JPH10182591A - Continuous production of alkali metal styrenesulfonate - Google Patents
Continuous production of alkali metal styrenesulfonateInfo
- Publication number
- JPH10182591A JPH10182591A JP34184996A JP34184996A JPH10182591A JP H10182591 A JPH10182591 A JP H10182591A JP 34184996 A JP34184996 A JP 34184996A JP 34184996 A JP34184996 A JP 34184996A JP H10182591 A JPH10182591 A JP H10182591A
- Authority
- JP
- Japan
- Prior art keywords
- alkali metal
- styrenesulfonate
- slurry
- crystallization
- continuously
- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、スチレンスルホン
酸アルカリ金属塩の連続式製造方法に関する、更に詳し
くは、高純度のスチレンスルホン酸アルカリ金属塩を結
晶として製造する際に、高い生産性で、運転操作性良
く、工業的に連続して製造する方法に関する。TECHNICAL FIELD The present invention relates to a continuous method for producing an alkali metal styrenesulfonate, and more particularly, to a method for producing a high-purity alkali metal styrenesulfonate as crystals with high productivity. The present invention relates to a method for industrially continuous production with good operability.
【０００２】[0002]
【従来の技術】従来より、スチレンスルホン酸アルカリ
金属塩は、β−ハロエチルベンゼンスルホン酸水溶液に
アルカリ金属水酸化物水溶液を作用させて製造されるこ
とは広く知られている。例えば、特公昭５３−２３２９
２号公報には、予め反応器に全量仕込まれたアルカリ金
属水酸化物のアルコール溶液にβ−ハロエチルベンゼン
スルホン酸水溶液を徐々に滴下しながら、５０〜７０℃
の温度で反応を行う方法が、又、特開昭５２−２３０３
８号公報では、苛性ソーダ水溶液に窒素雰囲気下９５〜
１０５℃に維持しつつ、β−ハロエチルベンゼンスルホ
ン酸水溶液を滴下して反応晶析させる方法がそれぞれ記
載されている。更に、特公昭３８−２０５７０号公報で
は、アルカリ金属水酸化物水溶液にβ−ハロエチルベン
ゼンスルホン酸水溶液を室温又はそれ以下の温度におい
て添加し、β−ハロエチルベンゼンスルホン酸のアルカ
リ金属塩を製造し、その後８０〜１００℃に昇温してア
ルカリ金属水酸化物水溶液を添加し、スチレンスルホン
酸アルカリ金属塩を結晶として取り出す、所謂２段階反
応による製造方法が開示されている。しかしながら、こ
れらの製造方法は何れも半回分式であり、生産性は低
く、又、運転操作は煩雑である。2. Description of the Related Art It has been widely known that an alkali metal styrenesulfonate is produced by reacting an aqueous solution of an alkali metal hydroxide with an aqueous solution of β-haloethylbenzenesulfonic acid. For example, Japanese Patent Publication No. 53-2329
No. 2 discloses that a β-haloethylbenzenesulfonic acid aqueous solution is gradually added dropwise to an alcohol solution of an alkali metal hydroxide previously charged in a reactor at 50 to 70 ° C.
The reaction is carried out at the temperature described in JP-A-52-2303.
No. 8 discloses that a caustic soda aqueous solution is added under a nitrogen atmosphere at 95 to 95%.
A method is described in which a β-haloethylbenzenesulfonic acid aqueous solution is added dropwise while maintaining the temperature at 105 ° C. to cause reaction crystallization. Further, in Japanese Patent Publication No. 38-20570, an aqueous solution of β-haloethylbenzenesulfonic acid is added to an aqueous solution of an alkali metal hydroxide at room temperature or lower to produce an alkali metal salt of β-haloethylbenzenesulfonic acid. Thereafter, the temperature is raised to 80 to 100 [deg.] C., an aqueous alkali metal hydroxide solution is added, and the alkali metal styrenesulfonate is taken out as crystals. However, all of these production methods are of a semi-batch type, and the productivity is low, and the operation is complicated.
【０００３】一方、特公昭３８−２０５７０号公報に
は、前記半回分式製造方法の他に連続製造方法が示され
ている。これは、β−ハロエチルベンゼンスルホン酸の
メチレンクロライド溶液と５０％苛性ソーダ水溶液と水
とを連続的に導入して反応させ、前記２段階反応を経
て、スチレンスルホン酸ナトリウムの１０％水溶液を
得、その後該水溶液を噴霧乾燥して、スチレンスルホン
酸ナトリウム４８〜５４％及び臭化ナトリウム２７〜３
３％の混合物を連続して製造する方法である。しかしな
がら、この方法はスチレンスルホン酸ナトリウムの連続
製造方法であるが、製品であるスチレンスルホン酸ナト
リウムの固体を得るのに噴霧乾燥を用いる。その為、有
効成分含量は約５０％であり非常に低い。又、通常噴霧
乾燥で得られる粉体は微細で無定形で取り扱い性が劣
る。さらに、該方法は操作が煩雑である。On the other hand, Japanese Patent Publication No. 38-20570 discloses a continuous production method in addition to the semi-batch production method. In this method, a methylene chloride solution of β-haloethylbenzenesulfonic acid, a 50% aqueous solution of caustic soda and water are continuously introduced and reacted, and a 10% aqueous solution of sodium styrenesulfonate is obtained through the two-step reaction. The aqueous solution is spray dried to give 48-54% sodium styrenesulfonate and 27-3% sodium bromide.
This is a method of continuously producing a 3% mixture. However, this method is a continuous method for producing sodium styrenesulfonate, but uses spray drying to obtain a solid product sodium styrenesulfonate. Therefore, the active ingredient content is about 50%, which is very low. In addition, powders obtained by spray drying are usually fine, amorphous and inferior in handleability. Further, the method is complicated in operation.
【０００４】[0004]
【発明が解決しようとする課題】本発明は上記の課題に
鑑みてなされたものであり、その目的は、従来のスチレ
ンスルホン酸アルカリ金属塩の製造方法が有する種々の
課題の解決、すなわち、高純度で、生産性、運転操作性
の良い、スチレンスルホン酸アルカリ金属塩の連続式製
造方法を提供するものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to solve various problems of a conventional method for producing an alkali metal styrenesulfonate, that is, to solve the problems described above. An object of the present invention is to provide a continuous method for producing alkali metal styrenesulfonate having high purity, high productivity and good operability.
【０００５】[0005]
【課題を解決するための手段】本発明者らは上記の課題
を解決すべく、高純度のスチレンスルホン酸アルカリ金
属塩の連続晶析方法について、その工業的見地から検討
を重ねた結果、以下の従来技術の問題点を推定した。す
なわち、通常、連続晶析での滞在時間は長く、その間
スチレンスルホン酸アルカリ金属塩が、自己重合や副反
応して品質及び収率の低下を招く。通常、結晶は板状
であり連続晶析によって更に板状化が進み、結晶は脆く
なり、又、粒径分布が広くなり、ろ過性の低下を招く。
連続晶析では母液の組成、及び析出結晶量のコントロ
ールが困難である。Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have studied the continuous crystallization method of a high-purity alkali metal styrenesulfonate from an industrial point of view. The problems of the prior art were estimated. That is, usually, the residence time in continuous crystallization is long, during which the alkali metal styrenesulfonate undergoes self-polymerization or side reaction, resulting in deterioration in quality and yield. Usually, the crystals are plate-like, and further crystallize further by continuous crystallization, the crystals become brittle, the particle size distribution is widened, and the filterability is reduced.
In continuous crystallization, it is difficult to control the composition of the mother liquor and the amount of precipitated crystals.
【０００６】そこで、本発明者等は、用いる原料種とそ
の導入方法及び抜き出し方法、そして晶析諸条件につい
て鋭意検討した結果、従来の問題点を全て解決し、高い
生産性で安定して連続的にスチレンスルホン酸アルカリ
金属塩を製造できる新規な方法を見い出し、本発明を完
成するに至った。The present inventors have conducted intensive studies on the types of raw materials to be used, their introduction and extraction methods, and various crystallization conditions. As a result, the present invention has solved all of the conventional problems and has achieved a high productivity and a stable continuous process. The present inventors have found a novel method for producing an alkali metal salt of styrenesulfonic acid, and have completed the present invention.
【０００７】すなわち本発明は、β−ハロエチルベンゼ
ンスルホン酸及び／又はそのアルカリ金属塩の水溶液と
アルカリ金属水酸化物水溶液を晶析槽に連続的に導入し
て、生成するスチレンスルホン酸アルカリ金属塩の母液
中濃度を１〜２０重量％とし、スチレンスルホン酸アル
カリ金属塩を反応晶析させ、このスチレンスルホン酸ア
ルカリ金属塩のスラリーを連続して抜き出すことを要旨
とするスチレンスルホン酸アルカリ金属塩の連続式製造
方法である。That is, the present invention relates to an alkali metal styrenesulfonate formed by continuously introducing an aqueous solution of β-haloethylbenzenesulfonic acid and / or an alkali metal salt thereof and an aqueous solution of an alkali metal hydroxide into a crystallization tank. The concentration of the alkali metal styrene sulfonate in the mother liquor is adjusted to 1 to 20% by weight, and the slurry of the alkali metal styrene sulfonate is subjected to reaction crystallization, and the slurry of the alkali metal styrene sulfonate is continuously extracted. It is a continuous manufacturing method.
【０００８】以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
【０００９】本発明の方法において使用されるβ−ハロ
エチルベンゼンスルホン酸やそのアルカリ金属塩におけ
るハロゲンとしては、塩素、臭素、ヨウ素等を挙げるこ
とができ、この内、経済性、反応性の面から臭素が好ま
しく使用される。又、β−ハロエチルベンゼンスルホン
酸アルカリ金属塩におけるアルカリ金属としては、例え
ば、リチウム、ナトリウム、カリウム等の何れでも用い
ることができるが、この内、ナトリウムが入手容易であ
り、経済的であり好ましく用いられる。Examples of the halogen in the β-haloethylbenzenesulfonic acid and the alkali metal salt thereof used in the method of the present invention include chlorine, bromine and iodine. Among them, from the viewpoints of economy and reactivity, Bromine is preferably used. As the alkali metal in the β-haloethylbenzenesulfonic acid alkali metal salt, for example, any of lithium, sodium, potassium and the like can be used. Of these, sodium is easily available, economical and preferably used. Can be
【００１０】本発明の方法において使用されるβ−ハロ
エチルベンゼンスルホン酸の濃度としては、５０重量％
以上、好ましくは６０重量％以上、さらに好ましくは７
０重量％以上である。このような条件であれば、生産性
良く、安定してスチレンスルホン酸アルカリ金属塩を反
応晶析することができる。又、β−ハロエチルベンゼン
スルホン酸又はそのアルカリ金属塩の水溶液には、硫酸
や塩化水素，臭化水素，ヨウ化水素等のハロゲン化水素
酸や、それらのナトリウム塩等の不純物を含有していて
もよい。The concentration of β-haloethylbenzenesulfonic acid used in the method of the present invention is 50% by weight.
Or more, preferably 60% by weight or more, more preferably 7% by weight.
0% by weight or more. Under such conditions, the alkali metal styrenesulfonate can be reacted and crystallized stably with good productivity. The aqueous solution of β-haloethylbenzenesulfonic acid or an alkali metal salt thereof contains impurities such as sulfuric acid, hydrogen chloride, hydrogen bromide, and hydrogen iodide, and sodium salts thereof. Is also good.
【００１１】本発明の方法において使用されるアルカリ
金属水酸化物としては、例えば水酸化リチウム、水酸化
ナトリウム、水酸化カリウム等を挙げることができ、こ
れらの何れでも好適に取り扱うことができるが、この
内、入手し易く、反応性も高く、経済的である水酸化ナ
トリウムが好ましく用いられる。又、その剤型として
は、固体でも水溶液でも良いが、取り扱いの容易さから
水溶液の形態で使用するのが好ましい。アルカリ金属水
酸化物の水溶液の濃度としては、通常市販されている約
５０重量％品でも、又、それを希釈したものでも用いる
ことができる。更に、その量は、スチレンスルホン酸ア
ルカリ金属塩を生成するのに必要な量であれば良く、β
−ハロエチルベンゼンスルホン酸１モルに対して２〜４
モルが好ましく、更に２〜３モルが好ましい。又、β−
ハロエチルベンゼンスルホン酸アルカリ金属塩に対して
は１〜２モルが好ましく、更に１〜１．５モルが好まし
い。As the alkali metal hydroxide used in the method of the present invention, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide and the like can be mentioned, and any of these can be suitably handled. Among them, sodium hydroxide which is easily available, has high reactivity and is economical is preferably used. The dosage form may be a solid or an aqueous solution, but is preferably used in the form of an aqueous solution from the viewpoint of easy handling. As the concentration of the aqueous solution of the alkali metal hydroxide, a commercially available product of about 50% by weight or a diluted product thereof can be used. Further, the amount may be an amount necessary for producing an alkali metal salt of styrene sulfonic acid, and β
-2 to 4 per mole of haloethylbenzene sulfonic acid
Mole, preferably 2 to 3 mole. Also, β-
The amount is preferably from 1 to 2 mol, more preferably from 1 to 1.5 mol, based on the alkali metal salt of haloethylbenzenesulfonic acid.
【００１２】本発明の方法において用いられる溶媒とし
ては、通常水が用いられる。又、生成するスチレンスル
ホン酸アルカリ金属塩の自己重合を防ぐために、例え
ば、亜硝酸塩等の重合禁止剤を加えることが望ましい。
又、反応中の雰囲気は空気でもよいが、窒素雰囲気が好
ましく、生成するスチレンスルホン酸アルカリ金属塩の
自己重合を抑制することができる。As the solvent used in the method of the present invention, water is usually used. Further, in order to prevent self-polymerization of the resulting alkali metal styrenesulfonate, it is desirable to add a polymerization inhibitor such as, for example, nitrite.
The atmosphere during the reaction may be air, but is preferably a nitrogen atmosphere, and can suppress self-polymerization of the resulting alkali metal styrenesulfonate.
【００１３】本発明の方法においては、β−ハロエチル
ベンゼンスルホン酸及び／又はそのアルカリ金属塩の水
溶液と、アルカリ金属水酸化物水溶液とは、晶析槽に同
時に別々に連続的に導入し、スチレンスルホン酸アルカ
リ金属塩を連続して反応晶析する。前記２液は間欠的に
連続して導入しても良い。そして、それらの水溶液の導
入は液中でも液面でもよいが、操作性、結晶成長性の面
から液中に導入するのが有利である。In the method of the present invention, an aqueous solution of β-haloethylbenzenesulfonic acid and / or an alkali metal salt thereof and an aqueous solution of an alkali metal hydroxide are separately and continuously introduced into a crystallization tank simultaneously and continuously. The reaction and crystallization of the alkali metal sulphonate is carried out continuously. The two liquids may be introduced intermittently and continuously. The aqueous solution may be introduced in the liquid or liquid surface, but it is advantageous to introduce the aqueous solution into the liquid from the viewpoint of operability and crystal growth.
【００１４】反応晶析時の母液中のスチレンスルホン酸
アルカリ金属塩濃度としては、母液全量に対して１〜２
０重量％、好ましくは３〜１３重量％、更に好ましくは
５〜１２重量％に保つ。この濃度範囲においてスチレン
スルホン酸アルカリ金属塩結晶の成長性を大きく、晶析
率を高くでき、又、ろ過性の良い結晶が得られる。この
理由として、母液中のスチレンスルホン酸アルカリ金属
塩濃度が１重量％未満では、その結晶成長性が著しく低
下し、純度の高い製品は得られず、２０重量％を超える
と晶析率が極めて低くなり、収率が低下し、又、スチレ
ンスルホン酸アルカリ金属の自己重合や副反応が進み、
品質も低下するからである。従って、本発明の方法にお
いては、反応晶析時の母液中のスチレンスルホン酸アル
カリ金属塩濃度が１〜２０重量％であることは必須であ
る。この範囲にあれば、連続反応晶析では、副生成物
量、重合生成物量は少なく、生成するスチレンスルホン
酸アルカリ金属塩の結晶成長性は大きく、濾布等での分
離が容易な、ろ過性の良い塩が結晶として高純度で得ら
れる。The concentration of the alkali metal styrenesulfonate in the mother liquor at the time of reaction crystallization is 1 to 2 with respect to the total amount of the mother liquor.
0% by weight, preferably 3 to 13% by weight, more preferably 5 to 12% by weight. Within this concentration range, the crystallinity of the alkali metal styrenesulfonate can be increased, the crystallization rate can be increased, and crystals having good filterability can be obtained. The reason for this is that if the concentration of the alkali metal styrenesulfonate in the mother liquor is less than 1% by weight, the crystal growth is remarkably reduced, and a product with high purity cannot be obtained. Lower, the yield decreases, and self-polymerization and side reactions of alkali metal styrenesulfonate progress,
This is because the quality also deteriorates. Therefore, in the method of the present invention, it is essential that the concentration of the alkali metal styrenesulfonate in the mother liquor at the time of reaction crystallization is 1 to 20% by weight. Within this range, in the continuous reaction crystallization, the amount of by-products and the amount of polymerization products are small, the crystal growth of the generated styrene sulfonate alkali metal salt is large, the separation with a filter cloth or the like is easy, and the filterability is high. Good salts are obtained in high purity as crystals.
【００１５】晶析槽としては、スラリーを均一に撹拌が
できれば良く、完全混合型のものでも、ＤＰ（Ｄｏｕｂ
ｌｅ−Ｐｒｏｐｅｌｌｅｒ）型やＤＴＢ（Ｄｒａｆｔ−
Ｔｕｂｅ−Ｂｕｆｆｌｅｄ）型等の分級型のものでも良
い。The crystallization tank only needs to be able to stir the slurry uniformly, and a DP (Dub)
le-Propeller) type or DTB (Draft-
A classification type such as a Tube-Buffled type may be used.
【００１６】反応晶析温度としては、反応速度を大き
く、かつスチレンスルホン酸アルカリ金属塩の結晶成長
を促進する面から、６０〜１２０℃の範囲が好ましく、
さらには８０〜１１０℃の範囲、特に好ましくは９０〜
１０５℃の範囲である。この範囲を越え、６０℃未満の
温度ではビニル化がやや進行し難くなったり、結晶の成
長性がやや低下したりすることがあり、１２０℃を越え
る場合には、スチレンスルホン酸アルカリ金属塩の自己
重合が起こることがある。The reaction crystallization temperature is preferably in the range of 60 to 120 ° C. from the viewpoint of increasing the reaction rate and promoting the crystal growth of the alkali metal styrenesulfonate.
Furthermore, it is in the range of 80 to 110 ° C, particularly preferably 90 to 110 ° C.
It is in the range of 105 ° C. If the temperature exceeds this range and the temperature is lower than 60 ° C., the vinylation may be slightly difficult to progress, or the crystal growth may slightly decrease. If the temperature exceeds 120 ° C., the alkali metal styrenesulfonate may be used. Self-polymerization may occur.
【００１７】又、反応晶析時の母液中のアルカリ金属水
酸化物濃度としては、結晶成長性が高く、ろ過性の良い
スチレンスルホン酸アルカリ金属塩結晶を得るために、
反応母液全量に対して０．５〜２０重量％が好ましく、
さらには、１〜５重量％、特に２〜４重量％が好まし
い。又、この範囲にあれば、スチレンスルホン酸アルカ
リ金属塩の自己重合は殆ど起こらず、スチレンスルホン
酸アルカリ金属塩が高い収率で反応晶析される。The concentration of the alkali metal hydroxide in the mother liquor at the time of the reaction crystallization is as follows.
0.5 to 20% by weight based on the total amount of the reaction mother liquor is preferred,
Further, it is preferably 1 to 5% by weight, particularly preferably 2 to 4% by weight. Further, within this range, the self-polymerization of the alkali metal styrenesulfonate hardly occurs, and the alkali metal styrenesulfonate is reacted and crystallized at a high yield.
【００１８】反応晶析における結晶見掛け滞在時間とし
ては、安定した連続運転ができ、高い生産性で結晶成長
性の大きい、ろ過性の良いスチレンスルホン酸アルカリ
金属塩結晶を得るために、１〜５時間が好ましく、さら
に好ましくは２〜３時間である。この範囲を越えて、１
時間未満では、生成するスチレンスルホン酸アルカリ金
属塩結晶の粒径は問題ないが、析出結晶は凝集晶となり
母液を多く包含し、得られるスチレンスルホン酸アルカ
リ金属塩の純度はやや低下することがあり、５時間を超
えると、結晶の厚み／幅比は大きくなり、ろ過性はやや
低下し、生産性もやや低下することがある。The apparent residence time of the crystal in the reaction crystallization is preferably 1 to 5 in order to obtain a stable continuous operation, a high productivity, a large crystal growth property, and a good filterability. Time is preferred, more preferably 2-3 hours. Beyond this range, 1
If the time is less than the time, the particle size of the generated styrene sulfonic acid alkali metal salt crystals is not a problem, but the precipitated crystals become aggregated crystals and contain a large amount of mother liquor, and the purity of the obtained styrene sulfonic acid alkali metal salt may slightly decrease. When the time exceeds 5 hours, the thickness / width ratio of the crystal becomes large, the filterability is slightly lowered, and the productivity may be slightly lowered.
【００１９】反応晶析におけるスラリー濃度としては、
反応スラリー全量に対して５〜３０重量％が好ましく、
さらには、１０〜２５重量％が好ましい。この範囲にあ
れば、安定した連続運転ができ、ろ過性の良いスチレン
スルホン酸アルカリ金属塩結晶が得られる。又、このス
ラリー濃度の範囲では、スラリーを強制撹拌することで
スラリーの均一流動が図れ、取り扱い性も良く、スラリ
ー移送も容易である。The slurry concentration in the reaction crystallization is as follows:
5 to 30% by weight based on the total amount of the reaction slurry is preferable,
Further, the content is preferably 10 to 25% by weight. Within this range, stable continuous operation can be performed and styrene sulfonic acid alkali metal salt crystals having good filterability can be obtained. Further, in this range of the slurry concentration, the slurry can be uniformly agitated by forcibly stirring the slurry, the handleability is good, and the transfer of the slurry is easy.
【００２０】この反応晶析によってスチレンスルホン酸
アルカリ金属塩の結晶が得られる。この結晶は、通常厚
みの大きい鱗片状で５０μｍ〜１０００μｍにも成長す
る。By this reaction crystallization, crystals of an alkali metal styrenesulfonate are obtained. This crystal usually grows in a scale-like shape with a large thickness of 50 μm to 1000 μm.
【００２１】スチレンスルホン酸アルカリ金属塩のスラ
リーは晶析槽から連続して抜き出される。抜き出し方法
は、オーバーフロー方式でも、ポンプによる方式でも、
グラビティによる方式でも良い。又、一定速度で抜き出
しても、一定時間毎に間欠的に抜き出しても良い。The slurry of the alkali metal styrenesulfonate is continuously withdrawn from the crystallization tank. The extraction method can be either the overflow method or the pump method.
A method based on gravity may be used. Further, it may be extracted at a constant speed, or may be extracted intermittently at regular intervals.
【００２２】抜き出したスラリーは、次に遠心分離、加
圧ろ過、減圧ろ過等により固液分離し該塩の湿潤ケーク
を得る。ここで、固液分離の方法としては公知の方法を
用いることができる。この固液分離はスラリーを抜き出
した直後に行ってもよいが、１０〜５０℃に撹拌下で冷
却した後、行なうことが好ましい。この理由としては、
冷却すると安全に運転操作性良く固液分離でき、かつ、
該塩の溶解度が低下するので、その回収率が向上する。
冷却を行う場合には、晶析槽の後に冷却槽を設けること
が好ましく、又、冷却は連続式又は回分式の何れでもよ
い。The extracted slurry is then separated into a solid and a liquid by centrifugation, filtration under reduced pressure, filtration under reduced pressure or the like to obtain a wet cake of the salt. Here, a known method can be used as the method of solid-liquid separation. This solid-liquid separation may be performed immediately after the slurry is extracted, but is preferably performed after cooling to 10 to 50 ° C. with stirring. This is because
When cooled, solid-liquid separation can be performed safely and with good operability.
Since the solubility of the salt is reduced, the recovery rate is improved.
When performing cooling, it is preferable to provide a cooling tank after the crystallization tank, and the cooling may be either a continuous type or a batch type.
【００２３】固液分離して得られた湿潤ケーク中のスチ
レンスルホン酸アルカリ金属塩の含有量は湿潤ケーク全
量に対して７０重量％以上、さらには８０重量％以上の
高純度であり、乾燥しないでそのまま製品にできる。
又、該湿潤ケークは、品質の均一化のために、強制流
動、すなわち、物理的、機械的に流動させても良い。そ
の装置としては、通常、撹拌羽根、回転ドラム、スクリ
ューブレンダー、一軸又は二軸押し出し機、Ｖ型混合機
等を用いることができる。又、湿潤ケークに乾燥処理を
施しても良い。さらには、造粒を行なうと該塩の取り扱
い性はさらに向上する。造粒に供する原料は湿潤ケーク
でも乾燥したものでもよい。The content of the alkali metal styrenesulfonate in the wet cake obtained by solid-liquid separation is 70% by weight or more, more preferably 80% by weight or more, based on the total weight of the wet cake, and is not dried. Can be used as a product.
In addition, the wet cake may be forcedly flowed, that is, physically and mechanically flowed, for uniform quality. As the apparatus, a stirring blade, a rotating drum, a screw blender, a single-screw or twin-screw extruder, a V-type mixer or the like can be usually used. Further, the wet cake may be subjected to a drying treatment. Further, when the granulation is performed, the handleability of the salt is further improved. The raw material to be granulated may be a wet cake or a dried cake.
【００２４】又、本発明の方法においては、連続的に抜
き出されたスチレンスルホン酸アルカリ金属塩スラリー
の母液の一部を反応槽に循環しても良い。母液は、スチ
レンスルホン酸アルカリ金属塩のスラリーを静定させて
得られる上澄液でも、固液分離して得られるろ液でも良
い。循環することにより、スラリー粘度を調節でき、発
泡を抑制でき、結晶の成長性は向上し、運転操作性も改
善でき、又、収率も向上させることができる。循環する
母液量は限定しないが、目安としてスラリー濃度１０〜
２５重量％になる量が好ましい。In the method of the present invention, a part of the mother liquor of the alkali metal styrenesulfonate slurry continuously withdrawn may be circulated to the reaction tank. The mother liquor may be a supernatant obtained by allowing a slurry of the alkali metal styrenesulfonate to stand still, or a filtrate obtained by solid-liquid separation. By circulating, slurry viscosity can be adjusted, foaming can be suppressed, crystal growth properties can be improved, operation operability can be improved, and the yield can be improved. The amount of circulating mother liquor is not limited, but as a guide,
Preferred amounts are 25% by weight.
【００２５】本発明の方法により、高純度なスチレンス
ルホン酸アルカリ金属塩が得られ、アクリル繊維の染色
補助剤やイオン交換樹脂、帯電防止剤、界面活性剤、減
粘剤等としての用途に有効に利用できる。By the method of the present invention, a high-purity alkali metal styrenesulfonate is obtained, and is effective for use as an auxiliary agent for dyeing acrylic fibers, an ion exchange resin, an antistatic agent, a surfactant, a viscosity reducing agent, and the like. Available to
【００２６】[0026]
【実施例】次に、実施例によりさらに詳細に本発明を説
明する。但し、本発明は下記実施例によってなんら制限
を受けるものではない。又、以下に記載される、部及び
％は重量に基づくものである。Next, the present invention will be described in more detail by way of examples. However, the present invention is not limited by the following examples. Also, parts and percentages described below are based on weight.
【００２７】実施例１ ジャケットを備えた撹拌機付のステンレス製反応器に反
応温度９０℃で、１時間当たり７０％β−ブロモエチル
ベンゼンスルホン酸水溶液２２３部と３５％苛性ソーダ
水溶液１７６部（０．２％亜硝酸ナトリウム含有）とを
別々に連続して導入し、スチレンスルホン酸ナトリウム
を連続して反応晶析させた。そして、その晶析スラリー
を５分間毎に間欠的に連続して１時間当たり３９９部抜
き出した。この時の結晶見掛け滞在時間は２．８時間で
あり、晶析槽内の母液中のスチレンスルホン酸ナトリウ
ム濃度は６．８％、苛性ソーダ濃度は２．４％であり、
スラリー濃度は２５％であった。晶析したスチレンスル
ホン酸ナトリウムは厚みのある平均粒径３３２μｍの鱗
片状結晶であった。抜き出したスラリーは３０℃まで冷
却し、その後遠心分離によって固液分離した。分離は極
めて容易であり、５分間の振り切りで、スチレンスルホ
ン酸ナトリウム含量が８８．０％の高純度の湿潤ケーク
が得られた。又、晶析時の生産速度は８７．５ｋｇ／
（時間・ｍ3）と高く、回収率は原料のβ−ブロモエチ
ルベンゼンスルホン酸基準で８８．４％であった。Example 1 In a stainless steel reactor equipped with a stirrer and equipped with a jacket, at a reaction temperature of 90 ° C., 223 parts of a 70% aqueous solution of β-bromoethylbenzenesulfonic acid and 176 parts of a 35% aqueous solution of caustic soda (0.2 part per hour) were added. % Sodium nitrite) were separately and continuously introduced, and sodium styrenesulfonate was continuously reacted and crystallized. Then, the crystallization slurry was intermittently continuously withdrawn every 5 minutes, and 399 parts were withdrawn per hour. At this time, the apparent stay time of the crystal was 2.8 hours, the sodium styrenesulfonate concentration in the mother liquor in the crystallization tank was 6.8%, the sodium hydroxide concentration was 2.4%,
The slurry concentration was 25%. The crystallized sodium styrene sulfonate was a thick scale-like crystal having an average particle size of 332 μm. The extracted slurry was cooled to 30 ° C., and then separated into solid and liquid by centrifugation. Separation was very easy and after 5 minutes shaking off, a highly pure wet cake having a sodium styrenesulfonate content of 88.0% was obtained. The production rate during crystallization is 87.5 kg /
(Time · m 3 ), and the recovery was 88.4% based on the raw material β-bromoethylbenzenesulfonic acid.
【００２８】実施例２ 実施例１と同様の装置を用いて、反応温度９０℃で、１
時間当たり７０％β−ブロモエチルベンゼンスルホン酸
水溶液１５７部と３５％苛性ソーダ水溶液２９６部
（０．２％亜硝酸ナトリウム含有）とを別々に連続して
導入し、スチレンスルホン酸ナトリウムを連続して反応
晶析させた。そして、その晶析スラリーを５分間毎に間
欠的に連続して１時間当たり４５３部抜き出した。この
時の結晶見掛け滞在時間は２．６時間であり、晶析槽内
の母液中のスチレンスルホン酸ナトリウム濃度は１．４
％、苛性ソーダ濃度は１８．１％であり、スラリー濃度
は２９％であった。抜き出したスチレンスルホン酸ナト
リウムのスラリーは３０℃まで冷却し、その後遠心分離
によって固液分離した。分離は極めて容易であり、５分
間の振り切りで、スチレンスルホン酸ナトリウム含量が
７０．８％の湿潤ケークが得られた。Example 2 Using the same apparatus as in Example 1, the reaction temperature was 90 ° C.
157 parts of a 70% aqueous solution of β-bromoethylbenzenesulfonic acid and 296 parts of a 35% aqueous sodium hydroxide solution (containing 0.2% sodium nitrite) are introduced separately and continuously, and sodium styrenesulfonate is continuously added to the reaction mixture. Was analyzed. Then, 453 parts of the crystallization slurry were continuously and intermittently withdrawn every 5 minutes per hour. At this time, the apparent residence time of the crystal was 2.6 hours, and the concentration of sodium styrenesulfonate in the mother liquor in the crystallization tank was 1.4.
%, Caustic soda concentration was 18.1%, and slurry concentration was 29%. The extracted slurry of sodium styrene sulfonate was cooled to 30 ° C., and then separated into a solid and a liquid by centrifugation. Separation was very easy and after 5 minutes shaking off, a wet cake having a sodium styrenesulfonate content of 70.8% was obtained.
【００２９】実施例３ 実施例１と同様の装置を用いて、反応温度６０℃で、１
時間当たり７０％β−ブロモエチルベンゼンスルホン酸
水溶液１７９部と２５％苛性ソーダ水溶液２０３部
（０．２％亜硝酸ナトリウム含有）とを別々に連続して
導入し、スチレンスルホン酸ナトリウムを連続反応晶析
させた。そしてその晶析スラリーを５分毎に間欠的に連
続して１時間当たり３８２部抜き出した。この時の結晶
見掛け滞在時間は３時間であり、晶析槽内の母液中のス
チレンスルホン酸ナトリウム濃度は６．２％、苛性ソー
ダ濃度は２．４％であり、スラリー濃度は２０％であっ
た。晶析したスチレンスルホン酸ナトリウムは厚みのあ
る平均粒径１６０μｍの鱗片状結晶であった。抜き出し
たスラリーは３０℃まで冷却し、その後、遠心分離によ
って固液分離した。分離は極めて容易であり５分間の振
り切りでスチレンスルホン酸ナトリウム含量が７７．７
％の高純度の湿潤ケークが得られた。又、晶析時の生産
速度は５９．１ｋｇ／（時間・ｍ3）と高く、回収率は
原料のβ−ハロエチルベンゼンスルホン酸基準で７６．
４％であった。Example 3 The same apparatus as in Example 1 was used at a reaction temperature of 60.degree.
179 parts of a 70% aqueous solution of β-bromoethylbenzenesulfonic acid and 203 parts of a 25% aqueous solution of caustic soda (containing 0.2% sodium nitrite) are introduced separately and continuously, and sodium styrenesulfonate is continuously reacted and crystallized. Was. Then, 382 parts of the crystallized slurry were continuously withdrawn every 5 minutes and withdrawn every hour. At this time, the apparent staying time of the crystal was 3 hours, the sodium styrenesulfonate concentration in the mother liquor in the crystallization tank was 6.2%, the sodium hydroxide concentration was 2.4%, and the slurry concentration was 20%. . The crystallized sodium styrene sulfonate was a thick scale-like crystal having an average particle diameter of 160 μm. The extracted slurry was cooled to 30 ° C., and then subjected to a solid-liquid separation by centrifugation. The separation is very easy and the sodium styrenesulfonate content is 77.7 after shaking off for 5 minutes.
% Pure cake was obtained. The production rate at the time of crystallization is as high as 59.1 kg / (hour · m 3 ), and the recovery rate is 76.7 based on the raw material β-haloethylbenzenesulfonic acid.
4%.
【００３０】実施例４ 実施例１と同様の装置を用いて、反応温度９０℃で、１
時間当たり７０％β−ブロモエチルベンゼンスルホン酸
水溶液１７９部と２５％苛性ソーダ水溶液２０８部
（０．２％亜硝酸ナトリウム含有）とを別々に連続して
導入し、スチレンスルホン酸ナトリウムを連続して反応
晶析させた。そしてその晶析スラリーを５分間毎に間欠
的に連続して１時間当たり３８７部抜き出した。この時
の結晶見掛け滞在時間は２．９時間であり、晶析槽内の
母液中のスチレンスルホン酸ナトリウム濃度は１１．３
％、苛性ソーダ濃度は１．５％であり、スラリー濃度は
１５％であった。晶析したスチレンスルホン酸ナトリウ
ムは厚みのある平均粒径７６０μｍの鱗片状結晶であっ
た。抜き出したスラリーは３０℃まで冷却し、その後遠
心分離によって固液分離した。分離は極めて容易であ
り、５分間の振り切りで、スチレンスルホン酸ナトリウ
ム含量が８９．５％の高純度の湿潤ケークが得られた。
又、晶析時の生産速度は６６．３ｋｇ／（時間・ｍ3）
と高く、回収率は原料のβ−ブロモエチルベンゼンスル
ホン酸基準で８３．９％であった。Example 4 The same apparatus as in Example 1 was used at a reaction temperature of 90.degree.
179 parts of a 70% aqueous solution of β-bromoethylbenzenesulfonic acid and 208 parts of a 25% aqueous sodium hydroxide solution (containing 0.2% sodium nitrite) are introduced separately and continuously, and sodium styrenesulfonate is continuously added to the reaction mixture. Was analyzed. Then, 387 parts of the crystallization slurry was continuously and intermittently withdrawn every 5 minutes. At this time, the apparent residence time of the crystal was 2.9 hours, and the sodium styrenesulfonate concentration in the mother liquor in the crystallization tank was 11.3.
%, Caustic soda concentration was 1.5%, and slurry concentration was 15%. The crystallized sodium styrene sulfonate was a thick scale-like crystal having an average particle diameter of 760 μm. The extracted slurry was cooled to 30 ° C., and then separated into solid and liquid by centrifugation. Separation was very easy and after 5 minutes shaking off, a highly pure wet cake having a sodium styrenesulfonate content of 89.5% was obtained.
The production rate during crystallization is 66.3 kg / (hour · m 3 )
The recovery was 83.9% based on the raw material β-bromoethylbenzenesulfonic acid.
【００３１】実施例５ 実施例１と同様の装置を用いて、反応温度９０℃で、１
時間当たり７０％β−ブロモエチルベンゼンスルホン酸
水溶液４９４部と２３％苛性ソーダ水溶液６４７部
（０．２％亜硝酸ナトリウム含有）とを別々に連続して
導入し、スチレンスルホン酸ナトリウムを連続して反応
晶析させた。そしてその晶析スラリーを５分間毎に間欠
的に連続して１時間当たり１１４１部抜き出した。この
時の結晶見掛け滞在時間は１時間であり、晶析槽内の母
液中のスチレンスルホン酸ナトリウム濃度は６．０％、
苛性ソーダ濃度は２．５％であり、スラリー濃度は２５
％であった。晶析したスチレンスルホン酸ナトリウムは
厚みのある平均粒径２４０μｍの鱗片状結晶であった。
抜き出したスラリーは３０℃まで冷却し、その後遠心分
離によって固液分離した。分離は極めて容易であり、５
分間の振り切りで、スチレンスルホン酸ナトリウム含量
が７８．２％の高純度の湿潤ケークが得られた。又、晶
析時の生産速度は１９９．７ｋｇ／（時間・ｍ3）と高
く、回収率は原料のβ−ブロモエチルベンゼンスルホン
酸基準で９３．１％であった。Example 5 The same apparatus as in Example 1 was used at a reaction temperature of 90.degree.
494 parts of a 70% aqueous solution of β-bromoethylbenzenesulfonic acid and 647 parts of a 23% aqueous solution of caustic soda (containing 0.2% sodium nitrite) per hour are separately and continuously introduced, and sodium styrenesulfonate is continuously reacted. Was analyzed. Then, the crystallized slurry was intermittently and continuously withdrawn every 5 minutes, and 1141 parts per hour were withdrawn. The apparent residence time of the crystal at this time was 1 hour, the sodium styrenesulfonate concentration in the mother liquor in the crystallization tank was 6.0%,
The caustic soda concentration is 2.5% and the slurry concentration is 25%.
%Met. The crystallized sodium styrene sulfonate was a thick scale-like crystal having an average particle diameter of 240 μm.
The extracted slurry was cooled to 30 ° C., and then separated into solid and liquid by centrifugation. Separation is very easy and 5
After shaking for 1 minute, a highly pure wet cake having a sodium styrenesulfonate content of 78.2% was obtained. The production rate at the time of crystallization was as high as 199.7 kg / (hour · m 3 ), and the recovery was 93.1% based on the raw material β-bromoethylbenzenesulfonic acid.
【００３２】実施例６ 実施例１と同様の装置を用いて、反応温度９０℃で、１
時間当たり７０％β−ブロモエチルベンゼンスルホン酸
水溶液９９部と２３％苛性ソーダ水溶液１３０部（０．
２％亜硝酸ナトリウム含有）とを別々に連続して導入
し、スチレンスルホン酸ナトリウムを連続して反応晶析
させた。そしてその晶析スラリーを５分間毎に間欠的に
連続して１時間当たり２２９部抜き出した。この時の結
晶見掛け滞在時間は５時間であり、晶析槽内の母液中の
スチレンスルホン酸ナトリウム濃度は５．５％、苛性ソ
ーダ濃度は２．６％であり、スラリー濃度は２０％であ
った。晶析したスチレンスルホン酸ナトリウムは厚みの
ある平均粒径２００μｍの鱗片状結晶であった。抜き出
したスラリーは３０℃まで冷却し、その後遠心分離によ
って固液分離した。分離は極めて容易であり、５分間の
振り切りで、スチレンスルホン酸ナトリウム含量が８
５．７％の高純度の湿潤ケークが得られた。又、晶析時
の生産速度は３８．８ｋｇ／（時間・ｍ3）、回収率は
原料のβ−ブロモエチルベンゼンスルホン酸基準で９
０．６％であった。Example 6 The same apparatus as in Example 1 was used at a reaction temperature of 90.degree.
99 parts of a 70% aqueous solution of β-bromoethylbenzenesulfonic acid and 130 parts of a 23% aqueous sodium hydroxide solution (0.
(Containing 2% sodium nitrite) separately and continuously, and sodium styrenesulfonate was continuously reacted and crystallized. Then, 229 parts of the crystallization slurry were withdrawn intermittently every 5 minutes per hour. At this time, the apparent residence time of the crystal was 5 hours, the sodium styrenesulfonate concentration in the mother liquor in the crystallization tank was 5.5%, the sodium hydroxide concentration was 2.6%, and the slurry concentration was 20%. . The crystallized sodium styrene sulfonate was a thick scale-like crystal having an average particle diameter of 200 μm. The extracted slurry was cooled to 30 ° C., and then separated into solid and liquid by centrifugation. Separation is very easy and the sodium styrenesulfonate content is 8 with shaking off for 5 minutes.
A 5.7% pure cake was obtained. The production rate at the time of crystallization was 38.8 kg / (hour · m 3 ), and the recovery rate was 9% based on the raw material β-bromoethylbenzenesulfonic acid.
0.6%.
【００３３】実施例７ 実施例１と同様の装置を用いて、反応温度９０℃で、１
時間当たりに７０％β−ブロモエチルベンゼンスルホン
酸水溶液１６５部と２５％苛性ソーダ水溶液（０．２％
亜硝酸ナトリウム含有）２００部と反応晶析母液１８部
とを連続して別々に導入し、スチレンスルホン酸ナトリ
ウムを連続して反応晶析させた。そしてその晶析スラリ
ーを５分間毎に連続して１時間当たり３８３部抜き出し
た。この時の結晶見掛け滞在時間は３時間であり、晶析
槽内の母液中のスチレンスルホン酸ナトリウム濃度は
５．８％、苛性ソーダ濃度２．８％であり、スラリー濃
度は２０％であった。晶析したスチレンスルホン酸ナト
リウムは厚みのある平均粒径２７０μｍの鱗片状結晶で
あった。晶析時及び抜き出したスラリーは均一に撹拌流
動し、発泡することなく、操作性は極めて良かった。該
スラリーは３０℃まで冷却し、その後遠心分離によって
固液分離した。分離は極めて容易であり、５分間の振り
切りで、スチレンスルホン酸ナトリウム含量が８５．９
％の高純度の湿潤ケークが得られた。又、晶析時の生産
速度は６７．４ｋｇ／（時間・ｍ3）と高く、回収率は
原料のβ−ブロモエチルベンゼンスルホン酸基準で８
９．７％であった。Example 7 The same apparatus as in Example 1 was used at a reaction temperature of 90.degree.
165 parts of 70% aqueous solution of β-bromoethylbenzenesulfonic acid and 25% aqueous solution of caustic soda (0.2%
200 parts (containing sodium nitrite) and 18 parts of the mother liquor of the reaction crystallization were continuously and separately introduced, and sodium styrenesulfonate was continuously reacted and crystallized. Then, 383 parts of the crystallization slurry were continuously withdrawn every 5 minutes per hour. At this time, the apparent residence time of the crystal was 3 hours, the sodium styrenesulfonate concentration in the mother liquor in the crystallization tank was 5.8%, the sodium hydroxide concentration was 2.8%, and the slurry concentration was 20%. The crystallized sodium styrene sulfonate was a thick scale-like crystal having an average particle diameter of 270 μm. The slurry at the time of crystallization and withdrawn was uniformly stirred and fluidized, and did not foam, and the operability was extremely good. The slurry was cooled to 30 ° C. and then separated into solid and liquid by centrifugation. The separation is very easy and the sodium styrenesulfonate content is 85.9 after shaking off for 5 minutes.
% Pure cake was obtained. The production rate at the time of crystallization is as high as 67.4 kg / (hour · m 3 ), and the recovery rate is 8 based on the raw material β-bromoethylbenzenesulfonic acid.
9.7%.
【００３４】比較例１ 実施例１と同様の装置を用いて、反応温度９０℃で、１
時間当たり７０％β−ブロモエチルベンゼンスルホン酸
水溶液５０部と３５％苛性ソーダ水溶液２８９部（０．
２％亜硝酸ナトリウム含有）とを別々に連続して導入
し、スチレンスルホン酸ナトリウムを連続して反応晶析
させた。そしてその晶析スラリーを５分間毎に間欠的に
連続して１時間当たり３３９部抜き出した。この時の結
晶見掛け滞在時間は３時間であり、晶析槽内の母液中の
スチレンスルホン酸ナトリウム濃度は０．８％、苛性ソ
ーダ濃度は２５％であり、スラリー濃度は４％であっ
た。晶析したスチレンスルホン酸ナトリウムは成長性が
悪く微細な結晶であり、又、液粘度が極めて高く、ろ過
性が劣り高純度のスチレンスルホン酸ナトリウムは得る
ことができなかった。Comparative Example 1 Using the same apparatus as in Example 1, at a reaction temperature of 90 ° C.,
50 parts of a 70% β-bromoethylbenzenesulfonic acid aqueous solution and 289 parts of a 35% aqueous sodium hydroxide solution (0.
(Containing 2% sodium nitrite) separately and continuously, and sodium styrenesulfonate was continuously reacted and crystallized. Then, the crystallization slurry was intermittently and continuously withdrawn every 5 minutes, and 339 parts were withdrawn per hour. At this time, the apparent residence time of the crystal was 3 hours, the concentration of sodium styrenesulfonate in the mother liquor in the crystallization tank was 0.8%, the concentration of sodium hydroxide was 25%, and the concentration of the slurry was 4%. The crystallized sodium styrenesulfonate had poor growth properties and was fine crystals, and the liquid viscosity was extremely high, the filterability was poor, and high-purity sodium styrenesulfonate could not be obtained.
【００３５】比較例２ 実施例１と同様の装置を用いて、反応温度９０℃で、１
時間当たり７０％β−ブロモエチルベンゼンスルホン酸
水溶液１２９部と１８％苛性ソーダ水溶液１９５部
（０．２％亜硝酸ナトリウム含有）とを別々に連続して
導入し、スチレンスルホン酸ナトリウムを連続して反応
晶析させた。そしてその晶析スラリーを５分間毎に間欠
的に連続して１時間当たり３２４部抜き出した。この時
の結晶見掛け滞在時間は３時間であり、晶析槽内の母液
中のスチレンスルホン酸ナトリウム濃度は２１％、苛性
ソーダ濃度は０．８％であった。母液中のスチレンスル
ホン酸ナトリウム濃度は極めて高く、副反応及び重合が
促進され、スチレンスルホン酸ナトリウムの連続反応晶
析を継続できず、各原料の連続フィードは３時間で中止
した。Comparative Example 2 Using the same apparatus as in Example 1, the reaction temperature was 90.degree.
129 parts of a 70% aqueous solution of β-bromoethylbenzenesulfonic acid and 195 parts of an 18% aqueous sodium hydroxide solution (containing 0.2% sodium nitrite) were introduced separately and continuously, and sodium styrenesulfonate was continuously added to the reaction mixture. Was analyzed. Then, 324 parts of the crystallized slurry were continuously withdrawn every 5 minutes and per hour. At this time, the apparent residence time of the crystal was 3 hours, the concentration of sodium styrenesulfonate in the mother liquor in the crystallization tank was 21%, and the concentration of caustic soda was 0.8%. The sodium styrenesulfonate concentration in the mother liquor was extremely high, side reactions and polymerization were promoted, continuous crystallization of sodium styrenesulfonate could not be continued, and continuous feed of each raw material was stopped in 3 hours.
【００３６】比較例３ ジャケットを備えた撹拌機付のステンレス製反応器に３
５％苛性ソーダ１７３５部と亜硝酸ナトリウム６．６部
を張り込み、撹拌しながら７０℃まで３０分かけて昇温
した。次に、撹拌下、３時間かけて、窒素雰囲気下、６
８％のβ−ブロモエチルベンゼンスルホン酸水溶液２１
４６部を滴下した。該液の滴下開始３０分後、反応器内
温度は９０℃になり、以後この温度に保持した。その結
果、得られたスチレンスルホン酸ナトリウム結晶のスラ
リーを３０℃まで冷却した後、遠心分離で固液分離し
て、平均粒径３０μｍのスチレンスルホン酸ナトリウム
の湿潤ケークを得た。この湿潤ケークのスチレンスルホ
ン酸ナトリウム含量は８３．０％であった。該反応晶析
方法では、１回の操作に計８時間要した。回収率は添加
したβ−ブロモエチルベンゼンスルホン酸基準で８８．
８％であったが、反応方法が半回分式であるため生産速
度は実施例１〜５と比較して極めて低く、２９．５ｋｇ
／（時間・ｍ3）であった。Comparative Example 3 In a stainless steel reactor equipped with a stirrer and equipped with a jacket,
1735 parts of 5% caustic soda and 6.6 parts of sodium nitrite were added, and the temperature was raised to 70 ° C. over 30 minutes with stirring. Next, under stirring, under nitrogen atmosphere for 3 hours, 6
8% aqueous solution of β-bromoethylbenzenesulfonic acid 21
46 parts were added dropwise. Thirty minutes after the start of the dropping of the liquid, the temperature in the reactor became 90 ° C., and was kept at this temperature thereafter. As a result, the obtained slurry of sodium styrenesulfonate crystals was cooled to 30 ° C., and then subjected to solid-liquid separation by centrifugation to obtain a wet cake of sodium styrenesulfonate having an average particle size of 30 μm. The sodium styrene sulfonate content of this wet cake was 83.0%. In the reaction crystallization method, one operation required a total of 8 hours. The recovery was 88. based on the added β-bromoethylbenzenesulfonic acid.
However, since the reaction method was a semi-batch type, the production rate was extremely low as compared with Examples 1 to 5, and 29.5 kg.
/ (Time · m 3 ).
【００３７】実施例１〜７、比較例１〜３で得られた湿
潤ケークのスチレンスルホン酸ナトリウム含量、生産速
度、回収率、そして運転操作性について比較した結果を
表１にまとめて示した。The results obtained by comparing the wet cakes obtained in Examples 1 to 7 and Comparative Examples 1 to 3 with respect to the content of sodium styrene sulfonate, the production rate, the recovery rate, and the operability are shown in Table 1.
【００３８】[0038]
【表１】 [Table 1]
【００３９】これらより、実施例１〜７の結果は比較例
１〜３の結果よりも生産速度が高く、更に運転操作性も
良く、特に比較例３の半回分式の反応方式よりも操作が
煩雑でないことが明らかである。From these results, the results of Examples 1 to 7 are higher in the production speed than the results of Comparative Examples 1 to 3, and the operability is also better. In particular, the operation is more excellent than that of the semi-batch reaction system of Comparative Example 3. It is clear that it is not complicated.
【００４０】[0040]
【発明の効果】本発明は、従来の方法では成し遂げるこ
とのできなかった、高純度のスチレンスルホン酸アルカ
リ金属塩を、連続式製造により、高い生産性で、運転操
作性良く製造できる方法であり、高い経済性と工業的価
値を有し、産業利用上極めて有用である。According to the present invention, a high-purity alkali metal salt of styrenesulfonic acid, which could not be achieved by the conventional method, can be produced by continuous production with high productivity and good operability. It has high economic efficiency and industrial value, and is extremely useful for industrial use.
Claims (7)
又はβ−ハロエチルベンゼンスルホン酸アルカリ金属塩
の水溶液とアルカリ金属水酸化物水溶液を晶析槽に連続
的に導入し、晶析槽内の母液中のスチレンスルホン酸ア
ルカリ金属塩濃度を全量の１〜２０重量％とし、スチレ
ンスルホン酸アルカリ金属塩を反応晶析させ、該スチレ
ンスルホン酸アルカリ金属塩のスラリーを連続して抜き
出すことを特徴とするスチレンスルホン酸アルカリ金属
塩の連続式製造方法。(1) β-haloethylbenzenesulfonic acid and / or
Alternatively, an aqueous solution of an alkali metal salt of β-haloethylbenzene sulfonic acid and an aqueous solution of an alkali metal hydroxide are continuously introduced into the crystallization tank, and the concentration of the styrene sulfonic acid alkali metal salt in the mother liquor in the crystallization tank is adjusted to 1 to 1%. A continuous method for producing an alkali metal styrenesulfonate, wherein the alkali metal styrenesulfonate is reacted and crystallized at 20% by weight, and a slurry of the alkali metal styrenesulfonate is continuously extracted.
を特徴とする請求項１に記載のスチレンスルホン酸アル
カリ金属塩の連続式製造方法。2. The continuous process for producing an alkali metal styrenesulfonate according to claim 1, wherein the reaction crystallization temperature is 60 to 120 ° C.
物濃度が全量の０．５〜２０重量％であることを特徴と
する請求項１又は請求項２に記載のスチレンスルホン酸
アルカリ金属塩の連続式製造方法。3. The alkali styrene sulfonate according to claim 1, wherein the concentration of the alkali metal hydroxide in the mother liquor during the reaction crystallization is 0.5 to 20% by weight of the total amount. A continuous production method for metal salts.
〜５時間であることを特徴とする請求項１ないし３のい
ずれかに記載のスチレンスルホン酸アルカリ金属塩の連
続式製造方法。4. An apparent residence time of the crystal in the reaction crystallization is 1
The continuous method for producing an alkali metal styrenesulfonate according to any one of claims 1 to 3, wherein the process is performed for 5 to 5 hours.
全量の５〜３０重量％であることを特徴とする請求項１
ないし４のいずれかに記載のスチレンスルホン酸アルカ
リ金属塩の連続式製造方法。5. The slurry according to claim 1, wherein the slurry concentration in the reaction crystallization is 5 to 30% by weight of the total amount of the slurry.
5. The continuous method for producing an alkali metal styrenesulfonate according to any one of items 4 to 4.
チレンスルホン酸アルカリ金属塩スラリーの母液の一部
を反応槽に循環することを特徴とする請求項１ないし５
のいずれかに記載のスチレンスルホン酸アルカリ金属塩
の連続式製造方法。6. A method according to claim 1, wherein a part of the mother liquor of the alkali metal styrenesulfonate slurry continuously withdrawn in the reaction crystallization is circulated to the reaction tank.
A continuous method for producing an alkali metal salt of styrene sulfonic acid according to any one of the above.
徴とする請求項１ないし６のいずれかに記載のスチレン
スルホン酸アルカリ金属塩の連続式製造方法。7. The method for continuously producing an alkali metal styrenesulfonate according to claim 1, wherein the alkali metal is sodium.
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|---|---|---|---|
| JP34184996A JP3890642B2 (en) | 1996-12-20 | 1996-12-20 | Continuous production method of alkali metal styrene sulfonate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34184996A JP3890642B2 (en) | 1996-12-20 | 1996-12-20 | Continuous production method of alkali metal styrene sulfonate |
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| Publication Number | Publication Date |
|---|---|
| JPH10182591A true JPH10182591A (en) | 1998-07-07 |
| JP3890642B2 JP3890642B2 (en) | 2007-03-07 |
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ID=18349234
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