Patented May 28, 1946

2,401,225

UNITED 'STATES PATENT ori-*ice

2,401,225
PRODUCTION OF AN THRAQUIN ON E
u Philip D. Caesar, Wenonah, and Alexander N.
- V.corporation of New York `

Socony-Vacuum Oil Company, Incorporated, a

Sachanen, Woodbury, N. J., assignors to

Application March 7, 1944, Serial N0. 525,360

20. -Claims. (Cl. 260-39) This invention has to do in a general way with th reaction mixture free of AlClz-complex and catalytic reactions and is more particularly con unreacted benzene, cerned with the production of Aanthraquinone (5) Reaction of o-benzoyl benzoic acid with and its homologs by a, novel catalytic'process. H2SO4 to form anthraquinone, and As is_Well known to those familiar with the (6) Separation of anthraquinone from the re art, several processes have been proposed for action mixture formed in (5). the production of anthraquinone, All of these It has beenI found that anthraquinone can be processes, however, have suered from one orl prepared directly-in one reaction-and inex more :disadvantageous features and, of these pensively from phthalic anhydride and benzene. processes, only two-so far as is known-have 10 Specifically, the present invention is predicated been utilized commercially. Of the latter, one upon the discovery that phthalic anhydride and process involves the oxidation of anthracene to benzene react in the vapor phase to form anthra~ . anthraquinone. Anthracene, however, is not quinone directly when brought together at an readily obtainable in the pure state and before elevated temperature in the presence of a cata it ls oxidized to anthraquinone, it is essential that 15 lyst of the type known as activated clays and the it be separated from phenanthrene, chrysene, so-called alumina-silica catalysts. From this fluorene and other impurities with which it is brief definition of the present process it will be normally associated. 'I'he separation of anthra apparent that it enjoys the advantage, over the cene' from phenanthrene. etc., is particularly aforesaid processes of the prior art, of being a difficult and expensive in view of the close simi 20 means of preparing anthraquinone in one step. larity in the properties of the said' compounds. Further the catalysts which serve the purposes

The other process presently in commercial use of the present process are inexpensive, are not involvese a two-stage condensation of phthalic consumed therein and are readily regenerated for anhydride with benzene. In the` first stage, further use.- Accordingly, the present process phthalic anhydride and benzene are reacted in 25 is particularly adapted to continuous opera the presence of aluminum chloride, or other tion as -well as batch operation; this character Friedel-Crafts catalyst, to form' o-benzoyl ben istie is not shared by processes hitherto proposed. zoic acid, The acid thus formed is then con Homologs of anthraquinonemay also be pre verted to anthrauuinone by contacting it with a pared directly from homologs of benzene and of suitable dehydrating agent, such as sulfuric acid, 30 phthalic anhydride in the present process. Sub phosphorus pentoxide or the like. While high stituted anthraquinone may be formed directly yields of anthraquinone are obtained in this way, by reacting, in the vapor phase, a substituted the product is expensive in view of the char benzene with phthalic anhydride, benzene with a acter of the process. Primarily, the process com substituted phthalic anhydride, or a substituted prises two distinct reactions such that anthra 35 benzene with a substituted phthalic anhydride, in quinone is not produced directly from the initial the presence of a catalyst of the aforesaid type

reactants, but indirectly through an interme diate, Ao-benzoyl benzoic acid. Also, the process

i , at an elevated temperature.

For example, mon

is fundamentally a batch process inasmuch as the

y two mols of Friedel-Crafts catalyst are consumed

ochlorobenzene and phthalic anhydride have

been so reacted to form a chloranthraquinone.

Friedel-Crafts catalyst, for example aluminum 40 Broadly, the reactants may be considered as those chloride, is consumed therein. Specically, about members of the benzene series--including ben

benzoic acid, ,

zene-_and of the phthalic anhydride series-in cluding phthalic anhydride-which are in the vapor phase under the reaction conditions of the stantially t0 the cost of the product. In detail, 45 process. TheV reactants contemplated herein this prior process involves the following consecu may be further described as those of the afore tive operations: said series which are characteristic by substan (1) Reaction of phthalic anhydride and ben tial resistance to decomposition under the said zene in the presence of AlCla to form o-benzoyl reaction conditions.
for each mol of phthalic anhydride used in the reaction; this one factor alone contributes sub

(2) Separation of the AlCla-complex fromthe

50

The catalysts operative in the present p'rocess

are associations of silica and various amphoteric

metal oxides, and particularly those of alumina, thoria and zirconia. They maybe classified, for reaction mixture free from AlCla-complex, (4) Separation of o-benzoyl benzoic acid from 65 example, as active clay, and synthetic alumina silica, thoria-silica. and zirconia~silica catalysts.

reaction mixture formed in ( 1), ~ (3) Separation of unreacted benzene from the '

2,401,225

Preferred of these synthetic catalysts are those

which contains an excess` of silica with smaller

after about 15 to 30 minutes of contact at about '

425 C., with a vapor mixture of phthalic anhy

dride and benzene fiowing therethrough at a rate

amounts of alumina, thoria and zirconia; and

which may or may not contain not more than 1

of 3.5 parts by weight per minute. The catalyst '

may be reactivated by passing a stream of air

per cent of a third nietal'or metal oxide, with

the exception of alkalies or alkaline earths which

therethrough under appropriate temperature

conditions for a suitable length of time, as about the same period as the catalytic operation. Care should be taken that the regeneration tempera ture does not exceed about 625 C., lest the activ

should not be present in amounts greater than approximately 0.1 per cent. The active clay catalysts should conform to these same specifica tions, except that they should contain not more
than 10 per cent of the oxides of calcium, mag neslum and iron, not more than/ 3 per cent of
said oxides being iron oxides. _

ity of the catalyst be impaired. As will be readily apparent to those skilled

in the art, the apparatus used in carrying out a process of the type contemplated-,herein may
take various forms. In the accompanying draw ing, Figure 1 is a diagrammatic view .illustrating
one form of apparatus which may be satisfac

Elevated temperatures of 350 C. and greater

are used in the present process. Preferred, how ever, are temperatures of the order of 350 to

, when atmospheric pressure is used. _Somewhat 25 inabove, to a vaporizing furnace wherein they lower temperatures may beA used with lower are mixed, vaporized and heated _to a tempera
pressures. ' .l ture in the neighborhood of 385 C. The heated The yield of anthraquinone, or a homolog vapor mixture leaves the furnace through a thereof, is affected by numerous factors of which valved conduit la and enters the bottom of a the following are representative: ratio of react 30 reactor I5 which contains a catalyst of the type

550 C., and particularly preferred are tempera torily used in carrying on an operation for the tures between about 370 C. and about 470 C. continuous production of anthraquinone from Temperature, to a large extent, inuences the benzene and phthalic anhydride. course of the reaction; if too high, for example, 20 Referring to the drawing for a more detailed the yield is decreased by virtue of side reactions, description of a typical procedure contemplated such as the decomposition of benzene or phthalic by this invention, benzene and phthalic anhy anhydride or both. All of the aforesaid 'reac dride are conducted through conduits Il and l2, tion temperatures are particularly applicable respectively, in the proportions indicated here

ants, ratio of charge to catalyst, contact time and rate of flow of reactants, duration of the catalytic operation, composition of the catalyst,

defined above. In the reactor l5, the vapor

mixture contacts the catalyst at a suitable tem perature, for example, about 385 C. for a suit etc. ' able time, all as more fullydescribed herein The proportions of the reactants, as phthalic 35 above, ` and anthraquinone is fonmed. It will

anhydride and benzene, may vary considerably.

For example, equal molar proportions of the re

be apparent, however, that instead of mixing

the reactants in the vaporizing furnacathe re

actants may be used, and so may an excess of

either reactant. It is preferred, however, to employa phthalic anhydride to benzene weight

of 1:8. Correspondingly, the ratio of the charge,

ratio of from 1:3 to 1:10 and particularly, a ratio ~

actants may be vaporized separately and then admixed prior to entering the reactor, or may be 40 _ admixed when contacting the catalyst in the

reactor. The. reactor l5 may be a shell containing an 1 inner shell I5' which carriesl a bed of catalyst, may also vary widely; yet, in general, a charge 45 and the catalyst may be heated by a suitable

phthalic anhydride and benzene, to the catalyst

to about 5:1 is preferred.

to catalyst weight ratio per pass of about 2.5:1

heat exchange medium circulated through the

space between the outer and inner shells. Con Another factor exerting an appreciable in nections for the inlet and discharge of the heat ' fluence upon the yield of anthraquinone is con exchange medium are indicated at I5| and |52. tact time; that is the time during which the Similarly, the reactor I5 may carry a number , reactance are in contact with the catalyst. In 50 of tubes or pipes containing the catalyst, and the order that' side reactions, such as the decomposi tubes may be heated by circulating a heat ex tion of the individual reactants, be-rninimized, change medium about the outer surface of said the contact time should be relatively short, and tubes, such an arrangement as shown and de is defined herein as a relatively short contact _scribed in Simpson et al. Patent No. 2,185,929. 55 time." Although contact times from a fraction Also the reactor may be of the type shown and of a second to several minutes may be used described in U. S. Patent No. 2,320,318, issued herein, those of the order of 1/10 second to 1 to Simpson et al., wherein the catalyst moves con

second, and particularly from about '1A second tinuously through thereactor and -the spent cata to about 1A second, are preferred. Related to lyst moves through a regenerator where it is re co contact time is another factor-_rate of flow of vivifled, and from which it is returned to the
reactants. By way of illustration, when 15 parts by weight of catalyst are used, a rate of flow of

reactor. The continuous cyclic system shown in the latter patent may be readily adapted to reactants of about 3 parts by weight to about the reaction and regeneration phases of the pres 5 parts by weight of solution (benzene and ent process. It will also be apparent that several 65 phthalic anhydride) per minute is preferred. reactors l5, connected in series, may be used and
This rate, however, is by no means the only rate which will serve the purposes of this invention, for it will be apparent that any rate may be used so long as the contact times defined above are
that as the reaction. is carried out in one or more

maintained. The duration of the catalytic operation may

of said reactors, regeneration of catalyst may be taking place in the other reactors. Other 70 suitable reactors which may be used satisfac

torily will be suggested by the foregoing.

vary greatly depending upon the activity and life

Reference numeral I6 indicates a valved inlet conduit through which oxygen or air may be in of the catalyst. For example, it has been found troduced into the reactor l5 to regenerate the cat that 15 parts by weight of a typical catalyst, a alyst which becomes reduced in activity through 75 synthetic aluminum silicate, were deactivated

2,401,225
the deposition oi carbonaceous materials thereon.` ,

as indicated hereinabove. The temperature of

' the catalyst during regeneration should be care~

iully controlled as discussed hereinabove. Ref

erence numeral I1 indicates a valved outlet con-t

tial condenser I4 wherein a portion of the unre acted phthalic anhydride is condensed. the tem perature oi' the condenser 44 being maintained at about 150 C. in order to eiect substantial

duit through which regeneration gases may be recovered. It will be clear that when the regen eration operation is carried on, the valve in the inlet conduit I4 and the valve in an outlet con
duit I8 will be closed. '

condensation of the phthalic anhydride without

condensation of the benzene and water vapor. The condenser may be constructed in the same manner as the reactor I5, that is, with an outer and an inner shell, and the temperature thereof may be regulated by circulating a suitable cool ing medium through the space between the two shells (means not shown). The overhead vapors from condenser 44 are conducted through an outlet conduit 45 to the upper section 46 of a jet condenser. the tem

The top of the reactor is equipped with the'

outlet conduit I8, joined to the conduit I6, _for

removing the reaction mixture formed in the re actor. In addition to anthraquinone, the reac- `

tion mixture removed through the conduit I8

contains unreacted benzene,v unreacted phthalic anhydride, water of reaction, etc. The conduit
I8 connects with a heat exchanger I3 wherein

perature and pressure being maintained, there

in, for example, at about 60 C. and about >5 pounds per square inch absolute (250 mms).

reaction products from the reactor I5. A'por

some of the heat carried by the reaction mixture respectively. The'upper section 46 of the jet is removed. The reaction mixture is carried from 20 condenser is connected to a lower section 48 the heat exchanger I9 through a conduit 20 and through a leg 41;_ the temperature and pressure heat exchangers 2l and 22, wherein a portion of of the lower section 48 are maintained at about the heat Vcarried by the reaction mixture is re 60 C. and 760 mms., respectively, and benzene moved, as described hereinafter. The reaction and some phthalic anhydride are there con mixture passes from the heat exchanger 22 densed. through a conduit 23, which is fitted with a pres Fresh benzene is introduced into the system sure reducing valve 24, to a distillation column through a line 5| which connects with the inlet 25. The reaction mixture enters the column 25 side of a pump 52, which in turn is equipped with at a temperature of about 200 C., the pressure an outlet line 53. Fresh benzene flows to the in the column 25 being maintained at about 7 30 top of the jet condenser 46 through the line 53 pounds per square inch absolute (350 mms), for to a conduit 54. To those skilled in the art, example. Anthraqulnone collects at the bottom it will be clear that the jet of benzene introduced of the column 25 which is maintained'at about into the upper section of the jet condenser 46, 340 C., for example, and is withdrawn therefrom through the conduit 54,' provides a partial con through a conduit 26 which connects with the 35 densation means whereby4 phthalic anhydride heat exchanger I8 through which pass the hot from the conduit 45 is condensed in the said
lower section 48. ,

tion of the anthraquinone is returned to the bot The upper section 46 of the jet condenser .is tom of the distillation column 25 through a', con equipped with an outlet conduit 6| for removing duit 21 in order to maintain the temperature 40 the uncondensed material therein. The un thereof in the neighborhood of about 340 C., or condensed material passes through the conduit within a, range such that the anthraquinone is 5| and a cooler 62, thence through a conduit B3 maintained in liquid phase and other reaction to a distillation column 64 which is kept at about products are maintained in the vapor phase. It 38 C. and 5 pounds per square inch absolute, will be apparent that with the apparatus shown, 4. for example. Water of reaction is removed from part of the heat withdrawn from the `reaction the bottom of _the column 64 through an outlet mixture in passing through the heat exchanger line 65, which connects with the inlet side of a I9 is utilized to maintain the desired temperature pump 66. and a conduit 61 which connects with in the lower portion of the distillation column 25. the outlet side of the pump 66. Benzene is with In the apparatus as illustrated in the drawing, 50 drawn from the column 64 through the line 68 the bulk of the anthraquinone is carried from which connects with conduits 69 and 10. A por the conduit 26, after passing through the heat tion of the >benzene is taken through _the con exchanger I9, to a conduit 21 which- connects duit 69 to the inlet side of a pump 1I which dis with the linlet side `of a pump 28. The anthra charges into a conduit 12 connecting with the quinone is discharged by the pump 28 through 55 benzene inlet connection 54 on the jet condenser. a conduit 28 into a cooler 30 from which it is The top of the distillation column 64 is shown conducted to container iilling means (not as equipped with an outlet conduit 8I through shown), or is delivered through a valved conduit which the reaction gases and some benzene, in 32 into a storage vessel 33. the vapor .phase in the' column 64, pass to a As previously indicated the conditions ln the 60 compressor l2. The compressor 82 has an out distillation column 25 are so regulated that all let line 83 which connects with a cooler 84

of the reaction products, except anthraqulnone,

are discharged as overhead vapors through a

vapor outlet 4I. In the system illustrated here

in, this is accomplished by maintaining the dis

tillation column under pressure in the neighbor hood cf '1 pounds per square inch absolute, and so regulating the amount of anthraquinone re

65 sure in the column 86 are maintained at about' '

wherein the said gases and benzene are cooled, whence they pass through a conduit 85 to a dis tillation column 86. The temperature and pres

38 C. and 260 pounds per square inch absolute,

for example, 'whereupon benzene is liquefied and

may be drawn oiT through a conduit 81 which circulated through the distillation column 25, carries a pressure release valve 88. As shown, by means of heat exchangers 2| and 22, that the 70 the conduit 81 connects with the conduit 12 and temperatures of the vapors in the top of the col provides a means for returning the `benzene umn 25 are in the neighborhood of 170 C. The taken from the column 86 to the top section of overhead vapors in the conduit -4I pass through the jet condenser 46. The tcp of the column 86 heat exchanger 42 wherein they are partially is equipped with a line 89 carrying a pressure cooled, and then through a conduit 43wto a par 75 release valve 90, for removing gases therefrom.

2,401,225
and the amounts of unreacted benzene and

Benzene may also be taken from the distille.-4 tion column t4 through the line @ to e conduit '10 which connects with the inlet side of a pump 9|. Benzene is discharged from the pump 2|
through a, conduit 92 into a conduit |03 carry

phthalic Nanhydride recovered.

To demonstrate the eiilcacy of the process con templated herein with an apparatus of the type
described in connection with Figure l, the fol lowing illustrative examples are provided below. Example I

ing benzene-together with some phthalic anhy dride-taken from the lower section 58 of the

jet condenser through an outlet connection lill

by means of a pump I2. Benzene, in the line

Phthanc anhydride (105 parte by weight) and

|03, is delivered to the conduit II which charges 10 benzene (820 parts by weight)y were vaporized ' and charged to a reaction chamber (as reactor the vaporizing furnace, and part or all of the 22 in Figure 1) containing 180 parts by weight of benzene stream in conduit |03 may be by-passed a synthetic alumina silicate (analysis: 7.3% through a line |05 and the heat exchanger t2 by alumina, 92.7% silica), over a period of 22 min regulation of the valve I0@ for the purpose of utes. The reaction chamber was maintained at 15 preheating same. Also part or all of the ben 380 C. and the contact time was about 0.6 sec zene stream may be by-passed through the rheat ond. The reaction mixture obtained from the exchanger 22 by regulation of valve |01 for pre reaction chamber was processed as indicated in heating purposes. ' the discussion of Figure 1. Referring back to the condenser t9 which is A quantity of anthraquinone-7~l parts by maintained at about I50 C., as indicated above, 20 weight-Was obtained. This represents a yield unreacted phthalic anhydride carried in through of 79% of the theoretical based'on the phthalic the line 43 is here condensed and is removed anhydride, 9 parts by weight, consumed in the through ' a line IIli. Part of the unreactcd process. Substantial quantities of unreacted phthalic anhydride may be returned as reiiux to the distillation column 25 through a line III, 25 benzene and unreacted phthalic anhydride were recovered for recycling. connecting with the line i II! and the inlet side of a pump H2 which is equipped with 'an out Example II let conduit H3, the latter connecting with the Phthalic anhydride (99 parts by weight) and upper portion of the column 25. Phthalic anhy dride enters the column 25 at about 170 C., the 30 benzene (820 parts by weight) were vaporized and charged to a reaction chamber (as reactor 22 means I Iii through I I3 being heated as by stream in Figure 1) containing 180 parts by weight of the tracer lines (not shown) ) . The greater portion synthetic alumina silicate used in Example I, over ' of the unreacted phthalic anhydride is taken from a period of 22 minutes. The alumina silicate the line II through a line I It, connecting thereu

with, to the inlet of a pump IIE. The pump 35 from Example I was regenerated, before use in this example, by passing air therethrough for one II5 discharges phthalic anhydride condensate hour at 510 C . through a conduit II6 into the phthalic anhy The reaction chamber was maintained at about dride feed line I2. Fresh phthalic anhydride is 380 C. and the contact time was 0.6 second. charged to the system from a phthalic anhydride melter I'IB, which is equipped with an inlet line 40 Anthraquinone (6.35 parts by weight) was ob tained; a yield of 79.5% of the theoretical based II9 through which fresh phthalic anhydride is

introduced into the system, and is also equipped

with a heating element, as a steam coil |20.

upon the quantity of phthalic anhydride, 8 parts by weight, consumed. Unreacted benzene and
unreacted phthalic anhydride were recovered for
recycling. .

Melted phthalic anhydride is taken from the

melter II8 through a valved line I 2| which con nects with the inlet side of a pump |22 which dis
45

charges into the phthalic anhydride feed line I2.

There is also provided a line I I1, connecting with '

Anthraquinone obtained by our process here inabove described is very pure. For example,
0.35 gram of anthraquinone so obtained was re

duced by zinc and a solution of sodium hydroxide. the line I I6, which, by proper regulation of valves The solution was iiltered whereupon unreacted 50 |28 and I 24' may be used to deliver part or all of zinc and impurities were removed, and the l the condensed phthalic anhydride into melter I I8. i trate was then oxidized by air to obtain pure Phthalic anhydride in the line i2 may, by proper anthraquinone. The quantity of pure anthra regulation of valve |25, be by-passed through quinonc was 0.33i0.01 gram. conduit |26 and heat exchanger 2|. Here again, heat removed from the reaction mixture in the Example III line 20, in passing through the heat exchanger Monochlorobenzene (90 parts by Weight) and 2|, may serve to heat phthalic anhydride phthalic anhydride (10 parts by weight) were >carried in the lin~|08. It will be clear that the vaporized and then contacted with 15 parts by means II4 through |26 and I2 are heated, as by stream tracer lines (not shown), in order to 80 weight of the synthetic alumina silicate described in Example I, at a rate of 4.5 parts by weight maintain a steady'fiow of -phthalic anhydride
per minute. The reaction chamber (as in Ex
therein.

ample I) was maintained at about 425 C. and the contact time was 0.6 second. Four parts by art that the desired proportions of reactants benzene and phthalic anhydride-can be main 65 Weight of chloranthra'quinone were obtained from the reaction product, Worked up as indicated here tained throughout the continuous process by reg inabove. ulating the amounts of yfresh benzene and It is to be understood that the foregoing ex phthalic anhydride, and of recycle or unreacted amples of procedures are merely illustrative and benzene and phthalic anhydride, introduced into the reactor I5. The amount of benzene and 70 that the invention includes within its scope such changes and modications as fairly come within phthalic anhydride consumed per pass-and, the spirit of the appended claims. therefore, the amount of :fresh benzene and The present application is a continuation-in phthalic anhydride to be added-can be deter
It will be apparent to those famliar with the
mined after one pass through the system by ob- .

'

part of copending application Serial No. 449,778, taining the amount of anthraquinone formed 75 flied July 4, 1942.

,2,401,225
Weclaim: t ,l ' '

. 5

1. The catalytic process for the direct produc

tion of an anthraquinone selected from the group l

mixture, for a relatively short contact time at

an elevated temperature between about 350 C. and about 550 C., with a catalyst selected ~from the group consisting of activated clays and syn--' 1

consisting of anthraquinone and a substituted. anthraquinone, from a. compound (A) selected

from the group consisting of benzene anda ` halo- ~

gen substituted benzene, and a' compound) selected from the group consisting ofV phthalic ^
anhydride and a. substituted,phthalic-anhydride, A '

silica catalysts.

thetic- alumina-silica, thoria-silica and zirconia- _

7. 'Ihe catalytic process for the direct produc- `_

tion of anthraquinone from benzene and phthalic anhydride, which comprises: forming a vapor

the said compounds (A) and (B) being in the

vapor phase and being characterized by substan

tial resistance to decomposition under the reac
tion conditions hereinbelow defined, which com-

,mixture of about eight parts by weight of benzene and one part by weight of> phthalic anhydride;
and contacting said vapor mixture, for a contact ltime of about 0.6~second at about 380 C., with a
synthetic alumina-silica catalyst. r

prises: forming a vapor mixture of a compound

(A) and a compound (B); andcontacting the 16 8. The catalytic processfor the direct produc-v said vapor mixture, for a relatively shortcontact tion of a halogen'ated anthraquinone from a halo time at an elevated temperature above about genated benzene and phthalic anhydride, which 350 C., with a catalyst comprising anassociation comprises: forming a vapor mixture of `said halo of silica and an amphoteric metal oxide. ' genated benzene and phthalic anhydride; and 2. The catalytic process for the direct produc-l contacting said vapor mixture for a relatively tion of an anthraquinone selected from the group 20 short contact time at a temperature between consisting of anthraquinone and a substituted about 350 C. and about 550 C., with a catalyst anthraquinone, from a compound (A) selected
from the group consisting of benzene and a halo- '

comprising an association of silica and an am

' ' -

gen substituted benzene, and a compound (B) 9. The catalytic process for the direct produc selected from the group 4consisting of phthalic 25 tion of a chloroanthraquinone from monochloro anhydride and a substituted phthalic anhydride, benzene and phthalic anhydride, which com the said compounds (A) and (B) being inthe prises: forming a vapor mixture of about nine vapor phase and being characterized by sub parts by weight of 'monochlorobenzene and> one _ stantial resistance to decomposition under the re part by weight of phthalic anhydride; and con action conditions hereinbelow deined, which tacting said vapor mixture, for a contact time comprises: forming a vapor mixture of a- corn
pound (A) and a compound (B): and contacting the said vapor mixture, for a relatively short con tact time at an elevated temperature between
of about 0.6 second at about 425 C., with a syn

photeric metal oxide.

thetic alumina-silica catalyst. 10. The continuous catalytic process for the

about 350 C. and about 550 C., with a catalyst selected from the group consisting of activated

direct production of an` anthraquinone selected

from the group consisting of anthraquinone and a substitutedanthraquinone, from a compound (A) selected from the group consisting of benzene

clays and synthetic alumina-silica, thorla-silica

and zirconia-silica catalysts.

and a, halogen substituted benzene, and a com 3. 'I'he catalytic process for the direct produc pound (B) selected from the group consisting of tion of anthraquinone. from benzene and phthalic 40 phthalic anhydride. and a substituted phthalic anhydride, ywhich comprises: forming a vapor ' anhydride, the said compounds (A) and (B) be mixture of benzene and phthalicanhydride; and ing in the vapor phase and being characterized contacting said vapor mixture, for a relatively by substantial resistance to decomposition under short contact time at an elevated temperature the reaction conditions hereinbelow defined, 45 between about 350 C. and about 550 C., with a which comprises: forminga vapor mixture of a catalyst comprising an association of silica andV compound (A) and of a compound (B): contact? an amphoteric metal oxide. ing said vapor mixture, for a relatively short con 4. The catalytic process for the direct produc tact time 'at an elevated temperature above about tion of anthraquinone from benzene and phthalic anhydride, which comprises: forming a vapor` 50 350 C., with a catalyst comprising an association of silica and an amphoteric metal oxide, thereby mixture of benzene and phthalic anhydride; and forming said anthraquinone; separating said an contacting said vapor mixture, for a relatively thraquinone from the reaction mixture formed short contact time at an elevated temperature in the preceding operation;` and recycling over between about 350 C. and about 550 C., with a catalyst selected from the group consisting of 55 said catalyst, in the vapor phase under the afore said reaction conditions, the said reaction mix activated clays and synthetic alumina-silica, ture, free of said'anthraquinone, with a. quantity thoria-silica, and zirconia-silica` catalysts. of fresh compound (A) and :fresh compound (B) 5. The catalytic process for the direct produc to replace compound (A) and compound (B) con tion of anthraquinone from benzene and phthalic sumed in the said preceding operation. 00 anhydride, which comprises: forming a vapor 11. The continuous catalytic process for the mixture of benzene and phthalic anhydride; and direct production of an anthraquinone selected contacting said vapor mixture, for wa contact time from the group consisting of anthraquinone and from about 0.1 second to about 1 second at an a substituted anthraquinone, from a compound elevated temperature between about 350 C. and (A)_selected from the group consisting of ben about 550' C., with a catalyst selected from the> 05 group consisting of activated clays and synthetic , zene and a halogen substituted benzene, and a

phthalic anhydride; and contacting said vapor 75

sisting of phthalic anhydride and a substituted phthalic anhydride, the said compounds (A) 6. The catalytic process for the direct produc tion of anthraquinone from benzene and phthalic 70 and (B) being in the vapor phase and being characterized by substantial resistance to de anhydride, which comprises: forming a vapor composition under the reaction conditions here mixture of from about three to about ten parts inbelow defined, which comprises: forming a by weight of benzene and one part by weight of vapor mixture of a compound (A) and of a com
' pound (B): contacting said vapor mixture, for a

alumina-silica, thoria-silica _and zirconia-silica catalysts.

compound (B) selected from the group con

. 6

2,401,225
silica, thoria-silica and zirconia-silica catalysts, thereby forming anthraquinone; separating said anthraquinone, unreacted benzene and unreacted phthalic anhydride from the reaction mixture formed in the preceding operation; and recycling
Y over said-catalyst, in the vapor phase under.the

relatively short contact time at 'an elevated tem

perature above about. 350 C., With'la catalyst

comprising an associationl of silica and an am

photeric metal oxide, thereby forming said an-thraquinone; separating said anthraquinone, un

reacted compound (A) and unreacted compound

aforesaid reaction conditions, said unreacted (B) from the reaction mixture formed in the , benzene and said unreacted phthalic anhydride preceding operation; and recycling over said with a quantity of fresh benzene and fresh catalyst, in the vapor phase under the afore-_ phthalic anhydride to replace benzene and 10. said*l reaction conditions, said unreacted com phthalic anhydride consumed in the said preced pound (A) vand, said unreacted compound (B) operation, with- a quantity of fresh compound (A) and ing l5. The continuous process for the direct pro fresh compound (B) 'to replace compound (A) duction of anthraquinone from benzene and and compound (B) consumed in the said pre-` phthalic anhydride, which comprises: forming a
ceding operation. , '

15

12. The continuous catalytic process for the - direct production of an anthraquinone selected from the group consisting of anthraquinone and a substituted anthraquinone, from a compound

vapor mixture of benzene and phthalic anhy

dride; contacting said vapor mixture for a con tact timefrom about 0.1 second to about l sec ond at an elevated temperature between about 350 C. and about 550 C., with a catalyst se

(A) selected from the group consisting'of ben

zene and a halogen substituted benzene, and a

20

compound (B) selected from the group consist ing of phthalic anhydride and a. substituted

phthalic anhydride, the said compounds (A) and ` (B) being in the vapor phase and being char 25 dride from the reaction mixture formed in the acterized by substantial resistance to decompo ypreceding operation; and recycling over said cata sition under the reaction conditions hereinbe lyst, in the vapor phase under the aforesaid re low defined, which comprises: forming a vapor action conditions, said unreacted benzeen and mixture of a compound (A) and of a compound said unreacted phthalic anhydride with a quan (B); contacting said vapor mixture, for a rela 30 tity of fresh benzeen and fresh phthalic anhy

lected from the group consisting of activated clays and synthetic alumina-silica, thoria-silica and zirconiasilic'a catalysts, thereby forming an thraqulnone;> separating said anthraquinone, un reacted benzene and unreacted phthalic anhy

tively short contact time at an elevated tem perature between about 350 C. and about 550

C., with a catalyst selected from the group con'-r

dride to replace benzene and phthalic anhydride consumed in the said preceding operation.
35 phthalic anhydride, which comprises: forming a vapor mixture of from about three to about ten

sisting of activated clays and synthetic silica

alumina, silica-thoria and silica-zirconia cata

16. The continuous process for the direct pro duction of anthraquinone from benzene and

lysts, thereby forming said anthraquinone;

separating said anthraquinone, unreacted com parts by Weight of benzene and about one part pound (A) and unreacted compound (B) from by weight of phthalic anhydride; contacting said the reaction mixture formed in the preceding vapor mixture, for a relatively short contact time operation; and recycling over said catalyst, in 40 at an elevated temperature between about 350 the vaporphase under the aforesaid reaction C. and about 550 C., with a catalyst selected conditions, Ysaid unreacted compound (A) and from the'group consisting of activated clays and said unreacted compound (B), withva quantity synthetic alumina-silica, thoria-silica and zir of fresh compound (A) and fresh compound (B) conia-silica catalysts, thereby forming anthra 45 to replace compound (A) and compound (B) quinone; separating said anthraquinone, unre consumed in the said preceding operation'. acted benzene and unreacted phthalic anhydride 13. The continous process for thedirect pro from the reaction mixture formed in the pre duction of anthraquinone from benzene andl ceding operation; and recycling over said cata phthalic anhydride, which comprises: forming 50 lyst, in the- vapor phase under the aforesaid .reac
a vapor mixture of benzene and phthalic anhy dride; contacting said vapor mixture, for a rela tively short contact time at an elevated tern

perature between about 350 C. and about550 C., with a catalyst comprising ran association of sumed in the said preceding operation. silica and an amphoteric metal oxide, thereby 55 1'7. The continuous process for the direct pro forming anthraquinone; separating said anthro duction of anthraquinone from benzene and quinone, unreacted benzene and unreacted phthalic anhydride, which comprises: forming a phthalic anhydride from the reaction mixture vapor mixture of about eight parts by Weight formed in the preceding operation; and recycling of benzene and one part by weight of phthalic over said catalyst, in the vapor phase under the 60 anhydride; contacting said vapor mixture, for a aforesaid reaction conditions, said unreacted contact time of about 0.6 second at about 380 benzene and said unreacted phthalic anhydride C., with a synthetic alumina-silica catalyst, with a quantity of fresh benzene and fresh thereby forming anthraquinone; separating said phthalic anhydride to replace benzene and anthraquinone, unreacted benzene and unre phthalic anhydride consumed in the said pre acted phthalic anhydride from the reaction mix
ceding operation.

tion conditions, said unreacted benzene and said unreacted phthalic anhydride with a quantity of fresh benzene and fresh phthalic anhydride to replace benzene and phthalicl anhydride con

14. The continuous process for the direct pro duction of anthraquinone from benzene and

ture formed in the preceding operation; and re- l

'

cycling over said catalyst, in the vapor phase under the aforesaid reaction-conditions, said un phthalic anhydride, which comprises: forming a reacted benzene and said unreacted phthalic an vapor mixture of benzene and phthalic anhy 70 hydride with a quantity of fresh benzene and contacting ysaid vapor mixture, for a dride; fresh phthalic anhydride to replace benzene and relatively short contact time at an elevated tem phthalic anhydride consumed in the said pre

perature between about 350 C. and about 550

C., with a catalyst selected from the group con

ceding operation.

sisting of activated clays and synthetic alumina 76

18. The catalytic process for the direct produc

2,401,225
tion of a haloge'nated anthraquinone from a

4which comprises: forming a vapor mixture of

halogenated benzene and phthalic anhydride,

said halogenated benzene and phthalic anhy dride: contacting said vapor mixture, for a rela tively shari; contact time at a temperature be

thetic alumina-suica'catalyst, thereby forming

said chloroanthraquinone; separating said chlo roanthraquinone, unreacted monochlorobenzene
and unreacted phthalic anhydride from the re action mixture formed in the preceding opera tion; and recycling over said catalyst, in the vapor

tacting said vapormixture, for a contact time of about 0.6 second at about 425 C., with a syn

tween about 350 C. and about 550 C., with a

catalyst comprising an association of silica and

an amphoteric metal oxide; thereby forming said

halogenated anthraquinone; separating s_aid halogenated anthraquinone, unreacted halo

genated benzene and unreacted phthalic anhy dride `from the reaction mixture formed in the
preceding operation; and recycling over .said catalyst, in the vapor phase under the aforesaid reaction conditions, said unreacted halogenated benzene and said unreacted phthalic anhydride with a quantity of fresh halogenated benzene

phase under the aforesaid reaction conditions,

said unreacted monochlorobenzene and said un

reacted phthalic anhydride with a quantity of4 fresh monochlorobenzene and fresh phthalic an hydride to replace monochlorobenzene and

phthalic anhydride. consumed in the said preced

ing operation. ,

20. The catalytic process for the direct produc tion of anthraqulnone from benzene and phthalic anhydride, which comprises: forming a vapor and fresh phthalic anhydride to replace halo- ' mixture o1' benzene and phthalic anhydride; and genated benzene and phthalic anhydride con 20 contacting said vapor mixture, for a relatively sumed in the said preceding operation. short contact time at an elevated tempera-ture 19. The catalytic process for the direct pro
duction of a chloroanthraquinone ,from mono
and under reduced pressure, with a catalyst com

chlorobenzene and phthalic anhydride, which

comprises: forming a vapor mixture of about

" `prising an association o1' silica and an ampho

v teric metal oxide.

nine pa'rts by weight of monochlorobenzene and one part by weight of phthalic anhydride; oon

PHHJIP D. CAESAR.

ALEXANDER N; SACHANEN.