JPH083097B2 - Method for producing aromatic compound - Google Patents
Method for producing aromatic compoundInfo
- Publication number
- JPH083097B2 JPH083097B2 JP62188850A JP18885087A JPH083097B2 JP H083097 B2 JPH083097 B2 JP H083097B2 JP 62188850 A JP62188850 A JP 62188850A JP 18885087 A JP18885087 A JP 18885087A JP H083097 B2 JPH083097 B2 JP H083097B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- fraction
- raw material
- aromatic compound
- catalytic reaction
- 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
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は芳香族化合物の製造方法に関し、詳しくはナ
フサを原料とし高選択率で芳香族炭化水素を製造しうる
とともに、触媒の寿命を延長することができ、長期にわ
たり連続運転可能な製造方法に関する。Description: TECHNICAL FIELD The present invention relates to a method for producing an aromatic compound, and more specifically, it can produce aromatic hydrocarbons from naphtha as a raw material with high selectivity and extends the life of the catalyst. And a manufacturing method capable of continuous operation over a long period of time.
従来よりベンゼン，トルエン，キシレンなどの芳香族
化合物の石油化学的製造法としてナフサ留分にZSM−５
のような強酸性ゼオライトを触媒として用いて触媒反応
させる方法が知られている（特公昭56−42639号公報，
同58−23368号公報，特開昭53−92717号公報，同56−14
0934号公報など）。Conventionally, ZSM-5 was used for naphtha fraction as a petrochemical production method for aromatic compounds such as benzene, toluene and xylene.
There is known a method of carrying out a catalytic reaction by using a strongly acidic zeolite as described above as a catalyst (Japanese Patent Publication No. 56-42639).
58-23368, JP-A-53-92717, 56-14.
0934 publication).
しかしながら、この方法では分解ガスの発生が多く、
芳香族分の収率が低いという問題がある。However, this method generates a large amount of decomposition gas,
There is a problem that the yield of aromatics is low.
そこで白金を担持したＬ型ゼオライト触媒を用いる方
法が提案されている（特開昭59−80333号公報など）。Therefore, a method using an L-type zeolite catalyst supporting platinum has been proposed (JP-A-59-80333, etc.).
この方法によれば芳香族化合物を高選択率で製造しう
るものの、活性低下が早く、触媒寿命が短いという問題
がある。また、触媒寿命を延長するためには芳香族選択
率を低く（50％以下に）押える必要がある。According to this method, an aromatic compound can be produced with a high selectivity, but there is a problem that the activity decreases quickly and the catalyst life is short. Also, in order to extend the catalyst life, it is necessary to keep the aromatic selectivity low (less than 50%).
本発明者らは上記従来の問題点を解消するため鋭意研
究を重ねた。その結果、白金を担持したＬ型ゼオライト
触媒に対して、原料ナフサ留分が含有するシクロペンタ
ンが触媒被毒の原因となるコークを多量析出し、このた
め触媒寿命が著しく短かくなることを見出した。本発明
はこの知見に基いて完成されたものである。The present inventors have conducted extensive studies to solve the above conventional problems. As a result, it was found that cyclopentane contained in the raw material naphtha fraction deposits a large amount of coke, which causes catalyst poisoning, against the platinum-supported L-type zeolite catalyst, which significantly shortens the catalyst life. It was The present invention has been completed based on this finding.
すなわち本発明は、ナフサ留分を、少なくとも１種の
周期表第VIII族の金属を含むＬ型ゼオライトからなる触
媒と接触させて芳香族炭化水素を製造するにあたり、触
媒反応塔に導入する原料中のシクロペンタンの量を１重
量％未満に調整することを特徴とする芳香族炭化水素の
製造方法を提供するものである。That is, the present invention relates to a raw material to be introduced into a catalytic reaction tower in producing an aromatic hydrocarbon by bringing a naphtha fraction into contact with a catalyst composed of an L-type zeolite containing at least one metal of Group VIII of the periodic table. The method for producing an aromatic hydrocarbon is characterized by adjusting the amount of cyclopentane to less than 1% by weight.
本発明において原料として用いるナフサ留分はいわゆ
るフルレンジナフサ、すなわち炭素数４〜10の炭化水素
混合物である。具体的にはｉ−ペンタン,n−ペンタン，
シクロペンタン,2,2−ジメチルブタン,2,3−ジメチルブ
タン,2−メチルペンタン,3−メチルペンタン，メチルシ
クロペンタン，ベンゼン等の混合物である。The naphtha fraction used as a raw material in the present invention is so-called full-range naphtha, that is, a hydrocarbon mixture having 4 to 10 carbon atoms. Specifically, i-pentane, n-pentane,
It is a mixture of cyclopentane, 2,2-dimethylbutane, 2,3-dimethylbutane, 2-methylpentane, 3-methylpentane, methylcyclopentane, benzene and the like.
本発明では上記原料ナフサ留分を、少なくとも１種の
周期表第VIII族の金属を含むＬ型ゼオライトからなる触
媒と接触させて芳香族炭化水素を製造するわけである
が、このような接触反応を行なう前に、まず原料ナフサ
留分の分留を行なう。In the present invention, the above-mentioned raw material naphtha fraction is contacted with a catalyst comprising an L-type zeolite containing at least one metal of Group VIII of the periodic table to produce an aromatic hydrocarbon. First, the raw material naphtha fraction is fractionated before carrying out.
本発明はこの分留時に、触媒被毒物質であるシクロペ
ンタンの含量を１重量％未満に低減させる原料分離調整
を行ない、触媒との接触反応を行なう触媒反応塔に導入
する原料中のシクロペンタンの量を１重量未満に調整す
ることを特徴とするものである。According to the present invention, during this fractional distillation, the content of cyclopentane, which is a catalyst poisoning substance, is reduced to less than 1% by weight, and the raw material is introduced into a catalytic reaction column for catalytic reaction with the catalyst. Is adjusted to less than 1% by weight.
すなわち、この分留工程において、原料ナフサ留分
を、炭素数５以下の炭化水素留分（C5 -留分）の塔頂油
と、炭素数６以上の炭化水素留分（C6 +留分）の塔底油
とに蒸留分離し、このC6 +留分を触媒反応塔に導入す
る。このときにC6 +留分中のシクロペンタンの量を１重
量％未満に調整しておくことが必要であって、C6 +留分
中のシクロペンタンの量が１重量％以上であると、コー
クを多量に析出して触媒寿命が著しく短かくなるため好
ましくない。That, in this fractionation step, a raw material naphtha fraction, 5 or less hydrocarbon distillate carbon - and overhead oil (C 5 fraction), the number 6 or more hydrocarbon fractions carbon (C 6 + fraction Fraction) and the bottom oil, and this C 6 + fraction is introduced into the catalytic reaction column. At this time, it is necessary to adjust the amount of cyclopentane in the C 6 + fraction to less than 1% by weight, and the amount of cyclopentane in the C 6 + fraction is 1% by weight or more. It is not preferable because a large amount of coke is deposited and the catalyst life becomes extremely short.
なお、シクロペンタンの沸点はC6留分の2,2−ジメチ
ルブタン等の沸点と接近していて分離しにくいため蒸留
塔段数を増加させたり、還流比を増加させるなどの手段
を講ずることが好ましい。The boiling point of cyclopentane is close to the boiling point of the C 6 fraction such as 2,2-dimethylbutane and is difficult to separate, so that means such as increasing the number of distillation column stages or increasing the reflux ratio may be taken. preferable.
但し、芳香族炭化水素の収量に影響するためC5 -留分
中のC6留分は極力低くする必要がある。However, C 5 to affect the yield of aromatic hydrocarbons - C 6 fraction in the fraction should be as low as possible.
このようにして分離調整されたC6 +留分はそのまま或
いは適宜第二段以降の分留工程を設け、塔頂油C6留分を
触媒反応塔に導入して接触反応を行なう。The C 6 + fraction thus separated and adjusted is provided as it is or by appropriately providing a fractionation step from the second stage onward, and the overhead oil C 6 fraction is introduced into the catalytic reaction column to carry out the catalytic reaction.
本発明の触媒としては、少なくとも１種の周期表第VI
II族金属を含むＬ型ゼオライト触媒が用いられる。The catalyst of the present invention includes at least one of the periodic table VI
An L-type zeolite catalyst containing a Group II metal is used.
ここでＬ型ゼオライトは、組成式 0.9〜1.3M2/nO.Al2O3・5.0〜7.0SiO2・０〜9H2O （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頁および特開昭59−80333号公報第５頁
に開示されているものである。Where L zeolite, the composition formula 0.9~1.3M 2 / n O.Al 2 O 3 · 5.0~7.0SiO 2 · 0~9H 2 O ( wherein, M represents an alkali metal or alkaline earth metal, n represents the valence of M.) and is specifically described in JP-A-58-133835.
It is disclosed on pages 9 to 10 of the publication and page 5 of JP-A-59-80333.
本発明の触媒は、上記Ｌ型ゼオライトに、少なくとも
１種の周期表第VIII族金属、例えば白金，鉄，コバル
ト，ニッケル等の金属の１種又は２種以上を担持させた
ものであり、特に白金を担持させたものが好適である。The catalyst of the present invention is obtained by supporting the above L-type zeolite with at least one Group VIII metal of the periodic table, for example, one or more metals such as platinum, iron, cobalt and nickel. Those supporting platinum are preferred.
この際の周期表第VIII族金属の担持量は特に制限はな
いが、通常は触媒全体の0.1〜5.0重量％、好ましくは0.
3〜1.5重量％の割合とすればよい。The loading amount of the Group VIII metal of the periodic table at this time is not particularly limited, but is usually 0.1 to 5.0% by weight of the whole catalyst, preferably 0.1.
The proportion may be 3 to 1.5% by weight.
なお、Ｌ型ゼオライトに白金等の金属を担持するには
様々な方法が可能であるが、一般には真空含浸法，常圧
含浸法，浸漬法，イオン交換法などにより行なえばよ
い。また、担持金属として白金を用いる場合の白金源と
しては各種のものが考えられるが、具体的には塩化アン
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などが挙げられる。Although various methods can be used for supporting the metal such as platinum on the L-type zeolite, generally, vacuum impregnation method, atmospheric pressure impregnation method, dipping method, ion exchange method and the like may be used. When platinum is used as the supporting metal, various sources are conceivable, and specific examples thereof include ammine platinum chloride, chloroplatinic acid, chloroplatinate, tetraammine platinum hydroxide, and dinitrodiamino platinum. To be
本発明の方法においては、上記触媒を充填した触媒反
応塔に、前記した如く分離調整されたC6 +留分を導入
し、高温，高圧，水素存在下で脱水素環化触媒と接触反
応させ、芳香族炭化水素と水素を製造する。この際の反
応条件としては温度350〜600℃、好ましくは400〜550
℃、圧力０〜40kg/cm2G、好ましくは０〜10kg/cm2G、LH
SV0.1〜20hr-1、好ましくは１〜10hr-1とすべきであ
る。さらに水素ガス／原料ナフサの供給比は１〜50モル
／モル、好ましくは２〜100モル／モルに選定すると一
層好結果が期待できる。In the method of the present invention, the C 6 + fraction separated and adjusted as described above is introduced into the catalytic reaction column filled with the above catalyst, and the catalytic reaction with the dehydrocyclization catalyst is carried out at high temperature, high pressure and in the presence of hydrogen. Produces aromatic hydrocarbons and hydrogen. The reaction conditions in this case are a temperature of 350 to 600 ° C., preferably 400 to 550.
℃, pressure 0-40kg / cm 2 G, preferably 0-10kg / cm 2 G, LH
The SV should be 0.1 to 20 hr -1 , preferably 1 to 10 hr -1 . Further, if the supply ratio of hydrogen gas / raw material naphtha is selected to be 1 to 50 mol / mol, preferably 2 to 100 mol / mol, more favorable results can be expected.
上記の反応条件以外の範囲で設定して反応を行なうと
所定の芳香族収率が得られなかったり急激に触媒活性が
低下するなどの問題が生じ好ましくない。When the reaction is carried out under a range other than the above reaction conditions, there arises a problem that a predetermined aromatic yield cannot be obtained or the catalytic activity is rapidly lowered, which is not preferable.
次に本発明を実施例によりさらに詳しく説明する。 Next, the present invention will be described in more detail with reference to Examples.
実施例１〜４および比較例1,2 フルレンジナフサを蒸留分離して、第１表に示す組成
を有する原料油を得た。Examples 1 to 4 and Comparative Examples 1 and 2 Full-range naphtha was separated by distillation to obtain a stock oil having a composition shown in Table 1.
触媒として0.5重量％白金担持したフロン処理Ｌ型ゼ
オライト触媒を用いた。A CFC-treated L-type zeolite catalyst supporting 0.5% by weight of platinum was used as a catalyst.
該触媒は予め、水素気流中、常圧,540℃で24時間前処
理を行なった。The catalyst was pretreated in a hydrogen stream at atmospheric pressure and 540 ° C. for 24 hours in advance.
上記前処理を行なった触媒0.5gを触媒反応塔に充填
し、該触媒反応塔に上記原料油を通油して接触反応を行
なった。反応は、温度500℃，圧力5kg/cm2G,LHSV 2hr
-1,水素／原料油の供給比（モル比）＝５の条件で連続
的に行なった。0.5 g of the catalyst subjected to the above-mentioned pretreatment was packed in a catalytic reaction tower, and the raw material oil was passed through the catalytic reaction tower to carry out a catalytic reaction. The reaction temperature is 500 ℃, pressure is 5kg / cm 2 G, LHSV 2hr
-1 , and the feed ratio (molar ratio) of hydrogen / feed oil = 5 was continuously performed.
芳香族炭化水素の選択率と反応時間との関係を第１図
（実施例1,実施例２および比較例１）および第２図（実
施例3,実施例４および比較例２）に示す。The relationship between the selectivity of aromatic hydrocarbons and the reaction time is shown in FIG. 1 (Example 1, Example 2 and Comparative Example 1) and FIG. 2 (Example 3, Example 4 and Comparative Example 2).
第１図および第２図より、C6 +留分中のシクロペンタ
ンの含量が１重量％未満であると、触媒寿命を著しく延
長させることができることがわかる。From FIG. 1 and FIG. 2, it can be seen that when the cyclopentane content in the C 6 + fraction is less than 1% by weight, the catalyst life can be significantly extended.
〔発明の効果〕 叙上の如く、本発明はナフサを原料として周期表第VI
II族の金属を含んだＬ型ゼオライト触媒を用いて、芳香
族に転化する際に反応に供する原料のジクロペンタンの
含有量を１重量％未満にすることにより、高選択率で芳
香族化合物が得られ、また触媒の寿命が著しく延長さ
れ、触媒再生の回数が減らせ、運転の長期化が図れるこ
とから経済上極めて有用である。 [Advantages of the Invention] As described above, the present invention uses naphtha as a raw material and the periodic table
By using the L-type zeolite catalyst containing a Group II metal to reduce the content of diclopentane, which is a raw material to be used for the reaction when converted to an aromatic compound, to less than 1% by weight, the aromatic compound can be produced with high selectivity. It is economically very useful because it can be obtained, the life of the catalyst can be remarkably extended, the number of times of catalyst regeneration can be reduced, and the operation can be prolonged.
第１図は、実施例1,実施例２および比較例１における芳
香族炭化水素選択率と反応時間との関係を示すグラフで
あり、第２図は、実施例3,実施例４および比較例２にお
ける芳香族炭化水素収率と反応時間との関係を示すグラ
フである。FIG. 1 is a graph showing the relationship between aromatic hydrocarbon selectivity and reaction time in Examples 1, 2 and Comparative Example 1, and FIG. 2 is Example 3, Example 4 and Comparative Examples. 3 is a graph showing the relationship between the aromatic hydrocarbon yield and the reaction time in 2.
Claims (1)
VIII族の金属を含むＬ型ゼオライトからなる触媒と接触
させて芳香族炭化水素を製造するにあたり、触媒反応塔
に導入する原料中のシクロペンタンの量を１重量％未満
に調整することを特徴とする芳香族化合物の製造方法。1. A naphtha fraction is prepared from at least one periodic table
In producing an aromatic hydrocarbon by contacting it with a catalyst composed of an L-type zeolite containing a Group VIII metal, the amount of cyclopentane in the raw material introduced into the catalytic reaction column is adjusted to less than 1% by weight. A method for producing an aromatic compound.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62188850A JPH083097B2 (en) | 1987-07-30 | 1987-07-30 | Method for producing aromatic compound |
| CA000571385A CA1300647C (en) | 1987-07-30 | 1988-07-07 | Process for production of aromatic hydrocarbons |
| KR1019880009132A KR930010568B1 (en) | 1987-07-30 | 1988-07-20 | Process for production of aromatic hydrocarbons |
| EP88111997A EP0303097B1 (en) | 1987-07-30 | 1988-07-26 | Process for production of aromatic hydrocarbons |
| DE8888111997T DE3869012D1 (en) | 1987-07-30 | 1988-07-26 | METHOD FOR PRODUCING AROMATIC HYDROCARBONS. |
| US07/462,298 US4962251A (en) | 1987-07-30 | 1989-12-28 | Process for production of aromatic hydrocarbons |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62188850A JPH083097B2 (en) | 1987-07-30 | 1987-07-30 | Method for producing aromatic compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6433188A JPS6433188A (en) | 1989-02-03 |
| JPH083097B2 true JPH083097B2 (en) | 1996-01-17 |
Family
ID=16230933
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62188850A Expired - Lifetime JPH083097B2 (en) | 1987-07-30 | 1987-07-30 | Method for producing aromatic compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH083097B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1333620C (en) * | 1988-03-31 | 1994-12-20 | Murray Nadler | Process for reforming a dimethylbutane-free hydrocarbon fraction |
| JP4907001B2 (en) * | 2000-10-05 | 2012-03-28 | ジャパンスーパークォーツ株式会社 | Carbon electrode holding device for arc melting |
| US7016394B2 (en) * | 2004-04-23 | 2006-03-21 | Ucar Carbon Company Inc. | Male-female electrode joint |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58133835A (en) * | 1982-02-01 | 1983-08-09 | シエブロン・リサ−チ・コンパニ− | Catalyst composition and use thereof |
| JPS60175548A (en) * | 1983-11-10 | 1985-09-09 | エクソン リサ−チ アンド エンヂニアリング コムパニ− | Zeolite catalyst and its use |
| JPS61283354A (en) * | 1985-04-17 | 1986-12-13 | シエブロン リサ−チ コンパニ− | Aromatizing catalyst having high activity and high selectivity |
| JPS6257653A (en) * | 1985-05-07 | 1987-03-13 | Res Assoc Util Of Light Oil | Catalyst for production of aromatic group and production of aromatic hydrocarbon by using said catalyst |
-
1987
- 1987-07-30 JP JP62188850A patent/JPH083097B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58133835A (en) * | 1982-02-01 | 1983-08-09 | シエブロン・リサ−チ・コンパニ− | Catalyst composition and use thereof |
| JPS60175548A (en) * | 1983-11-10 | 1985-09-09 | エクソン リサ−チ アンド エンヂニアリング コムパニ− | Zeolite catalyst and its use |
| JPS61283354A (en) * | 1985-04-17 | 1986-12-13 | シエブロン リサ−チ コンパニ− | Aromatizing catalyst having high activity and high selectivity |
| JPS6257653A (en) * | 1985-05-07 | 1987-03-13 | Res Assoc Util Of Light Oil | Catalyst for production of aromatic group and production of aromatic hydrocarbon by using said catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6433188A (en) | 1989-02-03 |
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