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| CAS号 [84-51-5] 生产工艺 2-乙基蒽醌 |
CAS号 [84-51-5] 生产工艺 2-乙基蒽醌
CAS名: 9,10-Anthracenedione, 2-ethyl- 历史参考文献: Beil. 7. E1, 425; E3, 4129; E4, 2583.
用途; 双氧水生产用催化剂。还原蓝66，有机合成等。反应类别: 酰化缩合（Friedel-Crafts反应），闭环。
生产工艺参考文献: 按本人手头资料整理如下。
FIAT 号不详 （=胶卷PB 44961） 2-Ethylanthraquinone. (Ludwigschafen). 1946年8月29日。 美国人译自德文。 抄录如下。
Abstract: Briefly describes process and equipment used at I. G. Farbenindustrie
plant at Ludwigshafen for the production of 2-ethylanthraquinone. （抄注：美国人未说明德文资料原件的PB报告号 – 本资料抄自上海染化十厂收藏本）。
Table of contents: 本资料内容: Subject.
Introduction. Chemical basic of
the process and yield.
First step - Production of ethyl-β-acid: 1.
Process Description. 2. Plant capacity
and Utilities. 3. Chemical control.
Second step – Production of 2-ethylanthraquinone: 1. Process Description. 2. Plant capacity and utilities. 3. Chemical control.
Description of equipment: Appendix 1: Fig 1. Flow sheet of the first step. Fig 2. Flow sheet of the second step. （抄注：未抄录）。
Introduction: （这是美国人介绍资料来源。当前，这类历史资料知道的人应该不多。）。
Objective: At the request of Department of commerce, a
brief study of the production of 2-ethylanthraquinone was made. The
Ludwigshafen plant of I.G. Farbenindustrie was visited on July 9. 1946. All information was obtained from Dr. F. Teller who is in charge of the
production of this chemical.
Evaluation: The plant was build during the war and
production started in 1942. The
highest daily capacity obtained was 3000
kg/day, however the maximum monthly production did not exceed 40 to 50 tons. The plant was damaged by bombing and the total
production of this material until the end of the war amounted to approximately 120
tons.
Guide to Reader: According to Dr. Teller, all drawings, records and operating data were burned during bombing attacks. The floe
sheets accompanying this report were rapidly sketched during the visit and may not be complete in all details.
Chemical basis of the
process and yields. 2-乙基蒽醌生产工艺的基础和收得率：
General: In the first step of the process, p-ethyl-benzoyl-0-benzoic
acid is produced by adding at 35-400C., phthalic anhydride to ethylbenzene of aluminium chloride, using an excess
of monochlorobenzene as solvent. It is a Friedel-Crafts condensation.
In the second step of the process the p-ethyl-benzoyl-o-benzoic
acid is reacted at 85-870C with concentrated sulfuric acid to effect ring closure, with the production of
2-ethylanthraquinone.
1) p-ethyl-benzoyl-o-benzoic acid. The formation of this chemical can be
represented as follows:
Theoretically the
following weights of materials are involved. 570 kg + 408
kg = 978 kg.
Practically a yield
of 90.3% of the theoretical is obtained and 0.903 x 978 = 883.5 kg of product are recovered from the above
quantities.
2) 2-ethylanthraquinone. The formation of this chemical can be
represented as follows; （抄注: 乙基蒽醌。本人有加注。）
Theoretically the
following weight of product should result: 100 kg
= 92.9 kg + 7.1 kg.
Practically a yield
of 75.33% of the theoretical is
obtained and 70 kg of crude
2-ethylanthraquinone are obtained from 100 kg of ethyl-β-acid.
First step – production of ethyl-β-acid (see Flow sheet Fig.1). 第一步 - 乙基-β-酸的生产（见流程图1.）。
1. Process
Description: 1. 酰化缩合操作步骤：
3400 kg of anhydrous
chlorobenzene and 430 kg of ethylbenzene are pumped from
storage tanks 1 and 2 into condensing vessel 3.
The agitator is set
in motion and 570 kg dry phthalic
anhydride are slowly introduced into this vessel.
1055 kg of pure aluminium
chloride, free of iron and passed through a crusher are
introduced into the condensing vessel 3, over a period of 5 to 6 hours. With the first addition of AlCl3, ceramic fan 26 started: gases driven off during
the reaction, consisting mainly of HCl traces of carbonyl chloride and some ethylbenzene and chlorobenzene are
conduced through a porcelain pipe of porcelain wash tower 25, through ceramic
tower 27 and discharged into the atmosphere（抄注：当时无环保问题，但已考虑到废气的吸收。）。Both towers 25 and 26 are provided with spray nozzles and water is used to was the gas。The wash water is collected in tank 6 and discarded.
In order to prevent
losses of AlCl3 the
chlorobenzene and the ethylbenzene must be very pure.
The condensation operation is started at room
temperature. After the raw materials are all introduced, the charge is agitated
for another hour at 35 to 400C
maximum. It takes about 10 hours to perform the whole operation including charging of raw materials. This
operation is performed in a batch wise manner and two condensing vessels are
used.
From the condensation vessel, the melt conduced to
proportioning pump 4 which discharges it to decomposer 5. The melt enters the
middle of the decomposer and flows over a porcelain distributing tray. To this
place is also introduced 10% sulfuric
acid from storage tank 28 in a volume ratio of 1 part of acid to 1 part of
melt. The decomposer is filled with clay
balls below the distributing tray. This operation takes about 6 to 7 hours.
The melt at 850 to 900C. flows
slowly from the decomposer to decompose separator 7, in which decantation takes
place. The melt should run uniformly and should be hot. If it cools down there is danger of crystalline obstructions forming in the pipe lines which are difficult
to remove. AlCl3 solution
is withdrawn from the bottom and the ethyl-β-acid from the top of the separator 7. The AlCl3 solution flows to separator 30 where a second decantation is performed; any
entrained chlorobenzene is with drawn from the top and sent to crude
chlorobenzene storage tank 12 and thence to chlorobenzene distillation system
described below. AlCl3 solution is withdrawn from the bottom and
sent to the sewer. It was planned to install an aluminium recovery system at a
later data.
The ethyl-β-acid coming from separator 7 enters the bottom of
washer 8 where all aluminium salts are removed, by agitating the melt with 1
cu.m. of hot water at 80 to 900C., per batch. The melt leaves the washer from the top and enters washer separator
9 in which another decantation takes place. The washed melt is withdrawn from
the top and the separated wash-water from the bottom.
The washed melt is then introduced into the bottom of
extractor 10. Also 2.7% NaOH coming
from storage tank 29 is introduced into the extractor. The caustic soda must not be stronger than 2.7%, otherwise the separation in the
next step is not satisfactory. The temperature should be about 800C and 160 kg of 100% NaOH are required per
batch.
The effluent from the extractor leaves it from the top
and flows to pure separator 11, where decantation takes place. The
chlorobenzene is withdrawn from the
bottom and flows to crude chlorobenzene tank 12. Centrifugal pump 13 takes
suction from this tank and discharges the crude chlorobenzene into continuously
operated evaporator 14, where a temperature of 130 to 1400C, is maintained. The distillate is condensed
in evaporator condenser 15 and enters evaporator separator 16 where decantation
takes place. Water is withdrawn from the top. The chlorobenzene withdrawn from
the bottom is dried by passing through two towers 17, connected in series and
packed with solid caustic soda, and returned to chlorobenzene storage tank 2.
From the top of the pure separator 11, the sodium salt
of ethyl-benzoyl-benzoic acid flows to two buffer vessel 18, provided with
agitators. The solution is withdrawn from the bottom and conducted to buffer separator
19 where decantation takes place. The last traces of chlorobenzene are
withdrawn from the bottom and reciprocating pump 20 taking suction from the top
discharging the liquid into precipitator 21. In this vessel the ethyl-β-acid is precipitated at 25 to 300C by 10% sulfuric acid. The liquid and the
acid are introduced from the bottom and the effluent leaves from the top of
vessel 21. Only enough acid should be fed, to barely turn Congo red indicator yellow. It
too much or too little acid is fed, troubles are experienced in the next
operation. The precipitated ethyl-β-acid coming from the top of precipitator 21 goes to
rotary filter 22. The ethyl-β=acid cake is washed neutral by water fed through spray nozzles and by
diluting the product with water in the filter tray. If any chlorobenzene gets
into the precipitation it may damage the filter cloth of the rotary filter.
The filter cake drops on a belt and is conducted to
shelf dryer 23. This cake should be neutral and the amount of wash-water is
adjusted accordingly. From there the final dried product is filled into
barrels.
As already mentioned above, a yield of 90.3% is obtained and 155
kg of ethyl-β-acid are obtained from 100 kg phthalic anhydride.
2. Plant
capacity and Utilities: 2. 酰化设备生产能力和公用工程单耗：
When operating with two condensing vessels it is
possible to make 4 batches per day and the plant capacity under those
conditions is about 3534 kg per day. Here is the time required for each operation: （including charging）.（抄注：以下抄录不再分项。）
Condensation about 10 hrs. Decomposition about 6 hrs. Extraction about 6 hrs. Precipitation about 12 hrs.
Drying about 12 hrs. For producing 100 kg ethyl-β-acid, the following utilities are required:
Electricity 42
KWh. Steam 2.7 tons. Cooling water at 200C 240 cu.m. Operating labor 11 man hours.
3. Chemical
control: 3. 酰化生产控制：
The following chemical tests are regularly made.
The raw materials, ethylbenzene, chlorobenzene and
phthalic anhydride must be 100% and dry. Phthalic anhydride is hygroscopic
especially when in fine powdered form, and special precaustions should be taken
to keep this material dry. Regular tests are made to check on the purity of
these materials.
At the outlet of condensing vessel 3 the product is
tested fro the quantity of unreacted phthalic anhydride.
A sample of chlorobenzene liquor leaving the pure
separator 11 is shaken with 2% NaOH and the aqueous layer is then precipitated with dilute sulfuric acid to make
sure that the crude chlorobenzene does not contain any ethyl-β-acid.
The liquor following to the filter has to be
continuously checked with Congo red indicator
to prevent an excess or deficiency of acid. This final product is given the
following tests.
a) Moisture test – 10 grams of ethyl-β-acid are dried for 3 hours at 1000. The loss of weight must not exceed 2%. b)
Ash test – The ash content must not exceed 1%. c) Chlorine test – The chlorine content must
be under 0.2%. d) Melting point test – The melting point
should be between 118 and 1230C.
Second step – Production of
2-ethylanthraquinone (see flow sheet Fig. 2). 第二步 – 2-乙基蒽醌的生产（见流程图2.）。
1. Process
Description: 1. 闭环操作步骤：
1868 kg of 96% sulfuric acid as well as 3012 kg of 24% oleum, giving together 4880 kg of 8% oleum, are introduced into pressure vessel 31 and
heated to 850C. When this
temperature is reached, 600 kg of pure
ethyl-β-acid are rapidly added. The mixture is stirred
for 4 hours while the temperature is
maintained at 850 to 870C. A sample is taken and if no presence of ethyl-β-acid is found, the charge is cooled to about 250C. Compressed air is let
into the vessel 31 and the charge is transferred to washing vessel 32,
previously filled with 16 cu.m. of cold water. The mixture is stirred for about 30 minutes and forced by compressed
air into filter press 33. During the filtration, the filter cake is washed with
warm water until it is neutral. The filter cake is then introduced into
dehydration vessel 34, which has been previously heated to 500C. The product is stirred and the temperature
increased to 125-1300C. during which time the 2-ethylanthraquinone is dehydrated and fused. Compressed
air is used to force the fused product on iron trays 35 and it is ready for the
final purification which is done by sublimation.
The tray assembly mounted on a carriage is introduced
into electrically heated sublimation furnace 36. Vacuum of 3 mm Hg absolute is
applied and the temperature is maintained at approximately 3000C. According to Dr.
Teller this final purification can also be done by distillation.
2. Plant
capacity and Utilities: 2. 闭环设备生产能力和公用工程单耗：
With the equipment as installed, 420 kg 2-ethylanthraquinone per 24 hours can be produced from 600 kg of ethyl-β-acid.
The final purification of the product is done by sublimation
in a furnace which is rather antiquated and designed for other production.
Therefore the utilities are divided between the production of raw
2-ethylanthraquinone and the final pure product.
For the production of raw 2-ethylanthraquinone from ethyl-β-acid, the following utilities are required:
Electricity 76
KWH. Steam 0.5 tons.
Cooling water at 200C
200 cu.m. Operating labor 11 man hours.
For the production of pure 2-ethylanthraquinone by
sublimation of the raw product, the following utilities are required:
Electricity 450
KWH. Steam 1.7 tons.
Cooling water at 200C
150 cu.m. Operating labor 10 man hours.
3. Chemical
control: 3. 闭环对原料质量要求和成品质量控制：
Ethyl-β-acid. Crude
2-ethylanthraquinone 94-96%. Pure 2-ethylanthraquinone 99%.
抄注: 设备: 36项，略！流程图; 2个，略！
加注: 本资料有胶卷版和书本版两种，国内均有进口，当然收藏单位是个位数。
陈忠源 2-乙基蒽醌生产工艺 。译自PB44961. 本人刻印于1983年5月。于 无锡 染料厂。内部参考，这里不再抄录。
读者如有需要，本人可以提供！为什么无人利用？1. 本资料收藏单位少。 2. 国内外无人编目，
法国专利 1528795. 1968,5,6. Proce’de’ de
purification de la 2-e’thyl anthraquinone et des alkul anthraquinones. 摘录如下。
Exemple 1. – On dissout 30 g d’acide
para e’thyl ortho benzoyl bensoique purifie dans 360 g d’ole’um a 20%; on
obtient ainsi une solution sulfurique rouge fonce’e; on chauffe cette solution pendant
5 heures a’ 70-750C et
alle deviant progressivement verte; on laisse la temperature revenir a’ 200C; on coule alors cette
solution sulfurique dans 300 g d’eau a une temperature inferieure a’ 200C.
On ajoute 100 ml de benze’ne et on agite pendant
une demi-heure, puris on laisse de’canter; on se’pare les deux phases; on
effectue une seconde extraction avec 50 ml de benzene frais et on re’unit les
deux solutions benzeniques.
On lave deux fois ces solutions benzeniques
avec 100 ml d’une solution de carbonate de soude a’ 5%, on lave ensuite deux
fois avec 100 ml d’eau; on seche sur carbonate de soude anhydre et on distille
enfin le benzene. On obtient ainsi
25 g de 2-ethyl anthraquinone don’t le fusion est de 110 a’ 1110C,
qui correspond a’ un redement de 90%.
译文（仅供参考）: 例一. 将30克对乙基苯甲酰基苯甲酸溶于360克20% 发烟硫酸中，得深红色硫酸溶液，将此溶液在70-750C闭环反应5小时，物料逐渐变成绿色，反应完毕，将温度降到200C，然后将其注入到低于200C的水中，加入100毫升苯，搅拌半小时，静置分层，将两相分开，再加50毫升新鲜苯进行第二次萃取（译注：这里指水层再萃取一次），将两次苯溶液合并，用100毫升5%碳酸钠溶液洗涤两次，洗完再用100毫升水洗二次，苯层用无水碳酸钠脱水干燥，最后蒸出苯，这样可得25克2-乙基蒽醌，其熔点为110-1110C，收率90%。（抄注: 有全部译文，这里不再抄录。）。
国内研究动态:
湯子羟 温亚龙（太原工业大学）。2-乙基蒽醌的合成研究。[J]染料工业,
1993, 3, 36-38 (11) 摘录如下。
一。 引言: ….。本文选择氯苯为溶剂，无水三氯化铝为催化剂。常压下进行乙苯与苯酐的缩合；再经分解，闭环，离析制备2-乙基蒽醌的工艺路线，并考察了各步反应的影响因素。（抄注：这是1946年已工业化生产的工艺路线！）
二。实验部分:
(1) 2-乙基苯甲酰基苯甲酸铝复盐的合成（缩合反应）：
将乙苯，苯酐，无水三氯化铝再一定温度下投入带有冷凝器的四口瓶中（加料前要开始通冷水冷却），控制在一定温度下反应至苯酐消失。
(2) 2-乙基苯甲酰基苯甲酸（简称BB酸）的制备（分解反应）：
在安装有回收溶剂装置的2000 ml三口瓶中配制好一定量的稀酸，在搅拌下经滴液漏斗加入2-乙基苯甲酰基苯甲酸铝复盐的氯苯溶液，按规定的反应条件进行分解反应。反应完毕，采用水蒸汽蒸馏除尽体系内的溶剂，最后在一定温度范围内加水粒化即得粒状2-乙基苯甲酰基苯甲酸。吸滤，热水洗涤至滤液呈中性。
(3) 2-乙基蒽醌的制备（脱水闭环反应）：
在装有冷凝器的四口瓶中，加入规定量的发烟硫酸和2-乙基苯甲酰基苯甲酸（加酸前要预先开冷却水，并应密闭反应器以防SO2流失）。在选定温度下进行脱水闭环反应至终点。
(4) 2-乙基蒽醌从稀酸中析出:
将脱水闭环物料降至一定温度后，搅拌下加水离析。加水完毕，将离析物料吸滤，洗涤至中性。
(5) 碱煮:
在2000 ml三口瓶中加入一定量的水，加入适量的碱液。搅拌，使之达一定碱度。在搅拌下加入粗2-乙基蒽醌，急速升温至规定温度，保持一段时间后，冷却。过滤，洗涤至滤液呈中性。
三。试验结果及讨论: 略！
四。结论; …。它比起国外普遍采用的工艺路线相比具有：常压操作，催化剂价廉，毒性小，工艺条件简单，易控制，设备要求不高等特点。 （抄注：本文无参考文献！）
崔洪波（辽宁石油化工规划设计院）。高纯2-乙基蒽醌的合成。[J] 染料工业,1993,
4, 27-28. 摘录如下。
一。 前言; 略。
二。 实验方法; 1. 实验原料: (1) 工业苯酐 150.0
g. (2) 工业乙基苯 144.0 g. (3) 无水三氯化铝 296.0 g. (4) 试剂保险粉 202.0 g. (5) 工业氯苯 870.0 ml. (6) 20% 发烟硫酸 642.0 g. (7) 95% 乙醇溶液 500.0 ml.
2. 实验过程:
酰化反应: 1500 ml三口烧瓶上装有搅拌，回流冷凝器及氯化氢气体吸收系统。首先在三口烧瓶内先后加入144 g乙苯和296 g 无水三氯化铝，开动搅拌并维持三口烧瓶内物料温度20-300C,然后分多次将干燥后的苯酐缓慢加入瓶内，控制加料速度使酰化反应温度低于400C.此时会发现随着苯酐的加入，会产生大量氯化氢气体，溶液逐渐变成桔红色。继续搅拌，待全部苯酐加完后，适当提高酰化温度直至无氯化氢气体逸出为止，可以认为反应完毕。
水解过程: 将酰化产物静置冷却后，小心滴加10% 盐酸溶液进行水解，快速搅拌控制水解温度低于400C，此时会同样发现随着盐酸的加入，逸出大量氯化氢气体，酰化物由红色逐渐生成乳白色油状物。将水解后产物移至分液漏斗内静置分层，收集油层物，即为BE酸和氯苯混合物。
蒸馏回收氯苯: 将BE酸和氯苯混合物置于减压蒸馏装置内，在55-600C下减压蒸馏。控制蒸馏系统真空度30
mmHg，将蒸出氯苯溶剂和多余乙苯回收重新使用。蒸馏瓶残留物BE酸送至闭环反应器。
闭环反应: 把蒸馏残留物BE酸置于三口烧瓶内，油浴加热至110-1200C，开动搅拌，小心滴加新配制的20% 发烟硫酸，控制加料速度使闭环温度低于1200C。此时，会发现瓶内白色物逐渐变为深黄色液体。待闭环反应完毕后，将闭环产物全部倒入已准备好的盛有冰水混合物烧瓶中，此时会发现有黄色物质析出，溶液呈红褐色，经过滤，碱洗，水洗后，可得浅黄色固体物2-乙基蒽醌粗品。经测得其熔点为104-1060C，按苯酐计收率89%。
提纯: 将上述2-乙基蒽醌粗品置于500 ml烧杯中，加入新配制的保险粉溶液和10%氢氧化钠溶液300 ml, 用玻璃棒搅拌，反应物剂几乎全部溶解；随后将此溶液过滤除去未氧化杂质，所得滤液即为无色的2-乙基-5,10-二羟基蒽溶液。于2-乙基-5,10-二羟基蒽溶液中鼓入清洁压缩空气，此时会发现溶液中逐渐析出浅黄色沉淀物。长时间通入空气，直至无固体产生为止。该浅黄色固体为经初步提纯后的2-乙基蒽醌。
精制过程: 将经提纯后的2-乙基蒽醌粗品置于1000 ml蒸馏烧瓶内，加入95% 乙醇500 ml进行蒸馏。蒸馏温度79-830C,馏出液乙醇收集后循环使用。蒸馏残留物即为高纯2-乙基蒽醌产品，该产品经800干燥后切片即可。
产品与日本同类产品相比（指标：略），基本达到了日本进口产品的要求，。。。超过了日本进口产品的质量。
（抄注：本文无参考文献！）
其它研究论文:
[J] 精细石油化工，1994, 1, 32-35. 未抄录。
[J] 化学世界。1997, 7, 363-365. 未抄录。
随想：
谢谢好心读者的提醒，因为本人离见上帝的时间已屈指可数了，应该多说些有用的话，少说些无用的话，有问题读者会考虑，所以到此为止。有不足的地方，还是有请大家谅解，谢谢！
本文主要仍然是要说明有未被利用的资料，而且已多次提出。当然是否有用？请读者评述！本人又是多操心了！！！
陈忠源 2017年9月3日星期日 于 无锡 明辉国际。
文章作者：陈忠源 |
