JPS5930702B2 - Crystallization separation method of "A"-xylene-4-sulfonic acid - Google Patents
Crystallization separation method of "A"-xylene-4-sulfonic acidInfo
- Publication number
- JPS5930702B2 JPS5930702B2 JP4839382A JP4839382A JPS5930702B2 JP S5930702 B2 JPS5930702 B2 JP S5930702B2 JP 4839382 A JP4839382 A JP 4839382A JP 4839382 A JP4839382 A JP 4839382A JP S5930702 B2 JPS5930702 B2 JP S5930702B2
- Authority
- JP
- Japan
- Prior art keywords
- xylene
- sulfuric acid
- sulfonic acid
- weight
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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見出させる方法に
関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for discovering m-xylene sulfonic acid in high yield from a reaction product liquid obtained by reacting xylene and sulfuric acid.
従来、キシレン類のスルホン化剤としては、濃硫酸が多
く使用されて来た。Conventionally, concentrated sulfuric acid has often been used as a sulfonating agent for xylenes.
しかし硫酸によるスルホン化反応を行なうためには、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。ｍ−キシレンのスルホン化反応
においても硫酸濃度６８重量％（残りは水、以下同じ）
前後に限界値が存在する。However, in order to carry out the sulfonation reaction using sulfuric acid, there is a limit value of the sulfuric acid concentration, and below this limit concentration, the reaction hardly progresses. In the sulfonation reaction of m-xylene, the sulfuric acid concentration is 68% by weight (the rest is water, the same applies below).
There are limit values before and after.
しかるに硫酸による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。一方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−キシレンー５−スルホン酸に異性化を起す。However, in the sulfonation reaction of m-xylene with 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 have been adopted. Therefore, the reaction product liquid contains a large amount of unreacted sulfuric acid. 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.
特公昭４９−３３１９３によると、この異性化の限界温
度は１５０℃であり、従つて反応生成液よりｍ−キシレ
ンー ４−スルホン酸を高収率で回収する方法としては
、一般に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。本発明者は、ｍ−キシレンと硫酸の反
応生成液からｍ−キシレンー 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つた結果、ｍ−
キシレンー ４−スルホン酸の硫酸水溶液に対する溶解
度が硫酸濃度によつて著しく異なり、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。According to Japanese Patent Publication No. 49-33193, the limit temperature for this isomerization is 150°C, and therefore, it has been generally used as a method for recovering m-xylene-4-sulfonic acid from the reaction product liquid in high yield. Sulfuric acid removal method by vacuum distillation cannot be adopted. The present inventor conducted intensive research on a method for efficiently separating m-xylene-4-sulfonic acid from the reaction product liquid of m-xylene and sulfuric acid, and found that m-
The solubility of xylene-4-sulfonic acid in an aqueous sulfuric acid solution varies significantly depending on the sulfuric acid concentration, especially when the sulfuric acid concentration is 60%.
The present invention was completed by discovering that a minimum value exists near the weight % range, and that the difference in solubility is small in the range of 50 to 70 weight %.
即ち本発明はｍ−キシレンと硫酸を反応させてｍ−キシ
レンー ４−スルホン酸を製造し、得られた反応生成液
よりｍ−キシレンー ４−スルホン酸の結晶を見出させ
るに際し、母液中の硫酸濃度５０〜７０重量％（残りは
水）の条件下早出させる方法である。本発明におけるｍ
−キシレンと硫酸の反応は反応温度７０〜８０℃、硫酸
濃度７０〜８０重量％（残りは水）の条件下連続的に行
なうのが好ましい。That is, in the present invention, m-xylene-4-sulfonic acid is produced by reacting m-xylene and sulfuric acid, and when crystals of m-xylene-4-sulfonic acid are found from the resulting reaction product liquid, sulfuric acid in the mother liquor is This is a method for rapid release under conditions of a concentration of 50 to 70% by weight (the remainder being water). m in the present invention
- The reaction between xylene and sulfuric acid is preferably carried out continuously at a reaction temperature of 70 to 80°C and a sulfuric 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％としたときの硫酸含有率である。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 it is 0% by weight.
硫酸濃度が７０％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は言えない。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
）の生成が顕著となり好ましくない。反応温度が７０℃
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。ｍ−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，
３〜１．９モル、好ましくは１．４〜１．９モルである
。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−キシレンー４−スルホン酸をそのまま晶析させる
ときはｍ−キシレンー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。A sulfuric acid concentration of 70% or less is not an economical condition because the reaction rate is significantly reduced. Moreover, if it exceeds 80%, the formation of sulfone (tetramethyldiphenyl sulfone) becomes noticeable, which is not preferable. Reaction temperature is 70℃
If it is below, the reaction rate will drop significantly, and in order to keep the m-xylene reaction rate high, it will be necessary to significantly extend the residence time, which will be uneconomical. When the reaction temperature is 80°C or higher, sulfone formation becomes significant. The molar ratio of m-xylene to sulfuric acid is 1 mole of m-xylene to 1 mole of sulfuric acid,
The amount is 3 to 1.9 mol, preferably 1.4 to 1.9 mol. When m-xylene-4-sulfonic acid is directly crystallized from the reaction product liquid obtained by carrying out the reaction by the method described above, 2 mol of water is incorporated as crystal water per 1 mol of m-xylene-4-sulfonic acid. Crystallizes as a watery substance.
このため反応生成液は晶出量に比例して硫酸濃度が上昇
し、硫酸濃度８０重量％以上ではｍ−キシレンー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−キシレンー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８０％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−キシレンー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。
晶析温度は２０〜４０℃の範囲が好ましい。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−キシレ
ンー４−スルホン酸の溶解度を０．５〜２重量％に押え
ることが出来る。晶析時のスラリー濃度は３０〜４５重
量％の範囲が結晶粒径、スラリー粘度の点で好ましい。Therefore, the sulfuric acid concentration of the reaction product liquid increases in proportion to the amount of crystallization, and when the sulfuric acid concentration exceeds 80% by weight, the solubility of m-xylene-4-sulfonic acid also increases rapidly. In addition, as the sulfuric acid concentration increases, crystals become finer and the viscosity of the slurry increases.
Since the washing-off of the mother liquor by the centrifuge becomes extremely difficult and it becomes difficult to produce high-quality m-xylene-4-sulfonic acid, the concentration of sulfuric acid during crystallization is reduced to 80% or less by diluting it with water. need to be maintained. On the other hand, if the sulfuric acid concentration is lowered to less than 50% by weight, this is also not preferred because the solubility of m-xylene-4-sulfonic acid will rapidly increase.
The crystallization temperature is preferably in the range of 20 to 40°C. When the sulfuric acid concentration is within the above range, the solubility of m-xylene-4-sulfonic acid can be suppressed to 0.5 to 2% by weight within this temperature range. The slurry concentration during crystallization is preferably in the range of 30 to 45% by weight in terms of crystal grain size and slurry 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
良く操作出来る。本発明によればｍ−キシレンー４−ス
ルホン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−キシレンー４−スルホン酸を晶出分離すること
が出来る。The crystallization operation of the present invention can be performed efficiently in either a batch method or a continuous method. According to the present invention, crystallization and separation of m-xylene-4-sulfonic acid is performed at low temperature, so that isomerization,
There are almost no side reactions such as disproportionation, and it is possible to crystallize and separate m-xylene-4-sulfonic acid of high quality, especially low sulfone.
実施例１
ｍ−キシレンー４−スルホン酸６８重量％、未反応硫酸
２３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重量部を撹拌機および
ジャケット付晶出器に仕込み、一旦５５℃に昇温して完
全溶解を確認後、徐冷を行なつた。Example 1 185 parts by weight of a reaction product liquid consisting of 68% by weight of m-xylene-4-sulfonic acid, 23% 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. 108 parts by weight, a total of 400 parts by weight, were charged into a stirrer and a jacketed crystallizer, and the temperature was once raised to 55°C to confirm complete dissolution, followed by slow cooling.
５１℃に降温時種晶を添加し、３０分後、４９．７℃に
おいて晶出が開始した。Seed crystals were added when the temperature was lowered to 51°C, and 30 minutes later, crystallization started at 49.7°C.
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。次に生成
スラリーを全量、遠心分離機（遠心効果１０００Ｇ１１
２０メッシュのＡ布使用）にかけ粗結晶とＡ液に分離し
、各々１６０重量部及び２４０重量部を得た。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. Next, transfer the entire amount of the slurry to a centrifuge (centrifugal effect 1000G11
The crude crystals were separated into crude crystals and liquid A (using 20 mesh A cloth) to obtain 160 parts by weight and 240 parts by weight, respectively.
沢液中のｍ−キシレンー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）であつた。The m-xylene-4-sulfonic acid content in the sap is 0.8
The sulfuric acid concentration was 60% by weight (the remainder was water).
Claims (1)
−スルホン酸を製造し、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。1 Reacting m-xylene and sulfuric acid to produce m-xylene-4
- When producing sulfonic acid and crystallizing m-xylene-4-sulfonic acid from the resulting reaction product liquid, crystallization is performed under conditions where the sulfuric acid concentration in the mother liquor is 50 to 70% by weight (the remainder is water). A method for crystallizing and separating m-xylene-4-sulfonic acid.
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 JPS58167559A (en) | 1983-10-03 |
| JPS5930702B2 true 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) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391159B (en) * | 2011-10-18 | 2013-07-17 | 金能科技股份有限公司 | Process and system for recovering sulfonic acid mother liquor by dewatering |
-
1982
- 1982-03-26 JP JP4839382A patent/JPS5930702B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58167559A (en) | 1983-10-03 |
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