C.I. 冰染重氮组分9 (C.I. 37040) 生产工艺  CAS号 [89-63-4] 红色基3GL。

CAS名: Benzenamine, 4-chloro-2-nitro-, 参考文献: Beil. 12, 729, E¹, 355, E², 396, E³, 1649, E⁴, 1669.

发明者: Winther, Laska, Zitscher  1911年。

用途: C.I.颜料黄2, 3, 6, 11, 73, 75, 98。C.I.颜料橙36。C.I.颜料红6, 14, 15。C.I.颜料棕23。C.I.分散黄85, 211。

C.I. 溶剂黄164.（俄）溶剂黄4Z。紫外线吸收剂 UV 326 [3896-11-5] 和紫外线吸收剂 UV 327 [3864-99-1]

生产工艺文献: 原版Colour Index. FIAT 764 – Echtrot 3GL Base. Echtrotsalz 3GL.

BIOS 986, 96-98. (=胶卷 77764) No. 50 4-Chloro-o-nitroaniline (I.G. Hoechst) 英国人译自德文。抄录如下。

反应式: 本人有加注。
 

Process:

400 kg. of 2,4-dichloronitrobenzene is charged with 2360 litres of 27% ammonia to the autoclave and the contents checked to ensure that the autoclave is not more than 81% full. The batch is heated to 150⁰C. in 2 hours, firstly with low pressure and then with high pressure steam. The steam is turned off at 150⁰C. and the temperature continues to rise due to the exothermal heat of reaction and reaches 170-175⁰C. in one hour, pressure = 32 – 35 ats.

The temperature is held for 2¹/₂ hours above 165⁰C. Pressure is then let off through the ammonia absorber and the batch cooled to 125⁰C., cooling from 140⁰C. to 125⁰C. being effected with warm water in the jacket. At 125⁰C. the ammonia release valve is closed and cooling water turned off. The ammonia release valve is re-opened at 119⁰C. but the cooling water is turned on only when the temperature has fallen to 95⁰C. The time required for pressure let-down and cooling to 75⁰C. is approximately 2¹/₂ hours.

The batch is then blown to the cooler, where two batches are combined and cooled to 30⁰C. The product is filtered on a nutsch and washed well with water and then sucked as dry as possible. The product contains 15% moisture and is dried at 75-80⁰C. in an air circulation even, an oven load of 1000 kg. dry requiring 40 hours’ drying. Yield 356 kg. （99% pure）= 99% theory. 

No. 51 4-Chloro-o-nitroaniline recrystallised (I.G. Hoechst) Used for Hansa Yellow 3G, 10G, GGR and GE.

The 4-chloro-o-nitroaniline as it comes from the amlidation（英译文如此，应为氨化）plant is too coarse for rapid diazotization and is converted to a finer from by solution in sulphuric acid reprecipitation in water.

Process:  1000 kg. crude 4-chloro-o-nitroaniline 100% in the form of 85% press cake is charged into 2000 kg. sulphuric acid monohydrate in item (1). The solution is effected by agitation and the temperature may rise to 60-70⁰C. The solution is blown slowly into 5000 litres of water in a rubber-lined precipitation agitated vessel. 1100 – 1200 kg. of ice is added during the drowing to keep the temperature below 38-40⁰C. The product is precipitated in an easily diazotisable form and is filtered and washed to complete neutrality.

Yield = 960 – 970 kg. 100% in the form of 35-40% solid filter cake.  Yield = 96-97% theory.

Plant:  Plant capacity: 30 tons per month.

(1) 2 agitated brick-lined tank each 7000 litre capacity. (2) M.S. Rubber-lined precipitation vessels 700 litres.

(3) 2 brick-lined nutsches. Annual productions: 1937 39,000 kg. 1943 257,000 kg.

FIAT 1313, I, 108-110. 60. 4-Chloro-2-nitroaniline (I.G. Hoechst) 美国人译自德文。抄录如下。 
（See BIOS 986, p. 97. Actually 2 batches are not combined in the cooler. However, this is not an important point.） 

Plant capacity: 25 tons per autoclave within 30 days.

Equipment: 1) cast steel autoclave, 3000 l., with heating jacket, propeller stirrer and 2 thermometer tubes;  2)  cast-iron vessel,

4500 l., with cooling jacket and stirrr;   3)  wooden box suction filter;   4)  Schilde drying installation with air circulation and 2 chambers;   5)  Teutonia mill with a magnetic separator and drum sieve.

Materials used per ton:    Nitro-p-dichlorobenzene  1125 kg.        Aqueous ammonia calculated as 100%   197 kg.

Service requirements per ton of product:   Electricity   350 kwh *  550 kwh ^x     Steam    8 ton *  10 ton ^x

Water    350 cu. m. *  350 cu. m. ^x      *) for moist chloronitraniline.    ^x) for dry chloroniitraniline,

Procedure:

400 kg. of nitro-p-dichlorobenzene and 2360 l. of aqueous ammonia of about 27% strength are added into (1). After controlling the space in the clear by means of a measuring stick the autoclave is closed and the agitator is started. After preheating to 60⁰C. by low pressure steam the batch is heated by high pressure steam up to 150⁰C within 2 hours. Due to reaction heat the temperature rises to 170-175⁰C within 1 hour and the pressure rises to 32-35 atm. The temperature is kept above 160⁰C for 2¹/₂ hours. Now the pressure is released and the batch is cooled down to 125⁰C, below 140⁰C by means of warm water. When the temperature has sunk to 125⁰C, the waste gas valve is closed and the cooling water is stopped. At 119⁰C the waste gas valve is opened again and at 95⁰C the cooling water is started again. At 75⁰C the batch is blown into (2), cooled down to about 30⁰C and then put on (3), where the mother liquor and wash waters are pumped away. The 3^rd wash water is sucked off by means of vacuum. The nitraniline obtained, with a moisture content of about 15-20%, is emptied into barrels.

The chloronitraniline not delivered in the moist state is dried on drying pans in (4) at 75-80⁰C. Within about 40 hours the charge of 1 chamber yields about 1000 kg of dry chloronitraniline, which is then ground in (5). Yield: 356 kg of 4-chloro-2-niataniline, dry ground.

Control:  Test of the moist chloronitraniline for water content.  Test of the dry chloronitraniline as to its suitability to be diazotized.

Quality:  Raw materials: commercial quality. Chloronitraniline: after being dissolved and reprecipitated from sulfuric acid, on diazotization leaves a residue of 0.1%

日文摘译。 细田豊 《理论制造染料化学》 1957年。P. 493. 摘译自PB 25623，77764. 抄录如下。

4-クロル-2-ニトロアニリ （フアスト レツト^”3GL ヘ^”-ス）

    2,5-シ^”クロルニトロヘ^”ンセ^”ン400 kgと27% NH₃ 2360 l.とを2 hて^”150⁰に上け^”れは^”反应热て^”1 hて^”170-175⁰(32-35气压)

に上り，165⁰以上に2 ¹/₂ h保温，NH₃をぬき75⁰に冷して排出，30⁰て^”滤過，水洗，75-80⁰て^”亁燥する。356 kg,收率99%。

    在结晶;  粗制1 t (85% ケ- ク 1.18 t) を100% 硫酸2 tにませ^”60-70⁰に上る。水5 t + 冰1.2 tに38-40⁰以下て^”排出，滤洗

する。960-970 kg。

中文摘译。张澍声 《精细化工中间体工业生产技术》1996年。P. 89-90. 摘译自FIAT 1313,I, 108: BIOS 986, 96; BIOS 1147, 12.

(一) 间隙法:  在高压釜中加入400 kg 2,5-二氯硝基苯和2360 L 27% 氨水，必须检查釜内物不多于高压釜容积的81%。于2

小时内加热至150⁰C,停止加热，由于是放热反应，温度继续上升，于1小时内达到170-175⁰C,压力32-35巴。在165⁰C以上保持2.5小时。经过氨吸收器将压力释去，冷却到125⁰C,由140⁰C冷却到125⁰C是在夹套中通温水实现的，在125⁰C关闭氨释放阀，关闭冷水。氨释放阀在119⁰C重新打开，但改通冷水是在温度降至95⁰C时。降压和冷却到75⁰C的时间约需2.5小时。然后将物料压入冷却器中，在这里将两次反应物合并，并冷却到30⁰C.产物抽滤，用水很好洗涤，尽可能抽干，含15%水分，在75-80⁰C干燥，在空气循环炉中进行，每炉装料1000 kg，需要干燥40小时。得到356 kg产品，纯度99%，为理论量的99%。

    精制 – 由氨化车间得到的2-硝基-4-氯苯胺用于快速重氮化时过于粗糙，为此将其溶于硫酸，并在水中重结晶，使其转化为精制状态。将1000 kg 100% 2-硝基-4-氯苯胺粗品（85%滤饼）加到2000 kg硫酸一水合物中，搅拌以加速溶解，温度可升至60-70⁰C. 将溶液缓缓压入5000 L水中，于此同时逐渐加入1100-1200 kg冰，使温度保持在38-40⁰C.产品以容易重氮化的状态沉淀出来。过滤，水洗至完全中性。得到960-970 kg 100%产品，为35-40%固体滤饼状态，收率96-97%。可用于制备颜料黄3G,颜料黄10G 等。

（二）连续法:  2,5-二氯硝基苯28 L/hr, 27%氨水 140 L/hr（二氯硝基苯与氨德摩尔比为1:10）和80⁰C的水 50 L/hr分别经计

量槽用泵送往混合喷嘴，混合后经过预热器加热至180⁰C，然后进入蛇管区，蛇管内温度205-208⁰C,反应的完成是在两个塔内。塔的内径90 mm,长 4 m, 塔内压力200巴，压力的调节是依靠膨胀器前面的膨胀阀进行的，4-氯-2-硝基苯胺，水，氯化铵和过量的氨经膨胀阀释出，以切线方向进入膨胀器，从而达到大气压力，膨胀器内温度85⁰C,是由膨胀器顶部喷洒热的冷凝水达到的。大部分过量的氨经冷却器去氨吸收塔，为了尽可能蒸发出更多的氨，膨胀器内的粘稠物加热到80-90⁰C. 粘稠物含有微细分散的4-氯-2-硝基苯胺，氯化铵溶液和3%游离氨，用螺旋出料器取出，进行抽滤，得到的4-氯-2-硝基苯胺熔点114-114.5⁰C.

如果其他反应条件不变，只是压力分别降至150巴，120巴或100巴，得到的4-氯-2-硝基苯胺熔点在150巴和120巴是不变的，而压力为100巴时，则产品熔点下降0.5⁰C.  抄注:  BIOS 1147 本人未收藏！  

PB 25623, 413-418 (共6页)  4-Chloro-2-nitraniline. 红色基3GL德文生产工艺 未抄录。 

PB 25625, 362-366. Echtrotsalz 3 GL  红色基3GL稳定重氮盐生产工艺。1926年9月。未抄录。

美国人介绍：p-Chloro-o-nitraniline is diazotized. The product is precipitated with zinc chloride. The trade product is obtained by

mixing the double salt with highly dehydrated aluminum sulfate. Preparation of the latter is also described. In German. 

PB 70150, 485-486.  P-Chloronitrailine. By Lanz.  1937年2月18日 红色基3GL德文生产工艺。未抄录。 

PB 70422, 1840-1843.  Fast red 3GL base special.  By Wollmann. 1943年5月31日 红色基3GL德文生产工艺。未抄录。 

PB 70423, 2791-2795.  Echtrotsalz 3GL  红色基稳定重氮盐德文生产工艺。未抄录。 

上海染料生产工艺汇编。1976年。P. 203. 红色基3GL （4-氯-2-硝基苯胺）抄录如下。

   将200公斤2,5-二氯硝基苯吸入高压釜内，加入28%氨水800升。在1-1.5小时内升温至165-712⁰C,压力为30-40公斤/厘米²，保温2.5小时。放压1小时，余氨经过蛇管冷却器用水在吸收塔中进行回收。将物料冷却至130⁰C.

   在结晶釜内放水1000升，在搅拌和冷却条件下，压入上述物料（在10-15分钟内压完）。冷却至30-40⁰C,过滤，滤饼用冷水洗涤。 收率:  90-95%. 

天津染料生产工艺汇编。 1980年。P. 146.  邻硝基对氯苯胺  （3GL 贝司）抄录如下。

在氨化釜内，投入25%的氨水800升，2,5-二氯硝基苯200公斤，密闭升温，在170-180⁰C,压力28-30公斤/厘米²，保温2.5小时之后，放压，氨气吸收回收至压力4-5公斤/厘米²时，将料压入盛有1200升底水的结晶罐中，在搅拌下，冷却降温至40⁰C放料，抽滤，水洗包装。

原料消耗定额: 2,5-二氯硝基苯  97% 1159.45. 氨水 1231. 

A. B. Eльцова  染料及中间体实验室合成方法（红色基3GL）。1985年。9.2 . ctp. 319. 译文如下。

在装有搅拌和温度计的500 ml钢压力釜中，加入28.8 g 2,5-二氯硝基苯和200 ml 25% 氨水，密闭压力釜，加热到180⁰C, 物料于180-185⁰C保温反应6小时，冷却至20⁰C，放压，开启压力釜。

将反应物倒入500 ml水蒸汽蒸馏烧瓶内，其直管冷凝器出口的应接管插入到装有150 ml水的锥形烧瓶内，将瓶内物料加热到95⁰C,通入水蒸汽蒸馏到流出液不再有氨味，冷却到室温，沉淀物用布氏漏斗过滤，抽干，用冰水洗涤（每次25 ml, 总量100 ml）,在抽干，于50-60⁰C干燥。

得量：24 g (93%),橙红色针状，熔点113-115⁰C, 由热水中结晶，熔点116-117⁰C,易溶于乙醇，乙醚，冰醋酸，可溶于石油醚。 

加注:

从上面抄录的BIOS和FIAT可以看出，同一德文生产工艺，因译者不同，二者的译文有明显的不同，实际上德文原件是完整的，可惜未抄录。当然现在有条件可以不用手抄了，问题是要有原件。

抄录英文原件是便于读者学习以及看抄录的中文译文是否可靠。

再次说明，特种文献未抄录者是指国内有原件，本人已看过。

在这里祝读者新春快乐！过完年再见。 

陈忠源  2017年1月23日       于 无锡   明辉国际。