JPH05194363A - Production of 2-methyl-5-nitrobenzenesulfonic acid and its sodium salt - Google Patents
Production of 2-methyl-5-nitrobenzenesulfonic acid and its sodium saltInfo
- Publication number
- JPH05194363A JPH05194363A JP496292A JP496292A JPH05194363A JP H05194363 A JPH05194363 A JP H05194363A JP 496292 A JP496292 A JP 496292A JP 496292 A JP496292 A JP 496292A JP H05194363 A JPH05194363 A JP H05194363A
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- Prior art keywords
- pnt
- water
- nitrotoluene
- methyl
- reaction
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、蛍光漂白剤、染顔料等
の中間体に用いられる２−メチル−５−ニトロベンゼン
スルフォン酸（以下、「ＰＮＴ−スルフォン酸」と略
す）及び２−メチル−５−ニトロベンゼンスルフォン酸
ソーダ塩（以下、「ＰＮＴ−スルフォン酸ソーダ塩」と
略す）の製造法に関するものである。FIELD OF THE INVENTION The present invention relates to 2-methyl-5-nitrobenzenesulfonic acid (hereinafter abbreviated as "PNT-sulfonic acid") and 2-methyl-former used as intermediates for fluorescent bleaching agents, dyes and pigments. The present invention relates to a method for producing 5-nitrobenzene sulfonic acid sodium salt (hereinafter abbreviated as "PNT-sodium sulfonic acid salt").
【０００２】[0002]
【従来の技術】従来、Ｐ−ニトロトルエン（以下、「Ｐ
ＮＴ」と略す）のスルフォン化法として各種の方法が検
討されている。例えば、発煙硫酸の場合にはＳＯ3濃度
２０〜２５ｗｔ％が一般的であるが、多量の廃酸を伴う
ため５０〜８５ｗｔ％の発煙硫酸でスルフォン化し、水
希釈後硫酸濃度６０〜７５ｗｔ％でＰＮＴ−スルフォン
酸を晶析により得ている（特開昭６０−１３２９５０
号）。2. Description of the Related Art Conventionally, P-nitrotoluene (hereinafter referred to as "P
Various methods have been studied as a sulfonation method for "NT"). For example, in the case of fuming sulfuric acid, a SO 3 concentration of 20 to 25 wt% is generally used, but since a large amount of waste acid is involved, it is sulfonated with 50 to 85 wt% of fuming sulfuric acid and diluted with water to a sulfuric acid concentration of 60 to 75 wt%. PNT-sulfonic acid is obtained by crystallization (JP-A-60-132950).
issue).
【０００３】しかし、この方法は若干廃酸の量が少なく
なるのみで廃酸の処理には問題がある。However, this method has a problem in treating the waste acid since the amount of the waste acid is slightly reduced.
【０００４】１００％ＳＯ3ガスを用いてスルフォン化
する方法では、少量の硫酸（０．１４部／ＰＮＴ１．０
部）を使用して反応の促進と反応終期の反応液の流動性
をはかっている（特開昭５８−１１８５５５号）。尚、
ＳＯ3ガスを用いる時、６０〜７０％がスルフォン化す
ると、反応が急激に遅くなる（ファインアロマチックス
中間体、ボロチェツオフ著、第４８頁；技報堂）。この
ため反応促進、完結のため硫酸を使用するか、或いは過
剰のＳＯ3を使用する必要がある。何れにせよ反応生成
物を水溶解後のＰＮＴ−スルフォン酸中に硫酸がかなり
残り（上記特開昭５８−１１８５５５号実施例１；Ｈ2
ＳＯ4／ＰＮＴ−スルフォン＝４．５％／３３．６
％）、この硫酸の量はそのまま次の工程に使用する場合
支障をきたす場合が多い。In the method of sulfonization using 100% SO 3 gas, a small amount of sulfuric acid (0.14 part / PNT1.0
Part) is used to promote the reaction and to improve the fluidity of the reaction solution at the end of the reaction (JP-A-58-118555). still,
When SO 3 gas is used, when 60 to 70% is sulfonated, the reaction is abruptly slowed down (Fine Aromatics Intermediate, Borochetsoff, p. 48; Gihodo). For this reason, it is necessary to use sulfuric acid or excess SO 3 for accelerating and completing the reaction. In any case, sulfuric acid remains in the PNT-sulfonic acid after the reaction product is dissolved in water (see JP-A-58-118555, Example 1; H 2 above).
SO 4 /PNT-Sulfone=4.5%/33.6
%), The amount of this sulfuric acid often causes trouble when it is used as it is in the next step.
【０００５】２０ｖｏｌ％ＳＯ3ガス（不活性ガス窒素
８０ｖｏｌ％）の場合、１００％ＳＯ3ガスよりも穏和
な反応になるが、反応完結が困難で未反応ＰＮＴ及び着
色成分を活性炭で吸着除去している（ＵＳＰ３８４０５
９１）。しかし活性炭はかなりの量を必要とし、高価で
ある。In the case of 20 vol% SO 3 gas (80 vol% of inert gas nitrogen), the reaction is milder than that of 100% SO 3 gas, but it is difficult to complete the reaction, and unreacted PNT and coloring components are adsorbed and removed by activated carbon. (USP38405
91). However, activated carbon requires a considerable amount and is expensive.
【０００６】１００％ＳＯ3ガスを使用して、７０％以
上の転化率で水溶解後、水と混合しない溶媒で未反応Ｐ
ＮＴを抽出する方法（特公昭６３−４０１８４号）は、
溶媒の回収、残存する溶媒の除去等の複雑な操作を伴
う。After using 100% SO 3 gas to dissolve water at a conversion rate of 70% or more, unreacted P is dissolved in a solvent immiscible with water.
The method for extracting NT (Japanese Patent Publication No. 63-40184) is
It involves complicated operations such as solvent recovery and residual solvent removal.
【０００７】[0007]
【発明が解決しようとする課題】本発明が解決しようと
する課題は、ＳＯ3ガスを用いてＰＮＴをスルフォン化
し、ＰＮＴ−スルフォン酸及びＰＮＴ−スルフォン酸ソ
ーダ塩を製造するに際し、硫酸（ソーダ塩の場合にはぼ
う硝）の残留を少なくし、且つ未反応ＰＮＴが残留しな
い製品とする点にある。The problem to be solved by the present invention is to sulphonate PNT using SO 3 gas to produce PNT-sulfonic acid and PNT-sulfonic acid sodium salt, and to remove sulfuric acid (soda salt). In the case of (1), there is a small amount of residual Glauber's salt, and there is no unreacted PNT remaining in the product.
【０００８】[0008]
【課題を解決するための手段】本発明は、ＰＮＴのＳＯ
3ガスによるスルフォン化反応に際して、ＳＯ3ガスをス
ルフォン化に必要な理論量の９０モル％から１４０モル
％使用してスルフォン化し、次いで熟成することによ
り、残存するＰＮＴ及びＳＯ3の相互反応によって未反
応ＰＮＴ及びＳＯ3を少なくし、しかる後に未反応ＰＮ
Ｔを除去することにより蛍光増白剤、染顔料等の中間体
としてそのまま使用可能なＰＮＴ−スルフォン酸及びそ
のソーダ塩を得るものである。The present invention relates to SO of PNT.
In the sulfonation reaction with 3 gas, SO 3 gas is sulfonated using 90 mol% to 140 mol% of the theoretical amount required for sulfonation, and then aged, whereby unreacted PNT and SO 3 remain unreacted. Reacted PNT and SO 3 are reduced, and then unreacted PN
By removing T, it is possible to obtain PNT-sulfonic acid and its soda salt which can be used as they are as an intermediate for fluorescent whitening agents, dyes and pigments and the like.
【０００９】以下に順をおって本発明を説明する。ＰＮ
ＴのＳＯ3ガスによるスルフォン化は連続法又は回分法
により５５〜１３０℃の温度で実施する。未反応ＰＮＴ
の残存量を少なくするために、ＳＯ3ガス導入工程であ
るスルフォン化反応工程に引き続き、ＳＯ3ガスを導入
せず１００〜１３０℃に保持する熟成工程を必要とす
る。反応温度が５５℃以下ではＰＮＴの融点以下であ
り、且つスルフォン化率が低下する。１３０℃以上では
得られるスルフォン酸の色調は著しく悪化するようにな
る。又、必要に応じ、２，２’−ジメチル−５，５’−
ジニトロビフェニルスルフォン（以下、「ＰＮＴ−スル
フォン」と略す）の生成を抑制する公知のスルフォン抑
制剤を使用することができる。The present invention will be described below step by step. PN
Sulfonation of T with SO 3 gas is carried out at a temperature of 55 to 130 ° C. by a continuous method or a batch method. Unreacted PNT
In order to reduce the remaining amount of the above, a aging step of maintaining the temperature at 100 to 130 ° C. without introducing SO 3 gas is required following the sulfonation reaction step which is an SO 3 gas introducing step. When the reaction temperature is 55 ° C. or lower, it is lower than the melting point of PNT, and the sulfonation rate decreases. At 130 ° C. or higher, the color tone of the sulfonic acid obtained becomes remarkably deteriorated. If necessary, 2,2'-dimethyl-5,5'-
Known sulfone inhibitors that suppress the production of dinitrobiphenyl sulfone (hereinafter abbreviated as "PNT-sulfone") can be used.
【００１０】ＰＮＴのＳＯ3ガスによる回分式スルフォ
ン化反応に際して、反応温度を前半上記反応温度範囲内
の比較的低温、例えば６０〜１０５℃で行い、原料ＰＮ
Ｔの逸散を防止する。これは特に原料ガス中の不活性ガ
ス（乾燥空気、窒素）によりＳＯ3濃度が低いとき効果
が大きい。反応が後半になると原料の逸散は少なくな
り、且つ反応速度も低下するので反応温度を１０５〜１
１５℃に上昇させる。In the batch sulfonation reaction of PNT with SO 3 gas, the reaction temperature is relatively low within the above reaction temperature range in the first half, for example, 60 to 105 ° C.
Prevent the escape of T. This is particularly effective when the SO 3 concentration is low due to the inert gas (dry air, nitrogen) in the raw material gas. In the latter half of the reaction, the dissipation of the raw materials decreases and the reaction rate also decreases, so the reaction temperature is 105 to 1
Raise to 15 ° C.
【００１１】ＳＯ3ガス供給量はスルフォン化に必要な
理論値の９０〜１４０モル％であるが、好ましくは不活
性ガスを含むＳＯ3の場合９５〜１３０モル％である。
これは不活性ガスで希釈される程、穏和な反応になる
が、反面ＳＯ3ガスの吸収は悪くなるため多くを必要と
する。スルフォン化反応の後半、反応温度を例えば１０
５〜１１５℃でＳＯ3を必要量作用させても、ＰＮＴは
６ｗｔ％以上残存する。これは、ＰＮＴ−スルフォン酸
にＳＯ3が付加したピロスルフォン酸及び溶存ＳＯ3の形
で残存するものと推定される。これらの残存ＰＮＴとＳ
Ｏ3の反応を促進するために、更に１０５〜１１５℃で
約３時間熟成反応を行うことにより、ＰＮＴ−スルフォ
ン酸とする。熟成後、ＰＮＴが約０．５％以上残るよう
に使用ＳＯ 3量を調節することにより、水分解後の硫酸
含有量を少なくすることができる。SO3Gas supply is necessary for sulfonation
90 to 140 mol% of theory, but preferably inactive
SO containing natural gas3In the case of, it is 95 to 130 mol%.
This becomes a mild reaction as it is diluted with an inert gas
But on the other hand SO3Gas absorption is poor, so much is needed.
To do. In the latter half of the sulfonation reaction, the reaction temperature is, for example, 10
SO at 5 to 115 ° C3Even if the required amount of
6 wt% or more remains. This is PNT-sulfonic acid
To SO3Pyrosulphonic acid with added SO and dissolved SO3Form of
It is estimated that it will remain in. These remaining PNT and S
O3In order to accelerate the reaction of
By carrying out the aging reaction for about 3 hours, PNT-sulfo
Acid. About 0.5% or more of PNT remains after aging
Used for SO 3By adjusting the amount, sulfuric acid after water decomposition
The content can be reduced.
【００１２】しかし、ＰＮＴ−スルフォン酸水溶液を製
品とする場合は、水溶解時の発熱量を有効利用する観点
から、ＰＮＴ−スルフォンの除去は未反応ＰＮＴ除去の
後の方が好ましく又、ＰＮＴ−スルフォン酸ソーダ塩を
製品とする場合にはソーダ塩の溶解度が低いので、中和
前（即ち未反応ＰＮＴ除去の前）にＰＮＴ−スルフォン
を除去することが好ましい。However, when a PNT-sulfonic acid aqueous solution is used as a product, it is preferable to remove the unreacted PNT after removing the unreacted PNT from the viewpoint of effectively utilizing the heat generation amount when water is dissolved. When the sodium sulfonic acid salt is used as a product, the solubility of the soda salt is low. Therefore, it is preferable to remove PNT-sulfone before neutralization (that is, before removing unreacted PNT).
【００１３】熟成後の反応生成物は水に溶解させて水溶
液とし、加温してＰＮＴを水と共に蒸留することによ
り、未反応ＰＮＴを除去することができる。この際、溶
液濃度を保持するため留出水と同量の水を補給する。
又、水蒸気を吹き込む水蒸気蒸留法も適用できる。尚、
僅かに副生するＰＮＴ−スルフォン除去のために水溶液
を３０〜４５ｗｔ％とし、冷却して析出するＰＮＴ−ス
ルフォンをろ過により除去する。このＰＮＴ−スルフォ
ンの除去工程は未反応ＰＮＴ除去の前でも、後でも可能
である。The unreacted PNT can be removed by dissolving the reaction product after aging in water to obtain an aqueous solution, heating and distilling PNT together with water. At this time, the same amount of water as the distilled water is replenished to maintain the solution concentration.
A steam distillation method in which steam is blown in can also be applied. still,
The aqueous solution is adjusted to 30 to 45 wt% to remove slightly produced PNT-sulfone, and the PNT-sulfone that precipitates by cooling is removed by filtration. This step of removing PNT-sulfone can be performed before or after removing unreacted PNT.
【００１４】熟成後の反応生成物は水に溶解して３０〜
４５ｗｔ％の水溶液とし、冷却後析出するＰＮＴ−スル
フォンをろ過により除去した後、３０％の苛性ソーダ水
溶液で中和してＰＮＴ−スルフォン酸ソーダ塩水溶液と
することができる。その後更に加温してＰＮＴを水と共
に蒸留することにより未反応ＰＮＴを除去することがで
きる。その際、溶液濃度を保持するため留出水と同量の
水を補給するか又は、水蒸気を吹き込む水蒸気蒸留法も
適用できる。未反応ＰＮＴを除去したＰＮＴ−スルフォ
ン酸ソーダ塩水溶液は更に濃縮が必要な場合には、水と
蒸留する時の補給水を減らして必要濃度にすることがで
きる。この際の濃縮温度は１０１〜１０３℃で、ＰＮＴ
−スルフォン酸ソーダ塩濃度は２５〜３０ｗｔ％であ
る。この濃度以上では、スラリーが濃くなり操作上好ま
しくない。The reaction product after aging is dissolved in water to 30 to 30%.
A 45 wt% aqueous solution is prepared, and after cooling, PNT-sulfone that precipitates after filtration is removed by filtration, and then neutralized with a 30% aqueous sodium hydroxide solution to obtain a PNT-sodium sulfonic acid salt aqueous solution. After that, the unreacted PNT can be removed by further heating and distilling the PNT with water. At that time, a steam distillation method in which the same amount of water as the distilled water is replenished or steam is blown in order to maintain the solution concentration can be applied. When the PNT-sodium sulfonic acid salt aqueous solution from which unreacted PNT has been removed needs further concentration, the make-up water at the time of distillation with water can be reduced to a required concentration. At this time, the concentration temperature is 101 to 103 ° C., and PNT is
-The sodium sulfonate salt concentration is 25-30 wt%. Above this concentration, the slurry becomes thick and is not preferable in operation.
【００１５】ここで得られた濃厚溶液はニーダー等の強
力な攪拌下、冷却して濃スラリーとするか、或いはドラ
ムドライヤー等の乾燥機で固形粉末とすることができ
る。The concentrated solution obtained here can be cooled under strong stirring with a kneader or the like to give a concentrated slurry, or can be made into a solid powder with a dryer such as a drum dryer.
【００１６】熟成後の反応生成物を水に溶解して、冷却
後析出したＰＮＴ−スルフォンを除去したＰＮＴ−スル
フォン酸水溶液、或いは更に中和したＰＮＴ−スルフォ
ン酸ソーダ塩水溶液を、充填塔の上部より供給し、下部
より水蒸気を向流で吹き込むことにより、未反応ＰＮＴ
を除去することができる。この連続法で使用するスチー
ムの量はバッチ法の場合よりかなり少ない量である。更
に濃縮したＰＮＴ−スルフォン酸水溶液、或いはそのソ
ーダ塩水溶液を得たい時には、充填塔下部に取り付けた
蒸留缶を加熱して、濃縮と同時に発生したスチームをＰ
ＮＴの水蒸気蒸留除去に使用するという効率的なＰＮＴ
除去法を採用することが可能である。The reaction product after aging is dissolved in water, and the PNT-sulfonic acid aqueous solution from which the PNT-sulfone precipitated after cooling is removed or the further neutralized PNT-sodium sulfonic acid salt aqueous solution is added to the top of the packed column. Is supplied from the bottom and steam is blown in countercurrently from the bottom, so that unreacted PNT
Can be removed. The amount of steam used in this continuous process is considerably less than in the batch process. When it is desired to obtain a more concentrated PNT-sulfonic acid aqueous solution or its soda salt aqueous solution, the distillation can attached to the lower part of the packed column is heated to remove steam generated at the same time as P concentration.
Efficient PNT used for steam distillation removal of NT
A removal method can be adopted.
【００１７】[0017]
【実施例】以下に実施例を挙げ本発明を更に詳細に説明
するが、本発明はこれらに限定されるものではない。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
【００１８】実施例 １ 攪拌機、バッフル、ガス吹き込み管を取り付けたＳＵＳ
３０４製の１０Ｌ反応槽に、原料溶融ＰＮＴ４．８７Ｋ
ｇ（３５．５モル）を仕込む。吹き込み管より乾燥空気
１．６ｍ3／ｈで５分間通して吹き込み管内のＰＮＴを
追い出す。次いで９％ＳＯ3ガスを１．６ｍ3／ｈで吹き
込みスルフォン化を開始した。温度は６０℃より徐々に
上昇させ約２時間で１０５℃に達した。更に１０５〜１
１５℃で４時間ＳＯ3ガスを吹き込み（ＰＮＴの１０８
モル％）反応を中止した。Example 1 SUS equipped with a stirrer, a baffle, and a gas blowing tube
304 melted raw material PNT 4.87K in 10L reactor
g (35.5 mol) are charged. The PNT in the blow-in pipe is expelled by passing it through the blow-in pipe with 1.6 m 3 / h of dry air for 5 minutes. Then, 9% SO 3 gas was blown at 1.6 m 3 / h to start sulfonation. The temperature was gradually raised from 60 ° C and reached 105 ° C in about 2 hours. Further 105-1
Blow SO 3 gas at 15 ° C for 4 hours (PNT 108
The reaction was stopped.
【００１９】この時点での未反応ＰＮＴはＨＰＬＣ分析
で９．０％であった。更に同温度で３時間熟成すると未
反応ＰＮＴは３．６％に減少した。分析のために水分解
し、生成した硫酸を電位差滴定分析により求めたとこ
ろ、３．６ｗｔ％であった。又、得られたＰＮＴ−スル
フォン酸の純度は９３．３ｗｔ％、収率は９５％であっ
た。Unreacted PNT at this point was 9.0% by HPLC analysis. Further, when the mixture was aged at the same temperature for 3 hours, unreacted PNT was reduced to 3.6%. It was 3.6 wt% when the sulfuric acid produced by water splitting for the analysis was determined by potentiometric titration analysis. The purity of the obtained PNT-sulfonic acid was 93.3 wt% and the yield was 95%.
【００２０】熟成後の反応生成物５００ｇ（ＰＮＴ含量
３．６ｗｔ％）を水６００ｇに溶かし、８０℃で３０分
間加温して粗ＰＮＴ−スルフォン酸水溶液とした。本溶
液を更に加温してＰＮＴを水と共に蒸留し、同時に留出
水と同量の水を補給し続けた。 留出水はＰＮＴを懸濁
して白濁状であるが、１６００ｍｌ留出後、液は透明と
なった。更に、２００ｍｌ留出すると釜残中のＰＮＴ−
スルフォン酸水溶液には未反応のＰＮＴは検出できなく
なった。本溶液を冷却して析出するＰＮＴ−スルフォン
４．５ｇをろ過により除去して４２．４％のＰＮＴ−ス
ルフォン酸水溶液１１００ｇを得た。500 g of the reaction product after aging (PNT content 3.6 wt%) was dissolved in 600 g of water and heated at 80 ° C. for 30 minutes to obtain a crude PNT-sulfonic acid aqueous solution. This solution was further heated to distill PNT together with water, and at the same time, the same amount of water as distilled water was continuously supplied. The distilled water had a white turbidity due to suspension of PNT, but after distilling 1600 ml, the liquid became transparent. Furthermore, if 200 ml is distilled, the PNT-
Unreacted PNT could not be detected in the aqueous sulfonic acid solution. This solution was cooled to remove 4.5 g of precipitated PNT-sulfone by filtration to obtain 1100 g of a 42.4% aqueous PNT-sulfonic acid solution.
【００２１】実施例 ２ 実施例１と同様に熟成後の反応生成物５００ｇ（ＰＮＴ
含量３．６ｗｔ％）を水分解後、得られた粗ＰＮＴ−ス
ルフォン酸水溶液を冷却して析出するＰＮＴ−スルフォ
ン４．５ｇをろ過により除去した。次いで３０％苛性ソ
ーダ水溶液３１０ｇ、水３１０ｇで中和した。中和後更
に加温して、ＰＮＴを水と共に蒸留し同時に留出水と同
量の水を補給し続けた。留出水はＰＮＴを懸濁して白濁
状であったが、１２００ｍｌ留出後、透明となった。更
に１５０ｍｌ留出すると釜残中のＰＮＴ−スルフォン酸
ソーダ塩水溶液には未反応ＰＮＴは検出されなくなっ
た。Example 2 As in Example 1, 500 g of reaction product after aging (PNT
The content of 3.6 wt%) was hydrolyzed, and the resulting crude PNT-sulfonic acid aqueous solution was cooled to remove 4.5 g of PNT-sulfone which was deposited by filtration. Then, it was neutralized with 310 g of a 30% aqueous sodium hydroxide solution and 310 g of water. After neutralization, the mixture was further heated, PNT was distilled together with water, and at the same time, the same amount of water as distilled water was continuously supplied. The distilled water was turbid due to suspension of PNT, but became transparent after 1200 ml of distilled water. When 150 ml was further distilled off, unreacted PNT was not detected in the PNT-sodium sulfonic acid salt aqueous solution in the bottom of the kettle.
【００２２】得られた溶液は更に濃縮・乾燥して粉末と
した。ＰＮＴ−スルフォン酸ソーダ塩の収量は５５２
ｇ、純度は９３％であった。The resulting solution was further concentrated and dried to give a powder. The yield of PNT-sodium sulfonate is 552.
g, the purity was 93%.
【００２３】実施例 ３ スチーム導入装置の付いた２Ｌの反応フラスコに充填物
として管状ガラス（外径４ｍｍ、内径２ｍｍ、長さ４ｍ
ｍ）を充填した保温付き精留塔（内径３０ｍｍ、高さ１
２００ｍｍ）を取り付け、上部より一定速度で滴下でき
る滴下管、留出液を６０℃の温水で冷却捕集できる装置
を取り付け、未反応ＰＮＴの水蒸気蒸留装置とした。Example 3 A 2 L reaction flask equipped with a steam introducing device was filled with tubular glass (outer diameter 4 mm, inner diameter 2 mm, length 4 m).
m) rectifying column with heat insulation (inner diameter 30 mm, height 1
200 mm) was attached, and a dropping pipe capable of dropping at a constant rate from the upper portion and a device capable of cooling and collecting the distillate with hot water of 60 ° C. were attached to form a steam distillation device of unreacted PNT.
【００２４】本装置の下部フラスコより精留塔にスチー
ムを７５０ｍｌ／ｈ（水換算値）で送りながら加温し、
上部よりの滴下により実施例１と同様に調製した粗ＰＮ
Ｔ−スルフォン酸水溶液を９５℃に加温して７６０ｍｌ
／ｈで滴下した。留出液はＰＮＴ懸濁のため白濁してい
た。下部に留まったＰＮＴ−スルフォン酸水溶液は未反
応ＰＮＴを検出しなかった。Steam was sent from the lower flask of this apparatus to the rectification tower at a rate of 750 ml / h (water conversion value),
Crude PN prepared in the same manner as in Example 1 by dropping from above
760 ml of T-sulfonic acid aqueous solution heated to 95 ° C
/ H. The distillate was cloudy due to PNT suspension. Unreacted PNT was not detected in the PNT-sulfonic acid aqueous solution remaining in the lower part.
【００２５】実施例 ４ 実施例３で例示した水蒸気蒸留装置と同じ装置で、充填
物のみをＭｃＭａｈｏｎパッキン（外型６ｍｍ）に変え
て、下部フラスコより精留塔にスチームを７５０ｍｌ／
ｈ（水換算値）で送りながら加温し、上部滴下管より実
施例２と同様に調製した後更に水を加え、約２５％のＰ
ＮＴ−スルフォン酸ソーダ塩水溶液を９５℃に保持して
１７５０ｍｌ／ｈで滴下した。留出する液はＰＮＴの懸
濁により白濁していた。下部フラスコに留まったＰＮＴ
−スルフォン酸ソーダ塩水溶液には未反応ＰＮＴは検出
されなかった。Example 4 Using the same apparatus as the steam distillation apparatus exemplified in Example 3, only the packing was changed to McMahon packing (external type 6 mm), and 750 ml of steam was introduced into the rectification column from the lower flask.
While heating while feeding at h (water conversion value), the water was further added from the upper dropping pipe in the same manner as in Example 2, and then P was added to about 25%.
The NT-sodium sulfonic acid salt aqueous solution was kept at 95 ° C. and added dropwise at 1750 ml / h. The liquid distilled out was cloudy due to the suspension of PNT. PNT remaining in the lower flask
-Unreacted PNT was not detected in the sodium sulfonic acid salt aqueous solution.
【００２６】[0026]
【発明の効果】本発明の方法によればＰＮＴをＳＯ3ガ
スでスルフォン化した反応生成物は、熟成により残留Ｐ
ＮＴ及びＳＯ3の相互反応で何れも減少させることがで
きる。熟成後の反応生成物は水分解して水溶液にした後
（ソーダ塩の場合には更に中和）水 蒸気蒸留により未反応ＰＮＴを除去できる。この結果Ｐ
ＮＴ臭がなく、且つ硫酸（ソーダ塩の場合にはぼう硝）
の残留量を低くコントロールされたＰＮＴ−スルフォン
酸或いはＰＮＴ−スルフォン酸ソーダが得られる。本発
明の方法では従来法では避けることが困難であった廃酸
を全く排出せず、環境問題に対応できる方法である。又
水蒸気蒸留により、留出した未反応ＰＮＴは再び原料と
して使用可能である。EFFECT OF THE INVENTION According to the method of the present invention, the reaction product obtained by sulfonating PNT with SO 3 gas produces residual P due to aging.
Both can be reduced by the mutual reaction of NT and SO 3 . The reaction product after aging can be decomposed into water to form an aqueous solution (further neutralized in the case of soda salt), and then unreacted PNT can be removed by water vapor distillation. This result P
No NT odor, and sulfuric acid (in the case of soda salt, sodium sulfate)
It is possible to obtain PNT-sulfonic acid or PNT-sodium sulfonate whose residual amount is controlled to be low. The method of the present invention does not discharge waste acid, which was difficult to avoid by the conventional method, and can deal with environmental problems. Further, the unreacted PNT distilled by steam distillation can be reused as a raw material.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成５年４月８日[Submission date] April 8, 1993
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項１[Name of item to be corrected] Claim 1
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項５[Name of item to be corrected] Claim 5
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００９[Correction target item name] 0009
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００９】以下に順をおって本発明を説明する。ＰＮ
ＴのＳＯ 3 ガスによるスルフォン化は連続法又は回分法
により５５〜１３０℃の温度で実施する。ＳＯ3ガス濃
度は廃ガス中へのＰＮＴの飛散を少なくし、且つ希釈効
果を得るため３〜４０ｖｏｌ％、好ましくは３〜２０ｖ
ｏｌ％に調製される。未反応ＰＮＴの残存量を少なくす
るために、ＳＯ 3 ガス導入工程であるスルフォン化反応
工程に引き続き、ＳＯ 3 ガスを導入せず１００〜１３０
℃に保持する熟成工程を必要とする。反応温度が５５℃
以下ではＰＮＴの融点以下であり、且つスルフォン化率
が低下する。１３０℃以上では得られるスルフォン酸の
色調は著しく悪化するようになる。又、必要に応じ、
２，２’−ジメチル−５，５’−ジニトロビフェニルス
ルフォン（以下、「ＰＮＴ−スルフォン」と略す）の生
成を抑制する公知のスルフォン抑制剤を使用することが
できる。The present invention will be described below step by step. PN
Sulfonation of T with SO 3 gas is carried out at a temperature of 55 to 130 ° C. by a continuous method or a batch method. SO 3 gas concentration
Degree reduces the dispersion of PNT in the waste gas and has a diluting effect.
3-40 vol% to obtain fruit, preferably 3-20v
ol%. In order to reduce the amount of unreacted PNT remaining, 100 to 130 without introducing SO 3 gas after the sulfonation reaction step, which is an SO 3 gas introducing step.
An aging step of holding at ℃ is required. Reaction temperature is 55 ℃
Below, it is below the melting point of PNT, and the sulfonation rate decreases. At 130 ° C. or higher, the color tone of the sulfonic acid obtained becomes remarkably deteriorated. Also, if necessary,
A known sulfone inhibitor that suppresses the production of 2,2′-dimethyl-5,5′-dinitrobiphenyl sulfone (hereinafter abbreviated as “PNT-sulfone”) can be used.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２４[Correction target item name] 0024
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２４】本装置の下部フラスコより精留塔にスチー
ムを７５０ｍｌ／ｈ（水換算値）で送りながら加温し、
上部より実施例１の熟成後の反応生成物５，０００ｇを
実施例１と同様に調製した粗ＰＮＴ−スルフォン酸水溶
液を９５℃に加温して７６０ｍｌ／ｈで滴下した。留出
液はＰＮＴ懸濁のため白濁していた。下部に留まったＰ
ＮＴ−スルフォン酸水溶液は未反応ＰＮＴを検出しなか
った。Steam was sent from the lower flask of this apparatus to the rectification tower at a rate of 750 ml / h (water conversion value),
From the top , 5,000 g of the reaction product after aging of Example 1 was added.
The crude PNT-sulfonic acid aqueous solution prepared in the same manner as in Example 1 was heated to 95 ° C. and added dropwise at 760 ml / h. The distillate was cloudy due to PNT suspension. P stayed at the bottom
The NT-sulfonic acid aqueous solution did not detect unreacted PNT.
【手続補正５】[Procedure Amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２５[Name of item to be corrected] 0025
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２５】実施例 ４ 実施例３で示した水蒸気蒸留装置と同じ装置で充填物の
みをＭｃＭａｈｏｎパッキン（外径６ｍｍ）に変えて、
下部フラスコより精留塔にスチームを７５０ｍｌ／ｈ
（水換算値）で送りながら加温し、上部滴下管より実施
例３の粗ＰＮＴスルフォン酸水溶液を実施例２と同様に
調製した水を加え、約２５％のＰＮＴ−スルフォン酸ソ
ーダ塩水溶液を９５℃に保持して１７５０ｍｌ／ｈで滴
下した。流出する液はＰＮＴの懸濁により白濁してい
た。下部フラスコに留まったＰＮＴ−酸スルフォン酸ソ
ーダ塩水溶液には未反応ＰＮＴは検出されなかった。Example 4 In the same apparatus as the steam distillation apparatus shown in Example 3, only the packing was changed to McMahon packing (outer diameter 6 mm),
Steam from the lower flask to the rectification tower at 750 ml / h
Heated while sending as (water conversion value), and conducted from the upper dropping pipe
Water prepared in the same manner as in Example 2 was added to the crude PNT sulfonic acid aqueous solution of Example 3, and about 25% of a PNT-sodium sulfonic acid salt aqueous solution was maintained at 95 ° C and added dropwise at 1750 ml / h. The liquid flowing out was cloudy due to the suspension of PNT. No unreacted PNT was detected in the PNT-sodium sulfonic acid salt aqueous solution remaining in the lower flask.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 木村 宏 愛知県名古屋市港区築地町７日産化学工業 株式会社名古屋工場内 (72)発明者 久保正雄 東京都千代田区神田錦町３丁目７番地１日 産化学工業株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroshi Kimura 7 Tsukiji-cho, Minato-ku, Aichi Prefecture, Nagoya Plant, Nissan Chemical Co., Ltd. (72) Inventor Masao Kubo 3-7-1, Kandanishiki-cho, Chiyoda-ku, Tokyo Sanka Kogyo Co., Ltd.
Claims (7)
りなる２−メチル−５−ニトロベンゼンスルフォン酸の
製造方法。 工程：Ｐ−ニトロトルエンとＳＯ3ガス（ＳＯ3濃度が
３〜６０Ｖｏｌ％）とを反応させるに際し、Ｐ−ニトロ
トルエンに対しＳＯ3が９０〜１４０モル％を用いて反
応させて反応混合物を得る工程 工程：次いで、該反応混合物を熟成させて、反応生成
物を得る工程 工程：次いで、該反応生成物から未反応のＰ−ニトロ
トルエンを除去する工程1. A method for producing 2-methyl-5-nitrobenzenesulfonic acid, which comprises the following steps, steps, and steps. Step: A step of reacting P-nitrotoluene with SO 3 gas (SO 3 concentration is 3 to 60 Vol%) using 90 to 140 mol% of SO 3 with respect to P-nitrotoluene to obtain a reaction mixture : Next, aging the reaction mixture to obtain a reaction product Step: Next, removing unreacted P-nitrotoluene from the reaction product
後、該溶液を水蒸気蒸留して未反応のＰ−ニトロトルエ
ンを除去する工程である請求項１記載の２−メチル−５
−ニトロベンゼンスルフォン酸の製造方法。2. The 2-methyl-5 according to claim 1, wherein the step is a step of dissolving the reaction product in water and then steam-distilling the solution to remove unreacted P-nitrotoluene.
-Method for producing nitrobenzene sulfonic acid.
を供給し、該塔の下部より水蒸気を吹き込むことである
請求項２記載の２−メチル−５−ニトロベンゼンスルフ
ォン酸の製造方法。3. The method for producing 2-methyl-5-nitrobenzenesulfonic acid according to claim 2, wherein the steam distillation is performed by supplying the solution from the upper part of a packed column and blowing steam from the lower part of the column.
応生成物を水に溶解して３０〜４５％水溶液とし、４０
℃以下に冷却後析出するＰＮＴ−スルフォンを除去する
か、或いは反応生成物を水に溶解して水蒸気蒸留後冷却
してＰＮＴ−スルフォンを除去する２−メチル−５−ニ
トロベンゼンスルフォン酸の製造方法。4. The method according to claim 1, wherein the reaction product obtained in the step is dissolved in water to obtain a 30 to 45% aqueous solution,
A method for producing 2-methyl-5-nitrobenzenesulfonic acid, which comprises removing PNT-sulfone which precipitates after cooling to below C, or dissolving the reaction product in water and steam-distilling and cooling to remove PNT-sulfone.
程よりなる２−メチル−５−ニトロベンゼンスルフォ
ン酸ソーダ塩の製造方法。 工程：Ｐ−ニトロトルエンとＳＯ3ガス（ＳＯ3濃度が
３〜６０Ｖｏｌ％）とを反応させるに際し、Ｐ−ニトロ
トルエンに対しＳＯ3が９０〜１４０モル％を用いて反
応させて生成物を得る工程 工程：次いで、該生成物を熟成させて、反応生成物を
得る工程 工程：次いで、該反応生成物を苛性ソーダで中和させ
て反応生成物のソーダ塩混合物を得る工程 工程：次いで、該ソーダ塩混合物から未反応Ｐ−ニト
ロトルエンを除去する工程5. A method for producing a sodium salt of 2-methyl-5-nitrobenzenesulfonic acid, which comprises the following steps, steps, and steps. Step: A step of reacting P-nitrotoluene with SO 3 gas (SO 3 concentration of 3 to 60 Vol%) using 90 to 140 mol% of SO 3 with respect to P-nitrotoluene to obtain a product : Next, aging the product to obtain a reaction product Step: Next, neutralizing the reaction product with caustic soda to obtain a soda salt mixture of the reaction step: Next, the soda salt mixture Of removing unreacted P-nitrotoluene from water
溶液を得たた後、水蒸気蒸留することである請求項５記
載の２−メチル−５−ニトロベンゼンスルフォン酸ソー
ダ塩の製造方法。6. The method for producing a sodium salt of 2-methyl-5-nitrobenzenesulfonic acid according to claim 5, wherein the step is to dissolve the mixture in water to obtain a mixed solution and then perform steam distillation.
溶液を供給し、該塔の下部より水蒸気を吹き込むことで
ある請求項６記載の２−メチル−５−ニトロベンゼンス
ルフォン酸ソーダ塩の製造方法。7. The production of sodium 2-methyl-5-nitrobenzenesulfonic acid salt according to claim 6, wherein the steam distillation is performed by supplying the mixed solution from the upper part of the packed column and blowing steam from the lower part of the column. Method.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP496292A JPH05194363A (en) | 1992-01-14 | 1992-01-14 | Production of 2-methyl-5-nitrobenzenesulfonic acid and its sodium salt |
| EP92116176A EP0534360A1 (en) | 1991-09-26 | 1992-09-22 | Method of preparing nitrotoluenesulfonic acids and sodium salts thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP496292A JPH05194363A (en) | 1992-01-14 | 1992-01-14 | Production of 2-methyl-5-nitrobenzenesulfonic acid and its sodium salt |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05194363A true JPH05194363A (en) | 1993-08-03 |
Family
ID=11598217
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP496292A Pending JPH05194363A (en) | 1991-09-26 | 1992-01-14 | Production of 2-methyl-5-nitrobenzenesulfonic acid and its sodium salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05194363A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55145661A (en) * | 1979-04-26 | 1980-11-13 | Bayer Ag | Manufacture of 44nitrotoluenee22sulfonic acid |
| JPS5724351A (en) * | 1980-05-30 | 1982-02-08 | Basf Ag | Separation of water-soluble salt of aromatic sulfonic acid from sulfonation mixture |
| JPS58118555A (en) * | 1981-12-31 | 1983-07-14 | チバ―ガイギ アクチエンゲゼルシヤフト | Process for manufacturing p-nitrotoluene-2- sulfonic acid |
-
1992
- 1992-01-14 JP JP496292A patent/JPH05194363A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55145661A (en) * | 1979-04-26 | 1980-11-13 | Bayer Ag | Manufacture of 44nitrotoluenee22sulfonic acid |
| JPS5724351A (en) * | 1980-05-30 | 1982-02-08 | Basf Ag | Separation of water-soluble salt of aromatic sulfonic acid from sulfonation mixture |
| JPS58118555A (en) * | 1981-12-31 | 1983-07-14 | チバ―ガイギ アクチエンゲゼルシヤフト | Process for manufacturing p-nitrotoluene-2- sulfonic acid |
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