxide catalyst with a Z'nO content of 2% by weight, and Figure 2 shows the conversion rate. Similarly, shows the relationship between elapsed time and aromatic selectivity. Applicant JGC Co., Ltd. Company Agent
Patent Attorney Ao Asa Shoji 2
Claims (1)
・シリカ、アルミナ拳ボリア、Ｙ望セオライト、モンモ
リロナイト及びセピオライトよりなる群から選ばれる少
なくとも１種の担体に酸化便船を担持した触媒に、炭素
数６以上のパラフィン、オレフィンまたはナフテンより
なる非芳香族炭化水素の少なくとも１種を接触させるこ
とよりなる芳香族炭化水素の製造法。A catalyst having an oxidizing carrier supported on at least one carrier selected from the group consisting of alumina, activated carbon, silicalite, titania, titania/silica, alumina kenboria, Yoboseolite, montmorillonite, and sepiolite has a carbon number of 6 or more. A method for producing aromatic hydrocarbons, which comprises contacting at least one non-aromatic hydrocarbon consisting of paraffin, olefin or naphthene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58099570A JPS59225130A (en) | 1983-06-06 | 1983-06-06 | Preparation of aromatic hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58099570A JPS59225130A (en) | 1983-06-06 | 1983-06-06 | Preparation of aromatic hydrocarbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59225130A true JPS59225130A (en) | 1984-12-18 |
| JPH0373530B2 JPH0373530B2 (en) | 1991-11-22 |
Family
ID=14250776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58099570A Granted JPS59225130A (en) | 1983-06-06 | 1983-06-06 | Preparation of aromatic hydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59225130A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS523025A (en) * | 1975-06-23 | 1977-01-11 | British Petroleum Co | Preparation of aromatic hydrocarbons |
| JPS55124722A (en) * | 1979-03-14 | 1980-09-26 | Shell Int Research | Manufacture of aromatic hydrocarbon and hydrogen |
| JPS59148728A (en) * | 1983-02-15 | 1984-08-25 | Mitsubishi Heavy Ind Ltd | Conversion of hydrocarbon |
-
1983
- 1983-06-06 JP JP58099570A patent/JPS59225130A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS523025A (en) * | 1975-06-23 | 1977-01-11 | British Petroleum Co | Preparation of aromatic hydrocarbons |
| JPS55124722A (en) * | 1979-03-14 | 1980-09-26 | Shell Int Research | Manufacture of aromatic hydrocarbon and hydrogen |
| JPS59148728A (en) * | 1983-02-15 | 1984-08-25 | Mitsubishi Heavy Ind Ltd | Conversion of hydrocarbon |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0373530B2 (en) | 1991-11-22 |
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