DE2122664C3 - Process for the production of anthraquinone - Google Patents

Description

in which R ₁ , R ₂ , R _{3 can be} identical or different and each represent an alkyl radical, R ₁ and / or R ₁ can also each denote a hydrogen atom ^,! i with oxygen in the gas phase in the presence of v <! ai vanadium pentoxide and / or vanadates of elements of groups IVa, IVb, Vb, VIIa and Vli of the periodic system, optionally in c |: mixed with oxides of elements of Griappen | liV to VI , a and b, VIIa and / or VIII of the l | ji: riodic system oxidized, according to patent 193 | 063, characterized in that | the reaction is also carried out in the presence of compounds of tellurium.

The subject of the main patent 19il4 06jf is a process for the production of anthraquinone by oxidation of indanes of the general formula

(D

in the, Ri, Rt, R »j and one-

ch or different] «im can mean ylfesteiB, R ₁ ind / or R ₁ can also each denote a 'Wittsse''ffatöffi, with oxygen in the jaspericase in ciegenwaft of vanadine pentoxide and / or' ^! Vanadates "on elements of groups IVa ₁ IVb, V:", VHa and VlIf of the periodic system, possibly in a mixture with oxides of elements eta groups IV to VI, a and b, Vita utnd / or VtU of the eriodtschen. Systems.

The aforementioned procedure is in d <§ add Patent 752049 described.

It has now been found that the method of Main patent can be further developed if the order Settlement is also carried out in the presence of compounds of tellurium.

With regard to the state of the art, which in the The abovementioned Belgian patent specification provides the method according to the invention in a simple and economical way, surprisingly Anthraquinone in good yield, higher space-time

Yield and purity with far better conversion. In comparison to the cleaning of the example 23 of Patent obtained, dark colored, impure end product, which from organic solvents such as Nitrobenzene has to be recrystallized, the separation and purification of the end product according to the invention is easier and more economical; «Recrystallization from water already provides a raw material for dye synthesis that meets the specifications. The oxidation is carried out with oxygen or expedient

ao with an oxygen-containing gas mixture, e.g. B. air performed. In the case of the 1-methyl-3-phenylindane, the load can be 5 to 100, advantageously 10 to 60, in particular 25 to 50 g of 1-methyl-3-phenylidane per 1 normal cubic meter of air. Man

a5 turns appropriately from 20 to 2000, advantageously 40 up to 500 g of starting material I per liter of catalyst (or catalyst on a carrier) and hour, with one or more vanadium (V> compounds and one or more compounds of tellurium lie. Regardless of the composition, the Compound and the valence of the element in the compound is the atomic ratio in the catalyst from vanadium to the additional element tellurium, expediently from 2550 to 10, preferably from 1200 to 15, esp special from 400 to 25, vanadium to 1 tellurium. the Catalysts are advantageously used together with a carrier material, ζ. B. pumice, titanium dioxide, steatite, Silicon carbide, iron, silicon, aluminum oxides, aluminum silicates such as mullite, for use.

As compounds of tellurium, the oxides, acids, salts and those compounds of the additional element are generally suitable, which are during convert the catalyst production or the reaction to a tellurium oxide.

The following are suitable as tellurium compounds: Oxygen acids of tellurium, ammonium tellurate, tellurium dioxide, potassium tellurite, telluivitrate, tellurium trioxide, Cesium tellurate, potassium tellurate, thalliurotellurate. The catalytically active components can after

such a common procedure (Houben - Weyl, Methods of Organic Chemistry, Vol. 4/2, pp. 143 to 240) are applied to inert supports, e.g. B. by impregnation, spraying or precipitation, and subsequent calcination of the supported SS catalyst produced in this way. The production of catalysts containing vanadium and tellurium has proven advantageous on spherical supports according to a flame spray or plasma spray process. The additional connections mentioned can be combined with the by means of flame spraying Vanadbipentoxjd to be applied or a compound that converts to vanadin pentoxide when heated, such as ZvB. Vanadic acid, mechanically mixed will. However, it can be beneficial «to start with one to produce a homogeneous solution that

Contains elements. From this solution, the »compounds to be applied, e.g. B. by evaporation, be won. It can also be beneficial to that the components to be applied

, 0

melt, let cool and then crush. The following results are obtained:

In the case of higher-melting compounds, this may be the starting material

- * to use a plasma torch. In this case i.Methvl-3-DhenvWndan 18 56 parts

i one ^ angularly a partially or fully · _Ab ^l _g Sge ^P * . . . '.'. '. 50) 000 volume rate.

Reduction of the Vanadmra (V) to Vana- 5 öS of the Abease

the formation of higher melting carbon monoxide and dioxide 2.40 percent by volume

do change _{n 5 TejJe}

,. at a temperature between 250 and 50O ⁰ C, in particular between In the raw end product are carried out by UV-Absorp-300 and 450 ° C. This temperature is determined to tion:. ... o—, ",. t. "- ^, λ- cooling medium *, z. B _{59 Q weight percent} anthraquinone = 10.33 parts

= 4.17 parts

Adjust indane (I) in the reaction mixture. Starting material 1-

In one embodiment of the process according to the (corresponds to a conversion of 99.7% of theory Invention, for example, the catalyst or and an anthraquinone yield, based on the disadvantageous starting material placed on a carrier in any way, of 55.6% of theory), preferably according to the aforementioned flame spraying or ao

Plasma spray applied catalyst on example _

a temperature of 450 to 650 ⁰ C, preferably of a mixture of 59.8 parts of vanadium pentoxide and

Heated and 500 to 600 ⁰ C at this temperature, 0.24 parts of telluric acid (H ₆ TeOe) is kept at 700 ° C zueinige time (calcination). Advantageously, when melted together and the solidified mass has a calcination time of 1 to 24, in particular 5 to »5, grain size of less than 250μzerkleinεrt.l5.25 parts 16 hours. It is preferably calcined against this comminuted mixture with 15.25 parts of oxygen-containing gases such. B. air vanadium pentoxide (> 100μ grain size) mixed, and or flue gas, and at a pressure of 1 to 3 at. The powder obtained in this way is applied to 341.3 parts of mullite balls (5 to 7 mm lung is sprayed onto UUmuins Encyclopedia of Technical 30 Diameters). Chemie, Vol. 9, p. 254 ff. 80.1 parts of the catalyst prepared in this way will be

Otherwise, the process is carried out under the conditions in a tubular reactor (21 now inner diameter) procedures of the procedure according to the Hr uptpatent. A mixture of 100,000 volume is now passed, in particular with regard to the conduct of the reaction, parts of air and 3.79 parts of 1-methyl-3-phenyl-indane Catalyst manufacture and composition. 35 passed hourly through the catalyst. The pipe

The parts listed in the examples mean wall temperature is 435 ° C., the temperature in parts by weight. They relate to the parts by volume inside the catalyst layer 462 ° C. This is like kilograms to liters. The starting material 1-methyl-tor leaving gaseous Resktionsgemisch is 3-phenyl-indane is cooled in all the examples in the form of to 50 ⁰ C, where the end product and the non 92gewichtsprozentigem l-methyl-3-phenyl-indan comparable 40 unreacted L-methyl-3-phenyl-indane condense, turn and is calculated in parts starting material. 100% The non-condensed portion is given with water, wash. After the wash water has evaporated

the remaining residue is combined with the condensate Example 1.

45 The following results are obtained:

A mixture of 59.8 parts of vanadium pentoxide and AiisBanesstoff

0,24Teilen Teuursäure (H.TeO.) At 700 ⁰ C tSe% l-3-phenyl-indan ... melted together 18,93TeUe and the solidified mass to 000 parts by volume Abßasmenge 500

Ä! J ^ f ^V0 Dr * ^CnigCr ο - ²⁵ ί ^{μ 26} S ⁶¹¹¹ ^ - content of the exhaust gas at

7.75 parts of this comminuted mixture throw with 50 carbon monoxide and carbon dioxide 2.20 percent by volume

23.25 parts of vanadium pentoxide (> 100 μ grain size) _{Ro) ter EnaA} or 17.85 parts

mixed, and the powder thus obtained is means

of a fuel spray device on 341.3 parts of mullite balls.

(5 to 7 mm diameter) sprayed on. tion determines:

78.1 parts of the catalyst prepared throw 55 weight percent of anthraquinone _6U = 10.93 Parts

in a tube reactor (21 mm inner diameter) _{24 8} weight percent phthalic acid:

filled. Now throw a mixture of 100,000 volume anhydride = 443 parts

wall temperature is 43S ° C, the temperature in the ft> ⁶ ^ * .. »· ■ ·

Infletβ »de« Katatysatof schicht 458 »C. The the reaction (corresponding to a Uöisatz 99, <i% of theory and tor leaving gaseous reaction mixture is a Anthrachinonausbeute, based on converted, jttrf 5 «* C cooled, wherein the end product and the starting material, of 57.9% of Theory), ^ richt implemented l ^ Methyt ^ phenyMntfan kondtn ».., .. ,,

siereti. The uncondensed portion is mixed with water _6j · ^{B l p}

* After evaporation deft bottles of wash water A mixture of 48 parts of vanadium pentoxide and wutfttef remaining residue with the condensate 2 parts Teffiifsäure (* Η Τβ €) ^ is at 700 ^e C to-VffeMp. melted together and the solidified mass autetflc

Grain size less than 250μ crushed, 3.97 parts this comminuted mixture is mixed with 27.83 parts of vanadium pentoxide. 0100 μ grain size) mixed, and the powder obtained in this way is applied to 341.3 parts of mullite balls (5 to 7 mm Diameter) sprayed on.

81 parts of the catalyst prepared in this way are introduced into a tubular reactor (? .L mm internal diameter). Now a Geraisch of 100,000 parts by volume of air and 3.79 parts of 1-methyl-3-pbenyl-indane is passed hourly through the catalyst. The Rohrwandteraperatur is 445 ⁰ C, the temperature inside the catalyst layer 468 "C. The leaving the reactor, the gaseous reaction mixture is cooled to 50 ^c C, where the end product and the unreacted l-methyl-3-phenyl-indan condense. The The uncondensed portion is washed with water, and after the washing water has evaporated, the residue that remains is combined with the condensate.

The following results are obtained.!:

Raw material

1-methyl-3-phenyl-indane ... 18.93 parts

Exhaust gas quantity 500,000 parts by volume

Content of the exhaust gas

Carbon monoxide and dioxide 1.92 percent by volume, raw end product 18.6 parts

In the raw end product, the following are determined by UV absorption:

60.1 weight percent anthraquinone = 11.18 parts

19.5 percent by weight of phthalic anhydride = 3.63 parts of 0.8 percent by weight of unreacted

Starting material I = 0.15 parts

(corresponds to a conversion of 99.2% of theory and an initial quinone yield, based on the converted Starting material, from 59.0% of theory).

Example 4

A mixture of 24.06 parts of vanadium pentoxide (> 100μ grain size) and 0.44 parts of teuuric acid (H ₆ TeO ₆ ) with a grain size of below 250 μ is sprayed onto 339.5 parts of mullite balls (5 to 7 mm diameter) using a flame spray device .

79.8 parts of the catalyst prepared in this way are introduced into a tubular reactor (21 mm internal diameter). A mixture of 100,000 parts by volume of air and 3.75 parts of 1-methyl-3-phenyl-indane is now passed through the catalyst every hour. The tube wall temperature is 435 ° C, the temperature inside the catalyst layer 463 ⁰ C. The leaving the reactor, the gaseous reaction mixture is cooled to 50 ⁰ C, where the end product and the unreacted l-methyl-3-phenyl-indan condense. The uncondensed portion is washed with water. After evaporation of the wash water, the ^remaining: Rückrstand with the condensate Confederates. . _: * '

The following results are obtained:

Raw material
l-MethyM-pheny l-indane ... 18.75 parts

Exhaust gas quantity, .. /.,.,. 500000 volume parts

Content of the exhaust gas

., Carbon monoxide and »dioxide 1.85 percent by volume Raw end product,., ■■■ ,, 18.9 parts

In the raw end product are determined by UV absorption; '

68 percent by weight of anthraquinone == 12.85 parts 17.2 percent by weight of phthalic acid anhydride = 3.25 parts

0.15 percent by weight unreacted

Starting material I = 0.03 part

(corresponds to a conversion of 99.8% of theory and ίο an anthraquinone yield, based on the converted Starting material, from 68.5% of theory).

Example 5

A mixture of 27.57 parts of vanadium pentoxide (> 100μ grain size) and 273 parts of telluric acid

(H ₆ TeO ₆ ) with a grain size of less than 250 μ is sprayed onto 339.7 parts of mullite balls (5 to 7 mm diameter) using a flame spray device.

82 parts of the catalyst prepared in this way are introduced into a tubular reactor (21 eud internal diameter). A batch of 100,000 parts by volume of air and 3.79 parts of 1-methyl-3-phenyl-indane is now passed through the catalyst every hour. The pipe wall temperature is 460 ⁰ C, the temperature in

as the inside of the catalyst layer 482 ° C. The leaving the reactor, the gaseous reaction mixture is cooled to 5O ⁰ C, the end product and the unreacted l-methyl-3-phenyl-indan condense. The uncondensed portion is washed with water. After the washing water has evaporated, the remaining residue is combined with the condensate.
The following results are obtained:

Raw material
1-methyl-3-phenyl-indane 18.93 parts

Exhaust gas quantity 500,000 parts by volume

Content of the exhaust gas

Carbon monoxide and dioxide 1.8 percent by volume, raw end product 18.85 parts

In the raw end product, the following are determined by UV absorption:

59.1 percent by weight anthraquinone
12.9 percent by weight phthalic acid

= 11.14 parts

anhydride = 2.43 parts

0.9 percent by weight unreacted

Starting material I = 0.17 parts

(corresponds to a conversion of 99.1% of theory and an anthraquinone yield, based on the converted Starting material, from 61.3% of theory).

Example 6

A mixture of 36 parts and 24 parts Vanulinpentoxid Teüursäure (H ₄ TeO,) is melted together at 700 ⁰ C and the solidified mass to a particle size of less than μ crushed 250th 14.61 parts of this comminuted mixture are mixed with 16.09 parts vanadium pentoxide (> 100 μ grain size) and the powder obtained in this way is sprayed onto 341.3 parts mullite balls (5 to 7 mm diameter) using a flame spray device

83.3 parts of the catalyst prepared in this way are introduced into a tubular reactor (21 mm internal diameter). A mixture of 100,000 parts by volume of air and 3.71 parts of 1-methyl-3-phenyl-i.idane is now passed through the catalyst every hour. The pipe wall temperature is 450 ⁰ C, the temperature in

Inside the catalyst layer 465 "C. The gaseous reaction mixture leaving the reactor is ^{cooled to SO 0} C, the end product and the unreacted i-methyte-4'ptienyl-frtdan condensing. The non-condensed AAfeil is washed with water Evaporation of the wash water, the remaining residue is combined with the condensate.

The following results are obtained:

Raw material 1-methyl-3-phenyi-indane

Exhaust gas quantity Content of the exhaust gas

IO

18.56 parts SOO 000 parts by volume

Carbon monoxide and dioxide 1.95 percent by volume Raw end product '...... 17.9 parts

In the raw end product, the following are determined by UV absorption:

56.5 percent by weight anthraquinone = 10.11 parts 15.2 percent by weight phthalic anhydride = 2.72 parts 0.64 percent by weight unreacted

Starting material! = 0.11 parts

(corresponds to a conversion of 99.4% of theory and an anthraquinone yield, based on the converted starting material, of 54.8%, the theory).

Claims (1)

Claim; ■ - "■ ■ ι Further development of the procedure! is for the production of anthraquinones where! ma "Indane of the general formula " . (D