CAS号 [88-50-6] 生产工艺 2,5-二氯-4-氨基苯磺酸

CAS名: Benzenesulfonic acid, 4-amino-2,5-dichloro- 参考文献: Beil. 14, 707; E¹,723; E²,440.

用途: 酸性黄49。酸性橙50。直接绿38。媒介黄9, 24。合成[84-51-7],可用于其它酸性和活性染料。

生产工艺文献: 按本人手头资料整理如下。

BIOS 1153,185-187.（=胶卷PB 85687）2,5-Dichlorosulphanilic acid. (Leverkusen)英国人译自德文。抄录如下。

反应式: 本人有加注，译者未说明译自哪个德文原件。
 

Plant:  1. Cast iron agitated pan, 3000 l. capacity. Cold and hot water coils.  2. Lead and tile-lines dilution vessel of 15,000 l. capacity.

3. Vat.  4. Filter press.  5. Blow-egg.  6. Nutsche.

Materials: Dichloroaniline  950 kg. Monohydrate 1900 kg. 65% Oleum  1200 kg.

Process:  (a) Sulphonation:

The sulphonator is charged with 1900 kg. of monohydrate and the temperature raised to 50⁰C. The dichloroaniline (950 kg.) in the form of flakes (ex Griesheim) is charged with cooling to keep the temperature below 50⁰C. At the same temperature, 1200 kg. of 65% oleum is run in and the batch then stirred at 80⁰C for 10 hours.

Test: 100 g. of the sulphonation mixture are diluted with ice and water, made alkaline with caustic liquor, and ether extracted. On evaporation the ether there must be no residue.

When sulphonation is complete, the batch is blown into 8000 l. of water and the suspension cooled to 20⁰C and filtered. The filtrate which contains the equivalent of 3.0 g. of sodium nitrite per litre, is run to drain.

(b) Conversion to Sodium Salt:

The filter cake is charged into water (approx. 8000-9000 l. depending on the water in the moist cake) and sufficient soda ash added to effect solution. The batch should still be faintly acid to litmus. Carboraffin is added and the batch screened. To the filtrate is added 300 kg. of salt and the batch is stirred cold for some time. The product, which is in a good physical form, is filtered and pilled as dry as possible. The filtrate containing the equivalent of 2.5-2.8 g. of sodium nitrite per litre is run to drain. Yield= 84-85% theory.

Notes on the Process:

    1. The dichloroaniline in the form of flakes dissolves more readily than in lump form. Dichloroaniline is very toxic.

2. The monosulphonic acid gives on diazotization and coupling with 1-naphthol-5-sulphonic acid in sodium carbonate medium. A bluish-red colour, the disulphonic acid on the other hand gives a yellow colour.

3. Complete removal of the disulphonic acid is necessary; material obtained from Wolfen in 1937 containing disulphonic acid was unsatisfactory for use in the Azo Section.

4. The original process used at Leverkusen was a bake process, superseded by a sulphonation process in 1922. This was modified in 1925 and the present process introduced, differing in the use of less oleum.

Estimation:  产品鉴定:

It is estimated for strength by diazotization, and also for % of unsulphonated dichloroaniline. It is used for Diazo Brilliant Green 3G.

Works Yields:  1931  73.2%;  1932  75.0%;  1933  77.0%;  1934  93.9%;  1935  -  ;  1936  85.7%;  1937  93.9%;  1938  95.5%. 

 The variation in yield is due to the small annual production, and the gradual increase to increased familiarity with the process. 

张澍声 编译。《精细化工中间体工业生产技术》 1996年。P. 44. 2,5-二氯苯胺-4-磺酸，译自BIOS 1153，185. 抄录如下。

    （一）磺化: 在3000 L铸铁磺化锅中加入1900 kg硫酸一水合物，升温至50⁰C。加入950 kg片状2,5-二氯苯胺，同时冷却保持温度在50⁰C以下。在同样温度流入1200 kg 65%发烟硫酸，反应物在80⁰C搅拌10小时。

检验: 取10 g磺化混合物用冰和水稀释，加NaOH使呈碱性，用乙醚萃取。蒸发去掉乙醚后应无残留物。

磺化完成后，反应物压入8000 L水中，悬浮物冷却至20⁰C，过滤。每升滤液消耗NaNO₂不大于3 g。

（二）转变为钠盐: 上述滤饼加到8000-9000 L水中，加入足够的碳酸钠使其溶解，反应物应对石蕊呈弱酸性。加入活性炭，过滤。滤液加入300 kg食盐，搅拌冷却，产品以好的结晶型态析出，过滤，尽可能抽干。每升滤液消耗NaNO₂ 2.5-2.8 g，排放。收率84-85%。（加注：以下为本人所译。仅供参考！）

操作要点: 1. 片状二氯苯胺比块状易溶，二氯苯胺剧毒物。2。一磺化物，在碳酸钠介质中重氮化与1-萘酚-5-磺酸偶合为蓝光红色，如果有二磺化物则显黄色。3. 必须除去二磺化物；1937年由Wolfen厂进的产品中含有二磺酸物，所以不适用于偶氮车间的使用。4. Leverkusen厂的原工艺是烘焙法，1922年改为磺化法，1925年改为本法，差别是发烟硫酸用量少了。

PB 25623, 590-591.   2,5-Dichlorosulfanilic Acid.  德文生产工艺原件。 未抄录。

    除PB 25623以外应该还有其他PB报告，本人暂未找到。 

PB 25629, 271. 2,5-Dichlorosulfanilic Acid.  产品分析方法。未抄录。

天津生产工艺汇编。1980年。P. 65. 2,5-二氯苯胺磺化。抄录如下。

在磺化锅中加入1080公斤20%以上的发烟硫酸，在20-28⁰C加入90% 2,5-二氯苯胺302公斤，升温至120⁰C,在120-125⁰C保温6小时，取样分析测磺化终点，未磺化物含量在0.25%以下为合格。

加注:

Leverkusen厂，即Bayer公司的生产工厂，按当时的生产工艺规程是：

A. Chemischer Teil. 化学部分。Konstitution. 结构式。Einsatz. 投料量。Ausbeute.收得率 。 Arbeitsweise.  操作步骤。Erfahrengen. 操作要点。

B. Technischer Teil. 工程部分。Apparatur. 设备。

英国人的译文：BIOS 1153,185-187. 已比天津生产工艺详细多了，但不能说明已是全文翻译！本产品目前仍有市场，我想多了解一点产品的历史应该是有好处的！

磺化是一个重要的单元操作，用什么磺化剂，如何减少副产的生成，如何减少三废等，是我们为之努力的目标。

陈忠源  2017年5月27日              于 无锡  明辉国际。