JPS63258436A - Production of para-dihalogenation benzene - Google Patents
Production of para-dihalogenation benzeneInfo
- Publication number
- JPS63258436A JPS63258436A JP62092737A JP9273787A JPS63258436A JP S63258436 A JPS63258436 A JP S63258436A JP 62092737 A JP62092737 A JP 62092737A JP 9273787 A JP9273787 A JP 9273787A JP S63258436 A JPS63258436 A JP S63258436A
- Authority
- JP
- Japan
- Prior art keywords
- reactor
- catalyst
- halogenating agent
- benzene
- lewis acid
- 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.)
- Pending
Links
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 238000006251 dihalogenation reaction Methods 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 230000002140 halogenating effect Effects 0.000 claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 21
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000010457 zeolite Substances 0.000 claims abstract description 21
- 238000005658 halogenation reaction Methods 0.000 claims abstract description 18
- 230000026030 halogenation Effects 0.000 claims abstract description 15
- 239000002841 Lewis acid Substances 0.000 claims description 13
- 150000007517 lewis acids Chemical class 0.000 claims description 13
- 239000000376 reactant Substances 0.000 claims description 7
- 239000007858 starting material Substances 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 abstract description 7
- 239000000460 chlorine Substances 0.000 abstract description 7
- 150000001555 benzenes Chemical class 0.000 abstract description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052794 bromium Inorganic materials 0.000 abstract description 4
- 239000011968 lewis acid catalyst Substances 0.000 abstract description 4
- 239000007795 chemical reaction product Substances 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 150000002505 iron Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000007789 gas Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- -1 iron halides Chemical class 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 241000220317 Rosa Species 0.000 description 2
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 2
- 229940117389 dichlorobenzene Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 235000014036 Castanea Nutrition 0.000 description 1
- 241001070941 Castanea Species 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000005171 halobenzenes Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- 239000002912 waste gas 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
皇栗よ■剋■分！
本発明は、種々の有機化合物を合成する際に原料物質と
して利用されるバラ−ジハロベンゼンの有利な製造方法
に関する。[Detailed Description of the Invention] Emperor Chestnut! The present invention relates to an advantageous method for producing bara-dihalobenzene, which is used as a raw material in the synthesis of various organic compounds.
従来技術
従来、バラ−ジハロベンゼンの製造法としては、塩化第
二鉄、五塩化アンチモン等のルイス酸を触媒として用い
て原料ベンゼンをハロゲン化する方法が知られているが
、この方法ではハロゲン化に用いたハロゲン化剤の反応
率をほとんど１００％までに高めることができるものの
、生成物として目的とするパラ置換体のほかにオルソ置
換体やトリハロゲン化ベンゼン等が副生ずるため、パラ
置換体生成の選択率が６０％程度に低いという問題があ
る。Prior Art Conventionally, as a method for producing dihalobenzene, a method is known in which raw benzene is halogenated using a Lewis acid such as ferric chloride or antimony pentachloride as a catalyst. Although the reaction rate of the halogenating agent used can be increased to almost 100%, in addition to the desired para-substituted product, ortho-substituted products and trihalogenated benzenes are produced as by-products, so the formation of para-substituted products is difficult. There is a problem that the selectivity is as low as about 60%.
また、近年、触媒として硫化鉄を用いる方法（特開昭５
０−６４２３１号）、セレンやセレン化合物を触媒とし
て用いる方法（特開昭５０−３４０１０号）等が提案さ
れているが、これらの方法においても目的のバラ置換体
生成の選択率が７０％程度にとどまる。In addition, in recent years, a method using iron sulfide as a catalyst (Japanese Unexamined Patent Publication No. 5
0-64231) and a method using selenium or a selenium compound as a catalyst (Japanese Unexamined Patent Publication No. 50-34010), but these methods also have a selectivity of about 70% for producing the desired rose substituted product. Stay in.
更に、最近、バラ置換体生成の選択率を高める方法とし
てゼオライトを触媒に用いる方法（例えば、特開昭５７
−７７６３１号、特開昭５９−１６３３２９号）が開示
されている。しかし、ゼオライトを触媒に用いる方法で
は、ルイス酸を触媒とする方法と比較すると、バラ置換
体生成の選択率は高いが、一方ハロゲン化剤の反応率が
ゼオライト触媒が新鮮な段階でも多少低いうえに、触媒
の長時間使用により反応率が急激に低下するという欠点
がみられる。Furthermore, recently, a method using zeolite as a catalyst has been proposed as a method of increasing the selectivity for the production of rose-substituted products (for example, JP-A-57
-77631, JP-A-59-163329) are disclosed. However, compared to the method using Lewis acid as a catalyst, the method using zeolite as a catalyst has a higher selectivity for the formation of a substituted substance, but on the other hand, the reaction rate of the halogenating agent is somewhat lower even when the zeolite catalyst is fresh. However, the disadvantage is that the reaction rate decreases rapidly when the catalyst is used for a long time.
したがって、ゼオライト触媒を用いてのバラ−ジハロベ
ンゼンの実際上の製造に際しては、未反応のハロゲン化
剤を回収して再利用するための工程を設ける必要があり
、プロセスが複雑になるのが避けられないという問題が
ある。Therefore, in the actual production of dihalobenzene using a zeolite catalyst, it is necessary to provide a step for recovering and reusing the unreacted halogenating agent, which avoids complicating the process. The problem is that there is no.
発明が解決Ｕようとず４４ｆｆ
本発明は、上述の状況に鑑みなされたものであって、バ
ラ置換体生成の選択率の高いゼオライト触媒を用い、し
かもハロゲン化剤の反応率、すなわち利用効率を高めて
バラ−ジハロベンゼンを有利に製造するだめの方法を提
供することを課題とする。The present invention has been made in view of the above-mentioned situation, and uses a zeolite catalyst with a high selectivity for producing a halogenating agent, and also improves the reaction rate of the halogenating agent, that is, the utilization efficiency. It is an object of the present invention to provide a method for producing baradihalobenzene in an advantageous manner.
以下本発明の詳細な説明する。The present invention will be explained in detail below.
光皿■檄戊
本発明の特徴は、出発物質としてのベンゼンをハロゲン
化してバラ−ジハロベンゼンを製造するにあたり、第１
反応器で出発物質としてのベンゼンをルイス酸型触媒を
用いてハロゲン化して主としてモノハロベンゼンからな
る反応物を得、該反応物をそれからルイス酸型触媒を除
去した後、第２反応器でゼオライト触媒を用いて更にハ
ロゲン化し、かつ該第２反応器から排出される排ガス中
に含まれる未反応のハロゲン化剤を上記第１反応器にお
けるハロゲン化のためのハロゲン化剤の少くとも一部と
して利用するために、上記排ガスを第１反応器に導入す
ることにある。A feature of the present invention is that in producing dihalobenzene by halogenating benzene as a starting material, the first
In a reactor, benzene as a starting material is halogenated using a Lewis acid type catalyst to obtain a reactant mainly consisting of monohalobenzene, which is then converted into zeolite after removing the Lewis acid type catalyst in a second reactor. further halogenating using a catalyst, and using the unreacted halogenating agent contained in the exhaust gas discharged from the second reactor as at least a part of the halogenating agent for halogenation in the first reactor; In order to utilize it, the waste gas is introduced into a first reactor.
１形】亡夫↓擾−茫孝ヅど〔段
本発明は、上述のように、原料ヘンゼン類のハロゲン化
を第１反応器と第２反応器の２段階で行うものであって
、第１反応器では原料ベンゼンをルイス酸型触媒の存在
下でハロゲン化する。ここで用いるルイス酸型触媒とし
ては、通常ハロゲン化触媒に用いられるものであって、
ハロゲン化鉄、ハロゲン化アンチモン、ハロゲン化アル
ミニウム等を例示し得る。Type 1] Dropped husband ↓ Turbula -Fumigate [Dan this invention, as described above, the halogenization of raw material henzene is performed in two stages, the first reactor and the second reactor, and the first. In the reactor, raw benzene is halogenated in the presence of a Lewis acid type catalyst. The Lewis acid type catalyst used here is one normally used for halogenation catalysts,
Examples include iron halides, antimony halides, and aluminum halides.
また、使用するハロゲン化剤は塩素又は臭素であって、
必要に応じ、これらは窒素のような不活性ガスで希釈し
てもよい。ハロゲン化反応は２０〜９０℃の温度、好ま
しくは３０〜７０°Ｃの温度で行うが、本発明では、こ
の第１反応器での反応を、ハロゲン化度が１．０種度以
下になるように制御することが好ましい。このことは、
次に述べるゼオライト触媒を用いてハロゲン化を行う第
２反応器において生成するバラ置換体の選択率を高める
ことを目的としていることによる。Further, the halogenating agent used is chlorine or bromine,
If necessary, these may be diluted with an inert gas such as nitrogen. The halogenation reaction is carried out at a temperature of 20 to 90°C, preferably 30 to 70°C, but in the present invention, the reaction in the first reactor is carried out so that the degree of halogenation is 1.0 degrees or less. It is preferable to control as follows. This means that
This is because the purpose is to increase the selectivity of the substituted substance produced in the second reactor which performs halogenation using the zeolite catalyst described below.
なお、ここでいう“ハロゲン化度”とは次式により定義
される。Note that the "degree of halogenation" herein is defined by the following formula.
（式中、ｎはＯ〜６の整数を表わす）
また、ここで用いる原料ベンゼンはベンゼン、モノクロ
ロベンゼンもしくはベンゼン、モノクロロベンゼン及び
ジクロロベンゼンの混合物を包含する。(In the formula, n represents an integer of O to 6.) Furthermore, the raw material benzene used herein includes benzene, monochlorobenzene, or a mixture of benzene, monochlorobenzene, and dichlorobenzene.
次に、本発明では、上記により第１反応器で原料ベンゼ
ンをハロゲン化して得た反応物から反応に用いたルイス
酸型触媒を除去した後、該反応物を第２反応器において
ゼオライト触媒を用いてハロゲン化する。ここで用いる
ゼオライト触媒としてはＡ型、Ｌ型、Ｘ型、Ｙ型等を例
示し得、これらは１種又は２種以上の金属イオンやプロ
トンで置換されていてもよい。使用するハロゲン化剤は
第１反応器と同様に塩素又は臭素であって、窒素のよう
な不活性ガスで希釈してもよい。Next, in the present invention, after removing the Lewis acid type catalyst used in the reaction from the reactant obtained by halogenating the raw material benzene in the first reactor, the reactant is transferred to the second reactor to halogenate the zeolite catalyst. halogenate using Examples of the zeolite catalyst used here include A type, L type, X type, Y type, etc., and these may be substituted with one or more types of metal ions or protons. The halogenating agent used is chlorine or bromine as in the first reactor, and may be diluted with an inert gas such as nitrogen.
また、反応は２０〜１１０℃の温度、好ましくは３０〜
９０°Ｃの温度で行う。Further, the reaction is carried out at a temperature of 20 to 110°C, preferably 30 to 110°C.
Carry out at a temperature of 90°C.
本発明では、この第２反応器における反応に際し、反応
器から排出される排ガスに含まれる未反応のハロゲン化
剤を再利用してその反応率を高める目的で、上記排ガス
（ハロゲン化剤とハロゲン化水素との混合物、もしくは
ハロゲン化剤を不活性ガスで希釈して用いた場合には更
に不活性ガスを含む）を、前記の第１反応器に導入して
該反応器における原料ベンゼンのハロゲン化に利用する
。In the present invention, during the reaction in the second reactor, the above exhaust gas (halogenating agent and halogen A mixture of hydrogen hydride (or a mixture containing an inert gas when the halogenating agent is diluted with an inert gas) is introduced into the first reactor to remove the halogen of the raw benzene in the reactor. Use for
また、上記排ガスの第１反応器への導入に際しては、必
要に応し、新しいハロゲン化剤を補給してもよい。Furthermore, when introducing the exhaust gas into the first reactor, new halogenating agent may be replenished as necessary.
なお、ゼオライト触媒を用いる第２反応器での反応に際
しては、該触媒は水分の存在を嫌うので反応器に仕込む
ベンゼン類の水分を１１００ｐｐ以下になるようにコン
トロールすることが好ましい。In the reaction in the second reactor using a zeolite catalyst, the catalyst dislikes the presence of water, so it is preferable to control the water content of the benzenes charged into the reactor to be 1100 pp or less.
また、本発明で用いる反応器は、第１反応器については
反応が液相で行われ、反応原料が十分混合されればその
型式は問わない。第２反応器についても同様であるが、
反応を気相で行う型式であってもよい。Furthermore, the type of reactor used in the present invention does not matter as long as the reaction is carried out in a liquid phase in the first reactor and the reaction raw materials are sufficiently mixed. The same applies to the second reactor, but
It may also be of a type in which the reaction is carried out in a gas phase.
上述したごとく、本発明においては、ベンゼン類のハロ
ゲン化を、ルイス酸型触媒を用いた第１反応器とゼオラ
イト触媒を用いた第２反応器でそれぞれ行うものである
が、これは、ゼオライト触媒は、ルイス酸型触媒と共存
させて反応を行うと、ゼオライト本来の触媒能を発揮し
難いという性質に基づいている。As mentioned above, in the present invention, benzenes are halogenated in the first reactor using a Lewis acid catalyst and the second reactor using a zeolite catalyst. This is based on the property that when a reaction is carried out in the coexistence of a Lewis acid type catalyst, it is difficult for zeolite to exhibit its inherent catalytic ability.
すなわち、ルイス酸型触媒によるハロゲン化とゼオライ
ト触媒によるハロゲン化を別々の反応器で行い、かつ第
２反応器から排出される未反応のハロゲン化剤を含む排
ガスを第１反応器に導入してハロゲン化反応に利用する
ことにより、各反応器で用いる上記各触媒の機能を十分
に発揮させて、目的とするバラ置換体であるパラ−ジハ
ロベンゼン生成の選択率及びハロゲン化剤の反応率の両
方を著しく高めることが可能となる。That is, halogenation using a Lewis acid type catalyst and halogenation using a zeolite catalyst are performed in separate reactors, and the exhaust gas containing the unreacted halogenating agent discharged from the second reactor is introduced into the first reactor. By using it in the halogenation reaction, the functions of each of the above-mentioned catalysts used in each reactor can be fully exhibited, and both the selectivity for producing para-dihalobenzene, which is the desired displacer, and the reaction rate of the halogenating agent. It becomes possible to significantly increase the
施例と発明の効果
以下に実施例を示して本発明とその効果を具体的に説明
する。EXAMPLES AND EFFECTS OF THE INVENTION The present invention and its effects will be specifically explained below with reference to Examples.
実施例１乃至６
■反応装置の仕様：
攪拌機、還流冷却管、温度計、ガス吹込管、試料採取管
を装備した内容積約２１の丸底フラスコＡとＢの２個を
用意し、フラスコＢの還流冷却管の出口をフラスコへの
ガス吹込管に接続させて直列に連設して、フラスコＢか
らの排ガスがフラスコＡに導入されるように配設した。Examples 1 to 6 ■Specifications of the reaction apparatus: Two round-bottomed flasks A and B each having an internal volume of about 21 cm were prepared, each equipped with a stirrer, a reflux condenser, a thermometer, a gas blowing tube, and a sample sampling tube. The outlet of the reflux condenser tube was connected to the gas blowing tube to the flask, and the flasks were connected in series so that exhaust gas from flask B was introduced into flask A.
また、この接続管の途中にガス試料採取管の分岐管並び
にハロゲン化剤を補給するための分岐管を設けた。なお
、この場合、Ｂのガス吹込管、ＢとＡの接続管に設置し
たハロゲン化剤補給用の分岐管にはそれぞれ流量計、流
量調節器を通してハロゲン化剤のボンベに接続した。上
記フラスコＡを第１反応器、フラスコＢを第２反応器と
してそれぞれ用い、両者ともに温度制御が可能な温浴上
にセットし、それぞれの還流冷却管には氷冷水を通して
冷却した。In addition, a branch pipe for the gas sampling pipe and a branch pipe for replenishing the halogenating agent were provided in the middle of this connecting pipe. In this case, the gas blowing pipe B and the branch pipe for replenishing the halogenating agent installed in the connecting pipes B and A were connected to a halogenating agent cylinder through a flow meter and a flow rate regulator, respectively. Flask A was used as the first reactor, and flask B was used as the second reactor, both of which were set on a temperature-controllable hot bath, and ice-cold water was passed through each reflux condenser tube for cooling.
■反応操作：
上記フラスコＡ、Ｂにそれぞれ表１に示した原料物質の
各１１を仕込み、第１反応器としてのフラスコＡには触
媒としての塩化第２鉄２０００ｐｐｍ。(2) Reaction operation: Each of the 11 raw materials shown in Table 1 was charged into flasks A and B, and 2000 ppm of ferric chloride as a catalyst was placed in flask A as the first reactor.
第２反応器としてのフラスコＢには触媒としてのゼオラ
イト（Ｌ型）５０ｇを加え、各フラスコに所定量（表１
参照）の塩素を吹き込み、反応温度７０℃に保ってそれ
ぞれハロゲン化を行った。50 g of zeolite (L type) as a catalyst was added to flask B as the second reactor, and a predetermined amount (Table 1) was added to each flask.
The halogenation was carried out by blowing in chlorine (see) and maintaining the reaction temperature at 70°C.
なお、フラスコＡには、フラスコＢよりの排ガス中の塩
素もしくは該排ガスとフラスコＡとＢと接続管に設けた
分岐管よりの補給塩素とを供給した。In addition, flask A was supplied with chlorine in the exhaust gas from flask B, or the exhaust gas and supplementary chlorine from a branch pipe provided between flasks A and B and a connecting pipe.
結果は表１に示すとおりである。The results are shown in Table 1.
実施例７
実施例５において、第１反応器としてのフラスコ八に触
媒として塩化第２鉄に代えて五塩化アンチモンを加える
ことを除いては、実施例５と同様にしてハロゲン化を行
った。その結果、フラスコＡよりの排ガス中の塩素濃度
は痕跡であって、フラスコＢにおけるパラ−ジクロロベ
ンゼン生成の選択率は８８．７％であった。Example 7 In Example 5, halogenation was carried out in the same manner as in Example 5, except that antimony pentachloride was added as a catalyst to flask No. 8 as the first reactor instead of ferric chloride. As a result, the concentration of chlorine in the exhaust gas from flask A was a trace, and the selectivity for producing para-dichlorobenzene in flask B was 88.7%.
実施例８乃至９
ハロゲン化剤として臭素を用い、実施例工並びに実施例
５に準じてそれぞれ反応を行った。Examples 8 to 9 Reactions were carried out according to Example 8 and Example 5 using bromine as a halogenating agent.
結果は表２に示すとおりである。The results are shown in Table 2.
上記表１及び表２にみられるとおり、第２反応器（フラ
スコＢ）より排出される未反応ハロゲン札割含有排ガス
を第１反応器（フラスコＡ）へ導入してハロゲン化反応
に利用することにより、第１反応器からの排ガス中の未
反応のハロゲン化剤は痕跡程度に減少する。すなわち、
本発明によるとハロゲン化剤の利用効率が高くなって、
反応率が実質上１００％に達する。As shown in Tables 1 and 2 above, the unreacted halogen-containing exhaust gas discharged from the second reactor (flask B) is introduced into the first reactor (flask A) and used for the halogenation reaction. As a result, unreacted halogenating agent in the exhaust gas from the first reactor is reduced to traces. That is,
According to the present invention, the utilization efficiency of the halogenating agent is increased,
The reaction rate reaches virtually 100%.
因に、ゼオライト触媒を用いた１段階でのハロゲン化で
は、反応条件により多少の違いがあるが、比較的良好な
条件下でも反応器からの排ガス中には１１０００ｐｐ程
度の未反応のハロゲン化剤が含まれている。Incidentally, in one-step halogenation using a zeolite catalyst, there are some differences depending on the reaction conditions, but even under relatively favorable conditions, about 11,000 pp of unreacted halogenating agent is left in the exhaust gas from the reactor. It is included.
また、表１及び２にみられるように、本発明によると第
２反応器におけるゼオライト触媒の有する機能を最大限
に利用して、目的とするパラ置換体であるパラ−ジハロ
ベンゼン生成の選択率を著しく高くすることが可能とな
る。Furthermore, as shown in Tables 1 and 2, according to the present invention, the functionality of the zeolite catalyst in the second reactor is fully utilized to increase the selectivity for producing para-dihalobenzene, which is the target para-substituted product. It is possible to increase the value significantly.
手続補正書
昭和６２年６月３日
特許庁審査 黒 １）明 雄 殿
１、事件の表示 昭和６２年特許願第９２７３７号２
、発明の名称 パラ−ジハロベンゼンの製造方法３、
補正をする者
事件との関係 特許出願人
名 称 （１１０）呉羽化学工業株式会社４、代理人
住 所 東京都港区東新橋２丁目７番７号新橋国際ビル
５、補正命令の日付 自 発
６、補正により増加する発明の数
７ 補正の対象 明 細 書 （凋９ゾ鼾）８
、補正の内容
明細書を下記のとおり補正する。Procedural amendment June 3, 1988 Examination by the Patent Office Black 1) Akio Yu 1, Indication of case Patent Application No. 92737, 1988 2
, Title of the invention Method for producing para-dihalobenzene 3,
Relationship with the case of the person making the amendment Patent applicant name (110) Kureha Chemical Industry Co., Ltd. 4, agent address 5 Shinbashi Kokusai Building, 2-7-7 Higashi-Shinbashi, Minato-ku, Tokyo, date of amendment order 6 , Number of inventions increased by amendment 7 Specification subject to amendment (凋9zosnoring) 8
, amend the statement of contents of the amendment as follows.
（１）第１４頁第８行に「実質上１００％」とあるを１
実質上略１００％」と補正する。(1) On page 14, line 8, change the phrase “substantially 100%” to 1.
"Substantially approximately 100%."
＝ ２−
手続補正書
昭和６３年２月１８日
特許庁長官 小 川 邦 夫 殿
１、事件の表示 昭和６２年特許願第９２７３７号２、
発明の名称 パラ−ジハロベンゼンの製造方法３、補正
をする者
事件との関係 特許出願人
名 称 （１１０）呉羽化学工業株式会社４、代理人
住 所 東京都港区東新橋２丁目７番７号新橋国際ビル
５、補正命令の日イ」 自 発
８、補正の内容
明細書を下記の如く補正する。= 2- Procedural amendment February 18, 1988 Director General of the Patent Office Kunio Ogawa 1, Indication of case Patent Application No. 92737 of 1988 2,
Title of the invention Process for producing para-dihalobenzene 3, Relationship to the amended case Patent applicant name (110) Kureha Chemical Industry Co., Ltd. 4, Agent address Shinbashi, 2-7-7 Higashi-Shinbashi, Minato-ku, Tokyo International Bill 5, Date of Order for Amendment A. Voluntary Issue 8, amend the statement of contents of the amendment as follows.
（１）特許請求の範囲を別紙のとおり補正する。(1) Amend the claims as shown in the attached sheet.
（２）第３頁第１２行に「反応率が急激に低下するとい
う欠点がみられる。」とあるを「反応率が急激に低下し
、多くの未反応ハロゲン化剤を排出するという欠点がみ
られる。ｊと補正する。(2) On page 3, line 12, the statement ``The disadvantage is that the reaction rate decreases rapidly.'' was replaced with ``The disadvantage is that the reaction rate decreases rapidly and a large amount of unreacted halogenating agent is discharged.'' It can be seen. Correct it as j.
（３）第３頁第１３行乃至第１７行に「したがって、ゼ
オライト触媒−−−−−−−−−一避けられないという
問題がある−」の記載を削除する。(3) On page 3, lines 13 to 17, the statement ``Therefore, there is an unavoidable problem with zeolite catalysts'' is deleted.
（４）第６頁第７行に「（式中、ｎはＯ〜６の整数を表
わす）」とあるを「（式中、ｎは０〜６Ｘはハロゲンを
表わす）」と補正する。(4) On page 6, line 7, the statement "(in the formula, n represents an integer from 0 to 6)" is corrected to "(in the formula, n represents 0 to 6X represents a halogen)".
（５）第６頁下から１０行に１−モノクロロベンゼン」
とあるを「モノハロヘンゼン」と補正する。(5) 1-monochlorobenzene in line 10 from the bottom of page 6.”
Correct the statement to "monohalohensen."
（６）第６頁下から１０行乃至９行に［モノクロロベン
ゼン及びジクロロベンゼン」とあるを「千ノハロヘンゼ
ン及びジハロヘンゼン」ト補正スる。(6) In lines 10 to 9 from the bottom of page 6, the words "monochlorobenzene and dichlorobenzene" have been corrected to "thousandohalohenzene and dihalohenzene."
（７）第７頁最終行に「ヘンセン類の水分を１１００ｐ
ｐ以下に」とあるを「ヘンセン類の水分は１１００ｐｐ
以下、ハロゲン化剤の水分は５ｏｐｐｍ以下に」と補正
する。(7) On the last line of page 7, write ``1100 p of Hensen's moisture.''
``The water content of Hensen's is 1100 pp or less.''
Hereinafter, the water content of the halogenating agent will be corrected to 5 oppm or less.
（８）第１０頁第８行に「２０００ｐｐｍ Ｊとあるを
［１，７〜２．３ｇＪと補正する。(8) On page 10, line 8, "2000 ppm J is corrected to [1.7 to 2.3 gJ.
（９）第１１頁の表１を別紙のとおり補正する。(9) Table 1 on page 11 will be amended as shown in the attached sheet.
００）第１３頁の表２を別紙のとおり補正する。00) Amend Table 2 on page 13 as shown in the attached sheet.
２、特許請求の範囲
（１）出発物質とし゛このベンゼンをハロゲン化し７で
パラ−ジハロベンゼンを製造するにあたり、第１反応器
で出発物質としてのベンゼンをルイス酸型触媒を用いて
ハロゲン化して主としてモノハロベンゼンからなる反応
物を得、該反応物をそれからルイス酸型触媒を除去した
後、第２反応器でゼオライＩ・触媒を用いて更にハロゲ
ン化し、かつ該第２反応器から排出される排ガス中に含
まれる未反応のハロゲン化剤を上記第１反応器における
ハロゲン化のためのハロゲン化剤の少（とも−・部とし
て利用するために、七記排ガスを第１反応器に導入する
ことを特徴とするバラ−ジハロベンゼンの製造方法。2. Claims (1) In producing para-dihalobenzene by halogenating this benzene as a starting material in step 7, benzene as a starting material is halogenated using a Lewis acid type catalyst in the first reactor to produce mainly mono- A reactant consisting of halobenzene is obtained, the reactant is further halogenated after removing the Lewis acid type catalyst in a second reactor using a zeolite I catalyst, and the exhaust gas discharged from the second reactor In order to utilize the unreacted halogenating agent contained in the halogenating agent as a small portion of the halogenating agent for halogenation in the first reactor, A method for producing rose dihalobenzene, characterized by:
（２）第１反応器におりるハロゲン化度を見−以下に制
御する特許請求の範囲第（１）項記載の製造方法。(2) The production method according to claim (1), wherein the degree of halogenation in the first reactor is controlled to be below.
Claims (2)
−ジハロベンゼンを製造するにあたり、第１反応器で出
発物質としてのベンゼンをルイス酸型触媒を用いてハロ
ゲン化して主としてモノハロベンゼンからなる反応物を
得、該反応物をそれからルイス酸型触媒を除去した後、
第２反応器でゼオライト触媒を用いて更にハロゲン化し
、かつ該第２反応器から排出される排ガス中に含まれる
未反応のハロゲン化剤を上記第１反応器におけるハロゲ
ン化のためのハロゲン化剤の少くとも一部として利用す
るために、上記排ガスを第１反応器に導入することを特
徴とするパラ−ジハロベンゼンの製造方法。(1) In producing para-dihalobenzene by halogenating benzene as a starting material, benzene as a starting material is halogenated using a Lewis acid type catalyst in the first reactor to produce a reactant mainly consisting of monohalobenzene. and after removing the Lewis acid type catalyst from the reactant,
The halogenating agent is further halogenated using a zeolite catalyst in a second reactor, and the unreacted halogenating agent contained in the exhaust gas discharged from the second reactor is used for halogenating in the first reactor. A method for producing para-dihalobenzene, characterized in that said exhaust gas is introduced into a first reactor for use as at least a part of said exhaust gas.
下に制御する特許請求の範囲第（１）項記載の製造方法
。(2) The manufacturing method according to claim (1), wherein the degree of halogenation in the first reactor is controlled to about 1.0 or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62092737A JPS63258436A (en) | 1987-04-15 | 1987-04-15 | Production of para-dihalogenation benzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62092737A JPS63258436A (en) | 1987-04-15 | 1987-04-15 | Production of para-dihalogenation benzene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63258436A true JPS63258436A (en) | 1988-10-25 |
Family
ID=14062729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62092737A Pending JPS63258436A (en) | 1987-04-15 | 1987-04-15 | Production of para-dihalogenation benzene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63258436A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009102275A (en) * | 2007-10-24 | 2009-05-14 | Tsukishima Kikai Co Ltd | METHOD FOR PRODUCING p-DICHLOROBENZENE |
| WO2010047392A1 (en) * | 2008-10-24 | 2010-04-29 | 東ソー株式会社 | PROCESS FOR PRODUCING p-DICHLOROBENZENE |
| JP2010229059A (en) * | 2009-03-26 | 2010-10-14 | Tsukishima Kikai Co Ltd | Method for producing para-dichlorobenzene |
| JP2010229060A (en) * | 2009-03-26 | 2010-10-14 | Tsukishima Kikai Co Ltd | Method for producing para-dichlorobenzene |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59163329A (en) * | 1983-03-07 | 1984-09-14 | Ihara Chem Ind Co Ltd | Production of dihalogenated benzene |
-
1987
- 1987-04-15 JP JP62092737A patent/JPS63258436A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59163329A (en) * | 1983-03-07 | 1984-09-14 | Ihara Chem Ind Co Ltd | Production of dihalogenated benzene |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009102275A (en) * | 2007-10-24 | 2009-05-14 | Tsukishima Kikai Co Ltd | METHOD FOR PRODUCING p-DICHLOROBENZENE |
| WO2010047392A1 (en) * | 2008-10-24 | 2010-04-29 | 東ソー株式会社 | PROCESS FOR PRODUCING p-DICHLOROBENZENE |
| JP2010120934A (en) * | 2008-10-24 | 2010-06-03 | Tosoh Corp | Process for producing p-dichlorobenzene |
| CN102197010A (en) * | 2008-10-24 | 2011-09-21 | 东曹株式会社 | Process for producing p-dichlorobenzene |
| US8524957B2 (en) | 2008-10-24 | 2013-09-03 | Tosoh Corporation | Process for producing p-dichlorobenzene |
| JP2010229059A (en) * | 2009-03-26 | 2010-10-14 | Tsukishima Kikai Co Ltd | Method for producing para-dichlorobenzene |
| JP2010229060A (en) * | 2009-03-26 | 2010-10-14 | Tsukishima Kikai Co Ltd | Method for producing para-dichlorobenzene |
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