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| CAS号 [51084-27-6] 生产工艺 2-氯-4-磺基苯甲酸 |
CAS号 [51084-27-6] 生产工艺 2-氯-4-磺基苯甲酸
CAS名: Benzoic acid, 2-chloro-4-sulfo- 历史参考文献: 暂未检索。
用途: 有机合成，染料中间体（如活性黄13和颜料红68用的 [5855-78-7]）。 反应类别: 甲基氧化。
BIOS 1153, 195.（=胶卷PB 85687）。 2-Chloro-4-sulphobenzoic
acid. (Höchst). 英国人译自德文（无资料来源）。
反应式: 本人有加注。（英国人译文和美国人译文，均未提到哪个德文原件？也未提到生产工艺的年份？）。
Process:
(a) Oxidation:
The reaction vessel (1) is charged with 3000 l. of
water and 50 l. of 33% caustic soda solution, and 413 kg. of
2-chlorotoluene-4-sulphonic acid (sodium salt, 65% strength) (made s in the “C”
acid process) then added. The solution
must be faintly alkaline. After heating
to 80℃, about 900 kg. of
potassium permanganate are introduced during 2 1/2 hours. Oxidation is complete when the pink colour
remains for 20 min. after the last addition.
The temperature during the oxidation must not exceed 95℃.
The batch is cooled to 650 and filtered through
(2). The manganese sludge is washed with
about 400 l. of hot water and then pasted in (1) with 2000 l. of water at 600
and refiltered. This wash-water is used
for the next batch.
(b) Precipitation: The filtrate is clarified through (3) into
(4), heated to 700 and acidified to Congo paper with 350 l. of 30% hydrochloric
acid. After cooling to room temperature
and stirring for 1 day, the mixture is filtered via (5) in (6). The product is dried at 1050 and ground.
Yield = 405 kg. @ 100% strength (as 73-75% strength) =
85% theory.
Analytical: 2-Chlorotoluene-4-sulphoniac
acid: Strength determinate by conversion
into the pure sodium salt, complete precipitation with salt and determination
of the NaCl content of the product dried at 1300 to constant weight.
2-Chloro-4-sulphobenzoic acid: (a) Indirect determination by estimation of
salt and calc. assuming the product is the mono potassium salt.
(b)
Determination of –COOH by splitting off and estimating the CO2.
Services: per tone
of product. Electricity 500 Kw/hr.
Steam 10 tones. Water
700 cu.m. Air 5500 cu.m.
FIAT 1313, I, 121-123. （=胶卷PB 85172）。 2-Chloro-4-sulfo-benzoic
acid. “Chlorsulfocarbonsäure 24” (Hoechst). 美国人译自德文。
Plant capacity:
5 tons. Equipment: 设备。共6台，略。（与英国人译文相同。）。
Materials used per ton: Chlorotoluene para acid 1030 kg.
Potassium permanganate 2250
kg. Caustic soda solution 33% 170 kg.
Hydrochloric acid 30%
1040 kg. By-products
produced: Manganese sludge 1100 kg.
Service requirements per ton of product: 公用工程单耗：与英国人译文相同。
Procedure:
(a) Oxidation:
In (1) containing 3000 l of water and 50 l of caustic
soda solution of 33% strength, 413 kg of chlorotoluene para acid are
dissolved. The reaction must be feebly
alkaline. The solution is heated to 80℃. and in the course of 2-1/2 hours about
900 kg of potassium permanganate are introduced until the blue-red coloration
remains for approximately 20 minutes.
During this operation, the temperature shall not exceed 95℃. The
batch is cooled to 65℃ and
filtered through (2) to (3). The
manganess sludge is at first washed with about 400 l of hot water and then
again pasted in (1) with about 2000 l of water of 60℃ and filtered in (2). This wash water is again used for the
following batch.
(b) Precipitation: The filtrate is clarified through (3) to (4);
here it is heated to 70℃ and
mixed with about 350 l of hydrochloric acid of 30% strength until distinctly
acid to Congo paper. The mixture is
allowed to cool to room temperature and filtered after stirring for 1 day by
way of (5) in (6). The product is dried
at 105℃ in the drying closet
with air circulation and ground in the Alexander mill. Yield:
405 kg of 100% strength.
Control: a) Chlorotoluene para acid: analysis by conversion into the pure sodium
salt, complete precipitation with common salt and determination of the comm. Salt
content in the product, dried at 130℃ until constant in weight.
b) Chlorosulfocarboxylic
acid 24: indirect determination of the
percentage by determination of the salt content and calculation of the mono
potassium salt as the free acid. M. W.
236.5. Determination of the carboxyl
group decarboxylation and determination of the CO2 .
Quality: Chlorotoluene
para acid: Sodium salt 65%. Potassium permanganate, pure, crystal
powder. Final solution: 10-120Be’.
Chlorosulfocarboxylic acid; acid potassium salt of 73-75% strength. （抄注：这里含量说明与英国人的译文比， 十分明确了！）。
张澍声 《精细化工中间体工业生产技术》1996年。 P.
173. 2-氯-4-磺酸基苯甲酸。 译自BIOS 1153, 195.
(1) 氧化: 在5000 L铁反应釜中加入3000 L水和50 L 33% 氢氧化钠溶液，然后加入413 kg 65% 2-氯甲苯-4-磺酸钠（制法入C酸工艺），溶液必须为弱碱性。 加热到80℃后，于2.5小时内加入约900 kg 高锰酸钾。当粉红颜色保持20分钟即为氧化完全，氧化温度不可超过95℃.
反应物冷却到65℃，抽滤。镁泥用约400 L热水洗涤，然后于2000 L水在60℃ 打浆，再过滤。该洗水用于下批反应。
(2) 沉淀: 滤液经压滤澄清后，加热到70℃，用350 L 30% 盐酸酸化至刚果红试纸变红。冷却至室温，搅拌1天，过滤，产品在105℃干燥并研磨。 得到405 kg 100% 2-氯-4-磺酸基苯甲酸，为73-75% 滤饼。 收率85%。
（抄注： 本译文未提到FIAT的译文，也未提到有德文原件？）。
PB 70254, 7005-7007. 美国人介绍：2-Chloro-4-sulfo
benzoic acid. 1934年德文生产工艺。 1.5美元。 未抄录！
PB 73377, 2474-22476.
Chlorosulfocarboxylic acid 24. 未抄录！这是美国人写的调査报告（有具体生产工艺！）。
学习与思考：
1. 1934年生产的2-氯-4-磺基苯甲酸，为什么其CAS号是[51084-27-6]的大号？本品可以有钠盐和钾盐，本人暂未找到他们的CAS号。读者知道吗？
2. 从1946年后进口原版BIOS，FIAT和德文原件PB报告，为什么只见有“前者”的零星译文，如，1986年出版的染料丛书《金属络合染料》，第114页到第到128页的译文均译自BIOS 1548. 请见已上网的“C.I. 酸性红179 （C.I. 19351）生产工艺”。最后列有“加注”。今天上网的这一产品同样存在译文的差别，当然今天已无需知道其德文原文的内容！本人只存在一点希望！
3. 本人虽已不是新时代所需要的人，也不可能有新的作为，今天只想讲点历史问题供年轻人参考。
本人手头收藏的FIAT
1016. 是“中外科学书社”翻印出版的。BIOS 959 是“The new China Book company”翻印出版的，其内页还印有“此书承中华化学工业会借印以供同好特此致谢”，读者应该明白当时对历史资料的重视度，也应该知道我国化学工业的发展。问题是德文原件（PB 报告）未见有出版社出版！所以国内对德文原件的了解是“零”。国内首次出版的中文译文是：张澍声 编译《精细化工中间体工业生产技术》。由《染料工业》编辑部 在1996年出版，无书号，应该是“非正式”出版物。然而，因历史原因，学习BIOS，在1976年以后 出版了“各类 xx 生产工艺汇编 内部资料”，到1991年以后出版了不同出版社出版的“各类 xx化学品技术手册 – 无一说明资料来源”，难道我们缺少英文或者德文人才？不是，这可能是抄录中文比翻译外文方便得多，买个书号就能出版，有名又有Money！这可能是小人之见！只希望年轻人多学点基础知识。多问点为什么？多关注一下资料的真实性！我想今后应该继续上我的网，总会有一天会得到同行的理解！谢谢年轻人的关心和支持！
奋斗是幸福的，高兴的是还有点用！谢谢各位读者！
陈忠源 2018年3月18日星期日。
文章作者：陈忠源 |
