10

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' I

Low T e m p e r a t u r e Carbon MonoxideConversion Catalysts R o b e r t Habermehl Kenton Atwood Catalysts a n d Chemicals Inc Louisville, Kentucky

The purpose of this paper is to r e p o r t on the initial commercial operation of a lowt e m p e r a t u r e carbon monoxide conversion catalyst a n d to show s o m e of the eccnomic advantages of using such a c a t a l y s t in the production of hydrogen and ammonia synthesis g a s . HISTORICAL: The production of hydrogen f o r making ammonia synthesis gas h a s r e a c h e d m a j o r proportions. The quantity of hydrogen used in ammonia synthesis in the U. S. l a s t year exceeded 540 billion cubic f e e t , m o r e than 1. 5 billion cubic f e e t p e r day. The consumption of hydrogen for ammonia synthesis world-wide now exceeds 1500 billion cubic f e e t p e r year and is growing a t the r a t e of somewhere between s e v e n and ten p e r cent p e r y e a r . In addition, the production of hydrogen for c h e m i c a l hydrogenations a n d for hydrotreating and hydrocracking is becoming a n increasingly important f a c t o r i n the consumption of hydrogen. Hydrocracking along with i n c r e a s e d ammonia production portends a continued i n c r e a s e in the r e q u i r e m e n t s for m o r e hydrogen production. Most of the hydrogen being consumed is produced by the reaction of s t e a m with a hydrocarbon

2
and i s commonly r e f e r r e d t o a s "reforming. S m a l l e r quantities of hydrogen a r e produced by the partial oxidation of hydrocarbons by the reaction

In o r d e r t o maximize the quantity of hydrogen produced in these p r o c e s s e s , i t i s e s s e n t i a l t o convert the c a r b o n monoxide to carbon dioxide and additional hydrogen by reacting i t with s t e a m

GO

HzO

COZ

Hz

T h i s r e a c t i o n is in equilibrium and tends t o go t o completion towards the right a s the t e m p e r a t u r e is d e c r e a s e d . P r e s s u r e h a s no effect on the equilibrium. It, t h e r e f o r e , becomes d e s i r a b l e t o promote this reaction a t the lowest possible t e m p e r a t u r e . In o r d e r to i n c r e a s e the reaction r a t e a t which equilibrium

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conditions a r e approached, it h a s been n e c e s s a r y to c a r r y out the reaction in the p r e s e n c e of a catalyst. The ca'talyst u s e d a l m o s t exclusively.for t h i s reaction f o r the l a s t 40, to 50-y e a r s has. been an i r o n oxide-chrome,oxide,promoted catalyst. This catalyst caus,ed the r,eactjon to p r o c e e d , a t c o m m e r c i a l l p feasible r a t e s a t . t e m p e r a t u r e s ,a-s,lowa s 6.5.0F, a n d i t had a useful life of t h r e e ' t o ' o v e r ten y e a r s , depending on the,.cons'ervatism of the design.: A'lthough 0the.r c a t a l y s t s have been investigated a n d r e p o r t e d (1) ( 2 ) f o r promoting the reaction between carbon' monoxide and steam' a t t e m p e r a t i i r e s 1owe.r.than 6 5 0 " F , none have .found comm e r c i a l acceptance, due principally to a n i m p r a c t i c a l l y s h o r t life when used a t n e a r atmospheric. p r e s s u r e . One l o w - t e m p e r a t u r e conversion c a t a l y s t , hnwexrer, found l i m i t e d c o m m e r c i a l acceptance when u s e d a t 'relatively high p r e s s u r e s . It 'was not untii 1953.that a c o m m e r c i a l plant was constructed f o r the production of hydrogen for'the manufacture of ammonia s y n t h e s i s gas by steam-,hydrocarbon reforming a t p r e s s u r e s appreciably higher than a t m o s p h e r i c , approximately 90 peig. Sinc.e that t i m e , m o s t of the plants constructed o p e r a t e a t p r e s s u r e s ranging f r o m 75 to 300 psig. The plants f o r m e r l y constructed to o p e r a t e a t n e a r atmospheric p r e s s u r e a r e now being r e p l a c e d o r converted into p l a n t s operating a t the higher p r e s s u r es . In 1931 L a r s o n (3) was granted a patent on a catalyst f o r promoting the reaction between carbon monoxide and s t e a m a t t e m p e r a t u r e s a s low a s 540'F. A c o m m e r c i a l plant was constructed e a r l y in the period of 1940-1950 f o r the production of hydrogen f r o m w a t e r - g a s f o r the manufacture of ammonia synthesis p a & . T h e conversion of carbon monoxide t o c a r b o n dioxide and hydrogen was c a r r i e d out over a catalyst apparently based on the L a r s o n patent a t appr0ximateJ.y 450 psig. Although exact operating t e m p e r a t u r e s and r a t e s have never b e e n published, they . a r e .known t o be i n the r a n g e of 350' to 650"F, and s p a c e velocities of 400 to 1000 S C F p e r cubic foot of catalyst. E v e n though the catalyst had a relatively s h o r t life, i t continued to be u s e d even to the p r e s e n t time. T h i s catalyst never found c o m m e r c i a l acceptance f o r .low p r e s s u r e operation, p r e s u m a b l y because cf an impractically s h o r t l i f e . Catalysts and Chemicals Inc. , soon a f t e r i t s formation in 1957, s t a r t e d successful development work on the adaptation of a c a t a l y s t , in g e n e r a l s i m i l a r to the L a r s o n cataly-st, f o r promoting the conversion of carbon monoxide in the t e m p e r a t u r e Over eight c o m m e r c i a l c h a r g e s of t h i s c a t a l y s t , designated range f 350.to 650F. as a r e in operation o r soon to g i in operation a t p r e s s u r e s ranging f r o m n e a r a t m o s p h e r i c to 350 psig; however, m o s t of t h e s e plants will o p e r a t e a t o v e r 100 psig. P i l o t plant and c o m m e r c i a l experience show that the c a t a l y s t w i l l operate at r a t e s appreciably in e x c e s s of those f o r the conventional i r o n oxide-chrome oxide type catalyst. With reasonable extrapolation of the available c o m m e r c i a l e x p e r i e n c e , a p r a c t i c a l life of a t l e a s t one and one-half .to t h r e e y e a r s . ' c a n be expected.
,

I/

I'

PRINCIPAL ADVANTAGES O F C18 T Y P E LOW-TEMPERA TURE CONVERSION CATALYST: The advantages of a low-temperature c a r b o n monoxide conversion cztalyst in hydrogen production a r e obvious 'from a study of the equilibrium ' reaction

CO

HzC*

COZ

H z

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The equilibrium constant f o r the reaction h a s a value of 22 a t 6 5 0 " F , which is the generally accepted minimum effective t e m p e r a t u r e f o r the u s e of the i r o n oxidec h r o m e oxide catalyst. The equilibrium constant is 207 a t 400"F, which i s a reasonable t e m p e r a t u r e f o r t h e C18 type low-temperature conversion catalyst. The p r a c t i c a l significance of t h i s is that a t t h e s a m e s t e a m concentration, the u s e of the C18 catalyst will r e s u l t in o v e r 99 p e r cent conversion of the carbon monoxide, w h e r e a s the i r o n oxide-chrome oxide c a t a l y s t will give only 90 to 95 p e r cent conversion a t i t s l o w e s t effective t e m p e r a t u r e .

If i t i s ass7imed that the p r o c e s s i n g scheme f o r hydrogen production for the manufacture of ammonia synthesis g a s is the conventional steam-hydrocarbon reforming-consisting of a p r i m a r y and secondary r e f o r m e r followed by carbon monoxide conv e r s i o n , carbon dioxide r e m o v a l and then methanation of t h e residual carbon monoxide--and that the acceptable l e v e l of residual carbon monoxide to b e methanated i s not m o r e than 0. 3 mol p e r c e n t , the s t e a m requirement f o r achieving this degree of conversion in a single s t a g e of carbon monoxide conversion with the usual i n t e r stage cooling is 3. 5 m o l s of s t e a m p e r mol of dky feed gas when a n i r o n oxidec h r o m e oxide catalyst is used. When the C18 low-temperature conversion catalyst i s u s e d , the steam r e q u i r e m e n t i s 0 . 7 mol p e r mol of d r y feed g a s , a reduction of 80 p e r cent. The g r e a t e r quantity of s t e a m required with the i r o n oxide-chrome oxide catalyst, however, is considered i m p r a c t i c a l and e i t h e r a l o w e r quantity of s t e a m is u s e d with a single s t a g e of conversion, followed by carbon dioxide removal and methanation, o r two s t a g e s of carbon monoxide conversion a r e used with c a r bon aioxide removal a f t e r e a c h stage, followed by methanation. In the f i r s t c a s e , the carbon monoxide to b e methanated ranges f r o m 0 . 6 to 1.0 m o l p e r cent. T h i s g r e a t e r quantity of carbon monoxide not only i n c r e a s e s the quantity of i n e r t s in the synthesis g a s , thus making the synthesis of ammonia l e s s efficient, but f o r e a c h mol of carbon monoxide methanated, 3 mols of hydrogen a r e consumed, requiring a l a r g e r plant to produce the expected quantity of ammonia. In the second c a s e w h e r e two s t a g e s of conversion a r e u s e d , the carbon monoxide to be methanated does not exceed 0 . 3 mol p e r cent; however, considerably m o r e equipment is req u i r e d , consisting of a s t a g e o carbon dioxide removal, h e a t e r s , s a t u r a t o r s , exchangers, c o o l e r s , etc. , which not only i n c r e a s e the capital cost of the plant, but a l s o the operating cost.
The additional steam that m u s t b e added to t h e gas f o r the second stage conversion reaction b r i n g s the over-all s t e a m requirements t o 1 . 4 m o l s of s t e a m p e r mol of dry g a s exit the secondary r e f o r m e r . This i s still twice the quantity of s t e a m required f o r achieving the s a m e d e g r e e of conversion in a single stage conversion s y s t e m using the l o w - t e m p e r a t u r e shift catalyst. T h e s e s t e a m requirements f o r the t h r e e basic carbon monoxide conversion s y s t e m s a r e s u m m a r i z e d in F i g u r e 1. Additional significance to the potential advantage of the l o w - t e m p e r a t u r e shift c a t a l y s t can b e seen by observing on the graph that the s t e a m level in the gas r e q u i r e d to achieve a methane leakage of 0. 2 mol p e r cent f r o m a secondary r e f o r m e r is 0. 5 m o l p e r m o l of d r y gas a t 150 psig and 0 . 7 mol p e r mol of d r y gas a t 300 psig. It h a s a l r e a d y been indicated that the 0. 7 s t e a m to dry g a s r a t i o is the required s t e a m l e v e l to r e a c h the 0. 3 p e r cent carbon monoxide level in the feed to the methanator. F u r t h e r , the p r a c t i c a l s t e a m levels required in t h e gas to supply the e n e r g y requirements of regenerating the carbon dioxide r e moval solution a r e shown f o r a n amine s y s t e m and f o r one of the newer carbon dioxide removal s y s t e m s . T h e s e s t e a m to g a s r a t i o s a r e 1.40 and 0 . 7 0 , respectively.

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Once a g a i n , the 0 . 7 0 value a p p e a r s a3d shows that the C18-i development i s a n important contributor to the advancing technology in ammonia synthesis g a s production. F i g u r e l ' a l s o shows the relative physical s i z e of the shift c o n v e r t e r s f o y the three basic conversion s y s t e m s . If the s i z e r e q u i r e m e n t ,of the s i n g l e s t a g e s y s t e m using the C18- 1 c a t a l y s t in conjunction with pre-conversion over a c'cmv.entinrial catalyst i s considered a s 1 , the s i z e of the two-stage conventional catal.ys;.t s y s t e m is 1 . 4 and f o r the single-stage conventional catalyst s y s t e m is 6. 0. The potentia.1 advantages of t.he low-temper2,tm-e shift c a t a l y s t i n ammonia synthesis g a s production a r e f u r t h e r shown in Table I, wherein a comparison .is m a d e i n s c m e of the c r i t i c a l conditions a n d r e q u i r e m e n t s for a hypothetical 300 t o n p e r day ammonia plant for the following t h r e e a l t e r n a t e p r o c e s s i n g s c h e m e s . The r e f o r m e r p r e s s u r e , l e v e l in a l l c a s e s is 300 psig exit the r e f o r m e r tubes. Case 1
A single-stage conversion s y s t e m employing conventional

c a t a l y s t in s e r i e s with low-temperature shift c a t s l y s t and using one cf the newer "lower energy" c s r b o n dioxide removal processes. Case 2 The s a m e as Case 1 except employing c o m e n t i o n a l catal y s t throughout the single- stage c o n v e r t e r a n d operating with higher i n e r t s in the synthesis gas loop. The s a m e a s Case 2 except using amine a s t h e carbdn dioxide r e m o v a l s y s t e m a n d obtaining a g r e a t e r conv e r s i o n of the carbon monoxide due to the higher s t e a m r e q u i r e m e n t s of the amine s y s t e m .

Case 3

Comparison of the hydrocarbon r e q u i r e m e n t s i n the above s y s t e m s i n TabIe X ind i c a t e s that the u s e of low-temperature shift c a t a l y s t p e r m i t s the s y n t h e e s gas section of the plant to be reduced in s i z e by approximately 12 p e r cent. The inc r e a s e d c o s t of the c a t a l y s t r e q u i r e d to give this advantage i s approximately $50,000, including the u s e of a p r i m a r y reforming catalyst with t h e b e s t known activity and h e a t t r a n s f e r c h a r a c t e r i s t i c s scch that full advantage c a n b e taken in reducing the physical s i z e of the plant. F i g u r e 2 shows the r e l a t i v e hydrocarbon r e q u i r e m e n t s f o r the p r o c e s s , including fuel and s t e a m production, for t h e s e t h r e e s y s t e m s of synthesis g a s production. The production of l a r g e quantities of relatively high-purity hydrogen, s u c h a s a r e n e c e s s a r y f o r the new hydrocracking of hydrocarbons p r o c e s s e s , is gaining rapidly in i n d u s t r i a l importance. The typical plant involves high p r e s s u r e r e f o r m i n g , single-stage conversion, carbon dioxide r e m o v a l , and methanation of r e s i d u a l c a r b o n oxides. The d e g r e e of conversion of the c a r b o n monoxide exit the r e f o r m e r influences the ultimate c o s t of t h e s e plants s i n c e unconverted c a r b o n monoxide ends up a s a methane impurity in the product and a f f e c t s the d e g r e e of r e f o r m i n g to r e a c h a given product purity. The g r e a t e r conversion of c a r b o n monoxide is made possible through the u s e of low-temperature shift catalyst a n d , t h e r e f o r e , p e r m i t s a substantial reduction in the physical s i z e of the r e f o r m e r with attendant lower s t e a m and fuel r e q u i r e m e n t s , o r alternatively, p e r m i t s r e f o r m i n g a t a higher

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I .

p r e s s u r e l e v e l with a subsequent reduction i n c o m p r e s s i o n costs. F i g u r e 3 shows a c o m p a r i s o n of a r e f o r m e r d e s i g n when using conventional c a t a !yst v e r s u s the use of l o w - t e m p e r a t u r e carbon monoxide conversion catalyst and the b e s t reforming c a t a l y s t available. The s i z e of the r e f o r m e r in t e r m s of c a t a l y s t volume required and the m a x i m u m tube wall t e m p e r a t u r e in the r e f o r m ing f u r n a c e a r e plotted a g a i n s t hydrogen p u r i t i e s of 95 t o 98 p e r c e n t f o r a production capacity of 50 MMSGFD of net hydrogen delivered a t 150 psig. It i s shown that the use of the l o w - t e m p e r a t u r e canversion catalyst p e r m i t s a 25 to 30 p e r c e n t reduction in the s i z e of the r e f o r m e r . F o r example, in the c a s e of 95 p e r cent hydrogen purity, it is o b s e r v e d that approximately 740 cubic f e e t of c a t a l y s t a r e r e q u i r e d in the r e f o r m e r when using the conventional catalyst, w h e r e a s approximately 550 cubic f e e t a r e r e q u i r e d when using the l o w - t e m p e r a t u r e shift c a t a l y s t and the b e s t reforming c a t a l y s t available. The maximum tube wall t e m p e r a t u r e i n both c a s e s is 1670F a s s u m i n g the s a m e physical s i z e of the tubes in t e r m s of inside d i a m e t e r and length in the f i r e d zone of the r e f o r m e r . F o r 97 p e r cent hydrogen p u r i t y , when using the conventional c a t a l y s t , the r e f o r m e r m u s t contain about 785 cubic f e e t of c a t a l y s t and the m a x i m u m tube wall t e m p e r a t u r e r e q u i r e d is 1720F. With C18 c a t a l y s t in the shift c o n v e r t e r , the r e f o r m e r s i z e m a y be reduced t o contain 665 cubic feet of c a t a l y s t and the tube wall t e m p e r a t u r e r e q u i r e d is now 1700F. LABORATORY DEVELOPMENT AND COMMERCIAL DEMONSTRATION OF THE EFFECTIVENESS OF C18 L O W - TEMPERATURE CARBON MONOXIDE CONVERSION CATALYST: Bench s c a l e and pilot plant work have been conducted i n the l a b o r a t o r i e s of Catalysts and Chemicals Inc. t o establish the p r e f e r r e d catalyst composition, the b e s t method of p r e p a r a t i o n of the c a t a l y s t , the method of reduction giving a catalyst of the highest activity, the optimum operating conditions, the effect of poisons, and the decline of activity with t i m e on s t r e a m v e r s u s operating te'mperature. Specific studies w e r e made on the effect of total p r e s s u r e , the p a r t i a l p r e s s u r e of c a r b o n dioxide, and the p a r t i a l p r e s s u r e of s t e a m on the kinetics of the r e s c t i o n . It i s not to be implied that t h e l a b o r a t o r y studies have r e s u l t e d in complete a n s w e r s to the quantitative e f f e c t of a l l the v a r i a b l e s involved; however, i t is believed that sufficient information i s known upon which to b a s e workable designs a t the u s u a l p r o c e s s i n g conditions. L i f e t e s t s in excess of 1 3 m o n t h s ' d u r a t i o n w e r e conducted a t typical operating conditions. The f i r s t c o m m e r c i a l c h a r g e of C18 w a s placed on s t r e a m on J a n u a r y 1. 1963 i n a 210 ton p e r day ammonia plant a t about 120 psig. An operating m i s h a p during reduction of the c a t a l y s t and a d v e r s e conditions during the initial s t a g e s of operation r e s u l t e d in below-normal i n i t i a l activity of the catalyst. Despite t h e s e f a c t o r s , h o w e v e r , the catalyst had sufficient activity t o show a distinct advantage over the previous conventional c a $ a l y s t , and operation h a s continued to the date of this writing with no m o r e than t h e anticipated decline in activity. The initial activity and the rate of decline i n activity a r e shown in F i g u r e 4. T h i s c h a r g e of catalyst h a s been on s t r e a m f o r 1 2 - 1 / 2 months a s of thls date.

I i

1 i

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T C s second c o m m e r c i a l charge of C1S catalyst was placed on s t r e a m on May 11, ! Q 6 3 in a 260 ton p e r day ammonix plant on the West Coast. In c o n t r a s t to the f . r s t c h a r g e of c a t a l y s t , the conditions of reduction and initial operation were in ?c,crdance with the recommended p r o c e d u r e s , and this c h a r g e of c a t a l y s t is continuing to o p e r a t e a t an inlet t e m p e r a t u r e of 400"F, which was t h e initial inlet t e m p e r a t u r e . The r e l a t i v e activity level and decline in activity of t h i s charge of ( z t a l y s t a r e shown i n F i g u r e 4 , and specific data a r e p r e s e n t e d i n Table 1 . 1 The p e r f o r m a n c e of this c h a r g e of catalyst h a s thus f a r exceeded the anticipated p e r f s r m a n c e based on the pilot plznt 'life t e s t s .

A rhird c h a r g e of C l 8 c a t a l y s t w a s placed in operation on July 2 4 , 1963, operating on a s l i p s t r e a m of a r e f o r m e r effluent a t 2 psig. It continues to p e r f o r m s a t i s f a c t o r i l y , and the r e l a t i v e activity and decline i n activity a r e shown i n F i g u r e 4. The design level of this operation, however, which was deduced f r o m e x p e r i m e n t s 3 t low p r e s s u r e , may p r o v e t o b e uneconomical i n many applications. F u r t h e r operating experience is r e q u i r e d before the u s e of the catalyst c a n be encouraged A t low p r e s s u r e s .
A s s t a t e d , F i g u r e 4 shows the performance of the C18 c a t a l y s t i n these t h r e e c o m m e r c i a l units. The r e l a t i v e activity with time on s t r e a m is shown i n r e l a t i o n to the p e r f o r m a n c e of the catalyst throughout the 13-month life t e s t in CCI's pilot plant.

A projection of these c u r v e s indicates a n anticipated life of the c a t a l y s t of one and one-half to t h r e e y e a r s in c o m m e r c i a l operation. A significant factor shown in F i g u r e 4 is the c o m m e r c i a l verification of the importance of r e d u c t i o n conditions

3n the activity of l o w - t e m p e r a t u r e conversion c a t a l y s t s when the p e r f o r m a n c e in P l a n t s 1 and 2 is compared.

A s of this writing, five m o r e c o m m e r c i a l c h a r g e s of C18 c a t a l y s t have b e e n sold f a r s t a r t u p i n e a r l y 1964.

SS'MMARY: The C l 8 low-temperature carbon monoxide c o n v e r s i o n catalyst h a s been d e m o n s t r a t e d c o m m e r c i a i l y to offer a proven economical l i f e i n hydrogen and ammonia synthesis g a s manufacture. The catalyst i s , in g e n e r a l , m o r e Fencitive t o both c a t a l y s t poisons and a b n o r m a l operating conditions than is the conventional i r o n oxide-chrome oxide catalyst a n d , t h e r e f o r e , r e q u i r e s m o r e careful operation and g r e a t e r attention to detail in p r o c e s s design. Specifically, the c a t a l y s t activity is s e v e r e l y affected by even t r a c e quantities of sulfur i n the feed g a s . The activity is appreciably affected by the subjection of the catalyst t o t e m p e r a t u r e s in e x c e s s of the n o r m a l operating level.
The C18 catalyst m u s t be reduced under s p e c i a l conditions and with g r e a t c a r e i n o r d e r to obtain m a x i m u m activity and long life. (5) Application of the c a t a l y s t i n low p r e s s u r e operations h a s not b e e n shown to be p r a c t i c a l and m o r e Operating experience w i l l b e r e q u i r e d b e f o r e this c a n be de!er mined. The c a t a i y s t h a s been proven to offer a n a t t r a c t i v e payout f a c t o r i n t e r m s of initial p: 3nt investment and operating economy. The ultimate life of the c a t a l y s t could well ex1 eed the projected minimum of one and one-half to t h r e e y e a r s based on the I ,mmercial operation to date.

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References: -

flj

S t o r c h , H. H. and P i n k e l , I. I., Industrial and Engineering Chemistry, 29, 715; 1937..

I

(2)

White, E. C. and S c h d t z , J. F. , Industrial and Engineering Chemistry, 26, 95-7; 1934.

-I -

(3)
j43

U. S. Patent 1 , 7 9 7 , 4 2 6 , March 24, 1931.

P a t e n t application pending. P a t e n t application pending (on reduction procedure).

'15)

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TABLE I
Comparison of P r o c e s s Design F e a t u r e s of Ammonia Synthe s i s Gas Manufacture U sing Low- T e m p e r a t u r e Carbon Monoxide Conversion Catalyst P r o c e s s Scheme: Steam-Hydrocarbon Reforming, P r i m a r y a n d Secondary; 300 p s i g ; Carbon Monoxide Conversion; Carbon Dioxide Removal; Methanation of Carbon Oxides. 300 Tons Per Day Ammonia 1 0. 2 m o l p e r cent, d r y b a s i s 2 1 . 1 mol p e r cent, d r y basis 3 0 . 5 mol p e r cent, dry basis

Basis:

Case

: :

CO i n Shift Converter Effluent$&* I n e r t s ( C H 4 t A) Exit Methanator, m o l s / h r Synthesis G a s Required for 300 T P D NH3 mols /hr Relative Amount

29.89 70. 85 38. 30 (0.96 m o l p e r cent)(2. 1 m o l p e r cent)(l. 21 mol p e r cent)

3114.98 100%

3361.01 107.9%

3165.46 101.6%

Hydrocarbon, m o l s / h r P r o c e s s Requirements F u e l Requirements Total Requirements Relative Amount Air, mols/hr P r o c e s s Requirements F u e l Requirements Total Reqiirements Relative Amount S t e a m Requirements Total L b s / H r Relative Amount Relative R e f o r m e r Size Relative Shift Converter Size
c
,.". .,.
.. I

702.44 295.63 998.07 100%

788.11 331.68 1119.79 112. 270

720.68 451.77 1172.45 117 47% .

988.47 2957.70 3946.17 100%

1054. 25 3318.42 437 2.67 110.81%

1001.99 4519.74 5521. 73 139. 9370

. ,

69,570 100% 100% 100%

75,200 108. 1% 112.9% 125. 1%

114, 350 164. 470 103. 0% 194. 670

C a s e s a r e defined in text. P r a c t i c a l level of c a r b o n monoxide in shift c o n v e r t e r effluent using the s t e a m r e q u i r e m e n t s of the c a r b o n dioxide r e g e n e r a t i o n s y s t e m to full effectiveness in the shift c o n v e r t e r .

18
Table I1 P l a n t Operating Data; C18 Low-Temperature Carbon Monoxide Conversion Catalyst (260 Tons/Day Ammonia P l a n t , 120 PSIC)

Date - 5-24-63

Days on Stream

D r y Gas S V. . Inlet SCFH/ Temp. V/Hr. OF

_ _ I _ _

Outlet Temp.

"F
_ -

Inlet S/G Ratio

-

Gas Analyses, Mol P e r Cent C02

- - 4.2 3.0 0.02 71.4 72.4 0.2 0.2

CO

H2

CH4

N2 + A

i
!
1

13

1925

410

445

0.336

In

out 7.0
6-27-63 47 1980 400 450 0.42,

21.2* 20.39*

In 0.8 Out 3.8

3.0 0.06

74.0 74.0

0.3 0.3

21.9 21.8

4
.J
1
1

9-4-63

116

1800

402

453

0.38

In

0. 11

3.16 0.06 3.10 0.05

71.76 72.97 75.69 76.40

0.27 0.27 0.28 0.27

24.70 23.80 20.70 20.10

Out 2.91 12-4-63 207 1840 405 456 0.388

In 0.23 Out 3.18

*Analyses by c u s t o m e r ' s laboratory. Nitrogen a n d argon by difference. All o t h e r analyses by CCI chromatograph and w e r e essentially confirmed by c u s t o m e r analyses.

4& I

A B

U 0,
Q) M

c-

- Low T e m p e r a t u r e Catalyst . - 2-Stages Conventional Catalyst

I-Stage Conventional Catalyst C

,
Relative Catalyst Volumes

6 -

5
Q)

3-

4'

w U

2
d m
ld

2-

3
0
.r( U

2----e

0 S / C Levels Required For:

Amine Regeneration

6 0
e
ld

B
1 -

--T- -- - - - -----.--I---

-+

Sulfinol Regeneration and 0.2% CH4 a t 300 PSIC 0. 270 CH4 a t 150 PSIG (Exit Secondary)

I -

i 2

0 -

Figure 2
4

- Low T e m p e r a t u r e CO Conversion Catalyst (C18)

8

Case 3 (5522) Case 2

U

C a s e I-Low T e m p e r a t u r e Catalyst and Sulfinol

.
m

Case 2-One Stage C o n v e n t i o d Catalyst and Sulfinol

Case 3-One Stage Conwntional Catalyst and Amine

Mols/Hour CH4 Required for 300 Tons/Day NH, at 300 PSIG' Reforming

Figure 4

- Low Temperature

CO Conversion Catalyst

I
c
M

C o m m e r c i a l P e r f o r m a n c e of C18 and Life T e s t R e s u l t s

Plant 2 Plant 3

120 psig

- 2 psig
CCI Life T e s t

- 150 psig

-*Plant
0

- 120 psig
18
20
22

8 10 12 14 16 T i m e on S t r e a m (Months)