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CAS号 [100-16-3] 生产工艺。 对硝基苯肼

CAS号 [100-16-3] 生产工艺。   对硝基苯肼

CAS名：Hydrazine, 4-(nitrophenyl)-    历史参考文献：Beil 15, 468; E1, 130; E2, 183; E3, 331; E4, 317.

用途：醛，酮，糖类的检测试剂。LookChem网登录生产与经营单位：色基42家；盐酸盐78家。反应类别：重氮化，还原。

BIOS 986, 336-337.（=胶卷PB 77764）。 4-Nitro-phenyl-hydrazine. (Hoechst).  英国人译自德文，无资料来源。

反应式：本人有加注，暂未找到德文原件。

Process: 操作步骤（不再按原件分项抄录）： 

Processes for 2-nitro and 4-nitro-phenyl-hydrazines are practically identical and process detail must be closely adhered to.

276 kg. p-nitroaniline (crude milled) is well stirred with 500 litres water at 35℃.  500 litres HCl 33% is added slowly and the mixture cooled to -10℃. by the addition of 1500 kg. ice.  265 litres 40% nitrite solution is then In.  The temperature will rise to +5℃ - +8℃. in a few seconds and there must be a definite excess of nitrite.  After 20 minutes a practically clear orange red cold diazo solution is obtained and this is filtered quickly through the big press to remove insoluble matter.

The diazo filtrate runs into a sulphite solution prepared from 1300 litres 40% bisulphite solution and 500 litres 40% NaOH.  The sulphite solution has previously been cooled to +10℃. with the use of ice if necessary and has a definitely alkaline reaction.  The sulphite solution must be vigerously agitated during addition of the diazo solution.  The bisulphite  addition takes place immediately and the diazo reaction disappears with the formation of a deep yellow brown solution at 15℃.

After 0.5 hour the mixture is treated in the hydrolysis vessel with 200 litres H2SO4 600Be’. (slow addition) and the temperature raised to 70℃.  All smell of SO2 has disappeared after 4 hours and yellow hydrazine sulphonate separates, which is filtered after cooling and stirring overnight.

a) In the case of the 4-nitro body, the sulphonate paste is charged to 350 litres of water and 500 litres H2SO4 600Be’ at 40℃. and everything goes almost completely into solution.  Heat to 50℃. and add further quantity of 380 litres H2SO4 600Be’ at 50℃.  the yellow run out on paper disappears and the solution becomes practically colourless and the hydrazine sulphate begins to separate out.  The temperature should not exceed 55℃. to avoid resinification.  Cool overnight to 15 – 20℃. and filter.  Mother liquor contains 4 to 5 g. per litre of product.

Yield: 273 kg. 4-nitro phenyl hydrazine (M. W. 153) = Yield 89% theory.

b) In the case of the 2-nitro body .  2-硝基苯肼，CAS号 [3034-19-3]，准备另列，不再抄录。 Annual productions: 年产量：1937 = 4,600 kg.

张澍声 《精细化工中间体及产品生产工艺》。沈阳院 出版。2006年。P. 482.  4-硝基苯肼，译自BIOS 986, 336.

276 kg对硝基苯胺与500 L水在35℃很好搅拌，缓缓加入500 L 33% 盐酸，加入1500 kg 水使混合物冷却到 -10℃。流入265 L 40% 亚硝酸钠溶液，温度将在数秒内升至 +5 - + 8℃，并要总保持亚硝酸钠过量。20分钟后得到实际上清晰的橙红色冷的重氮溶液，在大型压滤机上迅速过滤，以除去不溶物。

1300 L 40% 亚硝酸钠溶液中加入500 L 40% 氢氧化钠溶液，并预先冷却到10℃，在剧烈搅拌下加入上述重氮液，在15℃形成深黄棕色溶液，亚硫酸氢盐加成立即发生，重氮反应消失。

半小时后，缓慢加入200 L 78% 硫酸，升温至70℃，4小时后二氧化硫气味完全消失，黄色的肼磺酸盐分离出来，搅拌冷却过夜，过滤。

对于4-硝基苯肼，磺酸盐滤饼在40℃加到350 L水和500 L 78% 硫酸中，加热到50℃，再在50℃加入380 L 78% 硫酸。在纸上黄色渗圈消失，溶液变为无色。肼硫酸盐开始分离出来，温度不应超过55℃，以避免树脂化。冷却过夜达到15 – 20℃，过滤，母液含4 – 5 g/L的肼。得到273 kg 

4-硝基苯肼，收率89%。



侯乐山 主编 《中国精细化工产品集 – 原料及中间体10396种》。2006年。P. 286.  对硝基苯肼，摘录。

中国化工信息中心  全国精细化工原料及中间体行业协作组 出版。《版权所有  未经允许  不得翻印》。

【生产方法】将对硝基苯胺溶于盐酸，冷至0℃，加入亚硝酸钠溶液进行重氮化，过滤。将滤液加到冷却的亚硫酸钠和氢氧化钠混合溶液中，再加盐酸使成酸性，在25℃温热半小时，过滤得到对硝基苯肼盐酸。溶于水后加入乙酸钠溶液，析出对硝基苯肼，收率63 – 72%。

【生产厂】3家。



陈忠源 2020年6月28日星期日



文章作者：陈忠源