JPS63225339A - Production of aromatic nitro compound - Google Patents
Production of aromatic nitro compoundInfo
- Publication number
- JPS63225339A JPS63225339A JP62056791A JP5679187A JPS63225339A JP S63225339 A JPS63225339 A JP S63225339A JP 62056791 A JP62056791 A JP 62056791A JP 5679187 A JP5679187 A JP 5679187A JP S63225339 A JPS63225339 A JP S63225339A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- nitric acid
- reaction
- aromatic
- 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.)
- Granted
Links
- -1 aromatic nitro compound Chemical class 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 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 12
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 11
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 230000000802 nitrating effect Effects 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 5
- 239000007791 liquid phase Substances 0.000 claims description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 abstract description 18
- 238000006396 nitration reaction Methods 0.000 abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 9
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 239000007864 aqueous solution Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 229910052680 mordenite Inorganic materials 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000007789 gas Substances 0.000 description 15
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 11
- VNQABZCSYCTZMS-UHFFFAOYSA-N Orthoform Chemical compound COC(=O)C1=CC=C(O)C(N)=C1 VNQABZCSYCTZMS-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229920002866 paraformaldehyde Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229940117389 dichlorobenzene Drugs 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- ORPVVAKYSXQCJI-UHFFFAOYSA-N 1-bromo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Br ORPVVAKYSXQCJI-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- 241000567769 Isurus oxyrinchus Species 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
- 241000220317 Rosa Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 238000006172 aromatic nitration reaction Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KFZGFJXYQHKJJV-UHFFFAOYSA-N benzene dihydroiodide Chemical compound I.I.C1=CC=CC=C1 KFZGFJXYQHKJJV-UHFFFAOYSA-N 0.000 description 1
- QARVLSVVCXYDNA-IDEBNGHGSA-N bromobenzene Chemical group Br[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 QARVLSVVCXYDNA-IDEBNGHGSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000005171 halobenzenes Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、芳香族ニトロ化合物の製法に関するもので、
さらに詳しくは、芳香族化合物をシリカ／アルミナモル
比が少なくとも２０の結晶性アルミノシリケート含有触
媒の存在下に、硝酸の水溶液を用いて液相状態でニトロ
化することｔ％徴とする芳香族ニトロ化合物の製法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing aromatic nitro compounds,
More specifically, the aromatic nitro compound is produced by nitrating the aromatic compound in the liquid phase using an aqueous solution of nitric acid in the presence of a crystalline aluminosilicate-containing catalyst having a silica/alumina molar ratio of at least 20. This relates to the manufacturing method.
（従来の技術）
芳香族ニトロ化合物は、芳香族アミン比合物の原料等に
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
る混酸を用い実施されているが、多量の硫酸を用いる几
め、廃＠＃Ｒや廃水処理等の問題がある。一方、廃硫ｔ
ｌ１１に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。例えば１％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、 ハロベンゼンを気相ニトロ化する方法が。(Prior Art) Aromatic nitro compounds are useful organic chemical intermediates used as raw materials for aromatic amine compounds. Industrial methods for producing aromatic nitro compounds are carried out using a mixed acid, which is a mixture of nitric acid and concentrated sulfuric acid, but there are problems such as the use of a large amount of sulfuric acid, waste@#R, and wastewater treatment. On the other hand, waste sulfur t
A gas phase nitration method has been proposed as a method to prevent the generation of l11. For example, 1% Publication No. 50-121234 discloses a method of nitrating halobenzene in a gas phase using silica/alumina or aluminosilicate as a catalyst.
特開昭５４−９５５２１号公報には、約５〜１０又の細
孔径を有する分子ふるい触媒の存在下で。In JP-A-54-95521, in the presence of a molecular sieve catalyst having a pore size of about 5 to 10 pores.
クロロベンゼンを気相ニトロ化する方法が１％開昭５８
−１５７７４８号公＠、ｌ＃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、
芳香族化合物を気相ニトロ化する方法が開示されている
。1% method for gas phase nitration of chlorobenzene was developed in 1982.
-157748@, l#Kokai No. 59-216851 uses aluminosilicate zeolite as a catalyst,
A method for vapor phase nitration of aromatic compounds is disclosed.
（発明が解決しようとする問題点）
公知の気相ニトロ化方法は、廃硫酸等の処理の問題解決
にはつながるが、いずれも比較的高い反応温度を必要と
してｂるＫもかかわらず、触媒当りのニトロ化合物の収
率も比較的低く、満足できる水準にない。さらに、気相
で比較的高い＠度条件のｔめニトロ化剤の熱分解が生じ
、ニトロ化剤効率が低くなるし１発生する酸化窒素ガス
は有害であシ廃ガス処理が必要となる等の問題も有して
いる。(Problems to be Solved by the Invention) Known gas phase nitration methods solve the problem of processing waste sulfuric acid, etc., but all of them require relatively high reaction temperatures, The yield of nitro compound per unit is also relatively low and not at a satisfactory level. Furthermore, thermal decomposition of the nitrating agent occurs under relatively high temperature conditions in the gas phase, lowering the nitrating agent efficiency, and the generated nitrogen oxide gas is harmful and requires waste gas treatment. It also has the problem of
気相ニトロｆヒ反応はインダストリー・アンド・エンジ
ニャリングケミストリー、 Ｊｕｎｅ、 １９５６゜６
６２ページ等に記載の反応式として１次式にし九がって
いると推定されている。The gas phase nitro-f reaction is described in Industrial and Engineering Chemistry, June, 1956゜6.
It is estimated that the reaction equation described on page 62 is a linear equation.
ｔ７ｔ、硝酸をニトロ化合物として用いても、硝酸は気
相では次式にし友がって酸化窒素への分解が生じること
、水利し几硝酸はより安定であることがメラー著「イン
オーガニック・アンド・セオレテイカルケミストリー」
８巻、５７２頁等に記載されている。Even if nitric acid is used as a nitro compound, nitric acid decomposes into nitrogen oxide in the gas phase according to the following formula, and nitric acid is more stable for water use.・Theoretical Chemistry”
It is described in Volume 8, page 572, etc.
４ＨＮＯ□ → ４ Ｎｏ、 ＋ ２Ｈ，Ｏ＋０．
・・・・・−・・（２）し九がって、気相ニトロ化反応
におりては、酸ｆヒ窒素ガスの生成は本質的に避けられ
ないものである。4HNO□ → 4 No, + 2H,O+0.
(2) Therefore, in the gas phase nitration reaction, the production of acid and arsenic gases is essentially unavoidable.
これら酸素や酸化窒素の発生は、ニトロ化反応以外の副
反応を生じる恐れも有している。The generation of oxygen and nitrogen oxide may also cause side reactions other than the nitration reaction.
（問題点を解決する几めの手段）
本発明者ら＃′ｉ、比較的低い＠度で、かつ高い収率が
得られる芳香族化合物のニトロ化法について鋭意検討を
加え九結果、シリカ／アルミナモル比が少なくとも２０
の結晶性アルミノシリケートを触媒とし、硝酸水溶液音
用いて液相状態でニトロ化することにより目的が達成さ
れることを見い出したものである。すなわち、硝酸の水
溶液をニトロ化剤に用い、しかも液相状態で反応させる
ことにより、＃化窒素等の有害ガスの発生を抑制でき。(Elaborate means to solve the problem) The present inventors have conducted intensive studies on a method for nitration of aromatic compounds that can obtain a high yield at a relatively low degree, and have found that silica/ Alumina molar ratio is at least 20
It was discovered that the objective could be achieved by nitration in the liquid phase using a nitric acid aqueous solution using a crystalline aluminosilicate as a catalyst. That is, by using an aqueous solution of nitric acid as a nitration agent and reacting it in a liquid phase state, the generation of harmful gases such as #nitrogen can be suppressed.
かつ前述の触媒が比較的低温の液相反ろに高い活性を有
することを見か出し友ものである。It has also been discovered that the above-mentioned catalyst has high activity in liquid phase filtration at relatively low temperatures.
本発明方法は、従来公知のニトロ化方法に比べ。The method of the present invention is compared with conventionally known nitration methods.
ジニトロ体等の副生物がほとんど生成しない特徴も有シ
ている。［Ｌモノハロベンゼン等のニトロ化において生
成するオルト体、メタ体、パラ体の異性体分布において
有用なバラ置換体を高い選択率で得ることができる等の
特徴も合せ有している。Another feature is that by-products such as dinitro forms are hardly produced. [It also has features such as being able to obtain with high selectivity a para-substituted product useful in the isomer distribution of ortho, meta, and para isomers produced in the nitration of L-monohalobenzene, etc.
本発明で用いられる芳香族化合物としては、ベンゼン、
ペン（ン誘導体、ナフタレン、す７タレン誘導体が挙げ
られる。ベンゼン誘導体としては。Aromatic compounds used in the present invention include benzene,
Examples of benzene derivatives include pen derivatives, naphthalene, and 7talene derivatives.
トルエン、エチルベンゼン等のアルキルベンゼン。Alkylbenzenes such as toluene and ethylbenzene.
モノクロロベンゼン、ジクロロベンゼン、モノブロモベ
ンゼン、ジブロモベンゼン、モノヨウ化ベンゼン、ジヨ
ウ化ベンゼン等のハロゲン化ベンゼン類を、す７タレン
誘導体として＃′ｉ、メチルナフタレン等のアルキルナ
フタレン、モノクロロナフタレ７等のハロゲン化す７タ
レンを例示することができる。これら芳香族化合物は、
液相状態で反応に供する。Halogenated benzenes such as monochlorobenzene, dichlorobenzene, monobromobenzene, dibromobenzene, monoiodination benzene, and diiodide benzene are used as #'i, alkylnaphthalenes such as methylnaphthalene, monochloronaphthalene 7, etc. as 7talene derivatives. An example is halogenated 7-talene. These aromatic compounds are
It is subjected to the reaction in a liquid state.
本発明で用いるニトロ化剤は硝酸水溶液であって。硝酸
濃度としては１０〜９１１１６で、好ましくは３０〜９
０チである。硝酸濃度が低く過ぎると反応率が低（，９
８％を超えるとＮＯｘの発生が生じ、ニトロ化剤の効率
が減少する。The nitrating agent used in the present invention is an aqueous nitric acid solution. Nitric acid concentration is 10-91116, preferably 30-9
It is 0chi. If the nitric acid concentration is too low, the reaction rate will be low (,9
Above 8%, NOx generation occurs and the efficiency of the nitrating agent decreases.
硝酸の使用割合は、芳香族化合物１モルに対して０．１
〜１０モル、好ましくは０．２〜５．０モルが用いられ
る。The ratio of nitric acid used is 0.1 per mole of aromatic compound.
~10 moles are used, preferably 0.2 to 5.0 moles.
反応温度としては、用いられる芳香族化合物により異な
るが１通常５０〜１５０Ｃ，好ましくは６０〜１２０Ｃ
が用層られる。The reaction temperature varies depending on the aromatic compound used, but is usually 50 to 150C, preferably 60 to 120C.
is used.
反応圧力は通常常圧で実施されるが、反応系を液相に保
つため加圧にしてもさしつかえない。The reaction pressure is usually carried out at normal pressure, but it may be pressurized to maintain the reaction system in a liquid phase.
本発明で用いる結晶性アルミノシリケートとしては、シ
リカ／アルミナモル比が少なくとも２０で好ましくは６
０以上のものであり、特に細孔径が約５〜６．５Ｘの中
間細孔径を有するものが好都合に用いられる。これら結
晶性アルミノシリケートを例示すれば、ＺＳＭ−５，Ｚ
ＳＭ−ｆ ｉ。The crystalline aluminosilicate used in the present invention has a silica/alumina molar ratio of at least 20 and preferably 6.
0 or more, particularly those having an intermediate pore diameter of about 5 to 6.5X are advantageously used. Examples of these crystalline aluminosilicates include ZSM-5, Z
SM-f i.
ＺＳＭ−１２，ＺＳＭ−２３，ＺＳＭ−３４、高シリカ
モルデナイト、脱アルミ安定化Ｙゼオライ）、ＡＺ−１
ｆＪｌセオライト（％開昭５９−１２８２１０号公報開
示）、シリカライト等を挙げることができる。’Ｉ？Ｋ
ＺＳＭ−５ｆｉが活性も高く、かつモノハロベンゼン類
等のニトロ化において有用なパラ置換体の選択率が高く
、好都合に用いることができる。これら結晶性アルミノ
シリケートは１通常プロトン交換型で用いるが、多価カ
チオンで交換し友ものも用いることができる。ZSM-12, ZSM-23, ZSM-34, high silica mordenite, dealuminated stabilized Y zeolite), AZ-1
Examples include fJl theolite (disclosed in % JP-A-59-128210), silicalite, and the like. 'I? K
ZSM-5fi has high activity and high selectivity for para-substituted compounds useful in nitration of monohalobenzenes, etc., and can be conveniently used. These crystalline aluminosilicates are usually used in the form of proton exchange, but they can also be exchanged with polyvalent cations.
これら触媒の使用形態としては、懸濁状態あるいは固定
床方式等通常の液相反応に用いられる形態で用いること
ができる。触媒の使用量としては。These catalysts can be used in a suspension state, a fixed bed system, or other forms used in ordinary liquid phase reactions. As for the amount of catalyst used.
流通方式の場合は芳香族化合物と硝酸の合計１準に対し
て０．１〜２０ ｈｒ−’の重量空関速ＭＥ（ＷＨ８Ｖ
）が用いられる。懸濁状態で用りる場合は、芳香族化合
物と硝酸の合計重量に対して５〜５０慢、好ましくは１
０〜３０Ｓの触媒が用いられる。In the case of the flow system, the gravimetric air speed ME (WH8V
) is used. When used in suspension, the amount is 5 to 50, preferably 1, based on the total weight of the aromatic compound and nitric acid.
A 0-30S catalyst is used.
（発明の効果）
本発明の方法によれば、芳香族のニトロ化を比較的低温
で、かつ高い空時収率で実施することができるとともに
、廃硫酸の処理やＮＯｘ等の有害ガスの処理も不要であ
シ、その工業的利点は極めて大きい、さらに、副生成物
として取シ扱いが困難なジェトロ体の生成等もほとんど
なく１分離縁作上の利点もある。ざらに加えて、モノハ
ロベンゼン等のニトロ化において耐熱性高分子原料とし
て有用なパラ異性体の選択率を高められる等の利点も有
している。(Effects of the Invention) According to the method of the present invention, aromatic nitration can be carried out at a relatively low temperature and with a high space-time yield, as well as treatment of waste sulfuric acid and harmful gases such as NOx. It is also unnecessary, and its industrial advantages are extremely great.Furthermore, there is also the advantage of one-separation edge production, as there is almost no formation of jetro bodies, which are difficult to handle, as by-products. In addition to this, it also has the advantage of increasing the selectivity of the para isomer, which is useful as a raw material for heat-resistant polymers in the nitration of monohalobenzene and the like.
（実施例） 以下、実施例を挙げて本発明を具体的に示すが。(Example) The present invention will be specifically illustrated below with reference to Examples.
本発明は、これに限定されるものではない。The present invention is not limited to this.
実施例１
公知方法にし友がッテＨＭｌ Ｚ Ｓ Ｍ −５（Ｓｊ
Ｏ＊ ／Ａｔｏｍ −４６） ’ｉｅ １ｕｌｌ製り、
反応に供Ｌ７ｔ。Example 1 A known method was used to obtain HMl Z SM -5 (S
O* /Atom-46) 'ie 1ull made,
L7t used for reaction.
クロロベンゼン６．８ ？、 ６１ ％硝９１２．５？
およびＨ１ｊｌＺ８Ｍ−５粉末４ ｆｆｔ、 カ；スｇ
ｏ５ 。Chlorobenzene 6.8? , 61% nitrate 912.5?
and H1jlZ8M-5 powder 4 fft,
o5.
−の攪拌器付きフラスコに入れ、攪拌下９０ＤＫ加熱し
２時間反応を行なった。冷却後、有機層を取シ出し、ガ
スクロマトグラフを用い分析を行なった。その結果、ニ
トロクロロベンゼンの収車は４５モル−で、ニトロクロ
ロベンゼンの異ａ体比率はオルト体：メタ体：パラ体、
１９：１：８Ｇであった。なお、ジニトロ体の生成は見
られなかった。The mixture was placed in a flask equipped with a stirrer, and the mixture was heated at 90 DK under stirring to carry out a reaction for 2 hours. After cooling, the organic layer was taken out and analyzed using a gas chromatograph. As a result, the yield of nitrochlorobenzene was 45 moles, and the ratio of isomers of nitrochlorobenzene was ortho: meta: para.
It was 19:1:8G. Note that no dinitro form was observed.
実施例２
反応温度をａｏＣにし友以外は、実施例１と同様ニクロ
ロベンゼンのニトロ化反応を行なツ几。Example 2 The nitration reaction of dichlorobenzene was carried out in the same manner as in Example 1, except that the reaction temperature was set to aoC.
その結果、ニトロクロロベンゼンの収１１Ｉｆｉｓｏモ
ル僑で、オルト体：メタ体：パラ体−１９，７：０．８
： ７９．５であつ友。なお、ジニトロ体の生成は見
られなかつ友。As a result, the yield of nitrochlorobenzene was 11 Ifiso molar ratio, ortho form: meta form: para form -19,7:0.8
: 79.5 and my friend. In addition, no formation of dinitro isomers was observed.
実施例５
テア０ン内張りのＳＵＳ製１００−オートクレーブを用
い、クロロベンゼン１７２％６１ ｑｋ１１４Ｍ！（Ｍ
’および前述Ｏｎ！ＪｌｚｓＭ−５１０２を仕込み、窒
素加圧２ ｋｇ ／ ａｄ 、攪拌下加熱し、１２０Ｃ
で２時間反応を行なった。その結果、ニトロクロロベン
ゼンの収率６５．９モル−で、オルト体：メタ体：パラ
体！ １７．５ ： Ｑ、５ ； ８２．０でめつ几。Example 5 Using a SUS 100-autoclave with a tare lining, chlorobenzene 172%61 qk114M! (M
' and the aforementioned On! Charge JlzsM-5102, pressurize with nitrogen at 2 kg/ad, heat with stirring, and heat to 120C.
The reaction was carried out for 2 hours. As a result, the yield of nitrochlorobenzene was 65.9 moles, with ortho form: meta form: para form! 17.5: Q, 5; 82.0 and a loss.
実施例４ 実施例１と同様に、ただし、硝酸量１に６．２ ｆ 。Example 4 Same as Example 1, except that the amount of nitric acid is 1 and 6.2 f.
ＨＪｌｌＺ８Ｍ−５量’に２ｆにり、、反応温度８０Ｃ
で２時間反応を行なつ友、その結果、ニトロクロロベン
ゼンの収車は１４４モル％、異性体化第はオルト体：メ
タ体：パラ体＋−１９：０：Ｂ１であつ友。HJllZ8M-5 amount was 2f, reaction temperature 80C
As a result, the yield of nitrochlorobenzene was 144 mol%, and the isomerization ratio was ortho form: meta form: para form + - 19:0:B1.
実施例５
８ｆ％ ／Ａ／４０．−９０ （Ｄ ＨｍＺ Ｓ Ｍ
−５を公知方法によｌ）ｍｌ１４Ｌ、反応に用い友。ク
ロロベンゼン６．４ｆ、５０％硝酸１０ｆおよびＨｆｉ
ＺＳＭ−５４ｆｔ−実施例１と同様に、９０Ｃで２時間
反応を行なつ九。その結果、ニトロクロロベンゼンの収
率は２１．６モル％で、オルト体：メタ体：パラ体り８
： Ｏ： ８２であつ九。なお、ジニトロ体の生成は
見られなかつ几。Example 5 8f% /A/40. -90 (D HmZ S M
-5 was prepared by a known method and 14 L of ml was used for the reaction. Chlorobenzene 6.4f, 50% nitric acid 10f and Hfi
ZSM-54ft-Similar to Example 1, the reaction was carried out at 90C for 2 hours. As a result, the yield of nitrochlorobenzene was 21.6 mol%, and the ortho form: meta form: para form was 8
: O: 82 and nine. In addition, no formation of dinitro isomers was observed.
実施例６
実施例１と同様の方法で、ベンゼン５？、６１嘩硝酸１
２．５ ？および実施例５で用い友と同じＨ型ＺＳＭ−
５４ｆｆ用い、７５１．ｔ”２時間反応を行なった。そ
の結果、ニトロベンゼンの収率は３４モモル慢あり、ジ
ニトロ体等の副生物は見られなかつ九。Example 6 In the same manner as in Example 1, benzene 5? , 61 nitric acid 1
2.5? And the same H-type ZSM- used in Example 5.
Using 54ff, 751. The reaction was carried out for 2 hours. As a result, the yield of nitrobenzene was 34 mmol, and no by-products such as dinitro compounds were observed.
実施例７
クロロベンゼンをブロモベンゼン９ＰＫ賛、ｔた以外は
、実施例１と同様にニトロ化反応金行なった。Example 7 A nitration reaction was carried out in the same manner as in Example 1, except that chlorobenzene was replaced with bromobenzene 9PK.
その結果、ニトロブロモベンゼンの収率は２４．８モル
係でオルト体：メタ体：ノ（う体＝ １４．５ ：Ｑ、
３ ： ８５．４であった。なお、ジブロモベンゼン０
．５モル慢の生成が認められたがジニトロ体の生成は見
られなかつ７ｔ。As a result, the yield of nitrobromobenzene was 24.8 molar ratio, ortho form: meta form: no (deli form = 14.5: Q,
3: It was 85.4. In addition, dibromobenzene 0
．． Formation of 5 molar fractions was observed, but no dinitro compound was observed, and 7 molar fractions were observed.
実施例８
石英製反応管（１０關φ）Ｋ実施例１で用いたと同じＨ
型ＺＳＭ−５を圧縮成形し、１０〜２Ｇメツシユに砕い
友ものを４１元項して９０Ｃに加熱し、クロロベンゼン
４．２ｃｃ／Ｈｒ、６ ｊ ＊硝改１．８ ＣＣ／ Ｈ
ｒを同時に供給し１反応を行なつ九。Example 8 Quartz reaction tube (10 mm φ) K Same as used in Example 1
Type ZSM-5 was compression molded, crushed into 10-2G mesh, heated to 90C with 41 elements, and chlorobenzene 4.2cc/Hr, 6J*Nitsu Kai 1.8CC/H
9. Perform one reaction by simultaneously supplying r.
通液後６時間口の反応流出液（有機相）の分析結果ハ、
ニトロクロロベンゼンの収ｌＫ１７モル係で。Analysis results of the reaction effluent (organic phase) after 6 hours of passage
The yield of nitrochlorobenzene is 17 moles.
オルト体：メタ体：パラ体！１４：Ｏ：８４であり、ジ
ニトロ体の生成は見られなかった。また。Alt body: Meta body: Para body! 14:O:84, and no dinitro form was observed. Also.
反応中ＮＯｘガスの発生は見られなかつ九。No generation of NOx gas was observed during the reaction.
実施例９
市販の高シリカモルデナイト（５ｉＯ１／Ａｔ４０ｋ
＝２２）を公知方法によりＨｆｆｌとして触媒に用いた
以外は、実施例２と同様に行なつ几。その結果、ニトロ
クロロベンゼンの収＄２５モル囁でオルト体：メタ体：
パラ体＝ ５９．２ ： ０．２ ： ６ Ｑ、６であ
った。Example 9 Commercially available high silica mordenite (5iO1/At40k
Example 2 was carried out in the same manner as in Example 2, except that Hffl=22) was used in the catalyst as Hffl by a known method. As a result, the yield of nitrochlorobenzene was about 25 moles; the ortho form: the meta form:
Para body = 59.2: 0.2: 6 Q, 6.
実施例１０
市販の脱アルミＹｉゼオライト（ＳｉＯ，／Ａ！、Ｏ，
−１００）を触媒とし、実施例１と同様に、クロロベン
ゼンのニトロ化反応ｔａｓｃで２時間行なつ之。その結
果、ニトロクロロベンゼンの収率は２４モル僑で、オル
ト体：メタ体：バラ体＝３０：Ｏニア０であった。Example 10 Commercially available dealuminated Yi zeolite (SiO, /A!, O,
-100) as a catalyst, the nitration reaction of chlorobenzene (task) was carried out for 2 hours in the same manner as in Example 1. As a result, the yield of nitrochlorobenzene was 24 mol, and the ratio of ortho form: meta form: bulk form = 30: Onia 0.
実施例１１
実施例８と同様に、友だし、触媒として実施例５で用い
友と同じ触媒を成形して用す、クロロベンゼア ４ 、
２ Ｃ６／ Ｈｄ１硝酸０，９ （Ｘ：／Ｈｒ ｔ−供
給して反応を何なつ之。通液６時間口の反応流出液（有
機相）の分析結果は、ニトロベンゼンの収率９モル慢で
、オルト体：メタ体：バラ体−Ｉ Ｃ８： ０二８６．
２であシ、ジニトロ体の生成は見られなかつ友。ま几１
反応中ＮＯｘガスの発生は見られなかつ几。Example 11 In the same manner as in Example 8, the same catalyst used in Example 5 was molded and used as a catalyst, chlorobenzea 4,
2 C6/ Hd1 Nitric acid 0.9 (X:/Hr t- was supplied to carry out the reaction. The analysis result of the reaction effluent (organic phase) at the inlet for 6 hours showed that the yield of nitrobenzene was 9 molar. , ortho form: meta form: rose form - IC8: 0286.
2, no formation of dinitro form was observed. Mako 1
No generation of NOx gas was observed during the reaction.
比較例１
実施例１と同様で、７ｔだし、触媒を用いず反応を行な
った結果、クロロベンゼンの転化率は７囁テアシ、ニト
ロクロロベンゼンの異性体比はオルト体：メタ体：パラ
体±４１．５ ： ０，１ ： ５８，４であつｔ。Comparative Example 1 Same as Example 1, but the reaction was carried out at 7t without using a catalyst. As a result, the conversion rate of chlorobenzene was 7.5%, and the isomer ratio of nitrochlorobenzene was ortho form: meta form: para form ± 41. 5: 0, 1: 58, 4 and t.
比較例２
実施例１と同様に、友だし、触媒として市販のシリカ・
アルミナ（Ａ！４０Ｂ含有量１含有量１ラゼンのニトロ
化反応を行なつ九。その結果，ニトロクロロベンゼンの
収率８％で．オルト体：メタ体：バラ体−４０：０：６
０であつ之。Comparative Example 2 Similar to Example 1, commercially available silica was used as a friend and catalyst.
Nitration reaction of alumina (A!40B content 1 content 1 lazene) was carried out. As a result, the yield of nitrochlorobenzene was 8%. Ortho form: Meta form: Bulk form - 40:0:6
It's 0.
Claims (2)
とも２０の結晶性アルミノシリケート含有触媒の存在下
に、硝酸水溶液を用いて液相状態でニトロ化することを
特徴とする芳香族ニトロ化合物の製法。(1) A method for producing an aromatic nitro compound, which comprises nitrating the aromatic compound in a liquid phase using an aqueous nitric acid solution in the presence of a crystalline aluminosilicate-containing catalyst having a silica/alumina molar ratio of at least 20.
効細孔径を有するものであ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 crystalline aluminosilicate has an effective pore diameter of about 5 to 6.5 Å.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62056791A JPH0796533B2 (en) | 1987-03-13 | 1987-03-13 | Method for producing aromatic nitro compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62056791A JPH0796533B2 (en) | 1987-03-13 | 1987-03-13 | Method for producing aromatic nitro compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63225339A true JPS63225339A (en) | 1988-09-20 |
| JPH0796533B2 JPH0796533B2 (en) | 1995-10-18 |
Family
ID=13037235
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62056791A Expired - Lifetime JPH0796533B2 (en) | 1987-03-13 | 1987-03-13 | Method for producing aromatic nitro compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0796533B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1004570A1 (en) * | 1998-11-23 | 2000-05-31 | Council of Scientific and Industrial Research | A process for the production of nitroarenes with high para-selectivity from monosubstituted aromatic hydrocarbons using aluminosilicates as catalysts |
| US6376726B1 (en) * | 1997-10-14 | 2002-04-23 | Council Of Scientific & Industrial Research | Process for the production of nitroaromatic compounds from aromatic hydrocarbons using modified clay catalysts |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5163134A (en) * | 1974-01-21 | 1976-06-01 | Teijin Ltd | harobenzen no nitorokaho |
| JPS59216851A (en) * | 1983-05-26 | 1984-12-06 | Japan Synthetic Rubber Co Ltd | Preparation of aromatic nitro compound |
-
1987
- 1987-03-13 JP JP62056791A patent/JPH0796533B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5163134A (en) * | 1974-01-21 | 1976-06-01 | Teijin Ltd | harobenzen no nitorokaho |
| JPS59216851A (en) * | 1983-05-26 | 1984-12-06 | Japan Synthetic Rubber Co Ltd | Preparation of aromatic nitro compound |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6376726B1 (en) * | 1997-10-14 | 2002-04-23 | Council Of Scientific & Industrial Research | Process for the production of nitroaromatic compounds from aromatic hydrocarbons using modified clay catalysts |
| EP1004570A1 (en) * | 1998-11-23 | 2000-05-31 | Council of Scientific and Industrial Research | A process for the production of nitroarenes with high para-selectivity from monosubstituted aromatic hydrocarbons using aluminosilicates as catalysts |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0796533B2 (en) | 1995-10-18 |
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