CAS号[5522-43-0] 生产工艺  1-硝基芘

CAS名：Pyrene, 1-nitro-  参考文献：   Beil. 5, 694.

生产工艺文献：

BIOS 960, 81.  (=胶卷PB 65657)   1-Nitropyrene (Pyrenit S)  英国人摘译自德文。抄录如下。

反应式：  本人有加注。

Plant:  Earthenware jar (tontopf) 700 litres with V2A quick agitator. Brick lined nutsche.

       Brick lined receiver with connection to vacuum.   Grinding mill (Schwingmuehle).

(a)  Preparation of pyrene paste:

   100 kg. of finely ground iron-free pyrene si pasted with 150 kg. water and 0.9 kg. Nekal BX and ground in a “Schwingmuehle” for several (at least 4 ) hours. The mill is lined with porcelain tiles and filled with glass balls. The contents of the mill are washed on to a vacuum filter, and a moisture test, made in order to calculate the necessary acid dilution. Precaustions are taken against contamination with iron.

(b)  Nitration:

   240-260 kg. of paste, equal to 100 kg. dry material, are charged with a wooden shoval in ¹/₂ hour to the earthenware vessel containing 405 kg. 22% nitric acid and stirred at 40-45⁰C. for 8 hours (test), then filtered by vacuum, washed neutral and dried again taking precaustions against contamination by iron. The mother liquor is set aside for the next treatment and used again.

Note:  The quantity of nitric acid is not very important (4 to 5 parts), but the strength (22%) is critical.

Tests:  The melting point should be 148-150⁰C.; if necessary more nitric acid is subsequently added.

Properties:  Pyrene: iron free; must be very finely ground.

   In 1938, this was 97.8-98.5% pure.  By 1944 it had fallen to an average of 94.6-95.5%.  The latter quality was not satisfactory for F3GL and it had to be purified by crystallization from an organic solvent.  Final product: yellow brown powder m.p. 148-150⁰C.

PB 74120, 176-7. Fabrikationsvorschrift fuer Pyrenit S (Nitropyren). (Hoechst) 1938年11月28日。抄录如下。

I.  Einsatz:  Pyren   100 kg.   Salpetersaeure  22%   405 kg.  Nekal BX   1.2 kg.

II.  Ausbeute:   114-118 kg.    III. Kapazitaet:   5 Ansaetze pro Woche.

IV.  Verfahren:   a)  Muehlung:   a) 研磨： 这是原件。

100 kg. kolloplexgemahlenes Pyren, eisenfrei, Ruettgerswerke, werden mit 150 l. Wasser und 0.9 kg. Nekal BX angeruehrt und in der Schwingmuehle 4 Stunden gemahlen, abgefuellt und die Muehle mit 50 l. durch 2-3 Min. Laufen nachgespuelt. Muehlenfuellung nicht unter 230 kg. und nicht ueber 270 kg. Die Paste wird auf einer Nutsche abgesaugt. Nutschkuchen 240-260 kg.

b)  Nitrierung:   b) 硝化:

In einem Tonttopf 700 l. mit schnellruehrer werden aus der Mutterlauge der vorhergechenden Partie, aufgestaerkt mit conc, HNO₃ 405 kg. Salpetersaeure 22% eingestellt und paste entsprechend 100 kg. Pyren eingefuellt.

Die Temperatur steigt auf 40-45⁰ und haelt sich bei dieser Temperatur. Nach 6-8 Stunden (Probe 1) sofort auf einer Nutsche absaugen (Der kesselinhalt wird fest) Mutterlauge und 20 l. Waschwasser wird aufgefangen fuer die naechste Partie, dann neutralwaschen und trocknen.

V.  Apparatur:  1.  Tontopf 700 l. mit Schnellruehere (V2A).  2.  Ausgemauerte Nutsche.

 3.  Ausgemauerte Vorlage.  Leitungen V2A.    

VI.  Eigenschaften:  Gelbbraunes Pulver F. P. 148-150⁰.  Loesungsfarbe in H₂SO₄: Zuerst blau, schlaegt schnell ueber oliv nach braun um, wobei das pyrenit veraendert wird.

VII.  Chemische und technische Aufgabe:  ./.   VIII.  Verwendung:  略。

IX.  Betriebsprobe:  Probe 1.  Der Schmelzpunkt soll 148-150⁰ betragen, eventl. noch Salpetersaeure nachsetzen.

PB 73377, 2271-2.  Pyrenit S.    全英文调査问答卷。   抄录如下。

1.  Item:  Pyrenit S.  2.  Trade name:  Intermediate.  3.  Chemical Composition:  Nitropyrene.

4.  Principal uses for item:  Staring material for pyram, intermediate for Siriuslichtblau F3GL   

5.  Estimated monthly capacity:  2 tons.   6.  Is production seasonal? If so, on what does season depend?    No.

7.  Does this process depend on the By-product of some other process? (such as coal tar fractioning) If so, what process?  No.

8.  Describe equipment used for production of this item,listing by types numbers and capacity:

    Clay pot with V2A steel high speed stirrer, 700 l.   Bricklined suction filter.  Bricklined receiver with connection to the vacuum

Piping.   Swinging mill.

9.  Describe the process used in production, comprehersibly and fully at the same time as briefly as possible (use non-technical

Terms as far as possible. When using technical terms follow them if possible with an explanatory parenthetical comment. Use as Many sheets as may be necessary).

In the 700 l. clay pot 100 kg of pyren, ground on the Colloplex mill and afterwards on the swinging mill, are stirred with 405 kg. of

Nitric acid of 22% strength for 8 hours at 40-45⁰C. (test), then sucked off, washed until neutral and dried. The mother liquor is stored for the next bath and used again.

10.  Describe briefly any product or process control tests (ordinary or common tests or analyses may be described simply by mentioning the purpose of the test). Include in this description a description of any special or unusual types of testing apparatus

    Required.

    Test 1:  The melting point be at 148-150⁰C., if necessary, add nitric acid.

11.  List of each raw material, intermediate, and for the finished product, all specifications. (This si not be include all properties of the materials, but only those properties for which tests are customarily made).

    Pyrene, free iron.  Finished product:  Yellow-brown powder, m.p. 148-150⁰C.

12.  Raw materials or intermediats used.

 Item   Ammount used per ton of product     Source     possible substitute  

Pyrene      0.88 ton     Ruetgerswerk A.G. Rauxel 

13.  By-produced, if any:   None.

14.  Supplies required (other than raw material). To include catalysts, packing and Insulating materials etc.

Supply   Approximate per ton requirement & month      Source  

Nitric acid of 100% strength    2.1 tons    I.G. Hoechst

Nekal BX        0.02 ton          I. G. Ludwigshafen. 

15.  Heat and power requirement.

Item     Unit      per ton requirement   Source (from plant or from what outside source)

Electricity   Kwh        2000          I.G。Hoechst

Steam      tons           4              “

Water      cu. M.       100            “  

加注：1.  抄录3个资料，请读者对比。2.  英美调査团只是以英文摘译文公布了部分资料，但是大部分资料，仍是以原件，或是以问卷方式保存。您知道为什么？3.  国内为什么不利用后者？

      4.  我抄录的资料有用吗？哪个更有用？哪个真实？

陈忠源  2016年8月3日           于 无锡   明辉国际。