anthraquinone production

8/12/2019 Anthraquinone Production

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U N I T E D ' S T A T E S PATENT o r i - * i c e2 , 4 0 1 , 2 2 5

PRODUCTION OF ANTHRAQUINONu P h i l i p D. Caesar, Wenonah, and Alexander N.S a c h a n e n , W o o d b u r y , N . J . , a s s i g n o r s t oSocony-Vacuum O i l Company, Incorporated, a `

- V.corporation of NewYorkA p p l i c a t i o n March 7 , 1 9 4 4 , S e r i a l N 0 . 5 2 5 , 3 6 0

2 0 . C l a i m s . ( C l . 260-39)This i n v e n t i o n has t o do i n a g e n e r a l wa y withc a t a l y t i c r e a c t i o n s and i s more p a r t i c u l a r l y conc e r n e d w i t h t h e p r od u c t i o n o f A a n t h r a q u i n o n eand i t s homologs by , n o v e l c a t a l y t i c ' p r o c e s s .As i s _ W e l l known t o t h o s e f a m i l i a r w i t h t h ea r t , s e v e r a l p r o c e s s e s have been proposed f o rt h e p r o d u c t i o n o f a n t h r a q u i n o n e , A l l o f t h e s e

p r o c e s s e s , however, have suered from one o r lmore : d i s a d v a n t a g e o u s f e a t u r e s a n d , o f t h e s ep r o c e s s e s , only two-so f a r a s i s known-havebeen u t i l i z e d c o m m e r c i a l l y . Of t h e l a t t e r , onep r o c e s s i n v o l v e s t h e o x i d a t i o n o f anthracene t oa n t h r a q u i n o n e .r e a d i l y o b t a i n a b l e i n t h e pure s t a t e and b e f o r ei t l s o x i d i z e d t o anthraquinone, i t i s e s s e n t i a l t h a ti t b e s e p a r a t e d f r o m p h e n a n t h r e n e , c h r y s e n e ,f l u o r e n e and o t h e r i m p u r i t i e s w i t h which i t i snormally a s s o c i a t e d . I h e s e p a r a t i o n o f anthrac e n e ' from p h e n a n t h r e n e . e t c . , i s p a r t i c u l a r l yd i f f i c u l t and e x p e n s i v e i n view o f t h e c l o s e s i m il a r i t y i n t h e p r o p e r t i e s o f t h e s a i d compounds.T h e other p r o c e s s p r e s e n t l y i n commercial u s ei n v o l v e s e a two-stage condensation o f p h t h a l i canhydride w i t h b e n z e n e . In t h e ` f i r s t s t a g e ,p h t h a l i c anhydride and benzene a r e r e a c t e d i nthe presence o f aluminum c h l o r i d e , o r otherF r i e d e l - C r a f t s c a t a l y s t , t o f o r m ' o - b e n z o y l benz o i c a c i d , T h e a c i d thus formed i s then conv e r t e d t o anthrauuinone by c o n t a c t i n g i t w i t h as u i t a b l e dehydrating a g e n t , such a s s u l f u r i c a c i d ,phosphorus p e n t o x i d e o r the l i k e . While highy i e l d s o f anthraquinone a r e obtained i n t h i s way,the product i s expensive i n view o f t h e character o f the p r o c e s s . Primarily, the process comp r i s e s two d i s t i n c t r e a c t i o n s such t h a t anthraquinone i s not produced d i r e c t l y from t h e i n i t i a lr e a c t a n t s , b u t i n d i r e c t l y t h r o u g h a n i n t e r m ed i a t e , A o - b e n z o y l b e n z o i c a c i d . A l s o , t h e p r o c e s si s fundamentally a bat ch p r o c e s s inasmuch a s theF r i e d e l - C r a f t s c a t a l y s t , f o r example aluminumc h l o r i d e , i s consumed t h e r e i n . S p e c i c a l l y , a b o u ttwo mols of Friedel-Crafts catalyst a re consumedf o r each mol o f p h t h a l i c anhydride used i n t h er e a c t i o n ; t h i s one f a c t o r a l o n e c o n t r i b u t e s subs t a n t i a l l y t 0 t h e c o s t o f t h e p r o d u c t . In d e t a i l ,t h i s p r i o r p r o c e s s i n v o l v e s t h e f o l l ow i n g consecut i v e o p e r a t i o n s :

( 1 ) Reaction o f p h t h a l i c anhydride and benzene i n the presence o f A l C l a t o form o-benzoylbenzoic acid, ,( 2 ) S e p a r a t i o n o f t h e A l C l a - c o m p l e x f r o m t h ereaction mixture formed in ( 1 ) , ~

A n t h r a c e n e , h o w e v e r , i s not10

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3 5i at an elevated temperature.

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( 3 ) Separation of unreacted b enzene from the 'r e a c t i o n m i x t u r e f r e e from A l C l a - c o m p l e x ,( 4 ) S e p a r a t i o n o f o - b e n z o y l b e n z o i c a c i d from 65

t h r e a c t i o n m i x t u r e f r e e o f A l C l z - c o m p l e x andu n r e a c t e d b e n z e n e ,( 5 ) Reaction o f o - b e n z o y l b e n z o i c a c i d w i t hH2SO4 t o form a n t h r a q u i n o n e , and

( 6 ) Separation o f anthraquinone from t h e r eaction mixture formed in ( 5 ) .

I t has b e e n I found t h a t anthraquinone can beprepared d i r e c t l y - i n one reaction-and i n e xp e n s i v e l y from p h t h a l i c a n h y d r i d e and b e n z e n e .S p e c i f i c a l l y , t h e p r e s e n t i n v e n t i o n i s p r e d i c a t e dupon t h e d i s c o v e r y t h a t p h t h a l i c anhydride andb enzene react i n the vapor phase t o form anthra~q u i n o n e d i r e c t l y when brought t o g e t h e r a t ane l e v a t e d temperature i n the presence o f a c a t al y s t o f t h e t y p e known a s a c t i v a t e d c l a y s and t h es o - c a l l e d a l u m i n a - s i l i c a c a t a l y s t s . From t h i sb r i e f d e f i n i t i o n o f the present p r o c e s s i t w i l l b eapparent t h a t i t e n j o y s the advantage, o v e r t h ea f o r e s a i d p r o c e s s e s o f the p r i o r a r t , o f being ameans o f preparing anthraquinone i n one s t e p .Further the c a t a l y s t s which s e r v e the purposeso f the present process are inexpensive, are notconsumed therein and are r e a d i l y regenerated f o rf u r t h e r u s e . A c c o r d i n g l y , t h e p r e s e n t p r o c e s si s p a r t i c u l a r l y adapted t o c o n t i n u o u s operat i o n a s - w e l l a s batch operation; t h i s characteri s t i e i s not shared by p r o c e s s e s h i t h e r t o p r o p o s e d .Homologs o f anthraquinonemay a l s o b e p r ep a r e d d i r e c t l y from homologs o f b e n z e n e and o fp h t h a l i c anhydride i n t h e p r e s e n t p r o c e s s . Subs t i t u t e d a n t h r a q u i n o n e ma y b e formed d i r e c t l yby r e a c t i n g , i n t h e vapor p h a s e , a s u b s t i t u t e db e n z e n e w i t h p h t h a l i c a n h y d r i d e , b e n z e n e w i t h as u b s t i t u t e d phthalic anhydride, o r a s u b s t i t u t e dbenzene with a s u b s t i t u t e d p h t h a l i c a n h y d r i d e , i nthe presence o f a c a t a l y s t o f the a f o r e s a i d type

For example, mono c h l o r o b e n z e n e and p h t h a l i c a n h y d r i d e havebeen s o r e a c t e d t o form a chloranthraquinone.B r o a d l y , the r e a c t a n t s m a y be c o n s i d e r e d a s t h o s emembers o f t h e benzene s e r i e s - - i n c l u d i n g benzene-_and o f t h e p h t h a l i c anhydride s e r i e s - i nc l u d i n g p h t h a l i c anhydride-which a r e i n t h evapor phase under t h e r e a c t i o n c o n d i t i o n s o f t h ep r o c e s s . TheV r e a c t a n t s contemplated h e r e i nmay b e f u r t h e r d e s c r i b e d a s t h o s e o f t h e a f o r es a i d s e r i e s which a r e c h a r a c t e r i s t i c by s u b s t a nt i a l r e s i s t a n c e t o decomposition under t h e s a i dr e a c t i o n c o n d i t i o n s .The c a t a l y s t s o p e r a t i v e i n t h e p r e s e n t p r o c e s sare a s s o c i a t i o n s o f s i l i c a and v a r i o u s amphotericm e t a l o x i d e s , and p a r t i c u l a r l y t h o s e o f a l u m i n a ,t h o r i a and z i r c o n i a . They m a y b e c l a s s i f i e d , f o re x a m p l e , a s a c t i v e c l a y , and s y n t h e t i c aluminas i l i c a , t h o r i a - s i l i c a . and z i r c o n i a ~ s i l i c a c a t a l y s t s .


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2P r e f e r r e d o f t h e s e s y n t h e t i c c a t a l y s t s a r e t h o s ewhich contains a n e x c e s s ` of s i l i c a with smalleramounts o f alumina, t h o r i a and z i r c o n i a ; andwhich may or may not contain not more tha n 1per cent o f a third n i e t a l ' o r metal o x i d e , witht h e exception o f a l k a l i e s o r a l k a l i n e e a r t h s whichs h o u l d n o t b e p r e s e n t i n amounts g r e a t e r thana p p r o x i m a t e l y 0 . 1 p e r c e n t . The a c t i v e c l a yc a t a l y s t s s h o u l d conform t o t h e s e same s p e c i f i c at i o n s , e x c e p t t h a t t h e y s h o u l d c o n t a i n n o t morethan 1 0 per cent o f the o x i d e s o f c a l c i u m , magneslum and i r o n , not more than/ 3 per cent o fsaid oxides being iron oxides.E l e v a t e d t e m p e r a t u r e s o f 3 5 0 C . and g r e a t e ra r e used i n the p r e s e n t p r o c e s s . P r e f e r r e d , howe v e r , are temperatures o f the order of 3 5 0 t o5 5 0 C . , and p a r t i c u l a r l y p r e f e r r e d a r e temperat u r e s between about 3 7 0 C . and about 4 7 0 C .Temperature, t o a l a r g e e x t e n t , inuences t h ec o u r s e o f t h e r e a c t i o n ; i f t o o h i g h , f o r example,t h e y i e l d i s d e c r e a s e d by v i r t u e o f s i d e r e a c t i on s ,such a s the decomposition o f benzene o r p h t h a l i canhydride o r b o t h . A l l o f the a f o r e s a i d ' r e a ct i o n t e m p e r a t u r e s a r e p a r t i c u l a r l y a p p l i c a b l e

, when atmospheric pressure i s u s e d . _Somewhatlower temperatures may b e A used with lowerpressuresThe y i e l d o f anthraquinone, or a homologt h e r e o f , i s a f f e c t e d by numerous f a c t o r s o f whicht h e f o l l o w i n g a r e r e p r e s e n t a t i v e : r a t i o o f r e a c ta n t s , r a t i o o f c h a r g e t o c a t a l y s t , c o n t a c t timeand r a t e o f f l o w o f r e a c t a n t s , duration o f t h ec a t a l y t i c o p e r a t i o n , c o m p o s i t i o n o f t h e c a t a l y s t ,etc.The p r o p o r t i o n s o f t h e r e a c t a n t s , a s p h t h a l i ca n h y d r i d e and b e n z e n e , may a r y c o n s i d e r a b l y .For example, e q u a l molar p r o p o r t i o n s o f the r eactants may b e used, nd so may n excess ofe i t h e r r e a c t a n t . I t i s p r e f e r r e d , however, t oemploya p h t h a l i c a n h y d r i d e t o b e n z e n e w e i g h to f 1 : 8 . C o r r e s p o n d i n g l y , the r a t i o o f the c h a r g e ,p h t h a l i c a n h y d r i d e and b e n z e n e , t o t h e c a t a l y s tmay a l s o vary w i d e l y ; y e t , i n g e n e r a l , a charget o c a t a l y s t w e i g h t r a t i o p e r p a s s o f about 2 . 5 : 1t o about 5:1 i s prefer r ed.Another f a c t o r e x e r t i n g a n a p p r e c i a b l e i nf l u e n c e upon the y i e l d o f anthraquinone i s cont a c t t i m e ; t h a t i s t h e time during which t h ereactance a re i n contact with the c a t a l y s t . Ino r d e r t h a t ' s i d e r e a c t i o n s , such a s the decomposit i o n o f t h e i n d i v i d u a l r e a c t a n t s , b e - r n i n i m i z e d ,the c o n t a c t time should be r e l a t i v e l y s h o r t , andi s d e f i n e d herein as a r e l a t i v e l y short contactt i m e . Although contact times from a f r a c t i o no f a second t o s e v e r a l minutes may be usedh e r e i n , t h o s e o f the o r d e r o f 1 / 1 0 second t o 1s e c o n d , and p a r t i c u l a r l y from a b o u t 1 A s e c o n dt o a b o u t 1 A s e c o n d , a r e p r e f e r r e d . Related t oc o n t a c t t i m e i s a n o t h e r f a c t o r - _ r a t e o f f l o w o fr e a c t a n t s . By w a y o f i l l u s t r a t i o n , when 1 5 p a r t sby weight o f c a t a l y s t a r e u s e d , a r a t e o f f l o w o fr e a c t a n t s o f a b o u t 3 p a r t s by weight t o a b o u t5 p a r t s by weight o f s o l u t i o n ( b e n z e n e andp h t h a l i c a n h y d r i d e ) p e r minute i s p r e f e r r e d .This r a t e , however, i s by no means the only r a t ewhich w i l l s e r v e the purposes o f t h i s i n v e n t i o n ,f o r i t w i l l be apparent that any r a t e may be useds o long as the contact times defined above arem a i n t a i n e d .The d u r a t i o n o f the c a t a l y t i c o p e r a t i o n m a y

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40r a t i o o f from 1 : 3 to 1:10 and p a r t i c u l a r l y , a r a t i o ~

2,401,225a f t e r about 1 5 t o 30 minutes o f contact a t about4 2 5 C . , with a vapor mixture o f p h t h a l i c anhyd r i d e and benzene fiowing therethrough at a r a t eo f 3 . 5 p a r t s bymay be reactivated b y passing a stream o f a i rt h e r e t h r o u g h under a p p r o p r i a t e t e m p e r a t u r ec o n d i t i o n s f o r a s u i t a b l e l e n g t h o f t i m e , a s aboutt h e same p e r i o d a s t h e c a t a l y t i c o p e r a t i o n . Cares h o u l d b e taken t h a t t h e r e g e n e r a t i o n temperat u r e does not exceed about 6 2 5 C . , l e s t the a c t i vt y o f t h e c a t a l y s t b e i m p a i r e d .A s w i l l b e r e a d i l y apparent t o t h o s e s k i l l e di n t h e a r t , t h e apparatus used i n c a r r y i n g o u t ap r o c e s s o f t h e t y p e c o n t e m p l a t e d - , h e r e i n mayt a k e v a r i o u s f o r m s . In t h e accompanying dra wi n g , F i g u r e 1 i s a diagrammatic view . i l l u s t r a t i n gone form o f apparatus which may be s a t i s f a ct o r i l y used i n c a r r y i n g on a n o p e r a t i o n f o r t h ec o n t i n u o u s p r o d u c t i o n o f a n t h r a q u i n o n e fromb e n z e n e and p h t h a l i c a n h y d r i d e .Referring t o the drawing f o r a more d e t a i l e dd e s c r i p t i o n o f a t y p i c a l p r oc e d u r e c o n t e m p l a t e dby t h i s i n v e n t i o n , b e n z e n e and p h t h a l i c anhyd r i d e a r e conducted through c o n d u i t s I l and l 2 ,r e s p e c t i v e l y , i n t h e p r o p o r t i o n s i n d i c a t e d h e r e i n a b o v e , t o a v a p o r i z i n g furnace wherein theya r e mixed, v a p o r i z e d and heated _ t o a temperat u r e i n t h e neighborhood o f 3 8 5 C . The heatedvapor mixture l e a v e s the furnace through avalved conduit l a and e n t e r s the bottom o f ar e a c t o r I 5 which c o n t a i n s a c a t a l y s t o f t h e typed e f i n e d a b o v e . In t h e r e a c t o r l 5 , t h e v a p o rmixture c o n t a c t s the c a t a l y s t a t a s u i t a b l e temp e r a t u r e , f o r example, about 3 8 5 C . f o r a s u i ta b l e t i m e , a l l a s more f u l l y d e s c r i b e d h e r e i nabove, and anthraquinone i s fonmed. I t w i l lb e a p p a r e n t , h o w e v e r , t h a t i n s t e a d o f mixingthe r e a c t a n t s i n the v a p o r i z i n g furnacathe r ea c t a n t s may be v a p o r i z e d s e p a r a t e l y and thenadmixed p r i o r t o e n t e r i n g t h e r e a c t o r , o r m y beadmixed when c o n t a c t i n g t h e c a t a l y s t i n t h er e a c t o r .The. r e a c t o r l 5 may be a s h e l l containing a ninner s h e l l I 5 ' which c a r r i e s l a bed o f c a t a l y s t ,

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6 5

7 0vary greatly depending upon the a c t i v i t y and l i f e o f t h e c a t a l y s t . For example, i t has been foundt h a t 1 5 p a r t s by weight o f a t y p i c a l c a t a l y s t , as y n t h e t i c aluminum s i l i c a t e , were d e a c t i v a t e d 7 5

and the c a t a l y s t may be heated by a s u i t a b l eh e a t exchange medium c i r c u l a t e d through t h espace between the o u t e r and inner s h e l l s . Conn e c t i o n s f o r t h e i n l e t and d i s c h a r g eexchange medium a r e i n d i c a t e d a t I 5 | and | 5 2 .Similarly, the reactor I 5 may carry a numbero f t u b e s o r p i p e s c o n t a i n i n g t h e c a t a l y s t , and t h etubes may be heated b y c i r c u l a t i n g a heat exchange medium about the o u t e r s u r f a c e o f s a i dt u b e s , such a n arrangement a s shown and de

_ s c r i b e d i n Simpson e t a l . Patent N o . 2 , 1 8 5 , 9 2 9 .A l s o the r e a c t o r may be o f the type shown andd e s c r i b e d i n U . S . Patent N o . 2 , 3 2 0 , 3 1 8 , i s s u e dt o Simpson e t a l . , wherein the c a t a l y s t moves cont i n u o u s l y through h e r e a c t o r and t h e s p e n t c a t al y s t moves through a regenerator where i t i s r ev i v i f l e d , and from which i t i s returned t o ther e a c t o r . The c o n t i n u o u s c y c l i c system showni n t h e l a t t e r p a t e n t may be r e a d i l y adapted t ot h e r e a c t i o n and r e g e n e r a t i o n p h a s e s o f t h e p r e se n t p r o c e s s . I t w i l l a l s o be apparent t h a t s e v e r a lr e a c t o r s l 5 , connected i n s e r i e s , may e used andthat a s the r e a c t i o n . i s carried out in one o r moreo f s a i d r e a c t o r s , r e g e n e r a t i o n o f c a t a l y s t maybe t a k i n g p l a c e i n t h e o t h e r r e a c t o r s . Others u i t a b l e r e a c t o r s which may be used s a t i s f a ct o r i l y w i l l b e s u g g e s t e d by t h e f o r e g o i n g .Reference numeral I 6 i n d i c a t e s a valved i n l e tconduit through which oxygen or a i r may be i ntroduced i n t o t h e r e a c t o r l 5 t o r e g e n e r a t e t h e c a ta l y s t which becomes r e d u c e d i n a c t i v i t y through

weight per minute. The catalyst

of th e heat


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2 , 4 0 1 , 2 2 5the d e p o s i t i o n o i carbonaceous materials t h e r e o n . `a s i n d i c a t e d h e r e i n a b o v e . The t e m p e r a t u r e o fthe c a t a l y s t during regeneration should be care~i u l l y c o n t r o l l e d a s d i s c u s s e d h e r e i n a b o v e . Reference numeral I 1 i n d i c a t e s a valved o u t l e t con-td u i t through which r e g e n e r a t i o n g a s e s may ber e c o v e r e d . I t w i l l be c l e a r t h a t when the regene r a t i o n o p e r a t i o n i s c a r r i e d o n , t h e v a l v e i n t h ei n l e t conduit I 4 and t h e v a l v e i n a n o u t l e t conduit I 8 w i l l b e c l o s e d .The t o p o f t h e r e a c t o r i s e q u i p p e d w i t h t h e 'o u t l e t c o n d u i t I 8 , j o i n e d t o t h e c o n d u i t I 6 , _ f o rremoving the r e a c t i o n mixture formed i n the r ea c t o r .t i o n mixture removed through t h e c o n d u i t I8c o n t a i n s u n r e a ct e d b e n z e n e , v u n r e a c t e d p h t h a l i ca n h y d r i d e , w a t e r o f r e a c t i o n , e t c . The c o n d u i tI 8 connects with a heat exchanger I 3 whereinsome o f t h e h e a t c a r r i e d by t h e r e a c t i o n mixturei s removed. The r e a c t i o n mixture s c a r r i e d fromt h e h e a t exchanger I 9 through a c o n d u i t 2 0 andh e a t exchangers 2 l and 2 2 , wherein a p o r t i o n o ft h e heat V c a r r i e d by the r e a c t i o n mixture i s r emoved, a s d e s c r i b e d h e r e i n a f t e r .mixture p a s s e s from t h e heat exchanger 2 2through a conduit 2 3 , which i s f i t t e d with a p r e ss u r e reducing v a l v e 2 4 , t o a d i s t i l l a t i o n column2 5 . The r e a c t i o n mixture e n t e r s t h e column 2 5a t a temperature o f about 2 0 0 C . , the p r e s s u r ei n t h e column 2 5 b e i n g maintained a t about 7pounds per s q u a r e inch a b s o l u t e ( 3 5 0 mms , o re x a m p l e . Anthraqulnone c o l l e c t s a t t h e bottomo f t h e column 2 5 which i s maintained'at about3 4 0 C . , f o r example, and i s withdrawn therefromthrough a conduit 2 6 which connects with theheat exchanger I 8 through which p a s s t h e hotr e a c t i o n p r o d u c t s from t h e r e a c t o r I 5 . A'port i o n o f t h e anthraquinone i s r e t u r n e d t o t h e b o ttom o f the d i s t i l l a t i o n column 2 5 through , cond u i t 2 1 i n o r d e r t o maintain t h e temperaturet h e r e o f i n the neighborhood o f about 3 4 0 C . , o rwithin a , range such that the anthraquinone i smaintained i n l i q u i d phase and o t h e r r e a c t i o nproducts a r e maintained i n t h e vapor p h a s e . I tw i l l b e apparent t h a t with t h e apparatus shown,p a r t o f t h e h e a t withdrawn from t h e ` r e a c t i o nm i x t u r e i n p a s s i n g t h r o u g h t h e h e a t exchangerI 9 i s u t i l i z e d t o maintain t h e d e s i r e d temperaturei n t h e l o w e r p o r t i o n o f t h e d i s t i l l a t i o n column 2 5 .In t h e apparatus a s i l lu s t r a t e d i n the drawing,t h e b u l k o f t h e anthraquinone i s c a r r i e d fromt h e c o n d u i t 2 6 , a f t e r p a s s i n g through t h e h e a texchanger I 9 , t o a conduit 2 1 w h i c h - connectswith the l i n l e t s i d e ` o f a pump 8 . T h e anthraquinone i s discharged by the pump 2 8 througha conduit 2 8 i n t o a c o o l e r 3 0 from which i t i sconducted t o container i i l l i n g means ( n o tshown), o r i s d e l i v e r e d through a valved conduit3 2 i n t o a storage v e s s e l 3 3 .As p r e v i o u s l y i n d i c a t e d t h e c o n d i t i o n s l n t h ed i s t i l l a t i o n column 2 5 a r e s o r e g u l a t e d t h a t a l lo f t h e r e a c t i o n p r o d u c t s , e x c e p t a n t h r a q u l n o n e ,are discharged as overhead vapors through avapor o u t l e t 4 I . In t h e system i l l u s t r a t e d herei n , t h i s i s a c c o m p l i s h e d by m a i n t a i n i n g t h e d i st i l l a t i o n column under p r e s s u r e i n the neighborhood c f ' 1 pounds per square inch a b s o l u t e , ands o regulating the amount o f anthraquinone r ec i r c u l a t e d through t h e d i s t i l l a t i o n column 2 5 ,by means o f heat exchangers 2 | and 2 2 , t h a t t h etemperatures o f t h e vapors i n the t o p o f t h e c o lumn 5 are i n the neighborhood o f 1 7 0 C . Theoverhead vapors i n t h e c o n d u i t 4 I pass throughh e a t exchanger 4 2 wherein they a r e p a r t i a l l yc o o l e d , and then through a c o n d u i t 4 3 w t o a par

I n addition to anthraquinone, the reac-

20

The reaction

30

35

40

4 .

50

5 5

60

65

7 0

7 5

3t i a l condenser I 4 wherein a p o r t i o n o f t h e unrea c t e d p h t h a l i c a n h y d r i d e i s c o n d e n s e d . t h e temp e r a t u r e o i t h e c o n d e n s e r 4 4 b e i n g maintaineda t about 1 5 0 C . i n o r d e r t o e i e c t s u b s t a n t i a lc o n d e n s a t i o n o f t h e p h t h a l i c a n h y d r i d e w i t h ou tcondensation o f t h e benzene and water v a p o r .The condenser may be constructed i n the s amemanner a s t h e r e a c t o r I 5 , t h a t i s , with an o u t e rand an i n n e r s h e l l , and t h e temperature t h e r e o fmay e r e g u l a t e d by c i r c u l a t i n g a s u i t a b l e c o o li n g medium through t h e s p a c e between t h e twos h e l l s (means not shown).T h e overhead vapors from condenser 4 4 areconducted through a n o u t l e t c o n d u i t 4 5 t o t h eupper s e c t i o n 4 6 o f a j e t c o n d e n s e r . t h e t emp e r a t u r e and p r e s s u r e b e i n g m a i n t a i n e d , t h e r ei n , f o r example, a t about 6 0 C . and about > 5pounds p e r s q u a r e i n c h a b s o l u t e ( 2 5 0 mms).r e s p e c t i v e l y . The'upper s e c t i o n 4 6 o f t h e j e tcondenser i s connected t o a lower s e c t i o n 4 8through a l e g 4 1 ; _ t h e temperature and p r e s s u r eo f t h e l o w e r s e c t i o n 4 8 a r e maintained a t about6 0 C . and 7 6 0 mms., r e s p e c t i v e l y , and benzeneand some phthalic anhydride are there cond e n s e d .

Fresh benzene i s i n t r o d u c e d i n t o t h e systemthrough a l i n e 5 | which connects with t h e i n l e ts i d e o f a pump 2 , which i n turn i s equipped witha n o u t l e t l i n e 5 3 . Fresh benzene f l o w s t o thet o p o f t h e j e t c o n d e n s e r 4 6 t h r o u g h t h e l i n e 5 3t o a conduit 5 4 . To those s k i l l e d i n the a r t ,i t w i l l be c l e a r t h a t t h e j e t o f benzene introducedi n t o the upper s e c t i o n o f the j e t condenser 4 6 ,through t h e c o n d u i t 5 4 , p r o v i d e s a p a r t i a l cond e n s a t i o n means w h e r e b y 4 p h t h a l i c a n h y d r i d efrom t h e c o n d u i t 4 5 i s condensed i n t h e s a i dlowe r section 4 8 .T h e upper s e c t i o n 4 6 o f the j e t condenser . i seq uipped with a n o u t l e t c o n d u i t 6 | f o r removingthe uncondensed material t h e r e i n . T h e uncondensed m a t e r i a l p a s s e s through t h e c o n d u i t5 | and a c o o l e r 6 2 , thence through a c o n d u i t B 3t o a d i s t i l l a t i o n column 6 4 which i s kept a t about3 8 C . and 5 pounds per square inch a b s o l u t e ,f o r example. Water o f r e a c t i o n i s removed fromt h e bottom o f _ t h e column 6 4 through an o u t l e tl i n e 6 5 , which connects with the i n l e t s i d e o f apump 6 6 . and a conduit 6 1 which connects witht h e o u t l e t s i d e o f t h e pump 6 . Benzene i s withdrawn from t h e column 6 4 through t h e l i n e 6 8which connects with c o n d u i t s 6 9 and 1 0 . A port i o n o f t h e > b e n z e n e i s taken through _ t h e cond u i t 6 9 t o the i n l e t s i d e o f a pump I which d i scharges i n t o a conduit 1 2 connecting with thebenzene i n l e t c o n n e c t i o n 5 4 on t h e j e t c o n d e n s e r .The t o p o f t h e d i s t i l l a t i o n column 6 4 i s showna s equipped with a n o u t l e t conduit 8 I throughwhich the reaction gases and some benzene, i nthe vapor . p h a s e i n t h e ' column 6 4 , p a s s t o acompressor l 2 . T h e compressor 8 2 has a n outl e t l i n e 8 3 which connects with a c o o l e r 8 4wherein the s a i d gases and benzene a r e c o o l e d ,whence they p a s s through a conduit 8 5 t o a d i st i l l a t i o n column 8 6 . The temperature and p r e ssure in the column 86 a r e maint ained at about'3 8 C . and 260 pounds per square inch a b s o l u t e ,f o r e x a m p l e , ' w h e r e u p o n b e n z e n e i s l i q u e f i e d andmay be drawn o i T through a c o n d u i t 8 1 whichc a r r i e s a pressure r e l e a s e v a l v e 8 8 . A s shown,the conduit 8 1 connects with t h e conduit 1 2 andprovides a means f o r returning the ` b e n z e n etaken from the column 8 6 t o the t o p s e c t i o n o ft h e j e t condenser 4 6 . T h e t c p o f t h e column 8 6i s equipped with a l i n e 8 9 carrying a p r e s s u r er e l e a s e v a l v e 9 0 , f o r removing g a s e s t h e r e f r o m .


5/8

Benzene may l s o be taken from the d i s t i l l e . - 4t i o n column t 4 through the l i n e @ t o e conduit

' 1 0 which connects with the i n l e t s i d e o f a pump9 | . Benzene i s discharged from the pump 2 |through a , conduit 92 into a conduit | 0 3 carrying benzene-together with some phthalic anhydride-taken from the lower s e c t i o n 5 8 o f thej e t c o n d e n s e r through an o u t l e t c o n n e c t i o n l i l lb y means o f a pump I 2 . Benzene, in the l i n e| 0 3 , i s d e l i v e r e d t o t h e c o n d u i t I I which c h a r g e st h e v a p o r i z i n g f u r n a c e , and part o r a l l o f thebenzene stream i n c o n d u i t | 0 3 m a y be by -passe dthrough a l i n e | 0 5 and the heat exchanger t 2 byr e g u l a t i o n o f t h e v a l v e I 0 @ f o r the purpose o fp r e h e a t i n g same. A l s o p a r t o r a l l o f t h e benzene stream may be by-passed through the r h e a texchanger 2 2 by r e g u l a t i o n o f v a l v e | 0 1 f o r p r eheating purposes.

Referring back t o t h e condenser t 9 which i smaintained a t about I 5 0 C . , a s i n d i c a t e d a b o v e ,u n r e a c t e d p h t h a l i c a n h y d r i d e c a r r i e d i n t h r o u g ht h e l i n e 4 3 i s here condensed and i s removedthrough a l i n e I I l i . P a r t of the unreactcdp h t h a l i c anhydride may be r e t u r n e d a s r e i i u x t othe d i s t i l l a t i o n column 2 5 through a l i n e I I I ,c o n n e c t i n g with the l i n e i I I and the i n l e t s i d eo f a pump H2 which i s equipped with ' a n outl e t c o n d u i t H3, the l a t t e r connecting with t h eupper p o r t i o n o f t h e column 2 5 . P h t h a l i c anhyd r i d e e n t e r s the column 2 5 a t about 1 7 0 C . , t h eme ans I I i i through I I 3 being heated a s by streamt r a c e r l i n e s (not shown) . The greater portiono f the unrea cted phthalic anhydride i s taken fromt h e l i n e I I through a l i n e I I t , connecting t h e r e uw i t h , t o the i n l e t o f a pump I I E . The pumpI I 5 d i s c h a r g e s p h t h a l i c a n h y d r i d e c o n d e n s a t ethrough a conduit I I 6 i n t o the p h t h a l i c anhyd r i d e f e e d l i n e I 2 . Fresh p h t h a l i c anhydride i sc h a r g e d t o t h e system from a p h t h a l i c a n h y d r i d emelter I I B , which i s equipped with a n i n l e t l i n eI I 9 through which f r e s h p h t h a l i c a n h y d r i d e i si n t r o d u c e d i n t o t h e s y s t e m , and i s a l s o equippedwith a heating element, as a s t e am c o il | 2 0 .Melted p h t h a l i c a n h y d r i d e i s taken from t h emelter I I 8 through a valved l i n e I 2 | which connects with the i n l e t s i d e o f a pump 2 2 which d i sc h a r g e s i n t o t h e p h t h a l i c anhydride f e e d l i n e I 2 .T h e r e i s a l s o provided a l i n e I I 1 , connecting witht h e l i n e I I 6 , w h i c h , by proper r e g u l a t i o n o f v a l v e s| 2 8 and I 2 4 ' may e used t o d e l i v e r part or a l l o fthe condensed phthalic anhydride into melter I I 8 .Phthalic anhydride i n the l i n e i 2 may, by properr e g u l a t i o n o f v a l v e | 2 5 , b e b y - p a s s e d t h r o u g hc o n d u i t | 2 6 and heat exchanger 2 | . Here a g a i n ,heat re moved from the r e a c t i o n mixture i n thel i n e 2 0 , i n p a s s i n g through t h e heat exchanger2 | , may s e r v e t o heat p h t h a l i c anhydride

> c a r r i e d i n the l i n ~ | 0 8 . I t w i l l be c l e a r t h a t themeans I I 4 through | 2 6 and I 2 a r e h e a t e d , a s bystream t r a c e r l i n e s ( n o t shown), i n order t omaintain a s t e a d y ' f i o w o f - p h t h a l i c a n h y d r i d etherein ' YI t w i l l be apparent t o those famliar with thea r t t h a t t h e d e s i r e d p r o p o r t i o n s o f r e a c t a n t sbenzene and p h t h a l i c anhydride-can be maint a i n e d throughout t h e c o n t i n u o us p r o c e s s by r e gu l a t i n g t h e amounts o f y f r e s h benzene andp h t h a l i c a n h y d r i d e , and o f r e c y c l e o r unreactedb e n z e n e and p h t h a l i c a n h y d r i d e , i n t r o d u c e d i n t othe r e a c t o r I 5 . The amount o f benzene andp h t h a l i c a n h y d r i d e consumed p e r p a s s - a n d ,t h e r e f o r e , t h e amount o f : f r e s h benzene andp h t h a l i c anhydride t o be added-can be d e t e r

1 0

1 5

20

25

30

3 5

40

45

50

80

6 5

7 0

mined after one pass through the s y s t em b y ob-t a i n i n g t h e amount o f anthraquinone formed 7 5

2 , 4 0 1 , 2 2 5and t h e amounts o f unreacted benzene andp h t h a l i c N a n h y d r i d e r e c o v e r e d .T o demonstrate t h e e i i l c a c y o f the p r o c e s s contemplated h e r e i n with an a p p a r a t u s o f t h e t y p ed e s c r i be d i n connection with Figure l , t h e f o llowing i l l u s t r a t i v e examples are provided b e l o w .

Example IP h t h a n c a n h y d r i d e ( 1 0 5 p a r t e b y w e i g h t ) a n dbenzene ( 8 2 0 p a r t s by w e i g h t ) y were v a p o r i z e d

and charged to a reaction chamber (as reactor2 2 i n Figure 1 ) c o n t a i n i n g 1 8 0 p a r t s by weight o fa s y n t h e t i c alumina s i l i c a t e ( a n a l y s i s : 7.3alumina, 92.7 s i l i c a ) , over a period o f 2 2 minu t e s . T h e r e a c t i o n chamber wa s maintained a t3 8 0 C . and the contact time wa s about 0 . 6 s e co n d . T h e r e a c t i o n mixture obtained from t h er e a c t i o n chamber was p r o c e s s e d a s i n d i c a t e d i nth e discussion of Figure 1 .A q u a n t i t y o f a n t h r a q u i n o n e - 7 ~ l p a r t s b yweight-Was o b t a i n e d . This r e p r e s e n t s a y i e l d

o f 7 9 o f t h e t h e o r e t i c a l based'on t h e p h t h a l i ca n h y d r i d e , 9 p a r t s by w e i g h t , consumed i n t h ep r o c e s s . S u b s t a n t i a l q u a n t i t i e s o f unreactedbenzene and unreacted p h t h a l i c anhydride werer e c o v e r e d f o r r e c y c l i n g .

Example I IP h t h a l i c a n h y d r i d e ( 9 9 p a r t s by w e i g h t ) andbenzene ( 8 2 0 p a r t s by w e i g h t ) were v a p o r i z e dand charged t o a r e a c t i o n chamber ( a s r e a c t o r 2 2i n Figure 1 ) c o n t a i n i n g 1 8 0 p a r t s by weight o f t h e

s y n t h e t i c alumina s i l i c a t e used i n Example , o v e ra p e r i o d o f 2 2 m i n u t e s . The alumina s i l i c a t efrom E x ample I w a s regenerated, before use i nt h i s example, by p a s s i n g a i r therethrough f o r o n ehour a t 510 CT h e reaction chamber wa s maintained a t about3 8 0 C . and the contact time wa s 0 . 6 s e c o n d .Anthraquinone ( 6 . 3 5 p a r t s by w e i g h t ) was o bt a i n e d ; a y i e l d o f 79.5 o f the t h e o r e t i c a l basedupon t h e q u a n t i t y o f p h t h a l i c a n h y d r i d e , 8 p a r t sby w e i g h t , consumed. Unre acted benzene andunreacted p h t h a l i c anhydride were r e c o v e r e d f o rrecycling.Anthraquinone obtained by our p r o c e s s h e r einabove d e s c r i b e d i s very p u r e . For example,0 . 3 5 gram of anthraquinone so obtained w a s r educed by z i n c and a s o l u t i o n o f sodium h y d r o x i d e .T h e s o l u t i o n wa s i i l t e r e d whereupon unreactedz i n c and i m p u r i t i e s were removed, and t h e lt r a t e w a s then o x i d i z e d b y a i r t o obtain pureanthraquinone. Th e q u a n t i t y o f pure anthraquinonc was 0.33i0.01 gram.

Example I I IMonochlorobenzene ( 9 0 p a r t s by W e i g h t ) andp h t h a l i c anhydride ( 1 0 p a r t s by w e i g h t ) w e r ev a p o r i z e d and then c o n t a c t e d with 1 5 p a r t s b yw e i g h t o f t h e s y n t h e t i c alumina s i l i c a t e d e s c r i b e di n Example I , a t a r a t e o f 4 . 5 p a r t s by weight

per minute. The reaction chamber ( a s i n E xample I ) was maintained a t about 4 2 5 C . and t h ec o n t a c t time was 0 . 6 s e c o n d . Four p a r t s byWeight o f c h l o r a n t h r a ' q u i n o n e were o b t a i n e d fromt h e r e a c t i o n p r o d u c t , Worke d up a s i n d i c a t e d h e r ei n a b o v e .I t i s t o be understood that the f o r e g o i n g examples o f p r o c e d u r e s a r e merely i l l u s t r a t i v e andthat the invention i n c l u d e s within i t s scope suchchanges and modications a s f a i r l y come w i t h i nt h e s p i r i t o f t h e appended c l a i m s .Th e p r e s e n t a p p l i c a t i o n i s a c o n t i n u a t i o n - i np a r t o f c o p e n d i n g a p p l i c a t i o n S e r i a l N o . 4 4 9 , 7 7 8 ,f l i e d J u l y 4 , 1 9 4 2 .


6/8

Weclaim: , l1 . The c a t a l y t i c p r o c e s s f o r t h e d i r e c t p r o d u c, 2 , 4 0 1 , 2 2 5

t i o n o f a n anthraquinone s e l e c t e d from the groupc o n s i s t i n g o f anthraquinone and a s u b s t i t u t e d .a n t h r a q u i n o n e , from a . compound (A) s e l e c t e dfrom he group consisting of `gen s u b s t i t u t e d b e n z e n e , and a compound)s e l e c t e d from t h e

b e n z e n e anda halo- ~group c o n s i s t i n g o f V phthalic ^

anhydride and . su b s t i t u t ed ,pht ha lic- anhyd rid e , At h e s a i d compounds ( A ) and ( B ) b e i n g i n t h e v a p o r p h a s e and b e i n g c h a r a c t e r i z e d b y s u b s t a nt i a l r e s i s t a n c e t o decomposition under the r e a ct i o n conditions hereinbelow d e f i n e d , which com-p r i s e s : forming a vapor mixture o f a compound( A ) and a compound ( B ) ; andcontacting t h es a i d vapor m i x t u r e , f o r a r e l a t i v e l y s h o r t c o n t a c ttime a t a n e l e v a t e d temperature above about3 5 0 C . , with a c a t a l y s t c o m p r i s i n g a n a s s o c i a t i o nof s i l i c a and an amphoteric metal o x i d e .2 . The c a t a l y t i c p r o c e s s f o r t h e d i r e c t p r o d u c - lt i o n o f an anthraquinone s e l e c t e d from t h e groupc o n s i s t i n g o f anthraquinone and a s u b s t i t u t e da n t h r a q u i n o n e , from a compound ( A ) s e l e c t e dfrom the group consisting of b enzene and a halo-gen s u b s t i t u t e d b e n z e n e , and a compound ( B )s e l e c t e d from t h e group 4 c o n s i s t i n g o f p h t h a l i c

1 6

20

2 5anhydride and a substituted phthalic anhydride,t h e s a i d compounds ( A ) and ( B ) b e i n g inthev a p o r p h a s e and b e i n g c h a r a c t e r i z e d by s u bs t a n t i a l r e s i s t a n c e t o d e c o m p o s i t i o n under t h e r ea c t i o n c o n d i t i o n s h e r e i n b e l o w d e i n e d , whichcomprises: forming a v apor mixture o f a - c o r npound ( A ) and a compound ( B ) : and c o n t a c t i n gthe s a i d vapor mixture, f o r a r e l a t i v e l y short cont a c t time a t a n e l e v a t e d temperature betweenabout 3 5 0 C . and about 5 5 0 C . , with a c a t a l y s ts e l e c t e d from t h e group c o n s i s t i n g o f a c t i va t e dc l a y s and s y n t h e t i c a l u m in a - s i l ic a , t h o r l a - s i l i c aand zirconia-silica catalysts.3 . I h e c a t a l y t i c p r o c e s s f o r t h e d i r e c t product i o n o f a n t h r a q u i n o n e . from b e n z e n e and p h t h a l i ca n h y d r i d e , y w h i c h c o m p r i s e s : forming a vaporm i x t u r e o f b e n z e n e and p h t h a l i c a n h y d r i d e ; andc o n t a c t i n g s a i d v a p o r m i x t u r e , f o r a r e l a t i v e l ys h o r t c o n t a c t time a t a n e l e v a t e d temperaturebetween about 3 5 0 C . and about 5 5 0 C . , with ac a t a l y s t c o m p r i s i n g an a s s o c i a t i o n o f s i l i c a a n d Va n amphoteric metal o x i d e .4 . The c a t a l y t i c p r o c e s s f o r t h e d i r e c t product i o n o f anthraquinone from benzene and p h t h a l i ca n h y d r i d e , which c o m p r i s e s : forming a v a p o r `m i x t u r e o f b e n z e n e and p h t h a l i c a n h y d r i d e ; andc o n t a c t i n g s a i d vapor m i x t u r e , f o r a r e l a t i v e l ys h o r t c o n t a c t time a t a n e l e v a t e d temperaturebet ween about 3 5 0 C . and about 5 5 0 C . , with ac a t a l y st s e l e c t e d from t h e group c o n s i s t i n g o fa c t i v a t e d c l a y s and s y n t h e t i c a l u m i n a - s i l i c a ,t h o r i a - s i l i c a , and i r c o n i a - s i l i c a ` c a t a l y s t s .5 . The c a t a l y t i c p r o c e s s f o r t h e d i r e c t product i o n o f a n t h r a q u i n o n e from b e n z e n e and p h t h a l i ca n h y d r i d e , which c o m p r i s e s : forming a vaporm i x t u r e o f b e n z e n e and p h t h a l i c a n h y d r i d e ; andc o n t a c t i n g s a i d v a p o r m i x t u r e , f o r w a c o n t a c t t i m efrom about 0 . 1 second t o about 1 second a t a ne l e v a t e d t e m p e r a t u r e between about 3 5 0 C . andabout 5 5 0 C . , with a c a t a l y st s e l e c t e d from t h e >

clays and synthetic ,roup c o n s i s t i n g o f a c t i v a t e da l u m i n a - s i l i c a , t h o r i a - s i l i c a _ a n d z i r c o n i a - s i l i c ac a t a l y s t s .6 . The c a t a l y t i c p r o c e s s f o r t h e d i r e c t product i o n o f anthraquinone from benzene and p h t h a l i ca n h y d r i d e , which c o m p r i s e s : forming a v a p o rmixture o f from about t h r e e t o about ten p a r t sby w e i g h t o f b e n z e n e and o n e p a r t by w e i g h t o f

40

5m i x t u r e , f o r a r e l a t i v e l y s h o r t c o n t a c t t i m e a ta n e l e v a t e d temperature between a b o u t 3 5 0 C .and about 5 5 0 C . , with a c a t a l y s t s e l e c t e d ~ f r o mthe group c o n s i s t i n g o f a c t i v a t e d c l a y s and s y n t h e t i c - a l u m i n a - s i l i c a , t h o r i a - s i l i c a and z i r c o n i a - _s i l i c a c a t a l y s t s .7 . I h e c a t a l y t i c p r o c e s s f o r t h e d i r e c t p r o d u c - ` _t i o n o f anthraquinone from benzene and p h t h a l i ca n h y d r i d e , which c o m p r i s e s : forming a vapor, m i x t u r e o f a b o u t e i g h t p a r t s b y w e i g h t o f b e n z e n eand one p a r t by w e i g h t o f > p h t h a l i c a n h y d r i d e ;and c o n t a c t i n g s a i d vapor m i x t u r e , f o r a c o n t a c tl t i m e o f a b o u t 0 . 6 ~ s e c o n d a t about 3 8 0 C . , with asynthetic alumina-silica c a t a l y s t .8 . The c a t a l y t i c p r o c e s s f o r t h e d i r e c t p r o d u c - vt i o n o f a h a l o g e n ' a t e d anthraquinone from a halog e n a t e d b e n z e n e and p h t h a l i c a n h y d r i d e , w h i c hc o m p r i s e s : forming a vapor mixture o f ` s a i d halog e n a t e d b e n z e n e and p h t h a l i c a n h y d r i d e ; andc o n t a c t i n g s a i d vapor mixture f o r a r e l a t i v e l y

s h o rt c o n t a c t t i m e a t a t e m p e r a t u r e betweenabout 3 5 0 C . and about 5 5 0 C . , with a c a t a l y s tcomprising a n a s s o c i a t i o n o f s i l i c a and an amphotericmetal oxide. -9 . The c a t a l y t i c p r o c e s s f o r t h e d i r e c t product i o n o f a chloroanthraquinone from monochlorobenzene and p h t h a l i c a n h y d r i d e , which comp r i s e s : forming a vapor mixture o f about nineparts by weight of 'monochlorobenzene and> onep a r t by w e i g h t o f p h t h a l i c a n h y d r i d e ; and cont a c t i n g s a i d vapor m i x t u r e , f o r a c o n t a c t timeo f about 0 . 6 second a t about 4 2 5 C . , with a synt h e t i c a l u m i n a - s i l i c a c a t a l y s t .1 0 . The c o n t i n u o u s c a t a l y t i c p r o c e s s f o r t h ed i r e c t p r o d u c t i o n o f a n ` a n t h r a q u i n o n e s e l e c t e dfrom t h e group c o n s i s t i n g o f a n t h r a q u i n o n e anda substitutedanthraquinone, from a compound( A ) s e l e c t e d from t h e group c o n s i s t i n g o f benzeneand a , halogen s u b s t i t u t e d benzene, and a compound ( B ) s e l e c t e d from t h e group c o n s i s t i n g o fp h t h a l i c a n h y d r i d e . and a s u b s t i t u t e d p h t h a l i canhydride, the s a i d compounds (A) and (B) be

45

50

55

0 0

0 5

i n g i n t h e vapor phase and b e i n g c h a r a c t e r i z e db y s u bs t a n t i a l r e s i s t a n c e t o d e c o m p o s i t i o n undert h e r e a c t i o n c o n d i t i o n s h e r e i n b e l o w d e f i n e d ,which c o m p r i s e s : forminga vapor mixture o f acompound ( A ) and o f a compound ( B ) : contact?i n g s a i d vapor m i x t u r e , f o r a r e l a t i v e l y s h o r t cont a c t time a t an e l e v a t e d temperature a b o v e about3 5 0 C . , with a c a t a l y s t comprising a n a s s o c i a t i o no f s i l i c a and an amphoteric meta l o x i d e , t h e r e b yforming s a i d a n t h r a q u i n o n e ; s e p a r a t i n g s a i d ant h r a q u i n o n e from t h e r e a c t i o n m i x t u r e formedi n t h e preceding o p e r a t i o n ; ` and r e c y c l i n g o v e rs a i d c a t a l y s t , i n t h e vapor phase under t h e a f o r es a i d r e a c t i o n c o n d i t i o n s , t h e s a i d r e a c t i o n mixt u r e , f r e e o f s a i d ' a n t h r a q u i n o n e , with a . q u a n t i t yo f f r e s h compound ( A ) and : f r e s h compound ( B )t o r e p l a c e compound ( A ) and compound ( B ) consumed i n t h e s a i d preceding o p e r a t i o n .

1 1 . The c o n t i n u o u s c a t a l y t i c p r o c e s s f o r t h ed i r e c t p r o d u c t i o n o f an a n t h r a q u i n o n e s e l e c t e dfrom t h e group c o n s i s t i n g o f anthraquinone anda s u b s t i t u t e d anthraquinone, from a compound( A ) _ s e l e c t e d from t h e group c o n s i s t i n g o f benzene and a halogen s u b s t i t u t e d benzene, and acompound (B) selected from the group con

7 0

p h t h a l i c a n h y d r i d e ; and c o n t a c t i n g s a i d v a p o r 7 5

s i s t i n g o f p h t h a l i c anhydride and a s u b s t i t u t e dp h t h a l i c a n h y d r i d e , t h e s a i d compounds ( A )and ( B ) b e i n g i n t h e vapor phase and b e i n gc h a r a c t e r i z e d b y s u b st a n t i a l r e s i s t a n c e t o d ec o m p o s i t i o n under t h e r e a c t i o n c o n d i t i o n s h e r ei n b e l o w d e f i n e d , which c o m p r i s e s : f o r m i n g avapor mixture of a compound (A) and of a compound ( B ) : c o n t a c t i n g s a i d vapor m i x t u r e , f o r a


7/8

6

direct production of

dride;

r e l a t i v e l y s h o rt c o n t a c t time a t ' a n e l e v a t e d temp e r a t u r e a b o v e a b o ut . 3 5 0 C . , W i t h ' l a c a t a l y s tcomprising a n a s s o c i a t i o n l o f s i l i c a and a n amp h o t e r i c m e t a lt h r a q u i n o n e ; s e p a r a t i n g s a i d a n t h r a q u i n o n e , unr e a c t e d compound ( A ) and u n r e a c t e d compound( B ) from the r e a c t i o n mixture formed i n thep r e c e d i n g o p e r a t i o n ; and r e c y c l i n g o v e r s a i dc a t a l y s t , i ns a i d * l r e a c t i o n c o n d i t i o n s , s a i d u n r e a c t e d compound ( A ) v a n d , s a i d u n r e a c t e d compound ( B )

o x i d e , thereby forming s a i d a n

t h e vapor phase under t h e a f o r e _

2 , 4 0 1 , 2 2 5s i l i c a , t h o r i a - s i l i c a and z i r c o n i a - s i l i c a c a t a l y s t s ,t h e r e b y f o r m i n g a n t h r a q u i n o n e ; s e p a r a t i n g s a i da n t h r a q u i n o n e , u n r e a c t e d b e n z e n e and u n r e a c t e dp h t h a l i c anhydride from t h e r e a c t i o n m i x t u r eformed i n t h e p r e c e d i n g o p e r a t i o n ; and r e c y c l i n gY over s a i d - c a t a l y s t , in the vapor phase under.thea f o r e s a i d r e a c t i o n c o n d i t i o n s , s a i d u n r e a c t e dbenzene and said unreacted phthalic anhydride

1 0 .w i t h a quantity o f fresh compound (A) and f r e s h compound ( B ) ' t o r e p l a c e compound ( A )and compound ( B ) consumed i n t h e s a i d p r e `ceding operation.1 2 . T h e continuous c a t a l y t i c p r o c e s s f o r thea n anthraquinone s e l e c t e dfrom the group c o n s i s t i n g o f anthraquinone anda s u b s t i t u t e d anthraquinone, from a compound(A) s e l e c t e d from t h e group c o n s i s t i n g ' o f benzene and a halogen substituted benzene, and acompound ( B ) s e l e c t e d from t h e group c o n s i s ti n g o f p h t h a l i c a n h y d r i d e and a . s u b s t i t u t e dphthalic anhydride, the s a i d compounds ( A ) and( B ) b e i n g i n t h e vapor phase and b e i n g chara c t e r i z e d by s u b s t a n t i a l r e s i s t a n c e t o decompos i t i o n under t h e r e a c t i o n c o n d i t i o n s h e r e i n b elow d e f i n e d , which c o m p r i s e s : forming a vapormixture o f a compound ( A ) and o f a compound(B); contacting s a i d vapor mixture, f o r a r e l at i v e l y s h o r t c o n t a c t time a t an e l e v a t e d temp e r a t u r e between about 3 5 0 C . and about 5 5 0 C . , with a c a t a l y s t s e l e c t e d from the group c o n - rs i s t i n g o f a c t i v a t e d c l a y s and s y n t h e t i c s i l i c aa l u m i n a , s i l i c a - t h o r i a and s i l i c a - z i r c o n i a c a t al y s t s , t h e r e b y f o r m i n g s a i d a n t h r a q u i n o n e ;s e p a r a t i n g s a i d a n t h r a q u i n o n e , u n r e a c t e d compound ( A ) and u n r e a c t e d compound ( B ) fromt h e r e a c t i o n mixture formed i n t h e p r e c e d i n go p e r a t i o n ; and r e c y c l i n g o v e r s a i d c a t a l y s t , i nt h e vaporphase under t h e a f o r e s a i d r e a c t i o nc o n d i t i o n s , Y s a i d u n r e a c t e d compound ( A ) ands a i d u n r e a c t e d compound ( B ) , w i t h v a q u a n t i t yo f f r e s h compound ( A ) and f r e s h compound ( B )t o r e p l a c e compound (A) and compound ( B )consumed i n t h e s a i d p r e c e d i n g o p e r a t i o n ' .

1 3 . The continous p r o c e s s f o r t h e d i r e c t prod u c t i o n o f anthraquinone from benzene a n d lp h t h a l i c a n h y d r i d e , w h i c h c o m p r i s e s : f o r m i n ga vapor mixture o f benzene and p h t h a l i c anhyd r i d e ; contacting s a i d vapor mixture, f o r a r e l at i v e l y s h o rt c o n t a c t time a t a n e l e v a t e d t e r np e r a t u r e between about 3 5 0 C . and about550C . , with a c a t a l y s t comprising r a n a s s o c i a t i o n o fs i l i c a and an amphoteric metal o x i d e , t h e r e b yf o r m i n g a n t h r a q u i n o n e ; s e p a r a t i n g s a i d a n t h r oq u i n o n e , u n r e a c t e d b e n z e n e and u n r e a c t e dp h t h a l i c a n h y d r i d e from t h e r e a c t i o n m i x t u r ef o r m e d i n t h e p r e c e d i n g o p e r a t i o n ; and r e c y c l i n gover s a i d c a t a l y s t , i n the vapor phase under thea f o r e s a i d r e a c t i o n c o n d i t i o n s , s a i d u n r e a c t e db e n z e n e and s a i d u n r e a c t e d p h t h a l i c a n h y d r i d ewith a q u a n t i t y o f f r e s h benzene and f r e s hp h t h a l i c anhydride t o r e p l a c e b e n z e n e andp h t h a l i c anhydride consumed i n t h e s a i d p r eceding operation.1 4 . T h e continuous p r o c e s s f o r the d i r e c t prod u c t i o n o f anthraquinone from benzene andp h t h a l i c a n h y d r i d e , which c o m p r i s e s : f o r m i n g av a p o r m i x t u r e o f benzene and p h t h a l i c anhyc o n t a c t i n g y s a i d vapor m i x t u r e , f o r ar e l a t i v e l y s h o r t c o n t a c t time a t a n e l e v a t e d temp e r a t u r e between a b o u t 3 5 0 C . and a b o u t 5 5 0 C . , with a c a t a l y s t s e l e c t e d from the group cons i s t i n g o f a c t i va t e d c l a y s and s y n t h e t i c a l u m i n a

1 5

20

25

3 0

35

40

4 5

50

55

60

7 0

7 6

y pr e c e d i n g o pe r a t i o n ;

with a q u a n t i t y o f f r e s h benzene and f r e s hp h t h a l i c a n h y d r i d e t o r e p l a c e b e n z e n e andp h t h a l i c a n h y d r i d e consumed i n t h e s a i d p r e c e di n g o p e r a t i o n ,l 5 . T h e continuous p r o c e s s f o r t h e d i r e c t p r oduction o f anthraquinone from benzene andp h t h a l i c a n h y d r i d e , which c o m p r i s e s : forming avapor mixture o f benzene and p h t h a l i c anhyd r i d e ; contacting s a i d vapor mixture f o r a cont a c t timefrom about 0 . 1 second t o about l s e cond a t a n e l e v a t e d temperature be tween about3 5 0 C . and about 5 5 0 C . , with a c a t a l y s t s el e c t e d from t h e group c o n s i s t i n g o f a c t i v a t e dc l a y s and s y n t h e t i c a l u m i n a - s i l i c a , t h o r i a - s i l i c aand z i r c o n i a s i l i c ' a c a t a l y s t s , thereby forming a nt h r a q u l n o n e ; > s e p a r a t i n g s a i d a n t h r a q u i n o n e , unr e a c t e d benzene and u n r e a c t e d p h t h a l i c anhyd r i d e from the r e a c t i o n mixture formed i n theand r e c y c l i n g over s a i d c a t a l y s t , i n the vapor phase under the a f o r e s a i d r ea c t i o n c o n d i t i o n s , s a i d unreacted benzeen ands a i d unreacted p h t h a l i c anhydride with a quant i t y o f f r e s h benzeen and f r e s h p h t h a l i c anhyd r i d e t o r e p l a c e benzene and p h t h a l i c a n h y d r i d econsumed i n t h e s a i d p r e c e d i n g o p e r a t i o n .1 6 . T h e continuous process f o r the d i r e c t production o f anthraquinone from benzene andp h t h a l i c a n h y d r i d e , which c o m p r i s e s : f o r m i n g avapor mixture o f from about three t o about tenp a r t s by Weight o f benzene and about one p a r tby w e i g h t o f p h t h a l i c a n h y d r i d e ; c o n t a c t i n g s a i dvapor mixture, f o r a r e l a t i v e l y short contact timea t a n elevated temperature between about 3 5 0 C . and about 5 5 0 C . , with a c a t a l y s t s e l e c t e dfrom the'group c o n s i s t i n g o f a c t i v a t e d c l a y s ands y n t h e t i c a l u m i n a - s i l i c a , t h o r i a - s il i c a and z i rc o n i a - s i l i c a c a t a l y s t s , t h e r e b y f o r m i n g a n t h r aq u i n o n e ; s e p a r a t i n g s a i d a n t h r a q u i n o n e , unrea c t e d benzene and unreacted p h t h a l i c a n h y d r i d efrom the r e a c t i o n mixture formed i n the prec e d i n g o p e r a t i o n ; and r e c y c l i n g o v e r s a i d c a t al y s t , i n t h e vapor phase under t h e a f o r e s a i d . r e a ct i o n c o n d i t i o n s , s a i d unreacted benzene and s a i dunreacted p h t h a l i c anhydride with a q u a n t i t y o ff r e s h benzene and f r e s h p h t h a l i c anhydride t or e p l a c e benzene and p h t h a l i c l anhydride consumed i n t h e s a i d p r e c e d i n g o p e r a t i o n .1 7 . T h e continuous p r o c e s s f o r the d i r e c t production o f anthraquinone from benzene andp h t h a l i c a n h y d r i d e , which c o m p r i s e s : forming av a p o r m i x t u r e o f a b o u t e i g h t p a r t s by W e i g h to f benzene and one p a r t by weight o f p h t h a l i ca n h y d r i d e ; c o n t a c t i n g s a i d vapor m i x t u r e , f o r acontact time o f about 0 . 6 second a t about 3 8 0 C . , with a s y n t h e t i c a l u m i n a - s i l i c a c a t a l y s t ,t h e r e b y f o r m i n g a n t h r a q u i n o n e ; s e p a r a t i n g s a i danthraquinone, unreacted benzene and unrea c t e d p h t h a l i c anhydride from t h e r e a c t i o n mixture formed in the preceding operation; and r e -c y c l i n g over s a i d c a t a l y s t , i n the vapor phaseunder the a f o r e s a i d r e a c t i o n - c on d i t i o n s , s a i d unr e a c t e d benzene and s a i d unreacted p h t h a l i c anhydride with a quantity o f f r e s h benzene andf r e s h p h t h a l i c a n h y d r i d e t o r e p l a c e b e n z e n e andp h t h a l i c a n h y d r i d e consumed i n t h e s a i d p r eceding operation. ~1 8 . The c a t a l y t i c p r o c e s s f o r t h e d i r e c t p r o d u c


8/8

4 w h i c h c o m p r i s e s :

2 , 4 0 1 , 2 2 5t i o n o f a h a l o g e ' n a t e d anthraquinone from ah a l o g e n a t e d b e n z e n e and p h t h a l i c a n h y d r i d e ,

forming a vapor mixture o fs a i d h a l o g e n a t e d b e n z e n e and p h t h a l i c anhyd r i d e : c o n t a c t i n g s a i d v a p o r m i x t u r e , f o r a r e l at i v e l y s h a r i ; c o n t a c t t i m e a t a temperature between about 3 5 0 C . and about 5 5 0 C . , with ac a t a l y s t c o m p r i s i n g a n a s s o c i a t i o n o f s i l i c a andan a m p h o t e r i c m e t a l o x i d e ; t h e r e b y f o r m i n g s a i dh a l og e n a t e d a n t h r a q u in o n e ; s e p a r a t i n g s _ a i dh a l o g e n a t e d a n t h ra q u i n o n e , u n r e a c t e d h a l og e n a t e d b e n z e n e and u n r e a c t e d p h t h a l i c anhyd r i d e ` f r om t h e r e a c t i o n m i x t u r e formed i n t h ep r e c e d i n g o p e r a t i o n ; and e c y c l i n g o v e r . s a i dc a t a l y s t , i n t h e vapor phase under t h e a f o r e s a i dr e a c t i o n c o n d i t i o n s , s a i d u n r e a c t e d h a l o g e n a t e db e n z e n e and s a i d u n r e a c t e d p h t h a l i c a n h y d r i d ew i t h a q u a n t i t y o f f r e s h h a l o g e n a t e d b e n z e n eand fresh phthalic anhydride t o replace halo-genated benzene and p h t h a l i c anhydride consumed i n t h e s a i d p r e c e d i n g o p e r a t i o n .1 9 . T h e c a t a l y t i c p r o c e s s f o r the d i r e c t production o f a chloroanthraquinone , f r o m monoc h l o r o b e n z e n e and p h t h a l i c a n h y d r i d e , w h i c hc o m p r i s e s : forming a vapor mixture o f aboutn i n e p a r t s by w e i g h t o f monochlorobenzene ando n e p a r t by w e i g h t o f p h t h a l i c a n h y d r i d e ; oon

20

`prising an associationteric metal oxide.

7t a c t i n g s a i d vapormixture, f o r a c o n t a c t t i m e o fabout 0 . 6 second a t about 4 2 5 C . , with a synt h e t i c a l u m i n a - s u i c a c a t a l y s t , t h e r e b y f o r m i n gs a i d c h l o r o a n t h r a q u i n o n e ; s e p a r a t i n g s a i d c h l or o a n t h r a q u i n o n e , u n r e a c t e d m o n o c h l o r o b e n z e n eand unreacted p h t h a l i c anhydride from the r ea c t i o n m i x t u r e formed i n t h e p r e c e d i n g o p e r at i o n ; and r e c y c l i n g o v e r s a i d c a t a l y s t , i n t h e vaporp h a s e u n d e r t h e a f o r e s a i d r e a c t i o n c o n d i t i o n s ,s a i d unreacted monochlorobenzene and s a i d unr e a c t e d p h t h a l i c a n h y d r i d e w i t h a q u a n t i t y o f 4f r e s h monochlorobenzene and f r e s h p h t h a l i c anh y d r i d e t o r e p l a c e monochlorobenzene andp h t h a l i c a n h y d r i d e . consumed i n t h e s a i d p r e c e ding operation. ,

2 0 . The c a t a l y t i c p r o c e s s f o r t h e d i r e c t product i o n o f a n t h r a q u l n o n e from benzene and p h t h a l i ca n h y d r i d e , which c o m p r i s e s : forming a vaporm i x t u r e o 1 ' b e n z e n e and p h t h a l i c a n h y d r i d e ; andc o n t a c t i n g s a i d v a p o r m i x t u r e , f o r a r e l a t i v e l ys h o r t c o n t a c t t i m e a t an e l e v a t e d t e m p e r a - t u r eand under reduced p r e s s u r e , with a c a t a l y s t como 1 s i l i c a and an mpho

PHHJI P D . C A ES A R .A L E X A N D E R N ; SACH A N E N .

anthraquinone production

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