JPH0672126B2 - Method for producing 3-chloro-2-hydroxypropyltrimethylammonium chloride aqueous solution - Google Patents
Method for producing 3-chloro-2-hydroxypropyltrimethylammonium chloride aqueous solutionInfo
- Publication number
- JPH0672126B2 JPH0672126B2 JP1118090A JP11809089A JPH0672126B2 JP H0672126 B2 JPH0672126 B2 JP H0672126B2 JP 1118090 A JP1118090 A JP 1118090A JP 11809089 A JP11809089 A JP 11809089A JP H0672126 B2 JPH0672126 B2 JP H0672126B2
- Authority
- JP
- Japan
- Prior art keywords
- epichlorohydrin
- aqueous solution
- dichlorohydrin
- reaction
- cha
- 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 - Fee Related
Links
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 title claims description 30
- 239000007864 aqueous solution Substances 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000005703 Trimethylamine hydrochloride Substances 0.000 claims description 8
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 5
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 description 18
- 239000007788 liquid Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000001256 steam distillation Methods 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はトリメチルアミン塩酸塩水溶液とエピクロルヒ
ドリンとを反応させて３−クロロ−２−ヒドロキシプロ
ピルトリメチルアンモニウムクロライド水溶液を得る方
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method of reacting an aqueous solution of trimethylamine hydrochloride with epichlorohydrin to obtain an aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride.
３−クロロ−２−ヒドロキシプロピルトリメチルアンモ
ニウムクロライド（以下CHAと略記する）はデンプン，
セルローズ等のカチオン化剤として広く利用されてい
る。これはカチオン化時に苛性アルカリをCHAに対し等
モル以上に共存させれば、デンプンやセルローズの分子
内の水酸基と反応して容易にカチオン基を導入できる。
CHAを製造するには、トリメチルアミンを当量の塩酸で
中和し塩酸塩とした後、エピクロルヒドリンと反応させ
るのが従来より行われている方法である。この方法は副
生物として1,3−ジクロルヒドリンが生成しやすく、ま
た未反応のエピクロルヒドリンも生成物溶液中に残存す
る。これらの1,3−ジクロルヒドリンや未反応エピクロ
ルヒドリンを除去しないので、カチオン化剤として使用
の際、デンプンに添加するとこれらは架橋作用があるた
めデンプン溶液の濃度が上昇したりゲル化をまねくこと
がある。また未反応のトリメチルアミン塩酸塩が残留し
ていればアミン臭を発することになる。このような問題
点を解決するため例えば特開昭58−174349号には上記反
応の際トリメチルアミン塩酸塩とエピクロルヒドリンと
を等モルずつ連続的に使用し、かつ反応温度を70℃以下
に保ち1,3−ジクロルヒドリンの副生を抑制する方法が
記載され、また特開昭54−30149号には上記反応によっ
て得られたCHAの水溶液に水又は水蒸気を添加しつつ減
圧下又は常圧下で連続トッピングするか、又は濃縮する
ことにより未反応エピクロルヒドリン及び副生物を留去
除去する方法が記載されている。3-chloro-2-hydroxypropyltrimethylammonium chloride (hereinafter abbreviated as CHA) is starch,
It is widely used as a cationizing agent for cellulose and the like. This is because if a caustic alkali is allowed to coexist with CHA in an equimolar amount or more during cationization, a cation group can be easily introduced by reacting with a hydroxyl group in the molecule of starch or cellulose.
For the production of CHA, the conventional method is to neutralize trimethylamine with an equivalent amount of hydrochloric acid to form a hydrochloride and then to react it with epichlorohydrin. According to this method, 1,3-dichlorohydrin is easily produced as a byproduct, and unreacted epichlorohydrin also remains in the product solution. Since these 1,3-dichlorohydrin and unreacted epichlorohydrin are not removed, when used as a cationizing agent, when added to starch, they may crosslink because of their crosslinking action, which may lead to gelation. . If unreacted trimethylamine hydrochloride remains, it will give off an amine odor. In order to solve such a problem, for example, in JP-A-58-174349, trimethylamine hydrochloride and epichlorohydrin are continuously used in equimolar amounts in the above reaction, and the reaction temperature is kept at 70 ° C or lower. A method for suppressing the by-product of 3-dichlorohydrin is described, and JP-A-54-30149 discloses that an aqueous solution of CHA obtained by the above reaction is continuously topped under reduced pressure or normal pressure while adding water or steam. Alternatively, a method for distilling off unreacted epichlorohydrin and by-products by means of concentration is described.
しかし上記特開昭58−174349号の方法は、トリメチルア
ミン塩酸塩とエピクロルヒドリンを等モルずつ連続的に
使用することは大規模な装置でその調節が困難であり、
アミン臭を生じ易いという問題点がある。However, in the method of JP-A-58-174349, it is difficult to control trimethylamine hydrochloride and epichlorohydrin in equimolar amounts continuously in a large-scale apparatus.
There is a problem that an amine odor is easily generated.
また特開昭54−30109号においては水の添加は反応容器
内に粗反応液を仕込んで加熱し水の留去が始まった時点
で水の滴下を行っており、工業的に有用な水蒸気使用の
場合の具体的方法については開示又は検討がされていな
い。Further, in JP-A-54-30109, water is added by dropping a crude reaction solution into a reaction vessel and heating it to start the distillation of water. In this case, the specific method has not been disclosed or considered.
本発明は以上の問題点を解決するためのものであって、
トリメチルアミン塩酸塩とエピクロルヒドリンよりCHA
を製造し、さらにこれを精製する工業的に有用な方法を
提供することを目的とする。The present invention is for solving the above problems,
CHA from trimethylamine hydrochloride and epichlorohydrin
It is an object of the present invention to provide an industrially useful method for producing and further purifying it.
すなわち本発明はトリメチルアミン塩酸塩（ａ）水溶液
とエピクロルヒドリン（ｂ）とを反応させるにあたり、
（ａ）に対し（ｂ）を等モルより過剰に使用し、かつ反
応温度を30℃以下に保持することにより３−クロロ−２
−ヒドロキシプロピルトリメチルアンモニウムクロライ
ドの粗水溶液を得、次いで該粗水溶液を、充填塔内で真
空度を塔底温度70℃以下に調節して水蒸気と向流接触さ
せ、未反応エピクロルヒドリンと副生した1,3−ジクロ
ロヒドリンとを同時に溜去することを特徴とする３−ク
ロロ−２−ヒドロキシプロピルトリメチルアンモニウム
クロライドの製造法である。That is, in the present invention, in reacting an aqueous solution of trimethylamine hydrochloride (a) with epichlorohydrin (b),
By using (b) in excess of equimolar to (a) and maintaining the reaction temperature at 30 ° C or lower, 3-chloro-2
-Hydroxypropyltrimethylammonium chloride crude aqueous solution was obtained, and then the crude aqueous solution was countercurrently contacted with water vapor by adjusting the degree of vacuum to a column bottom temperature of 70 ° C or less in a packed column to produce unreacted epichlorohydrin as a by-product. A method for producing 3-chloro-2-hydroxypropyltrimethylammonium chloride, which comprises distilling off 3,3-dichlorohydrin at the same time.
本発明の第１工程は下記の反応式で示される。The first step of the present invention is represented by the following reaction formula.
−主反応− （Me＝メチル基を表わす） −副反応− 上記（１）の反応は反応率が高い程、製品のアミン臭が
少なく、（２）の反応は反応温度が高い程、起り易い。-Main reaction- (Me = methyl group) -Side reaction- The higher the reaction rate, the less the amine odor of the product in the reaction (1), and the higher the reaction temperature, the more easily the reaction (2) occurs.
したがって上記の反応温度を低く抑えて（２）の副反応
が起り難くし、また若干（２）の副反応が起ったとして
もこの際エピクロルヒドリンが不足してアミン臭が残ら
ぬようにややエピクロルヒドリンを過剰に用いる必要が
ある。Therefore, the above reaction temperature is kept low so that the side reaction of (2) is hard to occur, and even if a slight side reaction of (2) occurs, epichlorohydrin is slightly deficient at this time so that the amine odor does not remain. Must be used in excess.
その過剰度は10％程度が適当でトリメチルアミン塩酸塩
に対するエピクロルヒドリンのモル比を1.05〜1.20に保
つことが好ましい。この範囲を超えると未反応のエピク
ロルヒドリンが多く残留して精製工程に支障を来し、ま
たこの範囲未満では製品にアルカリを加えるとアミン臭
が残存する。An appropriate degree of excess thereof is about 10%, and it is preferable to maintain the molar ratio of epichlorohydrin to trimethylamine hydrochloride at 1.05 to 1.20. If it exceeds this range, a large amount of unreacted epichlorohydrin remains and interferes with the purification process. If it is below this range, an amine odor remains when an alkali is added to the product.
反応温度は30℃以下に制御する必要があるが、あまり低
温では反応し難いので10〜25℃の範囲に保たれるように
冷却しながらエピクロルヒドリンの滴下を調節するのが
好ましい。The reaction temperature needs to be controlled at 30 ° C. or lower, but it is difficult to react at a too low temperature, so it is preferable to control the dropping of epichlorohydrin while cooling so as to keep it in the range of 10 to 25 ° C.
例えばトリメチルアミン水溶液（濃度30重量％），塩酸
（濃度35重量％）及びエピクロルヒドリンを原料とした
場合、反応液組成はCHA40重量％，エピクロルヒドリン
４重量％,1,3−ジクロルヒドリン２重量％程度である。For example, when using trimethylamine aqueous solution (concentration 30% by weight), hydrochloric acid (concentration 35% by weight) and epichlorohydrin as raw materials, the composition of the reaction solution is about 40% by weight CHA, 4% by weight epichlorohydrin and 2% by weight 1,3-dichlorohydrin.
この組成物中の残留エピクロルヒドリン及び1,3−ジク
ロルヒドリンは前記のようにカチオン化剤として使用の
際、悪影響があるのでエピクロルヒドリンを10ppm以下,
1,3−ジクロルヒドリンを40ppm以下にまで除去する必要
がある。Since the residual epichlorohydrin and 1,3-dichlorohydrin in this composition have an adverse effect when used as a cationizing agent as described above, epichlorohydrin is contained at 10 ppm or less,
It is necessary to remove 1,3-dichlorohydrin to 40 ppm or less.
本発明の第２工程は以上のような不純物の除去すなわち
CHA粗水溶液の精製に係るものである。工業的には溶媒
による抽出よりも水蒸気蒸留によりエピクロルヒドリン
及び1,3−ジクロルヒドリンを留去させる方法が有効で
あるが、水蒸気蒸留を常圧下で行うと以下の反応が併発
するので好ましくない。The second step of the present invention is to remove the impurities as described above.
It relates to the purification of a CHA crude aqueous solution. Industrially, a method of distilling epichlorohydrin and 1,3-dichlorohydrin by steam distillation rather than extraction with a solvent is effective, but if steam distillation is carried out under normal pressure, the following reactions occur simultaneously, which is not preferable.
したがって水蒸気蒸留を減圧下で行う必要があるが、単
に減圧下で水蒸気を加えながら蒸留を行った場合、例え
ば60〜70mmHg,45〜50℃において1,3−ジクロルヒドリン
濃度を40ppm以下にするには、CHA粗水溶液の約３〜５倍
の水を留去しなければならず長時間を要する。 Therefore, it is necessary to perform steam distillation under reduced pressure, but when performing distillation while simply adding steam under reduced pressure, for example, to reduce the 1,3-dichlorohydrin concentration to 40 ppm or less at 60 to 70 mmHg, 45 to 50 ° C. , 3 to 5 times as much water as the CHA crude aqueous solution must be distilled off, which requires a long time.
本発明の第２工程は、充填塔内で減圧下でCHA粗液と水
蒸気とを向流接触させ、CHA粗水溶液に含まれるエピク
ロルヒドリンと1,3−ジクロルヒドリンを同時に留去す
るものである。In the second step of the present invention, the CHA crude liquid and steam are brought into countercurrent contact with each other under reduced pressure in a packed tower to simultaneously distill off epichlorohydrin and 1,3-dichlorohydrin contained in the CHA crude aqueous solution.
具体的には充填剤を詰めた塔の頂部に排気ポンプを接続
し、塔内を減圧にする。塔上部よりCHA粗水溶液，塔下
部より水蒸気の供給を開始すると、CHA粗水溶液中のエ
ピクロルヒドリンと1,3−ジクロルヒドリンは水蒸気に
同伴留去され、塔頂と排気ポンプとの間に設けた凝縮器
で凝縮され排液となる。精製されたCHA水溶液は塔底部
より缶出液として抜き出され、製品となる。Specifically, an exhaust pump is connected to the top of the column filled with the filler to reduce the pressure inside the column. When CHA crude aqueous solution is supplied from the upper part of the column and steam is supplied from the lower part of the column, epichlorohydrin and 1,3-dichlorohydrin in the CHA crude aqueous solution are distilled off together with the steam, and a condenser provided between the top of the column and the exhaust pump. Is condensed and becomes drainage. The purified CHA aqueous solution is withdrawn as a bottom product from the bottom of the column, and becomes a product.
真空度は塔底部70℃以下，好ましくは50℃以下となるよ
うに、排気ポンプと蒸気入口バルブによって調節する。
また充填剤の種類によって異なるが、フラッディングを
起さぬ限り、小さな液／ガス比で運転することが好まし
い。使用される充填剤としてはポリプロピレン，ポリエ
チレン等の合成樹脂製または磁製のものが挙げられる。The degree of vacuum is controlled by an exhaust pump and a steam inlet valve so that the degree of vacuum is 70 ° C or lower, preferably 50 ° C or lower.
Although it depends on the kind of the filler, it is preferable to operate at a small liquid / gas ratio as long as flooding does not occur. Examples of the filler used include those made of synthetic resin such as polypropylene and polyethylene, or those made of porcelain.
以下実施例，比較例により本発明を説明する。なお例中
の組成％はいずれも重量単位である。The present invention will be described below with reference to examples and comparative examples. All composition% in the examples are in weight units.
実施例1,比較例１ （第１工程） 攪拌器，温度計，還流冷却器を備えた反応槽（容量2m3,
グラスライニング製）に濃度30％のトリメチルアミン85
0kg（4.31kgmol）を仕込み、冷却しながら35％HCl450kg
（4.31kgmol）を滴下し中和した。続いてエピクロルヒ
ドリン438kg（4.74kgmol）を槽内温度12〜22℃となるよ
う数回に分け6.8時間で滴下した。滴下後30分間熱成し
た。このようにして反応粗液1738kg（Ａ）が得られ、そ
の分析結果は以下のとおりであった。Example 1, Comparative Example 1 (First Step) Reaction tank equipped with stirrer, thermometer, reflux condenser (volume 2 m 3 ,
Glass lining) with a concentration of 30% trimethylamine 85
Charge 0 kg (4.31 kgmol) and cool down 35% HCl 450 kg
(4.31 kgmol) was added dropwise for neutralization. Then, 438 kg (4.74 kg mol) of epichlorohydrin was added dropwise over 6.8 hours in several batches so that the temperature inside the tank was 12 to 22 ° C. After dropping, the mixture was heat-treated for 30 minutes. Thus, 1738 kg (A) of the reaction crude liquid was obtained, and the analysis results were as follows.
CHA 39.1％ エピクロルヒドリン 4.1％ 1,3−ジクロルヒドリン 2.1％ CHAの収率はトリメチルアミン基準で83.9％であった。CHA 39.1% Epichlorohydrin 4.1% 1,3-Dichlorohydrin 2.1% CHA yield was 83.9% based on trimethylamine.
比較のため上記反応槽を用い、濃度30％のトリメチルア
ミン680kg（3.45kgmol）を35％HCl60kg（3.45kgmol）で
中和し、次いでエピクロルヒドリン319kg（3.45kgmol）
を0.5時間で滴下した。反応温度は20〜65℃であり、滴
下後30分間熟成し反応粗液1359kgが得られた。分析結果
は以下のとおりであった。For comparison, using the above reaction vessel, 680 kg (3.45 kgmol) of trimethylamine with a concentration of 30% was neutralized with 60 kg (3.45 kgmol) of 35% HCl, and then 319 kg (3.45 kgmol) of epichlorohydrin.
Was added dropwise over 0.5 hour. The reaction temperature was 20 to 65 ° C, and the reaction was aged for 30 minutes to obtain 1359 kg of a reaction crude liquid. The analysis results are as follows.
CHA 35.2％ エピクロルヒドリン 0.1％ 1,3−ジクロルヒドリン 5.3％ CHAの収率はトリメチルアミン基準で73.7％であった。CHA 35.2% Epichlorohydrin 0.1% 1,3-Dichlorohydrin 5.3% CHA yield was 73.7% based on trimethylamine.
（第２工程） 塔径0.13m,充填高さ4mの塔に、充填剤として東洋ゴム工
業（株）製，商品名HEILEX−II125（1 1/4B,ポリプロピ
レン製，空間率90％，パッキングファクター210m-1）を
充填した。試験粗液として上記の反応粗液（Ａ）75kgを
使用し、塔上部より粗液，塔下部より水蒸気の供給を開
始した。定常時において、液供給速度13/hr,水蒸気供
給速度28kg/hr,液ガス比（L/G）0.45,真空度は塔頂で20
mmHg,塔底で60mmHg,温度は塔頂24〜27℃，塔底44〜47℃
であった。(2nd step) TOYO RUBBER CO., LTD., Trade name HEILEX-II125 (1 1 / 4B, polypropylene, 90% porosity, 90% packing factor) in a tower with a tower diameter of 0.13 m and a packing height of 4 m 210 m -1 ). 75 kg of the above reaction crude liquid (A) was used as a test crude liquid, and the supply of the crude liquid from the upper part of the tower and the supply of steam from the lower part of the tower were started. Liquid supply rate 13 / hr, water vapor supply rate 28kg / hr, liquid-gas ratio (L / G) 0.45, vacuum degree is 20
mmHg, 60mmHg at the bottom of the tower, the temperature is 24-27 ℃ at the top of the tower, 44-47 ℃ at the bottom of the tower.
Met.
６時間で液の供給を終了し、缶出液の分析を行った。さ
らに缶出液を精製するため後２回同様の操作をくり返
し、各回の缶出液の分析を行った。これらを次表に示
す。The liquid supply was completed in 6 hours, and the bottom liquid was analyzed. In order to further refine the bottom product, the same operation was repeated twice, and the bottom product was analyzed each time. These are shown in the following table.
実施例2,比較例２ 実施例１の第１工程と同様な方法で製造した反応粗液86
90kg（CHA38.0％,1,3−ジクロルヒドリン5.7％，エピク
ロルヒドリン2.0％）を塔径0.5m,充填高さ10mの塔を用
い、実施例１の第２工程と同じ充填剤を使用し同様の運
転条件で精製を行った。1passの所要時間は36時間，必
要水蒸気量は19300kgである。缶出液の分析値は1pass後
でCHA38.1％,1,3−ジクロルヒドリン0.005％，エピクロ
ルヒドリン0.001％以下であった。この缶出液は蒸発缶
に移送され濃縮された。濃縮液の分析値はCHA60.2％,1,
3−ジクロルヒドリン0.004％以下，エピクロルヒドリン
0.001％以下であり、所要時間は15時間，留出量は3190l
であった。 Example 2, Comparative Example 2 Reaction crude liquid 86 produced by the same method as in the first step of Example 1
90 kg (CHA 38.0%, 1,3-dichlorohydrin 5.7%, epichlorohydrin 2.0%) was used in a column having a column diameter of 0.5 m and a filling height of 10 m, using the same packing as in the second step of Example 1 Purification was performed under operating conditions. The time required for 1 pass is 36 hours and the required amount of water vapor is 19300 kg. The analytical values of the bottom effluent were CHA 38.1%, 1,3-dichlorohydrin 0.005% and epichlorohydrin 0.001% or less after 1 pass. This bottom solution was transferred to an evaporator and concentrated. The analytical value of the concentrate is CHA60.2%, 1,
3-dichlorohydrin 0.004% or less, epichlorohydrin
It is less than 0.001%, the required time is 15 hours, and the amount of distillate is 3190l.
Met.
比較のため同じ反応粗液8690kgを容量13m3の反応槽を用
いて水蒸気蒸留を行った。減圧下水を連続的に供給しな
がらほぼ同量の水（エピクロルヒドリン,1,3−ジクロル
ヒドリンを含む）を留去した。真空度は60〜70mmHg,槽
内温度は45〜50℃であった。開始後108時間で20,000l留
出させた後水の供給量を減少させながら開始後141時間
で合計31,400lの水を留出させた。反応液の分析値はCHA
63.1％,1,3−ジクロルヒドリン0.002％，エピクロルヒ
ドリン0.001％以下であった。For comparison, 8690 kg of the same reaction crude liquid was subjected to steam distillation using a reaction tank having a volume of 13 m 3 . While continuously supplying water under reduced pressure, almost the same amount of water (including epichlorohydrin and 1,3-dichlorohydrin) was distilled off. The degree of vacuum was 60-70 mmHg and the temperature in the chamber was 45-50 ° C. A total of 31,400 liters of water was distilled out 141 hours after the start while distilling 20,000 liters after 108 hours from the start and decreasing the supply amount of water. The analytical value of the reaction solution is CHA
The levels were 63.1%, 1,3-dichlorohydrin 0.002%, and epichlorohydrin 0.001% or less.
以上のように本発明における充填塔使用の水蒸気蒸留方
法は、反応槽を使用した水蒸気蒸留方法に比べ、所要時
間，必要蒸気量の面で大幅に有利である。As described above, the steam distillation method using a packed column according to the present invention is significantly advantageous in terms of required time and required vapor amount as compared with the steam distillation method using a reaction tank.
本発明方法によれば、３−クロロ−２−ヒドロキシプロ
ピルトリメチルアンモニウムクロライド（CHA）水溶液
の製造に際し、1,3−ジクロルヒドリンの生成を抑制
し、また粗液の精製にあたっては、充填塔方式を採用し
た水蒸気蒸留により、CHA濃度を変化させることなく粗
液中に含まれる1,3−ジクロルヒドリン及びエピクロル
ヒドリンの除去を効率よく行うことができる。さらに充
填高さと塔径を大にするほど、単位時間あたりの粗液処
理量は増加するので回分式で生産された粗液の精製時間
を著しく短縮することができる。According to the method of the present invention, in the production of an aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride (CHA), the production of 1,3-dichlorohydrin is suppressed, and in the purification of the crude liquid, a packed column method is adopted. The steam distillation enables efficient removal of 1,3-dichlorohydrin and epichlorohydrin contained in the crude liquid without changing the CHA concentration. Further, as the packing height and the column diameter increase, the amount of crude liquid treated per unit time increases, so that the purification time of the crude liquid produced by the batch method can be significantly shortened.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭53−130610（ＪＰ，Ａ) 特開 昭58−174349（ＪＰ，Ａ) 特開 昭62−212352（ＪＰ，Ａ) 特開 昭54−30109（ＪＰ，Ａ) 特公 昭37−1708（ＪＰ，Ｂ１) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-53-130610 (JP, A) JP-A-58-174349 (JP, A) JP-A-62-212352 (JP, A) JP-A-54- 30109 (JP, A) JP 37-1708 (JP, B1)
Claims (1)
ピクロルヒドリン（ｂ）とを反応させるにあたり、
（ａ）に対し（ｂ）を等モルより過剰に使用し、かつ反
応温度を30℃以下に保持することにより３−クロロ−２
−ヒドロキシプロピルトリメチルアンモニウムクロライ
ドの粗水溶液を得、次いで該粗水溶液を、充填塔内で真
空度を塔底温度70℃以下に調節して水蒸気と向流接触さ
せ、未反応エピクロルヒドリンと副生した1,3−ジクロ
ロヒドリンとを同時に溜去することを特徴とする３−ク
ロロ−２−ヒドロキシプロピルトリメチルアンモニウム
クロライド水溶液の製造法。1. When reacting an aqueous solution of trimethylamine hydrochloride (a) with epichlorohydrin (b),
By using (b) in excess of equimolar to (a) and maintaining the reaction temperature at 30 ° C or lower, 3-chloro-2
-Hydroxypropyltrimethylammonium chloride crude aqueous solution was obtained, and then the crude aqueous solution was countercurrently contacted with water vapor by adjusting the degree of vacuum to a column bottom temperature of 70 ° C or less in a packed column to produce unreacted epichlorohydrin as a by-product. A method for producing an aqueous 3-chloro-2-hydroxypropyltrimethylammonium chloride solution, which comprises simultaneously distilling off 3,3-dichlorohydrin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1118090A JPH0672126B2 (en) | 1989-05-10 | 1989-05-10 | Method for producing 3-chloro-2-hydroxypropyltrimethylammonium chloride aqueous solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1118090A JPH0672126B2 (en) | 1989-05-10 | 1989-05-10 | Method for producing 3-chloro-2-hydroxypropyltrimethylammonium chloride aqueous solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02295952A JPH02295952A (en) | 1990-12-06 |
| JPH0672126B2 true JPH0672126B2 (en) | 1994-09-14 |
Family
ID=14727749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1118090A Expired - Fee Related JPH0672126B2 (en) | 1989-05-10 | 1989-05-10 | Method for producing 3-chloro-2-hydroxypropyltrimethylammonium chloride aqueous solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0672126B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5463127A (en) * | 1995-01-17 | 1995-10-31 | The Dow Chemical Company | Process for preparation of halohydroxypropyl-trialkylammonium halides |
| CN1067982C (en) * | 1997-01-07 | 2001-07-04 | 中国石化齐鲁石油化工公司 | Process for synthesizing 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride |
| GB9914275D0 (en) * | 1999-06-18 | 1999-08-18 | Cerestar Holding Bv | Cationic cross-bonded starch with stable and tailor-made viscosity |
| CN1119320C (en) * | 1999-11-10 | 2003-08-27 | 中国石化集团齐鲁石油化工公司 | Process for separation of organic by-products of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride |
| KR100461567B1 (en) * | 2001-11-02 | 2004-12-14 | 삼성정밀화학 주식회사 | A process for eliminating impurities from halohydroxypropyltrialkyl- ammoniumhalide aqueous solution |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53130610A (en) * | 1977-04-19 | 1978-11-14 | Nippon Oil & Fats Co Ltd | Preparation of quaternary ammonium salt |
| JPS5430109A (en) * | 1977-08-10 | 1979-03-06 | Yotsukaichi Gosei Kk | Method of purifying quarternary ammonium solution |
| JPS58174349A (en) * | 1982-04-08 | 1983-10-13 | Yotsukaichi Gosei Kk | Preparation of aqueous solution of 3-chloro-2- oxypropyltrimethylammonium chloride |
| JPS62212352A (en) * | 1986-03-11 | 1987-09-18 | Kanegafuchi Chem Ind Co Ltd | Production of carnitine intermediate |
-
1989
- 1989-05-10 JP JP1118090A patent/JPH0672126B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02295952A (en) | 1990-12-06 |
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