JPH0149336B2 - - Google Patents
Info
- Publication number
- JPH0149336B2 JPH0149336B2 JP59081151A JP8115184A JPH0149336B2 JP H0149336 B2 JPH0149336 B2 JP H0149336B2 JP 59081151 A JP59081151 A JP 59081151A JP 8115184 A JP8115184 A JP 8115184A JP H0149336 B2 JPH0149336 B2 JP H0149336B2
- Authority
- JP
- Japan
- Prior art keywords
- benzene
- type zeolite
- reaction
- bromobenzene
- present
- 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
Links
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 39
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 26
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 22
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 19
- 229910021536 Zeolite Inorganic materials 0.000 claims description 17
- 239000010457 zeolite Substances 0.000 claims description 17
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 9
- 238000005342 ion exchange Methods 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 229910001431 copper ion Inorganic materials 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000005893 bromination reaction Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 230000031709 bromination Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 16
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 150000001879 copper Chemical class 0.000 description 4
- 229910002530 Cu-Y Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001555 benzenes Chemical class 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 239000011968 lewis acid catalyst Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 2
- FWAJPSIPOULHHH-UHFFFAOYSA-N 1,2,4-tribromobenzene Chemical compound BrC1=CC=C(Br)C(Br)=C1 FWAJPSIPOULHHH-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005406 washing Methods 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
〔産業上の利用分野〕
本発明はパラジブロムベンゼンの製造法に関す
るものである。
さらに詳しくは、ベンゼン、ブロムベンゼン又
はその両者を臭素、臭化水素又はその両者と酸素
を用いて酸化的にパラジブロムベンゼンを製造す
る際に、触媒として銅イオンをイオン交換容量の
50％以上含むＹ型ゼオライトを用いる事を特徴と
するパラジブロムベンゼンの製造法に関するもの
である。
〔従来の技術〕
パラジブロムベンゼンは、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
てや、各種耐熱性樹脂の原料として有用なもので
ある。
このパラジブロムベンゼンは、現在ベンゼン又
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、液相で臭素化する事
によつて製造する方法、及びベンゼンまたはブロ
ムベンゼンを液相において酸触媒と酸化触媒を用
いて臭素と酸素から酸化的にジブロムベンゼンに
する方法が提案されている。
〔問題点〕
しかしながら、上記ルイス酸触媒の存在下でパ
ラジブロムベンゼンを製造する方法では、ジブロ
ムベンゼン中のパラ体の割合は60〜70％であり、
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く、また、
反応によつて原料の臭素の半分が臭化水素となる
ため、臭素基準で50％でしかジブロムベンゼンが
得られないという欠点があつた。また、酸触媒と
酸化触媒を用いる方法もパラ体の割合は60〜70％
と満足のいくものではなかつた。
そこで、本発明者は、これらの問題を解決すべ
く鋭意検討を重ねた結果銅イオンをイオン交換容
量の50％以上含むＹ型ゼオライトを触媒として用
いて気相で反応を行うと、ジブロムベンゼン中の
パラ体の割合が80％以上と高くなる事を見い出
し、本発明を完成するに至つた。
〔構成〕
すなわち、本発明は、ベンゼン、ブロムベンゼ
ン又はその両者を臭素、臭化水素又はその両者と
酸素を用いて酸化的に臭素化してパラジブロムベ
ンゼンを製造する際に、触媒として銅イオンをイ
オン交換容量の50％以上含有するＹ型ゼオライト
を用いる事を特徴とするパラジブロムベンゼンの
製造法である。
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／Al2O3（モル比）が４〜６のゼオライトで
ある。そして、本発明の方法における触媒として
用いられるＹ型ゼオライトは、銅イオンをイオン
交換容量の50％以上、好ましくは70％以上含む必
要がある。
ここで言うイオン交換容量とは、ゼオライトの
アニオンサイトであるアルミニウムと当量関係に
あるカチオンサイトの数を表わす量であり、ゼオ
ライトのSiO2／Al2O3比によつて決まる量であ
る。銅イオンの含有量が50％以下ではパラ体の割
合が60〜70％程度となる。
この様な銅イオンを含む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イオン
交換法、含浸法が用いられるがイオン交換法が特
に好ましい。又、その場合に用いられる金属塩と
しては、塩化第１銅、硝酸第１銅等の１価の銅
塩、塩化第２銅、硝酸第２銅、硫酸銅等の２価の
銅塩等が用いられるが、好ましいのは２価の銅塩
である。
本発明の臭素化剤としては、臭素、臭化水素が
用いられる。
本発明におけるベンゼン及び又はブロムベンゼ
ン／Br2及び又はHBrのモル比は0.01〜50の範囲、
好ましくは0.1〜10の範囲で行なわれる。
本発明におけるジブロムベンゼン中のパラ体の
割合は、O2／Br2及び又はHBrのモル比によつて
影響を受け、この比が高くなるにつれてパラ体の
割合が上昇する傾向が見られる。しかしながらあ
まり酸素比を上げると原料の酸化等の副反応が起
るため、O2／Br2及び又はHBrのモル比は、0.5
〜5.0の範囲、好ましくは、0.8〜3.0で行う必要が
ある。
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。
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。
本発明は、常圧または加圧で行なわれ、反応方
式は固定床、流動床等を用いた流通反応方式が好
ましい。
次に、本発明を実施例を用いて説明する。
実施例 １〜３
Na―Ｙ型ゼオライト（Linde社製、商品名；
SK―40）を、10wt％Cu Cl2水溶液中で、60℃、
24時間イオン交換を行つたのち、濾過洗浄及び
120℃で６時間の乾燥をした。イオン交換液中の
銅濃度の原子吸光分析より求めたＹ型ゼオライト
の銅イオン含有率は80％であつた。
このCu―Ｙ型ゼオライトをブロムベンゼンの
酸化的臭素化反応の触媒として用いた。
反応条件は、下記の様にO2／Br2（モル比）を
変えて行つた。
WHSV（ブロムベンゼン基準）＝1.4hr-1
反応温度＝170℃ 圧力＝常圧
反応開始後、３〜４時間の成績を表１に示す。
[Industrial Application Field] The present invention relates to a method for producing paradibromobenzene. More specifically, when producing paradibromobenzene oxidatively from benzene, bromobenzene, or both using bromine, hydrogen bromide, or both and oxygen, copper ions are used as a catalyst to increase the ion exchange capacity.
The present invention relates to a method for producing paradibromobenzene characterized by using Y-type zeolite containing 50% or more. [Prior Art] Paradibromobenzene is 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. This paradibromobenzene is currently produced by brominating benzene or bromobenzene in the liquid phase in the presence of a Lewis acid catalyst such as iron bromide or aluminum bromide, and by brominating benzene or bromobenzene in the liquid phase in the presence of a Lewis acid catalyst such as iron bromide or aluminum bromide. A method to oxidatively convert bromine and oxygen to dibromobenzene using an acid catalyst and an oxidation catalyst in the phase has been proposed. [Problem] However, in the method for producing para-dibromobenzene in the presence of a Lewis acid catalyst, the proportion of para-isomer in dibromobenzene is 60 to 70%,
The method for producing paradibromobenzene, which is useful as various intermediate raw materials, is not satisfactory, and
Half of the bromine in the raw material becomes hydrogen bromide during the reaction, so the drawback was that dibromobenzene could only be obtained with 50% bromine. In addition, the percentage of para isomer is 60 to 70% in the method using acid catalyst and oxidation catalyst.
It was not satisfactory. Therefore, as a result of intensive studies to solve these problems, the inventors of the present invention found that dibrobenzene It was discovered that the proportion of para-bodies inside was as high as 80% or more, leading to the completion of the present invention. [Structure] That is, the present invention uses copper ions as a catalyst when producing paradibromobenzene by oxidatively brominating benzene, bromobenzene, or both using bromine, hydrogen bromide, or both and oxygen. This is a method for producing paradibromobenzene, characterized by using Y-type zeolite containing 50% or more of the ion exchange capacity. The Y-type zeolite used in the present invention has a crystal structure generally called faujasite,
The zeolite has a SiO 2 /Al 2 O 3 (molar ratio) of 4 to 6. The Y-type zeolite used as a catalyst in the method of the present invention must contain copper ions in an amount of 50% or more, preferably 70% or more of the ion exchange capacity. The ion exchange capacity referred to here is an amount representing the number of cation sites that have an equivalent relationship with aluminum, which is an anion site of the zeolite, and is determined by the SiO 2 /Al 2 O 3 ratio of the zeolite. When the content of copper ions is 50% or less, the proportion of para isomers is about 60 to 70%. As a method for producing such a Y-type zeolite containing copper ions, an ion exchange method using an ordinary metal salt aqueous solution and an impregnation method are used, but the ion exchange method is particularly preferred. In addition, the metal salts used in that case include monovalent copper salts such as cuprous chloride and cuprous nitrate, and divalent copper salts such as cupric chloride, cupric nitrate, and copper sulfate. Although divalent copper salts are preferred, divalent copper salts are preferred. Bromine and hydrogen bromide are used as the brominating agent in the present invention. The molar ratio of benzene and/or bromobenzene/ Br2 and/or HBr in the present invention is in the range of 0.01 to 50,
It is preferably carried out in the range of 0.1 to 10. The proportion of para-isomer in dibromobenzene in the present invention is influenced by the molar ratio of O 2 /Br 2 and/or HBr, and as this ratio increases, the proportion of para-isomer tends to increase. However, if the oxygen ratio is increased too much, side reactions such as oxidation of the raw materials will occur, so the molar ratio of O 2 /Br 2 and/or HBr is 0.5.
~5.0, preferably 0.8 to 3.0. These raw material gases may be introduced as they are or may be diluted with an inert gas. The reaction temperature in the present invention is 100 to 400°C, preferably 150 to 300°C. The present invention is carried out under normal pressure or increased pressure, and the reaction method is preferably a flow reaction method using a fixed bed, a fluidized bed, or the like. Next, the present invention will be explained using examples. Examples 1 to 3 Na-Y type zeolite (manufactured by Linde, trade name;
SK-40) in a 10wt% Cu Cl 2 aqueous solution at 60℃.
After 24 hours of ion exchange, filter cleaning and
It was dried at 120°C for 6 hours. The copper ion content of the Y-type zeolite was determined to be 80% by atomic absorption spectrometry of the copper concentration in the ion exchange solution. This Cu-Y type zeolite was used as a catalyst for the oxidative bromination reaction of bromobenzene. The reaction conditions were as follows, varying the O 2 /Br 2 (molar ratio). WHSV (based on bromobenzene) = 1.4 hr -1 Reaction temperature = 170°C Pressure = normal pressure Table 1 shows the results for 3 to 4 hours after the start of the reaction.
【表】
実施例 ４
実施例１〜３で用いたのと同じCu―Ｙ型ゼオ
ライトを用いて、ベンゼンの酸化的臭素化反応を
下記の条件で行つた。
Br2／C6H6／O2／N2（モル比）＝１／１／１／
８
WHSV（ベンゼン基準）＝2.0hr-1
反応温度＝200℃ 圧力＝常圧
反応開始後、２〜３時間の成績は、ベンゼン転
化率＝40％、臭素化ベンゼン選択率＝98％、臭素
化ベンゼン中の生成物の分布は、表２の通りであ
つた。[Table] Example 4 Using the same Cu-Y type zeolite used in Examples 1 to 3, an oxidative bromination reaction of benzene was carried out under the following conditions. Br 2 /C 6 H 6 /O 2 /N 2 (molar ratio) = 1/1/1/
8 WHSV (benzene standard) = 2.0hr -1 Reaction temperature = 200℃ Pressure = normal pressure After the start of the reaction, the results for 2 to 3 hours are: benzene conversion rate = 40%, brominated benzene selectivity = 98%, bromination The product distribution in benzene was as shown in Table 2.
【表】
実施例 ５
実施例１〜３で用いたのと同じCu―Ｙ型ゼオ
ライトを用いて臭化水素によるブロムベンゼンの
酸化的臭素化反応を下記の条件で行つた。
HBr／C6H5Br／O2／N2（モル比）＝１／１／
1.5／７
WHSV（ブロムベンゼン基準）＝3.0hr-1
反応温度＝250℃、圧力＝常圧
反応開始後、４〜５時間の成績は、ブロムベン
ゼン転化率＝66％、ジブロムベンゼン選択率＝90
％、１，２，４―トリブロムベンゼン選択率＝７
％、ジブロムベンゼン中の異性体組成＝Ｏ−９
％、ｍ−４％、ｐ−87％であつた。
実施例 ６
Na―Ｙ型ゼオライト（Linde社製SK―40）を、
10wt％CuCl2水溶液中で60℃、10時間撹拌した
後、濾過洗浄及び120℃で５時間の乾燥をして、
銅イオン含有率＝60％のＹ型ゼオライトを調製し
た。
このCu―Ｙ型ゼオライトを用いて臭化水素に
よるベンゼンの酸化的臭素化反応を下記の条件で
行つた。
HBr／C6H6／O2／N2（モル比）＝１／0.5／
１／６
WHSV（ベンゼン基準）＝1.5hr-1
反応温度＝280℃ 圧力＝常圧
反応開始後、２〜３時間の成績は、ベンゼン転
化率＝40％、臭素化ベンゼン選択率＝98％、
臭素化ベンゼン中の生成物の分布は表３の通り
であつた。[Table] Example 5 Using the same Cu-Y type zeolite used in Examples 1 to 3, oxidative bromination reaction of bromobenzene with hydrogen bromide was carried out under the following conditions. HBr/C 6 H 5 Br/O 2 /N 2 (mole ratio) = 1/1/
1.5/7 WHSV (based on bromobenzene) = 3.0hr -1 Reaction temperature = 250℃, pressure = normal pressure The results for 4 to 5 hours after the start of the reaction were: bromobenzene conversion rate = 66%, dibromobenzene selectivity = 90
%, 1,2,4-tribromobenzene selectivity = 7
%, isomer composition in dibromobenzene = O-9
%, m-4%, and p-87%. Example 6 Na-Y type zeolite (SK-40 manufactured by Linde),
After stirring in a 10wt% CuCl 2 aqueous solution at 60°C for 10 hours, filtering and washing and drying at 120°C for 5 hours,
A Y-type zeolite with a copper ion content of 60% was prepared. Using this Cu--Y type zeolite, oxidative bromination reaction of benzene with hydrogen bromide was carried out under the following conditions. HBr/C 6 H 6 /O 2 /N 2 (mole ratio) = 1/0.5/
1/6 WHSV (benzene standard) = 1.5hr -1 Reaction temperature = 280℃ Pressure = normal pressure The results for 2 to 3 hours after the start of the reaction are: benzene conversion rate = 40%, brominated benzene selectivity = 98%, The product distribution in brominated benzene was as shown in Table 3.
本発明方法は、製造されるジブロムベンゼン中
のパラ体の割合が85％以上と非常に高いことであ
る。
The method of the present invention is characterized in that the proportion of para-isomer in dibromobenzene produced is extremely high, at 85% or more.
Claims (1)
臭素、臭化水素又はその両者と酸素を用いて酸化
的に臭素化してパラジブロムベンゼンを製造する
際に、触媒として銅イオンをイオン交換容量の50
％以上含むＹ型ゼオライトを用いる事を特徴とす
るパラジブロムベンゼンの製造法。 ２ 酸素／臭素及び又は臭化水素（モル比）が
0.5〜5.0である事を特徴とする特許請求の範囲第
１項記載の方法。[Claims] 1. Benzene, bromobenzene, or both,
When producing paradibromobenzene by oxidative bromination using bromine, hydrogen bromide, or both and oxygen, copper ions are used as a catalyst at 50% of the ion exchange capacity.
% or more of Y-type zeolite. 2 Oxygen/bromine and or hydrogen bromide (molar ratio)
The method according to claim 1, characterized in that the ratio is 0.5 to 5.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59081151A JPS60224645A (en) | 1984-04-24 | 1984-04-24 | Production of p-dibromobenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59081151A JPS60224645A (en) | 1984-04-24 | 1984-04-24 | Production of p-dibromobenzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60224645A JPS60224645A (en) | 1985-11-09 |
| JPH0149336B2 true JPH0149336B2 (en) | 1989-10-24 |
Family
ID=13738431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59081151A Granted JPS60224645A (en) | 1984-04-24 | 1984-04-24 | Production of p-dibromobenzene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60224645A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0780798B2 (en) * | 1985-11-06 | 1995-08-30 | 東ソー株式会社 | Method for producing halogenated benzene derivative with improved zeolite catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4910658A (en) * | 1972-04-06 | 1974-01-30 |
-
1984
- 1984-04-24 JP JP59081151A patent/JPS60224645A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4910658A (en) * | 1972-04-06 | 1974-01-30 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60224645A (en) | 1985-11-09 |
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