JPH0625081B2 - Method for producing paradibromobenzene - Google Patents
Method for producing paradibromobenzeneInfo
- Publication number
- JPH0625081B2 JPH0625081B2 JP60233307A JP23330785A JPH0625081B2 JP H0625081 B2 JPH0625081 B2 JP H0625081B2 JP 60233307 A JP60233307 A JP 60233307A JP 23330785 A JP23330785 A JP 23330785A JP H0625081 B2 JPH0625081 B2 JP H0625081B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- dibromobenzene
- type zeolite
- benzene
- 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、アラミド系繊維の原料であるパラフエニレン
ジアミンの中間原料として、また、各種耐熱性樹脂の原
料として有用なパラジブロムベンゼンの製法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a process for producing paradibromobenzene useful as an intermediate raw material for paraphenylenediamine, which is a raw material for aramid fibers, and as a raw material for various heat-resistant resins. Regarding
（従来の技術） パラジブロムベンゼンの製造法としては、ベンゼンまた
はブロムベンゼンを、臭化鉄、臭化アルミニウム等のル
イス酸触媒の存在下に液相において臭素化する方法（フ
イザー最新有機化学III４７ページ）や、ベンゼンまた
はブロムベンゼンを液相において鉄イオンまたは銅イオ
ンを含む水性液の存在下で、臭素と酸素を用いて酸化的
に臭素化する方法（特開昭４９−２０１２６号）が知ら
れている。(Prior Art) As a method for producing paradibromobenzene, benzene or brombenzene is brominated in a liquid phase in the presence of a Lewis acid catalyst such as iron bromide or aluminum bromide (Fuiser latest organic chemistry III page 47). ) Or benzene or bromobenzene in the liquid phase in the presence of an aqueous solution containing iron ions or copper ions, by oxidative bromination using bromine and oxygen (JP-A-49-20126). ing.
（発明が解決しようとする問題点） 前記のルイス酸を用いる臭素による臭素化法は、ジブロ
ムベンゼン中のパラ体の割合が６０〜７０％と低く、各
種中間原料として有用なパラジブロムベンゼンの製法と
しては、満足できるものではなかつた。また、鉄イオン
または銅イオンを含む水性液の存在下に、臭素と酸素を
用いて酸化的に臭素化する方法については、ジブロムベ
ンゼン中のパラ体の割合に関するデータはなく、本研究
者らが検討した結果では、やはりパラ体の割合が６０〜
７０％と低いことが分つた。(Problems to be Solved by the Invention) In the bromination method with bromine using the Lewis acid described above, the ratio of para-form in dibromobenzene is as low as 60 to 70%, and para-dibromobenzene useful as various intermediate raw materials The manufacturing method was not satisfactory. Regarding the method of oxidative bromination using bromine and oxygen in the presence of an aqueous solution containing iron ions or copper ions, there is no data on the ratio of para bodies in dibromobenzene, and the present researchers As a result of examination by
It was found to be as low as 70%.
（問題点を解決するための手段） 本発明者らは、これらの問題を解決するため鋭意検討を
重ねた結果、触媒として、金属銅および／または銅化合
物を担持したＹ型ゼオライトを用い、気相において臭素
および／または臭化水素と酸素によつて、酸化的に臭素
化することにより、ジブロムベンゼン中のパラ体の割合
が８０％以上と高い選択率でパラジブロムベンゼンが得
られることを見い出し、本発明を完成するに至つた。(Means for Solving Problems) As a result of intensive studies to solve these problems, the present inventors have used Y-type zeolite carrying metallic copper and / or a copper compound as a catalyst, In the phase, by oxidatively brominating with bromine and / or hydrogen bromide and oxygen, it is possible to obtain para-dibromobenzene with a high selectivity of 80% or more of para-form in dibromobenzene. They have found the present invention and completed the present invention.
すなわち、本発明は、ベンゼン、ブロムベンゼンのいず
れかまたは両者を臭素、臭化水素のいずれかまたは両者
と酸素を用いて気相において酸化的に臭素化してパラジ
ブロムベンゼンを製造するに当り、触媒として金属銅お
よび／または銅化合物を担持したＹ型ゼオライトを用い
ることを特徴とするパラジブロムベンゼンの製造法であ
る。That is, the present invention is a catalyst for producing para-dibromobenzene by oxidatively brominating either or both of benzene and brombenzene in the gas phase using bromine, either or both of hydrogen bromide and oxygen. The method is a process for producing para-dibromobenzene characterized in that Y-type zeolite carrying metallic copper and / or a copper compound is used as.
本発明に用いられるＹ型ゼオライトとは、一般にフオー
ジヤサイトと呼ばれる結晶構造をもち、SiO2／Al2O
3（モル比）が４〜６のゼオライトである。The Y-type zeolite used in the present invention has a crystal structure generally called phosjasite, and is SiO 2 / Al 2 O.
It is a zeolite having a 3 (molar ratio) of 4 to 6.
本発明に用いられる触媒中の銅元素は、金属銅および／
または種々の化合物の形でＹ型ゼオライトに担持され
る。例えば、金属銅、酸化銅、ハロゲン化銅、硝酸銅、
硫酸銅、酢酸銅等が挙げられるが、反応系においては、
これらの金属銅や銅化合物は、少なくとも一部臭化銅の
形で触媒として働くものと考えられるので、臭化銅を担
持するのが好ましい。The copper element in the catalyst used in the present invention is metallic copper and / or
Alternatively, it is supported on Y-type zeolite in the form of various compounds. For example, metallic copper, copper oxide, copper halide, copper nitrate,
Copper sulfate, copper acetate, etc. may be mentioned, but in the reaction system,
Since it is considered that these metallic copper and copper compounds act as a catalyst in the form of at least a part of copper bromide, it is preferable to support copper bromide.
本発明中の触媒の金属銅および／または銅化合物の担持
量は、特に制限はないが、あまり少ないと活性が低くな
るので、好ましくは担体のＹ型ゼオライトに対して銅元
素が５〜２００重量％、さらに好ましくは１５〜１００
重量％の範囲である。The supported amount of metallic copper and / or copper compound of the catalyst in the present invention is not particularly limited, but if it is too small, the activity becomes low. %, More preferably 15-100
It is in the range of% by weight.
また、担体であるＹ型ゼオライトは、結晶構造内にカチ
オンを含んでいるが、本発明に用いられるＹ型ゼオライ
トのカチオンの種類は、特に制限はない。Further, the Y-type zeolite as the carrier contains a cation in the crystal structure, but the type of the cation of the Y-type zeolite used in the present invention is not particularly limited.
このような金属銅や銅化合物を担持したＹ型ゼオライト
の製造方法としては、通常の金属塩水溶液による含浸
法、銅化合物の昇華等を用いる気相担持法が考えられる
が、含浸法が好ましい。As a method for producing such Y-zeolite carrying metallic copper or a copper compound, an ordinary impregnation method with an aqueous solution of a metal salt and a vapor phase supporting method using sublimation of a copper compound can be considered, but the impregnation method is preferable.
本発明におけるベンゼンおよび／またはブロムベンゼン
とBr2および／またはHBrのモル比は0.０１〜５０、好ま
しくは0.１〜１０、さらに好ましくは0.５〜５の範囲で
ある。In the present invention, the molar ratio of benzene and / or bromobenzene to Br 2 and / or HBr is in the range of 0.01 to 50, preferably 0.1 to 10, and more preferably 0.5 to 5.
本発明におけるO2とBr2および／またはHBrのモル比は0.
５〜5.０、好ましくは0.８〜3.０で行なわれる。In the present invention, the molar ratio of O 2 to Br 2 and / or HBr is 0.
5 to 5.0, preferably 0.8 to 3.0.
これらの原料ガスは、そのまま導入しても、不活性ガス
で希釈してもよい。These source gases may be introduced as they are or diluted with an inert gas.
本発明における反応温度は１００〜４００℃、好ましく
は１５０〜３００℃で行なわれる。The reaction temperature in the present invention is 100 to 400 ° C, preferably 150 to 300 ° C.
本発明における圧力は、減圧、常圧、加圧いずれでもよ
いが、好ましくは0.５〜１０atm、さらに好ましくは0.
８〜５atmの範囲である。The pressure in the present invention may be any of reduced pressure, normal pressure and increased pressure, but is preferably 0.5 to 10 atm, more preferably 0.
It is in the range of 8 to 5 atm.
（発明の効果） 本発明の方法により、ジブロムベンゼン中のパラ体の割
合が８０％以上という高選択率でパラジブロムベンゼン
を得ることができる。このことは、工業的に実施する上
で非常に有利である。(Effect of the Invention) By the method of the present invention, para-dibromobenzene can be obtained with a high selectivity such that the proportion of para-form in dibromobenzene is 80% or more. This is very advantageous for industrial implementation.
（実施例） 実施例１ Na−Ｙ型ゼオライト（Linde社製，商品名；ＳＫ−４
０）を２０重量％CuBr2水溶液中に浸漬した後、蒸発乾
固してCuBr2を担持したＹ型ゼオライトを調製した。得
られた触媒のCu担持量は１８重量％であつた。(Example) Example 1 Na-Y type zeolite (manufactured by Linde, trade name; SK-4
0) was immersed in a 20 wt% CuBr 2 aqueous solution and then evaporated to dryness to prepare a CuBr 2 -supporting Y-type zeolite. The amount of Cu supported on the obtained catalyst was 18% by weight.
この触媒を用いて、ブロムベンゼンの臭化水素による酸
化的臭素化反応を、下記の条件で行つた。Using this catalyst, an oxidative bromination reaction of brombenzene with hydrogen bromide was carried out under the following conditions.
ブロムベンゼン／ＨＢｒ／O2／N2モル比＝２／１／１／
４反応温度２００℃、ＷＨＳＶ（ブロムベンゼン基準）
＝4.０hr-1、圧力：常圧。Brombenzene / HBr / O 2 / N 2 molar ratio = 2/1/1 /
4 Reaction temperature 200 ℃, WHSV (Brombenzene standard)
= 4.0 hr -1 , pressure: normal pressure.
反応開始後３〜４時間の成績は、ブロムベンゼン転化率
＝４５％、ジブロムベンゼン選択率＝９５％、トリブロ
ムベンゼン選択率＝３％、ジブロムベンゼン中のパラ体
の割合＝８８％であつた。3 to 4 hours after the start of the reaction, the conversion rate of brombenzene = 45%, the selectivity of dibromobenzene = 95%, the selectivity of tribromobenzene = 3%, and the ratio of para-form in dibromobenzene = 88%. Atsuta
実施例２ 実施例１で使用した触媒を用いて、ブロムベンゼンの臭
素による酸化的臭素化反応を、下記の条件で行つた。Example 2 Using the catalyst used in Example 1, an oxidative bromination reaction of brombenzene with bromine was carried out under the following conditions.
ブロムベンゼン／Br2／O2／N2／４／１／２／４、反応
温度２２０℃、ＷＨＳＶ＝2.０hr-1、圧力：常圧。Bromobenzene / Br 2 / O 2 / N 2/4/1/2/4, reaction temperature 220 ℃, WHSV = 2.0hr -1, pressure: atmospheric pressure.
反応開始後５〜６時間の成績は、ブロムベンゼン転化率
＝４７％、ジブロムベンゼン選択率＝９６％、トリブロ
ムベンゼン選択率＝３％、ジブロムベンゼン中のパラ体
の割合＝９０％であつた。5 to 6 hours after the start of the reaction, the conversion of brombenzene = 47%, the selectivity of dibromobenzene = 96%, the selectivity of tribromobenzene = 3%, and the ratio of para-form in dibromobenzene = 90%. Atsuta
実施例３ NaY型ゼオライトを３０重量％CuBr2水溶液に浸漬した
後、蒸発乾固して、CuBr2を担持したＹ型ゼオライトを
調製した。Cuの担持量は２３重量％であつた。Example 3 NaY-type zeolite was immersed in a 30 wt% CuBr 2 aqueous solution and then evaporated to dryness to prepare a Y-type zeolite carrying CuBr 2 . The supported amount of Cu was 23% by weight.
この触媒を用いて、ベンゼンの臭化水素による酸化的臭
素化反応を、下記の条件で行つた。Using this catalyst, an oxidative bromination reaction of benzene with hydrogen bromide was carried out under the following conditions.
ベンゼン／HBr／O2／N2＝１／１／１／８、反応温度１
９０℃、ＷＨＳＶ（ベンゼン基準）＝2.０hr-1、圧力：
常圧。Benzene / HBr / O 2 / N 2 = 1/1/1/8, reaction temperature 1
90 ° C, WHSV (benzene standard) = 2.0 hr -1 , pressure:
Normal pressure.
反応開始後３〜４時間の成績は、ベンゼン転化率＝６０
％、臭素化ベンゼン選択率９９％、臭素化ベンゼン中の
生成物の分布は表１のとおりであつた。The benzene conversion rate is 60 after 3 to 4 hours from the start of the reaction.
%, Brominated benzene selectivity 99%, and distribution of products in brominated benzene are shown in Table 1.
実施例４ 実施例３で使用した触媒を用いて、ベンゼンとブロムベ
ンゼンの混合物の臭化水素による酸化的臭素化反応を、
下記の条件で行つた。 Example 4 Using the catalyst used in Example 3, the oxidative bromination reaction of a mixture of benzene and bromobenzene with hydrogen bromide was carried out,
I went under the following conditions.
ベンゼン／ブロムベンゼン／HBr／O2／N2＝１／３／1.
８／1.８／6.８、反応温度２００℃、ＷＨＳＶ（ベンゼ
ン＋ブロムベンゼン基準）＝2.０hr-1、圧力：常圧。Benzene / bromobenzene / HBr / O 2 / N 2 = 1/3/1.
8 / 1.8 / 6.8, reaction temperature 200 ° C., WHSV (benzene + brominebenzene standard) = 2.0 hr −1 , pressure: normal pressure.
反応開始後２〜３時間、５０〜５１時間、１００〜１０
１時間の生成液の有機相の組成を表２に示す。2-3 hours, 50-51 hours, 100-10 after the start of the reaction
The composition of the organic phase of the product solution for 1 hour is shown in Table 2.
実施例５ Ｙ型ゼオライトを２０％硝酸銅水溶液に浸漬した後、蒸
発乾固し、さらに、４００℃で４時間空気中で焼成し
て、CuOを担持したＹ型ゼオライトを調製した。さら
に、この触媒を４５０℃、４時間水素気流中で還元処理
を行つて、金属銅を担持したＹ型ゼオライトを得た。金
属銅の担持量は１１重量％であつた。 Example 5 The Y-type zeolite was immersed in a 20% aqueous copper nitrate solution, evaporated to dryness, and then calcined in air at 400 ° C. for 4 hours to prepare a CuO-supporting Y-type zeolite. Further, this catalyst was subjected to reduction treatment in a hydrogen stream at 450 ° C. for 4 hours to obtain a Y-zeolite carrying metallic copper. The amount of metallic copper supported was 11% by weight.
この触媒を用いて、臭化水素によるブロモベンゼンのオ
キシブロム化反応を以下の条件で行つた。Using this catalyst, the oxybromination reaction of bromobenzene with hydrogen bromide was carried out under the following conditions.
ブロモベンゼン／HBr／O2／N2＝４／１／１／４、反応
温度２２０℃、ＷＨＳＶ＝2.０hr-1、圧力：常圧。Bromobenzene / HBr / O 2 / N 2 = 4/1/1/4, reaction temperature 220 ° C., WHSV = 2.0 hr −1 , pressure: normal pressure.
反応開始後３〜４時間の成績は、ブロモベンゼン転化率
＝２０％、ジブロモベンゼン選択率＝９５％、トリブロ
モベンゼン選択率＝３％、ジブロモベンゼン中の1,4−
体の割合＝８８％であつた。3-4 hours after the start of the reaction, the bromobenzene conversion rate = 20%, dibromobenzene selectivity = 95%, tribromobenzene selectivity = 3%, 1,4-
The body ratio was 88%.
Claims (3)
は両者を、臭素、臭化水素のいずれかまたは両者と酸素
を用いて気相において酸化的に臭素化してパラジブロム
ベンゼンを製造するに当り、触媒として金属銅および／
または銅化合物を担持したＹ型ゼオライトを用いること
を特徴とするパラジブロムベンゼンの製造法。1. A catalyst for producing para-dibromobenzene by oxidatively brominating either or both of benzene and bromobenzene in the gas phase with bromine, hydrogen bromide, or both and oxygen. As metal copper and /
Alternatively, a method for producing paradibromobenzene is characterized in that a Y-type zeolite carrying a copper compound is used.
担体のＹ型ゼオライトに対して５重量％以上であること
を特徴とする特許請求の範囲第１項記載の方法。2. The method according to claim 1, wherein the amount of metallic copper and / or copper compound supported is 5% by weight or more based on the Y-type zeolite as the carrier.
比が0.５〜5.０である特許請求の範囲第１項記載の方
法。3. The method according to claim 1, wherein the molar ratio of oxygen to bromine and / or hydrogen bromide is 0.5 to 5.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60233307A JPH0625081B2 (en) | 1985-10-21 | 1985-10-21 | Method for producing paradibromobenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60233307A JPH0625081B2 (en) | 1985-10-21 | 1985-10-21 | Method for producing paradibromobenzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6293242A JPS6293242A (en) | 1987-04-28 |
| JPH0625081B2 true JPH0625081B2 (en) | 1994-04-06 |
Family
ID=16953068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60233307A Expired - Lifetime JPH0625081B2 (en) | 1985-10-21 | 1985-10-21 | Method for producing paradibromobenzene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0625081B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2608677T3 (en) * | 2007-10-23 | 2017-04-12 | Sk Chemicals, Co., Ltd. | Manufacturing process for iodinated aromatic compounds |
-
1985
- 1985-10-21 JP JP60233307A patent/JPH0625081B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6293242A (en) | 1987-04-28 |
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