CAS号 [121-73-3] 生产工艺      3-硝基氯苯

CAS名: Benzene, 1-chloro-3-nitro-历史参考文献: Beil. 5, 243; E1, 129; E2, 182; E3, 611; E4, 722。用途: 染料及医药中间体。反应类别: 氯化。

生产工艺参考文献: 按本人手头资料整理如下。

BIOS 986, 101-103. （=胶卷PB 77764） m-Chloronitrobenzene.  (I.G. Griesheim).   英国人译自德文（未说明资料）。  抄录如下。

反应式: 本人有加注。本生产工艺分粗品，精馏和结晶三部分，德文原件暂未找到。

m-Chloronitrobenzene crude:  Produced by direct chlorination of nitrobenzene.

3500 kg. dry nitrobenzene (or first runnings from the fractionation of m-chloronitrobenzene) is chlorinated with dry chlorine at 35-40℃. in presence of 15 kg. anhydrous sublimed ferric chloride until density of crude product reaches 1.35 at 15℃  The crude product is washed neutral with water in a wooden vat, the washed product is then distilled 1 hr. with dilute caustic soda and washed free from alkali.

Materials consumptions/tone of m-chloronitrobenzene crude:  Nitrobenzene  0.87 tone.  Chlorine  0.37 t.

Services consumption/tone of m-chloronitrobenzene crude:  Elecricity  274 K.W.H. Steam  1 t. H.P.  6 t. L.P.

Water  186 M3.   Air  204 M3.

Plant for 24 tones/month of various chlorinated products:  1.  3 x 4 M3 C.I. chlorinators, agitated, with water jackets.  2.  1 x 15 M3 wooden vat.

m-Chloronitrobenzene pure (Ex chlorination of nitrobenzene):

The crude chlorination product contains nitrobenzene, m-chloronitrobenzene, a little o-chloronitrobenzene and some polychlorinated nitrobenzenes, and is purified by fractionation and crystallization (“Sweating”).

(A)  Fractionation:

Fraction No.  Composition of fraction  Disposal of fraction                

1.  1st  runnings containing nitrobenzene   Rechlorinated

2.  Intermediate fraction containing nitrobenzene and m-chloronitrobenzene  Rechlorinated

3. Crude m-chloronitrobenzene  Recrystallised or „Sweated“ for isolation

of pure m-chloronitrobenzene.

4. Tails    Refractionated

5. Residue, o-chloronitrobenzene and 2,5-dichloronitrobenzene.

(B)  Crystallisation “Sweating“.

The crude m-chloronitrobenzene is charged to the “sweating” plant, crystallized just below the crystallizing point and then cooled to 30℃. over a period of 24 hr.  The temperature is then raised slowly and the drainings collected until the latter reach C.Pt. 42℃.  The early drainings are combined with unaction 2 from the fractionation for refractionation: the latter drainings are combined with the crude m-chloronitrobenzene fraction from the fractionation for “re-sweating”.  The pure product is then melted and discharged from the “Sweating” apparatus.

Materials consumptions/tone m-chloronitrobenzene pure:

m-Chloronitrobenzene crude 1.98 tones, i.e. overall yield from nitrobenzene = 45.5% theory (This yield low and probably does not allow for return of the various fractions).

Plant:  1.  Fractionation column 40 plates.  100 cm. diameter.   2.  Crystallising pan, vertical multitubular construction (see trichlorobenzene pure) 4 M3 internal capacity of tubes.

m-Chloronitrobenzene pure (Ex ortho, para, chloronitrobenzene nitration):

The crude fraction from para chloronitrobenzene purification containing 72% m-chloronitrobenzene and 28% p-chloronitrobenzene is treated with caustic soda to convert p-chloronitrobenzene to p-niyrophenol, the m-chloronitrobenzene remaining unchanged.  The meta body is purified by fractionation and crystallization (“Sweating”).

2500 kg. of crude m- and p-chloronitrobenzene.  1800 l. water are heated to 140℃. (11 ats.) and 800 l. 400Be’ NaOH added in ten lots.  The pressure finally rises to 22-23 ats. (Due to presence of air used as oxidising medium) at 160℃.  The mixture is cooled to 80℃. and unchanged m-chloronitrobenzene drawn and purified as previously described.

细田豊  《理论制造染料化学》 1957年。 P. 458.  m-クロルニトロベンゼン.  译自PB 77764.  抄录如下。

    ニトロベンゼン3500 kg + FeCl3 15 kgに35-400でCl2を通じ比重1.35 / 150とし，水洗後真空蒸馏した主馏分をスウュ-チングにかけ300から次第に上温して凝固点が420になるまで行う。

张澍声  《精细化工中间体工业生产技术》 1996年。 P. 105.  间氯硝基苯。  译自BIOS 986, 101.抄录如下。

在35-40℃将3500 kg干的硝基苯（或间氯硝基苯分馏的初馏份）用干燥的氯气氯化，并有15 kg升华的无水三氯化铁存在，直至粗品比重达1.35 (15℃）。粗产品在木槽中用水洗至中性，将洗涤的产品减压蒸馏，最后与稀NaOH溶液搅拌1小时，并洗至不含碱。

精制 – 粗氯化产品含有硝基苯，间氯硝基苯，少量邻氯硝基苯和一些多氯化的硝基苯，并用精馏和结晶进行精制。

（一）精馏: 第一馏份含硝基苯，用于氯化：第二馏份为中间馏份，含有硝基苯和间氯硝基苯，进行再精馏，第三馏份为间氯硝基苯，进行重结晶或发汗，使纯的间氯硝基苯不溶化：第四馏份为尾馏份，进行再精馏；第五为残留物，主要为邻氯硝基苯和2,5-二氯硝基苯。

（二）结晶（发汗）:  间氯硝基苯粗品加到发汗盘中，在略低于结晶点进行结晶，然后在24小时内冷却到30℃。然后温度缓缓升高，并收集排出液体，直至排出液体温度42℃。 早期的排出液与用于再精馏的第二馏份合并，后期的排出液体与用于再发汗的间氯硝基苯粗品合并。

纯的产品熔融并从发汗设备中排放出来。每生产1吨纯的间氯硝基苯需使用1.98吨间氯硝基苯粗品，即以硝基苯计的总收率为45.4%。这一收率如此之低，似乎可能未计算各个馏份的回收部分。

在制备对位和邻位混合硝基氯苯的过程中，在精馏过程中，主馏份对硝基苯后有一中间馏份，该中间馏份含有72%间氯硝基苯和28%对氯硝基苯，将该中间馏份用NaOH处理，将对氯硝基苯转化为对硝基苯酚，而间氯硝基苯保持不变。2500 kg间和对氯硝基苯粗品和18000 L水加热到140℃（压力11巴），分10批加入800 L 35% NaOH溶液，压力最终升至22-23巴，温度16℃。混合物冷却到80℃，并抽出未变化的间氯硝基苯，如前法精制。

随想：已没有必要再多说，努力工作为新时代服务！谢谢读者Cited.

陈忠源 2017年11月21日