JPH0717536B2 - Method for producing alkylbenzene - Google Patents
Method for producing alkylbenzeneInfo
- Publication number
- JPH0717536B2 JPH0717536B2 JP2325939A JP32593990A JPH0717536B2 JP H0717536 B2 JPH0717536 B2 JP H0717536B2 JP 2325939 A JP2325939 A JP 2325939A JP 32593990 A JP32593990 A JP 32593990A JP H0717536 B2 JPH0717536 B2 JP H0717536B2
- Authority
- JP
- Japan
- Prior art keywords
- benzene
- solid acid
- acid catalyst
- debasing
- producing alkylbenzene
- 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
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
- 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、アルキルベンゼンの製造方法に係り、詳しく
は固体酸触媒を用いてベンゼンをアルキル化してアルキ
ルベンゼンを製造する方法に関する。TECHNICAL FIELD The present invention relates to a method for producing alkylbenzene, and more particularly, to a method for producing alkylbenzene by alkylating benzene using a solid acid catalyst.
アルキルベンゼンの製造方法として、固体酸触媒を用い
てベンゼンをオレフィン類やアルキルアルコール類と反
応させる方法が知られている（昭和42年12月１日付け
（株）技報堂発行“オライトとその利用”編集委員会編
「ゼオライトとその利用」）。しかしながら、この方法
では、固体酸触媒の活性が短期間に急激に低下するた
め、工業的に実施することは実質上不可能である。As a method for producing alkylbenzene, a method of reacting benzene with olefins and alkyl alcohols using a solid acid catalyst is known (edited by Gihodo Co., Ltd., “Olite and its utilization”, dated December 1, 1972). Committee edition "Zeolite and its use"). However, in this method, the activity of the solid acid catalyst is drastically reduced in a short period of time, and therefore it is practically impossible to carry out industrially.
本発明の目的は、固体酸触媒を用いてベンゼンをアルキ
ル化するアルキルベンゼンの製造方法を提供することに
ある。特に、固体酸触媒の活性が短期間に急激に低下す
ることのないアルキルベンゼンの製造方法を提供するこ
とにある。An object of the present invention is to provide a method for producing alkylbenzene in which benzene is alkylated using a solid acid catalyst. In particular, it is to provide a method for producing alkylbenzene in which the activity of a solid acid catalyst does not drop sharply in a short period of time.
本発明者は、上記のような課題を解決するために検討し
た結果、ベンゼンを固体酸触媒と接触させる前に脱塩基
処理することにより、固体酸触媒の活性低下を抑制でき
ることを見出し、本発明を完成した。The present inventor, as a result of studies to solve the above problems, found that debasing treatment of benzene before contacting it with a solid acid catalyst can suppress a decrease in activity of the solid acid catalyst. Was completed.
すなわち、本発明は、固体酸触媒を用いてベンゼンをア
ルキル化してアルキルベンゼンを製造する方法におい
て、ベンゼンを脱塩基処理してからアルキル化すること
を特徴とするアルキルベンゼンの製造方法である。That is, the present invention is a method for producing alkylbenzene by alkylating benzene using a solid acid catalyst, which comprises debasing benzene and then alkylating it.
原料として用いるベンゼンとしては、石炭系又は石油系
のものがあり、石炭系としては、ガス軽油やタール軽油
を精製して得られるものがあり、一般に工業的に用いら
れているベンゼンには微量ではあるが塩基性物質が含ま
れている。例えば、ベンゼンの工業的な製造方法の代表
的なものとして、水添精製した原料油からスルホラン系
溶剤により抽出し、抽出液を蒸留してベンゼンを回収す
る方法があるが、スルホラン系溶剤に由来する酸性物質
により蒸留設備が腐食されるのを防止するため、抽出液
を蒸留する際にアミン類等の含窒素塩基を防食剤として
添加しなければならず、この防食剤に由来する塩基性物
質がベンゼンに混入し、その窒素分含有量は元素Ｎに換
算して通常0.3ppm以上となる。一般に、ベンゼンを工業
原料に用いる場合には、この程度の塩基性物質が含まれ
ていても問題にならないが、固体酸触媒を用いてベンゼ
ンをアルキル化する場合、ベンゼン中の塩基性物質が固
体酸触媒の活性低下と密接な関係を有する。本発明者の
知見によると、これは、固体酸触媒の酸点に塩基性物質
が吸着するためである。As benzene used as a raw material, there are coal-based or petroleum-based ones, and as the coal-based ones, there are those obtained by refining gas gas oil and tar gas oil. However, it contains basic substances. For example, as a typical industrial production method of benzene, there is a method of extracting benzene from a hydrogenated and refined raw material oil with a sulfolane solvent and distilling the extract to recover benzene. In order to prevent the distillation equipment from being corroded by the acidic substance, a nitrogen-containing base such as amines must be added as an anticorrosion agent when distilling the extract, and a basic substance derived from this anticorrosion agent. Is mixed in benzene, and the nitrogen content thereof is usually 0.3 ppm or more in terms of element N. In general, when benzene is used as an industrial raw material, it does not matter even if such a basic substance is contained, but when alkylating benzene using a solid acid catalyst, the basic substance in benzene becomes solid. It is closely related to the decrease in the activity of the acid catalyst. According to the knowledge of the present inventor, this is because the basic substance is adsorbed on the acid sites of the solid acid catalyst.
また、本発明で使用する固体酸触媒としてはアルミノ珪
酸塩があり、ゼオライトが代表的である。このゼオライ
トは、塩基性物資を含むベンゼンを用いた場合に触媒活
性の低下が著しく、本発明を使用することが特に有効で
ある。The solid acid catalyst used in the present invention includes aluminosilicate, and zeolite is typical. This zeolite has a remarkable decrease in catalytic activity when benzene containing a basic substance is used, and the use of the present invention is particularly effective.
本発明では、ベンゼンを脱塩基処理してからアルキル化
する。脱塩基処理する方法としては白土処理が好まし
い。例えば、ベンゼンを白土と一定時間接触させる。白
土処理による脱塩基処理は、流通方式で行ってもよい
し、回分方式で行ってもよく、その条件としては、通
常、温度10〜60℃、圧力１〜5kg/cm2、LHSV0.3〜3Hr-1
程度がよい。白土処理することによりベンゼンの塩基性
物質含有量は通常0.3ppm未満となるが、本発明において
は0.1ppm以下とするのがよい。なお、白土はSiO2分及び
Al2O3分を主要成分とし、塩基性物質に対する吸着作用
を有するものであり、本発明においてはベントナイトを
酸性処理した活性白土が特に有効である。なお、脱塩基
処理の方法としては、白土処理の他、ベンゼンをゼオラ
イト、活性炭、シリカゲル、アルミナ等の吸着剤に接触
させる方法やイオン交換樹脂による方法も有効である。In the present invention, benzene is debased and then alkylated. As a method of debasing, a clay treatment is preferable. For example, benzene is contacted with clay for a certain period of time. The debasing treatment by the clay treatment may be carried out in a flow system or may be carried out in a batch system. The conditions are usually a temperature of 10 to 60 ° C., a pressure of 1 to 5 kg / cm 2 , and a LHSV of 0.3 to 3Hr -1
The degree is good. The basic substance content of benzene is usually less than 0.3 ppm by treating with clay, but in the present invention, it is preferably 0.1 ppm or less. It should be noted that the clay is SiO 2 and
Al 2 O 3 is the main component and has an adsorbing action for basic substances. In the present invention, activated clay obtained by acidifying bentonite is particularly effective. In addition to the clay treatment, a method of contacting benzene with an adsorbent such as zeolite, activated carbon, silica gel, or alumina, or a method using an ion exchange resin is also effective as a method of debasing.
ベンゼンのアルキル化は、ベンゼンをエチレン等のオレ
フィン類やエチルアルコール等のアルキルアルコール類
等のアルキル化剤とともに固体酸触媒に接触することに
より行うことができる。このアルキル化は、一段階で行
ってもよいが、工業的に実施する際には直列の二段階以
上で行うのが好ましい。また、モノアルキルベンゼンを
選択的に得ようとする場合、アルキル化により生成した
ポリアルキルベンゼンをアルキル化工程にリサイクルし
てトランスアルキル化させるのがよい。Alkylation of benzene can be carried out by contacting benzene with a solid acid catalyst together with an alkylating agent such as olefins such as ethylene or alkyl alcohols such as ethyl alcohol. This alkylation may be carried out in one step, but when industrially carried out, it is preferably carried out in two or more steps in series. Further, when monoalkylbenzene is to be selectively obtained, it is preferable that the polyalkylbenzene produced by the alkylation is recycled to the alkylation step to be transalkylated.
本発明者らの知見によると、固体酸触媒を用いてベンゼ
ンをアルキル化する際に触媒活性が低下し易いのは、原
料として用いるベンゼン中の塩基性物質が固体酸触媒の
酸点に吸着するためであり、本発明においては、アルキ
ル化する前に脱塩基理することによりベンゼン中から塩
基性物質が除去されるので、固体酸触媒の活性低下が起
こり難くなる。According to the knowledge of the present inventors, the catalytic activity tends to decrease when alkylating benzene using a solid acid catalyst because the basic substance in benzene used as a raw material is adsorbed on the acid sites of the solid acid catalyst. This is because, in the present invention, the basic substance is removed from the benzene by debasing before the alkylation, so that the activity of the solid acid catalyst is less likely to decrease.
粒状の活性白土（商品名：ニッカナイト）を充填した処
理塔に窒素分含有量0.4ppmのベンゼン（JIS K 8858）を
温度25℃、圧力1kg/cm2・Ｇ、LHSV1.5hr-1の条件で流通
させて脱塩基処理を行い、得られたベンゼン100重量部
とエチレン8.3重量部との混合油を温度212℃に加熱し、
ゼオライトを充填して圧力を38kg/cm2に維持した反応器
にガス空間速度10hr-1で連続的に流通させ、エチルベン
ゼンを得た。Benzene (JIS K 8858) with a nitrogen content of 0.4 ppm was placed in a processing tower filled with granular activated clay (trade name: Nikkanite) at a temperature of 25 ° C, a pressure of 1 kg / cm 2 · G, and LHSV1.5 hr -1 . Is subjected to a debasing treatment, and the resulting mixed oil of 100 parts by weight of benzene and 8.3 parts by weight of ethylene is heated to a temperature of 212 ° C.,
Ethylbenzene was obtained by continuously flowing it through a reactor filled with zeolite and maintaining the pressure at 38 kg / cm 2 at a gas space velocity of 10 hr -1 .
ベンゼンとエチレンとの混合油を反応器に流通開始して
から１日目のベンゼン転化量（反応器入口ベンゼン濃度
−反応器出口ベンゼン濃度）とエチルベンゼン生成量
（反応器出口エチルベンゼン濃度−反応器入口エチルベ
ンゼン濃度）とを測定し、ゼオライト触媒の触媒寿命推
定値を求めた。結果を第１表に示す。Benzene conversion amount (reactor inlet benzene concentration-reactor outlet benzene concentration) and ethylbenzene production amount (reactor outlet ethylbenzene concentration-reactor inlet) on the first day after the mixed oil of benzene and ethylene was started to flow into the reactor (Ethylbenzene concentration) was measured to obtain the estimated catalyst life of the zeolite catalyst. The results are shown in Table 1.
なお、触媒寿命は混合油流通開始後18日目の反応器内の
ホットスポットの入口からの距離と18日目から38日目ま
でのホットスポットの移動速度とからホットスポットが
反応器出口に達する期間を算出して推定値とした。ここ
で言うホットスポットは、反応器内でアルキル化反応が
活発に起こっている位置であり、周囲よりも相対的に高
温になっている位置のことである。ホットスポットは、
反応器入口側の触媒の活性が低下するに従って出口側に
移動するものと考えられる。The catalyst life depends on the distance from the hot spot entrance in the reactor on the 18th day after the start of the mixed oil flow and the moving speed of the hot spot from the 18th day to the 38th day, and the hot spot reaches the reactor exit. The period was calculated and used as the estimated value. The hot spot referred to here is a position where the alkylation reaction is actively occurring in the reactor and is a position where the temperature is relatively higher than that of the surroundings. Hotspot
It is considered that the catalyst moves to the outlet side as the activity of the catalyst on the inlet side of the reactor decreases.
また、比較例として、ベンゼンを白土処理せずに用いた
場合の結果を示す。In addition, as a comparative example, the result when benzene was used without the clay treatment is shown.
〔発明の効果〕 本発明によれば、触媒として用いる固体酸の活性低下が
抑制されるので、長期間にわたって操業を続けることが
できる。 [Effect of the Invention] According to the present invention, since the activity of the solid acid used as a catalyst is suppressed from decreasing, the operation can be continued for a long 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 Ｃ０７Ｂ 61/00 ３００ Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display area C07B 61/00 300
Claims (2)
してアルキルベンゼンを製造する方法において、ベンゼ
ンを脱塩基処理してからアルキル化することを特徴とす
るアルキルベンゼンの製造方法。1. A method for producing alkylbenzene by alkylating benzene using a solid acid catalyst, which comprises debasing benzene and then alkylating it.
のアルキルベンゼンの製造方法。2. The method for producing alkylbenzene according to claim 1, wherein the debasing treatment is a clay treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2325939A JPH0717536B2 (en) | 1990-11-29 | 1990-11-29 | Method for producing alkylbenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2325939A JPH0717536B2 (en) | 1990-11-29 | 1990-11-29 | Method for producing alkylbenzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04198139A JPH04198139A (en) | 1992-07-17 |
| JPH0717536B2 true JPH0717536B2 (en) | 1995-03-01 |
Family
ID=18182287
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2325939A Expired - Lifetime JPH0717536B2 (en) | 1990-11-29 | 1990-11-29 | Method for producing alkylbenzene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0717536B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1277680B1 (en) * | 1995-12-21 | 1997-11-11 | Enichem Spa | PROCEDURE FOR THE ALKYLATION OF AROMATIC COMPOUNDS |
| ES2173473T3 (en) | 1996-08-20 | 2002-10-16 | Dow Chemical Co | PROCEDURE FOR THE PRODUCTION OF RENTED BENZENS. |
| JP2005519103A (en) * | 2002-02-28 | 2005-06-30 | ストーン アンド ウェブスター インコーポレーテッド | Manufacture of alkyl aromatic compounds |
| US7744750B2 (en) | 2005-11-17 | 2010-06-29 | Exxonmobil Chemical Patents Inc. | Process for reducing Bromine Index of hydrocarbon feedstocks |
| US8057664B2 (en) | 2005-11-17 | 2011-11-15 | Exxonmobil Chemical Patents, Inc. | Process for reducing bromine index of hydrocarbon feedstocks |
| US7517824B2 (en) | 2005-12-06 | 2009-04-14 | Exxonmobil Chemical Company | Process for steam stripping hydrocarbons from a bromine index reduction catalyst |
| US9322793B2 (en) | 2010-05-20 | 2016-04-26 | Exxonmobil Chemical Patents Inc. | Method for monitoring performance of process catalysts |
-
1990
- 1990-11-29 JP JP2325939A patent/JPH0717536B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04198139A (en) | 1992-07-17 |
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