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| C.I. 碱性黄2 (C.I. 41000) 生产工艺。 CAS号 [2465-27-2] |
C.I. 碱性黄2 (C.I. 41000) 生产工艺。 CAS号 [2465-27-2]
CAS名：Benzenamine, 4,4’-carbonimidoylbis[N,N-dimethyl-,
monohydrochloride 发明者：Kern and Caro 1883年。
用途：腈纶织物染色及其他染料，颜料的合成等。下面按CAS号和LookChem网登录数列表如下：
[492-80-8] 溶剂黄34 – 26 家;
[2465-27-2] 碱性黄2 – 106家； [52497-46-8]
– 2家； [68845-37-4]
颜料绿3 – 0家；
[84255-15-2] – 4家；
[84255-116-3] – 3家。
BIOS 1482, 29-35.（=胶卷PB 86136）。 Auramine o (Ludwigshafen). 英国人译自德文（无资料来源）。
反应式：本人有加注。德文原件未抄录。
Operation time: 操作时间：略。 Plant:
设备：略。
Melt method: 熔融反应方法：
270 kg. Methane Base and 90 kg. sulphur are
ground together with 75 kg. oxalic acid.
This mixture is transferred to the Frederking vessel (1), mixed with
1,350 kg. salt and heated to 170℃ with agitation. The vessel is closed and all the air in the
system displaced with gaseous ammonia.
The pressure of ammonia is taken as it passes the drying tower. The ammonia goes from the compressor, through
the ammonia pre-warmer, through the distributor, through 4 serving pipes on the
under-side of the melt vessel and into the melt. In order to purify from carried-along melt,
the gas stream passes through the cyclone (vessel 2) and then into the liquor
washer, which has 2 bell washers (one over the other). The upper washer is charged with 1,700 kg.
NaOH liquor 400Be’ and the lower washer with 2,100 kg. NaOH liquor 400Be’. The temperature of the upper washer rises to
30-50℃. and that
of the lower washer rises to 50-60℃. Here
the gas stream freed from H2S and a small amount of organic sublimate. The gas stream is now laden with water vapor
, the majority of which is removed by passing through the tube cooler (vessel
No. 4). In order to remove the rest of
the admixed water, the gas-stream passes through the tower dryers, Nos. 5 and
6, which are charged with solid NaOH. A
gas purifier is attached to the tower and from here the ammonia goes to the
compressor which forces it again into the melt apparatus. The normal pressure in the melt apparatus is
one atmosphere.
The temperature of the melt rises slowly
during the process from 1450 to 172℃.
After 11 hours the melt apparatus is shut off from the rest of the plant
by 2 valves and the ammonia pressure released from the melt vessel. Still keeping the Frederking vessel stirring,
air blown through the melt to remove all ammonia, the expelled ammonia is
collected in the absorber to be used again.
The melt is then emptied through a special outlet into a concrete
pit. It is especially important to
attend to attend to the cleaning of the short ammonia-supply tube which becomes
encrusted with melt and also to go over all supply tubes as it is essential
that there should be no hindrance to the quick removal of the H2S.
Emptying and cleaning takes about 2 hours, the
total operation 13 hours. 本人佩服英国人的译文！
Washing the melt: 熔融物的洗涤： Plant: 设备：略。
The melt is washed through a sieve with a
little salt solution (from vessel 25) into the “Schmelyz-grube”, using a total
of 8 cbm. salt solution. Stir for at
least 30 minutes. Transfer the
suspension to the nutsches (16) by means of the Kreisel pump. Filter off the liquor (220Be’) to precipitate
the dissolved Auramine at a later stage.
Wash with salt solution (9-100Be’) and pull as dry as possible. The cake is stirred with a little water and
charged into the mill (17). The total
time of working and filtering on the nutsche is 3-4 hours. The milled paste is transferred to the
distributing vessel (19) which is then filled up with water.
Note: This suspension must not remain
standing in this vessel for any length of time or the hydrate is formed as a
hard mass on the bottom, which can only be set in motion again with great
difficulty.
From the distributing vessel, the suspension
is transferred to the dissolving vessel (21A and B) and here about 5 cbm. water
are added, heated with direct steam to 80-82℃. and then 5 kg. acetic acid 80% and 300 g.
:Blankit” added to each vessel. After
stirring 5 minutes, filter and wash the residue with 1 cbm. of water at 90-100℃.
Filtration takes 10-15 minutes.
The filtrate is run into the copper cylinder (23) containing 4 cbm. of
salt solution. After about 1 hour the
contents of the vessel are at 35℃. and 90Be’.
Add a solution of 180 gm. Nil Blue and 300 gm Indulin Scarlet (which
obviates any addition of hydrosulphite).
Filter at a temperature not higher than 35℃.
Mother liquor of 90Be’ serves to wash the crude melt out of melt vessel.
Drying of the press cake (25-30% water
content) is done in the automatic “Teller Trockner” under 15 mm. vacuum at 70℃., rising to 124℃. The
dry material is milled.
Points to Note: 操作要点：
(1) Melt temperature must be
strictly adhered to. (2) During the melt operation there should be no
strong smell of H2S after the liquor washer.
(3) Washing from the :Streich”
nutsche must be 9-100Be’. (4) In the dissolving process, temperature must
not exceed 80℃. for if it
is kept for any time at a higher temperature saponification results.
Works Samples: 取样分析：
(1) During the melt process,
while the ammonia is passing through the upper and lower washers, test both
with lead acetate paper. If the lower
washer does not give a positive reaction, then the wash liquor must be renewed. The liquor in the upper washer is not then
necessarily exhausted and after running off the NaHS liquor from the lower washer,
transfer the liquor from the upper to the lower washer. (2)
The progress of the melt reaction can be followed by testing the amount
of H2S produced.
A thin stream of gas given off from the melt
is lead for 2-3 minutes into a flask containing 500 g. hydrogen peroxide 3%,
the volume of gas passed being measured by means of a gas flow meter. The temperature is kept below 10℃. by external cooling. Add 25 cc. N NaOH solution to 1/10 of the
solution and boil for 3 minutes until no more NH3 is given off. Titrate with N HCl; from the reading take off
0.2 cc. The result taken from 25 cc.
(volume of NaOH taken) is converted to H2S per 100 cc. of gas flow.
Raw materials: 对原材料的要求：
Salt – Water content less than 0.5% tested at
170℃. Sulphur – Test solubility is CS2 and
estimate residus. Oxalic acid – Test
with permsngsnste.
Methane Base – M. Pt. 88-88.4℃.
Test: water content. When pressed
the base should not stick together.
Quantities:
投料量：
Methane Base
270 kg. Salt, special
industrial 1,350 kg. Oxalic acid
75 kg. Ammoniia 25% 181 kg.
Sulphur (milled) 90 kg.
Caustic soda solid 1280 32 kg.
Caustic soda liq. 34.5% 221
kg. Acetic acid tech. pure 8 kg.
Rock salt 236 kg.
Yield: 450 kg. type = 87% of theory. 收率：87%。 Literature:
DE. 53614. P. 34-35. 生产工艺流程图：略。
细田豊 《理论制造染料化学》1957年。 P. 780-781. オ- ラミン O. 译自BIOs 1482.
テトラメチルジアミノジフェニルメタン270 kg，硫黄90 kgおよび修酸75 kgを粉碎混合し，4.5 m3の熔融釜に入れ，NaCl 1350 kgとまぜて1700に加热し，密闭してNH3 ガスで空气を置换え，NH3ガスを预热し，4个のパイプに分配して下方から熔融物の中に吹入む。排出ガスはH2Sと升华物少量を含みサイクロンを经てNaOH 400Be’液を入れた上下2この洗净机を通り，冷却管と2こと固形NaOH塔を经て脱水され，压缩机によつて再び熔融釜に入る。熔融は11 hかかり1450から1720に上る， NH3を止め空气でNH3を追出して回收し，内容をコンクリ- ト槽に排出する。
熔融物に盐水8 m3とまぜ滤過し，9-100Be’盐水で洗い，ケ- クを少量の水とミルで粉碎し，2この溶解槽に分けそれぞれ水5 t と生蒸汽で800に热し酢酸80% 5 kgおよびブランキット300 gを加え5 m搅拌後滤過し，90-1000の湯1 t で洗い，滤液は盐水4 m3を入れた沉淀槽に流し入む。约1 hで350, 90Be’ になつた时，ナイルブル- 180 kg とインジュリンスカ- レット300 gを加え，滤過，自动真空亁燥机で亁燥する。450 kg 标准。收率87%。
抄注：国内未见有人翻译。
FIAT 1313, II, 367-368. Diaryl Methanes. Auramine O.
美国人摘译自德文（无资料来源）。摘录如下：
The mixer charge was 270 kg. methane base
(tetra methyl diamino diphenyl methane) 90 kg. sulfur, 75 kg. oxalic acid, and
1,350 kg. salt for Auramine O. The reaction was written: （抄注： 反应式，略）
The yield was stated to be 166.8 kg. of
Auramine O or 104.3 kg. of 100% Auramine per 100 kg. methane base, which is
87.4% of the theoretical. Auramine O was
further stated to be 70 kg. dried crude standardized with 30 kg. sodium
sulfate.
抄注：为什么美国人只是摘译，也未提及有德文原件？
PB 70135.
Directions for producing various dyes.
1929-1945年德文生产工艺。共861页。胶卷6美元。美国人介绍如下：
This FIAT microfilm reel consists of 125
items, all being plant directions for the production of various dyes. Individual items are listed below and will be
available as enlargement prints.（抄注：放大本86.5美元）In German.
PB 70135, 810-823. Auramin O (Auramine O). 1939年1月德文生产工艺。1.5美元。 未抄录。
PB 70135, 1289-1291. Auramin Base.
1940年德文生产工艺。1.5美元。 未抄录。
国内研究动态：
[J] 有机化学工业技术报导. 1959,4, 68.
盐基淡黄生产情况。
北京兴华染料厂在1958年盐基淡黄（Auramine O）已正式投入生产，其反应过程如下；
1） 氨化：氨化过程中首先是Base的熔化（80-90℃），然后为硫黄熔化温度约在119-120℃，已熔化的S及Base附着在Nael的表面，温度在140℃ H2S开始发生，以后温度上升至145-150℃ H2S发生最盛，然后反应逐渐成弱则接近反应终点（不少能完全没H2S）。 2） 水洗：以冷水洗掉其中的盐及过滤。 3） 洗色：将洗掉盐之酸的滤饼，再以60-70℃温水洗之使把染料洗于水中。 必要时滤饼进行磨细再洗。 4） 盐析：加入第一次洗下的盐水或新制盐。 5） 压滤：控制温度在35℃以下进行压滤。 6） 烘干：在蒸水排管烘箱中烘干温度控制在70℃。
本项产品产率平均已达到68%，本项产品为Base的后一部分生产技术情况，不包括前一部分。
抄注：未提参考文献。
阎一寒 董 源 《碱性嫩黄O的质量改进和单耗的降低》。 [J] 化工技术资料（染料及中间体专业分册）1965,5,43-45.
研究数据，略。结论：在亚胺基化反应过程中，减少进入锅内的空气量，有利于反应；反应温度在220-130℃是适宜的；反应时间7-8小时也是足够的。
参考文献：3篇。
化工时刊 1988, 12(3)：36-37. 本人未收录！也未能上网下载！今日见报，说从“知网”下载，每页是0.5元。
国内出版物：
何岩彬 主编 《染料品种大全》。 沈阳出版社 出版 2018年。 P. 416-417. C.I. 碱性黄2 .
上面的抄录文，只能作为新的补充。因为2016年提出修改时，本人尚未编号！
值得本人思考的问题：
“科技与市场”是本人要思考的问题：（1）PB 70135; （2）1959年国内的生产报导。两者都是历史资料，国内已有几家工厂在生产，技术已很先进，所以历史资料只能作为古董记载！本人也想做点与市场有关的新资料收集，可惜都是要收费的！
本人为什么还要抄录哪些历史资料？至少可以说明英国人和美国人也是有选择性的翻译，他们为什么要认真的翻译德文资料？当然我们也有人在翻译，所以才有哪些品种的开发和生产！
好在本人还健在，还能为读者提供看不到的，用处不大的，只能作为参考的历史资料！“老有所为，老有所养！”
至少资料的收集和整理还是有用的！
陈忠源 2019年2月21日星期四。
文章作者：陈忠源 |
