DE1934063B - Process for the production of anthraquinone - Google Patents

Description

R ₁ ,

346 212, 3 & 7 601, 407 079, Belgian patent specification 594 Q89). In the oxidation of l-methyl-3-phenylindane or l, l, 3-trimethyl-3-phenyl-indane with chromic acid in the liquid phase forms o-benzoyl-benzoic acid

in a mixture with other by-products, in particular o-Acetylbenzophenone (Journal of Organic Chemistry, Vol. 19 [1954], p. 17 ff .; Journal of the American Chemical Society, Vol. 72 [1950], pp. 4918 ff .; Beiichie of the German Chemical Society, Vol. 90 [1957],

ίο p. 1208 ff.).

It has now been found that anthraquinone is obtained in a simple manner if one of the general indanes formula

in which R ₁ , R ₂ , R _{3 can be the} same or different and each represent an alkyl radical, R ₁ and / or R ₃ can also each denote a hydrogen atom, with oxygen in the gas phase in the presence of vanadium pentoxide and / or vanadates by elements of groups IVa, IVb, Vb, VIIa and VIII of the periodic system, optionally in a mixture with oxides of elements of groups IV to VI, a and b, VII a and / or VIII of the periodic system.

The invention relates to a new process for the production of anthraquinone.

It is known to anthracene by oxidation with air in the presence of catalysts, e.g. B. of vanadium V compounds, to convert at elevated temperature to anthraquinone (German patents 347 610 and 349 089, Swiss patents in which R ₁ , R ₂ , R _{3 can be the} same or different and each represent an alkyl radical, R ₁ and / or R ₃ can also each denote a hydrogen atom, with oxygen in the gas phase in the presence of vanadium pentoxide and / or vanadates of elements of groups IVa, IVb, Vb, VIIa and VIII of the periodic system, optionally mixed with oxides of elements of groups IV to VI, a and b, VIIa and / or VIII of the Periodic System (Periodic System according to R ö m ρ ρ, Chemielexikon, Edition 1966, Vol. 3, columns 4752 to 4754, as well as Vol. 4, columns 7419 / 20).

The reaction can be carried out in the case of using 1-methyl-3-phenyl-indane by the following Display formulas:

CH ₃

+ 9O ₂

+ 2 CO ₂ + 2 CO + 8 H ₂ O

Compared to the known process, the process according to the invention provides anthraquinone in good yield and purity. If 1-methyl-3-phenylindane, which is readily available on the basis of styrene, is used as the starting material, the process is particularly economical with regard to the raw material anthracene, which is often only available in unsatisfactory quantities. Technical atithracene fractions also contain sulfur-containing impurities, the oxidation products of which make the catalyst unusable in a relatively short time (German Auslegeschrift 1 020 617). In contrast, the raw material styrene is sulfur-free. In view of the prior art, it is surprising that no o * benzoylbenzoic acid is obtained and anthraquinone is prepared directly from the indane in a reaction stage, since a thermal conversion of o-benzoylbenzoic acid into anthraquinone is not known.

The indanes used as starting materials I can be obtained by dimerizing substituted or unsubstituted styrenes, eg. B. according to the aforementioned publications or in Rabjohn, Organic Syntheses, Collective Volume IV (John Wiley Inc.

6ö New York, 1963), p. 665 ff., Produce the method described. Preferred indanes I are those in which the formula R ₁ , R ₃ , R _{3 can be} identical or different and each represent an alkyl radical having 1 to 4 carbon atoms, and R ₁ and / or R ₃ also mean

each can denote 1 hydrogen atom, Ge suitable indanes I are t, B. 1-methyl-, 1,3-dimethyl-1,1,3 trimethyl, 1 - propyl, 1 * isobutyl * 3 - phenyl indane,

The oxidation is usually described with a Sauer- in the Belgian patent 681,237

stolTüberscluiß carried out. A method to be produced is preferred.

ratio of 25 to 400 moles of oxygen per mole of Indian I The oxidation is usually at a temperature above the stoichiometric amount. Usually between 200 and 450 ° C., preferably between, oxygen is used in the form of air, likewise 5250 and 400 ° C., without pressure or under pressure, any mixtures of oxygen and under natural or preferably continuous reaction conditions can be inert Gases like argon lead to, One oxidizes ζ. B. the starting material I in the steam, nitrogen and / or carbon dioxide or the following way: The output indan is evaporated flue gas to use. The lower explosive and with an ^{air flow heated to more than 150 0} C sion limit corresponding mixtures is mixed at 20 to 10. It is also possible to use an oxygen-free 60 grams of Indan I per cubic meter of air. The Oxyda substream of the reaction exhaust gases with the steam of the tion is saturated in the presence of vanadium pentoxide and / or starting material and so the desired con-vanadates of elements of groups IVa, IVb, Vb, concentration of indane I in the reaction mixture-VIIa and VIII of the periodic system, e.g. B. iron, make. The gas-vapor mixture is then passed through the catalytic converter at the reaction temperature in a titanium, tin, antimony, lead and manganese vanadate 15 reactor. Lysator layers are conducted in continuous operation. The reactors expediently come from 20 to 200, advantageously 40 to moderately cooled tubular reactors with a salt bath, fluidized 100 grams of starting material I per liter of catalyst layer reactors with built-in cooling elements or (or catalyst on support) and oxidized per hour. Layer reactors with intermediate cooling in question. The same amounts of starting material I, based on the ao From the reaction mixture is now in the usual way catalyst (catalyst on support), are separated in the end product, for. B. one derives the Reak rule also used in discontinuous operation. The gases leaving the gate by one or more Ab- The vanadates can be mono- or poly-vanadates, in particular, around the anthraquinone from the greater part of the special ortho-, pyro, metavanadates. Separate the kata by-products. Optionally, a lysers can optionally also be used together with cleaning of the end product, e.g. B. by dissolving in a carrier material, ζ. B. pumice, titanium dioxide, steatite, alkaline NaJriumdithionitlösung and filtration of the silicon carbide, as well as iron, silicon and aluminum unreacted starting material. Then oxide is used. Vanadium pentoxide and / or the vanadate precipitates as a mixture and separated off from the filtrate. The reaction oxides ν r can also be used. Elements of groups IV to VI, 30 tion mixture in water or dilute sodium hydroxide solution a and b, VIIa and / or VIII of the periodic system and isolate the end product from the solid residue formed (periodic system according to Römpp, Chemielexi- by sublimation,
kon, Edition 1966, Vol. 3, Column 1 4752 to 4754, as well as Vol. 4, Columns 7419/20) which can be prepared by the process of the invention for the implementation as a catalyst anthraquinone is a valuable starting material for the catalysts. The shape and size of the catalysts can be used within a wide range as desired. With regard to the use will be preselected, it is advantageous to use spherical, named publications and Ulimann's Enzytablettierte or lumpy catalysts or Strang- klopadie der technischen Chemie, Vol. 3, pp. 659 ff., Referring to pressed fingers of an average diameter,
between 2 and 10 millimeters. 40 mean the parts listed in the examples

Vanadate catalysts can advantageously by parts by weight. They relate to the volume parts

Precipitation of a solution of ammonium vanadate with like kilograms and liters,
a corresponding metal salt, e.g. B. a solution

of ferric chloride, manganese sulfate or titanium tetra- Example 1
chloride, filtration and drying of the metal vanadate 45 ... ",",
precipitation can be produced. By adding the (making the catalyst)
Carrier material before or during the precipitation, the 10 parts of ammonium vanadate are dissolved in 175 parts of metal vanadate at the same time on the carrier of finely boiling water. It is divided under strong agitation. The solution or suspension of the ren, the solution of 7 parts of ferric chloride (6 H ₂ O) in vanadate, can also be added by soaking or spraying onto the 00 50 parts of water. Immediately after the addition, carrier can be applied. It is also possible that 100 parts by volume of pumice-dry or moist vanadate with the carrier 7u granules (2 to 3 mm diameter) are added to the ferric chloride solution in the brown suspension, optionally to comminute the mixture, and the mixture is added to dryness and then , e.g. B. with the help of an extruder, in evaporated. The residue is performed for 1 hour at 125 ⁰ C gesprechende moldings. After Ti ock- 55 dries and then in a muffle furnace in the air, the catalyst can advantageously be calcined for 4 hours at 40 ° C.

be e.g. B. at a temperature between 300 and ._,. ,

₇₀₀ » _c> (oxidation)

To prepare vanadium pentoxide catalysts, 21 parts of the catalyst prepared in this way can be poured into 2. B. Vanadium pentoxide in aqueous Oxal- 60 a tubular reactor (21 mm inner tubular acid or hydrochloric acid and dissolve the solution on a knife). A mixture of suitable carriers, e.g. B. titanium dioxide, apply, dry the 100,000 parts by volume of air and 2.99 parts of 1-methyl carrier and, if necessary, calcine. Ent- 3-phenyi-indane through the catalyst every hour, solutions of ammonium tet can also be used. The pipe wall temperature is 362 "C, using vanadate in water. It is also possible to use 65 temperature inside the catalyst layer 39O ⁰ C. Vanadium pentoxide together with titanium dioxide as a very thin gaseous reaction layer leaving the reactor, e.g. <0, 1 mm, on a carrier in mixture is cooled to 5O ⁰ C, wherein applying the end product and the catalyst in spherical form and the unreacted starting material I kondensie ·

i 934 063
5 ί 6

The non-condensed portion is mixed with water. In the raw end product, UV absorption

washed. After the water has been evaporated, the following is determined:

the remaining residue with the condensate contains 4.94 parts by weight of anthruchinone

^em '^ßl> . . . . ρ. . . . 1 weight percent phthalic anhydride 0.09 parts

Following results were obtained: 5 ₀₆ Q _{ewjchts [iro2enl not lim} ge _Se tzter

Starting material I 10.47 parts Starting material I 0.06 part

Amount of exhaust gas 335,000 parts by volume 5 percent by weight benzoic acid 0.46 parts

Exhaust gas content of, "·, · ,, ™ ..ni j ^. ι

Carbon mono-and-dioxide ... 1.21 volume (corresponds to a conversion vorι 99.4% of theory and

percent = ^{10 of an} anthraquinone yield, based on converted

4060 Vo- starting material 1, of 52.8% of theory.)

lumteile. .

Raw endsloff 9.55 parts example i

In the raw end product, UV absorbers (manufacture of the catalyst.)

tion determined: 42.0 parts of vanadium pentoxide are added with the addition

52 weight percent of anthraquinone = ^v 4.96 parts ⁿ ° ^{85 '8 T, rush} oxalic acid in 8 (TC in 80 parts of

13 percent by weight of phthalic anhydride 1.24 parts ^Wa = f ^r * ^s e ^elos' · f ^{Dl LüSU "g m} \ 16.5 parts

9 percent by weight of unconverted 91 6 ° / _ol ger o-phosphoric acid and mixed with water

Starting material I = 0 86 parts ²⁰ * brought ^{to a total of 140} parts by volume. This solution

¹ is then mixed with 3 (r 'parts of titanium dioxide (anatase)

(Corresponds to a conversion of 92 ° ' _o of theory and mixed in a kneading machine for 1.5 hours

an anthraquinone yield, based on the converted mass, is dried at 80 ° C. to give 2 to 4 mm grit

Starting material I, from 5O, 8 ° / _o of Theoiie.) Broken and ^rj 6 hours in air at 200 C cal

". . , - 25 ciniert.
Example 2

(Manufacture of the catalyst) (oxidation)

90 parts of titanium tetrachloride and 58 parts of vanadium - 75 parts of the catalyst prepared in this way are dissolved in pentoxide in 400 parts by volume of concentrated hydrochloric acid in a tubular reactor ^ 20 mm inner tube acid. The solution is poured in at the same time with 30 knives). A mixture of concentrated ammonia water is then placed in a stirred vessel charged with 200 parts of 100,000 parts by volume of air and 2.56 parts of 1-methyl-water, the 3-phenyl-indane thus formed being kept neutral every hour by the catalyst gelei mixture. After the precipitation is tet. The tube wall temperature is 300 ^° C., which is then stirred at 80 ° C. for 1 hour. Subsequently, the temperature inside the catalyst layer 320 C. The precipitate formed is suctioned off, washed with water 35 The gaseous reaction leaving the reactor and after drying for 8 hours at the mixture is cooled to 50 "C, the end-500 C calcined. 10 parts This titanium material produced in this way and the unreacted starting material I, condensate, are suspended in water. This suspension. The non-condensed portion is washed out with water to 100 parts by volume of pumice grains (2 to. After the evaporation of the wash 3 mm in diameter After drying with water, the remaining residue is combined with the condensate for 4 hours at 450 C in air,
calcined. The following results are obtained:

(Oxidation) Starting material I 10.24 parts

., _.,. , ,,.,. . Exhaust gas quantity 448,000 parts by volume

Δ parts of the catalyst produced in this way are contained in 45 _{% of the Ab}

a tubular reactor (21 mm inner tube diameter - carbon mono and dioxide .... 1.55 volume

knife). Now a mixture of nrn7pnt -

150,000 parts by volume of air and 3.43 parts of 1-methyl-6950 vol

3-phenyl-indane through the catalyst every hour

tet. The pipe wall temperature is 350 C, the 5 » _{raw ends {off} - _{0 Tej | e}

Temperature inside the catalyst layer 390 C.

The gaseous reaction leaving the reactor in the raw end product is absorbed by UV

mixture is cooled to 50 C, whereby the end product determines:

and the unreacted starting material I condenses - _{52 percent by weight of} anthraquinone 3.64 parts

Ren. The non-condensed portion is 55 3 ₈ percent by weight not reacted with water

washed out. After evaporation of the washing ^v AiKoino "tnff IO ^ Tp = Ip water the remaining residue with the will

Condensate united. (Corresponds to a conversion of 97% of theory and

Starting material I 9.42 parts

Exhaust gas quantity 423,000 parts by volume Example 4

Exhaust gas content of, _tf "",

Carbon mono. and -dioxide .. 1.15 vol- (making a catalyst)

percent - 6s 6 parts vanadium pentoxide and 94 parts titanium dioxide

4860 Vo- are mixed in a ball mill. This mixture

lumteile is applied as a thin layer on steatite balls (S up to 6 mm

Raw end product 9.15 parts diameter) applied. A coated sphere

contains about 6 parts vanadium poison pentoxide and titanium content of the exhaust gas dioxide. Carbon mono and

(Oxidation) * ^dioxide 1.0 ^volume *

percent =

153 parts of the catalyst produced in this way are S 35 850 Vo

into a tubular reactor (20 mm inner diameter)

filled. Now a mixture of 1,000,000 volume »raw end product is 41.84 parts

share air and 4.38 parts of l-methyl-3-phenyl-indane _r . . ". ".

passed hourly through the catalyst. The pipe. ^In . ^{the raw end} product are absorbed by UV

Wall temperature is 350 ° C. That determines the reactor ver io:

Allowing, gaseous reaction mixture is heated to 50 ° C 41 weight percent anthraquinone 17.15 part «

cooled and, as described in Example 3, further 16 percent by weight of phthalic acid

processed. anhydride 6.7 parts

The following results are obtained: ' ⁷ ' ⁷ % by weight of unreacted

° »5 Starting material I .... 3.22 parts

Starting material I 17.52 parts 4 percent by weight benzoic acid 1.67 part « Exhaust gas quantity 412,000 parts by volume ... Content of the exhaust gas (corresponding to a conversion of 93.5 ° / ₀ of theory unc Carbon mono and dioxide 2.3 ^volume anthraquinone yield, based on converted

Percent = ao starting material I, from 35.9% of theory.) 9500 Vo-

lumteiie example 6

Raw end product 14.3 parts In the raw end product, UV absorption _J5 (manufacture of the catalyst)

tion determined: _{n Tej} , _e ammonium vanadate are divided into 200 divisors

40 percent by weight of anthraquinone, 5.72 parts of boiling water, dissolved. It will be under strong rest

13 weight percent l-methyl-3-phenyl ren the solution of 14 parts of antimony trichloride ir

indan 1.86 parts of 5 parts of water were added. Immediately after the addition

30 dei

dries and then in the air for 4 hours Example M 400'C calcined.

(Oxidation) (Manufacture of the catalyst)

21 parts of the catalyst prepared in this way are used in

11.3 parts of tin (II) chloride (2 H ₄ O) are poured into a tubular reactor (21mm inner tube diameter, a few drops of concentrated hydrochloric acid in 40 meters). A mixture is then dissolved in front of 10 parts of water. With vigorous stirring, 100,000 parts by volume of air and 2.24 parts of 1-methyl, the solution of 11.7 parts of ammonium vanadate in 3-phenylindane, are added every hour to 200 parts of hot water flowing through the catalyst. Immediately after the tet. The pipe wall temperature is 337 ⁰ C, the addition of the ammonium vanadate solution is 100 Vo temperature inside the catalyst ^{layer 390 0} C, pumice grains (2 to 3 mm in diameter) are added to the gaseous reaction suspension leaving the reactor and the mixture to The dry mixture is cooled to 50 ° C. and evaporated as in Example 5. The residue is processed further for 1 hour at 125 ⁰ C described, dried and then in air for 4 hours at ..., _ ■ .. 450 ^c C calcined erhallen ^ ³ ^ "fen following results.:

(Oxidation) ⁵ ° starting material I 9.5 parts

Exhaust gas quantity 465,000 parts by volume

22 parts of the catalyst produced in this way are contained in the exhaust gas

a tube reactor (21mm inner diameter) carbon mono-and-dioxide .. 2.1 volume filled. Now a mixture of 200,000 volume percent =

share air and 3.19 parts l-methyl-3-phenyl-indane 55 9700 vol-

passed hourly through the catalyst. The pipe lumen parts

wall temperature is 33O ⁰ C, the temperature in the end product Raw 5.78 parts

Inside the catalyst layer 365 ⁰ C. The leaving the reactor, the gaseous reaction mixture is heated in the crude end product are Absorp-UV-50 cooled by C ^0, the end product and the non-environmentally determined tion 60:

Set starting material I condense. The inconsistent _{weight of} anthraquinone is 2.31 parts

the condensed portion is washed out with water. According to ₂₉ ο ^ _η 4 _ΓΟζεη1 phthalic anhydride .. 1 68 parts

Evaporation of the wash water _{does not convert the remaining Q} ο ^^ ο ^ Residue combined with the condensate. Starting material I 0 parts The following results are obtained: * ⁵ φ ^ ρ ^ _one Un, ^ _of 100% of theory and Starting material I 51.06 parts of an anthraquinone yield, based on converted Exhaust gas quantity 3,585,000 parts by volume of starting material I, of 24.3% of theory.)

2387

Example 7
(Manufacture of the catalyst)

Vanadium pentoxide is melted in a crucible and placed in a thin stream on carbonated snow to cool down infused. The resulting solid is crushed into grains 1.5 to 3 mm in diameter.

(Oxidation)

70 parts of the catalyst prepared in this way are introduced into a tubular reactor (20 "in the inner tube diameter). A mixture of 100,000 parts by volume of air and 2.39 parts of 1-methyl-3-phenyl-indane is then passed through the catalyst per hour. The Rohrwandteffipefatur is 405 ⁰ C, the temperature in the catalyst layer also Tnnern 405 ° C. The leaving the reactor, gaseous Reakttonsgemisch is cooled to 50 ° C, wherein the end product and the unreacted starting material I condense. The non-condensed portion is washed out with water. After the wash water has evaporated, the remaining residue is combined with the condensate.

ίο

The following results are obtained:

Starting material 1 7.17 parts

Exhaust gas quantity 334,000 parts by volume

Content of the exhaust gas
Carbon monoxide and

Carbon dioxide 1.16 percent by volume = 3876 parts by volume Raw end product 6.14 parts

ΐη the raw end product are due to UV absorption definitely:

59 weight percent anthraquinone 3.62 parts

0.5 percent by weight unreacted

Starting material I 0.03 part

(Corresponds to a conversion of 99.6% of theory and an anthraquinone yield, based on the converted Starting material 1, from 50.7% of theory.)

2387

Claims (1)

i 934 063 Claim: Process for the preparation of anthraquinone, characterized in that one Indane of the general formula R,