CAS号 [85-56-3] 生产工艺  邻(对氯苯甲酰基)苯甲酸

CAS名: Benzoic acid, 2-(4-chlorobenzoyl)-  参考文献：Beil. 10, 750.

生产工艺文献：

BIOS 987, 8-9. (=胶卷 PB 75860) 4’-Chloro-2-benzoylbenzoic acid. 英国人摘译自德文。抄录如下。

反应式： 本人有加注：
 

The fusion stage is batchwise, the isolation being continuous.

3,000 kg. of chlorobenzene are charged into a 5,000 litre iron pan (flat agitator at 40 r.p.m.)

1,055 kg. of anhydrous aluminium chloride are added down a chute from the floor above in such a manner that the aluminium chloride is not exposed to the atmosphere.

540 kg. of phthalic anhydride are now added over a period of 4 hours. The phthalic anhydride is fed by means of a worm conveyor to a 6 inch pipe down which the anhydride drops into the stirred mixture in the pan. The temperature during addition is maintained at 75-80⁰ by external cooling. After completion of the addition the temperature is maintained at 75-80⁰ for 1 hour.

The liberated hydrochloric acid is drawn away by fan for absorption in a tower by water spray. The water passes from the tower to a separator for chlorobenzene recovery.

The thick reaction mass is pumped via a valve at the base of the pan into a porcelain tower (see sketch). Here the melt flow is met by a stream of water which decomposes the aluminium salt. The time taken to empty one pan is 6 hours. The resulting mixture is run into a porcelain separator. This is so controlled that the chlorobenzene layer is continuously passing to the next washing tank and the water layer is passing to waste. In the washing vessel the chlorobenzene mixture is stirred with excess water and passed on to the second separator . Here again the controlled separation takes place and the chlorobenzene mixture passes on to be treated with caustic liquor. In this vessel in which the mixture is kept just alkaline, the chlorobenzoylbenzoic acid is extracted from the chlorobenzene as the soluble sodium salt. The separated chlorobenzene is run over caustic soda limps to remove traces of water and from there to a continuous still for re-distillation and further use.

The sodium salt solution is pumped into the acidification vessel where it impinges on to a stream of 10% sulphuric acid at such a rate that an acidity to Congo Red is always maintained. The temperature of precipitation is about 25⁰.

The acidified mixture drops to a rotating vacuum filter on which it is filtered and washed. The filter cake falls from the filter drum down a chute into a special dryer. This is a large tile lined vessel containing a series of circular shelves with numerous slots. The drying powder is made to drop from shelf to shelf by a series of revolving rakes, being dried by a current of hot air. The dry finished product passes from the base of dryer to metal drums.

Yield = 900 kg. = 95% theory.   M. P. 148-150⁰C. Loss of solvent is about 10%

Sketch of 4’-Chloro-2-benzoylbenzoic acid lay-out.  略！请见原书。未说明资料来源，为什么？

FIAT 1313,II, 37-9.  (=胶卷 PB 85172)   Chloro benzoyl benzoic acid (CBB). 美国人摘译自德文。抄录如下。

The Friedel-Craft reactions involved were carried out in two 6,000 liter cast iron kettles, operated alternately so that a continuous supply of finished condensation mass could be furnished for isolation equipment which was designed to operate continuously starting with the drowning of the condensation mass through to the dry product, Equipment for ring closing the products was also installed in this building.

The capacity of these sets was very large, being rated at four batches per day of 900 kg. each, or 3.6 metric tons per day, the rate being approximately the same for either product. Actual capacity rates were realized in 1939 when 1124 metric tons of CBB and 199 tons of PTB were manufactured in the equipment.  The charge for CBB was as follows:

3000 kg. of chloro benzene.  1053 kg. of aluminum chloride.   540 kg. of phthalic anhydride.

The operation in brief was as follows: The kettle was charged with the dry chlorobenzene and all of the aluminum chloride was then added. It was found necessary that good quality; i.e. fresh, coarsely ground anhydrous aluminum chloride, be used since, otherwise, the use of old aluminum chloride generally resulted in a thick condensation mass and if unground material were charged troubles with plugging usually resulted.

Following the addition of the aluminum chloride to the solvent the temperature of the mixture was adjusted between 75-80⁰C and addition of phthalic anhydride was begun. The phthalic anhydride was added by means of a screw conveyor type of charging apparatus, a plug of phthalic anhydride always being present in this apparatus. Approximately four hours were required to feed in the phthalic anhydride, the temperature being held between 75-80⁰C. by means of cooling water in the jacket of the kettle. When cgarging was complete, the charge was held for one hour longer at the same temperature and then sampled for completion of the reaction.

A small 5 cc. sample was withdrawn and diluted with 10 cc. of chlorobenzene in a test tube after which 5 cc. of dimethylaniline was added. The test tube was then warmed in a water bath to 90⁰ and 5 cc. of pyridine added. A green color formation (Fischers Green) indicated the presence of unreacted phthalic anhydride, whereas a completed reaction mass gave only an olive brown color.

When the reaction was complete, the charge was pumped from the bottom of the reaction kettle into the middle section of a porcelain decomposition tower by means of a motor driven reciprocating piston pump. The speed of this pump could be regulated so that a regulated stream of 10% sulfuric acid was added in sufficient amount to decompose the reaction product continuously within the tower with evolution of a constant stream of hydrogen chloride. The gas was drawn off and absorbed above and into a porcelain tower equipped with water jets, by means of a porcelain fan, while the drowned slurry ran off below through a porcelain solvent separator which separated the solvent layer containing the product continuously, the aqueous acid layer being run to the ditch. The solvent layer was then washed with water continuously and again separated in a second porcelain separator after which it flowed through a steel alkaline extractor where the product was dissolved continuously from the solvent layer as the sodium salt with 5% caustic soda solution.

The extracted solvent layer was then again separated in a steel separator following which it was dried by passage through a column packed with dry caustic soda and finally run through a continuous solvent recovery still and run to a dry solvent storage for reuse in the process. The alkaline aqueous layer containing the product was then passed continuously through an acid precipitator fed with a continuous stream of 10% sulfuric acid and the precipitated slurry run to a rubber covered rotary filter upon which the product was continuously filtered off, washed and discharged to the hopper of a porcelain lined continuous (Teller) dryer from which it was discharged to storage containers.

The 10% sulfuric acid used in the process was derived from ring closure of the CBB to 2-chloro anthraquinone which was carried out in an acid ring closing set installed in the same building and arranged for collection of the filtrates from this operation.

Normal yield from 540 kg. of phthalic anhydride was 900 kg. of CBB or about 95% and the melting point of the product was given as 148-150⁰C.

It was stated that, innormal operation, the solvent loss was about 10%.     未说明资料来源，不知道为什么？

日文摘译文。 细田豊《理论制造染料化学》 1957年。P. 552-3. 其参考是BIOS和FIAT。请见原书。 

中文摘译文。 张澍声《精细化工中间体工业生产技术》 1966年。P. 226. 译自BIOS和FIAT。请见原书。

PB 25623, 381-6.  Fabrikationsvorschrift  Chlorbenzsaeure.  （用于生产2-氯蒽醌）未抄录。

PB 25627, 2473-4.  Fabrikationsvorschrift  chlorbenzsaeure  （用于生产还原红10）1940年1月17日。抄录如下。

Fabrikationsvorschrift:   操作步骤：

In den Reaktionskessel werde 2800 kg. Chlorbenzol rein und 1250 kg. Aluminumchlorid K eingefuellt, auf 45⁰ aufgewaermt und bei 45-60⁰ in ca, 4 Stunden 500-520 kg. Phtalsaeureanhydrid 1 mal dest. (tel quel) eingefuellt dann eine Stunde bei 65⁰, 1 Stunde bei 75⁰ gehalten. Weitere Aufarbeitung und Umloesung wie bei T-saeure. Das Ausfaellen der umgeloesten und filtrierten Chlorbenzsaeure geschieht bei 75⁰, dann wird auf ca. 30⁰ heruntergekuehlt und abgenutscht.

Trocknen der Chlorbenzsaeure im Venuleth mit 1.5-2 atue Dampf. Probe vor dem Ablassen,wie bei T-saeure.

Ausbeute:  100 kg. Phtalsaeureanhydrid 100% geben 165-170 kg. Chlorbenzsaeure 100% = 93.7-96.6% der Th.

Untersuchung der Chlorbenzsaeure:  氯苯甲酰基苯甲酸的分析测定：

a) Trockenbestimmung: ca. 10 g. (genau gewogen) Chlobenzsaeure werden 3 Stunden bei 100⁰ getrocknet. Der Trockengehalt soll nicht unter 99.8% betragen, andernfalls muss die Partie nachgetrocknet werden.

b) Rueckstandsbestimmung: 50 g. Ungeloester Chlorbenzsaeure werden in 500 ccm Wasser und 30 ccm Ammoniak 25% gekocht, durch gewogenes Filter filtriert. Der ausgewaschene und getrocknete unloesliche Rueckstand soll nicht ueber 0.1-0.15 g betragen.

c) Schmelzpinkt: Smp. 147-150⁰

Pruefung der Ausgangsmaterialien:  原料分析:

Phtalsaeureanhydrid halbfertig K.  Die Ware muss absolut wasserfrei sein, was bei den laufenden Partien auch der Fall ist. Phtalsaeureanhydrid ist – besonders in feiner Vertielung – hygroskopisch; laengere Aufbewahrung (ueber 2-3 Monate) ist tunlichst zu vermeiden. Pruefung aud Wasser nach Methode “Aufhaeuser“. Der Reingehalt wird vom Lieferabten durch Titration festgestellt und betraegt beim Phtalsaeureanhydrid halbfertig K 90-93%. Rest: Cips (1%) und Kondensationsprodukte aus Phtalsaeyreanhydrid und Naphtochinon bezw. Verkohlungen.

Aluminumchlorid K. Die Ware soll aus braunroten Kristallen bestehen, Feines Pulver, das stark raucht (Titanchlorid) und stark nach Phosgen riecht, ist nicht geeignet. Gehalt an: Titanchlorid 0.5-1%, Eisenchlorid hoechstten 4%, Phosgen O –Spuren. Der Hersteller bestimmt den Wert des Aluminumchlorids nach der Waermpruefungsmethode und stellt ausserdem den in Wasser unloeslichen Rueckstand fest. Ungenuegende Partien gelangen nicht zur Ablieferung.

PB 70057, 8327-35. Fabrikationsvorschrift  Chlorbenzsaeure 1945年9月3日。（这是德文工艺原件。）摘译如下。

本生产工艺规程，前部略。

B.  操作步骤：1. 缩合：

由落地氯苯贮槽，用水环泵经流量计，向位于二楼（Lu 东侧）的二台缩合锅分别打入3000公斤 无水氯苯，在半小时内将其加热（用夹套蒸汽）到40-45⁰C, 然后通过三楼破碎机，经加料管加入1053公斤无铁三氯化铝，从40-45⁰C 开始在4小时内通过三楼配有铁齿的Alexander磨，经加料管均匀地加入540 公斤苯二甲酸酐（*要注意，无论是加三氯化铝或是苯酐，都要通过料斗计量后加料），因为是放热反应，所以加苯酐时温度会升高到75-80⁰C （注意冷却！），加完在75-80⁰C 保持一小时（取样1.）。

从加三氯化铝开始到分解完毕，应始终打开三楼（东侧）陶瓷通风装置，使盐酸气通过陶瓷管进入有喷水的陶瓷吸收塔（它装有四个喷水器），出来的气体再通过同样的陶瓷吸收塔，随气体带出的氯苯用喷洗分离器分离。

2. 络合物分解：

将缩合物从锅底放出，用拉杆泵迅速打入陶瓷分解塔，物料应在6-6.5小时内打完，分离塔高6.5米，直径1米，中间有陶瓷盘，物料从一侧进，另一侧进10% 硫酸（一份物料对一份稀硫酸），盘底装有锥形陶瓷，使要分解的物料在塔内有足够的停留时间。85-90⁰C 的物料经分解后流入装有拉希环的700升分离器，上层是氯苯甲酰基苯甲酸的氯苯液，下层是三氯化铝分解液，它放入立式平底受槽内，分出少量氯苯送Blankorol厂回收铝。（取样2.）

氯苯甲酰基苯甲酸料液进入有Hoe搅拌，450转/分的465升洗涤锅，用热水洗去铝盐，每批再用热水彻底洗净，放入陶瓷分离器，此时物料仍在上层，洗水在下层。

经洗涤分离的物料进入转速120-180转/分，有五层浆式搅拌的萃取器下部，与此同时从塔底进入1.5%的液碱，塔内温度为80⁰C, 每批物料约需100% 氢氧化钠150公斤，由萃取器上部连续流出的物料进入700升提纯分离器，此时上层分出的是氯苯甲酰基苯甲酸钠盐溶液，下层是氯苯（取样3.）

氯苯流入6立方米贮槽，用离心泵打入管式蒸发器（二楼）进行蒸馏，馏出液通过冷凝器进入250升分离器（分出水），而后进入内装有固体碱的2台氯苯干燥塔，每台700升，干燥后送氯苯贮槽。

从提纯分离器出来的氯苯甲酰基苯甲酸钠盐溶液进入2台缓冲器，陶瓷搅拌，转速36转/分，容量9900升，再进铁分离器分出微量氯苯，经分离后用拉杆泵打到离析器（二楼），在25-30⁰C，用10% 硫酸酸化析出氯苯甲酰基苯甲酸，酸化是控制到刚果红呈酸性（取样4.）

离析料用大型过滤器过滤，面积为1.5平方米，水洗到中性，（取样4.）滤饼用带式输送器送到Bruther干燥器干燥，

每批得量：907公斤。  收率：  95.5%。

本生产工艺规程，后部略。

国内工艺汇编：上海，p. 63-4. 天津，p. 58-9.（国内是参照BIOS和FIAT开发的。）

加注：抄录英国人摘译文，美国人摘译文以及德文工艺原件本人的翻译，是要说明原件的优点，另外各人理解不同，译文也会有所不同，问题是过去不知道，今天补上，供参考。请利用原件！国内有此类原件！

陈忠源   2016年8月19日             于 无锡   明辉国际。