JPS58167559A - Crystallization and separation of m-xylene-4-sulfonic acid - Google Patents
Crystallization and separation of m-xylene-4-sulfonic acidInfo
- Publication number
- JPS58167559A JPS58167559A JP4839382A JP4839382A JPS58167559A JP S58167559 A JPS58167559 A JP S58167559A JP 4839382 A JP4839382 A JP 4839382A JP 4839382 A JP4839382 A JP 4839382A JP S58167559 A JPS58167559 A JP S58167559A
- Authority
- JP
- Japan
- Prior art keywords
- xylene
- sulfuric acid
- sulfonic acid
- crystallization
- concentration
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はキシレンと硫酸を反応させて得た反応生成液か
らｍ−キシレンスルホン酸を高収率に晶出させる方法番
こ関する
従来、キシレン類のスルホン化剤としては。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for crystallizing m-xylene sulfonic acid in high yield from a reaction product liquid obtained by reacting xylene and sulfuric acid. .
撲硫酸が多く使用されて来た。しかし硫酸によるスルホ
ン化反応を行なうため各こけ、硫酸濃度の限界値が存在
し、この限界濃度以下では、反応はほとんど進行しない
。Sulfuric acid has been widely used. However, since the sulfonation reaction is carried out using sulfuric acid, there is a limit value for the concentration of sulfuric acid in each moss, and below this limit concentration, the reaction hardly progresses.
ｍ−キシレンのスルホン化反応においてモ硫酸濃度６８
重量％（残りは水、以下同じ）前後に限界値が存在する
。しかる１ζ硫酸によるｍ−キシレンのスルホン化反応
においては、反応の進行につれ等モルの水が生成し、硫
酸濃度が低下する。この為ｍ−キシレンの反応率を高く
保つためには、ｍ−キシレンに対し大過剰の硫酸を添加
する必要が有り、工業的には硫酸／ｍ−キシレンのモル
比＝１．５〜２が採用されて来た。このため、反応生成
液中には大量の未反応硫酸が含まれる。Mosulfuric acid concentration 68 in m-xylene sulfonation reaction
There is a limit value around the weight percent (the rest is water, the same applies below). In the sulfonation reaction of m-xylene with 1ζ sulfuric acid, equimolar amounts of water are produced as the reaction progresses, and the sulfuric acid concentration decreases. Therefore, in order to keep the reaction rate of m-xylene high, it is necessary to add a large excess of sulfuric acid to m-xylene, and industrially the molar ratio of sulfuric acid/m-xylene = 1.5 to 2 is required. I've been hired. Therefore, the reaction product liquid contains a large amount of unreacted sulfuric acid.
−方ｍ−キシレンー４−スルホン酸は、硫酸を含む系で
高温にさらすと容易にｍ−キシレン−５−スルホン酸に
異性化を起す。特公昭４９−５５１９５４こよると、こ
の異性化の限界温度は１５０℃であり、従って反応生成
液よりｍ −キシレン−４−スルホン酸を高収率で回収
する方法としては、一般番こ行なわれて来た減圧蒸留に
よる硫酸除去法は採用不可能である。On the other hand, m-xylene-4-sulfonic acid easily undergoes isomerization to m-xylene-5-sulfonic acid when exposed to high temperatures in a system containing sulfuric acid. According to Japanese Patent Publication No. 49-551954, the limit temperature for this isomerization is 150°C, and therefore, as a method for recovering m-xylene-4-sulfonic acid from the reaction product liquid in high yield, this is the general method. The conventional method of removing sulfuric acid by distillation under reduced pressure cannot be adopted.
本発明者は、ｍ−キシレンと硫酸の反応生成液からｍ−
キシレン−４−スルホン酸を効率良く分離する方法につ
いて鋭意研究を行なった結果、ｍ−キシレン−４−スル
ホン酸の硫酸水溶液に対する溶解度が硫酸濃度によって
著しく異なり、特に硫酸濃度６０重量％付近に極少値が
存在し、５０〜７０重量％の範囲では溶解度の差は小さ
い事を見出し本発明を完成した。即ち本発明はｍ−キシ
レンと硫酸を反応させてｍ −キシレン−４−スルホノ
ーナ製造し、得られた反応生成液よりｍ−キシレノ−４
−スルホン酸の結晶を晶出させるに際し、母液中の硫酸
濃度５０〜７０重量％（残りは水）の条件下晶出させる
方法である。The present inventor has discovered that m-
As a result of intensive research into methods for efficiently separating xylene-4-sulfonic acid, we found that the solubility of m-xylene-4-sulfonic acid in an aqueous sulfuric acid solution varies markedly depending on the sulfuric acid concentration, and in particular, reached a minimum value around 60% by weight of sulfuric acid. The present invention was completed based on the discovery that the difference in solubility is small in the range of 50 to 70% by weight. That is, in the present invention, m-xylene-4-sulfonona is produced by reacting m-xylene and sulfuric acid, and m-xylene-4-sulfonona is produced from the resulting reaction product liquid.
- A method of crystallizing sulfonic acid under conditions where the sulfuric acid concentration in the mother liquor is 50 to 70% by weight (the remainder being water).
本発明におけるｍ−キシレンと硫酸の反応は反応温度７
０〜８０°Ｃ，硫、酸濃度７０〜８０重１％（残りは水
）の条件下連続的に行なうのが好ましい。The reaction temperature of m-xylene and sulfuric acid in the present invention is 7.
It is preferable to carry out continuously under the conditions of 0 to 80°C, sulfuric acid, acid concentration of 70 to 80% by weight (the remainder being water).
ここで硫酸濃度とは、反応液中の硫酸と水の総和を１０
０重量％とじたときの硫酸含有率である。硫酸濃度が７
０％以下であると、反応速度が著しく低下するため経済
的な条件とけ言えナイ。また、８０％以上にすると、ス
ルホン（テトラメチル ジフェニルスルホンンの生成が
顕著となり好ましくない。反応温度が７［１’Ｃ以下で
あると、反応速度が著しく低下するため、ｍ−キシレン
の反応率を高く保つためには滞留時間を大幅に延ばす必
要が有り、経済性に欠ける。反応温度が８０℃以上であ
ると、スルホンの生成が顕著となる６ｍ−キシレンと硫
酸のモル比はｍ−キシレン１モルに対し硫酸 １．５〜
１．９モル、好ましくは１．４〜１．９モルである。Here, the sulfuric acid concentration refers to the sum of sulfuric acid and water in the reaction solution as 10
This is the sulfuric acid content when bound to 0% by weight. Sulfuric acid concentration is 7
If it is less than 0%, the reaction rate will drop significantly, so it cannot be said to be an economical condition. Moreover, if it exceeds 80%, the formation of sulfone (tetramethyl diphenyl sulfonne) becomes noticeable, which is undesirable. If the reaction temperature is below 7 [1'C, the reaction rate will decrease significantly, so the reaction rate of m-xylene In order to maintain a high residence time, it is necessary to significantly extend the residence time, which is uneconomical.If the reaction temperature is 80°C or higher, the formation of sulfone becomes noticeable. Sulfuric acid 1.5 to 1 mole
The amount is 1.9 mol, preferably 1.4 to 1.9 mol.
以上の如き方法で反応を行なわせて得た反応生成液から
ｍ−キシレン−４−スルホノ酸ヲソのま＼晶析させると
きはｍ−キシレン−４−スルホン酸１モル当り２モルの
水を結晶水として取り込み二水物として結晶化する。こ
のため反応生成液は晶出量ζこ比例して硫酸濃度が一ヒ
昇し。When m-xylene-4-sulfonoic acid is crystallized from the reaction product liquid obtained by the reaction as described above, 2 mol of water is crystallized per 1 mol of m-xylene-4-sulfonic acid. It is taken up as water and crystallized as a dihydrate. For this reason, the sulfuric acid concentration of the reaction product liquid increases in proportion to the amount of crystallization.
硫酸濃度８０重素置以上ではｍ−キシレン−４−スルホ
ン酸の溶解度も急激に上昇する。又、硫酸濃度上昇と共
に結晶の微細化が起り、スラリーの粘度が上昇し、遠心
分離機による母液の振り切れが極端に悪化し、高品質の
ｍ−キシレン−４−スルホン酸を製造する事は困難とな
るので、水で稀釈することにより晶析時の硫酸濃度を８
０％以下に維持する必要がある。一方、硫酸濃度が５０
重量％未満に低下した場合もｍ−キシレン−４−スルホ
ン酸の溶解度が急激に上昇するので好ましくない。The solubility of m-xylene-4-sulfonic acid also increases rapidly when the sulfuric acid concentration exceeds 80 hydrogen atoms. In addition, as the sulfuric acid concentration increases, crystals become finer, the viscosity of the slurry increases, and the ability to shake off the mother liquor using a centrifuge becomes extremely difficult, making it difficult to produce high-quality m-xylene-4-sulfonic acid. Therefore, by diluting with water, the sulfuric acid concentration during crystallization can be reduced to 8
It is necessary to maintain it below 0%. On the other hand, the sulfuric acid concentration is 50
It is also not preferable that the solubility of m-xylene-4-sulfonic acid is lowered to less than % by weight because the solubility of m-xylene-4-sulfonic acid increases rapidly.
晶析温度は２０〜４０°（゛の範囲が好ましい。The crystallization temperature is preferably in the range of 20 to 40°.
硫酸濃度が上記の範囲・内にあるときは、この温度範囲
でｍ−４７レンー４−スルホン酸の溶解度を０．５〜２
重１％に押えることが出来る。When the sulfuric acid concentration is within the above range, the solubility of m-47ren-4-sulfonic acid in this temperature range is 0.5 to 2.
The weight can be reduced to 1%.
晶析時のスラリー濃度ｉ＠’５ｎ〜４５重量％の範囲が
結晶粒径、ステ１１−粘度の点で好ましい。A slurry concentration in the range of i@'5n to 45% by weight during crystallization is preferable in terms of crystal grain size and viscosity.
本発明晶析操作は回分法、連続法いずれの場合でも効率
良く操作出火る。The crystallization operation of the present invention can be performed efficiently in either a batch method or a continuous method.
本発明によれば「ｎ−キシ１７ノー４−スルホ／酸の晶
出分離を低温操作で行なうため、異性化、不均化等の副
反応が皆無に近く、高品質、特に低スルホンのｍ−キシ
レン−４−スルホン酸ヲ晶出分離することが出来る。According to the present invention, since the crystallization separation of n-xy17-4-sulfo/acid is carried out at low temperature, side reactions such as isomerization and disproportionation are almost completely eliminated, resulting in high quality, especially low m -Xylene-4-sulfonic acid can be crystallized and separated.
実施例 １
ｍ−キシレン−４−スルホン酸６８ｆｉｌ１％、未反応
硫酸 ２５重量％、水 ８重量％、その他 １重量％の
組成から成る反応生成液 １８５重量部と、９８％硫酸
１０７重量部および水 １０８重量部、計４００重量
部を攪拌機およびジャケット付晶出器に仕込み、一旦５
５℃に昇温しで完全溶解を確認後、徐冷を行なった、５
１℃番こ降温時種晶を添加し、５０分後、４９゜７℃に
おいて晶出が開始した。さらに徐冷を続け、種晶添加後
２時間かけて２０℃まで降温させ、同温度でさらに１時
間晶出させた。Example 1 185 parts by weight of a reaction product liquid consisting of 68 fil 1% of m-xylene-4-sulfonic acid, 25% by weight of unreacted sulfuric acid, 8% by weight of water, and 1% by weight of others, 107 parts by weight of 98% sulfuric acid, and water. Charge 108 parts by weight, a total of 400 parts by weight, into a stirrer and a jacketed crystallizer, and once
After confirming complete dissolution by raising the temperature to 5°C, slow cooling was performed.
Seed crystals were added when the temperature was lowered by 1°C, and 50 minutes later, crystallization started at 49°C to 7°C. Slow cooling was further continued, and the temperature was lowered to 20° C. over 2 hours after the addition of the seed crystals, and crystallization was continued at the same temperature for an additional 1 hour.
次に生成スラリーを全量、遠心分離機（遠心効果１００
０Ｇ、１２０メツシユの炉布使用）にかけ粗結晶とｐ液
に分離し、各々１６＋１１ｊ看部及び２４０重量部を得
た。Next, the entire amount of the generated slurry was transferred to a centrifugal separator (centrifugal effect 100
(0G, using a 120 mesh furnace cloth) to separate into crude crystals and p liquid, yielding 16+11j parts and 240 parts by weight, respectively.
ｐ液中のｍ−キシレン・−４−スルホン酸含有率は０．
８重量％、硫酸濃度は６０重量％（残りは水）であった
。又、本発明晶出操作における最終スラリー濃度は４０
重術％であり、ｍ−キシレン−４−スルボン酸の収率は
９９％以上であった。The m-xylene/-4-sulfonic acid content in the p liquid is 0.
The sulfuric acid concentration was 60% by weight (the remainder was water). In addition, the final slurry concentration in the crystallization operation of the present invention is 40
The yield of m-xylene-4-sulfonic acid was 99% or more.
粗結晶中には５．５布帛％の硫酸分が含まれていたので
、粗結晶の１０％に相当する１６重量部の水でこれをリ
ンスしたところ、精結晶とリンス液各々１１２重量部及
び６４重量部を得た。精結晶中に含まれる硫、酸分け０
．８重量％であった。The crude crystals contained 5.5% sulfuric acid, so when they were rinsed with 16 parts by weight of water, which is equivalent to 10% of the crude crystals, the fine crystals and rinsing liquid were each 112 parts by weight and 64 parts by weight were obtained. Sulfur and acid contained in fine crystals are 0
．． It was 8% by weight.
特許出願人 二櫻瓦斯化学株式会社 代表者長野相吉 ４１５−Patent applicant: Nisakura Gas Chemical Co., Ltd. Representative Aikichi Nagano 415-
Claims (1)
ルホン酸を製造し、得られた反応生成液よりｍ−キシレ
ン−４−スルホン酸の結晶を晶出させるζこ際し、母液
中の硫酸濃度５０〜７０重量％（残りは水）の条件下晶
出させることを特徴とするｍ−キシレン−４−スルホン
酸の晶出分離法m-xylene-4-sulfonic acid is produced by reacting m-xylene and sulfuric acid, and crystals of m-xylene-4-sulfonic acid are crystallized from the resulting reaction product solution. A method for crystallization and separation of m-xylene-4-sulfonic acid, characterized by crystallization under conditions of a sulfuric acid concentration of 50 to 70% by weight (the remainder being water)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4839382A JPS5930702B2 (en) | 1982-03-26 | 1982-03-26 | Crystallization separation method of "A"-xylene-4-sulfonic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4839382A JPS5930702B2 (en) | 1982-03-26 | 1982-03-26 | Crystallization separation method of "A"-xylene-4-sulfonic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58167559A true JPS58167559A (en) | 1983-10-03 |
| JPS5930702B2 JPS5930702B2 (en) | 1984-07-28 |
Family
ID=12802046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4839382A Expired JPS5930702B2 (en) | 1982-03-26 | 1982-03-26 | Crystallization separation method of "A"-xylene-4-sulfonic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5930702B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391159A (en) * | 2011-10-18 | 2012-03-28 | 金能科技有限责任公司 | Process and system for recovering sulfonic acid mother liquor by dewatering |
-
1982
- 1982-03-26 JP JP4839382A patent/JPS5930702B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391159A (en) * | 2011-10-18 | 2012-03-28 | 金能科技有限责任公司 | Process and system for recovering sulfonic acid mother liquor by dewatering |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5930702B2 (en) | 1984-07-28 |
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