JP2558149B2 - Chlorination of benzene or mono-substituted benzene - Google Patents
Chlorination of benzene or mono-substituted benzeneInfo
- Publication number
- JP2558149B2 JP2558149B2 JP63194384A JP19438488A JP2558149B2 JP 2558149 B2 JP2558149 B2 JP 2558149B2 JP 63194384 A JP63194384 A JP 63194384A JP 19438488 A JP19438488 A JP 19438488A JP 2558149 B2 JP2558149 B2 JP 2558149B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid
- gas
- benzene
- reactor
- mono
- 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
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims description 59
- -1 mono-substituted benzene Chemical class 0.000 title claims description 23
- 238000005660 chlorination reaction Methods 0.000 title claims description 21
- 239000007788 liquid Substances 0.000 claims description 73
- 239000010457 zeolite Substances 0.000 claims description 51
- 229910021536 Zeolite Inorganic materials 0.000 claims description 49
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 49
- 239000003054 catalyst Substances 0.000 claims description 45
- 238000000926 separation method Methods 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 24
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 12
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 230000001174 ascending effect Effects 0.000 claims description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000006227 byproduct Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 239000000460 chlorine Substances 0.000 description 11
- 229910052801 chlorine Inorganic materials 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000000630 rising effect Effects 0.000 description 9
- 150000001555 benzenes Chemical class 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical class ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 150000004996 alkyl benzenes Chemical class 0.000 description 3
- 238000011001 backwashing Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 3
- 229910001950 potassium oxide Inorganic materials 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- IGYCPGJYQTZLOJ-UHFFFAOYSA-N 1,2,3,3,4-pentachlorocyclohexene Chemical compound ClC1CCC(Cl)=C(Cl)C1(Cl)Cl IGYCPGJYQTZLOJ-UHFFFAOYSA-N 0.000 description 2
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
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 having a para-position substituted with chlorine, which is useful as a raw material when synthesizing various organic compounds,
It relates to a continuous chlorination method for producing from benzene or mono-substituted benzene and chlorine gas using a zeolite catalyst.
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、オルト置換体や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KL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 and trichlorobenzene are by-produced, and the selectivity of para-substituted product formation is about 60% at most. As a method for increasing the selectivity of a parachlorobenzene derivative, Japanese Patent Laid-Open No. 163329/1984 discloses that L is used as a catalyst.
Methods using type zeolites are disclosed. There, the case where the L-type zeolite as a catalyst uses a KL-type zeolite having a potassium ion as a cation capable of exchanging ions, for example, the selectivity of paradichlorobenzene reaches 90% or more. However,
When chlorinating benzene or mono-substituted benzene using KL-type zeolite, when a newly prepared KL-type zeolite is used as a catalyst, a para-substituted product can be obtained with high reaction rate and high selectivity, When the catalyst 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 odorous polychlorinated adducts or substituted chlorinated substances 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. By using the L-type zeolite in an amount of wt%, it has been possible to remarkably suppress a decrease in the reaction rate due to 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 prepared in this way is used, and the starting material benzene or mono-substituted benzene and chlorine gas are increased using a liquid external circulation gas lift type reactor for continuous operation. When chlorinated by supplying from the bottom of the pipe, polychlorinated adducts such as pentachlorocyclohexene, which has an offensive odor, are by-produced as a selectivity of 0.2 mol% to 0.6 mol%, and like chlorinated 1,2,4-trichlorobenzene. A polychlorinated substitute is also produced as a by-product of 0.3 mol% to 1.2 mol%. Further, when the raw material mono-substituted benzene 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 gas phase reaction, it is described in JP-A-61-171444 that polychlorinated adducts decrease the activity of the zeolite catalyst over time, but the same applies to 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、液外部循環ガスリフト型反応器を
用いベンゼン又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抑制できる塩素化方
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 chlorinate benzene or mono-substituted benzene with chlorine gas in the presence of a zeolite catalyst using a liquid external circulation gas lift type reactor. A polychlorinated adduct such as pentachlorocyclohexene, a polychlorinated substitute such as 1,2,4-trichlorobenzene, and a chlorination method capable of suppressing by-products of side chain chlorinated alkylbenzenes are provided. Especially.
課題を解決するための手段 本発明者等は、液外部循環ガスリフト型反応器を用い
てゼオライト触媒の存在下、ベンゼン又はモノ置換ベン
ゼンの塩素化の際の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突き
止め、塩素ガスを該反応器上部の気液分離槽に導入し、
液循環のためには副生する塩化水素ガスの一部を、該反
応器の上昇管の下部に導入することにより、上記副生物
の抑制に成功し、本発明を完成するに至った。Means for Solving the Problems The present inventors have used a liquid external circulation gas lift type reactor in the presence of a zeolite catalyst to produce the above-mentioned byproduct during chlorination of benzene or mono-substituted benzene by introducing chlorine gas. Was found to increase when locally present in high concentration, chlorine gas was introduced into the gas-liquid separation tank above the reactor,
By introducing a part of hydrogen chloride gas produced as a by-product for liquid circulation into the lower part of the rising pipe of the reactor, the above-mentioned by-products were successfully suppressed, and the present invention was completed.
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抑制しなが
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. The present invention relates to a method for producing a benzene derivative having a para-position substituted with chlorine at a high reaction rate and a high selectivity while suppressing the generation of a substitution product.
本発明の構成上の特徴は、ベンゼン又はモノ置換ベン
ゼンをゼオライト触媒の存在下、塩素ガスにより液相で
塩素化するに当り、上昇管、気液分離槽、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、塩素ガスを気液
分離槽に供給し、かつ、気液分離槽より排出される塩化
水素ガスの一部を上昇管下部に導入すると共に、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、分離液に精製工程に送り、ゼオライト
触媒を反応器に戻すことにある。A structural feature of the present invention is that when benzene or mono-substituted benzene is chlorinated in the liquid phase by chlorine gas in the presence of a zeolite catalyst, it comprises an ascending pipe, a gas-liquid separation tank, and a descending pipe, and has a cooling means. Using a device having at least a liquid external circulation gas lift type reactor attached to an ascending pipe and / or a descending pipe, and a solid-liquid separator, benzene or monosubstituted benzene is supplied to any position of the device, and chlorine gas is supplied. Is supplied to the gas-liquid separation tank, and part of the hydrogen chloride gas discharged from the gas-liquid separation tank is introduced into the lower part of the rising pipe, and the reaction liquid extracted from the reactor is introduced into the solid-liquid separator. The purpose is to separate the zeolite catalyst, send it to the separation liquid in the purification process, and 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装置において、液外部循環ガスリ
フト型の反応器は、上昇管１、気液分離槽２及び下降管
３よりなり、冷却手段が上昇管及び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４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,
It shows the case of chlorination using a continuous chlorination device.
In the apparatus used in the present invention, the liquid external circulation gas lift type reactor comprises an ascending pipe 1, a gas-liquid separation tank 2 and a descending pipe 3, and a cooling means is attached to one or both of the ascending pipe and the descending pipe. . In the case of FIG. 1, the cooling means 4 is attached to the downcomer pipe.
本発明において用いる液外部循環ガスリフト型の反応
器の気液分離槽は、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、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。液深は浅すぎと未反応塩素が多
くなるので、好ましくは30cm以上にする。また、反応液
の循環の推進力となる塩化水素ガス供給量は、上昇管の
空塔速度が0.01m/sec以上、好ましくは0.1〜5m/sceにな
る量に決められる。The gas-liquid separation tank of the liquid external circulation gas lift type reactor used in the present invention has a cross-sectional area of at least 2 times or more, preferably 30 to 500 times the cross-sectional area of the rising pipe, and the superficial velocity of chlorine gas supplied. Is selected to be 1 m / sec or less, preferably 0.1 m / sec or less. If the liquid depth is too shallow, unreacted chlorine will increase, so it is preferably 30 cm or more. The supply amount of hydrogen chloride gas, which is the driving force for the circulation of the reaction solution, is determined so that the superficial velocity of the rising pipe is 0.01 m / sec or more, preferably 0.1 to 5 m / sce.
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官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-purpose heat exchanger by external circulation of the liquid in order to remove 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、布又はセラミックよりなる円筒状
材を内在し、加圧逆洗可能な密閉型過器が特に好まし
い。第１図の場合は、密閉型の過器が使用されてい
る。又、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撹拌槽６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, etc. are used, but the vessel is preferably used. As the filter, for example, a closed filter containing a cylindrical material made of cloth or ceramic and capable of backwashing under pressure is particularly preferable. In the case of FIG. 1, a hermetically sealed reactor is used. Further, FIG. 1 shows a case where the zeolite catalyst separated by the filter is in the form of a lump, and a stirring tank 6 is provided for making the separated lump of the zeolite into a slurry.
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.
Examples include chlorobenzene, bromobenzene, toluene and anisole.
原料ベンゼン又はモノ置換ベンゼンは、予め脱水器17
で水分100ppm（重量）以下、好ましくは10ppm（重量）
以下にな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。The raw material benzene or mono-substituted benzene can be used in
Water content is 100ppm (weight) or less, preferably 10ppm (weight)
It is dehydrated so that As the water content increases, the amount of polychlorinated adducts of benzene or mono-substituted benzene and the polychlorinated substitution products increases sharply.
脱水処理さたベンゼン又はモノ置換ベンゼンは連続塩
素化装置に供給されるが、反応器に直接供給されてもよ
く、又、過器５や撹拌槽６に供給されてもよい。第１
図においては、反応器の上昇管１の下部より連続的に供
給される。The dehydrated benzene or mono-substituted benzene is supplied to the continuous chlorination device, but may be directly supplied to the reactor, or may be supplied to the reactor 5 or the stirring tank 6. First
In the figure, it is continuously supplied from the lower part of the rising pipe 1 of the reactor.
一方、塩素ガスは、気液分離槽２の底部の多孔管より
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、モノ置換ベンゼン誘導体に対しては、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。On the other hand, chlorine gas is supplied from the perforated pipe at the bottom of the gas-liquid separation tank 2. 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 in a molar ratio for mono-substituted benzene derivatives and 1.5 to 1.7 in a molar ratio for benzene.
Is.
ゼオライト触媒は、予め所定濃度になる量を、気液分
離槽２に仕込まれる。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16で測定できる。勿論、ゼオライト触媒を
連続的または間欠的に供給し、使用済みゼオライトを連
続的または間欠的に抜き出して、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 advance in the gas-liquid separation tank 2 in an amount so as to have a predetermined concentration. During operation, a reaction liquid containing a zeolite catalyst at a predetermined concentration circulates in the reactor, and the circulating liquid amount can be measured by the vortex flowmeter 16. Of course, it is preferable to continuously or intermittently supply the zeolite catalyst and continuously or intermittently withdraw the used zeolite to maintain the zeolite catalyst at a predetermined concentration.
ゼオライト触媒は、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。反応液におけるゼオライト濃度
は、0.1〜10重量％、好ましくは1.5〜３重量％である。
ゼオライト触媒濃度が高くなると、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。The zeolite catalyst is preferably an L-type zeolite having a potassium content of 6 to 14% by weight, preferably 8 to 12% by weight, as potassium oxide. The zeolite concentration in the reaction solution is 0.1 to 10% by weight, preferably 1.5 to 3% by weight.
When the zeolite catalyst concentration is high, the reaction rate of chlorine is high, but the by-product of polychlorine adduct is increased, and when the concentration is too low, the chlorine reaction rate is low, and the polychlorine adduct and polychlorine substitution product are low. There are many by-products.
塩素化反応により生成した塩化水素ガスは、気液分離
槽２の上端部より冷却器14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15で所定圧に調整されて排
出される。塩化水素ガスの一部はパイプ18を通って圧縮
機19で加圧され、反応器下部、例えば上昇管１の下部に
導入され、反応液の循環の推進力となる。この循環のた
めの塩化水素ガス量は、上昇管１の空塔速度が0.01m/se
c以上、好ましくは0.1〜5m/secになる量に決められる。
残りの塩化水素ガスは、排ガス処理工程に送られる。The hydrogen chloride gas generated by the chlorination reaction passes through the cooler 14 from the upper end of the gas-liquid separation tank 2, is adjusted to a predetermined pressure by the pressure adjusting valve 15 according to the signal information shown by the dotted line in the figure, and is discharged. It A part of the hydrogen chloride gas is pressurized by the compressor 19 through the pipe 18 and introduced into the lower part of the reactor, for example, the lower part of the rising pipe 1, and serves as a driving force for circulating the reaction solution. The amount of hydrogen chloride gas for this circulation is 0.01 m / se if the superficial velocity of the rising pipe 1 is 0.01 m / se.
The amount is determined to be c or more, preferably 0.1 to 5 m / sec.
The remaining hydrogen chloride gas is sent to the exhaust gas treatment process.
反応温度は、気液分離槽２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４で冷却
することによって調整される。冷却手段４としては、例
えば、多管式熱交換器が用いられる。The reaction temperature is 50 to 100 in the gas-liquid separation tank 2.
It is adjusted by cooling by the cooling means 4 so that the temperature becomes ℃, preferably 60 to 80 ℃. As the cooling means 4, for example, a multi-tube heat exchanger is used.
反応液の一部は、圧力差により気液分離槽２より過
器５に送られる。過器における過は、気液分離槽２
と分離液（液）抜出しライン13との圧力差により行わ
れる。したがって、液抜出しライン13の内圧は、通
常、大気圧程度であるので、気液分離槽２の圧力は、0.
5〜5kg/cm2G、好ましくは１〜3kg/cm2Gに保たれる。
過器５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13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５による過中は、バルブ７及
び８を開き、バルブ９、10、11及び12は閉められてい
る。一定時間過した後、バルブ７及び８を閉め、バル
ブ11より窒素によって約6kg/cm2Gに加圧した後、バルブ
11を閉め、バルブ９を数秒間開いて、過器５の上部に
溜まっている液で加圧逆洗し、炉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５の底部に溜まっているゼオライト触媒を撹
拌槽６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６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10から
反応器の気液分離槽に戻される。加圧逆洗後、バルブ12
を数秒間開いて、過器５内圧を気圧分離槽２内圧より
低くして過を再開する。気液分離槽２の液面調節は、
液面調節弁も兼ねるバルブ７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で行われる。この様
な過器の加圧逆洗を一定時間ごと、好ましくは20〜60
分ごとに自動的に繰り返すことにより、反応器内のゼオ
ライト触媒濃度を略一定に保つことができる。Part of the reaction liquid is sent to the evaporator 5 from the gas-liquid separation tank 2 due to the pressure difference. A gas-liquid separation tank 2
And the separation liquid (liquid) withdrawal line 13 for the pressure difference. Therefore, since the internal pressure of the liquid extraction line 13 is usually about atmospheric pressure, the pressure in the gas-liquid separation tank 2 is 0.
It is kept at 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 5 is sent to the purification step for separating the target product via the separation liquid withdrawing line 13. During the pass by the pass switch 5, the valves 7 and 8 are opened and the valves 9, 10, 11 and 12 are closed. After a certain period of time, close valves 7 and 8 and pressurize with valve 11 to about 6 kg / cm 2 G with nitrogen, then
11 is closed, valve 9 is opened for a few seconds, and pressure backwashing is performed with the liquid accumulated in the upper part of the reactor 5 to peel off the zeolite catalyst adhering to the furnace material, and at the same time, it is peeled off in the previous excess. The zeolite catalyst accumulated at the bottom of the evaporator 5 is sent to the stirring tank 6. The zeolite catalyst sent out is agglomerated as a peeling piece, and thus is dispersed in a slurry in the stirring tank 6. This slurry liquid is returned from the valve 10 to the gas-liquid separation tank of the reactor during the period. After pressure backwash, valve 12
Is opened for several seconds to lower the internal pressure of the overpressure device 5 below the internal pressure of the atmospheric pressure separation tank 2 and restart the overpressure. Liquid level adjustment of the gas-liquid separation tank 2
This is performed by automatically opening and closing the valve 7, which also functions as a liquid level control valve, according to the signal information shown by the dotted line in the figure. The pressure backwashing of such a vessel is performed at regular intervals, preferably 20 to 60.
By repeating automatically every minute, the concentration of the zeolite catalyst in the reactor can be kept substantially constant.
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0.02
モル％以下、多塩素置換物は0.3モル％以下となる。ま
た、ト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 have a salinity of 1.
When the reaction solution chlorinated from 5 to 1.7 and other mono-substituted benzene to a chlorination degree of 0.5 to 0.7 is supplied to the reactor, the chlorine reaction rate is 99.
% 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 0.02
Mol% or less, and polychlorinated substitutes are 0.3 mol% or less. In addition, the amount of side-chain chloride by-products when an alkylbenzene such as toluene is used as a raw material is also 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図においては、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 above-mentioned FIG. 1, a multi-tube heat exchanger using 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50
μｍ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くなる。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、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
することができるので、多孔質のセラミックよりなる
材を使用するのが好ましい。In the present invention, it is composed of crystal particles of about 0.3 μm 50
Zeolite, which is agglomerated particles having a size of μm or less, is used as a catalyst, but when an excess vessel is used as a solid-liquid separator for separating the catalyst from the reaction solution, depending on the material used, the zeolite fine particles easily leak into the solution. For example, when the product obtained by the method of the present invention is paradichlorobenzene, after crystallizing paradichlorobenzene from the liquid, a continuous multistage melt refining apparatus (for example, a crystal refining apparatus described in JP-B-47-40621) If fine particles of the zeolite catalyst leak into the solution during dissolution and purification, they remain in the purified paradichlorobenzene, which is not preferable. Such a problem can be avoided by using a material made of porous ceramics, and therefore it is preferable to use a material made of porous ceramics.
また、本発明の方法では、液外部循環ガスリフト型の
反応器を使用することにより、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 a 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 depositing. While suppressing the by-product of polychlorinated adducts and substituted polychlorinated compounds, and by combining with a solid-liquid separator and a stirring tank, produce a benzene derivative in which the para position is chlorinated stably for a long period of time. be able to.
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4.3cm、長さ6mの上昇管、内径60cm、直胴部長さ
1.5mの気液分離槽、及び内径20.2mm、長さ5mの冷却管３
本を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図に示されるような液外部循環ガスリフト型の反応
器を用い、上昇管下部より含水率10ppm以下のクロロベ
ンゼンを44kg/hrで上昇管下部に供給し、塩素ガスを17
〜18kg/hrで気液分離槽に供給し、気液分離槽より排出
される塩化水素ガスのうち、5.8kg/hrを圧縮機により加
圧し、上昇管の下部に導入して、3.4m3/hrで反応液を循
環させた。気液分離槽における反応温度が70℃になるよ
うに下降管で冷却し、気液分離槽の圧力を1.5kg/cm2Gに
調節した。気液分離槽より塩化度1.62〜1.63の反応液を
気液分離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気液分離
槽に戻し、循環使用した。Example 1 4.3 cm inner diameter, 6 m long riser, 60 cm inner diameter, straight body length
1.5m gas-liquid separation tank and cooling pipe 3 with an inner diameter of 20.2mm and a length of 5m
Using a liquid external circulation gas lift type reactor as shown in Fig. 1 consisting of a downcomer having a multi-tube heat exchanger equipped with a book, 44 kg / ch of chlorobenzene with a water content of 10 ppm or less Supply chlorine gas to the bottom of the riser for 17 hours and supply chlorine gas to 17
It is supplied to the gas-liquid separation tank at ~ 18 kg / hr, and of the hydrogen chloride gas discharged from the gas-liquid separation tank, 5.8 kg / hr is pressurized with a compressor and introduced into the lower part of the rising pipe to produce 3.4 m 3 The reaction solution was circulated at / hr. It was cooled by a downcomer so that the reaction temperature in the gas-liquid separation tank was 70 ° C, and the pressure in the gas-liquid separation tank was adjusted to 1.5 kg / cm 2 G. A reaction liquid with a salinity of 1.62 to 1.63 is extracted from the gas-liquid separation tank so that the liquid surface of the gas-liquid separation tank is constant, and a cylinder made of porous silicon carbide with an average pore diameter of 10 μm, an outer diameter of 7 cm, an inner diameter of 4 cm, and a length of 50 cm. The zeolite material was sent to the three internal vessels, and the zeolite catalyst and the reaction solution were separated. Overkill
Pressure backwash with nitrogen gas at a pressure of 6 kg / cm 2 G every 30 minutes,
The zeolite catalyst was slurried in a stirring tank, returned to the gas-liquid separation tank, and reused.
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
うに反応開始前に気液分離槽に投入して用いた。The zeolite catalyst used was potassium oxide having a potassium content of 11.8% by weight of L-type zeolite of 0.1 mmHg, 150
It was dried at ℃ for 24 hours, and put into a gas-liquid separation tank before use 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２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 2 shows the concentration of the zeolite catalyst in the liquid after 50 hours of continuous chlorination and 10 minutes after the start of the chlorination. What is the concentration of zeolite catalyst in the liquid? 500 ml of the liquid was heated in a nitrogen stream at 100 ° C. for 2 hours, then at 200 ° C. for 1 hour, and then at 500 ° C. for 2 hours, and the residue was calculated as a zeolite catalyst.
実施例２ シリコーンカーバイド製材を、通気度1.5cm2/cm2・
sec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
２表に示す。 Example 2 A silicone carbide lumber was used to obtain an air permeability of 1.5 cm 2 / cm 2 ·.
Continuous chlorination was carried out under the same conditions as in Example 1 except that sec polypropylene cloth was used. Table 2 shows the concentration of the zeolite catalyst in the liquid after 50 hours of continuous chlorination and 10 minutes after the start of the continuous chlorination.
比較例１ 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、塩化水素ガスの導入を行わない以外は、
実施例１と同様な条件で塩素化した。液循環流量は3.2m
3/hrであった。結果を第３表に示す。 Comparative Example 1 Using the same reactor as in Example 1, except that chlorine gas was supplied from the lower part of the rising pipe and hydrogen chloride gas was not introduced,
Chlorination was carried out under the same conditions as in Example 1. Liquid circulation flow rate is 3.2m
It was 3 / hr. The results are shown in Table 3.
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、塩素ガスを気液分離槽に供給すると共に、副生する
塩化水素ガスの一部を反応器下部に導入することによ
り、塩化水素ガスが、反応液の循環の推進力となり、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、バラ
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 chlorine gas is supplied to the gas-liquid separation tank, and part of hydrogen chloride gas produced as a by-product is introduced into the lower part of the reactor. By doing so, hydrogen chloride gas acts as a driving force for the circulation of the reaction solution, and suppresses by-products of polychlorine adducts and polychlorine substitutions, and stabilizes the benzene derivative in which the para position is replaced with chlorine for a long period of time. Can be manufactured. Therefore, in the present invention, in order to produce a benzene derivative in which the bulk position is substituted with chlorine,
This is an extremely useful method industrially.
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……気液分離機、３……下降管、４…
…冷却手段、５……過器、６……撹拌槽、７、８、
９、10、11、12……バルブ、13……分離液抜出しライ
ン、14……冷却器、15……圧力調整弁、16……渦流量
計、17……脱水器、18……パイプ、19……圧縮機。FIG. 1 is a process drawing showing an example of the process of the present invention. 1 ... ascending pipe, 2 ... gas-liquid separator, 3 ... descending pipe, 4 ...
… Cooling means, 5 …… Transmitter, 6 …… Stirring tank, 7,8,
9、10、11、12 …… Valve, 13 …… Separated liquid extraction line, 14 …… Cooler, 15 …… Pressure adjusting valve, 16 …… Vortex flowmeter, 17 …… Dehydrator, 18 …… Pipe, 19 ... Compressor.
───────────────────────────────────────────────────── 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 Ｃ０７Ｃ 43/225 7419−4Ｈ Ｃ０７Ｃ 43/225 Ｂ // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C07C 43/225 7419-4H C07C 43/225 B // C07B 61/00 300 C07B 61/00 300
Claims (3)
ト触媒の存在下、塩素ガスにより液相で塩素化するに当
り、上昇管、気液分離槽、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、塩素ガスを気液分離槽に供給
し、かつ、気液分離槽より排出される塩化水素ガスの一
部を反応器下部に導入すると共に、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、分離液を精製工程に送り、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又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, it comprises an ascending pipe, a gas-liquid separation tank, and a descending pipe, and a cooling means is an ascending pipe and / or Alternatively, an apparatus having at least a liquid external circulation gas lift type reactor attached to a downcomer and a solid-liquid separator is used to supply benzene or mono-substituted benzene to any position of the apparatus, and chlorine gas is separated into gas and liquid. A portion of the hydrogen chloride gas supplied to the tank and discharged from the gas-liquid separation tank is introduced into the lower part of the reactor, and the reaction liquid extracted from the reactor is introduced into the solid-liquid separator to separate the zeolite catalyst. Then, the separated liquid is sent to the refining step, and the zeolite catalyst is returned to the reactor, which is a method for chlorinating benzene or mono-substituted benzene.
密閉型過器である請求項（１）記載の塩素化方法。2. The chlorination method according to claim 1, wherein the solid-liquid separator is a closed type reactor capable of intermittent pressure backwash.
材を有する過器である請求項（１）に記載の塩素化
方法。3. The chlorination method according to claim 1, wherein the solid-liquid separator is a filter having a material made of porous ceramics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63194384A JP2558149B2 (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 |
|---|---|---|---|
| JP63194384A JP2558149B2 (en) | 1988-08-05 | 1988-08-05 | Chlorination of benzene or mono-substituted benzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0245432A JPH0245432A (en) | 1990-02-15 |
| JP2558149B2 true JP2558149B2 (en) | 1996-11-27 |
Family
ID=16323704
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63194384A Expired - Lifetime JP2558149B2 (en) | 1988-08-05 | 1988-08-05 | Chlorination of benzene or mono-substituted benzene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2558149B2 (en) |
-
1988
- 1988-08-05 JP JP63194384A patent/JP2558149B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0245432A (en) | 1990-02-15 |
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