REGENERATION O "SPENT" ZnC 1, PRODUCT CATALYST F F O HYDROCRACKING SUBBITLMINOUS COAL RM Clyde W. Zielke, William A. Rosenhoover and Robert T.

Struck Conoco Coal Development Company Research Division Library, Pennsylvania 15129 INTRODUCTION

I t has been demonstrated i n batch and continuous bench-scale u n i t s t h a t molten z i n c c h l o r i d e i s a s u p e r i o r c a t a l y s t f o r l i q u e f a c t i o n of c o a l , c o a l e x t r a c t o r o t h e r heavy hydrocarbons. High q u a l i t y g a s o l i n e of 90-92 Research Octane Number is produced i n h i g h y i e l d in a s i n g l e hydrocracking s t e p (1,2,3,4,5). Large amounts o f z i n c c h l o r i d e a r e used a s t h e c a t a l y s t f o r high a c t i v i t y , i.e., u s u a l l y 1 gm of ZnC1, p e r gm of c o a l o r e x t r a c t feed. From 1 t o 2 p a r t s by weight of product c a t a l y s t i s generated during t h e hydrocracking process depending on t h e ZnCl,/feed r a t i o . T h i s product c a t a l y s t i s contaminated w i t h zinc s u l f i d e , a m o n i a o r ammonium c h l o r i d e complexed w i t h z i n c c h l o r i d e (formed by t h e c a t a l y s t p a r t i a l l y r e a c t i n g with t h e s u l f u r and n i t r o g e n i n t h e feed during t h e hydrocracking s t e p ) , carbonaceous r e s i d u e t h a t cannot b e d i s t i l l e d o u t of t h e melt, and c o a l ash, when c o a l i s t h e feed t o t h e hydrocracking process. To keep t h e c a t a l y s t a c t i v e , t h e s e i m p u r i t i e s must b e removed i n a regeneration process i n which t h e c a t a l y s t i s converted back t o e s s e n t i a l l y pure z i n c chloride. The i m p u r i t i e s do not s e t t l e o u t o f t h e molten product c a t a l y s t ; hence, t h e whole product c a t a l y s t must b e s u b j e c t e d t o t h e r e g e n e r a t i o n process. Thus, r e g e n e r a t i o n i s a key s t e p i n t h e ZnC1, c o a l l i q u e f a c t i o n process i n development a t Conoco Coal Development Company.
The r e g e n e r a t i o n i s accomplished by burning out t h e i m p u r i t i e s i n a combustor c o n t a i n i n g a f l u i d i z e d bed of "inert" s i l i c a sand:
( 1) ZnS + 3/2 0, -. ZnO + SO, 2 ZnCl,-NH, 3/2 0, 4 2 ZnC1, N, 3 H,O (2) CH4 + (1 X / ~ ) ~ O , CO, x/2 H,O (3) n Hydrogen c h l o r i d e gas i s added t o t h e feed a i r t o convert Z O t o ZnC1, and t o prevent formation of ZnO by h y d r o l y s i s of zinc c h l o r i d e i n t h e combustor:

(4)
A previous paper describe4 regeneration of e s s e n t i a l l y coal-ash-free s p e n t melt produced by hydrocracking c o a l e x t r a c t (6,7). However, t h e r e appear t o be economic advantages t o a process enploying d i r e c t c o a l hydrocracking over a two-step process c o n s i s t i n g o f c o a l e x t r a c t i o n followed by hydrocracking of t h e SRC therefrom. Therefore, d e s o n s t r a t i o n o f regeneration with low z i n c l o s s e s o f t h e ash-contaminated s p e n t melt proluced by d i r e c t hydrocracking of c o a l i s of high importance i n the process development. The f i r s t work i n t h i s regard was done u s i n g s y n t h e t i c s p e n t melt which simulated t h a t produced by hydrocracking subbituminous coal. This work has been published previously (5). Simulated s p e n t melt was used because n a t u r a l s p e n t m e l t was n o t a v a i l a b l e . Subsequent t o t h a t work, s u c c e s s f u l d i r e c t hydrocracking w i t h ZnC1, c a t a l y s t of C o l s t r i p subbituminous c o a l i n a continuous bench-scale hydrocracker furnished feedstock f o r f u r t h e r development of t h e regeneration process. Continuous regeneration of t h i s coal-ash-contaminated spent melt from d i r e c t hydrocracking of c o a l and e f f i c i e n t zinc recovery therefrom has now been demonstrated f o r t h e f i r s t time. I n t h i s work z i n c recovery was enhanced by introducing a secondary z i n c recovery s t e p i n which z i n c , r e t a i n e d i n t h e c o a l ash r e j e c t e d i n t h e primary regeneration s t e p , i s l a r g e l y recovered. This paper p r e s e n t s some of the r e s u l t s of t h i s regeneration work with n a t u r a l spent melt from d i r e c t c o a l hydrocracking.

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EXPERIMENTAL

Feedstocks Spent Melt The two feedstocks f o r t h e primary r e g e n e r a t i o n work were low-carbon spent m e l t s produced by d i r e c t hydrocracking of C o l s t r i p c o a l i n a 3 1b/h continuous bench-scale hydrocracking u n i t . Hydrocracking c o n d i t i o n s were: 413'C, 24.13 M a P (3500 psig), ZnCl,/MF s o l v e n t - f r e e C o l s t r i p c o a l r a t i o o f 1.5 and residence times ranging from 74 t o 95 m i n . Normally a ZnCl,/coal r a t i o of 1.0 i s used; t h e h i g h e r r a t i o of 1.5 was used t o speed up production o f spent melt. It gave a y i e l d of about 1.75 gm of s p e n t m e l t per gm of MF c o a l feed vs. about 1.25 which is produced a t a ZnCl,/coal r a t i o of 1.0. The carbon content of t h e two spent m e l t feedstocks used were 6.65 and 6.319., s l i g h t l y more than required t o f u r n i s h t h e h e a t when burned f o r c a r r y i n g out t h e r e g e n e r a t i o n a d i a b a t i c a l l y . The t o t a l a s h c o n t e n t of t h e feed melt i s based on t h e sum o f t h e e i g h t most prevalent c o a l a s h elements (Na, K, C a , Mg, Fey T i , S i , Al) expressed a s oxides, s i n c e t h e c o a l ash is mixed w i t h non-combustible m a t e r i a l s and, t h e r e f o r e , cannot b e determined d i r e c t l y . The t o t a l a s h determined i n t h i s manner i s . l o w e r than t h e ash determined i n c o a l s o r c h a r s i n t h e conventional manner, where s u l f a t e s and carbonates may be p r e s e n t , t h a t a r e n o t t a k e n i n t o account h e r e . Also, t r a c e s of minor elements a r e n o t considered here. Analyses of t h e s p e n t m e l t a r e given i n Table I. C o l s t r i p Coal Minus 100 mesh C o l s t r i p subbituminous c o a l (Rosebud Seam, Montana) w a s used a s t h e feedstock f o r t e s t i n g , i n a 3 lb/h continuous hydrocracker. The a c t i v i t y of regenerated s p e n t m e l t was compared with v i r g i n z i n c c h l o r i d e . Analyses of t h i s c o a l a r e given i n Table I. Cyclone Underflow Ash This m a t e r i a l , which is generated i n t h e primary regeneration s t e p , c o n t a i n s t h e c o a l a s h and g e n e r a l l y l e s s than 2% of t h e zinc i n t h e spent m e l t feed t o t h e primary regeneration. It i s f e d t o a secondary zinc recovery s t e p wherein t h e m a j o r i t y o f t h i s " l o s t " z i n c is recovered. Analyses of t h i s m a t e r i a l a r e given under the heading "Composite'' i n Table V I . Equipment and Procedure Primary Regeneration Figure 1 i s a diagram of t h e continuous 2-7/8" I.D. f l u i d i z e d bed combustion u n i t i n t h e c o n f i g u r a t i o n used f o r primary regeneration. The molten "spent" c a t a l y s t i s fed v i a a F l u i d Netering, Inc. Lab pump and i s dropped from a remote d r i p t i p i n t o a batch bed o f f l u i d i z e d s i l i c a sand. The feed gas c o n s i s t s o f a mixture of a i r and anhydrous hydrogen c h l o r i d e which e n t e r s a t t h e apex of t h e r e a c t o r cone. In t h e f l u i d i z e d bed, t h e z i n c c h l o r i d e i s vaporized, t h e carbon, n i t r o g e n and s u l f u r i m p u r i t i e s a r e burned o u t and any z i n c oxide i s l a r g e l y converted t o zinc c h l o r i d e by t h e H C l i n t h e f e e d gas. The gas and z i n c c h l o r i d e vapor e n t r a i n t h e c o a l ash, l e a v e t h e r e a c t o r and pass through t h e cyclone where t h e s o l i d s a r e c o l l e c t e d . The cyclone underflow s o l i d s d e r i v e s o l e l y from t h e melt s i n c e t h e s i z i n g of t h e s i l i c a sand bed s o l i d s i s such t h a t t h e r e i s e s s e n t i a l l y no e l u t r i a t i o n of t h i s material. The s o l i d s c o l l e c t e d a t t h e cyclone then c o n s i s t l a r g e l y of c o a l ash contaminated by small amounts o f z i n c i n t h e form of z i n c c h l o r i J e and zinc oxide o r o t h e r compounds, and any unburned carbon o r z i n c s u l f i d e . The gas then passes t o t h e condenser where z i n c c h l o r i d e i s condensed, t h e n t o t h e e l e c t r o s t a t i c p r e c i p i t a t o r t o remove zinc c h l o r i d e fog, and t h e n t o sampling and metering. The a n a l y t i c a l methods and calculat i o n a l procedures a r e s u b s t a n t i a l l y t h e same a s those previously described ( 7 ) . Hydrocracking The hydrocracker and i t s o p e r a t i n g procedure have been described previously ( 9 ) .

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Secondary Regeneration The apparatus used t o conduct t h e secondary recovery s t u d i e s was t h e same u n i t used f o r t h e primary regeneration s t u d i e s with some modifications m a d e t o accommod a t e t h e u s e of a s o l i d feed. The modifications c o n s i s t e d of r e p l a c i n g t h e melt feed system w i t h a metering powder feeder f o r feeding t h e cyclone underflow s o l i d s t o t h e u n i t . The d r i p t i p was plugged o f f s i n c e i t was not used. The cyclone underflow a s h is fed a t a metered r a t e i n t o t h e a i r feed g a s l i n e t h a t t r a n s p o r t s t h e a s h i n t o t h e bottom of t h e batch f l u i d i z e d bed of s i l i c a sand. Anhydrous HC1 i s i n j e c t e d i n t o t h e a i r stream j u s t upstream from t h e r e a c t o r . Some o f t h e ash is temporarily trapped i n t h e f l u i d i z e d bed o f s i l i c a sand, b u i l d i n g up t o a s t e a d y - s t a t e concentration. The remainder of t h e ash i s c a r r i e d out o f t h e bed by t h e gas stream. A t s t e a d y state, t h e amount of ash fed per minute equals t h e amount of ash p e r minute t h a t i s t r a n s p o r t e d by t h e gas stream o u t of t h e bed. The average ash residence t i m e i n t h e r e a c t o r i n minutes i s then "grams of ash inventory i n t h e bed divided by t h e a s h feed rate i n grams per minute." The gas, ZnC1, vapors, and e n t r a i n e d ash leave t h e r e a c t o r and follow t h e same c o u r s e described above f o r primary regeneration. The feed gas i s e l e c t r i c a l l y preheated t o 316C (600OF) b e f o r e it e n t e r s t h e r e a c t o r . The remaining h e a t required i s put i n through t h e r e a c t o r walls by e l e c t r i c a l heaters. The run was s t a r t e d when t h e cyclone underflow ash feed t o t h e r e a c t o r s t a r t e d . The product cyclone underflow was c o l l e c t e d i n 5 t o 10 min, increments a s a f u n c t i o n of running t i m e . The run w a s ended when t h e a s h feed stopped. The ash inventory i n t h e bed was measured t o enable precise c a l c u l a t i o n of t h e average residence t i m e i n t h e bed. Run d u r a t i o n was about 40 minutes, which required about 200 grams of a s h p e r run, This was low enough t h a t t h e r e l a t i v e l y l i m i t e d a s h supply was s u f f i c i e n t t o conduct a reasonably complete program. Thus, i n runs of 10-12 minutes residence time, t h e longest times i n v e s t i g a t e d , t h e r e were a t l e a s t t h r e e changes of ash inventory. The r e a c t i o n was followed by analyzing t h e product ash increments f o r t o t a l and water-soluble z i n c , c h l o r i n e and i r o n . S t e a d y r s t a t e was i n d i c a t e d by c o n s t a n t c o n c e n t r a t i o n s of z i n c i n t h e increments.

I n general, complete m a t e r i a l and elemental balances were n o t made because t h e small amount of m a t e r i a l c o l l e c t e d i n t h e l a b y r i n t h i n e c o l l e c t i o n equipment downstream from t h e cyclone made a c c u r a t e c o l l e c t i o n of small amounts o f product very
d i f f i c u l t . I n s t e a d t h e y i e l d of e f f h e n t a s h was determined by a s i l i c a b a l a n c e around t h e ash i n and t h e ash out. This, t o g e t h e r w i t h metals a n a l y s e s o f t h e feed and product a s h , provided t h e d a t a f o r c a l c u l a t i o n of metals removal, RESULTS AND DISCUSSION Primary Regenera t i o n The v a r i a b l e s and t h e l e v e l s a t which they were i n v e s t i g a t e d are: Temperature, "C Pressure, kPa (psig) '% of Stoichiometric A i r (nominal) Mol X of Anhydrous H C 1 i n Feed A i r Fluidized Bed S o l i d s Fluidized Bed Depth, meters s u p e r f i c i a l Linear Velocity, meters/sec 871, 927, 954, 982 119 (3) f 15 5.5, 8.5, 11.5 297 x 595 pm S i l i c a Sand
0.305

0.305

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operability The c r i t e r i o n f o r o p e r a b i l i t y i s t h a t t h e c o a l a s h leaves t h e bed by e l u t r i a t i o n and t h a t it i s n o t r e t a i n e d i n t h e bed due t o s i z e growth by s i n t e r i n g or c l i n k e r formation. Based on t h i s c r i t e r i o n o p e r a b i l i t y was a s follows:

1 .

W i t h 5.5% H C 1 i n t h e i n l e t a i r :

a. b. c.

927C (1700F) i s 954OC (1750OF) is s i n t e r i n g of 982C (1800F) is sintering in

a n operable c o n d i t i o n , a t l e a s t f o r s h o r t period. a marginally o p e r a b l e condition because of some ash i n t h e bed. a n i n o p e r a b l e c o n d i t i o n because of severe ash t h e bed leading t o c l i n k e r formation.

2.

With 8.5 o r 11.5% H C 1 i n t h e i n l e t a i r :

a. b.
c.

927C i s a n o p e r a b l e condition. 954C i s a n operable c o n d i t i o n . 982C probably is a marginally o p e r a b l e condition w i t h some minor s i z e growth i n t h e ash g r a i n s i z e t o be expected. This may be d e s i r a b l e from t h e s t a n d p o i n t of preventing ash buildup i n t h e regenerated m e l t .

Some s l i g h t s i n t e r i n g may b e d e s i r a b l e t o give more e f f i c i e n t cyclonic removal o f t h e ash from t h e gas stream. The s i n t e r i n g t h a t r e s t r i c t s o p e r a b i l i t y i s l i k e l y promoted by the f l u x i n g a c t i o n of ash metal c h l o r i d e s (NaCl, KC1, CaCl,, MgC1,) t h a t can be formed i n t h e hydrocracker by r e a c t i o n s such a s
Na,O

+ ZnC1,

= 2 NaCl -k ZnO

In general, 927C was found t o be t h e p r e f e r r e d temperature i n t h a t t h e temperature

was low enough f o r good o p e r a b i l i t y b u t high enough f o r good r e a c t i o n k i n e t i c s , y i e l d i n g e f f i c i e n t burnout of t h e impurities. Results The r e s u l t s p r e s e n t e d w i l l b e confined t o work done a t 927OC and t h e e f f e c t o f HC1 concentration i n t h e a i r on t h e s e r e s u l t s . Table I1 shows c o n d i t i o n s and m a t e r i a l balances f o r runs a t 927C w i t h 5.5, 8.5 and 11.5 mol % H C l i n t h e feed gas. Table I1 shows t h a t good m a t e r i a l balances were obtained. Products derived from four sources: t h 2 product m e l t , cyclone underflow s o l i d s , bed s o l i d s , and gas which includes water. The bed s o l i d s y i e l d p e r u n i t of feed decreases as run durat i o n , and hence t h e t o t a l amount of m e l t fed, i n c r e a s e s , s i n c e a batch bed of s i l i c a was used. Table 111 shows the e f f i c i e n c y o f r e g e n e r a t i o n f o r t h e t h r e e runs whose mater i a l balances have been given. Zinc recovery with 5.5% H C l i n t h e feed a i r was 97.9% and i t i n c r e a s e d t o 99.1% with 11.5% H C 1 i n t h e feed a i r . Higher recovery i s achieved with h i g h e r H C 1 c o n c e n t r a t i o n because t h e ZnC1, h y d r o l y s i s equilibrium i s s h i f t e d f a r t h e r t o t h e ZnC1, s i d e . Recoveries of c h l o r i n e (Table 111) g r e a t e r than 100% of the c h l o r i n e i n t h e feed melt r e f l e c t coilversion of ZnO and ZnS i n t h e feed t o ZnCl, by i n t e r a c t i o n w i t h the H C 1 i n t h e gas. The small a m u n t s of n i t r o g e n , carbon and s u l f u r i n t h e product melts (Table 111) r e f l e c t t h e h i g h effLciency o f burnout of t h e NH3, ZnS and carbonaceous r e s i d u e , s i n c e e s s e n t i a l l y a l l of the remaining carbon, n i t r o g e n and s u l f u r a r e i n t h e u n i t offgases a s com3ustion products: SO,, CO, CO,, N, and H,O. Nitrogen and s u l f u r burnout were g e n e r a l l y g r e a t e r than 97% and carbon burnout was g r e a t e r than 99%.
The low percentage of t h e feed ash i n t h e product melt (Table 111) shows t h a t ash r e j e c t i o n a t t h e cyclone was very e f f i c i e n t . Rejection of t h e i n d i v i d u a l metals of which t h e ash i s comprised, was a l s o e f f i c i e n t except f o r sodium and potassium, m o s t of which appear i n t h e melt. This i s undoubtedly d u e to t h e format i o n of thc h i g h l y - s t a b l e NaCl and K C 1 which 3 r e s l i g h t l y v o l a t i l e a t regeneration

282

c o n d i t i o n s (- 3 and 5 t o r r vapor pressure a t 927"C, r e s p e c t i v e l y ) . A s u b s t a n t i a l f r a c t i o n o f t h e i r o n , most l i k e l y a s FeC1, a l s o appears i n t h e melt. Over many c y c l e s of hydrocracking and regeneration, vapor-liquid e q u i l i b r i a with r e s p e c t t o NaCl and K C 1 a t a regeneration temperature of 927'C w i l l l i m i t t h e buildup of t h e sum of t h e i r c o n c e n t r a t i o n s i n t h e ZnC1, c a t a l y s t t o about 1.0 t o 1.5 mol %when t h e regeneration i s conducted a t 3 atm p r e s s u r e o r even l e s s a t h i g h e r p r e s s u r e s . The h y d r o l y s i s e q u i l i b r i u m

o r r e a c t i o n s such a s FeCl,

+ H,O + a s h

= FeO-ash

+2

HCI

w i l l r e s t r i c t t h e FeC1, c o n c e n t r a t i o n i n t h e regenerated ZnC1, c a t a l y s t t o l e s s than 10 mol %. A run i n which t h e melt t o r e g e n e r a t i o n was spiked w i t h FeC1, tends t o confirm t h i s . Batch hydrocracking d a t a i n d i c a t e t h a t , a t t h e s e l e v e l s , t h e s e a s h m e t a l c h l o r i d e s p r e s e n t e s s e n t i a l l y no problem regarding c a t a l y s t a c t i v i t y .
Table I V shows"ana1yses of t h e product regenerated melts. The melts obviously a r e c l o s e t o pure ZnC1, s i n c e t h e Zn:Cl atomic r a t i o s a r e 1.95, 1.97 and 2.02. A f t e r s e p a r a t i n g o u t t h e trapped ash and sampling, t h e used 28 x 48 mesh s i l i c a sand bed s o l i d s were employed i n consecutive runs. The s i l i c a bed i s almost i n e r t t o i n t e r a c t i o n with z i n c and c h l o r i n e a s shown by t h e i r extremely small c o n t e n t s i n t h e s i l i c a sand bed a f t e r 54 hours o f use i n s p e n t melt r e g e n e r a t i o n (Table V ) . There i s some r e a c t i o n of calcium and magnesium w i t h t h e s i l i c a sand bed as i n d i c a t e d by a n i n c r e a s e w i t h time up t o t h e c o n c e n t r a t i o n s of 1.49 and 0.44% of CaO and MO a f t e r 54 hours. g Table V I gives a n a l y s e s of t h e c o a l a s h r e j e c t e d by t h e cyclone during primary regeneration. The y i e l d s of t h e s e ashes w e r e about 5.8% per 100 grams of feed me'lt e x c l u s i v e of t h e s t e a d y - s t a t e c o n c e n t r a t i o n of a s h trapped i n t h e bed when t h e run was terminated. These ashes c o n t a i n e s s e n t i a l l y a l l of t h e feed z i n c n o t .found i n t h e product melt. The z i n c r e t a i n e d i n t h e ashes r e p r e s e n t 1 t o 2% of the feed z i n c t o regeneration, t h e r e t a i n e d z i n c being lower when t h e HC1 c o n c e n t r a t i o n i n t h e a i r increases. It is i n two forms: 1) z i n c i n t h e form of z i n c c h l o r i d e (waters o l u b l e zinc) which i s adsorbed on, e n t r a i n e d by, o r d i f f u s e s t o t h e cyclone underflow a s h during t h e r e g e n e r a t i o n process, and 2) z i n c i n t h e form o f ZnO, ZnO-SiO, and ZnO-Al,O, (water-insoluble zinc) which is n o t completely converted t o t h e ZnC1, because of e q u i l i b r i u m r e s t r i c t i o n s i n r e a c t i o n (4) and r e a c t i o n s o f t h e type ZnCl, ZnC1,

+ SiO, + H,O

+ A1,0, + H,O

= ZnO.Si0, = ZnO.Al,O,

+ 2 HC1 + 2 HC1

Accordingly, t h e Concentration of t h e w a t e r - i n s o l u b l e z i n c decreases a s the H C l conc e n t r a t i o n i n t h e feed a i r i n c r e a s e s , whereas t h e water-soluble ash c o n c e n t r a t i o n remains more o r less c o n s t a n t . Since 1%z i n c "loss" r e p r e s e n t s about 4 p e r g a l l o n gasoline, recovery of t h e { z i n c i n t h e ash i s worthwhile from t h e economic a s p e c t a s w e l l a s from t h e environmental and conservation a s p e c t s . Therefore, i n v e s t i g a t i o n s of "Secondary Zinc Recovery," t h a t is, recovery of t h e z i n c r e t a i n e d i n t h e cyclone a s h were made. Secondary Zinc Recovery Secondary recovery c o n s i s t e d of treatment of t h e cyclone underflow a s h from t h e primary regeneration w i t h ZnC1,-free a i r p l u s HC1. The p r i n c i p l e o f t h i s t r e a t ment i s t o r e v e r s e e q u i l i b r i a such a s i n r e a c t i o n s ( 4 ) , (6) and (7) so t h a t t h e w a t e r - i n s o l u b l e z i n c values a r e converted t o ZnC1, which is evaporated from t h e ash s u b s t r a t e and recovered. The cyclone ash used a s feed i n t h i s work was a composite from a number of primary regeneration runs. Analysis of t h i s feedstock i s given i n Table VI.

283

The l e v e l s of t h e v a r i a b l e s s t u d i e d i n secondary z i n c recovery are t a b u l a t e d below: Temperature, "C "F p r e s s u r e , kPa psig Mol Anhydrous HC1 i n Feed A i r Feed Ash Residence Time, min F l u i d i z e d Bed S o l i d s F l u i d i z e d Bed Depth, meters S u p e r f i c i a l Linear Velocity, meters/sec Operability Runs a t a l l c o n d i t i o n s t e s t e d gave e x c e l l e n t o p e r a b i l i t y . a s h w a s found i n any o f t h e runs, even t h o s e a t 1 3 ' . 08C Results Figures 2, 3 and 4 s u m r i z e t h e r e s u l t s . Figure 2 shows t h e breakdown of t h e recovery o f water-soluble and water-ins o l u b l e zinc as f u n c t i o n s o f time and temperature, w i t h a feed gas c o n s i s t i n g o f 20 mol % H C 1 i n a i r . E s s e n t i a l l y 100% of t h e water-soluble z i n c i n t h e cyclone ash was recovered i n as l i t t l e a s one minute residence t i m e a t a l l t h e c o n d i t i o n s t e s t e d . This i s n o t s u r p r i s i n g s i n c e no r e a c t i o n is required, only v o l a t i l i z a t i o n o f t h e ZnC1, t h a t the w a t e r - s o l u b l e z i n c r e p r e s e n t s . I t has been shown t h a t H C 1 i s n o t required f o r t h i s H,O-soluble z i n c recovery, t h a t e s s e n t i a l l y 100% recovery can b e obtained u s i n g HC1-free a i r or n i t r o g e n . Figure 2 shows t h a t t h e e x t e n t of secondary recovery of z i n c is l i m i t e d by t h e r a t e o f r e a c t i o n of t h e water-insolub l e z i n c t o form v o l a t i l e z i n c c h l o r i d e . The r a t e of recovery of t h e water-ins o l u b l e zinc i s very f a s t i n i t i a l l y b u t slows down markedly a f t e r the f i r s t minute o f r e a c t i o n time. Recovery i s b e t t e r t h e h i g h e r t h e temperature i n t h e range o f 816 t o 1038C. Figure 3 i s a p l o t similar t o F i g u r e 2 b u t i t shows t h e t o t a l combined recovery of w a t e r - s o l u b l e and w a t e r - i n s o l u b l e zinc. It i s apparent from t h i s p l o t t h a t as high a s 70% o f t h e t o t a l z i n c i n t h e cyclone s o l i d s was recovered i n a s l i t t l e a s one minute r e s i d e n c e time. Greater t h a n 73% of t h e c h l o r i n e i n t h e cyclone underflow ash was v o l a t i l i z e d and removed from t h e feed a s h a t a l l c o n d i t i o n s t e s t e d . Figure 4 shows t h a t t h e w a t e r - i n s o l u b l e z i n c recovery i n c r e a s e s moderately with i n c r e a s i n g HC1 p a r t i a l pressure. The i n c r e a s e i s unaffected by the HCl/air r a t i o . Hence, a t a given HC1 concentration i n t h e feed a i r , t h e z i n c recovery can be enhance3 by i n c r e a s i n g t h e t o t a l p r e s s u r e and thereby t h e H C 1 p a r t i a l pressure. Therefore, a t t h e p r o j e c t e d commercial o p e r a t i n g p r e s s u r e of 5 atm, 4 mol % H C 1 i n t h e feed a i r should g i v e r e s u l t s e q u i v a l e n t t o t h e use of 20% H C I a t 1 atm. Thus, i t h a s been shown t h a t 70% o r more of t h e zinc i n t h e a s h r e t a i n e d i n t h e cyclone s o l i d s c a n be recovered i n a r e l a t i v e l y s i m p l e s t e p added t o t h e primary r e g e n e r a t i o n system. With secondary recovery of 75%, overa 11 zinc recovery of 99.6 t o 99.7% has been demonstrated. The secondary z i n c recovery gives a s a v i n g s i n z i n c makeup c o s t s of about 3.5+ p e r ga1lo;l o f g a s o l i n e produced from c o a l v i a t h e ZnC1, p r o c e s s (8). Hydrocracking A c t i v i t y of Regenerated Melt
A run was made i n t h e continuous bench-scale 3 lb/h hydrocracker i n which the product ZnC1, c a t a l y s t from regeneration Run 19 was t e s t e d i n hydrocracking C o l s t r i p c o a l . A s shown i n Table V I I , t h e regenerated c a t a l y s t was somewhat more r e a c t i v e

816, 927, 1038 1500, 1700, 1900 119, 195, 271 3, 14, 25 o t o 60 1.5 t o 12.7 297 x 595 pm S i l i c a Sand 0.013, 0.062, 0.124 0.18, 0.24, 0.30 No s i n t e r i n g of

284

than v i r g i n zinc c h l o r i d e . T h i s i s l i k e l y due t o t h e f a c t t h a t t h e regenerated c a t a l y s t contained l e s s ZnO, which depresses ZnC1, a c t i v i t y , than t h e v i r g i n z i n c chloride. References

1.

Consolidation Coal Co., R&D Report N o . 39, O f f i c e o f Coal Research, U. S. Dept. of t h e I n t e r i o r . I n t e r i m Report No. 2 , "Research on Zinc Chloride Catalyst f o r Converting Coal t o Gasoline--Phase I--Hydrocracking of Coal 1, and E x t r a c t w i t h Zinc Chloride," Vol. 1 1 Book 1, March, 1968. Zielke, C.W., Struck, R.T., Evans, J.M., Costanza, C.P., Design Develop.," Ind. Eng. Chem. (1966) 5, 151. Ibid., 158. Zielke, C.W., Gorin, Struck, R.T., Clark, W.E., Dudt, P.J., Rosenhoover, W.A., E., Ind. Eng. Chem. (1969) 8, 546. Gorin, E., "Process

2.
3. 4. 5.

Rosenhoover, W.A., Gorin, E. Shale O i l . Tar Sands. and Zielke, C.W., Related Fuel Sources (T. F. Yen, ed.) Advances i n Chemistry S e r i e s No. 151, 153 (1976). Zielke, C.W., Struck, R.T., Gorin, E., Ind. Eng. Chem. (1969) 8, 552. Consolidation Coal Co., R&D Report No. 39, O f f i c e of Coal Research, U. S. Dept. of t h e I n t e r i o r . I n t e r i m Report No. 2, "Pre-Pilot P l a n t Research on t h e CSF Process--Phase I--Regeneration of Zinc Chloride Catalyst," Vol. 111, Book 2, March 1968.

--

6.

7.

8.
9.

et a l . , Conoco Coal Development Co. Report No. FE-1743-45 t o Parker, W.A., DOE, Nov. 20, 1977.
Zielke, C.W., Klunder, E.B., Maskew, J . T . and Struck, R.T., "Continuous Hydrol i q u e f a c t i o n of Subbituminous Coal i n Molten Zinc Chloride," presented a t t h e 85th N a t i o n a l Meeting, A.I.Ch.E., Philadelphia, Pa., June 1978. Submitted f o r p u b l i c a t i o n i n I&EC, Proc. Des. Dev.

Acknowledgment Appreciation i s expressed for support of t h i s work by t h e United S t a t e s Department of Energy, S h e l l Development Company and Conoco Coal Development Company under DOE Contract EX-76-C-01-1743.

285

- 4 1

5 82

4 0

? m
m

rl

? d
rl

0
\

U A
. A

286

TABLE I11

TABLE

E f f i c i e n c y of Primary Regeneration Run no. Mol % H C 1 i n A i r

1 6
5.5

22 19 - 8.5 11.5

Primary Regeneration Analysis of E f f l u e n t Bed S o l i d s Run No. Hours Used

H C
5

19 22 - 32 54
Weight 9. 0.06 0.03

% of Feed Melt Component i n Regenerated Melt

c1
C

Zn

S N
T o t a l Coal Ash N a K Ca M g Fe Si A1

97.9 102.0 0.6 9.7

00 .

6.4 63 80 1.9 1.7 33 1.6 2.1

98.8 . .~ 107.3 0.7 2.0 2.7 3.2 92 122 1.7 1.4 12 1.2 1.7

99.1 106.2 0.9 2.4 2.5

0134
00 .0 0.01

0.06
00 .0

Zn

0.05
00 .0

0.02 0.15
0.00 0.01

44 .
75 66 2.6 2.6 20 1.7 0.2

c1

Na , O

k20
CaO MO g
Fe203

TiO, SiO,

0.02 0.05 0.78 0.30 0.20 00 .4 97.35 0.79

0.04 1.49

0.44
0.19
0.00

96.23 1.30

TABLE I V

Primary Regeneration Analysis of Product M e l t s Run No. Anal. of Melt, W t . %

1622
0.15 0.05
0.00

19 0.17 0.07
0.02 0.40 0.00 0.01 0.00

H
C

N
0 (by d i f f . ) Organic S Sulfide S Sulfate S Zn

1.49
0.00 0.04 0.00

0.13 0.05 0.02 1.63

0.00 0.01 0.00

c1
Ash Anal. of Ash, W t . % NazO

47.61 50.30 0.36 10.22 5.23 4.03 1.43 49.21 11.06 12.41 6.41

47.40 50.59 0.17

19.00

47.32 51.83 0.18 24.98 8.71 11.29 4.36 20.11 1.46 27.72 1.37

K2O
CaO MO g
TiO, SiO,

12.55 9.20 3.01 19.55 1.73 23.68 11.28

287

TABLE V I Primary Regeneration Analysis of Cyclone Underflow Solids Run NO. % HC1 i n Feed A i r Analysis, W t . % zn i n ZnCl,* Z i n ZnO, ZnO-SiO,, n 16 5.5 4.73 11.08 5.30 0.11 0.35 0.34 0.17 0.04 9.65 4.04 3.67 0.67 33.36 14.20 22 8.5 3.57 4.07 4.80 0.12 0.14 0.30 0.08 0.02 11.87 4.41 4.06 0.00 44.75 18.19

2
11.5 4.10 3.33 5.54 0.13 0.35 0.23 0.12 0.02 9.48 4.14 2.98 0.84 43.21 19.48

Composite

ZnC)*A1,O,w

c1
H
C S (sulfate)

N, a O

K2O
CO a

MgO
TiO,

sio,

2.94 4.54 4.92 0.08 0.09 0.37 0.10 0.03 11.40 4.45 3.90 0.94 42. a6 18.41

*
w 6

Water-soluble z i n c Water-insoluble z i n c

TABLE V I 1

Comparison of Hydrocracking R e s u l t s With New and Regenerated ZnCl, C a t a l y s t Conditions Feedstock Temperature, O C T o t a l Pressure, p s i g Melt Residence Time, h ZnCl,/W Coal, Wt. R a t i o

-100 Mesh C o l s t r i p Coal 399 3500 1.29

1.0

Yields, W t .
c1-c3

7.M F Coal A

Regenerated ZnC1, Catalyst

New ZnC 1 Catalyst

12 .
4.2 41,5 16.2 6.0 17.7 2.5 6.4 79.8

2.1
2.7 33.5 20.9 6.1 15.8 4.9 6.8 79.3

c4

C x 200C D i s t i l l a t e ,
200 x 475C D i s t i l l d t e 4475C D i s t i l l a t e MEK-Soluble Residue MEK- Insolub l e Residue

H Consumed
Conversion t o D i s t i l l a t e

288

m e N U
0

a-4
N

289

SECOXWRY Z I N C RECOVERY GRAPHS FIGURE 2 Zinc Type Recovery a s a Function of Temperature and Time T o t a l P r e s s u r e = 3 p s i & Feed Gas = 2 0 mol % t I C 1 i n A i r

,Insoluble Zinc

Ash Residence Time, minutes

FIGURE 3
T o t a l Zinc Recovery a s a Function o f Temperature and Time
80

2 270
N
3

H
U

u u

o 60
500

HF?:

OPI

4 5 6 7 8 9 10 Ash Residence Time, minutes FIGURE 4

11

1213

Water-Insoluble Zinc Recovery vs. HC1 P a r t i a l Pressure Residence Time = 10 min; Temperature = 927C T o t a l P r e s s u r e of Run i s l i s t e d a t Data Points

H C 1 P a r t i a l Pressure, a t m .

290