DE2122664A1 - Process for the production of anthraquinone - Google Patents

Description

Badische Anilin- & Soda-Fabrik AG 2122664

Our reference: 0.Z.27 497 WB / Be 6700 Ludwigshafen, 6.5. 1971

Process for the production of anthraquinone Addition to patent. ... ... (patent application P 19 34 063.7-42)

Subject of the main patent. ... ... (patent application P 19 34 063.7-42) is a process for the production of anthraquinone by oxidation of aromatic compounds with oxygen in the gas phase in the presence of a catalyst at increased Temperature, one indanes of the general formula

I,

in which R ^, Rp, R-z can be the same or different and each mean an alkyl radical, R .. and / or R, in addition can also each denote a hydrogen atom, in the presence oxidized by vanadium V compounds as catalysts.

The aforementioned method is described in Belgian patent specification 752 049.

It has now been found that the process of the main patent can be further developed if the reaction is carried out in the presence of Vanadium-V compounds and, in addition, compounds of tellurium.

In view of the prior art, which is described in the aforementioned Belgian patent, the process according to the invention a simple and economical way surprisingly anthraquinone in good yield, higher space-time yield and purity in far better sales. Compared to the 188/71 cleaning

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received,

that in Example 23 of the patent / dark colored, impure End product obtained from organic solvents such as nitrobenzene must be recrystallized, the separation and purification of the end product according to the invention is simpler and more economical; recrystallization from water already provides one for dye synthesis specification-compliant raw material.

The oxidation is carried out with oxygen or, expediently, with an oxygen-containing gas mixture, e.g. air. In the case of 1-methyl-3-phenyl ~ indane, the load can be 5 to 100, advantageously 10 to 60, in particular 25 to 50 grams of 1-methyl-3-phenylindane per 1 normal cubic meter of air. It is expedient to use from 20 to 2,000, advantageously from 40 to 500 ) Grams of starting material I per liter of catalyst (or catalyst on support) and hour, with one or more in the catalyst Vanadium-Y compounds and one or more compounds of the Tellurium present. Regardless of the composition of the compound and the valence of the element in the compound is the atomic ratio of vanadium to the additive element in the catalyst Tellurium expediently from 2,550 to 10, preferably from 1,200 to 15, in particular from 400 to 25, vanadium to 1 tellurium. The catalysts are advantageously used together with a carrier material, e.g. pumice, titanium dioxide, steatite, silicon carbide, Iron, silicon, aluminum oxides, aluminum silicates such as mullite, for use.

The compounds of tellurium generally include the oxides, acids, salts and such compounds of the additional element Questions that convert to a tellurium oxide during catalyst production or the reaction.

Examples of suitable tellurium compounds are: Oxygen acids des tellurium, ammonium tellurate, tellurium dioxide, potassium tellurite, tellurium nitrate, tellurium trioxide, cesium tellurate, potassium tellurate, Thallium tellurate.

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The catalytically active components can by a conventional method (Houben-Weyl, methods of organic chemistry, Volume 4/2, pages 143 - 240) can be applied to inert carriers, e.g. by soaking, spraying or precipitation, and then Calcining of the supported catalyst thus prepared, The preparation of catalysts containing vanadium and tellurium on spherical supports has proven to be advantageous after a flame spray or plastic spray process, e.g. after

that in the German patent specification (patent application

P 20 25 430.2) described procedure. The additional compounds mentioned can with the vanadium pentoxide to be applied by means of flame spraying or a compound that occurs when heated converts into vanadium pentoxide, such as vanadic acid, are mixed mechanically. However, it can be beneficial initially to produce a homogeneous solution containing the elements to be applied. From this solution, the connections to be applied, e.g. by evaporation. It can also be advantageous to first melt the components to be applied together, let cool and then chop. If necessary, a plasma torch is required for higher-melting connections to use. In this case, it is advisable to avoid a partial or complete reduction of the vanadium-V to Vanadium-IV to prevent the formation of higher-melting vanadium-IV.

The oxidation is advantageously carried out at a temperature between 250 and 500 ⁰ C, in particular between 300 and 450 ⁰ C. This temperature is usually measured as the temperature of the cooling medium, for example a saltpeter bath (pipe wall temperature). A partial flow of the reaction exhaust gases that is poor in oxygen can be saturated with the vapor of the starting material in order to set the desired concentration of indane I in the reaction mixture.

In one embodiment of the method according to the invention is for example the catalyst or, advantageously, of a support in any desired manner, preferably according to the aforementioned flame spraying or plasma spraying process supported catalyst to a temperature of 450 to 650 ⁰ C, preferably from 50O ⁰ C to 600 ⁰ C. heated and at this temperature for some time

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held (calcination). Advantageously, the calcining time is 1 ms 24, in particular 5 "to 16 hours. It is preferably calcined in the presence of oxygen-containing gases, Z ₈ as air or flue gas, and at a pressure 1 to 3 For further details of the catalyst preparation is to Ullmann's Encyclopedia of Industrial Chemistry, Volume 9, pages 254 ff.

Otherwise, the procedure is carried out under the conditions of the procedure carried out according to the main patent, in particular with regard to the conduct of the reaction, catalyst preparation and composition.

The parts given in the examples are parts by weight. ™ You_ behave to parts by volume like kilograms to liters.

example 1

A mixture of 59.8 parts of vanadium pentoxide and 0.24 parts of telluric acid (HgTeOg) is melted together at 700 G ⁰ and the solidified mass to a particle size of less / u disintegrated 250th 7.75 parts of this comminuted mixture are mixed with 23.25 parts of vanadium pentoxide (> 100 / U grain size), and the powder thus obtained is sprayed onto 341.3 parts of mullite balls (5 to 7 mm diameter) using a ram spraying device.

78.1 parts of the catalyst prepared in this way are introduced into a tubular reactor (21 mm internal diameter). Fun, a mixture of 100,000 parts by volume of air and 3.71 parts of 1-methyl-3-phenyl-indane is passed through the catalyst every hour. The tube wall temperature is 435 ⁰ C, the temperature inside the catalyst layer 458 ⁰ C. The leaving the reactor, the gaseous reaction mixture is cooled to 50 ⁰ C, where the end product and the unreacted i-methyl-3-phenylindan condense. The uncondensed portion is washed with water. After the washing water has evaporated, the remaining residue is combined with the condensate.

changed as entered

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OHQMM.

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The following results are obtained:

Starting material 1-Methy1-3-phenyl-indane: 18.56 parts Exhaust gas quantity: 500,000 parts by volume

Carbon monoxide content of the exhaust gas

and dioxide: 2.40 volume- ^

Raw end product: 17.5 parts

In the raw end product, UV absorption determines:

59.0 weight percent anthraquinone = 10.33 parts 23.8 "phthalic anhydride = 4.17 parts 0.33 "unreacted

Starting material I = 0.06 parts

(corresponds to a sales of $ 99.7 of theory and one Anthraquinone yield, based on converted starting material, of $ 55.6 of theory).

Example 2

A mixture of 59.8 parts of vanadium pentoxide and 0.24 parts of telluric acid (HgTeOg) is melted together at 700 ⁰ C and comminuting the solidified mass to a particle size of less than 250 / U. 15.25 parts of this comminuted mixture are mixed with 15.25 parts of vanadium pentoxide (> 100 / U grain size), and the powder thus obtained is sprayed onto 341.3 parts of mullite balls (5 to 7 mm diameter) using a flame spray device.

80.1 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 3.79 parts of 1-methyl-3-phenyl-indane is then passed through the catalyst every hour. The tube wall temperature is 435 ⁰ C, the temperature inside the catalyst layer 462 ⁰ C. The leaving the reactor, the gaseous reaction mixture is cooled to 50 ⁰ C, where the end product and the unreacted i-methyl-3-phenylindan condense. The uncondensed portion is washed with water. After the wash water has evaporated

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the remaining residue is combined with the condensate. The following results are obtained:

Starting material 1-methyl-3-phenyl-indane: 18.95 parts Exhaust gas quantity: 500,000 parts by volume

Carbon monoxide content of the exhaust gas

and dioxide: 2.20 volume- ^

Raw end product: 17 _f 85 parts

In the raw end product, UV absorption determines:

61.2 weight percent anthraquinone = 10.93 parts 24.8 "phthalic anhydride = 4.43 parts 0.41 "unreacted

Starting material I = 0.07 parts

(equivalent to a conversion of 99.6 fo the theory and a Anthrachinonausbeute, based on converted starting material, 57.9 i> of theory).

Example 3

A mixture of 48 parts of vanadium pentoxide and 2 parts of telluric acid (HgTeOg) is melted together at 700 ⁰ C and comminuting the solidified mass to a particle size of less than 250 / U. 3.97 parts of this comminuted mixture are mixed with 27.83 parts of vanadium pentoxide (> 100 / U grain size), and the powder thus obtained is sprayed onto 341.3 parts of mullite balls (5 to 7 mm diameter) using a flame spray device.

81 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 3.79 parts of 1-methyl-3-phenyl-indane is now passed through the catalyst every hour. The tube wall temperature is 445 ⁰ C, the temperature inside the catalyst layer 468 ⁰ C. The leaving the reactor, the gaseous reaction mixture is cooled to 50 ⁰ G, the end product and the unreacted 1-methyl-3-phenyl-indan

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condense. The uncondensed portion is mixed with water washed. After the washing water has evaporated, the remaining Combined residue with the condensate.

The following results are obtained:

Starting material 1-methyl-3-phenyl-indane: 18.93 parts Exhaust gas quantity: 500,000 parts by volume

Carbon monoxide content of the exhaust gas

and dioxide: 1.92 volume- ^

Raw end product: 18.6 parts

In the raw end product, UV absorption determines:

60.1 weight percent anthraquinone = 11.18 parts 19.5 "phthalic anhydride = 3.63 parts 0.8" unreacted

Starting material I = 0.15 parts

(corresponds to a conversion of $ 99.2> of theory and an anthraquinone yield, based on converted starting material, of 59.0 in general of theory).

Example 4

A mixture of 24.06 parts of vanadium pentoxide (> 100 / U grain size) and 0.44 parts of telluric acid (HgTeOg) with a grain size of less than 250 yes 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). Fun, a mixture of 100,000 parts by volume of air and 3.75 parts of 1-methy 1-3-plieny! -Indan is passed through the catalytic converter 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 1-methyl-3-phenylindan condense. The uncondensed portion is washed with water. After the washing water has evaporated, the

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remaining residue combined with the condensate.

The following results are obtained:

Raw material. 1-methyl-3-phenyl-indane: 18.75 parts Exhaust gas volume: 500,000 parts by volume

Carbon monoxide content of the exhaust gas

and dioxide: 1.85 volume- ^

Raw end product: 18.9 parts

In the raw end product, the UY absorption is determined:

68 weight percent anthraquinone = 12.85 parts 17.2 "phthalic anhydride = 3.25 parts 0.15 "unreacted

Starting material I = 0.03 part

(corresponds to a conversion of 99.8 % of theory and "an anthraquinone yield, based on converted starting material, of $ 68.5 of theory).

Example 5

A mixture of 27.57 parts of yanadine pentoxide (> 100, u grain size) and 273 parts of telluric acid (HgTeO ₆ ) with a grain size of less than 250 / rev 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 mm internal diameter). A mixture of 100,000 parts by volume of air and 3.79 parts of 1-methyl-3-phenyl-indane is then passed through the catalyst every hour. The tube wall temperature is 460 ⁰ C, the temperature inside the catalyst layer 482 ⁰ C. The leaving the reactor, the gaseous reaction mixture is cooled to 50 ⁰ C, where the end product and the unreacted 1-methyl-3-phenyl-indan condense. The uncondensed portion is washed with water. Subject to evaporation of the wash water, the remaining residue is combined with the condensate. '-

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The following results are obtained:

Starting material 1-methyl-3-phenyl-indane: 18.93 parts Exhaust gas quantity 5 500 000 parts by volume

Carbon monoxide content of the exhaust gas

and dioxide: 1.8 volume- ^

Raw end product: 18.85 parts,

In the raw end product are determined by UV absorption;

59.1 weight percent anthraquinone = 11.14 parts 12.9 "phthalic anhydride = 2.43 parts 0.9" unreacted

Starting material I = 0.17 parts

(corresponds to a conversion of 99 »1 $> of theory and an anthraquinone yield, based on converted starting material, of 61.3 io of theory).

Example 6

A mixture of 36 parts of vanadium pentoxide and 24 parts of telluric acid (HgTeOg) is melted together at 700 ⁰ C and comminuting the solidified mass to a particle size of less than 250 / U. 14.61 parts of this comminuted mixture are mixed with 16.09 parts of vanadium pentoxide (> 100 / u particle size) and the powder thus obtained is sprayed onto 341.3 parts of 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). Fun, a mixture of 100,000 parts by volume of air and 3.71 parts of 1-methyl-3-phenyl-indane is passed through the catalyst every hour. The tube wall temperature is 45O ⁰ C, the temperature inside the catalyst layer 465 ⁰ C. The leaving the reactor, the gaseous reaction mixture is cooled to 50 C, the end product and the unreacted i-methyl-3-phenylindan condense. The uncondensed portion is washed with water. After the washing water has evaporated, the remaining residue is combined with the condensate.

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The following results are obtained:

Starting material 1-methyl-3-phenyl-indane: 18.56 parts Exhaust gas quantity: 500,000 parts by volume

Carbon monoxide content of the exhaust gas

and dioxide: 1.95 volume- ^

Raw end product: ' ^fe 17 _f 9 parts

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

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

Starting material Γ = 0.11 parts

(corresponds to a conversion of 99> 4 % of theory and an anthraquinone yield, based on converted starting material, of 54.8% of theory).

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Claims (1)

O.Z. 27 497 Claim Further embodiment of the process for the production of anthraquinone by oxidation of aromatic compounds with Oxygen in the gas phase in the presence of a catalyst at an elevated temperature, indanes of the general formula I, in which R ₁ , Rp »R ^ can be the same or different and each mean an alkyl radical, R ^ and / or R ~ can also each denote a hydrogen atom, oxidized in the presence of vanadium-Y compounds as catalysts Patent. ... ... (patent application P 19 34 063.7-42), characterized in that the reaction is carried out in the presence of yanadium-V compounds and, in addition, of compounds of tellurium. Badische Anilin- & Soda-Eabrik AG 209849/1116