JPH0774183B2 - Halobenzene nitration method - Google Patents
Halobenzene nitration methodInfo
- Publication number
- JPH0774183B2 JPH0774183B2 JP62138271A JP13827187A JPH0774183B2 JP H0774183 B2 JPH0774183 B2 JP H0774183B2 JP 62138271 A JP62138271 A JP 62138271A JP 13827187 A JP13827187 A JP 13827187A JP H0774183 B2 JPH0774183 B2 JP H0774183B2
- Authority
- JP
- Japan
- Prior art keywords
- magnesium
- catalyst
- weight
- nitration
- halobenzene
- 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
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Classifications
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、ハロベンゼンのニトロ化方法に関し、詳しく
はハロベンゼンをニトロ化剤と気相で反応させてニトロ
化する方法において、シリカ／アルミナモル比が少なく
とも20で、制御指数が１〜16であるZSM−５またはAZ−
１に、0.5〜５重量％のマグネシウムを含有させてなる
触媒を用いることを特徴とする選択的にパラニトロ体を
得る方法に関する。Description: TECHNICAL FIELD The present invention relates to a method for nitrating halobenzene, and more specifically, in a method for reacting halobenzene with a nitrating agent in a gas phase to perform nitration, the molar ratio of silica / alumina is ZSM-5 or AZ- with a control index of 1-16 at least 20
1. A method for selectively obtaining a para-nitro compound, characterized in that the catalyst containing 0.5 to 5% by weight of magnesium is used in 1.
（従来の技術） 芳香族ニトロ化合物は芳香族アミノ化合物の原料等に用
いられる有用な有機化学品の中間体である。芳香族ニト
ロ化合物の工業的製法は、硝酸と濃硫酸の混合物である
混酸を用いて実施されているが、多量の硫酸を用いるた
め、廃硫酸や廃水処理等問題がある。一方、廃硫酸を発
生させない方法として気相ニトロ化法が提案されてい
る。(Prior Art) Aromatic nitro compounds are intermediates of useful organic chemicals used as raw materials for aromatic amino compounds. The industrial production method of aromatic nitro compounds is carried out by using a mixed acid which is a mixture of nitric acid and concentrated sulfuric acid, but since a large amount of sulfuric acid is used, there are problems such as waste sulfuric acid and waste water treatment. On the other hand, a gas phase nitration method has been proposed as a method that does not generate waste sulfuric acid.
例えば、特開昭50−121234号公報には、シリカ・アルミ
ナやアルミノシリケートを触媒に用い、ハロベンゼンを
ニトロ化する方法が、特開昭54−95521号公報には、約
５〜10Åの細孔径を有する分子ふるい触媒を用い、クロ
ロベンゼンをニトロ化する方法が、特開昭59−216851号
公報には、アルミノシリケートゼオライトを触媒として
芳香族化合物をニトロ化する方法が開示されている。For example, JP-A-50-121234 discloses a method of nitrating halobenzene using silica-alumina or aluminosilicate as a catalyst, and JP-A-54-95521 discloses a pore size of about 5 to 10Å. JP-A-59-216851 discloses a method of nitrating chlorobenzene using a molecular sieving catalyst having a sulphate, and a method of nitrating an aromatic compound using aluminosilicate zeolite as a catalyst.
ハロベンゼンのニトロ化法として、生成ニトロ化合物の
パラ体／オルト体の比を制御する方法が前述の公報以外
にも、特開昭57−13541号公報、特公昭58−40535号公報
等に開示されている。As a method for nitrating halobenzene, a method of controlling the ratio of para-form / ortho-form of the produced nitro compound is disclosed in Japanese Patent Application Laid-Open No. 57-13541 and Japanese Patent Publication No. 58-40535 in addition to the above-mentioned publications. ing.
（発明が解決しようとする問題点） 混酸を用いる液相法では、ハロベンゼンのニトロ化反応
により生成するパラ体／オルト体（p/o）比率は、種々
条件を変えても２留まりである。(Problems to be Solved by the Invention) In the liquid phase method using a mixed acid, the para-form / ortho-form (p / o) ratio generated by the nitration reaction of halobenzene is 2 or less even if various conditions are changed.
公知の気相ニトロ化方法では、p/o比は液相法に比べ改
善されているが、不充分で満足できるレベルにない。In the known vapor phase nitration method, the p / o ratio is improved as compared with the liquid phase method, but it is insufficient and not at a satisfactory level.
（問題点を解決するための手段） 本発明者らは、ハロベンゼンのニトロ化において、工業
的に有用なパラ異性体を選択的に得る方法について鋭意
検討を加えた結果、シリカ／アルミナモル比が少なくと
も20で、制御指数が１〜16であるZSM−５またはAZ−１
に、0.5〜５重量％のマグネシウムを含有させてなる触
媒を用いて気相ニトロ化することにより、高いパラ体比
率が得られることを見い出したものである。(Means for Solving Problems) The inventors of the present invention have earnestly studied a method for selectively obtaining an industrially useful para isomer in nitration of halobenzene, and as a result, the silica / alumina molar ratio was at least ZSM-5 or AZ-1 with a control index of 1 to 16 at 20
It was found that a high para-form ratio can be obtained by gas phase nitration using a catalyst containing 0.5 to 5% by weight of magnesium.
本発明で用いられるハロベンゼンとしては、クロロベン
ゼン、ブロモベンゼン、ヨウ化ベンゼンを挙げることが
できる。これらハロベンゼンは気相状態で反応に供す
る。Examples of the halobenzene used in the present invention include chlorobenzene, bromobenzene, and iodide benzene. These halobenzenes are used in the reaction in the gas phase.
本発明で用いられるニトロ化剤としては、二酸化窒素、
硝酸等通常用いられるニトロ化剤を用いることができ
る。硝酸を用いる場合の硝酸濃度は、30重量％以上が好
ましく、さらに好ましくは50重量％以上である。As the nitrating agent used in the present invention, nitrogen dioxide,
A commonly used nitrating agent such as nitric acid can be used. When using nitric acid, the nitric acid concentration is preferably 30% by weight or more, more preferably 50% by weight or more.
ニトロ化剤の使用割合は、ハロベンゼン１モルに対して
0.1〜10モル、好ましくは0.2〜３モルである。The ratio of nitrating agent used is 1 mol of halobenzene.
It is 0.1 to 10 mol, preferably 0.2 to 3 mol.
ニトロ化の反応温度は原料により異なるが、通常100〜3
00℃、好ましくは120〜250℃が用いられる。反応圧力は
通常常圧で実施するが、加圧条件で行なつてもさしつか
えない。The reaction temperature for nitration varies depending on the raw material, but is usually 100 to 3
00 ° C, preferably 120-250 ° C is used. The reaction pressure is usually atmospheric pressure, but it may be carried out under pressure.
また、反応系に窒素、アルゴン等の不活性ガスを存在さ
せることもできる。ハロベンゼンの供給量としては、0.
1〜20hr-1の重量空間速度（WHSV）、好ましくは0.2〜10
hr-1が用いられる。Further, an inert gas such as nitrogen or argon can be present in the reaction system. The supply amount of halobenzene is 0.
Weight hourly space velocity (WHSV) of 1 to 20 hr -1 , preferably 0.2 to 10
hr -1 is used.
本発明で用いる触媒は、シリカ／アルミナ比が少なくと
も20で、制御指数が１〜16のZSM−５またはAZ−１に、
0.5〜５重量％のマグネシウム、好ましくは１〜４重量
％のマグネシウムを含有させてなるものである。マグネ
シウムの含有量が0.5重量％より少ないと、パラ異性体
比率の向上効果が充分でなく、５重量％を超えると、パ
ラ異性体比率の向上効果が低下を示し、さらには活性も
小さくなり実用的でない。The catalyst used in the present invention is a ZSM-5 or AZ-1 having a silica / alumina ratio of at least 20 and a control index of 1 to 16,
It contains 0.5 to 5% by weight of magnesium, preferably 1 to 4% by weight of magnesium. When the content of magnesium is less than 0.5% by weight, the effect of improving the para isomer ratio is not sufficient, and when it exceeds 5% by weight, the effect of improving the para isomer ratio is reduced, and the activity is also reduced. Not relevant.
本発明でいう制御指数は、ジヤーナル・オブ・キヤタリ
シス67巻,218〜222頁（1981年）に記載されている定義
方法により測定されたものである。この方法で測定され
たゼオライトの制御指数を下記に例示する。The control index as referred to in the present invention is measured by the defining method described in Journal of Charterization Vol. 67, pp. 218-222 (1981). The control index of zeolite measured by this method is exemplified below.
なお、AZ−１は特開昭59−128210号に開示のゼオライト
である。AZ-1 is the zeolite disclosed in JP-A-59-128210.
REY 0.4 ZSM−５ 8.3 ゼオロン（モルデナイト） 0.4 ZSM−11 8.7 ZSM−12 ２ ZSM−23 9.1 ZSM−35 4.5 TMAオフレタイト 3.7 エリオナイト 38 非晶質シリカアルミナ 0.6 AZ−１ 12 本発明においては、ZSM−５またはAZ−１が用いられる
が、ZSM−５およびAZ−１のシリカ／アルミナ比が低く
すぎると、触媒の安定性が劣る。本発明においては、ア
ルミナ以外の第３成分を含むZSM−５型のメタロ−アル
ミノシリケート、例えば、クロム、鉄、ホウ素、ランタ
ン等でアルミの一部を替えて合成されたものも同様に用
いることができる。REY 0.4 ZSM-5 8.3 Zeolone (mordenite) 0.4 ZSM-11 8.7 ZSM-12 2 ZSM-23 9.1 ZSM-35 4.5 TMA offretite 3.7 Elionite 38 Amorphous silica alumina 0.6 AZ-1 12 In the present invention, ZSM- 5 or AZ-1 is used, but if the silica / alumina ratio of ZSM-5 and AZ-1 is too low, the stability of the catalyst will be poor. In the present invention, a ZSM-5 type metallo-aluminosilicate containing a third component other than alumina, for example, one synthesized by replacing a part of aluminum with chromium, iron, boron, lanthanum or the like is also used. You can
マグネシウムを含有させる方法としては、公知の方法、
例えば、含浸法、イオン交換法、混練法、あるいはゼオ
ライト合成時にマグネシウム塩を存在させて合成する方
法等により含有させることができる。用いられるマグネ
シウム塩としては、酢酸マグネシウム、塩化マグネシウ
ム、硝酸マグネシウム、硫酸マグネシウム等を挙げるこ
とができる。As a method for containing magnesium, a known method,
For example, it can be contained by an impregnation method, an ion exchange method, a kneading method, a method of synthesizing a zeolite in the presence of a magnesium salt at the time of zeolite synthesis, or the like. Examples of the magnesium salt used include magnesium acetate, magnesium chloride, magnesium nitrate, magnesium sulfate and the like.
触媒は通常成形のためバインダーとして、例えば、アル
ミナ、シリカ、シリカアルミナ、粘土等を用い、成形し
て用いるのが好都合である。Since the catalyst is usually molded, it is convenient to use, for example, alumina, silica, silica-alumina, clay or the like as a binder for molding.
（発明の効果） 本発明の方法によれば、ハロベンゼンより極めて高い比
率でパラハロニトロベンゼンを得ることができる。本発
明の効果を示す代表例として、触媒中のマグネシウム含
有量に対するクロロニトロベンゼン中のパラ体選択率の
変化を図面に示した。ただし、触媒は実施例１のＨ型ZS
M−５に種々の量のマグネシウムを含有させて調製した
ものであり、クロロベンゼンのニトロ化条件は、実施例
１の同様の条件である。さらに、副生成物として取り扱
いが困難なジニトロ体の生成もほとんどなく、もちろん
廃硫酸、廃水も問題もない等工業的な意義は極めて大き
い。(Effect of the Invention) According to the method of the present invention, parahalonitrobenzene can be obtained at a much higher ratio than halobenzene. As a representative example showing the effect of the present invention, the change in para-body selectivity in chloronitrobenzene with respect to the magnesium content in the catalyst is shown in the drawings. However, the catalyst was the H-type ZS of Example 1.
It was prepared by adding various amounts of magnesium to M-5, and the nitration conditions of chlorobenzene are the same as those in Example 1. Furthermore, the dinitro compound, which is difficult to handle as a by-product, is hardly generated, and of course, there is no problem with waste sulfuric acid or waste water, which is of great industrial significance.
（実施例） 以下、実施例を挙げて本発明を具体的に示すが、本発明
は、これに何ら限定されるものではない。(Examples) Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
実施例１ 公知方法によりＨ型ZSM−５粉末（SiO2/Al2O3＝46制御
指数8.3）を調製した（触媒Ａ）。このＨ型ZSM−５に３
重量％の酢酸マグネシウム・４水塩の水溶液を加え含
浸、蒸発乾固し、ついで120℃で乾燥後、500℃で３時間
空気中で焼成し、マグネシウムとして0.7重量％含むＨ
型ZSM−５触媒（触媒Ｂ）を得た。この触媒を圧縮成型
し、ついで８〜20メツシユに破砕して反応を供した。H-type ZSM-5 powder (SiO 2 / Al 2 O 3 = 46 control index 8.3) prepared according to Example 1 a known method (catalyst A). This H-type ZSM-5 has 3
An aqueous solution of magnesium acetate tetrahydrate (weight%) was added to impregnate it, evaporate it to dryness, dry it at 120 ° C., and bake it in air at 500 ° C. for 3 hours.
A type ZSM-5 catalyst (catalyst B) was obtained. This catalyst was compression-molded and then crushed into 8 to 20 meshes for reaction.
成形触媒Ｂを石英ガラス製反応管（10mmφ×200mm）に4
g充填し、クロロベンゼンおよび硝酸を定量ポンプで所
定量供給し、所定温度でニトロ化反応を行なつた。触媒
中のマグネシウムの定量は、ケイ光線分析により、反応
生成物分析にはガスクロマトグラフを用いた。ニトロ化
は次の条件で実施した。硝酸は濃度61重量％を使用し
た。Formed catalyst B into a quartz glass reaction tube (10 mmφ x 200 mm) 4
It was filled with g, chlorobenzene and nitric acid were supplied at a predetermined amount by a metering pump, and the nitration reaction was performed at a predetermined temperature. Quantitative determination of magnesium in the catalyst was carried out by silica light analysis, and gas chromatograph was used for reaction product analysis. The nitration was carried out under the following conditions. The nitric acid used had a concentration of 61% by weight.
反応温度:175℃、圧力：大気圧、HNO3/クロロベンゼン
／窒素＝1.4:1:1、WHSV＝2.2hr-1（クロロベンゼン基
準） 実施例２〜４ 実施例１と同様に、ただし、マグネシウム溶液の濃度を
替えることにより、各々マグネシウムを1.5重量％、２
重量％、４重量％含有する触媒Ｃ、Ｄ、Ｅを調製した。
これら触媒を用い、実施例１と同様にクロロベンゼンの
ニトロ化反応を行なつた結果を、第１表に合わせて示し
た。Reaction temperature: 175 ° C., pressure: atmospheric pressure, HNO 3 /chlorobenzene/nitrogen=1.4:1:1, WHSV = 2.2 hr −1 (chlorobenzene standard) Examples 2 to 4 As Example 1, but magnesium solution By changing the concentration of each, 1.5% by weight of magnesium, 2 respectively
Catalysts C, D and E containing 4% by weight were prepared.
The results of nitration reaction of chlorobenzene using these catalysts as in Example 1 are also shown in Table 1.
比較例１ 実施例１に示したマグネシウムを含まないＨ型ZSM−５
を用い、実施例１と同様にクロロベンゼンのニトロ化反
応を行なつた。結果は第１表に合わせて示した。Comparative Example 1 Magnesium-free H-type ZSM-5 shown in Example 1
Was used to carry out the nitration reaction of chlorobenzene in the same manner as in Example 1. The results are shown in Table 1.
比較例２ 実施例１と同様の方法でマグネシウムを８重量％含有す
る触媒を調製し、同様の方法でクロロベンゼンのニトロ
化触媒に用いた（触媒Ｆ）。結果は第１表に合わせて示
した。Comparative Example 2 A catalyst containing 8% by weight of magnesium was prepared in the same manner as in Example 1 and used as a nitration catalyst for chlorobenzene in the same manner (Catalyst F). The results are shown in Table 1.
比較例３ 実施例１の同様の方法で、ただし、酢酸マグネシウムに
替えて塩化ナトリウム、塩化リチウム、塩化セシウム、
酢酸カルシウム、硝酸亜鉛、硝酸銀、硝酸ガリウム、硝
酸鉄を用い、各々金属として2.0重量％含有する触媒を
調製し、実施例１と同様の方法、条件でクロロベンゼン
のニトロ化反応に用いた。 Comparative Example 3 In the same manner as in Example 1, except that magnesium chloride was replaced by sodium chloride, lithium chloride, cesium chloride,
A catalyst containing 2.0% by weight of each metal was prepared using calcium acetate, zinc nitrate, silver nitrate, gallium nitrate, and iron nitrate, and used in the nitration reaction of chlorobenzene under the same conditions and conditions as in Example 1.
結果は第２表に示した。The results are shown in Table 2.
比較例４ 実施例１のＨ型ZSM−５ 10gを、25ccの純水に酢酸マグ
ネシウム４水塩11.6gを溶解させた水溶液に浸漬し、60
℃で一昼夜放置後、過、水洗し、ついで110℃で乾燥
後、500℃で３時間焼成した。このものは、0.2重量％の
マグネシウムを含んでいた。この触媒を実施例１と同様
の方法でクロロベンゼンのニトロ化反応に用いた。その
結果、クロロベンゼンの収率は40モル％で、異性体比率
はオルト体：メタ体：パラ体＝18.4:1.8:79.8であつ
た。 Comparative Example 4 10 g of the H-type ZSM-5 of Example 1 was immersed in an aqueous solution prepared by dissolving 11.6 g of magnesium acetate tetrahydrate in 25 cc of pure water.
After leaving at ℃ for a whole day and night, it was washed with water and then dried at 110 ℃ and baked at 500 ℃ for 3 hours. It contained 0.2% by weight of magnesium. This catalyst was used for the nitration reaction of chlorobenzene in the same manner as in Example 1. As a result, the yield of chlorobenzene was 40 mol%, and the isomer ratio was ortho isomer: meta isomer: para isomer = 18.4: 1.8: 79.8.
比較例５ 比較例８と同様に、ただし、酢酸マグネシウムに替えて
酢酸銅を用い、Ｈ型ZSM−５をイオン交換し、銅として
1.2重量％含む触媒を調製し、実施例１と同様にクロロ
ベンゼンのニトロ化反応触媒に用いた。その結果、クロ
ロベンゼンの収率は53モル％で、オルト体：メタ体：パ
ラ体＝19.9:1.6:78.5であつた。Comparative Example 5 Similar to Comparative Example 8, except that copper acetate was used instead of magnesium acetate, and H-type ZSM-5 was ion-exchanged to obtain copper.
A catalyst containing 1.2% by weight was prepared and used as a chlorobenzene nitration reaction catalyst in the same manner as in Example 1. As a result, the yield of chlorobenzene was 53 mol%, and the ortho-form: meta-form: para-form = 19.9: 1.6: 78.5.
比較例６ 比較例４と同様の方法で、ただし、過後、水洗せずに
乾燥、焼成した。この触媒は、マグネシウムを5.7重量
％含んでいた。この触媒を用い、実施例１と同様にクロ
ロベンゼンのニトロ化反応を行なつた。その結果、クロ
ロベンゼンの収率８モル％で、異性体比はオルト体：メ
タ体：パラ体＝17.9:1.7:80.4であつた。Comparative Example 6 The same method as in Comparative Example 4 was used, except that after passing, it was dried and baked without washing with water. This catalyst contained 5.7% by weight of magnesium. Using this catalyst, nitration reaction of chlorobenzene was carried out in the same manner as in Example 1. As a result, the yield of chlorobenzene was 8 mol%, and the isomer ratio was ortho isomer: meta isomer: para isomer = 17.9: 1.7: 80.4.
実施例5,6 公知の方法にしたがいSiO2/Al2O3比80、制御指数8.6の
Ｈ型ZSM−５を調製し、実施例２と同様の方法でマグネ
シウムを1.5重量％および3.0重量％含む触媒G,Hを調製
し、実施例１と同様にクロロベンゼンのニトロ化反応を
行なつた。Examples 5 and 6 H-type ZSM-5 having a SiO 2 / Al 2 O 3 ratio of 80 and a control index of 8.6 was prepared according to a known method, and 1.5% by weight and 3.0% by weight of magnesium were prepared in the same manner as in Example 2. Catalysts G and H containing the same were prepared, and nitration reaction of chlorobenzene was performed in the same manner as in Example 1.
その結果を第３表に示した。The results are shown in Table 3.
ジニトロ体の生成は認められなかつた。 No formation of dinitro form was observed.
実施例７ 特開昭59−128210号開示の方法にしたがつて、SiO2/Al2
O3比90、制御指数12のAZ−１ゼオライトを合成した。こ
れに実施例１と同様の方法でマグネシウム２重量％含む
触媒を調製した。この触媒を用い、実施例１と同様の方
法で、ただし、反応温度を200℃、WHSV＝0.7hr-1とし、
クロロベンゼンのニトロ化反応を行なつた。その結果、
クロロニトロベンゼンの収率は12モル％で、異性体比は
オルト体：メタ体：パラ体＝10.9:1.6:87.5であつた。Example 7 According to the method disclosed in JP-A-59-128210, SiO 2 / Al 2
AZ-1 zeolite with an O 3 ratio of 90 and a control index of 12 was synthesized. A catalyst containing 2% by weight of magnesium was prepared in the same manner as in Example 1. Using this catalyst, in the same manner as in Example 1, except that the reaction temperature was 200 ° C., WHSV = 0.7 hr −1 ,
The nitration reaction of chlorobenzene was performed. as a result,
The yield of chloronitrobenzene was 12 mol%, and the isomer ratio was ortho isomer: meta isomer: para isomer = 10.9: 1.6: 87.5.
比較例７ Ｈ型ZSM−５に替えて市販の脱アルミＹ型ゼオライト（S
iO2/Al2O3＝100、制御指数0.5）を用い、実施例１と同
様の方法でマグネシウム1.5重量％含む触媒を調製し、
実施例１と同様にクロロベンゼンのニトロ化反応を行な
つた。ただし、反応温度を150℃、WHSV＝1.4hr-1に変え
て行なつた。Comparative Example 7 Instead of H-type ZSM-5, commercially available dealuminated Y-type zeolite (S
Using iO 2 / Al 2 O 3 = 100, control index 0.5), a catalyst containing 1.5% by weight of magnesium was prepared in the same manner as in Example 1,
The nitration reaction of chlorobenzene was carried out in the same manner as in Example 1. However, the reaction temperature was changed to 150 ° C. and WHSV = 1.4 hr −1 .
その結果、クロロニトロベンゼンの収率は20モル％で、
異性体比はオルト体：メタ体：パラ体＝17.0:1.8:81.2
であつた。As a result, the yield of chloronitrobenzene was 20 mol%,
The isomer ratio is ortho: meta: para = 17.0: 1.8: 81.2
It was.
図面は本発明の効果を示す代表例として、触媒中のマグ
ネシウム含有量に対するクロロニトロベンゼン中のパラ
体選択率の変化を示すグラフである。As a typical example showing the effect of the present invention, the drawing is a graph showing changes in the para-body selectivity in chloronitrobenzene with respect to the magnesium content in the catalyst.
Claims (1)
せてニトロ化する方法において、シリカ／アルミナモル
比が少なくとも20で、制御指数が１〜16であるZSM−５
またはAZ−１に、0.5〜５重量％のマグネシウムを含有
させてなる触媒を用いることを特徴とするハロベンゼン
のニトロ化方法。1. A method of reacting halobenzene with a nitrating agent in a gas phase for nitration, wherein ZSM-5 having a silica / alumina molar ratio of at least 20 and a control index of 1-16.
Alternatively, a method for nitration of halobenzene, which comprises using a catalyst containing 0.5 to 5% by weight of magnesium in AZ-1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62138271A JPH0774183B2 (en) | 1987-06-03 | 1987-06-03 | Halobenzene nitration method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62138271A JPH0774183B2 (en) | 1987-06-03 | 1987-06-03 | Halobenzene nitration method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63303957A JPS63303957A (en) | 1988-12-12 |
| JPH0774183B2 true JPH0774183B2 (en) | 1995-08-09 |
Family
ID=15218021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62138271A Expired - Lifetime JPH0774183B2 (en) | 1987-06-03 | 1987-06-03 | Halobenzene nitration method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0774183B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5946638A (en) * | 1997-08-22 | 1999-08-31 | Jayasuriya; Keerthi | Regioselective nitration of aromatic compounds and the reaction products thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59216851A (en) * | 1983-05-26 | 1984-12-06 | Japan Synthetic Rubber Co Ltd | Preparation of aromatic nitro compound |
-
1987
- 1987-06-03 JP JP62138271A patent/JPH0774183B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63303957A (en) | 1988-12-12 |
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