JPH0692331B2 - Chlorination of benzene or mono-substituted benzene - Google Patents
Chlorination of benzene or mono-substituted benzeneInfo
- Publication number
- JPH0692331B2 JPH0692331B2 JP63194383A JP19438388A JPH0692331B2 JP H0692331 B2 JPH0692331 B2 JP H0692331B2 JP 63194383 A JP63194383 A JP 63194383A JP 19438388 A JP19438388 A JP 19438388A JP H0692331 B2 JPH0692331 B2 JP H0692331B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction tank
- liquid
- benzene
- mono
- zeolite catalyst
- 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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、種々の有機化合物を合成する際の原料として
有用なパラ位が塩素で置換されたベンゼン誘導体を、ベ
ンゼン又はモノ置換ベンゼンと塩素ガスから液相でゼオ
ライト触媒を用いて製造するための連続塩素化方法に関
する。TECHNICAL FIELD The present invention relates to a benzene derivative in which para-position is substituted with chlorine, which is useful as a raw material for synthesizing various organic compounds, from benzene or mono-substituted benzene and chlorine gas. It relates to a continuous chlorination process for producing with a zeolite catalyst in the liquid phase.
従来の技術 従来ベンゼン又はモノ置換ベンゼンの塩素化方法として
は、例えば、塩化第二鉄、五塩化アンチモンなどのルイ
ス酸を触媒とする方法が知られているが、目的とするパ
ラ置換体の他に、オルト置換体がトリクロロベンゼンな
どが副生し、パラ置換体生成の選択率が高々60％程度で
ある。パラクロロベンゼン誘導体の選択率を高める方法
として、特開昭59-163329号公報には、触媒としてＬ型
ゼオライトを用いる方法が開示されている。そこでは、
触媒とするＬ型ゼオライトがイオン交換可能なカチオン
として、カリウムイオンを有するにＬ型ゼオライトを用
いる場合が例示されており、例えばパラジクロロベンゼ
ンの選択率は90％以上に達している。しかしながら、KL
型ゼオライトを用いてベンゼン又はモノ置換ベンゼンを
塩素化する際、触媒として新たに調整されたKL型ゼオラ
イトを用いた場合には、高反応率、高選択率でパラ置換
体が得られるが、触媒を繰り返し使用するときは、反応
率、選択率の低下が起こると同時に、ベンゼン又はモノ
置換ベンゼンの異臭のある多塩素付加物や多塩素置換物
の生成量が増大してくるという不都合がある。BACKGROUND ART Conventionally, as a chlorination method of benzene or mono-substituted benzene, for example, a method using a Lewis acid such as ferric chloride or antimony pentachloride as a catalyst is known. In addition, the ortho-substituted product is trichlorobenzene and the like is by-produced, and the selectivity of para-substituted product formation is about 60% at most. As a method for increasing the selectivity of the parachlorobenzene derivative, JP-A-59-163329 discloses a method using L-type zeolite as a catalyst. Where,
The case where the L-type zeolite used as the catalyst has potassium ions as the cations capable of exchanging ions is exemplified, and for example, the selectivity of paradichlorobenzene reaches 90% or more. However, KL
When chlorinating benzene or mono-substituted benzene by using type zeolite, para-substituted product is obtained with high reaction rate and high selectivity when using newly prepared KL type zeolite as a catalyst. When the above is repeatedly used, there is a disadvantage that the reaction rate and the selectivity are lowered, and at the same time, the production amount of the offensively odorous polychlorine adduct or polychlorine substitution of benzene or monosubstituted benzene is increased.
本発明者等は、この触媒の繰り返し使用による反応率及
び選択率の低下を抑制するべく研究した結果、Ｌ型ゼオ
ライトに於けるイオン交換可能なカチオンとしてのカリ
ウム含量が、酸化カリウムとして６〜14重量％であるＬ
型ゼオライトを用いることにより、触媒の繰り返し使用
による反応率の低下を著しく抑制することに成功した
（特開昭62-87536号公報参照）。The present inventors have studied to suppress the decrease in the reaction rate and the selectivity due to the repeated use of this catalyst, and as a result, the potassium content as an ion-exchangeable cation in the L-type zeolite is 6 to 14 as potassium oxide. Wt% is L
By using type zeolite, it has succeeded in remarkably suppressing the decrease in the reaction rate due to the repeated use of the catalyst (see JP-A-62-87536).
発明が解決しようとする課題 しかしながら、この様に調整されたＬ型ゼオライト触媒
を使用し、連続運転のために液外部循環ガスリフト型の
反応器を用いて、原料ベンゼン又はモノ置換ベンゼン及
び塩素ガスを上昇管の下部より供給して塩素化する場
合、異臭のあるペンタクロロシクロヘキセンのような多
塩素付加物が選択率として0.2モル％〜0.6モル％副生
し、1,2,4-トリクロロベンゼンのような多塩素置換物も
0.3モル％〜1.2モル％副生してくる。更に原料のモノ置
換ベンゼンがトルエンのようなアルキルベンゼンの場合
には、側鎖の塩化物が１モル％〜２モル％副生してく
る。気相反応の場合、多塩素付加物がゼオライト触媒の
活性を経時的に低下させることが特開昭61-171444号公
報に記載されているが、液相反応の場合も同様である。
したがって、この様な多塩素付加物や多塩素置換物の副
生を抑制することが望まれる。SUMMARY OF THE INVENTION However, the L-type zeolite catalyst thus prepared is used, and a liquid external circulation gas lift type reactor is used for continuous operation to feed the raw benzene or mono-substituted benzene and chlorine gas. When supplied from the bottom of the riser for chlorination, polychlorinated adducts such as pentachlorocyclohexene, which have an offensive odor, are by-produced as a selectivity of 0.2 mol% to 0.6 mol%, and 1,2,4-trichlorobenzene Polychlorinated products such as
0.3 mol% to 1.2 mol% is produced as a by-product. Further, when the mono-substituted benzene as a raw material is an alkylbenzene such as toluene, a chloride of a side chain is produced as a by-product of 1 mol% to 2 mol%. In the case of the gas phase reaction, it is described in JP-A-61-171444 that the polychlorinated adduct reduces the activity of the zeolite catalyst over time, but the same applies to the case of the liquid phase reaction.
Therefore, it is desired to suppress such by-products of polychlorinated products and polychlorinated products.
本発明は、上記のような実情に鑑みてなされたものであ
って、その目的は、ベンゼン又はモノ置換ベンゼンを、
液外部循環ガスリフト型反応器を用い、ゼオライト触媒
の存在下、塩素ガスにより塩素化するに当り、ペンタク
ロロシクロヘキセンのような多塩素付加物及び1,2,4-ト
リクロロベンゼンのような多塩素置換物、更にはアルキ
ルベンゼンの側鎖塩素化物の副生を制御できる塩素化方
法を提供することにある。The present invention has been made in view of the above circumstances, and an object thereof is to provide benzene or mono-substituted benzene,
When chlorinating with chlorine gas in the presence of a zeolite catalyst using a liquid external circulation gas lift type reactor, polychlorine adducts such as pentachlorocyclohexene and polychlorine substitution such as 1,2,4-trichlorobenzene. The object of the present invention is to provide a chlorination method capable of controlling the by-product of a side chain chlorinated compound of alkylbenzene and further alkylbenzene.
課題を解決するための手段 本発明者等は、上記副生物の生成は、導入塩素ガスが局
部的に高濃度に存在するときに多くなることをつきと
め、塩素ガス導入部として、液外部循環ガスリフト型反
応器の上昇管の断面積の２倍以上の断面積を有し、か
つ、導入塩素ガスの空塔速度が1m/sec以下となる反応槽
を設けることにより、上記副生物の生成を抑制すること
に成功し、本発明を完成するに至った。Means for Solving the Problems The present inventors have found that the generation of the by-product increases when the introduced chlorine gas locally exists at a high concentration, and the liquid external circulation gas lift is used as the chlorine gas introduction unit. Suppress the generation of by-products by providing a reaction tank that has a cross-sectional area that is at least twice the cross-sectional area of the rising pipe of the reactor and that has a superficial velocity of chlorine gas introduced of 1 m / sec or less. It succeeded in doing so and came to complete the present invention.
本発明は、ベンゼン又はモノ置換ベンゼンのパラ位を塩
素化する方法であって、パラ位への選択率の高いゼオラ
イト触媒を用い、ゼオライト触媒の使用時に副生し易い
多塩素付加物及び多塩素置換物の生成を制御しながら、
高反応率かつ高選択率でパラ位が塩素で置換されたベン
ゼン誘導体を製造する方法に関する。The present invention relates to a method for chlorinating the para-position of benzene or mono-substituted benzene, wherein a zeolite catalyst having a high selectivity to the para-position is used, and a polychlorine adduct and a polychlorine which are easily by-produced when the zeolite catalyst is used. While controlling the generation of substitutions,
The present invention relates to a method for producing a benzene derivative in which para-position is substituted with chlorine with high reaction rate and high selectivity.
本発明の構成上の特徴は、ベンゼンまたはモノ置換ベン
ゼンをゼオライト触媒の存在下、塩素ガスにより液相で
塩素化するに当たり、下段反応槽、該下段反応槽の上部
に設けた上昇管、該上昇管の上部に設けた上段反応槽及
び下降管よりなり、冷却手段を上昇管及び／又は下降管
に付した液外部循環ガスリフト型の反応器及び固液分離
機を少なくとも有する装置を用い、ベンゼンまたはモノ
置換ベンゼンを該装置のいずれかの位置に供給し、塩素
ガスを下段反応槽または下段反応槽と上段反応槽に供給
し、反応器より抜き出した反応液を固液分離機に導入し
てゼオライト触媒を分離し、分離液は精製工程に送り、
ゼオライト触媒を反応器に戻すことにある。The structural feature of the present invention is that when benzene or mono-substituted benzene is chlorinated in a liquid phase by chlorine gas in the presence of a zeolite catalyst, a lower reaction tank, an ascending pipe provided above the lower reaction tank, and an ascending pipe. A reactor having at least a liquid external circulation gas lift type reactor having an upper reaction vessel and a downcomer provided at the upper part of the tube and a cooling means attached to the upcomer and / or the downcomer and a solid-liquid separator are used, and benzene or Mono-substituted benzene is supplied to any position of the apparatus, chlorine gas is supplied to the lower reaction tank or the lower reaction tank and the upper reaction tank, and the reaction liquid extracted from the reactor is introduced into a solid-liquid separator to be a zeolite. The catalyst is separated, the separated liquid is sent to the purification process,
It is to return the zeolite catalyst to the reactor.
本発明を図面を参酌して説明する。The present invention will be described with reference to the drawings.
第１図は本発明の工程の一例を示す工程図であって、連
続塩素化装置を用いて塩素化する場合を示している。本
発明において用いる連続塩素化装置において、液外部循
環ガスリフト型の反応器は、下段反応槽２、該下段反応
槽の上部に設けた上昇管１、該上昇管の上部に設けた上
段反応槽３及び下降管４よりなり、冷却手段が上昇管及
下降管の一方又は双方に付されている。第１図の場合
は、冷却手段５が下降管に付されている。FIG. 1 is a process chart showing an example of the process of the present invention, and shows a case where chlorination is performed using a continuous chlorination device. In the continuous chlorination apparatus used in the present invention, a liquid external circulation gas lift type reactor includes a lower reaction tank 2, a rising pipe 1 provided above the lower reaction tank, and an upper reaction tank 3 provided above the rising pipe. And the downcomer 4, and the cooling means is attached to one or both of the upcomer and the downcomer. In the case of FIG. 1, the cooling means 5 is attached to the downcomer pipe.
本発明において用いる反応器の上昇管の直径としては、
下段反応槽への供給塩素ガス基準の空塔速度が0.01m/se
c以上、好ましくは0.1〜5m/secになるように選ばれる。
空塔速度が小さいと、ゼオライト触媒の流動化ができず
閉塞し、液循環ができなくなる。空塔速度を大きくし過
ぎると流動の抵抗が増大し、液循環の流速がそれ程大き
くならず、したがって液循環流量が減少して好ましくな
い。上昇管の長さは少なくとも、0.5m以上、好ましくは
３〜10mである。短いと冷却のための伝熱面積が不足
し、また長過ぎると装置が大型化する。The diameter of the rising tube of the reactor used in the present invention,
Superficial velocity based on chlorine gas supplied to the lower reaction tank is 0.01 m / se
It is selected to be c or more, preferably 0.1 to 5 m / sec.
If the superficial velocity is low, the zeolite catalyst cannot be fluidized and clogged, making it impossible to circulate the liquid. If the superficial velocity is too high, the flow resistance increases, the liquid circulation flow velocity does not increase so much, and the liquid circulation flow rate decreases, which is not preferable. The length of the riser is at least 0.5 m or more, preferably 3 to 10 m. If the length is short, the heat transfer area for cooling is insufficient, and if it is too long, the device becomes large.
下段反応槽としては、上昇管の断面積の少なくとも２倍
以上、好ましくは30〜500倍の断面積を有し、かつ、導
入塩素ガスの空塔速度が1m/sec以下となる槽であり、深
さ／直径が0.5〜２程度のものが用いられる。The lower reaction tank is a tank having a cross-sectional area of at least twice the cross-sectional area of the riser, preferably 30 to 500 times, and a superficial velocity of introduced chlorine gas of 1 m / sec or less, A depth / diameter of about 0.5 to 2 is used.
上段反応槽は、上昇管の断面積の少なくとも２倍以上好
ましくは30〜500倍の断面積を有し、全供給塩素ガスの
空塔速度が1m/sec以下好ましくは0.1m/sec以下になる断
面積が選ばれる。液深は浅すぎると未反応塩素が多くな
るので、好ましくは30cm以上のものが用いられる。な
お、上段および下段反応槽の下部はゼオライト触媒粒子
の堆積を防止するためにコニカル状にするのが好まし
い。The upper reaction tank has a cross-sectional area of at least twice the cross-sectional area of the riser, preferably 30 to 500 times, and the superficial velocity of the total chlorine gas supplied is 1 m / sec or less, preferably 0.1 m / sec or less. The cross-sectional area is chosen. If the liquid depth is too shallow, the amount of unreacted chlorine will increase, so that the liquid having a depth of 30 cm or more is preferably used. The lower parts of the upper and lower reaction vessels are preferably conical in order to prevent the deposition of zeolite catalyst particles.
また、冷却手段としては、大量に発生する反応熱の除去
のために、液外部循環による多管式熱交換器を使用する
のが好ましい。Further, as the cooling means, it is preferable to use a multi-tube heat exchanger by liquid external circulation for removing a large amount of reaction heat generated.
一方、固液分離機は、ゼオライト触媒を分離するための
ものであって、過器、遠心沈降機、シックナーなどが
用いられるが、過器が好ましく用いられる。過器と
しては、例えば布またはセラミックスよりなる円筒状
の材を内在し、加圧逆洗可能な密閉型過機が特に好
ましい。第１図の場合は、密閉型の過器６が使用され
ている。また、第１図は、過器によって分離されたゼ
オライト触媒が、塊状をなす場合であって、分離された
塊状のゼオライトをスラリー状にするための攪拌槽７が
設けられている。On the other hand, the solid-liquid separator is used for separating the zeolite catalyst, and a vessel, a centrifugal settler, a thickener, or the like is used, and the vessel is preferably used. As the filter, a sealed filter which has a cylindrical material made of, for example, cloth or ceramics therein and can be backwashed under pressure is particularly preferable. In the case of FIG. 1, a sealed type reactor 6 is used. Further, FIG. 1 shows a case where the zeolite catalyst separated by the filter is in a lump form, and a stirring tank 7 is provided for making the separated lump zeolite into a slurry form.
本発明においては、ベンゼン又はモノ置換ベンゼンが原
料として用いられるが、モノ置換ベンゼンとしては、ク
ロロベンゼン、ブロモベンゼン、トルエン、アニソール
などがあげられる。In the present invention, benzene or mono-substituted benzene is used as a raw material, and examples of the mono-substituted benzene include chlorobenzene, bromobenzene, toluene and anisole.
原料のベンゼン又はモノ置換ベンゼンは、予め脱水器18
で水分100ppm（重量）以下、好ましくは10ppm（重量）
以下にるように脱水される。水分含量が多くなると、ベ
ンゼン又はモノ置換ベンゼンの多塩素付加物及び多塩素
置換物の生成量が急激に増加する。脱水処理さたベンゼ
ン又はモノ置換ベンゼンは反応器に供給されるが、反応
器に直接供給される場合のほか、固液分離器６や撹拌槽
７に供給されてもよい。第１図においては、下段反応槽
２へ連続的に供給される。The raw material benzene or mono-substituted benzene should be previously removed from the dehydrator 18
Water content is 100ppm (weight) or less, preferably 10ppm (weight)
It is dehydrated as follows. As the water content increases, the amount of polychlorinated adducts of benzene or mono-substituted benzene and the amount of polychlorinated substitutions increases rapidly. The dehydrated benzene or mono-substituted benzene is supplied to the reactor, but may be supplied to the solid-liquid separator 6 or the stirring tank 7 in addition to the case of being directly supplied to the reactor. In FIG. 1, it is continuously supplied to the lower reaction tank 2.
一方、塩素ガスは、下段反応槽２、又は下段反応槽２と
上段反応槽３とに分割して、それぞれの反応槽底部の多
孔管より供給される。塩素ガスは、水分が400ppm（容
量）以下、好ましくは120ppm（容量）以下のものを用い
る。供給する塩素ガス量は、モノ置換ベンゼンに対して
は、モル比で0.5〜0.7、ベンゼンに対してはモル比で1.
5〜1.7である。塩素ガスは、必要量の20〜100％、好ま
しくは40〜70％を下段反応槽２に導入し、残量は上段反
応槽に導入される。塩素ガスの必要量の少なくとも20％
を下段反応槽２に導入することにより、そこで発生する
塩化水素ガスが液循環の推進力となる。因みに、下段反
応槽を設けず、上昇管に塩素ガスの全量を直接導入する
ときは、多塩素付加物や多塩素置換物の生成量が増大す
る。On the other hand, the chlorine gas is divided into the lower reaction tank 2, or the lower reaction tank 2 and the upper reaction tank 3, and is supplied from the perforated pipe at the bottom of each reaction tank. Chlorine gas having a water content of 400 ppm (volume) or less, preferably 120 ppm (volume) or less is used. The amount of chlorine gas to be supplied is 0.5 to 0.7 for mono-substituted benzene and 1 for benzene.
5 to 1.7. The required amount of chlorine gas is introduced into the lower reaction tank 2 in an amount of 20 to 100%, preferably 40 to 70%, and the remaining amount is introduced into the upper reaction tank. At least 20% of the chlorine gas requirement
Is introduced into the lower reaction tank 2, the hydrogen chloride gas generated there becomes a driving force for liquid circulation. Incidentally, when the whole amount of chlorine gas is directly introduced into the rising pipe without providing the lower reaction tank, the amount of polychlorinated adducts or polychlorinated substitutes increases.
ゼオライト触媒は、予め所定濃度になる量が、上段反応
槽３に仕込まれ、運転中反応器にはゼオライト触媒を所
定濃度で含む反応液が循環しており、循環液量は、渦流
量計17で測定できる。勿論、ゼオライト触媒を連続的ま
たは断続的に供給し、使用済みゼオライト触媒を連続的
または断続的に抜き出して、ゼオライト触媒を所定濃度
に保つのが好ましい。The zeolite catalyst is charged in the upper reaction tank 3 in such an amount that a predetermined concentration is reached in advance, and a reaction liquid containing a predetermined concentration of the zeolite catalyst is circulated in the reactor during operation. Can be measured at. Of course, it is preferable that the zeolite catalyst is continuously or intermittently supplied and the used zeolite catalyst is continuously or intermittently withdrawn to maintain the zeolite catalyst at a predetermined concentration.
ゼオライト触媒としては、カリウム含量が酸化カリウム
として６〜14重量％、好ましくは８〜12重量であるＬ型
ゼオライトが好ましい。ここで使用すＬ型ゼオライト
は、酸化アルミニウム／酸化ケイ素がモル比で0.1〜0.2
の範囲であるものである。反応液中におけるゼオライト
触媒濃度は、0.1〜10重量％、好ましくは1.5〜３重量％
である。ゼオライト濃度が高くなると塩素の反応率は高
いが、多塩素付加物の副生が多くなり、また低濃度に過
ぎると塩素反応率が低く、しかも多塩素付加物及び多塩
素置換物の副生が多くなる。As the zeolite catalyst, L-type zeolite having a potassium content of 6 to 14% by weight as potassium oxide, preferably 8 to 12% by weight is preferable. The L-type zeolite used here has an aluminum oxide / silicon oxide molar ratio of 0.1 to 0.2.
Is the range of. Zeolite catalyst concentration in the reaction solution is 0.1 to 10% by weight, preferably 1.5 to 3% by weight
Is. When the zeolite concentration is high, the reaction rate of chlorine is high, but the by-product of polychlorine adduct increases, and when the concentration is too low, the chlorine reaction rate is low, and moreover, the by-product of polychlorine adduct and polychlorine substitution product is generated. Will increase.
反応温度は、上段反応槽３における温度が50〜100℃好
ましくは60〜80℃になるように冷却手段５で冷却するこ
とによって調整される。冷却手段５としては例えば多管
式熱交換器が用いられる。The reaction temperature is adjusted by cooling with the cooling means 5 so that the temperature in the upper reaction tank 3 becomes 50 to 100 ° C, preferably 60 to 80 ° C. As the cooling means 5, for example, a multi-tube heat exchanger is used.
反応液の一部は、圧力差により反応器より過器６に送
られる。過器における過は、上段反応槽３と分離液
（液）抜出しライン14との圧力差により行われる。し
たがって、液抜出しライン14の内圧は通常大気圧程度
であるので、上段反応槽３の圧力は0.5〜5kg/cm2G、好
ましくは１〜3kg/cm2Gに保たれる。過器６でゼオライ
ト触媒を別した反応液は、分離液抜出しライン14を経
て、目的生成物を分離するための精製工程に送られる。
過器６による過中は、バルブ8,9を開け、バルブ10,
11,12,13を閉めている。一定時間過後、バルブ8,9を
閉め、バルブ12より窒素によって約6kg/cm2Gに加圧した
後、バルブ12を閉め、バルブ10を数秒間開けて、過器
６の上部に溜まっている液で加圧逆洗し、材に付着
しているゼオライト触媒を剥離させると同時に、前回の
過で剥離して過器６の底部に溜まっているゼオライ
ト触媒を攪拌槽７に送り出す。送り出されたゼオライト
触媒は、剥離片として塊になっているため、撹拌槽７で
スラリー状に分散される。このスラリー液は過中にバ
ルブ11から上段反応槽３に戻される。加圧逆洗後、バル
ブ13を数秒間開いて、過器６内圧を上段反応槽３内圧
より低くして過を再開する。上段反応槽３の液面調節
は、液面調節弁も兼ねるバルブ８を、図中点線で示され
る信号情報により自動的に開閉することによって行われ
る。このような過器の加圧逆洗を一定時間ごと、好ま
しくは20分〜60分ごとに自動的に繰り返すことにより反
応器内の触媒ゼオライトを略一定に保つことができる。Part of the reaction liquid is sent from the reactor to the reactor 6 due to the pressure difference. Passage in the reactor is performed by the pressure difference between the upper reaction tank 3 and the separation liquid (liquid) withdrawal line 14. Therefore, since the internal pressure of the liquid withdrawal line 14 is usually about atmospheric pressure, the pressure in the upper reaction tank 3 is maintained at 0.5 to 5 kg / cm 2 G, preferably 1 to 3 kg / cm 2 G. The reaction liquid from which the zeolite catalyst has been separated in the filter 6 is sent to the purification step for separating the target product via the separation liquid withdrawing line 14.
During the overrun by the device 6, open the valves 8 and 9,
Closed 11,12,13. After a certain period of time, close the valves 8 and 9, pressurize the valve 12 with nitrogen to about 6 kg / cm 2 G, then close the valve 12 and open the valve 10 for a few seconds. At the same time as the zeolite catalyst adhering to the material is peeled off by backwashing under pressure with a liquid, the zeolite catalyst that has been peeled off at the previous time and accumulated at the bottom of the filter 6 is sent to the stirring tank 7. Since the zeolite catalyst sent out is in the form of a lump as a peeling piece, it is dispersed in a slurry in the stirring tank 7. This slurry liquid is returned to the upper reaction tank 3 from the valve 11 during the excess. After backwashing under pressure, the valve 13 is opened for a few seconds to lower the internal pressure of the reactor 6 below the internal pressure of the upper reaction tank 3 and restart the excess. The liquid level of the upper reaction tank 3 is adjusted by automatically opening and closing the valve 8 which also functions as a liquid level adjusting valve according to the signal information shown by the dotted line in the figure. The catalyst back-filling in the reactor can be kept substantially constant by automatically repeating such pressure backwashing of the reactor every fixed time, preferably every 20 to 60 minutes.
塩素化反応により生成した塩化水素ガスは上段反応槽３
の上端部より冷却器15を経て、図中点線で示される信号
情報に応じて圧力調整弁16で所定圧に調整されて排出さ
れ、排ガス処理工程に送られる。Hydrogen chloride gas generated by the chlorination reaction is in the upper reaction tank 3
After passing through the cooler 15 from the upper end of the, the pressure is adjusted to a predetermined pressure by the pressure adjusting valve 16 according to the signal information shown by the dotted line in the figure, and is discharged and sent to the exhaust gas treatment process.
上記の如くしてベンゼン、クロロベンゼンを塩化度1.5
〜1.7、他のモノ置換ベンゼンを塩化度0.5〜0.7まで塩
素化した反応液を過器に供給するとき、塩素反応率99
％以上、パラ選択率85％以上で、パラジクロロベンゼ
ン、パラクロロトルエンなどのパラ位が塩素で置換され
たベンゼン類が得られる。多塩素付加物の選択率は0.06
モル％以下、多塩素置換物は0.3モル％以下となる。ま
た、ルエンなどのアルキルベンゼンを原料とするときの
側鎖塩化物の副生量も0.5モル％以下となる。As described above, benzene and chlorobenzene are added with a salinity of 1.5.
~ 1.7, chlorine reaction rate of 99 when the reaction liquid obtained by chlorinating other mono-substituted benzene to a chlorination degree of 0.5 to 0.7 is supplied to the reactor.
% Or more and a para selectivity of 85% or more, benzenes such as paradichlorobenzene and parachlorotoluene in which para-position is replaced with chlorine can be obtained. Selectivity of polychlorine adduct is 0.06
Mol% or less, and polychlorinated substitutes are 0.3 mol% or less. In addition, the amount of side-chain chloride by-products when alkylbenzene such as ruene is used as a raw material is 0.5 mol% or less.
なお、ここでいう「塩化度」及び「選択率」は、それぞ
れ下記式により定義される。The "chlorination degree" and the "selectivity" referred to here are respectively defined by the following equations.
（式中、 のモル分率を表わし、ｎは０〜６の整数を表わす） （式中、Xiは各生成物のモル分率を表わす） 上記第１図の場合、大量に発生する反応熱の除去のため
に、液外部循環による多管式熱交換器を使用している。 (In the formula, Represents the mole fraction of n, and n represents an integer of 0 to 6) (In the formula, Xi represents the mole fraction of each product.) In the case of FIG. 1 described above, a multi-tube heat exchanger by liquid external circulation is used to remove a large amount of reaction heat generated. .
本発明においては、約0.3μｍの結晶粒子からなる50μ
ｍ以下の凝集粒子であるゼオライトを触媒として用いる
が、反応液より触媒分離の為の固液分離機として過器
を用いる場合、使用する材によっては、ゼオライト微
粒子が液中にリークし易い。例えば、本発明の方法に
より得られる生成物がパラジクロロベンゼンである場
合、その精製を液よりパラジクロロベンゼンを晶析
後、連続多段溶融精製装置（例えば、特公昭47-40621号
公報に記載の結晶精製装置）により溶解精製するとき、
液中にゼオライト触媒の微粒子がリークすると、精製
パラジクロロベンゼン中に残留して好ましくない。多孔
質のセラミックよりなる材を用いれば、この様な問題
は回避することができる。In the present invention, 50 μ consisting of crystal particles of about 0.3 μm
Zeolite, which is agglomerated particles of m or less, is used as a catalyst. When an excess vessel is used as a solid-liquid separator for separating the catalyst from the reaction liquid, depending on the material used, the zeolite fine particles easily leak into the liquid. For example, when the product obtained by the method of the present invention is paradichlorobenzene, the purification is performed by crystallizing paradichlorobenzene from a liquid, and then a continuous multistage melt purification apparatus (for example, crystal purification described in JP-B-47-40621). When dissolving and refining with equipment)
If fine particles of the zeolite catalyst leak into the liquid, they remain in the purified paradichlorobenzene, which is not preferable. Such a problem can be avoided by using a material made of porous ceramic.
また、本発明の方法では、液外部循環ガスリフト型反応
器を使用することで、大きな総括伝熱係数と大きな循環
液流量が得られ、容易に反応熱を除去し、同時にゼオラ
イト触媒の沈積防止をしながら、多塩素付加物や多塩素
置換物の副生を抑制し、更に固液分離機、撹拌槽との組
合わせによって、長期間安定にパラ位が塩素化されたベ
ンゼン誘導体を製造することができる。Further, in the method of the present invention, by using the liquid external circulation gas lift type reactor, a large overall heat transfer coefficient and a large circulating liquid flow rate can be obtained, the reaction heat is easily removed, and at the same time the zeolite catalyst is prevented from being deposited. However, by suppressing the by-product of polychlorinated adducts and polychlorinated substitutions, and by combining with a solid-liquid separator and a stirring tank, it is possible to stably produce a benzene derivative in which the para position is chlorinated. You can
実施例 次に、本発明を実施例によって説明する。EXAMPLES Next, the present invention will be described by examples.
実施例１ 内径50cm、直胴部長さ50cmの下段反応槽、内径4.3cm、
長さ4.5mの上昇管、内径60cm、直胴部長さ1.5mの上段反
応槽、及び直径20.2mm、長さ5mの冷却管を３本設けた多
管式熱交換器を有する下降管で構成される第１図に示す
ような液外部循環ガスリフト型反応器を用い、含水率10
ppm以下のクロロベンゼン44kg/hrと塩素ガス17〜18kg/h
rを下段反応槽に供給し、反応液を3.7m3/hrで循環させ
た。下段反応槽に於ける反応温度が70℃になるように下
降管で冷却し、上段反応槽の圧力を1.5kg/cm2Gに調節し
た。上段反応槽より、塩化度 1.61〜1.63の反応液を上
段反応槽の液面が一定になるように抜き出し、平均孔径
10μｍ、外径7cm、内径4cm、長さ50cmの多孔質シリコン
カーバイド製円筒状材を三本内在した過器に送り、
ゼオライト触媒と反応液の分離を行った。過器は30分
ごとに圧力6kg/cm2Gの窒素ガスにより加圧逆洗し、ゼオ
ライト触媒は、撹拌槽でスラリー状にして上段反応槽に
戻し、循環使用した。Example 1 Inner Diameter 50 cm, Straight Body Length 50 cm Lower Reaction Chamber, Inner Diameter 4.3 cm,
It consists of a 4.5 m long riser, an inner diameter of 60 cm, an upper reaction tank with a straight body length of 1.5 m, and a downcomer having a multi-tube heat exchanger with 3 cooling pipes of 20.2 mm in diameter and 5 m in length. Using a liquid external circulation gas lift type reactor as shown in FIG.
Chlorobenzene less than ppm 44kg / hr and chlorine gas 17-18kg / h
r was supplied to the lower reaction tank, and the reaction solution was circulated at 3.7 m 3 / hr. It was cooled by a downcomer so that the reaction temperature in the lower reaction vessel was 70 ° C., and the pressure in the upper reaction vessel was adjusted to 1.5 kg / cm 2 G. The reaction solution with a salinity of 1.61 to 1.63 was withdrawn from the upper reaction tank so that the liquid level in the upper reaction tank was constant, and the average pore size was
Send 10μm, outer diameter 7cm, inner diameter 4cm, length 50cm cylindrical material made of porous silicon carbide to the internal equipment of three
The zeolite catalyst and the reaction solution were separated. The filter was backwashed under pressure with nitrogen gas at a pressure of 6 kg / cm 2 G every 30 minutes, and the zeolite catalyst was slurried in a stirring tank and returned to the upper reaction tank for recycling.
なお、ゼオライト触媒は、カリウム含量が酸化カリウム
として、11.8重量％のＬ型ゼオライトを0.1mmHg、150℃
で24時間乾燥し、反応液中濃度が1.75重量％になるよう
に反応開始前に上段反応槽に投入して用いた。As for the zeolite catalyst, potassium oxide has a potassium content of 11.8% by weight of L-type zeolite of 0.1 mmHg and 150 ° C.
It was dried for 24 hours, and charged into the upper reaction vessel before the reaction so that the concentration in the reaction solution would be 1.75% by weight.
上記のようにして、400時間連続塩素化した。50時間
後、200時間後、300時間後、及び400時間後の塩素反応
率及び主な生成物の各選択率を第１表に示す。反応液
は、ガスクロマトグラフィーで分析した。As described above, continuous chlorination was performed for 400 hours. Table 1 shows the chlorine reaction rates and the respective main product selectivities after 50 hours, 200 hours, 300 hours, and 400 hours. The reaction solution was analyzed by gas chromatography.
また、連続塩素化50時間後で過開始10分後の液中の
ゼオライト触媒濃度を第３表に示す。液中のゼオライ
ト触媒濃度は、液500mlを窒素気流中100℃で２時間、
次に200℃で１時間加熱した後、500℃で２時間加熱し
て、残留したものをゼオライト触媒として計算した。Table 3 shows the concentration of the zeolite catalyst in the liquid after 50 hours of continuous chlorination and 10 minutes after the over-start. The concentration of zeolite catalyst in the liquid was 500 ml of the liquid in a nitrogen stream at 100 ° C for 2 hours.
Next, after heating at 200 ° C. for 1 hour, it was heated at 500 ° C. for 2 hours, and the residue was calculated as a zeolite catalyst.
実施例２ 実施例１と同じ反応器を使用し、塩素ガスの供給方法
を、塩素ガス量の50％を下段反応槽に、残りの50％を上
段反応槽に供給するように変える以外は実施例１と同様
な条件で塩素化した。ただし、下段反応槽の反応温度を
70℃に調整した。その場合、上段反応槽の反応温度は72
℃になり、液循環流量は2.7m3/hrであった。結果を第２
表に示す。 Example 2 The same reactor as in Example 1 was used, but the chlorine gas supply method was changed except that 50% of the chlorine gas amount was supplied to the lower reaction tank and the remaining 50% was supplied to the upper reaction tank. Chlorination was carried out under the same conditions as in Example 1. However, the reaction temperature of the lower reaction tank
The temperature was adjusted to 70 ° C. In that case, the reaction temperature in the upper reaction tank is 72
C., and the liquid circulation flow rate was 2.7 m 3 / hr. Second result
Shown in the table.
実施例３ シリコーンカーバイド製材を、通気度1.5cm3/cm2・se
cのポリプロピレン製の布に変えた以外は、実施例１
と同様な条件で連続塩素化した。連続塩素化50時間後で
過開始10分後の液中のゼオライト触媒濃度を第３表
に示す。 Example 3 A silicone carbide lumber was used to obtain an air permeability of 1.5 cm 3 / cm 2 · se.
Example 1 except that the polypropylene cloth of c was changed.
Continuous chlorination was performed under the same conditions as in. Table 3 shows the concentration of the zeolite catalyst in the liquid after 50 hours of continuous chlorination and 10 minutes after the start.
比較例１ 下段反応槽を除いて、上昇管をその部分まで延長し、塩
素ガス及びモノクロロベンゼンの導入管を接続した以外
は、実施例１と同じ反応器を使用し、塩素ガスを上昇管
下部より供給し、実施例１と同様な条件で塩素化した。
但し、反応温度を上段反応槽で70℃になるように冷却し
た。液循環流量は3.2m3/hrであった。結果を第４表に示
す。 Comparative Example 1 The same reactor as in Example 1 was used, except that the riser pipe was extended to that portion and the chlorine gas and monochlorobenzene introduction pipes were connected, except for the lower reaction vessel, and chlorine gas was added to the lower part of the riser pipe. And chlorinated under the same conditions as in Example 1.
However, the reaction temperature was cooled to 70 ° C. in the upper reaction tank. The liquid circulation flow rate was 3.2 m 3 / hr. The results are shown in Table 4.
発明の効果 本発明の方法によれば、ゼオライト触媒存在下、塩素ガ
スを用いてベンゼンまたはモノ置換ベンゼンを連続塩素
化するに当り、液外部循環ガスリフト型反応器を用いる
ことにより、大きな総括伝熱係数と大きな循環液流量が
得られ、容易に反応熱を除去することができ、そして、
その反応器において、上昇管の下部に下段反応槽を、ま
た上部に上段反応槽を設け、塩素ガスを下段反応槽また
は下段反応槽と上段反応槽に供給することにより、多塩
素付加物や多塩素置換物の副生を抑制して、パラ位が塩
素で置換されたベンゼン誘導体を長期間にわたり安定に
製造することができる。したがって本願発明は、パラ位
が塩素で置換されたベンゼン誘導体を製造するのに、工
業的に極めて有用な方法である。 EFFECTS OF THE INVENTION According to the method of the present invention, in the continuous chlorination of benzene or mono-substituted benzene with chlorine gas in the presence of a zeolite catalyst, by using a liquid external circulation gas lift type reactor, a large overall heat transfer is achieved. Coefficient and large circulating liquid flow rate can be obtained, reaction heat can be easily removed, and
In the reactor, a lower reaction tank is provided in the lower part of the rising pipe and an upper reaction tank is provided in the upper part, and chlorine gas is supplied to the lower reaction tank or the lower reaction tank and the upper reaction tank, so that polychlorine adducts and It is possible to suppress the by-product of a chlorine-substituted product and stably produce a benzene derivative in which the para-position is replaced with chlorine for a long period of time. Therefore, the present invention is an industrially extremely useful method for producing a benzene derivative in which the para-position is substituted with chlorine.
第１図は、本発明の工程の一例を示す工程図である。 １……上昇管、２……下段反応槽、３……上段反応槽、
４……下降管、５……冷却手段、６……固液分離機、７
……攪拌槽、８、９、10、11、12、13……バルブ、14…
…分離液抜出しライン、15……冷却器、16……圧力調整
弁、17……渦流量計、18……脱水器。FIG. 1 is a process drawing showing an example of the process of the present invention. 1 ... Ascending pipe, 2 ... Lower reaction tank, 3 ... Upper reaction tank,
4 ... Downcomer, 5 ... Cooling means, 6 ... Solid-liquid separator, 7
…… Agitation tank, 8, 9, 10, 11, 12, 13 …… Valve, 14…
… Separated liquid extraction line, 15 …… cooler, 16 …… pressure control valve, 17 …… vortex flowmeter, 18 …… dehydrator.
Claims (3)
イト触媒の存在下、塩素ガスにより液相で塩素化するに
当たり、下段反応槽、該下段反応槽の上部に設けた上昇
管、該上昇管の上部に設けた上段反応槽及び下降管より
なり、冷却手段を上昇管及び／又は下降管に付した液外
部循環ガスリフト型の反応器及び固液分離機を少なくと
も有する装置を用い、ベンゼン又はモノ置換ベンゼンを
該装置のいずれかの位置に供給し、塩素ガスを下段反応
槽または下段反応槽と上段反応槽に供給し、反応器より
抜き出した反応液を固液分離機に導入してゼオライト触
媒を分離し、分離液は精製工程に送り、ゼオライト触媒
を反応器に戻すことを特徴とするベンゼンまたはモノ置
換ベンゼンの塩素化方法。1. When chlorinating benzene or mono-substituted benzene in the liquid phase with chlorine gas in the presence of a zeolite catalyst, a lower reaction tank, a rising pipe provided above the lower reaction tank, and an upper pipe above the rising pipe are provided. Using an apparatus having at least a liquid external circulation gas lift type reactor and a solid-liquid separator, which comprises an upper reaction tank and a downcomer provided, and a cooling means attached to the upcomer and / or the downcomer, benzene or mono-substituted benzene is used. It is supplied to any position of the apparatus, chlorine gas is supplied to the lower reaction tank or the lower reaction tank and the upper reaction tank, and the reaction liquid extracted from the reactor is introduced into a solid-liquid separator to separate the zeolite catalyst. A method for chlorinating benzene or mono-substituted benzene, characterized in that the separated liquid is sent to a refining process and the zeolite catalyst is returned to the reactor.
閉型過器である特許請求の範囲第１項に記載の方法2. The method according to claim 1, wherein the solid-liquid separator is a closed type reactor capable of intermittent pressure backwashing.
材を有する過器である特許請求の範囲第１項または
第２項に記載の方法3. The method according to claim 1 or 2, wherein the solid-liquid separator is a vessel having a material made of porous ceramics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63194383A JPH0692331B2 (en) | 1988-08-05 | 1988-08-05 | Chlorination of benzene or mono-substituted benzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63194383A JPH0692331B2 (en) | 1988-08-05 | 1988-08-05 | Chlorination of benzene or mono-substituted benzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0245431A JPH0245431A (en) | 1990-02-15 |
| JPH0692331B2 true JPH0692331B2 (en) | 1994-11-16 |
Family
ID=16323687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63194383A Expired - Lifetime JPH0692331B2 (en) | 1988-08-05 | 1988-08-05 | Chlorination of benzene or mono-substituted benzene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0692331B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9598184B2 (en) | 2003-02-14 | 2017-03-21 | Eastman Chemical Company | Method for packaging fiber material |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5089227B2 (en) * | 2007-04-12 | 2012-12-05 | 住友化学株式会社 | Filtration method |
| JP5366610B2 (en) * | 2009-03-26 | 2013-12-11 | 月島機械株式会社 | Method for producing paradichlorobenzene |
| JP5474389B2 (en) * | 2009-03-26 | 2014-04-16 | 月島機械株式会社 | Method for producing paradichlorobenzene |
-
1988
- 1988-08-05 JP JP63194383A patent/JPH0692331B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9598184B2 (en) | 2003-02-14 | 2017-03-21 | Eastman Chemical Company | Method for packaging fiber material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0245431A (en) | 1990-02-15 |
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