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| CAS号 [96-67-3] 生产工艺 2-氨基4-硝基苯酚-6-磺酸 |
CAS号 [96-67-3] 生产工艺 2-氨基4-硝基苯酚-6-磺酸
CAS名: Benzenesulfonic acid,3-amino-2-hydroxy-3-nitro- 参考文献: Beil. 14,811; E1,747; E2,486.
用途: 酸性黄99。酸性橙74,125,148。酸性红184,185,315,357,407。酸性棕42, 145, 282, 355。媒介橙4, 29。
媒介绿26。媒介棕19,21,97。溶剂黄19, 32, 79。溶剂橙5, 56。溶剂红109。
生产工艺文献: 按手头资料整理如下：
BIOS 1153, 228-232.（=胶卷PB 85687）Crude 4-nitro-2-aminophenol-6-sulphonic
acid. (Ludwigshafen).英国人译自德文。
反应式: 本人有加注，译者未说明译自哪个德文原件。
Plant: 设备:以下抄录不再分项！
No. 904. 1 Agitated kettle, wrought
iron, rubber-lined, lead cooling and heating coil. Plate stirrer, 40 r.p.m.
Motor 3.7 Kw. And 9.7 m3 in capacity. No. 900. 1 Stirring kettle, rubber-lined, blow-out, heating
and cooling coil of iron. Capacity 9.7 m3, 36 r.p.m. No. 906. 1 Storage vessel, wrought iron, rubber-lined,
for sodium hydrogen sulphide solution. No.
31.A. 1 Storage vessel, wrought
iron, for caustic liquor. No.807. 1 Storage vessel, wrought iron, rubber-lined,
and blow-out, fitted under agitator, with lead cooling and heating coils. Plate
stirrer, 24-32 r.p.m., 7.5 Kw. Motor. Capacity 15 m3. No. 808.A/B. 2 Nutsches, cast iron, “Kerasolithiert”, 5.5
m2. Capacity 2.8 m3.
Materials: 1-Chloro-2,4-dinitrobenzene-6-sulphonic acid. Soda ash. Hydrochloric acid 200Be’. Caustic soda liquor 34.5%.
Magnesium chloride (Fused 62%). Sodium hydrogen sulphide (100%). Wash acid 380Be’ or H2SO4 500Be’.
Process:
The kettle No. 904 is charged with the sodium hydrogen
sulphide solution. This is titrated with N/10 CuSO4 and N/10
hydrochloric acid to determine strength and acidity. The solution is diluted
with water to 27-280Be’ and is about 40% strength.
Kettle No, 900 is charged with 3,300 l. of water (=95
cm.) and to it is added 1,300 kg. of 1-chloro-2,4-dinitrobenzene-6-sulphonic
acid or about 2,800 kg. nutsche cake; when heated to 600C this gives
5,5250 l. (= 155 cm.). Any residual acid is neutralized with about 20 kg. soda
ash and the solution is then run to vessel (31.A.). During 2 hours is added
1,300 kg. of 34.5% caustic liquor, the temperature rising to 90-950C.
The solution should be slightly alkaline to phenol phthalein and this must
persist for 1 hour. Volume is now 6.1-6.5 m3 (175-187 cm.). At this
point, any excess caustic is neutralized with about 20-30 kg. of 20%
hydrochloric acid.
The amount of magnesium chloride and sodium hydrogen
sulphide required for the reduction is calculated as follows:
(Kg. NaOH 34.5% charged – Kg. HCl @30% required for neutralization)
x 2.72 = number of litres magnesium chloride solution and (Kg. Naoh 34.5%
charged – Kg. HCl @ 30% required for neutralization) x 0.84 = Kg. NaSH 100%.
Normally approx. 3,470 l. of magnesium chloride
solution 250Be’ Sp.Gr. 1.210 (1 cm. in vessel 900 = 37 litres)
prepared from 1,980 kg. magnesium chloride are required. This is added over a
long period during 11/2 hours with cooling. Unless the
solution is added slowly and over a period, the very heavy magnesium salt of
the dinitro sulpho acid is precipitated in large crystals at the bottom of the
vessel.
The cooling may not be required during manufacture in
winter.
It is
then pumped from vessel 900 to storage vessel No. 807. The former vessel is
rinsed out with water and incorporated with the main1 bulk of liquor (dip
190-100 cm.). 1,070 kg. NaSH (100%),
i.e. ca. 2,500 l. liquor are now run from the storage vessel No. 906 into the
suspension under 250C. During the winter this can be accomplished in
about 7 hours. A further period of 3-4 hours’ stirring is now given (test). As soon as the reduction is
completed it is cooled further with water to 200C. Volume 12.2 m3 (= 250 cm. dip). Then in about 3 hours, 800-900 kg. of sulphuric acid is run in
in a thin stream. For good crystallization it is necessary that the acid is not
run down too quickly. There is extensive foaming. When this ceases, SO2 and H2S are no longer present, stirring is continued a further 2
hours and, if necessary, more acid added. The final temperature is 45-480C.
Stirring is continued until the danger of
free H2S is no longer
present.
The batch is now cooled to 350C.
and sufficient water added to bring the dip to 300-310 cm. The product is
filtered off onnutsches 808 A. and B. and followed with about 6000 l. of wash
water.
The mother and wash liquors are run to
drain. A test of the mother liquor
should show that it is about 250Be’ (Sp.Gr. 1.210) and 100 cc.
should absorb 7.5 cc. N/1 NaNO2.
The washing is ended when the gravity is
less than 10 Be’ (Sp. Gr. 1.008). 100 cc. ofthis liquor should not
take more than 5 cc. N/1 NaNO2. Yield:=960 kg. at
100% (M.W. 234) by nitrite titration. 抄注: 反应式，略！
Theory
Yield: 83% of the
1-chloro-2,4-dinitrobenzene-6-sulphonic acid. Working Yield: 74%
=89% of theory.
Purification of crude 4-nitro-2-aminophenol-6-sulphonic
acid:
Plant: 设备: 以下抄录不分项。
No. 901. 1
Stirring kettle, cast iron, rubber-lined, with lead heating and cooling coils.
Plate stirrer, 30 r.p.m. Motor 2.2 Kw. Volume 10 m3. No. 308.
1 Stirring steam-heated kettle, cast iron, with plate stirrer, 23-31
r.p.m. Motor 4.5-5.5 Kw. Double heating and cooling coils fitted with hot water
attachment. Volume 6.6 m3.
No. 813. 1 Filter press with
nitro filter cloths and wooden plates and frames. No. 807A/B.
2 Nutsches, cast iron, “Kerasolithiert”, 5.5 m2. Capacity 2.8
m3. No. 814. Pressure egg, cast iron, rubber-lined,
capacity 7.5 m3.
Process:
Kettle No. 901 is charged from kettle No. 308 with
6,500 l. (= 184 cm.) of hot water and 700 kg. of crude 4-nitro-2-aminophenol-6-sulfonic acid at 100%. The solution is
heated to 900C. during 1/2 hour, and then has
a Be’ of 1.5 (Sp.Gr. 1.010). It is filtered through Press No. 813 and returned
to kettle No. 807. The temperature during filtration of the liquor must be at
least 850C.
The kettle is re-charged with 400 l. water, heated up
and followed through the press. A drop of the cooled liquid should not show any
precipitation. The sludge in the press contains about 800 kg. moist sulphur
which is discarded. The contents of Vessel No. 807, before washing are 7600 l.
and after washing, 8,400 l. = 175 cm.
During a long period it is allowed to cool to 730C.
later to 600C. and when this temperature is reached, cooled to 200C.
in not less than 4 hours. From time to time the crystals of material clinging
to the cooling coil and agitator are scraped off. The mass is blown to nutsches
808A/B, with air from pressure egg. No. 814 and crystalline mass washed with
about 400 l. of cold water. The original liquor from this is about 10Be’,
Sp.Gr. 1.008. 100 cc. = 4 cc. N/1 NaNO2.
The wash liquor is about 0.50Be’ (Sp.Gr. 1.004).
100 cc.= 2 cc. N/1 NaNO2.
Yield: 595
kg. purified 4-nitro-2-aminophenol-6-sulphonic acid at 100%. Theoretical
Yield: 100% from crude.
Actual Yield: 85% of material charged = 85% of theory.
(Overall yield = 61% on p-chloronitrobenzene).
张澍声 编译。《精细化工中间体工业生产技术》1996年。p. 111-112. 译自BIOS
1153, 225. 抄录如下。
4-硝基-2-氨基苯酚-6-磺酸粗品: 在9700 L搅拌锅中加入NaHS溶液，用0.1 N CuSO4和0.1 HCl滴定，以测定浓度和酸度，溶液用水稀释至比重1.23-1.24，浓度约40%。在另一9700 L搅拌釜中加入3300 L水，并加入1300 kg 2,4-二硝基氯苯-6-磺酸或约2800 kg滤饼，加热至600C时，其体积为5250 L。用20 kg Na2CO3中和任何残留的酸，于2小时内加入1300 kg 34.5% NaOH溶液，温度上升至90-950C。溶液必须对酚酞为微碱性，这一点必须持续1小时，现在的体积为6100-6500 L。在这一点任何过量的NaOH用约20-30 kg 20% HCl中和。
还原所需的NaHS和MgCl2的数量计算如下：（34.5% NaOH 加料kg数 – 中和所需30% HCl kg数）x 2.72 =氯化镁液L；（34.5% NaOH加料 kg 数 – 中和所需30% HCl kg数）x 0.84 = 100% NaHS kg数。
通常需要约3470 L MgCl2溶液（比重1.210），由1980 kg氯化镁制得。该溶液于1.5小时的长时间内加入，同时进行冷却。除非溶液加得很慢，二硝基磺酸的镁盐在容器底部会以大的结晶沉淀出来。在冬天制造时可无需冷却。将1070 kg 100% NaHS即约2000 L溶液于250C加到上述悬浮体中，在冬天这需要7小时完成，再搅拌3-4小时。一经还原完成，再用水冷却到200C，体积为12200 L。于3小时内以细流加入800-900 kg H2SO4。为了有好的结晶，酸的流入不可太快。有强烈的起泡，当起泡停止，SO2和H2S 不再存在，再继续搅拌2小时，必要时再加一些酸，最终温度45-480C，继续搅拌直至游离H2S不存在。
反应物冷却到350C，加入足够的水，使高度达300-310 cm（12200 L相当于250 cm高度）。产品过滤，用约6000 L水洗涤。
母液及洗水均放至排水沟，母液比重1.210，每100 ml吸收7.5 ml 1 N NaNO2。当比重低于1.008，洗涤完毕。100 ml该洗水消耗不多于5 ml 1 N NaNO2。得到960 kg 100%产品，用亚硝酸钠溶液滴定。收率89%，以2,4-二硝基氯苯-6-磺酸计。
4-硝基-2-氨基苯酚-6-磺酸粗品的精制: 在1000 L搅拌锅中加入6500 L热水和700 kg 4-硝基-2-氨基苯酚-6-磺酸（100%），溶液于0.5小时内加热至900C，压滤，过滤温度必须至少850C,滤液流入15000 L锅中。再用400 l 水洗锅，加热，压滤，一滴滤液冷却后应不显示沉淀。压滤器的滤渣约含800 kg湿硫黄，将其弃去。锅中滤液体积洗前7600 L，洗后8400 L。
经过很长时间冷却到730C，然后到600C，达到600C后冷却到200C（于≥4小时内）。附着在冷却蛇管和搅拌器上的结晶物要随时刮下。压滤，用400 L冷水洗涤。得595 kg 100% 精制的4-硝基-2-氨基苯酚-6磺酸，收率为加料的85%。以对氯硝基苯计，总收率61%。
PB 25602, 715-729. No. 3521-1.
Nitraminsaeure SF. 德文生产工艺原件。未抄录。
本胶卷沈阳院有收藏，共有相同两卷：BP. 32-42和BP. 472-24.
PB 25623, 235-237.4-Nitro-2-aminophenol-6-sulfonic acid =
Nitraminsaeure SF. 德文生产工艺原件。未抄录。
本胶卷，中科图书馆收藏编号Mo
7657, 上海染料所为放大复印本。共665页。含苯系，萘系和蒽醌系中间体。
宋东明 曹传贞 杨志清 （大工）。2-氨基-4-硝基苯酚-6-磺酸的合成。 [J] 染料工业，1998, 4, 17-19. 摘录如下。
2,4-二硝基氯苯-6-磺酸碱性水解: 在三口瓶中加入60 ml水和28.3 g（0.1摩尔）2,4-二硝基氯苯-6-磺酸。搅拌升温至600C,调pH = 7-8，滴加20%氢氧化钠溶液（含有氢氧化钠9.6 g, 0.24摩尔），升温至950C反应2-3小时。终点用蒲层色谱检测，展开剂为乙酸乙酯：甲醇 = 5:1. 反应液冷至室温，用盐酸中和，酸化至pH = 1-2 ,得白色针状结晶。抽滤，盐水洗滤饼，干燥。得含盐产物折100%重24.5 g, 收率92.8%。
2,4-二硝基苯酚-6-磺酸选择性还原: 在三口瓶中加入100 ml水，26.4 g（0.1摩尔）2,4-二硝基苯酚-6-磺酸。用20%氢氧化钠溶液调pH ≥7。升温至600C，滴加20% 硫化钠溶液（含硫化钠14.1 g， 0.18摩尔），升温至750C反应3-4小时。终点用蒲层色谱检测，展开剂乙酸乙酯：甲醇= 5:1。冷至室温，用盐酸中和，酸化至pH = 1-2, 得浅棕色沉淀。抽滤，滤饼干燥。得棕灰色粉末22 g，重氮化滴定测定含量95.4%，收率89.7%。
结果与讨论: 略。 参考文献: 12篇。未引用上述文献。
加注:
从上述抄录的历史文献可以看出，国内缺乏历史文献的整理和归纳，再加上国外手册没有收集这类资料（特种文献），进口了，不用有点浪费吧！当然，本人有点多余！我是以上网一天，过好一天！
张澍声 编译： 《精细化工中间体工业生产技术 – BIOS FIAT PB Reporter》 《染料工业》编辑部 出版。1996年4月第一版。2006年应该是第二版。说是有PB Reporter，其实编者未看过这类德文原件（胶卷）。部分译出的资料，是书本式PB报告。应该说没有这类资料，一样没有问题！
陈忠源 2017年5月30日 于
无锡 明辉国际。
文章作者：陈忠源 |
