苯胺基甲烷磺酸钠盐 生产工艺  CAS号: [26021-90-9]

CAS名：   Methanesulfonic qcid, phenylamino-

CAS号：  酸式：[103-06-0]    钠盐：[26021-90-9]    钠盐，含结晶水：[69340-12-1]

用途：  性黄6.  酸性红70；142；151.  直接红32；81；84；117.  分散橙3.  食品黄6.

    媒介橙6；10.  溶剂橙9. 等。

合成路线：  CH₂O +  NaHSO₃  à HOCH₂SO₃Na

       CH₂O = 30.03  HNaO₃S = 104.06  CH₃NaO₃S = 134.09

       CAS号： [50-00-0]   [7631-90-5]   [870-72-4]

参考文献：

Beil. 12. 184. E 1. 167. E3. 307.  Syst. No. 1603.

A. B. Ельцова: 染料及中间体实验室合成方法。§7.24   1985年。 (本人已译)

生产工艺：   天津染料生产工艺汇编。 1980年。 第124-5页。
    ω-酸的制备： 
  在反应锅内加入900升水及亚硫酸氢钠100% 52公斤，控制温度60⁰C. 慢慢加入30% 甲醛500公斤，升温至65⁰C，此时介质应对酚酞试纸不呈红色，在60-65⁰C 与1小时内加入苯胺100% 46.5公斤，加完作用2半小时，取样测终点，冷到35⁰C. 体积2000升，按体积18%加再制盐，搅拌2小时，抽滤，滤饼用饱和盐水洗到石蕊试纸不呈碱性，抽干，滤饼称重分析纯度，
  产率95%。

国外生产工艺：   鉴于不少读者未见过资料原件，资料也未上网，现将部分抄录供参考。

BIOS 1153, 82.   N-Methylaniline-ω-sulphonic acid  (Leverkusen 厂)  一般有收藏。
(N-ω-Sulphonmethylaniline)
Method:
  Aniline is heated from 25⁰C to 70⁰C with sodium bisulphate and formaldehyde.

Plant: 1  Brick lined vat, 8000 l., with blade agitator and copper coil.    1  Nutsche.    1  Measure vessel for aniline.

Materials:   745 kg. Sodium bisulphate 100% in form of 40% solution.

      770 kg. Formaldehyde 28%. 
      606 kg. Aniline.
      490 kg. Sodium sulphate.

Process:
  The agitated vat is charged with 745 kg. of sodium bisulphate 100% in the form of 40% solution and 770 kg. formaldehyde 28%,

And heated ¹/₂ hour at 70⁰C. After cooling to 25⁰C., 606 kg. aniline (= 450 kg. nitrite), are run in and the temperature held at 25-30⁰C.

For 3 hours, and then heated to 35⁰C. for a further hour. Test for completion of coupling. 490 kg. of sodium sulphate and 650 l. of mother liquor from previous batches are added and the precipitated product filtered on a nutsche, and washed with sodium sulphate solution 28⁰Be’.   Yield:  92-93% theory.

     上面的BIOS。日文译文。见 细田豊“理论制造染料化学” 1957年。P. 637.
    中文译文。见 张澍声“精细化工中间体工业生产技术” 1996年。P. 113. No. 252.

PB 25623, 269.  Anilinmethansaeure – Leverkusen      1932年6月28日。     网上不可能査到。

Hierbei ist es nach unseren Intersuchungen wesentlich, das dass Bisulfit in Verhaeltnis zum Formaldehyd in erheblichen ueberschuss eingesetzt wird. Wir verwenden auf 100 Mol. Anilin: 119 Mol. Formaldehyd als 40%ig und 140 Mol. Bisulfit als 40%ig. Die Bestimmung den ueberschussigen Bisulfit nach Bildung des Formaldehydbisulfits erfolgt mit Jod, wobei des entstandene Formaldehydbisulfit die Bestimmung nicht stoert.  1 ccm ¹/₁₀ n Jod = 0.0032 g.  SO₂ = 0.0652 g  NaHSO₃.

Praktisch wird so gearbeitet, dass im Bottich erst das Bisulfit vorglegt und mit Jod titriert wird. Dann wird den Formaldehyd zugefuegt und bei ca, 70⁰ wieder titriert wird. Damit wird nicht nur der Bisulfitueberschuss, sondern gleichzeitig auch aus der Differenz der Einsatz an Formaldehyd bestimmt. Die Zugabe des Anilin erfolgt dann zwischen 70-80⁰.     （这是有关[870-72-4]的论述）

PB 25628, 3652.  General Aniline Works, Inc. – Albany Division.    12/15/37.     网上不可能査到。

Charge into enamel kettle # 097  800 lbs water 214 lbs 100% Sodium Bisulphite (MW.104) and stir to good solution = 3.34 mol.

100 lbs 100% Formaldehyde (MW.30) as ordinary 40% solution = 3.33 moll. N. B. Both Bisulphite and Formaldehyde must be previous analysed and care must be exercised in charging. The reaction is exothermic and after the temperature has risen somewhat, warm to 60 – 65⁰C for 15 minutes and at this temperature add rapidly from the drum a previously accurately weighed amount of 310 lbs. Aniline oil

(3.33 mol). Ordinarily the heat of the reaction will maintain the temperature of 60-65⁰c while the cold aniline is being added. Maintain the temperature, never over 65⁰c, until the mixture, at first cloudy, becomes a clear solution. In some cases this may be instantaneous, and some charges may require 10 minutes or longer. Keep this temperature 50 minutes longer. If per chance too much Formaldehyde is noticed previous to adding Aniline, allow the manhole to remain open for a time, otherwise Anhydro Formaldehyde Aniline will formed as small insoluble globlets.

PB 25628, 3662.  General Aniline Works, Inc. – Albany Division.   1/31/38.      网上不可能査到。

   Charge into enamel kettle # 097  345 lbs water 207 lbs Sodium bisulphate 100% (MW.104) = 3.22 mol. Stir to good sol. And add 95 lbs Formaldehyde 100% (MW. 30) as a 40% solution = 3.16 mol. Both the Bisulphite and the Formaldehyde must be accurately analysed previous to charging. The temp. will rise, sometimes as high as 60⁰c. Maintain at 60-65⁰c and run in 292 lbs Anilin oil = 3.14 mol. Which has previously been weighed out into drum from which it may be empted quickly. Most of reaction will help maintain the temperature. If not clear on adding the oil keep at 60-65⁰c for a few minutes until OK’d by the Lab. Stir 1 hour and than blow to the enameled open pot where some evaporation takes place and the mass solidifies. Remove into barrels and dry in vacuo at 65⁰c. Above size change convenient for use in Bldg. 85 as paste.

N.B. Original manufactures always contained a little free Bisulphite or Formaldehyde complex due to the fact that several percent excess over the aniline was charged. This can be avoided if analyses are made of each drum charged and excess care in weighing is employed.

PB 25625, 11-23.  Darstellung der Anilinomegasulfosaeure.       3/30/1933.     网上不可能査到。

   196 kg. Bisulfit 38/40⁰Be’ warden unter Ruehren mit 70 kg. Formaldehyd 30% vermischt. Die Temp. steigt dabei auf ca. 50-55⁰c. Durch Einleiten von Dampf wird auf 60⁰C gebracht. Hierauf laufen bei 60⁰C. 56 kg. Aniline in. Man haelt das Ganze ¹/₂ Std. bei 60⁰C bis das Anilin vollstaendig in Loesung gegangen ist, was im Laboratorium sprueft wird. Das fertige Kondensationsprodukt laeuft in 4000 l. vorgelegtes kaltes Wasser, in welche 102 kg. Natriumbicarbonat 100% zuvor kalt geloest sind.

PB 73561, 546.  Anilin-ω-methansulfosaeure.    1943年6月11日。     网上不可能査到。

483 kg. Natriumbisulfitloesung 38/40⁰Be’ weren unter Ruehren mit 175 kg. Formaldehydloesung 30%ig vermischt; dabei Temp.-steigerung auf 50-55⁰C; man heist mit direktem Dampf nach, bi seine Temp. von 60⁰C erreicht; bei dieser Temperatur last man 139.5 kg. Anilin einlaufen; nach beendigtem Einlaufen wird ¹/₂ Std. bei 60⁰C weitgeruehrt; danach ist des Anilin in Loesung gegangen. Betribsprobe Nr. 2. Wenn Probe 2 in Ordnung, last man die Loesung der Anilin-ω-methansulfosaeure in eine kalt bereite Loesung aus 4000 l. Wasser und 255 kg. Natriumbicarbonat 100%ig, welche Loesung in Kupplungsbuette Nr. 3 corgelegt ist.

Probe 2.  Anilin muss klar geloest sein, es duerfen keine oeligen Troepfchen zugegeben sein.         如有需要，可提供译文。

BIOS 1548, 199,   1946年。(原文未说明出处，其实它摘译自PB 73561,546.)       一般有收藏。

To 483 kg. Sodium Bisulphite liquor 38/40⁰Be’ add 175 kg. formaldehyde solution 30% when the temperature rises to 50-55⁰C. Heat to 60⁰C. and add 139.5 kg. aniline. Stir ¹/₂ hour at 60⁰C. and then add this solution to 4,000 l. water and 255 kg. NaHCO_3.

编注：   上面是产品的历史，供参考。



文章标签：苯胺基甲烷磺酸钠盐 生产工艺  
文章作者：陈忠源  相关链接：尚无链接  文章来源：网络
打印时间：2025/5/22 22:04:08