The Design and Operation of Fluidized-Catalyst P h t h a l i c Anhydride ? l a n t s .

E. L. Riley

C ~ t e d Coke and Chemicals Coapany, Limited, Botherwood L a b o r a t o r i e s , S h e f f i e l d , 1. 3

The c a t a l y t i c oxLdation of naphthalene t o FhthdLic anhydride by atmospheric oxygen i s a r e a c t i o n admirably s u i t e d f o r a f l u i d i z e d r e a c t o r . W l y attempts t o produce p h t h a l i c anhydride oc a commercial s c a l e by this means ran i n t o This was because of mistzkes i n design and a l a c k of serious difficu1ti.s. a p p r e c i a t i o n of may of t h e f a c t o r s involved. It is proposed i n t h i s paper t o describe how t h e s e d i f f i c u l t i e s have been overcome aod a l s o to i n d i c a t e t h e e s s e n t i a l f e a t u r e s i n design ana o p e r a t i o n f o r t h e t r o u b l e - f r e e rcanufacturn of p h t h a l i c an!!ydride by t h i s method.
Fluidized-bed
V.

Fixed-bed.

P h t h a l i c anhydride h a s been manufactured by t h e o x i d a t i o n of naphthalene During t h i s time considerable i n fixed-bed r e a c t o r s for more t h a n f o r t y years. Xevertheless, i t i s widely design and o p e r a t i o n a l experience h a s been accumulated. known t h a t such r e a c t o r s have i n h e r e n t d e f e c t s wliich make impossible t h e d e s i r e d c o n t r o l of r e a c t i o n conditions. , T i e advent o f tine fluidized-bed r e a c t o r has made p o s s i b l e not only a much c l o s e r approach t o t h e s e i d e a l r e a c t i o n c o n d i t i o n s but a l s o s e v e r a l o t h e r important advantages which favourably i n f l u e n c e t h e economics of t h e process. Fig. 1. i s a flow diagram of a f l u i d i z e d - c a t a l y s t p h t h a l i c anhydride p l a n t and below a r e l i s t e d some of t h e important advantages gained by this method of manufacture. ?ne presence of f i n e l y divided c a t a l y s t i n tine r e a c t o r G r e a t e r Safety. p r e v e n t s explosions and so permits o p e r a t i o n w e l l i n s i d e t h e explosive range of air:naphthalene r a t i o s . Hore p r e c i s e c o n t r o l of r e a c t i o n conditions. The h i g h thermal conductivity and good heat-exchange c h a r a c t e r i s t i c s of this f l u i d i z e d - c a t a l y s t bed permiss an e x a c t c o n t r o l of r e a c t i o n temperature without t h e formation of hot spots. Temperatures varying o n l y by one or two OF. c a n be h e l d throughout a f l u i d i z e d P r e s s u r e , temperature, air: bed containing up t o 30 t o n s of c a t a l y s t or more. naphthalene r a t i o and c o n t a c t t i n e can each be v a r i e d , independently and quickly, so p e r m i t t i n g a r a p i d and exact adjustment of o p e r a t i n g c o n d i t i o n s t o meet p a r t i c u l a r requirements.
A s u b s t a n t i a l l y l o w e r air: Nore e f f i c i e n t condensation of p h t h a l i c anhydride. naphthalene r a t i o makes p o s s i b l e t h e more e f f i c i e n t condensation of t h e r e a c t i o n product because o f i t s g r e a t e r p a r t i a l p r e s s u r e i n t h e product gases. Operating t h e r e a c t o r a t i n c r e a s e d p r e s s u r e permits t h e condensation of P h o r m o r e o f t h e product d i r e c t l y as l i q u i d , t h e balance being condensed as s o l i d i n switch condensers. The l o d e r c o n c e n t r a t i o n of oxygen i n t n e product gases, compared with that o b t a i n i n g i n fixed-bed p l a n t s , reduces t h e hazard of f i r e and explosion down stream from t h e r e a c t o r .

h
A

Lipuid naphthalene mixture of air and evaporator. This l i q u i d naphthalene

Fixed-bed phthakic anhydride r e a c t o r s a r e fed with a feed. naphthalene vapour involving t h e use of a s e p a r a t e can g i v e trouble. jlith a fluidized-catalyst reactor i s pumped-directly i n t o t h e reactor.

C a t a l y s t charging. The t e d i o u s operation of charging c a t a l y s t p e l l e t s i n t o t h e tubes of t h e f i x e d bed r e a c t o r is avoided. O t h e fluidized-bed p l a n t n c a t a l y s t can be moved pneumatically from t h e r e a c t o r t o t h e c a t a l y s t s t o r a g e v e s s e l or i n t h e o p p o s i t e d i r e c t i o n , even w h i l s t t h e p l a n t is operating.

?he o p e r a t i o n o f f l u i d i z e d - c a t a l y s t r e a c t o r s Operation a t i n c r e a s e d a r e s s u r e . a t increased p r e s s u r e (1 t o 2 a t m . gauge) permits a s u b s t a n t i a l i n c r e a s e i n t h e o u t p u t of a p a r t i c u l a r u n i t compared wLth i t s c a p a c i t y a t atmospheric pressure. Air compression c o s t m s be balanced a g a i n s t h i g h e r throughput i n o r d e r t o ut The removal of t h e a d d i t i o n a l heat determine t h e optimum o p e r a t i n g pressure. l i b e r a t e d as throughput is increased p r e s e n t s no s e r i o u s design problems.
The p r e c i s e c o n t r o l of r e a c t i o n c o n d i t i o n s i n a Jiqn y x i t y product. f l u i d i z e d c a t a l y s t r e a c t o r r e s u l t s i n t h e formation of a c-ude product of high purity. The r e d i s t i l l a t i o n process i s thereby considerably s i m p l i f i e d , and a f i n a l sales product of a high s t a n d a r d o f p u r i t y is obtained. Table ?. givee t h e r e s u l t s of t h e a n a l y s e s o f a number of c o m e r c i d l samples of p h t h a l i c anhydride all taken independently and analysed blind. The h i g h e r q u a l i t y of t h e samples from t h e f l u i d i z e d - c a t a l y s t p l a n t s is apparent.

R. Landau and E H q e r (7) have given a c r i t i c a l , h i s t o r i c a l review of . Tney mention t h e d i f f i c u l t i e s t h e development of p h t h a l i c anhydride technology. t h a t have troubled t h e p i o n e e r s of t h e f l u i d i z e d c a t a l y s t process. How t h e s e d i f f i c u l t i e s have.Seen overcome is described below.
Condensation TEe e a r l y fixed-bed p h t h a l i c auhydride p l a n z s were s m a l l and operated w i t h high air:naphthalene r a t i o s . The product, w a s condensed i n the so-called barns o r They served t o M y boxes, which were l a r g e v e s s e l s , u s u a l l y s e v e r a l i n s e r i e s . slow down t h e g a s v e l o c i t y and wire n e t i n t h e boxes provided a d d i t i o c a l s u r f a c e f o r The natural t h e condensation of t h e needle-shaped c r y s t a l s of p h t h a l i c anhydride. cooling o f the boxes w a s u s u a l P j s u f f i c i e n t f o r e f f i c i e n t condensation. With l a r g e production {:nits, however, such b a r n s a r e i n p r a c t i c a b l e on t h e grounds of c o s t , I n modern p l a n t s they have danger and d i f f i c u l t i e s i n handling t h e s o l i d product. During been replaced by t u b u l a r h e a t exchmgers operated as switch cordensers. condensation t h e t u b e s a r e cooled by water or o i l a t 35 t o k 0 C . Lower temperatures would promote t h e condensation of excessive axounts of water vapour *.6th t h e For melting o u t , t h e cold water concomitant formacion of p h t h a l i c aqd maleic acids. i s replaced by high p r e s s u r e stem and t h e c o l d o i l by hot o i l . A cemperature high enough t o dehydrate q h t i a l i c a c i d is e s s e n t i a l otherwise i t ell accumulate i n s i a e t n e cordenser r e d u c h g i t s e f f i c i e n c y and c a p a c i t y and f i n a l l y causing blockages. D i f f e r e n t t y p e s of t u b u l a r switch condensers have Seen d e s c r i b e d (3, 12); Besides simple some a r e t o o corrplicated t o be 3 r a c t i c a b l e i n large production u n i t s . heat-exchange c o n s i d e r a c i o n s , o t h e r f a c t o r s a r e involved i n t h e design of e f f i c i e n t switch condensers. e.g., (1) Spare capacity i s necessary t o permit p e r i o d i c cleaning of t h e t u b e burrdles without i n t e r r u p t i n g production. ( 2 ) The c a ? a c i t y of t h e i n d i v i d u a l condensers must be such t h a t t h e switch o p r a t i o n i s r e l a t i v e l j r infzequent, otherwise t h e r e would be an excessive thermal load due t o t h e r e l a t i v e l y high heat caFacity of the condensers which could be even more t h a n t h e h e a t r e q u i r e d t o melt t h e p h t h a l i c anhydride. (3) The c o n s t r u c t i o n o f t h e condensers should b e such that

207.

208.

Ihe o i l system for cooling and melting is t h e h e a t capacity i s kept t o a riieumm. t h e r e f o r e p r e f e r r e d r a t h e r t h a t h e w a t e r h g h -pressure s t e m system. (4) , E e design s h o d 2 b? such as t o ~ n i i x i z e e l i n i n a t e f - k e and es$.osion hazards. or This car. Se ackieved by the u s e of a c l o s e l y packed g i l l e d tabe b u d l e . (5) It is not s u f f i c i e n t i n csndecser.s OS this type merely t o pro-cLde adequate cooling surface. Trovision z u s t also be nade f o r e n s u r i r g t h a t t h e product g a s e s have t h e opportunity of c o n t a c t i n g yeformed p h t h a l i c anhydride c r y s t a l SL-faces, otherwise even mLth more khan adequate c o o l i q , s o l i d d e p o s i t i o n Will not n e c e s s a r i l y occur. Fig. 2. shows The tube w a s cooled by a 6 ft. length of finned t u b e enclosed i n g l a s s pipe-line. Ar s a t u r a t e d srith p h t h a l i c anhydride vapour at 14O0C i _sassing water throush it. 'i : = passed downwards through t h e annulus between t h e finned and t i e g l a s s tubes. S o l i d Dhthalic anhydride w a s deposited on grefo,%ed c r y s t a l s r a t h e r Y?an on t h e Bapocr super-saturated k i t h p h t h a l i c c o o l e r base Fortions of t h e l i m e d tube. &ydri.de w i l i leave t h e t u b e i f t i e speed of t h e g a s exceeds a low minimum value. Fig. 3. shows d i a g r a m t i c a l l y a switch condenser which meets t h e s e It c o n s i s t s of a r e l a t i v e l y l i g h t gauge s t e e l box packed requirements ( I & ,1 ) 5. During t h e condensation with rows of v e r t i c a l g i l l e d tubes connected t o manifolds. p a r t of tk-e c@e, c o l d o i l (Q0C) i s aassed t'mough t h e s e tubes. The product gases from tine f l u i d i z e d r e a c t o r e n t e r t h e condesser and a t f i r s t p a s s at r e l a t i v e i y low v e l o c i t y , more o r l e s s s t r a i g L t through t i e hs Xassive, s o l i d & of g i l l e d tubes. p h t h a l i c anhydride condenses on t h e f i r s t banks w'hich become blocked and an i n c r e a s i n g anount OS t h e product g m passes through t h e gaps a t t h e ends of t h e banks of g i l l e d ,%?lese gags a t o p p o s i t e ends of adjacent r o w s prevent excessive b u i l d up of tubes. back s r e s s ' a e b e f o r e a s u b s t z n t i a l q u a n t i t y of p h t h a l i c anhydride is condensed. .Tne i n c r e a s e < gas v e l o c i t y as t h e gas flows p a r a l l e l t o t h e rows improves heat exchange and &ves good c o n t a c t i n g of tKe p r o d m t va-pours with preformed p h t h a l i c As t h e product gases progress through t h e condenser the ar&.Ydri.de c q s t a l s . c o n c e n t r a t i o n of g h t h a l i c azAg&5.de decreases and condensation occurs on t h e l a t e r banks of g i l l e d t c b e s in t h e fori: of long needles. Tiie c l o s e >aclung of tize tubes no doubt a l s o has a f i l t e r i n g a c t i o n OE a: g a s borce p a r t i c l e s of p h t h a l i c arhydride. i: At 3 predeterrzlred t i m e a cozianser is t k e n oi'f streais,and t h e cold oil %e p l i s t a l i c '2rCiydridt m t i t s uld i s r-unb storage. The hot o i l r e p l a c e d 55- iict. , is Lkl a switched 5ack t o c o 1 d ; a f t e r a Feriod f o r cooling t h e empty condenser is ; is z s s e r t i a l t o aae a tnermally s t a b l e o i l for this purpose. t a g a i n put 3n s t r e m . The S n i t e d Coke and Cinexical Co;o-,ar-g's p l a n t o p e r a t e s on e i g n t of t h e s e s w i t c h condensers t o g e t h e r u i t i a n i n t h stand-by for p e r i o d i c s p e c i a l cleaning: A t oormal tkioughput a s?quence of a i x condensing m d two ffieltizg I s employed. Tine c a p a c i t y of the boxes i s such t h a t switching is c a r r i e d o u t a t long i n t e r v a l s and Analyses have l i t t l e o r no advantage itould > e gained from automatic operation. shown t h a t a small amount of s l i p t&ies p l a c e aF the commencement of t h e condensation i.e., ,,;her; t i e tube s u r f a c e s a r e clean and cool.$ng must be at its b e s t , b u t when t h e r e I s l i t t l e or no s o l i d p h t h a l i c anhydride t o promote condensation. Long i n t e r v a l s betvureen switching reduces t h e loss by s l i p t o a very l o w v d u e . These c o n a e r s e r s have been t e s t e d f o r long p e r i o d s v i t h air:naphthalene r a t i o s as high as j0:l and t h e r e s u l t s o j t a i n e d i n d i c a t e t h a t they could be used advantageously with fixed-bed r e a c t o r s . F l d i z e d - c a t a l y s t r e a c t o r s , o p e r a t i n g with low air:naphthalene r a t i o s and a t i n c r e a s e d p r e s s u r e can advantageously condense an a p p r e c i a b l e proportion of tine product d i r e c t l y a s l i q a i d ( 2 ) and so decrease the t h e m a l l o a d on t h e switch condensers.

7 .

r1ltration

209.

I n o28er t o ?revent contamination of t h e 3rodnct a d loss of an exgensl?ve caza1;sz i t i s e s s e n t i a l i n a fluidized-bed p h t h a l i c anhydride p l a n t n$'i r ~ s l y t o filter the p r o l u c t gsses. ----cie Z z l y design z r o s o s a l s (4) suzgested tine use of cyclones. ~n z k e ~ ' i r s t 2roduction a n i t , t h e S h e r u i n >IilLiams Con;ar,y (5) Le devslcpeci $fie Y s of sorous ceramic f i l t e r s for t h e coE2lete e l i m i s a t i o n of t h e = ~ - -&st at hi;h & a v , - e - s - . . b-..,>--A:Lre. 2 o r o u s s t 2 2 n l e s s steel f i l t t r s hsve been u s e d i n S i l o t _clanks. ?ne i'nited Coke Jlid Chemicals i o n p m y (73) have d e v e h o e d a fibre-glass f i l t e r . It c o n s i s t s e s s e n t i a l l y of a s e r f o r a t e d s t e e l c:rlin&er ( 3 ~) .h a v i n g a s p i g o t a t each er,d. + The uzper s p i g o t i s threaded and eerves t o concect t h e f i l t e r t o a c o l l e c t o r box. Tine l o v e r s p i g o t i s closed ard s e r v e s t o orotecc the f i l t e r . i t also a c t s a s a journal w h i l s t t h e f i l t e r is being wrapped. 7 .- i . wrapsing, ::hich ' i s done on a simple mac?dne, c o n s i s t s of a l t e r n a t i n g lajrers of coztinuous-filaxtzt g l a s s c l o t h and silper-fine f i b r e - g l a s s mat. The f i r s t 5 l a y e r s ( 5 c i o t h a n d 2 mat; a r e h e l d in p o s i t i o n bj. an open siound h e l i x o f g l a s s t q e . .. .w.oz:?er similar s e r i e s of c l o t k , super-fine n a t , c l o t h and t a o e , is ad2ed follo.;ied Sj- an overlspping s g i r a l wrap of & l a s s tape and t h e whole bound f i r m l y bu; not t o o tightly w i t h j u b i l e e o r similar metal c l i p s a t 18Ir i n t e r v a l s . Tne overlapping ends sf t h e glass c l o t h a r e securot in grooves at t h e two ends of t h e f i l t e r tube, by nieans of f;bre-slass cord. T h i s i s an a d d i t i o n a l precaution t o prevent end leakage. Four se?ma:e c o l l e c t e r boxes a r e used, each c a r r y i n g s e v e r a l of t h e s e f i b r e - g i a s s f i l t e r s . 3 y mea25 of a y o c e s s c o n t r o l l e r each b2ank of f i l t e r s can be blown back in t u r n t o 2stach f i l t e r cdce from t h e o u t e r sL-face. Nore t h a n t e n y e a r s of o ? e r a t i o n a l s : q e r i e s c e has snoiln t h a t t n e s e f i l t e r s a r e a r e l i a b l e means of o b t a i n i n g 10@6 f i l t r a t i o n of c a t a l y s t d u s t from t h e product gases at a temperature of about w O C . They have advantages over porous c e r a i c f i l t e r s i n t h a t they &-e not b r i t t l e , they can be quickly azd r e l a t i v e l y cheaply re-.wra;;ped and i f necessary, can be made t o On blow-back, tine s l i g h t "give" i n t h e f i b r e - g l a s s operate a t low back pressure. wrasping tends t o cause b e t t e r removal of t h e accumulated f i l t e r cake. The back 2ressiirz a c r o s s the f i l t e r s depends, of course, on t i e s u r f a c e a r e a of t h e f i l t e r a d t h e volume of gas ?assing. It i s custonary t o olserate f l u i d i z e d - c a t a l x s t pnt'naEc a & y d r i d e p l z n t s u n d e r p r e s s u r e so a f i l t e r > r e s s a - e d r o p of k t o 6 ltr. p.s.i. o r mora can be accomodated. F i l t e r candles up t o 12 f t . i n l e n g t h have been c x c e s s f u l l y used. Z q e r i m e n t s have a l s o been c a r r i e d out i n which t h e s e f i l t e r s have been o p i r a t e d a t 10 t o 20 ins. w.g. back p r e s s u r e for 3rolonged periods at 5 0 0 O C .
&

ri,

\>

is "ne s o s i t i o n i n g of t h e f i l t r a t i o n u n i t i n t h e ~ l a n t i q o r t a n t and is discussed below.

The Fluidized-bed Catadyst. The :!iysical and c h e c i c a l natu-e of t h e c a t a l y s t is o f g r e a t imFortance f o r t h e trouble-free operation of a l a r g e fiuidized-bed p h t h a l i c anhgdride plant. 2 o t only nuat i t have high and s p e c i f i c r e a c t i v i t y but a l s o good f l u The c a t a l y s t s used i n t h e :high a t t r i t i o n r e s i s t a n c e and l o n z l i f e . this net;; teciiiiioue vere formulated on the'grounds of t h e i r c a t d y t i c a c t i v i t y v i t h ii;*- o r EO a t t e n t i o n t o t h e i r f l u i d i z i n g F r o p e r t i e s and a t t r i t i o n r e s i s z a c e . ."le I: i s ;oEsi'de ir, laboratorjr a 2 s a r a t u s a d small p i l o t p l a n t s t o o b t a i n reasonably f k i i i i i z a t i o n and s x c e l i e n t conversions o f naphthalene i n t o p h t h a l i c d y d r i d e a x i d e ra?;e of c a t a l y s t s . Nevertheless, i n f u l l s c a l e r e a c t o r s t r o u b l e s can aris- froll: t h e use of f r i a b l e c e t a i y s t s v i t h t h e consequent r a p i d accumulation of an This may bring about uneven excessjjie grogartion of f i n e s i n 'the f i u l d i x e d bed. fluidization and an u n d t s i r a b l y nigh concentration of f i n e s i n t h e eqa.nded phase. 50th t h e s e s t a t e s can s i v e r i s e t o t r o u b l e ; t h e l a t t e r is 9roba'sl-g a c o n t r i b u t o r p cause t o " a f t e r b l u n i X t ' ( s e e below), w h i l s t t h e former --.a7 b r l r g about t h e f o r c a t i o z of s t a t i c poc>:ets of c a t a l y s t . 3uch pockets i n c o n t a c t iiith the r e a c t o r w a l l s c a The k x t u r e of s o l i d na3hthaiene and c a t a l p t so a c t as nophthalene ccndensors.

'

210.
f o m e d , i f suddenly d i s t a b e d a c l Fgnited can r e a c t very vigorously with t h e production of excessively high temperatures x i t h i n tile f l u i d i z e d bed. Fluidized-bed p h t h a l i c w b g d r i d e c a t a l l - s t s mst have a f a i r l y higt s p e c i f i c surface ana a r e l a t i v e l y l a r g e pore d i a x e t e r . These p r o p e r t i e s a r e not It comcatible with hiigh a t t r i t i c n r e s i s t a n c e so i t is necessary t o comprcmise. i a s bser. icund p o s s i b l e t o f o r m l a t e a highly s - J e c i f i c c a t a l y s t u i t h tine r e q u i r e d I n a favourably designed r e a c t o r , s i z e a t t r i t i o n r e s i s t a n c e m e lorg l i f e . degradation is s t r p r i s i n g j j i slow and ? r e s e n t i n d i c a t i o n s a r e t h a t i t should be p o s s i b l e t o iLaintain t h e a c t i v i t y and good f l u i d i z i n g _ : r o p e r t i e s of t h e c a t a l y s t . d t h a replacement l e v e l as l o w as 107' p e r annum. ,O

One of t h e most s e r i o u s and dangerous c i i f f i c u l t c e s which beset pioneers i n t E s i i e l d was " a f t e r burning", 5.e. t h e i g n i t i o r . of t h e product vapours above t h e f l u i d i z e d - c a t a l y s t bed with a consequent excessive and sometimes d i s a s t r o u s T h i s h a s a l r e a d y beer described i n some d e t a i l (1). Ir. the r i s e i n temperature. absence of e f f e c t i v e temperature c o n t r o l i n t h e expanded phase, t e q e r a t u r e s as high as 750 t o 10oOC o r more m y be reached *with consequent s e r i o u s damage t o t h e f i l t e r s , c a t a l y s t and r e a c t o r . Tne most l i k e l y explanation of .this phenomenon is excessive s l i p of naphthalene through the f l u i d i z e d , c a t a l y s t dense phase occasioned by poor f l u i d i z a t i o n , p a r t i c u l a r l y s l u g g i n g , spoutin,o, r a t - h o l i n g or an excessive A s m a l l amount of p a r t i c u l a r l y a c t i v e , proportion of bubble phase i n t h e b o i l i n g bed. s t a t i c c a t a l y s t lodged amewhere above the fluidized-bed p o s s i s l y starts the exotherpic oxidation o f this naphthalene. (11) and with a r e l a t i v e l y r a p i d r i s e of >inatever t h e cause, a f t e r burning can be temperatiire i n i t i a t e s t h e after b u n i r y . >rev-nted by keeping t h e temFerature-of t h e expaqded phase well below that of t h e bed. Various methods of doing t h i s can b e 12sed;'Jooling tubes i n t h e exDanded 3hase. Although t h e i.eat-exchaqe c o e f f i c i e n t on t h e gas s i d e of t h e t u b e s is not favourable, t h e d u s t c o z c e n t r a t i o n i n the gas i n c r e a s e s t h e z c u n t sf toolir,- over t h a t w;ich xouid a'ctain with a c l e a n gas.
I

i s p e c i a l l y cooled extension 0 t h e fluirlizad bed t o c o o l t h e l : .&ench Zone. g a s e s leaving the r e a c t i o n zone h a s been described by the h e r i c a n Cyananid It 2 e c e s s i t a t e s t h e use of ax a d d i t i o n a l d i s t r i b u t o r p l a t e , C o q a n y (.?I. s p e c i a l cooling c o i l s and a s t a d p i p e . T i s u p p r p a r t of t h e f l u i d i z e d 3ed is termed t h e "quench zone" and i t is recomeEded t h a t the temgerature of this zone i s kept at l e a s t jOuC below t i t of t h e main f l u i d i z e d bed. Such an a r r m g e n e n t could, if n o t p r o p e r l y designed and operated, l e a d t o an i n c r e a s e d r a t e of c s t d y s t a t t r i t i c n ( s e e below).

&each ,Gas. T3e feinperature ab:= the bed can be e f f e c t i v e l y c o x t r o l l e d by t h e izzroduction of c c l d air, or j e t t e r , c o l d inert gas. T P i s s i q l e and a r a c t i c a b i e methori h a s t h e advantage of r e d x i n g t h e c o n c e n t r a t i o n of p h t h a l i c b y d r i d e i n t h e prcduct S a s e j , w'hich, 3f c c u r s e , is not good from the condensation angle. 3ecycling cooled c a t a l y s t . Xecycling cooled c a t a l y s t through t h e e x p k d e d phase c a be used co c o o l t h e Sases l e a v i n g t h e b o i l i n g bed. This, however, inay r e s u l t I s increasLng c a t d p t a t t r i t i o n t o an o b j e c t i o n a b l e r a t e . Z x t e r r i d cooling. I f t h e c e t a l y s t f i l t e r s a r e hocsed i n s e p a r a t e v e s s e l s , then i t i s p i S i b l P t o cool t L e product gases by u t i l i z i n g the s u r f a c e of t h e i n t e r c o x e c t i n g 2ipe-lines. This i s e f f e c t i v e i n preventing after burning but a izvol-res c a t a l y s t c i r c a l a t i o n ' a t high v e l o c i t y , which m y c o n t r i b u t e t o c a t a l y s t a t t r i t i o n ( s e e below).

21 1.
Another f a c t o r which makes an i a p o r t a n t c o n t r i b u t i o n t o a i n i m i s i n g t h e r i s k This i s of a f t e r burning is low oqrgen p a r t i a l pressure i n t h e product Sases. achieved 5y o > e r a t i n s a t t h e lowest p o s s i b l e air:m p h t h a l e n e r a t i o compati b l e with crude l;rociuct p a r i t y a d bed teciperiture.
Trouble from a f t e r burning has been v i r t u a l l y eliminated from modern f l u i ~ z e d - c a t a l y s tp h t h a l i c anhydride p l a n t s by t h e use of one or more of t h e above d ewlc es

3soctor i2esign and C a t a l y s t A t t r i t i o n

Ynere i s an upper limit t o t:?.e a t t r i t i o n rssist3i?cs which czn b e b u i l t i n t o an a c c e s t a b l e naphthalene o x i d a t i o n c a t a l p t . Beactor d e s i g should t h a r e f o r e 5e such o t h e r v i s e excessive c a t a l y s t reglacement as t o k.eep c a t a l g s t a t t r i t i o n t o a U&&LU; w i l l be r,ecessary i n order t o prevent a h i l t up of a~? excessive -,roportion of c a t a y s t TIES a l s o p l a c e s a li-mit o n t h e ilui.tizi-g gas v e l o c i t j - m-d enahasises t h e fines. inporfant advantage of o p e r a t i = f l a i d i z e i - c s t a l y a t r e a c t o r s a t i n c r e a s e d r r e s s u r e i n i ! : a ~ h c x o x i c throughput. e :-ree desi,:. order t o o b t a i n t h e necess&-7 c o n t a c t t? f e a t u r e s a r e involved. i n r i n i z i s i n g c s t d j - s t a t t r i t i o n viz., ( 3 ) t h e disaositisr. s f t h e c a t a l l j s t c o o l e r , ( 2 ) i;-e d i s p o s i t i o n of t h e f i l t e r s and ( 3 ) t h e d i s t r i b u t o r ? l a t e . 2,ese a r e disclissed below.
Sone o f t h e e a r l i e r F a t e n t s (16) d e s c r i b e f l u i d i z e d LE Catilyst Cool-r. c..-l.r-+ r a c c o r s having estern2.l :heat sxchar4ers. -5 Ihese r q i i i r e t h e 3neumatic c;cve;--inj of c a t a i s t az high v s l o c i t j - through t r a n s f e r $pes mi the r a z r o w I..:o b*Ls of t t e hest exchangers. ,Tie a c t i o n 2 t k e f r i c t i c n a l arrd iziipact f o r c e s 1 involved on t h e c a t a l y s t p a r t i c l e s , p a r t i c u l a r l y so uhen sudden changes i n d i r e c t i o n a r e invclved, st i n c r e a s e the r a t e o f a t t r i t i o n . ?he csnsequent concentration o f c a t a l y s t f i n e s not o n l y g i v e s rise mors ra$& b u i l d up i n f z o tile i i i i i c s l t i e s :nentionei above but must a l s o d x r e a s e t h e e f f i c i e n c y of the 3. X Sraca and A. A. F r i e d (5) have d e s c r i b e a t h e a t t r i t i o n . cooling system. iTo c a t a l y s t which occurred i n a f l u i d i z e d - c a t a l y s t p h t h a l i c a n h i d r i d e p l a n t . m&e up was used and a f t e r two y e a r s operation t h e proportion of c a t a l y s t .p-ticles l e s s than 20,. had i n c r e a s e d from 9 t o 48 p e r cent.This f i n e m a t e r i a l p l a t e d out on t n e tiubes of t h e c a t a l y s t c o o l e r and about h a l f of then T:?e i n s t a l l a t i o n of cooling tubes within t h e gradually became blocked. ,The e x c e l l e n t thermal f l u i d i z e d - c a t a l j s t bed overcomes t h i s drawback. c o n h c t i v i t y of t h e f l u i d i z e d c a t a l y s t and t h e good heat-exchange c h a r a c t e r i s t i c s of t h e sj-stem make this possible.
,7;;

Commercial -Jhi;halic anhyd5cie p l a n t s u f f e r ic tiie d i s p o s i t i o n The F i l t e r s . Some of thea house t h e f i l t e r s i n a n w b e r of of t i e c a t a l y s t f i l t e r s . ; : s e p a r a t e v e s s e l s , each c o m e c t e d t o t h e top of t h e r e a c t o r D a pipe-=ne. :-<e c e t a l y s j f i n e s which accunulate on t h e s u r f a c e of t h e f i l t e r s a r e p a r i o d i c s l l y b1oi.m o f f a n d coilveyed back i n t o t h e base of t h e fluiriized-bed by The a t t r i t i o n t o t h e c a t a l y s t f i n e s c.eais cf some cf t h e f l u i d i z i n g air. thereby caused w i l l , ?f c o w s e , be such l e s s than t h a t which would o b t a i n i f csa-ser p a r t i c l e s were involved. Wevertheless, i t w i l l -make some c o n t r i b u t i o n t o the r a t e of c a t a l j s t a t t r i t i o n . p l a x t s nave t h e f i l t z r 2unLts l o c a t e d i z j t h e Cther p h t h i l i c &@ride On blow-back, t h e c a t a l y s t f i l t e r cake f a l l s top of t h e r e a c t o r i t s e l f . back i n t o t h e r e a c t o r 2nd t i e t r a n s f e r of c a t a l y s t a t : i h & v e l o c i t y through T N s slnple arrangement of f i l t e r s , hovever, pipe-lines is t h u s avoided. n&es so:newhat more d i f f i c u l t t h e problem o f cooling t h e groduct gases i s s u i n g An i n c r e a s e in t h e heigh? of t h e hock-out zone f-om t h e j o i v n g c a t a l y s t bed. above t h e f l u i d i z e d bed overcomes t h i s d i f f i c u l t y .

I n the fluiciized-catalyst r e a c t o r i t is important t o The D i s t r i b u t o r ? l a t e . e s t a b l i s h reasonably UIXifOrQ d i s t r i j u t i o n of air and ria2hthalene vaDour a c r o s s t h e whole bed, o t h e r r h e t h e air:r;aohthalene r a t i o would vary from p l a c e t o p l a c e and kiixier t h e n t 5 a i m e r t cf optimum r e a c t i o n conditiocs. The hei$.t: d i a i l t e r r a t i o of t h e f l u i d i z e d - c a t a l y s t 5ed and t h e low d e n s i t y of t h e c a t a l y s t Nevertheless, i n a l a r z e f l u i . i i z e a =e b o t h fzvocrable t o good f l u i d i z a t i o n . r e a - t o r , say i C f t . d i a n e t e r o r more, i t is esse.ctial t o s p e r a t e .with a.a s2yrociable p r e s s u r ? dro? a c r o s s the d i s t r i b u t o r ; l a t e , o t l i e m i s e t h e r e is a Various methoffiof a t t a i l l i n g Bven danser of uneven air d i s t r i b u t i s n . e.g., ( a ) tine use oi m l t i - j e t s i n s t e a d of d i s t r i b u t i o n have j e e n Trcposed. 5 o l e s ( 9 ) ; (b) t h e gas i s introduced through a i'iared, conical-shaced zoce a t the base of t h e r e a c t o r , hiah turbuience being maintained i n t'nis zone and a d i s t r i b u t o r p l a t e is n o t used ( 8 ) . Another g-ooosal (17) i s t o s u b j e c t t h e r e a c t o r , which has a c o n i c a l bottom, t o v e r t i c a l l i n e a r o s c i l l a t i o n s , IC0 p e r . These methods would l e a d t o a d d i t i o n a l sec., with an amplitude of 15 m. c a t a l y s t a t t r i t i o n , p a r t i c u l a r l y t h e one using h i g h v e l o c i t y jets. TZP ... P e a c e and I.C.I. Ltd., (IO) have suggested t h e use of a s u i t a b l e porous ceramic k plate. Its saintenm-ce Ln a i a r g e r e i c t o r would p o s s i b l y be d i f f i c u l t . method of obtaining m-y- d e s i r e d p r e s s - a e d r o p a c r o s s a d i s t r i b u t o r s l a t e 'aithout high v e l o c i t r air s t r e a m i n c r e a s i n g c a t a l y s t a t t r i t i o n would be by use of t l e device shown i n F i g . 5. Znstead of a simple h o l e t h e oonical f i l t e r elements are i n s e r t e o ir t h e d i s t r i b u t o r p l a t e . Tie entzy h o l e s t o t h e f i l t e r s could be riiade snall enough t o g i v e back pressure necessary f o r good d i s t r i b u t i o n . T h e air used f o r f l u i d i z a t i o n would have t o be f i l t e r e d t o prevent t h e slow c l o s g i q of t h e snall f i l t e r s from the underside.

?
1

ml a

It is not d L f f i c u l t i n a l a b o r a t o r y f l u i d i z e d r e a c t o r , o r i n a p i l o t p l a n t r e a c t o r t o o b t a i n r e l a t i v e l y uniform f l u i i i z a t i o n and consequently a This i s evidenced by t h e Ligh degree of c o n t r o l of r e a c t i o n conditions. results given i n Table 2.

R e s u l t s obtained i n a 2 in. dim. l a b o r a t o r y f l u i d i z e d - c a t a l y s t r e a c t o r using pure n a c h t h d e n e (0.07; s. ) Temp.

Air: Raphthalane aatio

OC

P.A.

Yields

ww /.

X.A.
1e 7 11 .

350 333
j20

15:4
1: 1:

145 0.
lC4.1
104.2

07 .
0.9 12 .

;: 40

1-5

P i l o t p l a n t r e s u l t s o s t a i n s d i n a 6" d i m . SluicEzed-car;alyst r e a c t o r using petroleum na-.,hthalene (S f r e e ) C.P. 79.4OC. zenp. 2ir:Saphthalene Batio Crude Yield %
100.2

;inalysis of Crude

OC

?A .. -

3.A.

.~'\.a.
7

15: 1 75:l 15:l

99.7 59.3

58.0 35.5 57.5

0.09 01 .3 0.79

.o

07 .
1.1

I , is a o s a i b l s t h a t t h e q u a l i t y of f l u i d i z a t i o n and d i s t r i j u t i o n i n a t f u l l s c a l e p l a n t can b e assessed 5y t h e i r approach t o l a b o r a t o r y r e s u l t s .

213.
Sulohur i n Naphthalene The p i n c i p a l impurity i n p h t h a l i c grade', c o a l tar naphthalene i s Japhthaiene thionaphthene which > o i l s only hoc above t h e b.p. of naphthalene. derived from tar from sulphurous c o a l s may c o n t a i n 1s sulphur, which i s equivalent t o 4.1% thionaphthene. C a t a l y s t s which have .been used i n t h e p a s t i n f l u i d i z e d bed r e a c t o r s have tended t o d e a c t i v a t e when sulphurous naphthalene i s used a s the f e e d () 6 . i t has been s t a t e d t h a t sulphur-free naphthalene (sodium t r e a t e d ) is This i s no longer so as a r e q u i r e d f o r optimum conversion t o p h t h a l i c anhydride. It h a s a l s o been claimed sulphur-resis-ant fluidized-bed c a t a l y s t i s now a v a i l a b l e . (78) t h a t t h e presence of sulphTlr i n t h e naphthalene i s a d v a t a g e o u s i n preventing c a t a l y s t deactivation. The oxidation of thionaphthene, however, cannot y i e l d g h t h a l i c aniqdride, so i t s presence i n naphthalene must mean a equivalent loss of p h t h a l i c anhydride y i e l d . I n order t o Aeternine whether or not excessive amounts o f tirionaphthene had a n y d e a c t i v a t i n g a c t i o n on t h e new fluidized-bed c a t a l y s t t h e following work vas Xaphthalenes were prepared containing i n c r e a s i n g p r o p o r t i o n s of c a r r i e d out. ,These were oxidized with air t h i s n a r h t h e n e ( 0 t o ' 4.73; S) as t:ie p r i n c i p a l imguritg. The r e s u l t s obtained a r e showc i n i n a Laboratory f l u i d i z e d c a t a l y s t apparatus. There i s a p r o p o r t i o n a t e f a l l i n g o f f i n t h e p h t h a l i c anhydride y i e l d a s t h e Fig. 6. thionaphthene content of t h e naphthalene feed i n c r e a s e s and t h e r e i s a l s o a steady A f i z a l o e d a t i o n a s i n g ag3in a sulghuri n c r e a s e i n t h e maleic anhydrlde yield. f r e e EaFhthdene feed gave r e s u l t s q u i t e c l o s e t o those obtained i r L c i d l g , i n d i c a t i n g that t h e excessive proportion of s u l ~ h u r had not d e a c t i v a t e d t h e c a t a l p t . A s u l 3 h u r f r e e naphtinalene g i v e s a proportlonzzely h i g h e r y i e l d and probably a l s o , l e s s c o r r o s i o n i n t h e conaensatioo system. ? .e ' loyver maleic anhydride ccntent of the crude product will probablg reduce d i s t i l l a t i o n l o s s e s during the f i n a l p u r i f i c a t i o n . Yhether o r n o t pure o r sulphurous naptdhlme sizoulci be x e d as feed for a f l u i d i z e d +-,ti.zlic anhjdride p i a n t is a question t o be answered by t h e econonics of t h e operations. i i l o t p1ar.t ex?eriments i n a 6" diam. f l u i d i z e d c a t a l y a t r e a c t o r ';rere c a r r i e d out using t i j o d i f f e r e n t ccke-oven naphthalenes ( a ) c.p.. 7 7 . 5 ; S, 0.8$ and S, 0 0 k .W. 5 , 0.51;; and ;skla?d petroleum naphthalene c.p. 79.4OC; (5) C.O.- , 79.6OC; A range o f q e r a t i n g c o n d i t i o n s was used f o r each nq!ithaiene. "able 3 gives the These r a s u l t s i n d i c a t e y i e l d s obtained under t h e optimum o p e r a t i n g c o x i i t i o n s . t h a t t h e prasence of thionaphtifiene i n the naphthalene f e e d does not uholly account i o r t h e reduction i n y i e l d .

::qzLthalene

Temw.

2eacthon
C

Average Y i e l d of Cruie 5

h d l y s i s of 3roduct $A P.A. M.A. ? & !,;

91.3 96.1
100.2 Conclusion

97.5 98.5 97.9

0.56
0.19

0.6

0.13

trace
1.1

&n frsm t h e c a t a l y t i c cracking o f p e t r o l e u n , t h e developmer-c of t h e i . f i u i S i z e d - c a ~ a l p t technique i n t h e chenlical n a n u f i c x r i n g i c d u s t r i e s nas been Tnis kas beer. l a r g e l y due t o t h e s t a - e of cur f u n d m e n t a l knowledge r e l a t i v e i y slow. of t h e ? r o ? e r t i e s of f l u i d i z e d beds and of heterogeneous c a t a l j s i s i n such beds.

zL4.

ir; d s v s i o p i n s the f l u i a z e d rsthod fcr na2hthaiene oxidazLon described above are a l r e a d y be&: auccessr'liliy --~ There is l i t t l e a g p i i e d i o o t h e r y o c e s s e s , ?art'*, i a r k r t o exothermic oxidations. dcubt tbzc t h e ~ c c e s sa c k L f ~ e d . with t h e 2ht'rdLic s&.yiria? process ,&niiil accelerate t h s iriaer industria: use o f fluidizad-bsd c a t a g s i s .
jed

-. xetnods s&octed for ovar.zo!rLng t h e b i f f i c r ; l t i e s .. -',?e

215.
L i t e r a t u r e Cited
0

(11
(2)

h e r i c a n cyy
B.X.A.F.,

d C O . , U.K. Fatent

Patent

754,665 (A?=.

76, i 5 ) 93.

A . 3 . r UK ..

787,924 (Aug. 7, 1 5 ) 94.

Patent

. , (3) Barton E
(Apr.
-

( t o Imperial Chemical I n d u s t r i e s Ltd.),.U.K.

715,384

4, 1.1. 95)
Tatents

(4)
(5)

Zecker S.B., ( t o S t a n d a r d O i l Co. of Indiana) 3.S. (June 27, 1 4 ) 9 1 , 2,453,740 (Peb. 16, 1 4 ) 95. Braca 2 . M., and F r i e d A. A . ,

2,373,008
p.

" F l u i d i z a t i o n " ed. O c h e r

DF, ..

19 2.

2einhold Publis-hing Corp.,

New York,

15. 96

(6)
\\

Graham J. J.,

'Xay P. F.,

and Chase S . ,
Ches. and Ind.,

Chern. Eng. Proe;.,

30.

58, 96 (19621.

. (7) Landau 8 and

Iiarper X, .

p, 1143 ( 9 1 . 16)

.. ( 8 ) : i e t a l l g e s e U s c h a f t AG,

UK ..

Patent

772,364 (Kay 16, 1 5 ) 92.

Patent

(9)

t. !

7 de a a t a a f s c h e Fetroleun Xaatschappij, C.K. .

659,048 (Dec. 9, 1 4 ) 99.

(10) P e a c e C. J .
\

P, ( t o I m p e r i a l Cheaical i n d u s t r i e s Ztd.), U.K. P a t e n t 68j,70j .

9er. atsch. &en.
Ges.,

(Jan. 23, 1 5 ) 90.

(ill T o r y r a t z A. and B c h o l t i s K.,

76, ;7 ( 9 3 . :9 1 4 )
2atent

i
\

. '

(12) X e g l e r R., ( t o i i a t i o r a l Aniline and Chenical C O ~ , G.5. (2%- 5 1 3 ) 9 97.

2,G67,019

(13) Riley H L., and Norris J , U.K. . .

P a t e n t 713,560

(Dec. 17,

15) 91.
(hr. 24, 1953).

(14) = l e y H L, . .

Caates 2 . G.,

and i J o r r i s J.,

Uk.

Patent

31,352

(15) Riley a. L., &em. and Ind.,

1464, 1956.

(16) R i l e j r

H .

L, Trans. I n s t . Chem. Z q . , .
K. E.,

2,2i (1959).
1,112,060
(Xpr.

(17) S f a d c a r b o n (18) i e n d e r l e i n

V, 5.K. .

Patent

779,826 (SeFt. 17, 1 5 ) 94.

Geman P a t e n t

( t o a.A.5.F.

AG) ..

3, 1960).

216.

. M Y . L .

Fiz. 1.

F l u i d i z e d Catalyst P k t h a l i c Anhydride P l a n t .

Fig. 2.

Condensation of p h t h a l i c anhydride on cooled finned tube.

z
a

218.

Pig. 5 .

G i s t r i b u t o r Plate T i l t e r .

.-c

_ -_ -

_.--

I'