138.

C F Gray and W. J. Metrailer

Esso Research Laboratories Humble O i l & Refining Company Baton Rouge Refinery Baton Ruuge, Louisiana
I3"FlOIXJCTION

Petroleum coke i s produced by coking of high boiling petroleum fractions (residua) t o obtain more valuable l i g h t e r hydrocarbon products and coke. The two more prominent cammercial processes f o r carrying out the coking operation are Fluid Coking and Delayed Coking. Fluid Coking is a continuous process. It is carried out in equipm e n t similar t o that used extensively for Fluid Catalytic Cracking (1,2). A t 9 0 vessel system i s used i n which the s m a l l product coke p a r t i c l e s a r e heated by partial combustion i n a burner vessel and these p a r t i c l e s a r e circulated t o t h e coking vessel t o supply t h e heat needed. Finely dispersed residuum feed i s injected i n t o t h e coking vessel which operates at gOO-fl5"F. The coke formed by cracking i s deposited on the surface of the s m a l l coke p a r t i c l e s which are then returned t o the burner. The burner is, of course, operated at a higher temperature than the reactor. This r e s u l M i n some d w o l a t i l i z a t i o n of t h e coke. These v o h t i l e s along Kith p a r t of the product coke ( i f necessary) a r e burned t o supply heat.

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I n the Delayed Coking process, residuum is preheated i n a furnsce and i s then introduced i n t o a soaking drum. This large drum provides suff i c i e n t holding time t o crack the residuum with t h e light hydrocarbons passing overhead. The drum eventually fills w i t h coke which is then mechanically removed. Delayed Coking i s thus a cyclic process. Coking temperatures i n the drum may vsry between 800 and 8 5 0 " ~ . I n both processes t h e coke product represents a bottoms fraction and i t s chemical quality i s dependent on t h e quality of the residuum feed. Nonv o l a t i l e metals and ash constituents i n t h e feed a r e deposited essentially lOO$ i n the coke. Sulfur compounds, which a r e u s u a l l y concentrated i n the heavier petroleum fractions, are f u r t h e r concentrated i n t h e coke t o t h e extent that petroleum coke product normally contains 1.2 t o 2.0 tFmes t h e s u l f u r concentrat i o n of t h e residuum feed.
The v o l a t i l e s content and physical properties of petroleum coke produced by Fluid coking a r e quite different from the coke produced i n Delayed Coking. Fluid coke is exposed t o a higher temperature than i s delayed coke, about llOO-ll50"F. vs. 800-850"F. As a r e s u l t green ( i . e . , uncalcined) f l u i d coke contains about 7 w t . $ volatiles (measured a t 1742°F.) vs. 10-15 wt.3 v o l a t i l e s i n green delayed coke. Also, i n Fluid Coking a layer of coke I s deposited during each pass and the product has a characteristic onion ring structure, whereas delayed coke product is amorphous i n nature. The differences between the two cokes . m i l l u s t r a t e d by photomicrographs i n Flgure 1 , which

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shows cross sections of p a r t i c l e s of t h e two cokes. Petroleum cokes vary i n t h e i r resistance t o oxidation. This i s an important property of coke i n many end uses. Good W i t y cokes, i . e . , those having low metals and sulfur contents, generally are calcined and then f i n d t h e i r way into carbon electrodes where resistance t o oxidation i s desirable. LOWquality cokes generally a r e used green as a f u e l and r a p i d oxidatibn is desirable.

In t h e work described i n t h i s paper, t h e r e a c t i v i t y of t h e various , cokes was measured by placing t h e coke i n a flowing stream of C Q a t 1742'F. . 1< % and recording t h e weight l o s s continuously. This technique permits close cont r o l of t e s t conditions and does not require removal of l a r g e quantities of heat. Other investigators have studied t h e reaction o f C q with carbon. In a recent paper (3), C i v r y and S c a l l i e t reported on an investigation relating anode r e a c t i v i t y with CQ t o performance i n an e l e c t r o l y t i c reduction c e l l .

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EXPERIMENTAL

MATERIALS

Samples of green f l u i d coke from several commercial,fluid coking units were calcined i n a muffle furnace t o a temperature of 2400'F. The delayed cokes and t h e coal tar coke were from commercial production. These cokes had been calcined fUr use i n carbon electrodes p r i o r t o receipt. Normally, a calcining temperature of about 2400'F. is used in this commercial operation.

A commercially available coal tar binder was used i n the preparation of all o f the molded carbon specimens. This material was obtained f r o m t h e Barr e t t Division of Allied Chemical Company.

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PRYSICAL AND CHEMICAL INSPECTIONS OF MATERIALS
Pertinent inspections of the calcined cokes used i n this study a r e given i n Table I. All t e s t s and inspections were obtained by using techniques w h i c h are common i n t h e carbon industry. The coal tar binder had a 2 1 5 ' F . softening point, a coking value of 67.5 and C/H r a t i o o f 1.6. FWK!TIvITY TEST The r e a c t i v i t y of t h e cokes with carbon dioxide (C@ + C -2CO) was measured i n t h e r e a c t i v i t y apparatus s h a m i n Figure-2. %e sample of carbon w a s a s placed i n the quartz tube. m e r heating dried overnight a t 275°F. and then w t o 1742'F. i n an atmosphere of purified nitrogen, a flow o r p u r i f i e d Co;! was s t a r t e d over t h e sample. The CQ r a t e was about l2 l i t e r s per hour. This gave a velocity of 2.2 cm./sec. i n t h e annulus between the sample and t h e quartz tube. A continuous weight recording device measured t h e l o s s o f weight of the sample due t o reaction with C02. The i n l e t and e x i t gas r a t e s and e x i t gas composition were obtained. The CO concentration i n the off-gases ranged from about 3 t o 30 percent varying with the r e a c t i v i t y of the sample.

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Test data were obtained on granular coke samples and on samples o f bound together with coke which had been molded i n t o cylindrical test spec-s, coal tar binder. When t h e reactivLty of a granubr coke sample was t o be measur-ed, a 16 gram sample of 14-35 mesh coke w a s supported i n a platinum mesh basket. Reactivities of t h e molded carbon specimens were determined by suspending t h e sample on a platinum wire whlch passed through a small hole in the specimen. Upon completion of the test on molded specimens, the carbon body was cooled and b r i s t l e brush. Loosely held carbon parweighed and then brushed with a t i c l e s which could be brushed from t h e sample w e r e reported as "dust." The amount o f "dust" measured in this manner i s related t o the amount of carbon w b i c h w i l l be l o s t from the carbon body as it is consumed.

The molded carbon specimens used i n this study were prepared by mixing the coke and pitch binder i n a steam jacketed sigma blade mixer. m n gw a s continued for 30 minutes at 300'~. The mixhrre was molded t o forma 3 inch diameter by 5 inch long carbon body which was then baked slowly t o about 1 9 0 0 ' F . in a muffle furnace. Reactivity t e s t specimens about 3/4 inch i n diameter by 2 inches long were cored from the baked carbon body. Three levels of b i n d e r content were used i n t h e work reported herein and both f i n e grained and coarse grained carbon aggregate@were emplopd.?he f i n e grained aggregate consisted of about 75 I&.$ 35-200 mesh coke and 25 w t . $ coke ground t o pass a 100 mesh screen. The coarse @ b e d aggregate was made up of 50 w t . $ 4-48 mesh coke and 50 w t . $ coke ground t o pass a 100 mesh screen.

RESULTS AlJD DISCUSSION
Comparison of Gramdar Coke Reactivity

R e s u l t s of the study of cokes i n granular form (14-35 mesh) show that f l u i d cokes react Kith C@ at a m c h lower r a t e than do delayed cokes. (Table I) The coal tar coke which was prepared i n a manner simiLar t o delayed coke had the highest reactivity. These data confirm r e s u l t s obtained by Walker e t al (4) i n a more detailed study of cokes. It i s well. known that oxidiition of carbon occurs more rapidly along c r y s t a l edges than along t h e basal planes. Deposition of carbon in r e l a t i v e l y t h i n layers on t h e spherical f l u i d coke particles results in t h e onion s k i n structure of f l u i d coke (5) which i s shown i n Figure 1 . The carbon i n this t h i n onion skin layer is probably oriented such that b a s a l planes of the carbon structure are exposed t o a greater extent than a r e t h e c r y s t a l edges. Thus, one would expect t h a t t h e r e a c t i v i t y of f l u i d coke would be low. It i s also possible that t h e higher temperature at which carbon i s &posited in f l u i d coking results in t h e lower r e a c t i v i t y o f this material compared t o c l e w e d coke.
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The reactivity of petroleum coke increases wlth i t s t o t a l ash content (Figure 3 ) . The coke was also andlyzed f o r V, Bi, Fe, m a , T i , Cu, Al, Cr, and S i . m n g these metallic contaminants, the concentration of iron appears t o correlate best Kith coke reactivity. It i s evident that, f o r a given ash content, the reactivLty of fluid coke is lower than that of delayed coke.

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3 f i n e coke as . $ binder show a higher r e a c t i v i t y than those prepared with 16-18 Wt. samples were prepared using delayed coke having the same p a r t i c l e s i z e d i s t r i b u t i o n . t h e binder coke is not baked (calcined) t o as high a temperature as were t h e petroleum cokes and t h i s would be expected t o r e s u l t i n i t s having a higher r e a c t i v i t y . Both r e a c t i v i t y and dust format i o n ( a t the sane carbon consumption) were lower f o r t h e carbon specimens containing the low r e a c t i v i t y f i n e f l u i d coke. When t h e carbon i s consumed t h e r e i s a tendency t o form loose p a r t i c l e s of carbon o r "dust. granular cokes a r e given i n Table 1 1 . one with delayed coke and one with f l u i d coke. It i s immediately obvious t h a t t h e quantity of "dust" formed w a s much lower f o r the carbon bodies prepared with f l u i d cokes than f o r those prepared f r o m delayed cokes. ista have been obtained which show (Figure 5 ) t h a t t h e use of low rea c t i v i t y f l u i d coke t o supply t h e carbon f i n e s reduces t h e formation of "dust. This i s t r u e f o r both f i n e grained and coarse grained carbon aggregates. Neither coke showed much difference i n consumption r a t e between f i n e and coarse grained carbon bodies." The generally accepted explanation f o r "dusting" i s that t h e binder carbon i s consumed f a s t e r than t h e carbon a g g r e e t e .i41.$ binder. $ coarse coke and 50 wt." High r e a c t i v i t y delayed coke was used t o supply t h e coaxse carbon aggregate i n these samples. This means t h a t t h e bodies prepared with f l u i d cokes have lower consumption r a t e s than those prepared from delayed cokes. This is not surprising i n t h a t t h e binder coke from coal tar has a higher r e a c t i v i t y than any of t h e petroleum cokes. One p o s d b l e explanation is that t h e low r e a c t i v i t y coke f i n e s a c t as a diffusion b a r r i e r and reduce t h e r a t e of consumption of the bonding carbon. I i 1 b t a on nine conrmercially available cokes show that t h e process used t o prepare t h e coke i s a major f a c t o r influencing i t s r e a c t i v i t y . Ash content. Also. i P' Most carbon bodies a r e consumed i n commercial use e i t h e r as part of t h e process operation or as a result of exposure t o oxidizing atmospheres. The amount of loose carbon formed during our experiments is sham i n Table 1 1 . which were made up of 50 w t . Additional data w i l l have t o be obtained a t equivalent t o t a l consumption t o establish how t h e amount of "dusting" obtained with f l u i d coke aggregate compares with delayed coke a t a given consumption level. The unconsumed portion of t h e carbon aggregate then becomes loose and can be brushed from t h e main body of carbon. Thus t h e o v e r a l l r e a c t i v i t y of t h e carbon surface is more i n balance and l e s s dust i s formed. -4Reactivities of W e d Carbon Specimens The r e a c t i v i t i e s of baked carbon specimens prepared from t h e various 4 that t h e r a t e of consumption of t h e carbon specimen i s d i r e c t l y r e l a t e d t o t h e r e a c t i v i t y of the granular cokes.. t h e f l u i d coke specimens were not as reactive and less t o t a l carbon w a s consumed i n the standard four hour t e s t . However.described previously. The caxbon bodies prepare&with 28 w t . t o have a major influence on ccmsumption r a t e of t h e carbon bodies. . It i s seen i n Figure The p a r t i c l e s i z e d i s t r i b u t i o n of t h e carbon aggregate does not appear Only two comparisons of t h i s f a c t o r were made i n this study. For comparison.

3. Jr.. . February l8-22. 1957.. 4. J. Jr. and Scalliet. Fluid coke has a lower r e a c t i v i t y than delayed coke a t t h e same impxirity level. O i l Gas J. Them5 is a l s o an indication that l e s s carbon dust (loose carbon) is formed &en low r e a c t i v i t y coke is used t o w l y the f i n e coke m e g a t e . 52. and t&rtin. New York: Pergamn EYess. A. L. 5. Jr. i s of secondary inporta. Voorhies. Binder content also influences r e a c t i v i t y of t h e carbon bodv. Rome: Carlo Colombo Publishers. 1 . Reprint 1 ..nce. 28. "Fluid Coking of Residua". H. W a l k e r . M. Rskszawski. D. I. R. 1962.. Section I I I F . F. Hew York.-5p a r t i c u l a r l y iron content.. Proceedings of the Fourth World Petroleum Congress. J.. 8.. 2&-7 (1953). Paper presented a t the AIME Annual Meeting. P. New Ymk.. L. Griffin. Dunlop. Voarhies. 1955. 643-58.. Jr. "Proceedings of 1957 Conference on Carbon". and Liggett. 2. Chanical W i n e e r i n g Progress 54. Jr. No. D.. The lower rea c t i v i t y measured on granular cokes i s carried mer i n t o carbon bodies prepared fronr these cokes. No. Ftuinko. 39-43 (1958). Z. P.. J. Jr. G i v r g . and Moser. L. A. F. F.

x m 0 C D E hl d 5 c => 0 m U m U .

144. / FIGURE 2 R E A C T I V I T Y MEASURING APPARATUS 1 4 3 .

WT. PPM I I I TOTAL A S H .% .FIGURE 3 CARBON REACTIVITY IS AFFECTED BY ASH CONTENT 1E h N I 0 -DELAYED 0 -FLUID FEED I COKED PETROLEUM 1 I I - COKE PETROLEUH FEED d 2 12 N 0 V - DELAYED COKES FLUID COKES $ 100 200 300 400 500 600 700 F e CONTENT.

18% P I T C H SLASHED P O I N T S .16% P I T C H CLOSED P O I N T S .% L O S S I N 4 HOURS 16 .F I N E GRAINED .DELAYED COKED COAL TAR FEED F L U I D COKED PETROLEUM FEED DELAYED COKED PETROLEUM FEED OPEN P O I N T S COARSE GRAINED . 12 WT.COARSE GRAINED 28% P I T C H - - 28% B I N D E R 16 - 188 B I N D E R 0 4 8 GRANULAR COKE R E A C T I V I T Y .FIGURE 4 COMPARISON OF R E A C T I V I T I E S OF CARBON B O D I E S AND GRANUZAR COKES 3 [7 0- a .

1 40 - 0100%DELAYED ()MIXTURE COKE AGGREGATE OF COARSE DELAYED COKE AND FINE FEUID COKE ‘b- P / / 100%DELAYED COKE / 1 I / / / / / / / / / / / / COARSE DELAYED COKE PLUS / ’ / / F I N E LOW R E A C T I V I T Y F L U I D COKE / 0 / . 0 8 36 .I A - . ’ 0 ’ I 32 12 16 20 24 28 CARBON CONSUMED. WT.$ NOTE: NUMBERS I N D I C A T E HOURS OF EXPOSURE TO C 0 2 @ 1 7 4 2 ° F . .

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6 72. . CHBRS AND COALS (Moisture Free. ranking from high ?volatile C Bituminous t o subbituminous C. Foundry CFandI 0.4 65.6 93. t h r e e Wyoming c o a l s were chosen.6 1. The heating r a t e was 5OC per minute.8 1.R e a c t i v i t i e s of Low Rank Coals Neal R i c e and Edward PEostel N a t u r a l Resources Research I n s t i t u t e University o f Wyoming Laramie .9 1.7 80.0 42.3 43.0 90. These c o a l s were carbonized i n a c l o s e d r e t o r t t o 950OC.8 1.7 3.1 5. I n conn e c t i o n w i t h t h e development work on reducing carbon. the p o r o s i t i e s were c a l c u l a t e d .0 1 .4 1. From t h e d e n s i t i e s . t h e r e a c t i v i t y t o a i r was i n v e s t i g a t e d .2 1.1 The r e a c t i v i t y of t h e c h a r t o carbon dioxide was measured by c p n p c t i n g GO over 2 t h e char and measuring t h e p r o p o r t i o n of CO t o CO i n t h e e f f l u e n t . v a r i o u s i n v e s t i g a t i o n s were undertaken a t the University of Wyoming on t h e u t i l i z a t i o n o f low rank coal.0 54.8 1 .9 83.8 1.2 83. R e s u l t s are shown i n T a b l e 1 1 . Carbon Dioxide R e a c t i v i t x -- I n order t o show r e s u l t s from as wide a rank of c o a l s as p o s s i b l e . I n s e v e r a l of t h e s e . were a l s o measured.3 0.2 1.7 5.5 0.5 91. R e s u l t s of t h i s work are r e p o r t e d here as they appear of g e n e r a l s i g n i f i c a n c e .4 3. t h i s r e l a t i o n s h i p is shown g r a p h i c a l l y .5 1.7 2.8 5.7 1.5 47.9 13140 12250 13580 13510 12400 13220 12580 11340 950° Chars DOClark Elkol Wyodak Coals DoClark Elkol Wyodak 39.1 5.0 91. 6 1. t h e r e a c t i v i t y of t h e c o a l products was important and t h e r e f o r e w a s given consideration.2 57. The chars from a lower r a n k c o a l have a higher r e a c t i v i t y than t h e chars from a higher rank coal and a l l are higher than the r e a c t i v i t i e s of t h e cokes.4 17.4 93.4 2. * As i t i s known that t h e s u r f a c e area o f t e n i s c l o s e l y r e l a g e d t o t h e r e a c t i v i t y .4 0.4 0. Wyoming During t h e p a s t y e a r s . t h e d e n s i t i e s . TABLE I ANALYSES OF COKES. I n Figure I.3 14.0 1.5 0. a l s o t h e heating values o f t h e chars. one Western coke furnished by t h e Colorado Fuel and I r o n Corpor a t i o n and one E a s t e r n coke f u r n i s h e d by P i t t s b u r g h Coke and Chemical Company. Table I shows t h e proximate and u l t i m a t e analyses.4 0. i n Percent) NAMEANDRANK VM mab Hvab Hvab Subb Subc Hvcb Subb Subc F C Ash H2 0.5 4. i n methanol as well as i n mercury.2 82. 0 0.5 10.4 0.0 4.0 ' Btu/lb.5 2.7 13.5 C O2 N2 S 0.5 1.3 17. The lower t h e rank of t h e c o a l . L i s t e d are a l s o t h e c o a l s from which the c h a r s a r e derived and two commercial cokes.2 72.1 0. t h e r e a c t i o n of the carbon to CO was t e s t e d and i n connection with t h e u s e of processed c o a l f o r barbecue b r i 2 q u e t s . Cokes P i t t .1 93.1 2.3 15. t h e higher the r e a c t i v i t y of t h e carbon residue.

if ybout 27 m per g whereas those of t h e two cokes are 2 and 3 m per g r e s p e c t i v e l y . a l s o affec'ts t h e C02-reactivity of t h e coke. The c o n c e n t r a t i o n s . 'and would have been higher. Milliken3.145 0. w i t h i n the p a r t i c l e .135 0. . There a r e thus many carbon-to-OH and carbon-to-oxygen linkages broken and probably l e f t i n a condition which encourages r e a c t i o n of the p e r i p h e r a l carbon molecules with the oxidizing gas. Oxygen. e ermined by i t would difference.The s u r f a c e area of t h e lowest rank char u*$er study. . CO. The higher porosity of t h e low rank chars f a c i l i t a t e s t h e access of t h e oxidizing gas t o the carbon s u r f a c e s . I t wouli appear l o g i c a l t o assume that t h e rough low rank s u r f a c e s a r e more open t o a t t a c k by the CO than t h e glossy s u r f a c e s of th5 coke.382 1. 840 1. A s w i l l be seen the moisture and a s h f r e e chars and cokes are shown i n Table 1 carbon and hydrogen content i s s i m i l a r down t h e columns. I t would perhaps be more t o t h e point t o say t h a t t h e r e a c t i v i t y i s governed by t h e concentrations of C O and CO a t t h e surfaces r e g a r d l e s s how these concentrations were achieved.820 I. never having been f r e e d of such an amount of water and oxygen. i f t h e cokes had been made a t the same conditions as the chars. Extende perjods a t high temperature reduce t h e C02-reactivity.031 1. It i s widely believed t h a t d i f f u s i o n i s a l i m i t i n g f a c t o r i n r e a c t i o n r a t e s when gas reacts with a porous s o l i d . As has been pointed out by Peters''f.223 0. o f t h e two gases are a f f e c t e d by the r a t e a t which t h e one i s supplied and t h e other i s removed. and by t h e r e l a t i v e concent r a t i o n s which p r e v a i l .249 0.1 137. I t a l s o should be considered t h a t t h e lower rank c o a l s y i e l d much water and carbon dioxide while being carbonized i n t h e lower temperature ranges.617 1.415 1. Thus t h e two p o i n t s . has fewer s i t e s open f o r a t t a c k and thus a lower reactivity .736 1.869 1. The longer period a t coking temperature. Wyodak.0 2. t h i s so-called soaking period. t h e u l t i m a t e analyses of 1 1 . c l o s e r t o t h e level of t h e c h a r s . appear t h a t the chemical a n a l y s i s g i v e s no explanation f o r t h e d i f f e r e n c e s i n r e activity .) has suggested t h a t t h e micelles of t h e lower rank c o a l s may be composed a t l e a s t p a r t i a l l y of di-phenyl linkages and t h a t t h e s e linkages are o r i e n t e d about s i x t y degrees from planar.TABLE I1 R e a c t i v i t y . thus leaving a g r e a t e r random porosity.3 M c OH 151. I n order t o examine t h e p o s s i b i l i t y t h a t t h e a n a l y s i s of t h e c o a l substance would throw some l i g h t on t h e s e d i f f e r e n c e s i n r e a c t i v i t y . i s n o t s i g n i f i c a n t . * Diffusion deeply i n t o the piece of coke or char may t a k e place but r e a c t i o n i s r e t a r d e d by mounting concentrations of t h e product gas.810 It appears t h a t t h i s tendency i s r e l a t e d t o the p o r o s i t y of t h e material. Density and P o r o s i t y of Chars and Cokes Moisture Free Rank Hvab Hvab Hvcb Subb Subc Rank Reactivity O 2 Foundry Coke C F & I Coke DOClark Char Elkol Char Wyodak C h a r 13.100 0. Density Porosity Hg 1. This r e s u l t s i n s t e r i c hindrance which prevents formation of l a r g e blocks of o r i e n t e d and planar molecules.8 119.5 146. The higher rank coke.392 71. The two commercial cokes shown i n Figure I were made under conventional coking conditions which involve comparatively slow temperature r i s e and longer periods a t maximum temperature.

The b r i c k i s placed off t h e f l o o r . The amount of h e a t . TABLE I11 U l t i m a t e Analyses of Chars and Cokes (Moisture and Ash Free) Rank Hvab Hvab Hvcb Subb Subc Name Foundry Coke C F & I Coke DOClark C h a r Elkol Char Wyodak Char =2 C 96. In t h e i g n i t i o n t e s t . t h e optimum i g n i t i o n time was achieved with 15 t o 18% of v o l a t i l e matter. and t h e r e i s a p p a r e n t l y an optinrum compounded of t h e amoun matter r e t a i n e d by t h e char and t h e q u a l i t y of t h i s v o l a t i l e matter"' I t had been known for a long t i m e t h a t i n t h e s t a t e d v o l a t i l e range. and e s p e c i a l l y by the degree of compaction which a f f e c t s t h e apparent s p e c i f i c g r a v i t y . 30 m l of l i g h t e r f l u i d i s poured over t h e b r i q u e t s uniformly and the b r i q u e t s a r e ignited. and then subjected t o t h e r e a c t i v i t y t e s t . r e a c t i v i t y t o CO and d o u b t l e s s t o other gases i s decreased with extended heating 2 cycles. t h e c o a l i s b e s t s u i t e d for ! .8 O2 1. 5 b r i q u e t s of uniform p i l l o w shape a r e placed on a b r i c k . 36.d r y North Dakota l i g n i t e with 9. Thus. and the char and 10. t h e v o l a t i l e matter o f t h e c o a l has been reduced by about 80%. and the average recorded.3 1.1 To examine the e f f e c t of h e a t soak on r e a c t i v i t y . The 1 . r e s u l t s i n higher d e n s i t i e s and lower p o r o s i t i e s . R e a c t i v i t y Measured by I g n i t a b i l i t y of Smokeless Briquets Several i n v e s t i g a t i o n s were made on the s u i t a b i l i t y of processed c o a l f o r barbecue b r i q u e t s . i n t e n s i t y of smoke and odor a r e o u t s i d e t h e scope of t h i s d i s cussion. The Gigher r e a c t i v i t y of t h e c h a r s made from lower rank c o a l s must be ascribed t o t h e i r s u r f a c e s t r u c t u r e . 1 1 shows t h e i g n i t a b i l i t y r e l a t i v e t o t h e v o l a t i l e content. and one on t o p .4 1.3 96.8 96. All carbon dioxide has been f volatile evolved.2 1.2% of ash.4 0. Such b r i q u e t s should be easy t o i g n i t e and should develop a reasona b l e amount of heat. one-fourth i n c h a p a r t . a char from DOClark c o a l was h e a t soaked f o r various p e r i o d s . However.6% of moisture. If. t h e n a t u r e of t h e s u r f a c e of t h e char made f r o n subbituminous coal i s so open that no w u n t of h e a t soaking w i l l lower i t s r e a c t i v i t y t o t h a t of a m e t a l l u r g i c a l coke. however. The time elapsed when 80% of t h e s u r f a c e i s burning i s termed " I g n i t i o n time".5 2.2 N2 1.6 0.0 0. This.9 0. I t i s n o t too d i f f i c u l t t o t r a i n an operator w i t h i n a few days S O t h a t the e s t i m a t i n g can be done with reasonably c l o s e r e p r o d u c i b i l i t y . A s w i l l be seen from the curve. Room temperature i s k e p t uniform and n o t i c e a b l e d r a f t i s avoided.8 1.4 95.6 0.0 95. The percentage of s u r f a c e burning i s estimated a t c l o s e i n t e r v a l s f o r each b r i q u e t . t h e s e and other f a c t o r s of processing a r e kept uniform. It i s known t h a t any c h a r and any coke shrinks with continued h e a t soaking.152. This i s determined t o a l a r g e e x t e n t by the shape and s i z e of t h e b r i q u e t . and i t must b e expected that such changes r e s u l t in c l o s u r e o r p a r t i a l c l o s u r e of openings and a reduction of t h e r e a c t i o n surface. of course.5 0. four i n a square. The c o a l Figure I used was a i r . they should burn with a minimum of odor or smoke.0 0. t h e i g n i t a b i l i t y can s e r v e as measure of the r e a c t i v i t y of t h e carbon substance.5 0. Remains t h e i g n i t a b i l i t y .0 1.0 ' s 0. A t t h i s s t a g e .2 1. F u r t h e r . Heat soaking f o r 3 hours reduced t h e r e a c t i v i t y by r e s u l t s are shown i n Figure 1 about 15% and soaking f o r 48 hours by 35%. and such chars must f i n d a p p l i c a t i o n s where high r e a c t i v i t y i s an advantage. The c o a l w b r i q u e t t e d with c e r e a l binder.0% of v o l a t i l e matter a s carbonized t o various v o l a t i l e c o n t e n t s .6 1.7 1.

997-1006. Sominers and W. References 1. A g r e a t number of v a r i o u s l i g n i t e s were carbonized. There were again considerable v a r i a t i o n s i n i g n i t i o n time. P e t e r s . Pennsylvania S t a t e University. College of Mineral I n d u s t r i e s . No. Mueller. Doctor's Thesis. 'Qapid Method f o r Determining t h e R e a c t i v i t y of coke With C02: BRENNSTOFF CHEMIE. To accomplish i t . S i z e s beyond t h e s e l i m i t s had t o b e r u l e d out f o r reasons of operating procedures. W. 20 and 70 screen s i z e s . and uniform grading was used i n each case. . Some were t r a c e d t o v a r i a t i o n s i n ash c o n t e n t . CHEMIE-INGENIEUR - TECHNIK. Spencer R. o r even 18 minutes i g n i t i o n time. a p p a r e n t l y .. and J a n d l . a t l e a s t i n p a r t of t h e c o a l . Very good b r i q u e t s showed 20.) H. t h e lower i g n i t i o n t i m e was achieved with char from a c o a l with laminated s t r u c t u r e . . and t h e o t h e r from s o l i d wood. I n another i n v e s t i g a t i o n . GLUECKAIJF. Neal and P r o s t e l . A l l the r e p o r t e d r e s u l t s point t o t h e importance of s u f f i c i e n t r e a c t i o n s u r f a c e . t h e s i z e of t h e aggregate w a s varied. 81. These were t r a c e d f i n a l l y t o t h e s t r u c t u r e of t h e coal. however. 2 . Edward. Many b r i q u e t s of commercial production were t e s t e d which showed an i g n i t i o n time of 40 minutes. 2. But t h i s seemed t o be t h e minimum. 45-48. 1960. It appeared that f u r t h e r r e d u c t i o n i n aggregate s i z e o r f u r t h e r r e d u c t i o n i n ash c o n t e n t d i d not lower t h e i g n i t i o n time f u r t h e r . The oxidation of the char is of course a heterogeneous process5'). pp. "Properties of Chars Produced from Low Rank Coals of t h e Rocky Mountain Region". other f a c t o r s involved. a l s o the ash content. the i g n i t a b i l i t y increased w i t h decreasing aggregate s i z e . Processing c o n d i t i o n s were uniform. 19.'16. and t h e b r i q u e t s subjected t o t h e i g n i t i o n t e s t . . some t o aggregate s i z e . velvety appearance. London. "The K i n e t i c s of t h e Oxidation of Coal a t Moderate Temperatures". It may b e s u r p r i s i n g . A . r e t n a t . b r i q u e t s were t e s t e d which were produced from char derived from subbituminous C c o a l . Any p o s s i b l e i n t r o d u c t i o n of promoters o r o x i d i z i n g agents i s r u l e d o u t here and only the r e a c t i v i t y of t h e c o a l substance and t h e oxygen of t h e a i r i s considered. t h e same v o l a t i l e content i n d i c a t e d t h e h i g h e s t r e a c t i v i t y . The v o l a t i l e matter was kept uniform. Figure I V shows samples of t h e laminated and of t h e more compact s t r u c t u r e . A l l aggregates were graded. Rice. The aggregate s i z e s shown a r e nominal. t h e c h a r b r i q u e t t e d . For t h i s reason t h e amount of s p e c i f i c s u r f a c e beyond a c e r t a i n optimum cannot be u t i l i z e d . pp. Volume 19.) 5. J.) Inouye. pp. 1938. however. Yet t h e r e remained d i s t i n c t d i f f e r e n c e s .. The one a p p a r e n t l y o r i g i n a t e s from e i t h e r l e a f y o r b a r k matter.) 3. "Comparison of R e a c t i v i t y T e s t s on Coke". January 1962. To vary t h e amount of r e a c t i o n s u r f a c e . No. 441-453.S. pp. Within t h e s t a t e d l i m i t s . The former is black and has a shiny. E. Volume XLI. t h e r e a r e . Milliken.153e f f e c t i v e combustion at ordinary furnace temperatures. I t w i l l be seen t h a t the t e s t s were conf i n e d between U. 1954. t h e r e must be n o t only s u f f i c i e n t r e a c t i o n s u r f a c e but a l s o s u f f i c i e n t open space f o r t h e a i r t o e n t e r and f o r t h e products of combustion t o leave. t h a t under t h e s t a t e d extreme c o n d i t i o n s where the low ambient temperature slows t h e combustion. I n every i n s t a n c e . Volume 96. June. However. Changes i n i g n i t a b i l i t y obtained w i t h changes i n aggregate s i z e are shown i n Figure V. 1954. Werner P e t e r s Dr.) - 4. the l a t t e r i s d u l l and o f t e n brownish. and r a t h e r complicated. K. July 30. FUEL. Good smokeless b r i q u e t s u s u a l l y showed an i g n i t i o n time of l e s s than 30 minutes.

Figure I REACTIVITY O F CHAR AND COKE RELATIVE TO RANK OF COAL * 100 IS0: t L u 4 1 w OCHAR 0 COKE O K 5 4 3 e i *I Subc * Subb Hvcb Hvab RANK OF COALLower @ and higher C than coal for 2 Hvab Figure IT E F F E C T O F HEAT SOAK ON R E A C T I V I T Y I50 0 U n 100 t w D 0 0 0 * E 50 0 Heat Soak Hours a t 950% .

c I I 4 6 8 IO 12 14 1 6 18 20 22% 2o V o l a t i l e M a t t e r o f Char ___I) t FIGURE N i .

156. Figure P I GNlTAB I L l T Y INCREASES w 1TH DECREASING S I Z E OF AGGREGATE 0 No-20 Na7O Size of Aggregate d o c \ \ .

Furthermore. I n t h i s m e r . a heterogeneous mixture of i r o n ore . They concluded t h a t because t h e increase in surface a r e a i s not accompanied b y a decrease i n p a r t i c l e diameter. I \ The combustion process can be considered') t o occur in two regions. Furthermore. . only a comparatively small region (combustion zone) of t h e bed is being heated t o s i n t e r i n g temperatures a t any one time. the reaction r a t e i s independent of a i r velocity. / t i 1 r' 7' i i Wicke5) suggests t h a t f o r t h e combustion of carbon t h e a c t i v a t i o n energy i s about 58 k cal/g mole and t h a t lower values than t h i s are probably due t o diffusional e f f e c t s i n t h e porous i n t e r i o r of t h e carbon. t h e s p e c i f i c surface increase by as much as 1400 percent as carbon is gasified. fuel. et. AS t h e bed moves i n t o position over t h e f i r s t windbox. whereas above t h i s temperature t h e r a t e of combustion i s d i r e c t l y Fnfluenced b y velo i t y and is l i m i t e d b y t h e mass t r a n s f e r r a t e of oxygen. t h e p a r t i c l e must develop i n t e r n a l porosity. and ( 2 ) t h e region i n which t h e mass t r a n s f e r of oxygen from t h e bulk gas stream t o t h e carbon surface is controlling. Grendon a d Wright77 have studied t h e combustion of cokes and coals as well as low-ash carbons . and conduction t o preheat t h e portion of t h e bed l y i n g beneath t h e advancing combustion zone. and u s u a l l y f l u x is deposited as a bed about 8 t o 15 inches deep on an endless. Smith and PolleJT'report s i m i l a r r e s u l t s f o r t h e oxidation of f i n e thermal carbon a t 600 C . These r e s u l t s a r e in accord with Wickets and tend t o confirm h i s observation t h a t a r e a c t i o n a l s o occurs on t h e i n t e r n a l carbon s t r u c t u r e . t h e f u e l i n t h e top of t h e bed is ignited by gas burners. A t temperatures below about 1500 F. In t h i s process. Much of t h e heat released i n t h e combustion zone is then t r a n s f e r r e d b y forced convection. Kant. Pelczarski .&) showed t h a t t h e oxidation of carbon i s f i r s t order with respect t o t h e p a r t i a l pressure of oxygen. Kuchta. and Damn2! have shown t h a t in t h e second region t h e reaction r a t e i s proportional t o t h e 0. The s t r a n d moves over a s e r i e s of windboxes t h a t by means of suction d r a w a downdraft of a i r through t h e bed. moving s i n t e r strand. because of t h e low concentration of f u e l in t h e bed. However. United S t a t e s S t e e l Corporation Applied Research Labor a t ory Monroeville. The f u e l is randomly d i s t r i b u t e d throughout t h e bed and may be considered as d i s c r e t e p a r t i c l e s embedded within a massive m s t r i x of i n e r t material. Pennsylvania Introduction The s i n t e r i n g process is used t o agglomerate t h e smaller s i z e s of i r o n ores t h a t a r e t o o s m a l l t o be fed d i r e c t l y i n t o t h e b l a s t furnace. t h e f u e l p a r t i c l e s a r e well dispersed-and can be visualized as d i s t i n c t e n t i t i e s oxidizing e s s e n t i a l l y independently of each other when enough a i r is available f o r t h e i r combustion. Bhrany E.47 power of t h e a i r v e l o c i t y . because of good heat recovery. t h e a i r flow through t h e bed sustains t h e oxidztion reaction and a t t h e same time causes the combustion zone t o propagate downward t o the bottom of t h e bed.. Thus. The bulk of t h e work reported in t h e l i t e r a t u r e f o r oxidation r tes of carbon has d e a l t with low-ash-content m a t e r i a l s . radiation. A . m. He further s t a t e s t h a t differences in r e a c t i v i t y are due s o l e l y t o v a r i a t i o n s i n i n t e r n a l surface area and t h a t depending upon t h e type of carbon being oxidized. t h e process rea-uires only a s m a l l amount of f u e l (about 3 t o 5$ carbon). a t very high a i r v e l o c i t i e s t h e r a t e approaches t h a t given by t h e Arrhenius equation f o r an activation energy of about 30 k cal/g mole Meyer3) reported similar a c t i v a t i o n energies and he a s w e l l as Mei C h i 0 Chen. a s follows: (1)t h e region where t r u e chemical reaction controls t h e oxidation r a t e .al. After ignition.\ 157 * R O U OF FUEL REACTIvlTy IN SINTEEUNG U.

092 t o 0. a r e a c t i v i t y index i s developed f o r c l a s s i f y i n g fuels with regard t o t h e i r behavior i n t h e s i n t e r i n g operation. the r e a c t i v i t y of t h e f u e l should have l i t t l e e f f e c t on the processes inherent in sintering. Too high a r e a c t i v i t y l o w e r s t h e t h e m e f f i c i e n c y of the process and necessitates a higher f u e l content in t h e s i n t e r bed. For all runs. . The sample was then placed in an inconel w i r e basket haviag i n s i d e dimensions of 0.6 by 0. Two other thermocouples s i t u a t e d d i r e c t l y above and below t h e carbon sanple measure t h e i n c m h g k d e x i t gas temperatures. The present paper gives t h e r e s u l t s of a study completed w i t h eight d i f f e r e n t f u e l s f o r characterizing t h e fuels w i t h respect t o their performance in t h e s i n t e r i n g process. a d an automatic continuously weighing and recording a n a l y t i c a l balance. Mounted on one pan of the balance is a s i l i c a rod f o r supporting a f u e l sample in t h e m f f l e furnace. After t h e basket containing t h e coke was placed on t h e s i l i c a support rod of t h e Thembalance. two rotameters. The furnace may b e raised or lowered b y means of pulleys t o provide access t o t h e sample holder. e f f i c i e n c y of t h e s i n t e r i n g process was noted. except f o r t h e temperature study. ash l a y e r surrounding p a r t i a Y y burnt commercial f u e l s influences the. in which a unique combustion s i t u a t i o n exists. with f u e l re c t i v i t i e s varying from c r i t i c a l a i r b l a s t (C. t h e y have s t a t e d that since t h e in r a t e of combustion of f u e l i n the s i n t e r i n g process is d i f f u s i o n controlled. Figure 1 is a schema-cic drawing o f t h e experimental assembly.158. For example. The oxidation k i n e t i c s o f cokes containing d i f f e r e n t amounts of ash are a l s o included. Dixon and Voiceg) state that t h e s i n t e r i n g process demands a r e l a t i v e l y unreactive fuel. The chemical composition and t h e physical properties a r e given in Table I. t h e muffle furnace was s e t a t a control point of 1250 p l u s or minus 4 F. through ash b a r r i e r s . burning rate.5 inch. .dl) an attempt t o predict the width of t h e f u e l combustion zone present in sintering processes.) values of 0.6 by 0. coals. However. A t y p i c a l run w a s made as follows: t h e fufnace was s e t a t t h e desired temperature and &owed t o come t o equilibrium with a s y n t h e t i c a i r mixture f l a r i n g through t h e furnace a t a flow r a t e of 1 1 l i t e r s per minute. A Stanton T h e m b a l a n c e . an& associated hardware f o r transporting a s y n t h e t i c a i r mixture t o t h e r e a c t i o n chamber were used in this work. t h e r e was a considerable drop i n thermal efficiency. with a h i g h l y r e a c t i v e wood charcoal (C. I n general.B. Furthermore. the l o s s of weight with time was recorded continuously. no appreciable e f f e c t on t h e thermal. d a t a are presented Fn s u b s t a n t i a t i o n .A. However. (3) Made in En- and d i s t r i b u t e d b y Burrell S c i e n t i f i c Company. their model i s l i m i t e d t o a case where t h e f i e 1 is assumed t o be a dense sphere of shrinking radius that burns only on i t s s u r f a c e and hence cannot allow for the e f f e c t of porosity and ash that would a f f e c t t h e d i f f u s i o n a l resistances. In a prepared discussion of t h e i r paper. and charcoal.003 ft3/ min). t h e measured widths were two. Furnace temperatures are indicated and c o n t r o l l e d by means of a thermocouple l o c a t e d near t h e furnace w a l l ( s e e Figure 1).035 f tI !/min. They advance t h e p o s s i b i l i t y that the permeability of the residual. The coke sample (0. Materials and Experimental Work The materials used in this work were commercially a v a i l a b l e cokes. SchLuter and Bitsianes') have used the combustion model proposed b y Tu e-t. The bed depth of the coke sample in the basket was 0 . no experimental.5000 gram each) obtained by r i f f l i n g a Large batch of coke (-20 +28 Tyler mesh) w a s dried a t 130 C f o r two hours p r i o r t o weighing.B. From these studies.A. the muffle furnace w a s lowered in place. = 0. a height-adjustable muffle furnace. The Thennobalance is an i n t e g r a l u n i t housing a contimously recording temperature c o n t r o l l e r . E inch. t o three thnes l a r g e r than those predicted.

Hence t h e carbon combustion can be approximated by modifying equation (1)t o *g WlzPbm D = diffusion coefficient (ft2/hr) = gas constant ( f t j ) ( a t m ) / ( l b mole)(%) R P = t o t d pressure (atm) kg = mass t r a n s f e r c o e f f i c i e n t ( l b moles)/(hr) ( f t 2 ) (atm) z = e f f e c t i v e film thickness ( f t ) T = temperature (OR) = l o g mean pressure of i n e r t gas in t h e f i l m (3) H c =P x = k a p % = DPa (4) where am Equation (4) implies that in a diffusion-cantrolled regime. because t h e oxidation o f carbon i s highly exothermic and t h e reaction temperature tends t o r i s e . Second. but with cokes or carbons of widely d i f f e r e n t p o r o s i t i e s and varying ash contents. t h e oxidation r a t e of carbon i s controlled by the mass transport of oxygen from t h e bulk gas phase t o t h e carbon surface. that is. BkPg a = area a v a i l a b l e f o r reaction k = t h e s p e c i f i c reaction rate constant as given by t h e Arrhenius equation In t h e case of a packed bed of p a r t i c l e s having appreciable depth. it becomes necessary t o integrate equation (2) between t h e l i m i t s of t h e i n l e t and o u t l e t gas compositions t o obtain t h e average value of t h e r a t e s e x i s t i n g i n every p a r t of t h e bed. equation (1)reduces t o Nc where =Pg = R. R c 9 R d . with f u e l s having a h i g h a s h content. under isothermal conditions. that is. equation (2) becomes N.') r a t e of carbon i s given by Pg IC = where pg is t h e Q is t h e & is the Nc equals + it can be shown t h a t t h e combustion Rd Rc p a r t i a l pressure of oxygen i n t h e bulk gas stream (atm) d i f f u s i o n a l resistance t o mass t r a n s f e r (hr)(atm)/lb mole chemical r e s i s t a n c e (hr)(atm)/(lb mole) t h e r a t e of carbon consumption ( l b moles/hr) Now i f reaction conditions a r e chosen such t h a t chemical r e a c t i o n controls t h e r a t e of carconsumption. it is lmuwn that an ash s t r u c t u r e can surround t h e unburnt carbon7) and may impede combustion through i t s e f f e c t on t h e diffusion . r i s i n g temperatures a r e e a s i l y t r e a t e d because r a t e data may be obtained a t each incremental temperature change. Under t h e s e circumstances. d i f f u s i o n a l resistance is much l a r g e r than t h e resistance due t o chemical reaction.al. = d a w h e r e d is a constant Q u a t i o n (3) describes the oxidation of carbon i n a chemical-reactioncontrolled regime. pg v a r i e s with the depth of t h e bed. t h i s i s true.Theory In t h e m e r proposed by Tu et. Generally it i s d i f f i c u l t t o maintain isothermal conditions. t h e s i n t e r i n g process occurs a t high temperatures of about 2700 F . However. WithFn limits. Hence. by use of a d i f f e r e n t i a l reactor. t h e e f f e c t i v e film thickness ( 2 ) and t h e area available f o r reaction ( a ) may be v a s t l y different a t i d e n t i c a l a i r flow r a t e s . the oxidation r a t e i s independent of t h e carbon being burned and depends only on t h e t r a n s p o r t of oxygen.. . In this region. However.

Frm the k i n e t i c data of curve 2. whereas t h e BE3 method gave a value of 5. t h a t is.2 m2/gram f o r a f r e s h sample. d i s c r e t e pazrtidles o f coke could b e seen burning more b r i l l i a n t l y thEm others in various parts of t h e bed. whereas t h e EEL' method makes no d i s t i n c t i a s h and carbon contributions t o t h e t o t a l area. In t h e study of the e f f e c t of temperate on t h e oxidation r a t e . V i s u s l observation of t h e bed showed a considerable nonuniformity in burning.0 m2/grsram (standarddeviation 0. O n l y a t temperatures below about L h O F do the experimental data l i e along t h e curve given by Wicke. It should be mentioned that t h e s e calculations are based only on t h e fixed carbon available in the coke sample. s u r f a c e area. Conse?p. These two f u e l samples cover t h e extreme oxidation r a t e s encountered in t m r e p o r t . coke C burns a t the slowest rate and charcoal H a t the most rapid. But optfcal-pyromter measurements of t h e t o p of the packed bed of p a r t i c l e s at temperatures abwe-1400 F gave temperatures about 25 t o 50 degrees higher t h a n the exit gas temperatures.39). A l s o included in t h i s p l o t are the data given by Wicke57 for electrode carbon. a more fundamental study wouLd probably r e v e a l t h a t . w h i c h i n d i c a t e s that the oxidation of carbon is c o n t r o l l e d by chemdcal reaction. exit gas temperatures w e r e assumed t o b e r e p r e s e n t a t i v e of the bed temperature. The c a l c d a t e d surface a r e a based on points taken over the entire curve was 3. these temperatures are about L5O F higher than the m a c e temperature. an Arrhenius p l o t w a s made of the reaction rate expressed in pound moles o f carbon consumed p e r hour p e r square f o o t of total. surface a r e a o f coke C w a s calculated w i t h t h e use of a known s p e c i f i c r e a c t i o n r a t e constant for electrode carbon. These values indicate t h a t the combustion of d i f f e r e n t f u e l s is primari2. This corresponds t o an a c t i v a t i o n energy o f 9 k cal/g mole. The r e s u l t a r e presented in Figure 3.l i n e Arrhenius relatiohship. T h e v o l a t i l e matter lass is then subtracted frm the gross w e i g h t loss t o obtain t h e weight Loss b e t o oxidation. As t h e temperature is increased above LkOO F. In these t e s t s . Experimental n i t r o g e n adsorption (BEP) surfacearea measurements showed that the surface area of coke C was e s i e n t i d l y constant a t 3. With these data.umtly. the t o t a l .y dependent on t h e surface area of the material. the c o r r e l a t i n g temperatures were the exit gas temperatures Leaving t h e bottom of the dFfferentidL reactor. Far proper evaLuetion of the reaction r a t e . Consequently. Hovever.a t various temperatures are presented in Figure 2.G O f c o e f f i c i e n t . t h e weight-loss data must be corrected for v o l a t i l e matter.8 &/gram. As the oxidation r a t e s for both fuels c o r r e l a t e r a t h e r well with t h e i r BET surface areas. Figure 2.4 m2/gram a t various degrees of oxidation. the e f f e c t of diffusion becomes increasingly s i a i f i c a n t an& t h e data deviate considerably from the s t r a i g h t . This was done by heating the coke t o various temperatures in I?2 and obtaining d e v o l a t i l i z a t i o n r a t e curves. the exit gas temperature increases a d reaches a maximum and t h e r e a f t e r decreases w i t h time t o a constant l e v e l . Thus the p r o p e h i e s of t h e f u e l c a n i n f l u a c e the combustion rate of carbon in t h e sintering-temperature (diffusion-controlled) region. The r e s u l t s of t h e oxidation t e s t s . f o r high-ash between a materials it is expected that the adsorption technique w i l l field surface areas considerably d i f f e r e n t from t h o s e calculated f r o m the oxidation curves. L c d a i o a for c h a r c o d H (Figure 4) at 30 percent weight l o s s gave a t o t a l surface area o f 4. In general. A similar c a . it appears that the gross oxidation phen-on in a chemicaL-reaction-controYed r e g b e where excess oxygen is a l w a y s a v a i l a b l e i s d i r e c t l y r e l a t e d t o the totsL surface a r e a o f t h e solids. Results an&Discussion The Effect of Temerature on the Oxidation Rate of Coke M o s t of the k i n e t i c s work w a s performed with coke (r because it had been found t o b e an excellent fuel for s i n t e r i n g .

A slight anomaly does e x i s t : the low-temperature work indicates that charcoal D and coke A should behave s i m i l a r l y . Each f u e l was t e s t e d in duplicate runs t o check on data reproducibility.161. These data. Figure 4 indicates that t h e f u e l s can be raaked in order of increasing r e a c t i v i t y . and H. The s i z e of ‘the sample and t h e cross-sectional area of the reactor basket used i n both cases were t h e same. P I . t h e oxidized sample s t i l l contained 71. Consequently. The r e s u l t s of t h i s work are presented in Figure 5. A comparison of Figures 4 and 5 shows t h a t i n general t h e oxidation curves f o r both low. as more and more carbon is consumed. I n p a r t i c u l a r . A s t h e initial p a r t i c l e s i z e was all minus 20 plus 28 mesh. as follows: C. The Reactivity Index as a Measure of Fuel Performance in S i n t e r i n g f 1. This has t v o adverse e f f e c t s on t h e oxidation r a t e : (1)the pressure drop across t h e basket increases causing more a i r t o flow around t h e basket r a t h e r than through it. . A.compared with t h e height f o r charcoal D v a r i e s with t h e r a t i o o f t h e apparent s p e c i f i c g r a v i t i e s . e i g h t d i f f e r e n t f u e l s were oxidized in a i r a t a furnace temperature of 12jO F. In t h e s i n t e r i n g process. f o r coke C i n i t i a l l y minus 20 plus 28 mesh. I n addition. (The compositions of the f u e l s a r e given in Table I. Several t e s t s were a l s o completed t o obtain oxidation data a t a furnace temperature of 1600 F. and t h e r a t e of oxidation diminishes. t h e impurities a l s o have an e f f e c t on the oddation rate. t h e ash becomes i n c r e a s i n d y s i m i f i c a n t in preventing the exposure of carbon surface t o t h e oxidizing gas. 2 percent of a plus 20-mesh f r a c t i o n . Voice and Dixong i n summarizing t h e a v a i l a b l e l i t e r a t m e on t h e subject report t h a t any heat generated by t h e cambustion of v o l a t i l e s lowers t h e thermal e f f i c i e n c y of t h e s i n t e r i n g process. a corresponding decrease in r a t e should occur. I I . however. the oxidation r a t e of high-ash fuels may be a f f e c t e d by partial fusion o r s i n t e r i n g of the ash. the height of t h e sample in t h e basket f o r coke A as./ A short study was made t o determine t h e v a r i a t i o n of t h e coke p a r t i c l e s i z e with increasing degree of oxidation. t h a t is.jJ6T A sample oxidized a t a furnace temperature o f 1600 F exhibited considerable fusion of t h e p a r t i c l e s as r e f l e c t e d by t h e creation of 2 l . The p a r t i c l e s i z e i s r e l a t i v e l y independent of t h e percent oxidation. Thus t h e sample height f o r coke A i s 1. Coke B behaves somewhat anomalously i n t h a t it has t h e f a s t e s t i n i t i a l burning r a t e . this r e s u l t is not evidenced because t h e reaction r a t e i s slow and t h e a i r flow is l a r g e enough t o o f f s e t any e f f e c t s due t o changes in p a r t i a l pressure of oxygen. t h e data suggest t h a t a t higher temperatures. Consequently. only t h e f i x e d carbo i s considered t o be u s e f u l f o r generating t h e required h e a t f l u x . A t l o w temperatures. coke C is s t i l l represented as t h e slowest burning coke regardless of the temperature of oxidation. E. t h a t t h i s difference i s due t o t h e experimental technique and may be explained as follows. F. D.48 times t h a t f o r charcoal D.) The resulzs of t h i s study i r e presented i n Figure 4. whereas the nightemperature data suggest a higher r e a c t i v i t y f o r the a c t i v a t e d charcoal. This i s i n agreement with t h e r e s u l t s reported by others. G. t h a t is. the ash can slows down. a r e presented in Table 11. W decrease t h e carbon surface a v a i l a b l e f o r r e a c t i o n and &so increase t h e d i f f u s i o n a l path across which t h e mass t r a n s f e r of 02 occurs. and (2) t h e p a r t i a l pressure of C 0 2 increases in t h e bed.5 percent of t h e r i g i n a l screen s i z e . It i s believed. The A i r Oxidation of Various S i n t e r Fuels To determine t h e i r r e l a t i v e ease of oxidation. if t h e ash becames s u f f i c i e n t l y f l u i d t o occlude t h e surface of t h e carbon. These two f a c t o r s tend t o depress t h e reaction r a t e . Even a f t e r 87 percent weight l o s s . ease of oxidation.and high-temperature tests a r e ranked in t h e same manner. additional carbon properties such as anisotropy and l a t t i c e d e f e c t s influence t h e t r u e k i n e t i c s of oxidation. and s i m i l a r l y f o r t h e other cokes. but quickly e believe t h a t because of i t s high ash content (Table I).

then a s i g n i f i c a n t portion of t h e carbon may be l o s t through oxidation with a i r in t h e preheat zone. such as i g n t t i o n temperature. Below an index of 1. As s i n t e r feed mixture passes under t h e i g n i t i o n burner. Thus the r e a c t i v i t y index is defined as 6 where t Jt) m. the unreacted f u e l in the preheat zone is exposed t o temperatures varying between t h e ambient bed temperatures and those of the approaching flame f r o n t . Furthermore. These f u e l s a r e acceptable f o r t h e s i n t e r i n g process. A t t h i s p a r t i c u l a r time. the d a m d r a f t of a i r dram through t h e bed i s r a p i d l y t r a n s f e r r i n g heat from t h e combustion zone t o t h e immediately preceding preheat zone. the data e s t a b l i s h t h e general trend. o r ash content. The r e a c t i v i t y index @ is c o r r e l a t e d w i t h s l a t e r production rate as shown I S u f f i c i e n t samples w e r e not a v a i l a b l e f o r s i n t e r pot tests t o be run on all t h e fuels studied. Fuels having a r e a c t i v i t y index g r e a t e r than 1. A measure of the r e a c t i v i t y of f u e l s under t h e s e conditions is the area under t h e percent weight loss versus time curve (Figure 4). T h i s is due t o inccnq. f u e l s having a f i x e d carbon content of as low as 5 0 percent may be included in t h i s index. Fuel Reactivity and t h e Mechanism of S i n t e r i q W e have ObSeNed that t h e oxidation o f the more reactive f u e l s r e s u l t s i n a higher carbon monoxide concentration i n t h e waste gas. w e choose t o set t h e a i r oxidation t e s t conditions j u s t outside of t h e region in which chemical r e a c t i o n alone controls the oxidation rate. The area under the curve is then normalized to place all measurenents on a p e r g a m of f i x e d carbon basis. and t h e s i n t e r cooling zone. this corresponds t o an a i r flow rate of 4l i t e r s p e r minute an&a furnace temperature s e t t i n g of 1250 F. where the differences in t h e r e a c t i v i t i e s of fuels could be e a s i l y distinguished.65. t h e r e are t h e e regions of major i n t e r e s t : t h e sinter-mix preheat zone. A t t h e same t i m e .l62. For our equipment . t h e . In general.1’) ~n a bwndraft s i n t e r i n g process. As no one property of the f u e l . and thus reduces the heat flux for s i n t e r i n g . Fuels having an index of l e s s than 1. f i x e d carbon content. I n e i t h e r case.Lete combustion of t h e fuel and/or t h e g a s i f i c a t i o n of carbon. This results i n smaller amounts of carbon being available f o r combustion in t h e combustion zone. the thermal e f f i c i e n c y of t h e s i n t e r i n g process is lowered and a higher f u e l content in the s i n t e r bed i s often required t o accomplish the desired result. The performance of those f u e l s haring a r e a c t i v i t y index between about 1.65 appesr t o y i e l d a s i n t e r production rate of about 4. the conbustion zone. the fuel in t h e t o p part of t h e bed is i g n i t e d t o i n i t i a t e t h e formation o f the combustion zone.65 can be improved by blending with a b e t t e r . can adequately describe i t s behavior d u r a the combustion process. a r e a c t i v i t y index based on 50 percent weight LOSS of f u e l has been defined.35 and 1. Highly r e a c t i v e fuels a l s o tend t o minimize thermal e f f i c i e n c y because of their s u s c e p t i b i l i t y t o rapid weight loss a t r e l a t i v e l y low temperatures. For this purpose.2 tons p e r day per square foot. However. f w(t) F = t i m e for 50 percent weight loss = wei&t l o s s in grams as a h c t i c o l of time = i n i t i a l sample weight (grams) = weight f r a c t i o n of f i x e d carbon in sample = percent weight l o s s of s-e as a m c t i o n of time = percent w e i g h t f r a c t i o n of f i x e d carbon in sample nTable m. the production r a t e decreases.q u a l i t y fuel. The decrease in thermal e f f i c i e n c y may be visualized by considering t h e temperature p r o f i l e that e x i s t s in a s i n t e r bed. In t h i s manner. If t h e f u e l is highly r e a c t i v e .35 are u n s a t i s f a c t o r y f o r u s e as s i n t e r f u e l . Consider now only t h e preheat and conbustion zones. these zones leave the bottom of the packed bed in t h e given order.

1146. a good sinter f u e l w i l l permit operation between these two extremes.. W. and Voice. Physik. C. H. G 10. Grendon. 9. New York. J.. . in “Agglomeration... 1953. Phys.. Conchs ions Evidence i s presented t h a t tends t o show t h a t in a chemical-reactioncontrolled regime. R. 245. H. I n general. If a l e s s r e a c t i v e fuel is used. the normal h e a t . and Eyring. It is known that excessive fusion tends t o cause t h e sinter bed t o s l a g over-and thus t o depress production r a t e s . References 1. C. W. and (2) prevents l o c a l i z e d melting because more uniform temperatures are obtained in t h e combustion zone. 1961. Tu. Interscience Publishers. Ban. t h e oxidation k i n e t i c s of carbonaceous f u e l s depend upon t h e t o t a l (BEC) surface a r e of t h e f u e l p a r t i c l e s ..529. W. Pa. a l . M. and W r i g h t . 1932. e t . Consequently. p .. The t e s t is p a r t i c u l a r l y u s e f u l f o r t h e evaluation of s m a l l samples. . “Transactions of t h e ELeventh Annual Anthracite Conference of Lehigh University. 1955. Z.” May 7-8. LFC.. 4. 9. T h i s index correlates with t h e production rates of i r o n ore s i n t e r s . A. Dixon. 1952. 1956. Consequently. K. 511. T. when t h e y a r e r e l a t i v e l y unreactive. t h e r e a c t i v i t y index appears t o y i e l d useful information on t h e expected production r a t e t h a t may be obtained with a given f uel . in “Agglomeration” edited by Knepper. In general. 52. EX. J. Pittsburgh.. J. 689. t h a t is. 1954 (Published 1955).. Journal of t h e I n s t i t u t e of Fuels. and Polley. C. and Damon.r e a c t i v e f u e l burns quickly and generates an i n t e n s e heat in a narrow combustion zone. G.. A. E. C .t r a n s f e r process from gas t o s o l i d cannot keep up with the r a p i d l y moving combustion zone. J. Kant. Kuchta. 5. M. Chem. 1559. t h e r e s u l t s tend t o i n d i c a t e t h a t t h e slower burning fuels a r e most desirable f o r s i n t e r i n g purposes. Interscience Publishers. 26 749. 6.. P h p . R. whereas t o o l i t t l e fusion results in weak s i n t e r .. H. Davies.385. 8.“ e d i t e d by Knepper. Chem. and Bitsianes. A. 57 A r e a c t i v i t y t e s t based on the oxidation c h a r a c t e r i s t i c s of various s i n t e r f u e l s has been developed. a a . premature oxidation of the carbon in t h e preheat zone is minimized.. 1962. N e w York. and Hottel. Wicke. Smith. Bethlehem. p . W.. and more complete burning occurs. 1934. 1962. This is in agreement with t h e observations of Wicke. p. and t h e r e s u l t is t h e formation of a weak sinter.... It ranks s i n t e r f u e l s on a r e l a t i v e s c a l e with respect t o t h e i r performance in t h e s h t e r i n g process. This i s consistent with our present understanding of t h e s i n t e r i n g process. 2. Mei Chi0 Chen. 5 t h Symposium on Combustion. Meyer. as well as t h e oxidation data of Figure 4. T. Chem. t h e b e s t s i n t e r production r a t e s are obtained when t h e s i n t e r f u e l s a r e slow burning. E. E. M. Schluter... H. H. 585. This causes a r e l a t i v e increase in t h e width of t h e combustion zone t h a t (1)permits t h e heat-transfer processes occurring i n t h e bed t o operate in phase with the combustion process. Christensen. G. H. On t h e b a s i s of the r e a c t i v i t y index.. C .. 7 . 3. 251.

.

9 9 9 . 1 97.50 1.6 9 8 .4 +35 +48 + 6 5 - +loo - 9 6 . Furnace temperature 1600 F.25 1 . Ro-tapped f o r 15 minutes.4 9 6 .a4 1.5 * * + e x ! + * Samples oxidized a t a filrnace $emperatme o f 1250 F a t an a b flow r a t e o f ll l i t e r s per minute. 0 98.3 98.70 1 . 7 7 7 . 5 93.2 8 9 . 4 9 1 . 1 9 6 . 2 4 *Insufficient sample t o r m s i n t e r pot sest. Screen analysis obtained by hand screeniag of samples f o r two minutes.0 8 5 .2 9 6 . x .5 95.43 1 . 1 9 9 .0 -97. 4 0 1. 5 9 6 .) F (zoke) G (coke) D (charcoa) A (coke) H (charcoal) B (coke) C I 2. 0 9 3 . TABLE 1 1 1 The Correlation of S i a t e r Production Raze With t h e Revctivity Index of Siater JFuels Fuel R e a c t ivit y Index (0) S i n t e r Production Rate Tons/day/ft2 coke) E cod. 8 98. 5 96. 6 8 1. 9 97. 8 n. 1 92.\ TABLE I1 The Effect of A i r Oxidation on the P a r t i c l e S i z e of Coke C Percent Oxidized* I 0 10 21 4 - 6 7 .9 9 9 .7 - 5 . 5 8 7 - Screen Analysis o f ” Oxidized Fuels (Cumulative $) Tyler Mesh +20 -20 +28 A 1 o 1 0 0 5. 6 21.1 2.

156.

TO FURNACE TEMPERATURE 1 CONTROLLER

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SAMPLE SUPPORT ROD TO I RECORDING ANALYTICAL BALANCE

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TO POTENTIOMETER

SWITCH

SCHEMATIC DRAWING OF EXPERIMENTAL EQUIPMENT

F I m 1
WEIGHT LOSS MILLIGRAMS

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200
240

200 160 120

-

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40

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1564 1663 1723 1745

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PERCENT

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1 2 3 4 5 6
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COKE C COAL E COKE B COKES G 81 F COKE A & CHARCOAL 0 CHARCOAL H

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2

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6 TIME

8

10

12

14

16

18

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FIGURE 4 AIR OXIDA!I’ION OF VARIOUS FEELS

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COKE C COKE A CHARCOAL

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TIME

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FIGURE 5
A J R OXIDATION OF VARIOUS FUELS AT 1600 F

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Chicago 1. To attain this. n this test various proportions of normal furnace coke w e r e Oberscheld. and higher concentration of carbon dioxide in the off-gas. with a low internal surface dense foundry coke. the "solution loss" would be reduced. They concluded that a. The data show the average practice for normal coke and for a mixture o f 2/3 normal coke and 1/3 o f H-C Coke.coke arriving at the f coke tuyeres in larger proportions was desirable. Table I summarizes the results of a 166-hour test on the Oberacheld blast f u r nace in which 33. higher combustion temperatures. A coke of this type contains less internal pore surface and thicker cell w d a . w a s made in a small blast furnace producing foundry pig iron at Hessische Berg-Und Huttenwerke. When used in cupolas. the gasification o carbon further up the shaft must be reduced. The increased carbon dioxide concentration indicates that the reaction of coke carbon with carbon dioxide can be depressed in cupolas. T h i s coke w a s produced by Verkaufs Vereinigung Fur Teererzeugnisae who operate under a license agreement with Great Lakes Carbon Corporation. Hence. Germany. Combustion and gasification of the coke f the furnace provide the required temperatures and reducing near the bottom o atmosphere. Our experience with special foundry coke indicates that a furnace coke less reactive to gasification in the upper and cooler portion of the furnace can be produced. A. in addition t o use of more air p e r pound of coke charged. i I . a coke reduction is experienced. and Broche and Nadelman (2) in Germany. I l l i n o i s P i Pig iron is produced in blast furnaces by heating and reducing iron o r e with furnace coke anti products o f cambustion. a special foundry coke. are typical of many investigators who have speculated f o r many years on desirable coke characteristics for blast furnace use. GERMANY A one month test. plant scale blast furnace t e s t s were planned. This paper deals with coke savings observed on commercial blast f u r naces when petroleum coke was added t o the coal blend before carbonizing ' h by product ovens. This gasification is called "solution loss" which imrolves the reaction of coke carbon with carbon dioxide originating f r o m indirect reduction of iron oxides and calcination of carbonates.4 percent H-C Coke was substituted for normal coke.BLAST FURNACE TEST'SWITH COKES OF DIFFEFUNG REACTIVITY By A. T r i s k a Great Lakes Carbon Corporation. - HISTORY Blakley and Cobb (1) in England. The practical advantage experienced by the use of special foundry coke i n cupolas led to the idea that blast furnace cuke could similarly be improved. An analysis of the furnace operating results indicate that changes in coke structure which affect reactivity were responsible for reduction in coke rate. PRELJMIXARY PLANT TESTS AT OBERSCHELD. Thus. I replaced with dense H-C Coke. if the same can be accomplished in a blast furnace.

170.

T h e replacement of 33.4 percent normal coke by H-C Coke w a s ascompanied by an increase Ln silicon and a reduction o f sulphur in t h e hot metal, reflecting increased hearth temperatures. AS a result, the operator chose the following changes in practice while producing iron of comparable sulfur content :

1) Coke rate reduction of 44 pounds per ton o f hot metal 2) Blast temperature reduction of 1 4 4 ' F 3) Increase i n hard t o reduce o r e of 174 pounds p e r ton of hot metal 4) Reduction of s c r a p iron of 192 pounds p e r ton o f hot metal 5) Reduction in stone rate of 138 pounds per ton o f hot metal with equal slag volume at a basicity Seduction from 1.40 to 0.95.
TABLENO, I

H-C COKE PERFORMANCE X S NORMAL COKE OBERSCHELD BLAST FURNACE TEST LI (Working Volume - 7230 Cu. F ' t . )
TEST CONDITIONS
FURNACE COKE NormalCoke, % H-C Coke, % COKE ANALYSIS Ash, % sulfur,% FURNACE CHARGE Pounds Coke/THM ( As charged ) Pounds StoneITHM Ore, % Fe Pounds Scrap IronlTHM Pounds Hard To Reduce Ore/TFiM Pounds Oxygen in Ore ITHIM PRODUCTION Tons H o t Metal Per Day Hot Metal, % Silicon
NORMAL COKE H-C COKE MIX ( 2 8 Days 1 ( 166 Hours)
100 Days

66.6 33.4
7.2 0.97

8.7 0.92 I860 384 40.2 426 224 618 167,O 3.22 0.016 1338 1 . 4 0 8.2 32.3 2 . 4 57.1 1526 9.38 10430

1816 246 41.7 234 398 732

% 'sulfur
Slag Volume, Pounds/TRBI Slag Basicity, Base/Silica and Alumina O f f Gas, 70 CarbonDioxide % Carbon Monoxide 70 6Hydrogen 70 Nitrogen OPERaTMG CONDPTIONS Blast Temperature, "F B M Pressure, PSIG WindDelivered, CFM

173.6 2.93 0.021 1342 0.95 9.1 31.5 2.0 57.4
1382 9.41 10400

171,

It w a s difficult t o evaluate the results given in Table I in respect t o coke sav h g s by the use of H-C Coke as the bur'den used during the test period differed considerably from the one normally used. During the test period on H-C Coke 398 pounds of SO called hard to reduce o r e were used per ton of hot metal compared with 224 f pounds during the base period. With normal practice it w a s reported a n excess o 250 pounds or hard t o reduce o r e results in cold iron at Oberscheld. The significance of an increase of 174 pounds of o r e p e r ton of hot metal cannot be fully appreciated unless it f s pointed out that extremely dense Kiruna D, Swedish Magnetite, was charged in 4-6 inch lumps. Such o r e s would tend to contribute to carbon dioxide at low levels in the blast furnace and result in more solution l o s s . A reduction in the scrap per ton of hot metal from 426 pounds in the base period to 234 pounds in the test period is also significant because an additional amount of iron had to be reduced from ore.
In order to obtain a better understanding of coke saving, the practice values obtained were evaluated with the use of the Flint Coke Rate Formula (3) (4) which corrects for burden and iron analysis variations. The results thus calculated are shown on Graph No. I. The significance of this Graph was that a calculated coke saving occurred and increased linearly with H-C Coke replacement of normal f u r nace coke. Of special importance w a s the excellent correlation af the results with variation of percentages of H-C Coke used from which it w a s concluded that the data obtained are reliable. This conclusion ultimately led t o the development of a special furnace coke.

-

-

TABLE NO. I1
RESULTS O F H-C COKE REACTIVITY OBERSCHELD TEST II OPERATING VARIABLES Coke Reduction,pounds /THM Blast Temp. Reduction "F Stone Reduction, Pounds/THM Slag Basicity Reduction, Base /Silica and Alumina C 0 2 , Increase in Off-Gas, 70 (a) Corrected for burden variation with Flint Coke Rate Formula. Table No. II. shows that the preliminary Oberscheld blast flrrnace t e s t s with special foundry coke resulted in reduced cake rate, reduced stone usage and in creased carbon dioxide content in the off-gas. O f special interest is the fact that normal desulfurization w a s obtained despite the reduction of 0.45 slag basicity from 1.40 to 0.95 at equivalent slag volume and slag sulfur content. (1.3); These findings were anticipated f r o m our cupola experience with dense f o d d r y coke. CHANGE IN PRACTICE VALUE
87 (a)

144 13 8
0.45 0.9

-

172. DEVELOPMENT O F P-C COKE Before making further blast furnace tests a special low cost furnace coke was developed simulating the useful reactivity characteristics displayed by 33.4 percent E-C Coke mixtures with normal furnace coke. This coke, called P-C Coke, was manufactured in normal by-product ovens and was produced from coal blends con taining appropriately sized petroleum coke. A t h r e e (3)month and a one (1) manth plant scale blast furnace test w e r e made w i t h this coke at two (2) large steel plants in the States. COOPERATIVE COLORADO FUEL AND IRON CORPORATION TESTS The initial use of P-C Coke in a blast furnace w a s made at the Pueblo Plant of The Colorado Fuel and Lron Corporation. This coke w a s produced from their normal high volatile coals and t h e replacement of low volatile coals with minus 118 inch petroleum coke furnished by Great Lakes Carbon Corporation. Petroleum coke is the residue obtained from coking residual petroleum o i l . TABLENO. ILI P-C COKE PERFORMANCE VS REGULAR COKE CF&I THREE MONTH PLANT TEST ( H e a r t h D k . , 20 Ft., 3 In., WorkingVol., 26015 Cu. Ft.)

TEST CONDITIONS

COKE ANALYSIS Ash, yo sulfur, 7 0 FURNACE CHARGE Pounds Coke/THM ( AS charged Pounds Stone /THM Theoretical Pig - Yield, 70
PRODUCTION Tons Hot M e t a l Per Day Hot Metal, % Silicon Hot M e t d , 70 Sulfur OPERATING CONDITIONS B l a s t Temperatures, "F Blast Pressure, PSIG Wind Delivered, CFM

REGULAR COKE P - c COKE B ASE PERIOD AVERAGE AVERAGE(a) (158 Days) ( 85 Days) ( 23 Days) 11.6 11.8(b) 11.8(b) 0.57 0.63 0.61
)

1514 605 53.3 651 1.13 0.044
1075 19.9 35560

1414 547 52.8
655 1.10 0.045 981 21.5 34410

13 50 509 53.6 709 1.08 0.047
1000 21.4 35320

,

Note (a) Snowfall 0. I" w a t e r compared to normal o f 0.03".

Note (b) Problems in Washery caused coal a s h increase. Petroleum coke
contains 0.3 percent Ash.

It is to be noted that t h e informaticn was under gathered from operating records. HEAT EFFECTS O F REDUCING SOLUTION LOSS Heat Loss due to Solution Loss Heat Gain due to Combustion Additional Heat Available I 4C 4C + + 4 C02 202 = 8 CO = 4 CO 296. changes in practice to produce hot metal of the usual analysis. This f iron did not change signifi follows because the heat required p e r ton o ca.bringing more carbon to the tuyeres is larger than one might at first anticipate. This shows that a l a r g e r percentage of the coke reaches the tuyeres and less of it w a s gasified above the tuyeres. Solution Loss . Hearth Temperature Increase Visual inspection of the tuyeres. showed an increase in temperature.ntly a s the chemical and physical character of the burden remained fairly constant. Average changes in practice for the 85 day period on P-C Coke follows : 1.A reduction in solution loss is indicated by the use of more air ( 1 . 8 cubic feet per pound of P-C Coke charged.200 BTU 486. This increase in hearth temperature permitted. The values appearing in the last. The reduction in gasification above the tuyeres is attributed to the lower reactivity of the P-C Coke towards c a r b e dioxide.173 Table ILI summarizes the r e s u l t s of a three (3) month blast furnace P-C n Table 111 rep Ccke test in comparison with normal practice. at the t h e . when P-C Coke first reached the hearth.780 BTU 190. - 2. The twofold effect of decreasing solution loss and . b 1 1 1. Coke rate reduced 100 pounds. conscc-dive period included in the 85 day test run. 2.980 BTU . - I Inasmuch as the carbon content of the coke remained essentially constant a reduction of t h i s order of magnitude in the coke rate indicates that more heat was obtained f r o m each pound of P-C Coke charged. c o l ~ m n the heading "Average" ( 23-day ) represent a 23 day. Stone rate reduced by 58 pounds. Blast temperature reduced by 94' F. For simplicity it will be assumed that solution l o s s of carbon is decreased by 48 pounds or 4 pound mols per ton hot metal. An increase in the percent of silicon and a reduction in sulfur in the hot metal produced also reflected an increase in hearth temperature. The data shown i resent the average values obtained. and in fact required. 3 . A review of Table IXI indicated the following : - ! . despite a reduction of 2620 cubic feet of wind per ton hot metal.

0 t o 14. The effect of blast humidity i s manifest in the 23 d q period when the average rainfall (snow) was above normal. They slmw a coke saving results fram a x increase Ln air per pound of C O " charged ~ with concomitant reduction in air per ton hut metal.Thus from the above tabulation it can be seen that a reduction I n soh tion loss of 50 pounds increases the available heat by about 500. foundry experience with dense coke leads to the theory that dioxide concentration in the combustion zone with P-C Coke is higher and located closer t a the tuyeres than with normal coke. Manes and Mackay ( 7 ) w i t h thermal and equilibrium data. constructed a simplified d e l of a blast furnace t o derive a quantitative estimate o f coke rate. Credence to this hypothesis was further given by the practice in the 23 day period resulting in normal wind rates and 9 percent capacity increase with a 164 pound coke re duction. As an alternate some 3 to 4 grahS of moisture could have been added to the blast to obtain a faster rate o f drivLng and more tonnage. B y improving the physical character of the burden ( such as pellets. Table IV summarizes the change in practice values attributed. A condition of this type would explain the tightening of the furnace and loosening with steam. . This i s the same finding as found i n the cF&I test. The iucrease in air requirement p e r p o M af coke charged and reduction i~air required p e r ton of h o t metal is in agreement with our dense foundry coke experience in cupolas and i g sigaificant . T o some extent the reduction in coke rate was also contributed t o by the increase of 11. - 3. ascribed to a reduction of the volume of the raceway.6 pounds wa~. ) SO as t o reduce blast pressure.000 BTU per ton of hot metal.in the main. OPERATING VARIABLES CHANGED BY USE O F P-C COKE to improved useful cuke reactivity. B l a s t Pressure - The slight tightening of the furnace w€th P-C Coke result ing iu a blast p r e s s u r e increase of 1. B l a s t Temperature Because the furnace was a little . in the main. a still further improvement irr coke rate would have been possible by keeping the blast temperature closer to normal levels.. Hot metal tormage and coke rates were more favorable during t h i s period as shown in Table I I I .etc. the maximum carbon - - Further.ti&ter the operators chose to operate wit0 a 9 4 ' F lower blast temperature on P-C Cake. The increased coke rate reduction shows the potentials that exist with improved practice such as increased humidity in blast and better gas solid contact.2 percent i u the iron concentration in the charge caused by 2 reduced coke and lime volume i n the 85 and 23 day periods respectively. The reasoning for this was that the conditions appeared similar to those experienced by others with increased blast temperature (5) or oxygen enrichment ( 6 ) . 4.

The reason for this is the lack of photographic sensitivity with the bright lighting required. The black portions are t h e pores filled with a black resin while the light portions are the cell walls. Pounds Less B l a s t Temp. In FIgure 1 the normal blast furnace coke produced with low volatile coals is shown. It is.6 75 96 8. O characteristics which affect i t s rate o f gasification at various temperatures experienced in a blast furnace. 'F L e s s StonelTHM. Pounds Increase in Daily Metal Production. .5 6450 2620 100 164 94 58 0. 70 P-C COKE STRUCTURE Before reviewing the reducing and temperature conditions in a blast furnace a s related to fundamentals of coke gasifications.9 The physical coke characteristics relating to gasification are significantly n the coal blend when producing P-C f u r affected by inclusion of petroleum coke i nace coke. Normal furnace coke in Figure 1 at 1OX magnification gives the appearance of discontinuity of some of the fine white cell walls. great c a r e was exercised so that some of the fragile extremely thin cell w a l l s are not in part destroyed. to be noted that in Figure 4 at 40X magnification the discontinuity of the fine cell walls is again noted. the significant structural characf special importance are those P-C Coke teristics of P-C Coke are discussed.TABLE I V .LessCoke /THM. This type of lighting is required for accentuating the petroleum coke highlights and was used for all photographs. t PRACTICE VALUE AVERAGE AVERAGE (85 Days) . The specimen before photographing requires a high degree of polish.0 3 Days) 1. RESULT O F P-C COKE REACTIVlTY CF&I THREE MONTH P U N T TEST CHANGE IN OPERATING VARIABLES More-Air/Pound Coke Chg. Ft. LessAir/THM.. however. Ft. In this operation. -Y c 4 / .8 1. The effect of replacement of low volatile c o a l with petroleum coke in a given blast furnace coal blend is shown in Figures 1 and 2 at 1OX magnification. When this is viewed under a microscope at 40X magnification the continuity of the cell walls can be observed. These become readily apparent when viewed under a microscope. Further comparing the 1OX magnUicatian o f normal and P-C Coke it is noted that P-C Coke hag larger pores. Cu. When keeping this in m i n d it is noted that the normal furnace coke shows iy larger number of relatively small pores with considerable thin cell walls a s compared to P-C Coke shown in Figure 2. Cu.

It was therefore concluded that it is diffused with the plastic material from the coal contributing to both bonding and coalescence of the cell walls. To accomplish this the petroleum coke must have altered the coalescence a€the plastic coal in such a manner as to produce thicker cell walls in the P-CCake. An impact type miU has been found quite satisfactory for this purpose. Of interest a r e the black lines traversing the cell walls. These fissures. In order to eliminate this weakness. a coke was produced La a commercial oven without the use d low volatile coal in the high n Figure 5 at 40X magnificavolatile coal blend. The black portions a r e the pores filled with a black resin and the light portion represents the cell walls. In o r d e r t o assist in clarification of this property. These lines are thermal shrinkage cracks and on carbonization result in structural weakness in the P-C Coke produced.176. However. That petroleum coke contributes to the coalescence of cell walls a t fLrst may seem surprising as f . This again shows in camparisan to Figure 3 that the cell walls in P-C Coke are massive and thick. This plastic portion o f petroleum coke is not visible in P-C Coke.particles are fncluda r comparison purposes ed in the cell wall8 thus contributing to their thickness. attention i s called to the amorphous-appearing white highlights in the cell walls. From the macroscopic analysis it was concluded that the major structural differences between P-C Coke and normal furxiace coke a r e : c . Therefore. 1 On carbonization of petroleum coke the thermal shrinkage cracks are accent.petroleum coke was macroscopically inspected before and after carbonization. petroleum coke must be preigptished to about 90 percent or m o r e minus 1/8 inch i n size. This is the carbdization product of the heavier volatile content of the petroleum coke as it was expelled thermally from f the thermal treatment the internal portion of the petroleum coke. can be substantially uated as illustrated in Figure 7 eliminated by precrushing. I n Figure 2. These highlights are petroleum coke particles which are firmly bonded into carbonked coal matrix. t does m€become plastic i n the same manxer as bituminous c o k k e coals on heating. Figure 6 shows a 1 O X magnification of petroleum coke before carbonization. At one point o during carbonization this material w a s plastic. of course. before inclusion in the coal blend. A n inspection shows that even thinner cell walls resulted with the r e m d of low volatile coal from the normal furnace coke blend. but rather to i t s replacement with petroleum coke. This may explain why a m o r e thorough blending with petroleum coke is desirable for higher tumbler values. The amorphous appearing cell walls a r e bordered by a darker appearing homogeneous mass. as the plastic mass is limited. The coke thus produced is shown i tion. In order t o observe the effect of low volatile coal in the n t x m a l furnace blend. petroleum coke does not exhibit the bonding characteristics on heating typical of bituminous coking coals. F Figure 4 shms I 40X magnification o f normal furnace coke. the thicker cell walls i r ~ P-C Coke are not attributed to the remaval of low volatile coal from the blend. Close inrrpection as shown by 40X magnification a€ P-C Cake in Figure 3 also r e v e d s that larger particles o f petroleum coke are tightly bonded into the mactrix and that fine petroleum coke.

. Internal Surface .4 to 0. when beehive coke was replaced by heavier high temperature by-product coke. The accepted theory states gasification is a surface phenomenon which i s greatly accelerated by temperature and retarded by surface films. (This is also confirmed by a 1 2 .7 power of the mass velocity. These enumerated P-C Coke characteristics enhanced the coke performance in the blast furnace test runs. temperature has relatively little effect ~d t h e rate o f combustion f o r a given carbon in air.. the r a t e of combustion varies approximately as the 0 . 6 to 1. In this range. (13)sheds further light on the f i l m diffuf the pertision theory of carbon combustion.There i s a substantial reduction of internal surface area due to reduction of the number of fine porea. In addition in this range. LU summarizes some o ne nt results showing variation o f combustion r a t e with temperature.1. 5 percent increase in apparent specific gravity of P-C Coke as compared to normal furnace coke. The work of Dubinsky (14)shows carbon gasification with c a r bon dioxide increases enormously in the temperature range o f 1200 t o 1400°C. This has been amply demonstrated in blast furnaces with oxygen enrichment of the blast. Increased nomenon occurs with a variation o specific gravity results in more available carbon per unit surface under the f i l m . Diffusion through the surface f i l m to the coke a t high temperatures follows the mass law in that increase in available reactants results in increased r a t e of coke gasification in a given volume and thus higher temperatures result. Carbon Concentration There is a higher concentration o f carbon or a m o r e continuous outside carbon surface of P-C Coke due to thicker cell w a l l s caused by coalescence and inclusion of fine petroleum particles in the cell walls. This is a dJQamic balance and increased gas velocities passing over the coke reduce the f i l m thickness. The surface f i l m which is the boundary between coke ami oxidizing gases varies in thickness depending on the rate of coke gasification and disengagement of these gases. In the past it has been demonstrated in the blast furnaces that higher temperatures and better driving r a t e s w e r e obtained when relatively light charcoal was replaced by heavier beehive coke and then again. as the carbon is more densely packed. The work reported by Tu. T h i s same phef apparent specific gravity of coke. Graph NO. A t high temperatures where d+ffusion through the surface f i l m is controlling. gas velocity f combustion varies linearly oxygen concentration.1 power o f the arithmetic mean temperature in degrees Kelvin. FUNDAMENTALS O F COKE GASIFICATION Coke gasification h a s been studied extensively by a l a r g e r number of investigators over the years and reported in the literature. He also shows that the rate o withpercent oxygen up t o 25 percent. e t al. - Before discussing the gasification characteristics of P-C Coke i n relation to blast furnace conditions it may be well to enter into a brief review of the fundamental coke gasification concepts. ) 2 . Larger P o r e s There are larger pores in P-C Coke due to coalescence of the plastic material from coals. the r a t e of reaction v a r i e s as the 0. - 3 .

P e t e r s and E€. N. Williams (81. 7 4 O f considerable interest on coke gasification i s the work reported by B. the r a t e o f 'increase of the reaction aloaa and a transition stage "att is entered. carbon dioxide. that a desirable coke is one that w i l l depress the reduction s t o b e noted.illustrates this concept. is Step U. 1 STEP I . From this Graphs it readily can be seen. I 1 . In this range the r a t e of conversion of carbon dioxide to carbon monoxide is determined by total available surface carbop and the activation energy of coke. i s in part converted and therefore the amount of carbon dioxide concentration reachmg t h e internal pore surfaces of the coke is reduced. Graph No. It i I I '. . Heynert and J . la i n the range of two (2) square m e t e r s per gram. hvegtigators have ahown that cake gasification can be considered to occur in three steps. The tutal available (carbon) surface. A literature search revealed a considerable fund of information which must be carefully sifted to permit rationalization applicable to conditions existing in a blast furnace. An approximation of this is possible with the sampling procedure used by Schurmam e t al (10). depending on temperature (8). (15). BLAST FURNACE CONDITIONS AFFECTING COKE GASIFICATION An analysis was made o f the fundamentals concerning blast furnace conditions and coke gasification to permit an explanation of the significant coke savings obtained with P-C Coke. Echterhoff (9) and others (lo). the r a t e of increase of the reaction slows and a transition stage "b" is entered. 1 1 STEP 1 1 With increasing temperatures. that inthe temperature of carbon dioxide. Step I occurs. Step I t is reached in which the rate af reaction is so rapid that carbon dioxide. -A. Subsequently. Step III is reached in :itich the rate o f reaction is so high that no carbon dioxide i s available for internal pore diffusion. (9) . Graph 1 1 . Subsequently. The concentrations of carbon monoxide and dioxide. From Graph IV it is noted that the rate of reaction increases rapidly with ternperatare in Step I.At further increasing temperatures. This area.. ( 1 l ) a (1Z). As a result l e s s total effective surface becomes available for reaction and the r a t e of increase of the reaction is reduced to one half of that in Step I. can be referred to a s pore diffusion zone. for f m c e coke. t u carbon monaxide. and tatal percent of carbon gases in a commercial blast furnace. One of the main difficulties is to assess the relation of temperature in the blast furnace with gas composition. I V a accord ing to Wicke.. The diffusion coefficient is only slightly affected by temperature increases and theref o r e the rate af reaction increase is slowed down. with percent carbon monoxide. (16). for convenience. based on work by Schurmann. shows the relation of temperature.At low temperatures. are strongly affected by temperature and the Boudouard reaction. - 1 STEP Ln.178. a$ it approaches the coke and ita pores through t h e gas film. by definition. 1 . The temperature range in which it occurs. includeg both the e x t e r n a l m a c e and internal pore surface which. In this area gas diffusion through the f i l m is controlling.

Under these conditions the overall reaction of coke carbon with hot blast is : (1) - c + +o. decomposes t o carbon monoxide.290 BTU F e O .290 BTU This reaction is pictured as going through the following mechanism : (2 a) FeO ( 2 b) CO2 (2) + + CO-Fe + + C02 - 6. ZONE I I .The a r e a immediately above the combustion zone is characterized by the absence of carbon dioxide. + -C-+Fe I Since reaction (2) consumes a considerable amount of heat the temperature drops rapidly in this area and as carbon monoxide is formed i t s concentration inc r e a s e s rapidly. The termination of this zone is the temperature range in which the Boudouard reaction reverses. is shown in Graph IL. ZONE I The combustion zone in front of the tuyeres is considered @ Zone I. carbon dioxide is available from carbonate and iron oxide reduction in addition t o that from carbon monoxide oxidation accompanied by carbon deposition. To a s s i s t in showing ZQnE I11 . High temperatures. I The relation of temperature at various blast furnace elevations above the tsyeres. however.550 BTU This reaction provides heat and reducing gases f o r iron o r e reduction.This a r e a above the "direct I . If. as reported by Heynert and co-workers.905 BTU C k 2 CO +74. High temperatures a r e developed which play an important role in hearth reactions. Therefore. High temperatures result in hot metal with high silicon and low sulfur content due to the f slag reactions.195 BTU CO -+67. This is due to the existing high temperatures at w-hich carbon dioxide is unstable and. in the presence of carbon. other conditions being equal.+co . This area is the pure "direct reduction zone" in which the overall r e action of iron oxide is : (2) FeO -t C+Fe + CO + 67. Analyzing this curve from the point of view of carbon gases.47. carbon dioxide and t h total percent of c a r bon gases.region where reactions of this type predominate. a coke saving results w i t h a coke which promotes increased concentration of: carbon dioxide in the off gas.four distinct zones a r e apparent. are the result o more carbon reaching the tuyeres and therefore the coke r a t e can be reduced to obtain comparable quality iron. In this zone for practical purposes no iron oxides a r e present and temperatures are a t 3000°F and somewhat higher. reduction zone" is characterized by the appearance of stable carbon dioxide as temperatures have dropped sufficiently and a reduction of carbon monoxide occurs. with percent carbon monoxide. the higher temperatures are also contributed to by the combust ion characteristics of the coke then additional coke savings are possible by a stone saving to obtain comparable iron. as it is more effectively used in oxygen removal.

o f course. Manes aud J. it is apparent that a coke having the follow % characteristics w i l l result in a coke r a t e reduction in a blast furnace: - . Besides this reaction a n d e r of others occur with the end products consisting principally of Wustite. 3. AS there is an excess of carbon monoxide from Zone 11 f o r conversion of iron curides to carbon dioxide. Reduced reaction rate with carbon dioxide to form carbon monoxide. Inspecting the temperature profile on Graph II. carbon monoxide and carbon dioxide. T strong endothermic reactions occur on its surface. Again in this zone it i s obvious that a coke favoring the stabilization of carbon dioxide w i l l result in a coke saving. S. The higher con. 2. The total carbon oxide volume is reduced due to carbon deposition from the reaction o f two volumes of carbon monoxide to one volume of carbon dioxide. They further deduced that "secondary reduction I' ( ore reduction below 1000°C ) increased under these conditions. DESIRABLE COKE CFWRACTERISTICS Considering the conditions affecting coke gaaification in a blast furnace and the coke gasification fundamentals presented. This area is where the main portion o f the carbonates decompose and possibly other endothermic reactions occur. a9 "indirect reduction" The bulk of these reactions requires k 6 S heat than "direct reduction" and therefore the temperature drop in this zone U less u n t i l a point is reached where a strong endothermic reaction occurs. From the foregoing thermal and chemical considerations it was shown that a reduction in coke rate w i l l occur in a blast furnace with a coke r e s u l t h g i n: 1.. it is obvious that an unreactive coke. It is. Increased temperature when gasified at the tuyeres. minimizing the reduction a f carbon D . spong iron.180. T h e iron o r e reduction reactiolls. Mackay (71.results in a coke rate reduction. centrations of carbon dioxide favor the oxidation of free metallics. they showed that a coke rate reductiorroccnrs w i t h an increase ih air per pound of coke charged with a concomitant reduction of air per unit of ore. of coke gasifying at the tuyeres. This phenomenon is due to the fact that the temperature profile measures the ambient temperature while t h e Boudouard reaction is controlled by the reacting carbon surface h i s surface temperature i s lower t h a n the ambient temperature as temperature. proceed in this area with the modification that the end products favor carbon dimide formation m e r carbon monoxide formation. By means of a simplified mathematical model of a: blast furnace. Increased percent f coke gasified at the tuyeres r e s u l t s in coke That an increase in the percent o saving was alsa demonstrated by M. this the total carbon oxides are plotted on Graph I I . dioxide i n Zone I ZONE IV-Zone Tv is characterized by the falling off of the total carbon oxide concentration and a rapid drop in ambient temperature. Zone III can be referred to zone. recognized that even though the direct reduction h a s been depressed some of it still praceeds. s h Uarly as in Zone III. it is noted that the carbon dioxide concentration is higher than predicted by the Boudouard equilibrium.

when used in blast furnaces. EFFECT OF SPEClAL COKES VS NORMAL COKE IM BLAST FURNACES. 2. higher temperatures occur. SUMMARY AND CONCLUSIONS P-C Cake and €I-C Coke. The furnace level to which the direct reduction zone extends depends on temperature.8 2820 94 87(4 6120 - . Consequently in the combustion zone. Therefore. ! B A coke with increased-pore diameters results i n increased gasification with iron oxide in the pore diffusion range. Less Blast Temp. Ft. the combustion temperature is increased as the reaction takes place in a smaller volume due to the m a s s action law. 58 144 138 . Required OF Stone Sad. LessAir/THM. Pwnds (a)Corrected for burden variation. at the tuyeres. resulted in significant changes in operating results. As direct reduction consumes f this reaction has a cooling effect large amounts of heat. Pounds More Air/Po~lnd Coke Charged. 3 . 100 1. Ft. Increased Carbon Concentratinn A coke with higher concentration of carbon on its surface furnishes more reactants per unit area. a larger proportion w i l l remain for gasification a tuyeres and thus mare heat is releaged in the hearth. I. Cu. . Further it would appear that the carbon dioxide concentration becomes higher and also occurs at a point. a coke with large pores presents more available surface and gasifiea more rapidly at temperatures existing in the direct reduction zone. closer to t h e tuyere nose. Hence.181. at equal total heat release. Increased Pore Diameter 1 .ng/THM. These are summarized in Table V. Reduced Internal Surface A coke with reduced internal surface will produce less carbon m 0 2 1 0 & ide in the cooler upper portions of the stack and therefore a cake saving t the results. TABLE V .'. It m a y also b e speculated that the higher temperatures occurring at the higher carbon dioxide concentration at localized areas in the combustian zone of the blast furnace contributes to the f limestone usage ( more acid slag 1 for proper metal quality reduction o control. T h i s zone i s significantly extended in a blast furnace from about 1OOO'C t o as high a s 1700'C due to the existing high gas velocities reducing surface film thickness. C u . Coke Saving/TBM. the acceleraticm o and therefore the direct reduction zone stops at a lower level Ln the furnace. Further.

R .182. L e s s internal surface. retired Coke Plant Superintendent. ACKXOWLEDGEMENT This work could not have been accomplished without the active interest and efforts of J. Carlson. Grateful thanks are extended to both these companies for permission to u s e data developed at their plants and to Professor T. Thicker c e l l w a l l s . showing that a smaller proportion of coke is gasified in the stack and a larger proportion a t the tuyeres. LOOS. 2. W. and H. Higher temperatures w e r e experienced i n the combustion z m e as verified by a reduction in stone usage while producing comparable quality iron despite a reduction of both coke rate and blast temperature. Joseph for his many timely suggestions. Coke Plant Superintendent. This improvement was attributed to the following coke characteristics : 1. In the case o f P-C Coke. J. L e s s air was required per ton of hot metal produced showing that the coke carbon was mre effectively used with the oxygen from the ore. it was concluded that the reduced coke rate obtained with P-C Coke w a s caused by improved useful coke reactivity. Pudy. L. Oberscheld plant and his staff. and their staffs. Larger pores. Price. Hessische Berg U Huttenwerke AG. Works Manager. More air was required at the tuyeres p e r pound o f coke charged. it was noted : 1. lnspectian o f the changes in operating results obtained with P-CCoke and H-C Coke clearly indicates that use of these special cokes effect a substantial coke saving as a result o f reactivity characteristics dFffering from normal by-product furnace coke. 2. a l l of The Colorado F u e l and Iron Corporation. Blast Furnace Superintendent. In view o f the results obtained and the fundamental concepts presented. . J. D. 3. 3. and by the indications obtained with H-C Coke.

Ind-Techn. 36 (1916) 477-434 and 530-536. V. 1962 (5) T. 845-861. Mass. Zischkale and E. Fellowship Rept. Eisen. and H..931-990. 26.308-314 \ (8) G. Schurman. Blast Furnace & Steel Plt. J.(1956) (16) G. V. W. Eisen. Manes and J. Stahl U’Eisen 80. Hedden. H. Wicke. AIME (1952) (4) R. March & April 1961 M. Warme Kraft 8. Heynert. Flint. Blakley. of Metals. Stahl U. Dubinsky.A. H. 30. Stahl. (1958) (17) B. Stahl U Eisen. P.749-759 (1934) (14) M. 1931-1934 Com. Mackay. 53 (1953) (3) R. W. Thesis. and M. LITERATURE CITED (1) T. W. (6) . Lecture “Second European Simp. April 1962. (1960) i’ (12) G. Jan. Peters. Tech. May 1958 (7) M. Flint.183. Hedden. Engr. Heynert and J. Inst. Wiliams. Stahl U Eisen. No.S.. on Chem. Cobb. Chem. (1960) (11) G .AIME(1961) I (10)E.Osann. 535-538. Blast Furnace & Coke Oven Proc. Lnd. Joseph. Ischebeck and G. Rossberg.1545-1554. 80. S. Schurman. Chem. Inst. Gas Res. H. 79. Davis. L. 47-76. Zischkale..’Sfapovalov. Echterhoff. 104 (2) Broche and N a d e l m Stahl U. Hottell. Heynert. Blast Furnace & Coke Oven Proc. Blast Furnace & Steel Plt. H-5. M. . (1932) (15) E. Jr. K. Tu. (1958) (9) W.125-132. Hedden.” Amsterdam (1960) (13) C. Engr.C. Brenst.

GRAPH COKE SAVING v s W T c p o OF - I H-c COKE IN CHARGE i 125 I 75 25 u 40 50 60 W T .90 H-C COKE I N COKE CHARGE GRAPH II PROF1LE O F TEMPERATURE AND OXIDES OF CARBON IN BLAST FURNACE VOL%cOz 4 VOLSoCO 28 8 i 12 32 36 I6 40 TOTAL CARBON OXIDES 41 42 20 u? a w I - 1 2 - s f 4t 0 0 too I I 400 I 600 I 800 I 1000 I It00 TEMP ' C .

K E L V I N . 0.6 0.08 E 0.3 - VELOCITY CM/sEC .04 I 0 U 5 0.GRAPH IIA OXIDES OFCARBON A T VARIOUS TEMPERATURES I 1 I I I GRAPH III RATE OFCOKECOMBUSTION W I T H GAS VELOCITY AND OXYGEN CONCENTRATION i 0.06 2 0.4 0.02 a" ul " 900 I100 1300 1500 1700 FURNACE TEMPERATURE .5 0.

GRAPH Izz: RATE OF GASIFICATION I m I I b \. .

1OX d . 1 CF&I NORMAL COKE.187. 1 O X It Fig. c Fig. 2 CF&I P-C FURNACE COKE..

C F & I NORMAL COKE. 4UX . C F & I P-C FURNACE COKE. Fig.188. 4. 3 . 4UX Fig.

COAL. C Fig. 10X J .189.V. 40X Fig. 5 COKE FROM 100% H. 6 RAW PETROLEUM COKE.

7 . 1OX Fig.190. 8 DENSE FOUNDRY COKE. CARBONIZED PETROLEUM COKE. 1OX . Fig.

or w i t h more reactive feedstocks. In previous studies. The coal r e a c t i v i t y . E a r l i e r results obtained w i t h low-temperature bitumjllous coal char in a fluid-bed reactor a t 1400' t o 150O0F. Feldkirchner and H e n r y R. the extent of conversion. although they might become important a t higher temperatures. The f e a s i b i l i t y of this approach had been indicated in batch reactor tests (&).g. I n work a t the I n s t i t u t e . Where the r a t e s o f formation of low molecular w e i g h t hydrocarbons from reactive coals and low-temperature chars have been measured.. l n turn. To o b t a i n high conversions of hydrogen and coal t o a high-methane content gas.u.varies w i t h the i n i t i a l coal properties. . Linden l n s t i t u t e of Gas Technology Chicago 16.s.i. (10) d i d not f u l l y a t t a i n the desired objective of 30 t o 50$ c h a r conversion t o a gas of goo B. I l l i n o i s One of the major obstacles t o the design of a reactor f o r d i r e c t conversion of coal t o high heating value gas by destructive hydrogenation a t high pressure (hydrogasification) has been the lack of Wormation 'on the r a t e and course of the reactions during the i n i t i a l period of rapid conversion of the more reactive coal constituents. pressure and feed gas composition. experimental conditions did not permit both rapid heatup and s h o r t product gas residence times t o minimize side and secondary reactions. the length of time a t reaction conditions and the se ve r ity of the reaction conditions. The primary variables affectin g the rate of hydrogasification a r e c o a l reactiv ity . long coal and hydrogen residence times and l o w hydrogen t o coal feed r a t i o s were used. temperature.and has recently been confirmed in a countercurrent moving-bed continuous reactor. per SCF .signFTicant diffusional resistances have not been encountered (15. Kinetic studies have generally been made w i t h highly devolatilized chars and carbons t o avoid the problem of changes i n fe e d composition during heatup. and 500 t o 2000 p.16). the major objective has been the determination of the conditions f o r the meet production o f a high heating value gas in a p r a c t i c a l continuous reactor system. (standard cubic fo o t a t 60°F. since the e f f e c t s of equilibrium hindrance cannot be accurately defined because of lack of thermodynamic a c t i v i t y data f o r coal and char a t le ve ls o f conversion.t.REACTIVITY O F CQALS I N HIGH-PRESSURE GASIFICATION WITH HYDROGEN AM) STEAM Harlan L. . 30 inches of mercury and saturated w i t h water vapor). These conditions mke i t d i f f i c u l t t o interpr et the r a t e data.

A pressure-equalization line connecting the top of the hopper and the reactor i n l e t kept both vessels a t the same pressure. metering and manitoring. residual material. Pressures up t o 6000 g.9 ) employed a reactor tube. was opened and the coal charge was dropped i n t o the reactor.s. olefins and aromatics being formed. a l i q u i d s knockout pot. Standard) were fed cocurrently with hydrogen t o t h e h o t f l u i d i z e d bed. Feed gases were preheated t o the desired operating temperature w i t h i n th e reactor. Some carbon oxides and nitrogen were a l s o evolved during the i n i t i a l phases of the reaction. Steam vas generated a t the desired operating pressure i n a n e1ec. S. so that the r a t e s of gasification observed lo? a t OOOC. In these t e s t s . an increase in gas residence time . S. However. r e s u l t i n g in rapid heatup.rically-heated stainless s t e e l c o i l by feeding water from a weigh t a n k w i t h a metering Pump. +325 sieve size. Standard) coal charges were fed Fn single batches (usually 5 o r 1 0 grams) f’rom a hopper mounted on top of the reacto r. A f l o w diagram o f the reaction s g s t e m i s shown in Fig. tests were conducted in which both coal heatup and product gas residence time were of‘ the order of a f e w seconds.i. of a high-volatFILe bituminous coal. n eg lig ib le q u antitie s of l i q u i d hydrocarbons w e r e formed in the fluid-bed tests a t the Institute ( 1 0 ) . aureau of ! m e s ( 7 . The -16. In contras t . No measurable amounts of l i q u i d products were formed and methane w a s the major gaseous hydrocarbon produced. A t zero time. air-operated b a l l valve. 3 . 1.) w e r e e l e c t r i c current through i t . (1472 F.192.g.5 w e i g h t $ (moisture-. The liquids yields decreased with decreases I n hydrogen rate as a r e s u l t of the increase i n residence time. whZc5 vas heated by passing an and a nominal operating temperature of 80oOc. w i t h only trace qua ntitie s of higher paraffins. A syntran v ib rato r was mounted on the hopper t o a i d I n solids feeding. For example. low-temperature bituminous coal char or I_Tgnite (-60. m u g the 2-minute heatup period. s o the absence of l i q u i d products could have been the r e s u l t of secondary vapor-phase reactions. product gas residence times were on the order of one minute. before sampling. and afterward. The U. / . Gas i n l e t flow rates were controlled manually and were measured by an o r i f i c e meter. U.from 6 t o 30 seconds resulted in a decrease in l i q u i d hydrocarbons from 26 t o 4. &O sieve size (U. a high-pressure f i l t e r and a pressure-reducing back-pressure regulator. 5/16 inch i n inslde diameter. Substantial yields of liquids were obtained during the r e l a t i v e l y heatup period. investigated. In the work described herein. a fXLl-openlng. hydrogen was passed through the tube a t a suf f ic ie ntly hlgh r a t e t h a t gas residence times were only 4 f e w seconds. were f o r the l e s s reactiva. Exit gases passed through a watercooled c o i l . ash-free b a s i s ) . connecthg&he reactor and feed hopper.

I description of the reactor has been given elsewhere X along w i t h design d e t a i l s concerning the use of externallyheated rea. stain less s t e e l i n s e r t . The sottom o f the insert was f i l l e d w i t h sufficien t alundum p e l l e t s t o position the coal charge in the center of the t h i r d heating zone from the top.8% pure). upstream of the metering and monitoring system t o allow rapid sampling a t small time in terv als.i. ) . All feed gases. were stored a t pressures up t o 3000 p .6%pure) . each 12 inches long. The inches l n Outside reactor was 2 inches in inside diameter. from the e x i t gas system. except steam. Reactor pressures were controlled a t the desired values by means of a back-pressure regulator and were continuously recorded along w i t h orif'ice pressures. Commercially available grades of e l e c t r o l g t i c hydrogen 799.0% pure) were used. T closures were rated f o r 1400OF. operqtion a t 1500 p. 3/8 inch in outside diameter. was used ofi a l l c l o s u r e threads and on the s e a l rings. applied i n aerosol f o r m t o produce a thin boundary layer coating. A boundary lubricant of molybdenum disulfide.ctors a t high temperatures and ressures.g. nitrogen (99. a t a maxhum temperature of l7OO0F. The double-ended reactor contained an Autoclave Engineers h e self-seallng (modifTed B rid p an ) closure a t each end. The feed gas o r i f i c e was calibrated before each run w i t h a wet t e s t meter and the e x i t gases were a lso metered w i t h this meter a s a check on the helium tr a c e r method Tor e x i t gas f l o w r a t e measurement. which were prepared by mixing during compression. In t e s t s w i t h pure steam feed. The e x i t gas specific gravity was monitored continuously w i t h a recording gravitometer a s an a i d in selecting times for e x i t gas sampling. the small volumes of permanent gases formed. A n Inconel X thermowell.g. contained approximately 2 mole % helium tracer for e x i t gas f l o w r a t e measurement.99% pure) and technical grade methane (95.3. i . helium (99. The combined nitrogen and carbon monoxide . Gas analyses were performed by mass spectrometer. was mounted i n the center of the bottom closure arid extended 58 inches i n t o the Peactor. f Feed gas mixtures. 1-5/8 inches in inside diameter and containing a 1/2-inch outside diameter thermowell sleeve. .1. A complete (. was installed in the reactor t o contain the coal charge and provide f o r complete recovery o f the coal charge a f t e r each t e s t . diameter and 60 inches in inside length. s . A sampling manifold was i n s t a l l e d i n the e x i t gas l u e .The reactor barrel was constructed of N-155 super a lloy and was designed f o r operation a t a maximum pressure of 1500 p.s. A removable. This high-temperature service was f a c i l i t a t e d by use of e i t h e r 16-25-6 o r Inconel allo y s e a l rings. Reactor temperatures were maintained by four individuallycontrolled e l e c t r i c a l resistance heating elements. helium sweep gas was used t o purge.

except in selected t e s t s where-carbon monoxide was d e t e r g n e d by infrared spectrophotometer. T h e f o u r coals Investigated were a medium v o l a t i l i t y anthracite.. content of the e x i t g a s . The char was prepared from bittrminous coal from the Montour No. samples were . Most runs were conducted f o r a t o t a l time o f 15 mirrutes o r less. the f i r s t hydrogaslfication products appeared i n the exLt gas a t the sampling m o l d in approximately 1 0 seconds. without impairing a na lytic a l accuracy. A t typical conditions of 1500 p.194. 1700°F. w i t h a hydrogen f l o w r a t e of 100 SCF Per hour. and 1700°F.s.second Intervals. waa assumed t o be carbon monoxide. d e t e m h e d by mass spectrometer. DurFng the F n i t i a l period of high conversion r a t e . Temperatures a t the center of the coal charge. When the system was s t a b i l i z e d completely. Analyses of these feeds a r e shown i n Table 1.g.s. It was necessary t o s e l e c t sample weights which gave small temperature changes and low concentrations o f methane i n the e x i t gas. The heat input t o the reactor was then adjusted s o that a l l temperatures w i t h i n the r e a c t o r remained constant. the run w a s stopped. was s t a r t e d through the reactor. a t a p o h t 6 inches above the charge and a t the bottom of the i n s e r t were recorded co n tinwusly by means of a high-speed temperature recorder w h l c h recorded each temperature a t approximately 3. The reactor w a s kept f i l l e d w i t h nitrogen u n t i l the temperature had reached a low enough value t o allaw r e t r i e v a l of the c o a l residue. heaters were turned off and the reactant gases were purged f’rom the reactor w i t h nitrogen. 1 0 Mine by a fluidized-bed pretreatment process of the Cansolidation Coal Co. several exploratory Before the t e s t program w t e s t s were conducted a t t h e base conditions of 1000 o r 1500 p. a North Dalsota l i g n i t e . the run was i n i t i a t e d by opening the valve between the feed hopper and reactor. The e l e c t r i c . a Pittsburgh Seam bituminous c o a l and a low-temperature bLtuminous c o a l char.i. Then gas flow.g. When the reactio n r a t e had reached a value too small t o be measured accurately a t the h i g h gas r a t e s employed (usually a f t e r about 600 seconds). REWJIPS EKploratory Tests a s Fnitiated. less nitrogen introduced In the feed gas. .1. and a hydrogen f l o w r a t e of 100 SCF p e r hour. W e n a t time i n t e r v a l s a s short as 5 secmds t o d e l h e a t e the exact course of the reaction. a t the desired r a t e . The reactor was f i r s t heated up t o the desired operating temperature. .

4 Mine) -16.91 6.5 3. Bureau o f U e s -16.49 23.3 2. w t $ (dry basis) Carbon Hydrogen Nitrogen and (by ddfferen? -S Bituminous Coal P i t t s b u r g h Seam Consolidation Coal Co. (Montour No.4 m e Source Coal P a r t i c l e Size. +50 -16. +20 .7 83.01 83.12 0. ! . Standard Sieve Ultimate Analpis.3.3 17.01 65. w t $ Moisture 1. w t $ Moisture Volatile Matter F k e d Carbon Ash A 1.1 33-5 8. 75.9 5. +2O -40. 0 Ugnite North Dakota Trmax.3 3.7 Volatlle kbtter 1 7e.Traer CO (Velva MFne) -16. I . Standard Sieve Ultimate Analysis. S .99 1 o o .3 Fixed Carbon 73.01 79. 0.0 .9 1 0 0 .2 46.-COAL ANALYSES Coal Type Source P a r t i c l e Size. -1-20 10.8 41.9 73.47 2.0 6. +20 78. Wt $ ( d r y basis) Carbon Hydrogen Nitrogen and (by difference Sulflcr Bituminous Coal Char Low Temperature Consolidation Coal Co. (Montour No.Table 1 .46 10.7 5. U.4 4.90 Ash Tot a l Proximate Analysis.03 1.2 Ash Total & l o o .21 Ash Total Proximate Analysis.9 .S.46 10. U. o 6. U. 10 Mine) Anthracite Medium V o l a t i l i t y Anthracite Experiment Station. 0 0 2.

. +16 sLeve s i z e ) the maxirmun e x i t gas methane content was too high and the temperature changes during the ( T h Temperature t 1 7 0 0 ' F . and with bituminous coal char a t 1 3 0 0 9 . Sample weight : 5 and 1 0 grams Coal p a r t i c l e size: -16.and 5-gram samples of -16.and 20-paam samples of low-temperature bituminous coal char (-8. In tests with 10. These t e s t r e s u l t s indicate negligible e f f e c t s o p a r t i c l e s i z e on the reaction r a t e . This w a s substantiated by conducting a m t h e r t e s t w i t h a 3-gram sample weight.1. unless otherwise noted: With 50. and 1500°F. With low-temperature bitumFnous coal char a t nominal run temperatures of 1700°F.. It was a l s o necessary t o s e l e c t a coal p a r t i c l e s i z e f o r the remainder of the test program. From the r e s u l t s of these exploratory t e s t s . In t e s t s w i t h unpretreated coals. Tests w e r e conducted w i t h 10-gram s l e s of -16. occurring a f t e r approximately 30% carbon gasification. two periods of high r a t e were observed (Fig. 1500 p. An e f f e c t of p a r t i c l e s i z e on the r a t e o f reactio n could indicate the presence of significant dFffUsiona1 resistances. The displacemext of the r a t e curve f o r the -40. The second period of high r a t e .196. the exit. Based on duplicate t e s t s t o check reproducibility. +50 sieve s i z e material was probably due t o the slower feeding r a t e of the more finelg divided material. 1 run were t o o great t o allow the assumption of Ciifferential reaction conditions. Y . o r t o an i n i t i a l holdup in the coal feed hopper.s. the following base conditions were selected f o r the remainder of the t e s t s . . no second period of high r a t e was ob served. 2 ) .g. and r e a c t on r a t e s (expressed a s pounds carbon converted t o gaseous hydrocarbons per pound of carbon remainhg in bed per hour) were similar. Here only a slight increase in r a t e was obtained a t carbon conversions above 30%. +20 sieve s i z e Feed g a s flow r a t e : 100 SCF per hour Pressure: Tgpical results f o r the four feeds used in this s t u d y a r e given i n Table 2 . it was believed t h a t these small differences were within the limits of experimental and an alytic a l accuracy. was a r e s u l t of increases in the temperature of the char sample due t o the I n a b i l i t y t o d issip ate the high heat of reaction t o the surroundings. +20 and -40. s methane contents approached the desired le ve ls. +20 sieve s i z e low-temperature bituminous coal char. 6 0 sieve s i z e material l 7 i g .

9 -- 41.. =lo % A .67 0.6 46.2 98.89 t ~ c d o .95 0.02 3. 3 .2 101. 9 66.08 98.:a 97. 0.6 0.93 0.2 95. 1 .01 0. . 98. : 7 1 104.S.5 0.3.49 92: 9.. 6 10 25 100.01 16% 97.25 -- 3:P 0. G 1.1 0.01 89.5 1 .iaous Coal Char.03 .9 0.82 1 % 97.1 102.0. 5 ~pana or a 17c 104.3 93. 1. AND 1500 P.06 600 -- 99.9 5 6 . 9 9 .+20 U.65 3.01 94.47 93.95 o:?.3.04 -99.22 9. P Peed Time of Sampling.k 9 6 .3 100. mTo-o7m 34 5:2 --- 15.1 62.-TYPICAL TEST RESULTS OBTAINED AT 1700°F.01 _.3 101.2 -- 5.22 1 6 9 ' .28 0. E a C & C1& ?:if 0 .01 -- 960% 2.02 9 % 97.2 42. 0. 0 7 99. Exit Gas Compoaltlon. Teqmratum % Peed wdIvg. 3 99. 7 53.55 1.1 _- s SIWM 9 : 98.0.04 17c 104.0 94.6 0. 9 _- -- :A _- .oi ------0.04 u ) o 172s 103.I. ssc. -i6.04 0. .G. carbm id-hr Tot41 Cdv&lm of Carton in ked.06 Bslrsne Total Pate or Folmstlou or Oaaswus edmcarkm Carbon lb Ab.13 0.04 98.98 0.99 _- IUrJ35 4.2 98. -16. : 7 1 104.2 --.01 -.8 96.10 0.1 0.E 3:: 0.8 -- 39.6 1W.7 0.15 9 8 .01 l m % a 0. lo M 80 120 240 95.43 0. S Total CaFbcm Rscoveq.3 100. 99.3 95.1 96.58 2.0.03 1 % c o . + co 54 or w i t e ..03 96.24 0.2 98.4 0.0.01 -- -- 0.12 S i ve sits 1 % 104.90 0.Y 101.+20 ~ 0.1 97.2 98.0 97.08 $% 2 .+20 U.72 &:E U.0 99.91 98.3 95.2 98. -. Exlt Gaa Rate.6 96.3 0.51 % ! g 5.4 94.2 1 % 97.15 ____- 5 ~ r a m aor Iov-Temperatulp Bltw.11 0 . -16.01 -.7 5 .15 5.8 0.03 -99.08 8.1 5 0.01 1 4 104.G 5.a 1714 -- l-m% _--- Tim% x E a % --- U.88 0. siem 31W. .20 0.3.197 Table 2.0 96.56 0.02 -0.S.3 _- 1.8 0.0 96.7 96.n -.7 0.08 0.9 . 0.04 240 1732 104. . 1 95.05 99 90.17 91.5 0.15 0.75 0.3 82.25 17% 97..4 0. Aatbraolte.?:E -.37 9 9 . 31eve 31m. .04 99. SCF)&.9 _- 0 .7 0.03 99. 8 6 -- %:P 0.52 0.S 8 : : 3 9.+20 0 3 . 2 9 $ P $ -- 95.5 0.8 0. 97.01 --**&&as& 0.01 -9 8 .1 TmG 1 .20 9z:g 17% 97. 6 71.03 9 63 L o 0.S 4 8 0 1713 97.9 95.7 2 0 .B 0.6 1 . 0 _- 24. 14s 97.S.3 94.2 98.69 0.3 ~pams of M e d i m Volatlllt.7 94.3 101.3 1.3 : .3 93.77 0.02 1 7 % 104.8 32. Slam 3125 54 60 10 20 1720 1720 1717 i E 1 % 1 % 98.1 -- -_ 1 .05 0.S.5 0.n late scF/hr. -16.2 98.01 0 .2 1.57 8.6 0.4 96.61 9. 8 2 8O:Z 97.3 100.01 99.95 0.0 87.77 5.o.9 97.1 0.

(Fig. but this i s not significant in view of the low conversions. methane concentrations i n the product gases were low enough t o mFnimize equilibrium hindrance effects. P = hydrogen p a r t i a l pressure In atmospheres. i n the temperature range of 1500' t o 1700 F. 1 During the i n i t i a l phases. and a t 1300°F. A l l of the above results were obtained i n M f e r e n t i a l bed reactors of various types.g.I Effects o f Variables The e f f e c t of temperature and extent of conversion on the r a t e of reaction of low-temperature bituminous coal char and hydrogen was measured i n a series of tests conducted a t 5 0 0 ' F . (1382' t o 1742OF. with d ev o latilized Disco bituminous coal char the apparent reaction order i s 2 a t low pressures and approacnes 1 a t high pressures. In T a b l e 3 . Agreement is quite good. and a t 1 t o 30 atmospheres. which were obtained in an i n t e g r a l fluid-bed reactor. 1500 p.. pseudo-first-order hydrogasification r a t e constants f o r these chars are compared w i t h the values f o r low-temperature bituminous coal char a f t e r 25 t o 30% carbon conversion (Fig. (A) . onlg a f t e r approximately 20% carbon ga sif ic a tion did the e f f e c t s of temperature become apparent. = This expression has been shown by Blackwood (2 ) t o be applicable in the temperature range of 650' t o 87OUC. k = r a t e constant. The rates f o r t h i s specially-prepared low-reactivity material a r e up t o one order of magnitude lower. 4) . The data f o r coconut char are based on the carbon m t i a l l y present i n the bed. However.s. The rate constants f o r the residual char would be expected t o follow the pseudofirst-order relationship: I i 1 where r r a t e of reactio n i n pounds o f carbon as methane equivalent per hour per pound of carbon in bed. except f o r the data f o r Australianbrown coal. Birch has a l s o applied i t successfully t o c or r e la te data on the hydrogenation of the resid u al (aromatic) carbon portion o f Australian brown coal w i t h excess hydrogen i n a fluid-bed reactor for the temperature ran e from 7 5 0 ' to 9 5 0 ' C . and 170O0F. a s would be expected. high-temperature coconut char.) f o r the reaction of coconut char w i t h excess hydrogen a t pressures up t o 40 atmospheres. .) Zielke and Gorin showed that.i. 4 ) . Methane equivalent includes carbon in a l l gaseous hydrocarbons produced. except f o r the acid-extracted. the reaction r a t e w a s not signFticantly affected by temperature i n the range studied. (1202' t o 1598OF.

Coal Char More than Conversian 40% Carbon Carbon Gasification 25-30s Carbon GasFfication 1 x 10 k rate constant* -- 2 x 10- 9 x 10-4 4 x 10-3 x lo-= 6-2 x 10-3 4 x 10-3 1700 6x 2 1 x 10- 3 x lo-= * For Birch. . 1 Temperature. C in bed-hr. of C as CHq equiv. For Blackwood. of C as C& equiv.-COMPARISONO F RATE CONSTANTS O F VARIOUS INVESTIGATORS 1 b I I Coal Conversion High-Temperature Coconut Char I \ Less t h a n 10% Char Conversion OF. H2 part.J Table 3. units are lb.-atm. Zielke and Gorin and this study./lb. C o a l Char 0-30s hw-Temp. HB part. 1300 1500 Brown Coal Disco Bit.-atm. B i t ./lb. C fed-hr. press.k has units of lb. press.

O n t h a t basis. is shown i n Figs.. However. s .s. However. Fn s p i t e of the large reduction in driving force f o r the Ci&. i s shown in Fig. Fig. of a decrease i n hydrogen p a r t i a l pressure f r o m 1500 t o 1000 p . The apparent r a t e constants with the la r ge r samples were much higher f o r l i g n i t e a d considerably lower f o r anthracite. o f nitrogen and with a p a r t i a l pressure of 500 p. during the F n i t i a l high-rate period. 8. and increased i t s peak.1. both pyrolysis and hydrogenolysis occur. W a carbon a c t i v i t y of 1 i s reaction C + 2% assumed. The absence of a hindrance e f f e c t a t low conversions i s f'urther evidence of the much higher i n i t i a l carbon a c t i v i t y . a t 1700°F. The e f f e c t of 500 p . 3 . An increase in hydrogen partial pressure a t constant t o t a l pressure both broadened the r a t e curve. i s o n l y about 700 p . o f methane were not signif'icantl dif f e r e nt during the F n i t i a l high-rate p e r i o d (Fig. methane p a r t i a l pressure i n the feed gas during the low-rate period could not be determined because the product gas rnetl%ne concefitration measurement was not accurate enough t o obtain meanindata. 87 This indicates no subs t a n t i a l equilibrium hindrance e f f e c t during this period. With devolatilized Disco bituminous c c a l char. i . i t can s t i l l be observed t o t a l pressure a s well as in qualitativ ely t h a t increases hydrogen p a r t i a l pressure gave the expected lncreases i n rate. The combined e f f e c t o f changes Fn t o t a l and in hydrogen p a r t i a l pressure a t 1500° and 1 7 0 0 ' F . but a t high conversion l e v e l s they approach one another. the r e s u l t s obtained with a p a r t i a l pressure of 5 0 0 p . 4 I .200. i . This i s not believed t o be primarily due t o lack of reproducibility. These results apparently reflect t h a t . s . i . during the in-itial high-rate period. i . Increases i n hydrogen p a r t i a l pressure would increase the r a t e o f hydrogenolyais compared t o pyrolysis. The separate e f f e c t . The r a t e constants during the high-rate period a r e roughly proportional t o the v o l a t i l e matter content of the feed. whereas with bituminous coal good agreement was obtained. 6 and 7. The true e f f e c t of hydrogen p a r t i a l pressure during the highly ex0thermic resid u al char hydrogenolysis period was 7 0 0 ' F . and 1500 p . by the addition of nitrogen. i . obscured a t 1 depending on sample weight. theequilibrium methane p a r t i a l pressure a t 1700°F. by the large temperature increases. s . s . Thus. ZieUre and Gorin showed that the e f f e c t of methane p a r t i a l pressure on hydrogasification r a t e i s simple equilibrium hindrance (15). It c m be seen that the r e s u l t s obtained w i t h 5-gram samples of l i g n i t e and an th racite could not be closely duplicated with 10-gram samples. an increase i n t o t a l pressure tended t o broaden the range of the i n i t i a l high-rate period. 7 - I . 5 further demonstrates the simila r ity i n hydrogasification r a t e constants of the residual portion of coals and chars with g r e a t l y d if f e r e nt i n i t i a l properties.

The upper s e t of p l o t s in Fig. g . A b e t t e r picture of the sequence of coal-hydrogen reactions under coal hydrogasification conditions can be obtained from the changes Fn hydrogen d i s t r i b u t i o n w i t h conversion of various feeds. Although no measurable l i q u i d hydrocarbon formation occurred. The lower s e t of curves in Fig. 9 ) . s .i. there was no major e f f e c t on the high-rate period from temperature changes in the 1300° t o 1700°F. i s i n agreement w i t h observed experimental r e s u l t s of t h i s study. Evidence f o r the two steps during the high-rate period can be found in the increase i n organic l i q u i d products formation with decreases in pro&ct gas residence time observed by a t r e l a t i v e l y l o w reaction temperatures Hiteshue and others (I) encountered during heatup. A low-rate period of d i r e c t a t t a c k o f hydrogen on the resid u al aromatic carbon str uc tur e . ethane concentrations actu ally d l d exceed equilibrium values a t the peak of the high-rate period (Fig. 2 . this sequence is: 1.1 4 ) .s. the presence o f small amounts of CB. 1 0 shows the changes i n gaseous feed hydrogen consumption w i t h conversion. A high-rate period comprising pyrolysis of the more reactive s t r u c t u r a l units such a s a l i p h a t i c hydrocarbon side chains and oxygenated functional groups. In this case. a t s u f f i c i e n t l y high temperatures.t o C4-aliphatic hydrocarbons during the high-rate period indicates the i n i t i a l formation of higher molecular weight intermediates which have been converted t o methane by hydrogenolysis ( 1 2 . a physical process m a g have been controlling under these conditions of extremely rapid hydrogenolysis. Absence of substa ntia l organic l i q u i d product yields would correspond t o the completion o f the vapor-phase hydrogenolysis reactions. as a r e s u l t of rapid heatup o f the coal charge. f o r the same s e r i e s of t e s t s . and 1500 p. and hydrogenation and hydrogenolysis of the intermediate pyrolysis products.g. ethane would have t o be present in q u a x i t i e s exceeding the methane-ethane-hydrogen equilibrium values. 1 0 shows the r a t i o of t o t a l hydrogen in the e x i t gas t o the t o t a l hydrogen in the feed gas f o r a s e r i e s of tests conducted a t 1 7 0 0 ' F . i . range a t a pressme of 1500 p . In somewhat modified form. even a t 1300°F.. The formation o f small amounts o f benzene during the high-rate period i s f'urther evidence of the simil a r ity with hydrocarbon hydrogenolysis. Since. in t h i s study. which would then be the chemical rate-controlling ste p i n methane formation during the i n i t i a l high-rate period. pressures anc? residence times t o give methane a s the major product. In tests with bituminous coal char.? / Course of Coal-€@drogen Reactions The descriptian by Birch and others ( 1 ) of the sequence of coal-hydrogen reactions. . 1' I I I' I .

the char-hydrogen reaction proceeded much more rapidly than the char-steam reaction. In t h e present study.charac t e r i s t i c of the char-hydrogen tests a t 1 7 0 0 ' F . hydrogen c. This i s due t o the large amount of water formation which can be r e a dily measured In flow reactors. except that w i t h the low. Thus. with both exothermic hydrogenatlon reactions and endothermic steam-carbon reactions occurring simultaneously.202. and 1500 p. indicating the occurrence o f both pyrolysis and hydrogenolyais reactions. mixtures and char e x i s t s f o r temperatures of 1500° t o 1 a t hydrogen p a r t i a l pressures below 30 atmospheres (a. the only other major path f o r oxygen rejectio n is a s carbon monoxide. as w e l l as by larg e consumption of feed hydrogen. but could not be determined experimentally In the present work. The addition of steam was found t o substantially increase =e rate of methane formation a t these low hydrogen p a r t i a l pressures. e spe c ia llg a t the higher conversions. 7 and 8. Ektrapolation t o hydrogen p a r t i a l pressures s u f f i c i e n t l y high t o give rates of methane formation which a r e of p r a c t i c a l i n t e r e s t .temperature bituminous coal char. %-e results of the two t e s t s conducted w i t h 5.s. from comparison w i t h Figs.g. a second period of high consumption uccurs a s a result of uncontrollable temperature increases. since carbon dioxide formation i s PractiCallY sqpr e sse d. The maximum feed.s. donated relatively l i t t l e hydrogen and consumed a disproportionately large amount of gaseous feed hydrogen. in accordance with the sequential nature of the pyrolysis and hydrogenolysis reactions. The rates o f these two reactions (measured by the rates o f evolution of gaseous carbon oxides and gaseous hydrocarbons) are shown i n Fig. the r e l a t i v e l y high r a t e s of 4 I' I 4 1 I . It should be noted that. . the rates of the steam-char and hydrogen-char reactions w i t h an equimolal steam-hydrogen mFxture were measured a t 1700°F. and the second high-rate period . Steam-mdrogen Coal Gasification mch k in etic information on the reaction of steam-hydrogen 7 0 0 ' F . a t the high hydrogen p a r t i a l pressures used in this study.1. ll as functions o f t o t a l carbon g a s i f i c a t i o n .and 10-gram sample weights are in good agreement.g. anlike much o f the e a r l i e r work a t r e l a t i v e l y l o w hydrogen partial pressure. indicates that the e f f e c t of steam becomes less sig n ifican t.s.is absent. Ugnite.However. . It can be seen that the l n i t i a l 'high rate period is characterized by donation o f hydrogen from the coals and char .onsmption tends t o occur a t higher carbon gasif'ications than the maxirmun hydrogen evolution. because of its high oxygen content.F. the r a t e of char conversion t o gaseous hydrocarbons w a s below the l e v e l expected f o r a f e e d gas hydrogen partial pressure of 750 p. This is probably due t o smaller temperature changes.l6). The r a t e of feed hydrogen consumption i s an excellent indication of feed reactivity .

. shown i n Fig. The rate of the steam-char reaction w i t h an equimolal steam-helium mixture a t 1700°F. the r e a c t i v i t y of the pyrolysis intermediates formed d u r h g the high-rate period appears t o be much greater than t h a t of t y p i c a l petroleum hydrocarbons since no measureable l i q u i d products were obtained a t temperatures a s low a s 1300°F. A t the high hydrogen partial pressures employed i n t h i s study. However. . However. . s .1 carbon oxide formation a t low conversion l e v e l s may have been largely due t o steam reforming. probably largely by pyrolysis rather than by reaction of char with hydrogen formed in steam decomposition. was much higher than in the previous t e s t with a steam-hydrogen feed a t equal steam p a r t i a l pressiire. i . This i s supported by the f a c t that more hydrogen was produced than could be accounted f o r by carbon oxide-forming reactions. and hydrogen consumption and carbon oxide formation w a s affected by oxygen content. 1 2 . Materials a s dif'ferent as lignite. Substantial q u a n t i t i e s of gaseous hydrocarbons were a l s o formed i n i t i a l l y . there i s no FndlCatiOn of the acceleration of methane formation by steam addition which has been observed a t lower hydrogen p a r t i a l pressures. o r d i r e c t reaction of steam and char. bituminous coal. on reactions w i t h steam which form carbon oxides. CONCLUSIONS GasFfication o f various coals with hydrogen and added steam a t high temperatures and pressures. gaslf'ication rates are very rapid and the course of the methane-forming reactions is similar t o t h a t i n hydrogenolysis of hydrocarbons. under conditions of very rapid coal heatup and product gas residence time of only a f e w seconds. The i n h i b i t i n g e f f e c t of hydrogen. as well as during the conversion of the r e sidua l char. anthracite and low-temperatxre bituminous coal char behaved similiarly. and methane was the predominant product. g . and 1500 p . catalyzed by the r e a c tor Walls. This i s the r e s u l t of the well-established i n h i b i t i o n of the steamcarbon reactions by hydrogen ( 6 ) . was observed for the i n i t i a l high-rate period. the conversion r a t e s of the r e l a t i v e l y unreactive residues were approximately the same. has confirmed the generally accepted model derived from data without a s d etailed a de f inition of the c r i t i c a l i n i t i a l stages of conversion. However. except t h a t i n i t i a l conversion rates increased roughly in proportion t o their v o l a t i l e matter content. During this i n i t i a l period. n a even i f the t o t a l gasification r a t e i s considered 3 comparison with char-hydrogen results. steam addition d i d not accelerate methane formation a s observed Fn previous s t u d i e s a t r e l a t i v e l y low hydrogen p a r t i a l pressures. of a portion of the gaseous hydrocarbons produced.

C. 396-403 (1957) z . 9. 820-5 (1955 16. P.. American Gas Asscciation.... 13. Blackwood. B. P r o p . J.. . 900-5 (1956) 5. Zielke. .%derson. who designed most of the apparatus and helped develop the experimental procedure. E. Cumen. S.F. 590-4 (1960)1 1 . 580-3 (1960j. Ind. &. a. R n . P. 2hg. R. E. Shultz. R. 44. Ind. M. Eng. Neuzil supervised the ana lytic a l work. C . Operating Section.. Ind.. 577-9 (1960). 45. B.. T. fta. E. Zielhe.. Channabasappa. Linden. Chem. Shultz. C . Gorin. Ind. Eng. G. r . Lhden.. . J. G.. Ena. 47. H.. E. Paper CEP60-9. Ind. Richter and R. LFnden.. Curran... S. Pyrcioch.. Schlesinger. G. R. Chem. R. 48... . K. R.204. 6. P. Gorin. Jr. H. ki. W. kim? - . E. B. Ind. S. E. L s w i s . I and EC Process Design and Development 1. P. E. Mechales. B. . mea. Mson and J.. Benson. Birch. G. W. . Anderson.. Eng.. E.. . Chem. Goring. Shultz. Ehg. C. . Thanks a r e due t o E. 52. Friedman. M.. J . E. Gorin. Fuel 422-35 (1960j. Johnson a s s i s t e d i n data collection and D. Linden. - Ehi- z . Eng. R. Chem. Ind. 7. 2011-16 (1957 . K.. Chem.. Hiteshue. U r i e . REEEliENCES C I T E D 1 . t e s ue. Q .. Vandaveer and H. Jr. Hall.. 14. Ind. H. R. W. 16-33 (1958) 4. Gorin. Jr. 2hg. H. N. E. 2008-10 (1957). Jr. Shultz. Eng. L. B. A.. 3. E . 1960. R. W. J. 2. cioch. B. Goring. Chem.73-80 * (1961) 12. Chem. H. D. E. W.. J. D. 1051-65 (1952). ACKNOWIEEMEXT This work was conducted under the sponsorship of the Research Department of th e Consolidated Natural G a s System (now Con-Gas Service Corporation) under the guidance of F.111-6 (1962). R. J. Ind. D. No. Hiteshue.... 52. E. R. Shultz. Inst. 52. R . H. Blackwood. Feldkirchner. Friedman. R.. E. 15. Zielke. E.. Eng . Linden. Chem. E. Tarbox.. 2586-91 (1953). Symposium Ser. E. 10. Chem.

Semiflow r e a c t o r s y s t e m f o r study of r a t e s of h y d r o g a s i a t i s n of solld f o s s i l f u e l s at t e m p e r a t u r e s to 1700' F. i . 2 PRESSURE R E G U L A T O R 3 F E E 0 GAS PETERIWG V b L V E 4 SOLIDS FEED H O P P E R S 6 i Pt!EU!?hTlCPLLY OPERATED FULL-OPENING V A L V E PRESSURE E 9 V A L I Z A T I O N L I I : E P E A C T O R . fic .205. 2-INCH ID 6 0 .T E S T U E T E R 13 SYNTROt! V I B R A T O R 11 R U P T U R E DISK 15 R P t l A R E X R E C O R D E R !b L I Q U I D P R O O U C T S K N O C K O U T !I G P S S A M P L E E O T T L E i 8 'nATER-COOLED CONDENSER 19 W A T E R WEIGH T A N K 1 . and p r e s s u r e s t o 3000 p . s .I. g . P 2 0 'YET E R III G P U 1 6 4 - 1 1 1-q FILTER FILTER 2 1 S T E A l GENERATOR 22 HIGH-TE!2PERbTURE VbLVES PR-PRESSURE RECORDER D P T . 1 . 3600 P.I N C H !L I X T E R C H A K G E P B L E FEED G A S A N 0 P R O D U C T G A S L I N E S 7 3 9 F09 C P F L O i V AND DOWKFLOW O P E R A T I O N BACK-PRESSURE R E G U L A T O R :3 B Y P A S S FOR F E E D G A S O R I F I C E C A L I B R A T I O N 11 G A S SPTURPTORS 12 P R O D U C T GAS P E T . O I F F E R E N T I A L PRESSURE TRANSMITTER D P R .S. D l F F E R E I T l b L PRESSURE R E C C R D E R F i g . I3 l J FILTER U 1 F E E C GAS S T O R A G E C Y L I N D E R S . 0 !1" . .

0 m 4 1 00 I 2 W O I I n 0 ooglI 0 1 0 1 1 10 1 1 30 1 I o I 1 YO 1 1 sa 1 1 70 1 1 . F i g .. and 1500 p. Fig.s.s. TOTAL CIRBON GASIFIED. I d E irso n w 1: W g 30 0 m troo ? 20 L s i 0 1 0 z 0 4: m 7 WS $ 3 0 k 20 1 0 20 30 40 ¶O TOTAL CARBON GASIFIED.-Reaction'rate constants f o r v a r i o u s feeds a t 1700°F. Y. a n d 1500 p. 4.-Effect of c h a r p a r t i c l e s i z e on r a t e of hydrogasification a t 1700" F.-Effect of t e m p e r a t u r e and conversion on r e a c t i o n rate cons t a n t f o r bituminous c o a l c h a r . 3. ' Z .g. 4 SAMPLE WT. X 1 10 J d F i g .g.g. 9 2 70 80 TOTAL CARBON GASIFIED.i. TOTAL CARBON GASIFIED.s.i.G= 0 3 I800 dS 0 1 0 .i. c h a r h y d r o g a s i f i c a . tion at 1 7 0 0 ° F . 2.-Apparent effect of s a m p l e weight on r a t e o f .26. =so ' . % F i g . and 1500 p. 5.

0 1 0 x) 30 40 50 KO TOTAL CARBON GASIFIED.-Effect of p r e s s u r e on r a t e of c h a r hydrogasification at 1500" F. .G. Fig.-Approach of ethane concent r a t i o n s to e q u i l i b r i u m values as a function of t e m p e r a t u r e .g. '2 .d I300 1400 1500 1600 OF 1700 TEMPERATURE.a 2. I500 1000 500 AT 1500 PS. and a total p r e s s u r e of 1500 p. ' I I I b l \ I I . 9. 5 . 8.. 2 70 80 F i g .-Effect of p r e s s u r e on r a t e of c h a r hydrogasification at 1700' F.i.P I( L 4 U W \ 0 2 ' \ IK 3 U 5 W 4 IW TOTAL CARBON GASIFIED.-Effect of hydrogen and methane p a r t i a l p r e s s u r e on r a t e of c h a r hydrogasification at 1700 "F. 'r 30 40 E ' u $ 2 I Fig. 70 n 50 m r z 0 . 100 =. 6. 7.s.0 wIO . F i g . 5 5 03 g 02 0 IO 20 TOTAL CDRBON GASIFIED. m 0 30 20 u 8 I n '0 07 0 2 05 w 4 2 .1. 207. % 3.

s. 40 h F i g . 11.i. 12. and 1500 p. s . 10. with an equimolal s t e a m . 70 F i g . i . with an equimolal s t e a m helium mixture.-Effect of conversion on r a t e of gasification of c o a l c h a r at 1700 O F and 1500 p .208. % PO 30 40 50 60 70 TOTAL CARBON GASIFIED. .-Effect of conversion on rate of gasification of c o a l c h a r a t 1700 " F .hydrog e n mixture . -Gaseous hydrogen b a l a n c e s as a function of conversion of v a r i o u s f e e d s .0 $ 0. % 80 90 F i g .095 090 $i 2 i ai a 0 1 0 a85 3 080 075 070 I I io I I 40 20 30 TOTAL CARBON OASIFIED. 50 z K 0 g 20 sD 3 2 1.g.7 cas K a3 i= ga2 a ai 0 M 50 TOT& CARBON GASIFIED. $13 0 BlTUMlNovs COALCHAR 0 ANTHRACITE 0 LIGNITE A BITUMINOUS W U I I I I I I I $ i g 4 z . g .

which can be used i n the design of improved types of &. Several investigators (2) ( l l )(12) (13) studied t h e kinetics of the reactions of coals. generally w i t h air. (3) (7) (8) ( 9 ) (10) (14) (15) (16) (18) is related to the reaction of steam vith Despite this relationship.700. U . ) - i John J . pal-ticle size. IIbe method origbally devised for finely divided carbons was recently m o d i f i e d by the authors and developed for the rapid determination of the r e a c t i v i t i e s of coals. fsxed beds of coarse particles. S. F . usually q. Bureau of Mines.. which has been widely investigated a t the Morgantwn coal Research Oenter of the Bureau of Mines ( 5 ) and elsevhere. t h e texm "relative reactivity" . have failed. oqrgen o r carbon diozdde. modifying their constants accordingly. "Relative reactivity" is defined he= 88 the relative rapidity of reaction between a fuel and an o d d i z i n g 5 s (steam i n OUT case) i n a given apparatus under the same set of experimental conditions. ccamnercial coal gasification equipent. type o r grade. Deparbnent of the mterior. A t t e m p t s to extrapolate these results to other types of coals suspended or entrained i n steam a t considerably higher temperatures and pressures (4) have never proved satisfactory and. S . Va. ( 1 . W . i I 'Ihe purpose of reactivities" of various 1. deccanposition end actual temperatures. for the detenuination of the reaction rates of carbons with steam. cokes or chars. but restricted their research to relatively low temperatures. or Qo. i n masy cases. specific types of coals. W . It i s an experimentally obtained index figure. or the use of questionable assumptions to extend the applicability of a rate equation t o a l l gasification conditions does not seem Justified. and bulk density. pressure ( 4 ) . %e conclusions drawn from studies of the r e a c t i v i t i e s of varlous types of carbon furnish l i t t l e o r no infomation on process rates. Specifically. Sebastian and Robert L. structurally and as widely different i n composition a s coals of various rank. A "falling particle' technique has been developed by Dotson and Holden (5) of the Bureau of Mines a t Plorgantown.aag R E A OF susmKSIrnS (IF CQAIS I N SPgAM J U 900 950' C. the work here described was to detemine the "relative w s of coals vhen t h e i r particles react with steam a t the object was to separate the overlapping effects of t h e w steam-carbon reaction vhen steam interacts with coats at high "Reactivityw of solid fuels is generally defined (7) as the velocity or tbe-rate of the reaction betveen a solid f u e l and an oxidizing gas. Ibvestigators generally agree that the reaction of steam with w r i o u s types of carbon and cokes. Va. pertaining to an average (measured) residence time. Moreantown coal Research Center. Morgantown. i n c h d i n g temperature. 7 0 0 . s i z e consist. knowledge of the kinetics of the steam-carbon reaction does not disclose nor reveal the kinetic behavior of coals of various rank and type in coal gasifiers. Generalization f o r all types of coals. under a given set of experimental conditions. useful i n c m s o n with other fuels. Others t r i e d t o flt theoretical rate equations to data fYam Largescale gasifiers. It is doubtful t h a t a geneapplicable rate equation can be established for substances as camplw. F. m. etc. The essential feature of the method is that it closely simulates the conditions existing when povdered coals entrained i n steam are gasified in large-scale gasifiers.

and the steam thus formed I s preheated to 800 1. I n either case. this paper I s restricted to the study of the more rapidly detemLned relative reactivities 00 coals (-60 + 65 mesh) interscting with sta t 1. (900 9 5 0 ' C . the latter surmmded by a 5/16-1nc11 wide a n d m (not shown i n Hgve 1)throagh which the steam is passed downward a t about l. tbrough a hole Into t h e feed-tube and thence into the reactor. generally 3 pounds of s a per pound of dry mineral matter free fuel. % e kinetic reaction rate . particularly temperature and pressure (4) ( 1 7 ) .OOOo F." shown as grtnns of carbon gasified per of carbon i n the coal. CLiLcrilrrted f o r a reactor tenrperature of 1 . should also be known. is controlled by adjusting.usraallg exprebaes.the volt age input t o the vibzating mechanimn. Ihe reactor developed and used to detenrdne the relative reactivities of coals by the falling p a r t i c l e technique is shown schematically i n pigure 1 . blanketed nitrogen. The unifozmly sized (-60 + 6 m e s h per inch) coal particles in the feed bowl m o v e uprwrd a l o n g a spiral track until each particle is swept by nitmgen. cu. generslly 50 g.OOO* F .70O0 F. f t .210. but direct contact with the uall is prevented as they are carried damvard i n m n ~ r flow (cormationsl Reynolds number about 20) blanketed with w e s . fall knmledge of the kinetic rate includes the effects oi all variables on the reaction rate. - - 'Ibe coal particles. 2 std. m i n matter free coal. H o w ~ e r . nitrogen. o r (2) "carbon conversion. and bulk aenSity. Accelerated by gravitg. insofar as they affect the overaU reaction rate. The coal feed-rate. its detemlnation is more time consuming. bngitudinrd tenpexatum profiles or traverses are determined from time t o time. 5 inches e high and 5 inches outside a e t e r . such a s particle size. "be coal particles thus preheated in the feed-tube a r e entrslned i n the steara and enter the top of the reactor-tube t h r o e a 1-Inch inside dim&xr circdlar apening a t its center. For zecdmum usefulness imaa a desi@ standpoint. t h q continue to fall through the st-. and the vibratorg feeder is started.q steel reactor tube is electrically heated by 9 (pairs) prefabricated semicircular embedded-coil-type hesting elements 1 1 ." %e tenu Tdnetfc reaction rate" is a more fundamentel chsrscteristic of a given fud reactiag x L t h a e v e n gas. s i z e consist. and th@ heat input is adjusted to maintain i S O t h a E d conditions. %e 3-inch inside diemeter 9-foot loag a3J. The enterlng psrticles together with steam and nitrogen spread somewhat. and generated gases V i at free-falling velocity. and the physical s t a t e of the reactants. flowing a t a rate of about 1 . ) and for a luv-volatile biftmdnaaa coal fed a t 50 gmms per hoar. I)oubly distilled pster passing through a mtslaeter is vaporized in a small electrically heated tube. and atmospheric pressure. *e steam flow-rate is a&justed for the desired steslo-to-coal ratio. per hour in the resctivlty tests described. the functional relation betveen reactton late and IBBEtant concentrstion a t aqy given tenperature and pressme. the other 7 eleraents control the temperature io the @-inch long i s o t h d zone. before injection i n t o the reactor. simmes no more than a to each other." even as weight-loss i n grams per gram of dry.and is usually more simificant Aarm a process W e e r i n g standpoint. the conversion of the coal to &BS is due both to t h d &camposition and reactloo w l t h - Steam. 'Ihe reactivities a m expressed in terms of (1) "fuel conversion. wltb - . n ments a t the top and bottcmr serve t o balance the heat losses. The effects of mass transfer rate and floor pattarn. 7 0 0 ' F . each controUed by a variable trsnsfonner. t t h e name implle~: reactivities of osriC0a-fuel. in fozm of a rate eqpation. it is independent of the gasifier &si@. p e r hour. i s l l throu& a 7-inch long 5/16-inch inside diameter feed-tube. Although wrk is being planned on the detenulnation of the kinetic rates of the reaction of steam with coals a t hisher temperatures and pressures.s r e l a t e & It should not be copfased pith ' % h e t i c reaction rate.

7 0 0 ' F. the linear velocity of the steam-nitrogen mixture in the upper part of the reactor uas 0. Since the coal particles t r a v e l 6 times faster than the entraining steamnitrogen mixture. As the reactivity of powdered o r granular f u e l i s affected by the size of the particles.700" F. a p p r o x i m a t e 8 1/2 particles of -60 + 65 mesh coal are i n p a r t i a l entrainment (suspension) at any given time i n each ad of steam-nitrogen m i x t u r e flowing a t a r a t e of 265 cc. The solid residual is collected i n a receiver bottle. and vented. Next to the control board i n the foreground. and the term "falling p a r t i c l e techniqueD properly describes it. (An isotope tracer method used to determine the residence time of the fiel particles. per see. the extent of degradation i n (-60 + 65 mesh per inch size) throua the reactpr-tube. a stetnu-to-coal r a t i o of 3:1. per sec. As shown i n Flgure 1 . but is rather e m unsteady o r partial suspension. w i l l be described in another paper to be published by the authors. convc32*jely. veighed and analyzed. a t rom temperature. per hour) i n the upper part of the reactor a t 1. decrease i n bulk density be due to (1) formation of fines (degradation).U m m . per sec.700' F . ft. 'Ihe fuel-feeding and steam-generating systems a r e located on the upper platform partly vlsible a t the top of the picture. The htter m u e thus estimated i s analogous to the tern "mean free path. the rest of the soot i s remaved from the gas by + s a r e caugbt on filter means of a wash bottle. --- --- The concentration of fuel particles in the upper part of the reactor. . Most of the excess steam and some f i n e soot collects i n the condensate receiver. it i s clear t h a t t h e fuel particles f a U i n the reactor tube almost freely through the gases. under the conditions stated. AWycmring hi&-volatile bitwinous-C f a vas detelmined by drop-testing samples . i s not so much of the entrainment type. The f l o v .9 cu. is estimated to be about 50 mg per dns of reactor volume containing a gas mixture of 85 percent steam and 15 percent nitrogen. and thus t h e i r tenninal velocity. and the gas i s metered.OOO' F. the residue and product gas recovery system is a t the b o t t m of the reactor tube. unifolmly tapping.211. graduated cylinder with the particles. before and after a s i n g l e passage through the reactor under the usual conditions a t 1 . As the measured average terminsl velocity of the coal particles m a s 1 . the difference is their freef a l l i n g velocity: 1. On an average. i n case of bituminous coals. Specific volmes were d e t e m h e d by f i l l i n g a 10-cc. Nevertheless.. Do the solid fuel particles abrade each other and. i s this size reduction balanced.19 ft. the apparent (or bulk) specific volumes of tu0 different coals and a char were detelrmined. if they are assumed to be spherical and have an avenge diameter of about 0. it was necessary to investigate possible degradation of particles a s they fall through the reactor-tube. and 1. i addition to the microscopic examinations. by swelling of the particles when they pass through the p l a s t i c stage. The specific volume data shown on these pictures a r e helpful in t h i s evaluation since any increase i n the apparent (bulk) specific volume or. A photograph of the apparatus is shown i n Hgure 2.) Iaminar flov inside the reactor prevents direct contact between the particles and the heated reactor tube. (33. and i s coded. 3 3 ft. and then weighing the contents.? To answer these questions." although used here i n a different sense. is approldmately 6 nun. therefore. usually between 700' F. i n s t i l l air. The average distance between the suspended particles. if so. Traces of tar vapors i n the product . and the effect i v e transfer of h e a t partly by radiation from the reactor v a l l s and partly by convection and conduction through the steam medium the f a l l i n g particles are rapidly heated to the isothemal reactor temperature of 1. The results a r e shown in Figures 3 and 4 w i t h the apparent (bulk) specific volume i n each case given below the photamicrogmph of the sample. papers i n a Eiuchner funnel. senpled. per sec.14 f t . because of the s m a l l heat capacity of the fuel particles. and/or (2) swelling of each p a r t i c l e wlth corresponding increase i n porosity. the i n s u l a t e d reactor tube i s seen v i t h the product recovery B t r a i n below it.

variables affecting the reactivities of povdered coals are: (1) type and s i z e of test-reactor. me yields o f gases are seen t o increase with increasing stesm-to-car~o ratios. l6) and a char. ‘Ihese results conf5. There is plenty of evldence of svelllng and foxmation of hollow spheres. 7). Ngure 5 shows the effect of steam concentration (in tenns of stetaa-to-carbon veight-ratios) on the components of the gases evolved. This may result in the formation of ”defect sites.although the char ya8 samewhat more r e s i s t a n t t o breakage than the coal. (3) part i d e s i z e of the coal. w i n g the detachment of 1 groups and other radicals &rm C&On atms in the coal matrix. as v e l l as by the considerable increase i n bulls specWc volumes. and It appears that t h e interaction increases with the steam concentration.and the product vaS screened -ugh a @-mesh per inch s&ndard s c m . other p a d f i n h@marbons. me results of this study are i l l u s t r a t e d in T h e intersction of s t e m appears to f a c i l i t a t e thenual decampsition at a lover temperature. per -. T h i s Interesting fact points t o a possible interaction of stem vith hydrocarbon groups and other radicals attached t o the coal molecule. but not excessive. me results vere negative. Yere so tested f o r s i z e degradation. as shovn by the photcaoicrographs i n Figures 3 and 4. d e t e n e d vis-.5 seconds for the char. In both cases the slze degrsdation was m . The breakage index.v o l a t i l e bituminous coals. Even this slight size redaction i s more than balanced i n the case of bituminous coals by the s w e l l i n g o f the particles as they pass through the p l a s t i c stage. Although the d i a in Mgare 5 refers to 8 low-volatile bituminous coal. ( 6 ) residence (or contact) t b e . 7 percent for the coal and 0. (5) s t e a a inpat rate (or steam-to-ccd wight-ratio).. ethane. (2) chemical ccmposition and microstructure (porosity) of the c a . coal (Serial No. yield curves shoving Identical trends were obtained w i t h h i e . made by Iw-teupeFsture carbonization from a @lorsdo bituminous-A coal. etc. (M BoJo. An b p o r t s n t variable i n need of study was the required steam-to-coal ratio.2 percent f o r the char.212. uniformily shaklllg and tappins i t i n each case. Experhental amdsmentals Tests to detennine the r e l a t i v e reactidties of coals vere c a f i i e d out under as nearly identical conditions as possible. fuel and carbon conversions. (7) tenperatuse. For emmple : (refoming reaction) Caq + -0 =~ 0i 2 4% ami c o + E 2 0 “ c q + ~ (wakr-gas ahipt reaction). was 1 . vhich is the pement retained on the 65-1aesh screen before the drop-test minus that retained after the drop-test.2 g. carbon monoxide. me time of fall during the --tests. The most essential. its s i z e consist and d a s i t y . me. (4) coal thmughput. but m o s t of the increase in the total e s yield vas due to the r i s i n g trend i n hydrogen evolution.).4 seconds f o r the coal and 3. Plgures 5 and 6. vas 4. and (8) pressure. thus maintaining a t all times the major operating variables as constant as practicable. the objective uas t o establish the correct magnitude f o r these variables i n o r d e r to obtain measurable. I n e d 123 inches e c h case the procebre was identical: 100 grams of the sample vas m at a rate of 72 &rams per hour (1. thus entering the gas phase n w react with additional steam to fonn Cq and H2.m what is evident frena Figures 3 and 4: any s i z e degradation frcim attrition of the particles by theaselves and by the reactor y8u is negligible and is veil v i t h i n the expected experimental error. . The existence of such defect sites owing t o electron absences (or “positive holes”) has been recognized by G r a y (6) and his cowrkers. In dweloping a rapid practical method for testing coals for reactivity. ’Be methane.” probably vlth an electron lost or removed f r a n t h e carbon atan fmm which a radical (possibly i n ionic s t a t e ) was detached.

'he average residence time of the coal particles in the isothennal zone ranged fmn 5. standard sieve but retained on a 65-mesh sieve. and microstructure of the coal tested." thus formed are vulnerable to attack by s t e a : C + H20 = CO + E2 and CO + E20 = Cor + H2. additional steam does not significantly increase the carbon conversion. Materials Tested Descriptions of the types of fuels tested f o r their r e a c t i v i t i e s are given i n Table 1 . Proxlmate and ultimate analyses of the fuels tested are shown in Table 2 on a d r y . as too much excess steam mould increase the flov-rate. S. a t h o u g h the r e a c t i v i t i e s of these chars were determined i n the sane apparatus by the sane technique described above for coals. accurately measurable conversion was t h e criterion used in determining o r &oosing the optimum values of other essential variables. were kept as constant as possible so that t h e results of the reactivlty tests depended only on the w e . whenever therm a l decomposition of coal takes place i n the presence of steam (14). but in some cases up t o five. (!Be detezmination of these values by an isotope-tracer method will be discussed by the authors in a future paper.) ao The optimum values f o r the variables.650 and 1. ranging fnrm l i g n i t e s t o anthracites. The test results for each batch of coal were averaged and plotted on the f o l l a r i n g diagrams. the ma&num variation being f F..750" F. r e a c t i v i t y tests yere made on each of the 12 types of coals l i s t e d i n lLBbles 1and 2. Above t h i s r a t i o . ccarrpositioh. The importance of steam-to-carbon r a t i o thus established. The coals a r e presented i n the order of increasing rank. Thus. All of the reactivitg test data (including data on s e v d chars produced by low-temperature carbonization at the mesa of Mines Denver Coal &search Center fnrm . thereby decreasing the contact time belov the l i m i t of effective conversion needed for most of the reactivitg tests. Similarly. Use of the "mineral matter f r e e basis" resulted in a much b e t t e r alignment of data along the curves shown i n various diagrams representing the functional relation between reactivity and various coal constituents or ratios.e. m e a s u r e d a s fuel o r carbon conversion. "mineral matter free" basis.e. Included i n this t a b l e are i n each case the percent mineral matter. a l l of the t e s t s were made vlth coals closely sized t o pass a 60-mesh per inch U . calculated i n confonnity with ASTM standards (1) and the C/H ratio. i.. the objective of the work with chars w a s sufficiently different to merit separate discussion i n a future paper. The temperature was kept uniform throughout the @-inch long isothermal zone betveen 1.213. .. A r a t i o of 3 : l was thus chosen. each test. thus detemined. - - Results and 'Mscussion U s u a l l y two. a maximum has been reached. experiments vere . made to detemine its effect on the reactivity. The coal-feed xate was fixed a t about 50 grams per hour and kept a s constant a s possible throughouC. I The defect carbon s i t e s . i. This i s a plausible explanation of the hydrogen evolution (Figure 5) accamwnying the interaction of steam with t h e coal molecule. often called "reaction sites" or "active sites. Figure 6 shows that for both high and law v o l a t i l e coals the reactivity r i s e s asympt o t i c a l l y up t o a r a t i o of about 3 : l .2 seconds for subbituminous and l a w o r hi&v o l a t i l e b i t i d n o u s coals to 6.6 seconds for anthracites. Bere is plenty of evidence that steam thus interacts w i t h coal both in carbonization and gasification. Also included in Table 1 are several types of chars derived by low-temperature carbonization fropl the specific types of coals shown i n the table.

or C/H r a t i o could be used as the sole index of d . 89 hss b ~eversl ime&i@to= coals of various rank and tJrpe are f'unctions of the volattle the standard ASIM test. the reactivity test i s a ccaubination of carbonization and gasification in steam medium a t about 1. index of rank. The devFations in slopes. it is not suggested that either the volatile mtter. - --- --- Ihus. and mrrg also be an indicator of the quality of synthesis gas. but it does include the product gases resulting fmm the steam-carbon reaction (0. and rapidly again in c8se af 1. bituminous coals. v o l a t i l e matter and gas yield measured in reactivity tests are related terms. ) . Most of the lines tend to be horizontal or slightly upward sloping and ate usually pruriuel. or that of high-B. (13). may not be signiflcant owing t o experimental ermrs in analyses or sampling. although atudliary. of c o a h of various rank ( g d o g ical age) and their corresponding cham (connected wlth broken lines and arrovs). H m e r .700' F . but a mild-sweep F-Jal=e 8. hovever. the results of this investigation show that the total carbon content and C/H r a t i o are more sensitive indicators of the ranks of coals. as claimed i n the &curve. density. very -idly in case of pounger coals. b u t the latter curve is much s t e e p e r . selection of cabla f o r effectLve gasification.. gas or liquid fuel that can be produced by gasification and sabsequent synthesis. i. W h e n fuel conversion is plotted versus volatile m a t t e r takes place a t 1. therefore. relation is not past w i t h considerable deviations admitted.t. 7 4 0 ' F . weight-ratios. it may be concluded t h a t the reactivlties of coals are inversely proportional t o their mnk o r geological age. and H2) to the extent that this reaction . as a function of steam concentration.2 to 3.3 shown in Flgure 7. Y e t . expressed i n tenns of either fuel or cazbon conversion. o r total carbon Content. I n s p i t e of this. coke oven conditions in small-scale carbonization i n a crucible a t 9 5 0 ' c. in turn. When plotted on mineral natter free basis. pisureS l 2 An entirely W e r e n t metbod of plotting the reactiviQr data is presented i n and 1 3 . the functional. ?be C/H r a t i o appears t o b e an excellent indicator of rank.v. although for the shorter range of steam-to-coal. the reactivities of coals. the r. investigated) are shown in figure 7 . although by no means a r e they identical. similar S-curves result. each line indicating coals of the same rank f a U appro-tely a given reactivity level. i n tenus of fuel conversion. mineral matter free basis.eactivities of matter as detennined by linear. 2. bituminous coals and anthracites. are nearly perfect hyperbolic functions of the carbon-tohydrogen weie. htuaUy. not a straight l i n e but a well-defined S-curve is obtained (see Figure 10). 'Ihis dhgmrn Uustrates the sane of the n l a t i v e reactivities. q. much more slowly VlW h.u. Since coals of various rank characterlsticaUy m e r in v o l a t i l e matter the ASlM (1) classifies them into ranks l a r g e l y on the basis of v o l a t i l e matter (on mineral matter free basis) and calorific value it is &dent that the reactivitg must be related to the volatile matter as determined by the standard ASPI t e s t . - I n general.u 4 . etc.e. as i n F i j p r e 6.) of the coal as these. In plotting the reactivitg a&nst the carbon i n coals.700" F (pigare 8) sad againat gas yield (Figure 9). it vas found that both the fuel and carbon conversions are cublc parabolic functions of the total carbon content. as shown in m i l e volatile matter h a s served for sane time as an appmximte. ( 1 . This a to be significant both from the standpoint of fuel classification and process englneering. 'Ibe gas yield. llhe reactie* decreases with increasing carbon content. 89 shovn i n Figure 1 1 . aCpressed on dry.v. t o some extent. along straight lines. does not include the water formed as a result of carbonization. - C b the other hand. depended on the tspe of vegetation and geologic factors that &st& when the coal beds were formed i n various prehistoric ages. Fraa this it follows that the resctivity is a function of the c h e n n i d ccanposition and microstructure (porosity. The siepificance of t h i s difference is subject to further interpretation with a d d i t i o n a l experimental evidence on hand. me purpose of these diagrams was to d e m e the extent of the .ht-ratio (C/H). the upaard trend is not as noticeable. The v o l a t i l e matter test is intended to duplicate. they should slope slightly upward.

740. and H 2 . CO. in term of fuel conversion. etc. Le. it reacts w i t h the so-called 'fixed carbon. An interesting observation can be made and conclusion dravn b y w i n g i a w in Flgute 12 011 the reactivitg of fixed carbon in relation to the closer the d total carbon content of coals of various rank. q. I n other words.e. which explains the decreasingly lower r e a c t i v i t i e s of coals from lignites t o anthracites. It shows that the actual steam-carbon reaction generally decreases w i t h increasing order of rank from l i g n i t e s to anthracites. F . bituminous rank to anthracites is nearly equally reactive. ?he two temperatures. as detewined by the AslkI test at 1. L. 'Ihe steam thereupOn reacts with carbon atoms deprioea of hydrocarbon. Dr.: Harry Perry. E ." As the v o l a t i l e matter evolved in thenual decaposition consists of much v o l a t i l e carbon (in the fom of Ca4. Lignites and other young coals have many more alkyl side chains and several other radicals attached to the benzenoid coal matrix than older bitmninous coals.700. reacts with carbon in younger coals wlth surprising ease. I reactivity. a similar p l o t of conversion by the steam-carbon reaction alone versus the fixed carbon content (Figure shows more clearly than the previous diagrsm that the rapidly descending clMe tends to beccme asymptotic beyond 63 percent fixed carbon on d r y minezal m a t t e r free basis. from the fuel. while the carbon in coals from h. but less and less e a s i l y vith carbon in older cosls of increasing rank.. and s t i l l less in anthracites. the "defect" s i t e s reaaining a r e vulnerable to attack by E20 molecules.and 1 .70Oa F. 7 0 0 . carboxyl. caused by (1)t h d deccrmposition (devalatilizstion) and (2) t h e actual steam-carbon reaction. mus. y e t understandable in l i e t of the explanation given above under Experimental Fundamentals.. conversion ( i n terms of grams of coal converted t o gas per 1 0 0 g m n @e) a t about 1. ( 9 0 ' C. However. Lowry.. if we aedJlct the percent of v o l a t i l e matter (i. t h e difference WFU be the percent fixed carbon that reacted w i t h steam t o form CO.). Uhen these radicals crack off the carbon atms as 8 result of the interaction of steam. u) - 1~ \ I 'Ibe conclusion &am is significant. . r3+.that each psrticle of coal thermally decomposes vith the evolution o f ' vola t i l e matter a8 its tearperstare r l s e s to 1. and Dr. F . L. grams of coal converted to gas per 100 gram sample). steam a t 1. F . *e fixed carbon remaining is a l ~ a y s numerically less than the total carbon i n the coal. t i Acknarledgppents The authors vi& to acknovledge the h e l p f u l suggestions of the f o l l m i n g Rareau of Mines personnel. 1.700. W e can say wlth considerable certain.215. F.740. H i r s t . are sufficiently close to p d t the approximation. and other side chains. F. me effects of these t m *tors overlsp i n t h e reactivity tests described.v.). E. hydro-1.

.An a s t e r i s k next t o the s e r l a l number signifies char. respectively. 4 Island Creek coal (30. McDovell Own*. ae8tvirgLnia B l o . Perm.1T 3 9 Medium-volatile bituminous coal Low-volatile coal sendbituminous Anthrscite sevell Pocahontas m e + 4 3 . west V i r g i n i a LocUSt SMrmit. 80 RBadiW coal8ndIronco. Pe?ulsulvania %e s e r i a l numbers shown identif'y the type of fuel tested in subsequent tabulations and aiagrams. AU coals are sham i n the order of increasing rank. See the corresponding heading 8bave for coals m a chars.

1 t h 217. t m d 8 0 k 0 R 2 0 I .

&. “Le Problene de la E e a c t i f i t e des cembustibles Solid.. F . Ausixalian 5. Austin. B . D .. Gas R e a c t i o n s of Carbon. Hew York. and Schqyer. S. R . Zielke. B . Dotson. J . 396 (1957). I ) .g. B . . 137. C. .. IXrem: 60.. x . paris. J . L. . . A . 1 9 6 l . et a l . Orin.. W . in ”Advances in c8tsJysis. J r . Elsevier.N w Y O r k . E. “The Defect Solid Gclerin. 1 1 \ Warner. 1 ! . 1447 (1943). “ C c d Science. J . KoeIaler. P .” kncd. Jr.” Pol. E . J . U .E . 6 6 . 1 3 .U8. P . J. 2. 148 (1. Detuiler. Rprs.37). D . J .988 (Oct. . Busche. Sebastian. 1959. E . w n g . 1945. =. J. Bnnstmng. E .955. No. Jr. . 16 ( 1 9 5 8 ) . Fqg.m p. S . s . ll. 9. 2. . . Pat. 5. . . Ptlblisher~. Businlro. Holden. E . XcGroq. Qrem. & . Interscience Grq. S. z. 3U-335. 1 $ 6 486 (LH). . Blaclnrpod. R . . . . Y . F .. 1. &. Walker. Literature cited Batchelder. s. P . . L . J .. (1953 Binf’ord. 1 9 6 0 ) . NeaYork. U. . A c a d d c Press. . . T . . l3C6 (1w). 9. 384 m . Z. =. G. 5. e . Van m e n . H .

\ I I t .219.

V. I No.13 cm3/g 0 1 2 3 4 5 SCALE: MILLIMETER 1.7C0° F i3 Steam E.0 mm = 1. R . Photomicrographs o r a Bitminous-A Coal and its Residue from iieactivlty Test made a t l. 6-R. 6 coal. No. Wotomicrographs of a Zitminous-C Coal and i t s 3esidue f r o m Reactivirity Tesz inade a t 1. BituminousC coal.000 microns ?igure 3. Sp vol: 4.000 microns Figae 4 .7CQ0 F i n Steam Medium (approxjmate enkugement l n ) . 11 coal. 6 . Sp vol: 2. Size: -60 t 65 mesh/in. 1 l .0 mm = 1. Single pass residue obtained from iesting No.39 cm3/g + No.220. Bituminous-A coal.’edivm (appmmte a r g a n e n t l n ) . 65 mesh/in: sp vol: Size: -60 1.32 cm3/g 0 No.V. . Single pass residue obtained from testing No. sp vol: 1. 11 -Wyoming H. Colorado H.99 cm3/g 1 2 3 4 5 SCALE: MILLIMETER 1.

.221.0 coals 3A \ \ \I \ z v)o . 1 I' ' Figure 5. Mfect gf Steam Concentration on Gas Yield. Ccaapgrative Reactivities of C o a l s and Chars .60- ' \ .70 - 1 ' 1 .Eefect of Steam Concentration on Carbon Conversion. I ~ \ \ \ . 1 ' 7 0 0 ' F Figure 6. 1 I I I I I 3 . 1700" F 0.50 O F - 38 P s U -%I2 I1 a W > m .40 - 2. I 1 . H v b coals - Figure 7 .

- Conversion as a Function of V o l a t i l e Matter Steam Reacting w i t h Coals a t 1 7 0 0 ' F I 1 1 I I I I 1 4 of a given rank. Figare 8 .222. Arobic serial numbers indicate the type of fuel tested as listed in Table I . I I I 15 20 25 s t d c u n per Ib dry m m f coal I 30 35 1 I Figure 9 . . . . Relation Between Fuel Conversion and Gas Yield Steam Reacting with Coals a t 1 7 0 0 ' F - . . 01 0 5 I 1 IO GAS YIELD.

?del as a P a c t i o n of Carjon Contert . 2.SConversicn t e m ?. O 60 'OI I 70 I I I I I 1 I t 75 EO e5 CARBON IN C O A L .eecting -d. Carbon Conversion as a FunctLon of Carbon-'co-Eydrogec ?&io Steam Reacting v i t h Coals a t 1700° F - I . dry mmf basil 90 94 _.s_t'n Coals a t 1700' F o"i . ArablC serial numbers 8ndicate the type o f fuel tested a s listed i n Table I .50 o-coa1s o f varmus r a n k x-Focal p o i n t s for coats o f a given rank. DerEent.223. '201 10 0 1 1 0 15 I 20 1 25 30 RATIO 35 40 CARBON-TO-HYDROGEN 7iglre 11.xg-i'lre IC.

.224. . p e r c e n t . percent. Arabic serial numbers indicate . Arabic serial numbers indicate the type of fuel tested as listed in table I. Relation Between Mxed Carbon in t h e Coal and the Reactivity of Fixed Carbon Steam %acting w i t h Coals at 1 7 0 0 ' F - . d r y m m f b a s i s Figure 13. X-Focal points for cwls of a given rank. : 0 W I LL -Coals of vorlous mnk X-Focal Points for coals of 0 g v e n rank. dry m m f b s i s Figure 12.. I os 74 76 78 72 80 82 04 86 88 90 92 CARBON IN COAL. Relation Between Total Carbon in Coal and the ReactPrikof Fixed Carbon Steaa 3eacting v i t h Coals a t 1700° F - 0-Coals of varlous rank.the type o f fuel tested a s listed in Table I. I1 X #I5 X O4 O8A 140 x 0 9 2 -5 1 55 €a I I 65 I 1 0 I I 80 75 I 85 I 90 I FIXED CARBON.

5. i s burn-out of t h e s o l i d carbon r e s i d u e l e f t a f t e r g e n e r a t i o n and combustion of t h e v o l a t i l e s . and t h e second. It has. burn-out s t a g e is a heterogeneous process i n which oxygen r e a c t s d i r e c t l y .5). and t h e n e x t one chosen f o r i n v e s t i g a t i o n . been s t u d i e d extensively.'> K i n e t i c s of Coal Combustion: The I n f l u e n c e of Oxygen Concentration on t h e Burning-Out Times of S i n g l e P a r t i c l e s Geoffrey Beeston and Robert H. and t h e conditions too imprecise. t h i s i s of p a r t i c u l a r i n t e r e s t a s it a l s o has d i r e c t bearing on t h e assumed but disputed ( 6 ) order of r e a c t i o n a t t h e s o l i d surface. o r e f f e c t i v e l y SO. been done i n t h e p a s t but t h e r e s u l t s (1-3) have g e n e r a l l y been t o o few. and ambient v e l o c i t y . THEORY As t h e general. thcrefore. through a boundary d i f f u s i o n layer. The theory i s based on t h e o r i g i n a l a n a l y s i s by Nusselt (10) i n which he assumed t h a t t h e r a t e c o n t r o l l i n g process i n t h e r e a c t i o n was t h e r a t e of d i f f u s i o n of oxygen from t h e mainstream t o t h e s o l i d p a r t i c l e surface. F u r t h e r experiments have. t h i s second. Reaction a t t h e s o l i d s u r f a c e was assumed t o be instantaneous. of course. been c a r r i e d out on s i n g l e p a r t i c l e s of c o a l under more p r e c i s e l y s p e c i f i e d conditions. were concerned w i t h t h e v a r i a t i o n of burning time as a f u n c t i o n of p a r t i c l e diameter and c o a l rank. therefore. but a s it were by proxy using r e l a t i v e l y pure carbon i n p l a c e of t h e c o a l . England 1 . Essenhigh Department of F u e l Technology and Chemical Engineering University of Shef f i e l d . very much f o r granted. The f i r s t r e s u l t s obtained. N u s s e l d p r e d i c t i o n was t h a t t h e t o t a l burning time (tb) of a s o l i d carbon sphere would be p r o p o r t i o n a l t o t h e square of t h e i n i t i a l p a r t i c l e diameter (do): . temperature. described elsewhere (4. The f i r s t is a v o l a t i l e comb u s t i o n stage. w i t h o t h e r parameters such as oxygen concentration. t h e r e f o r e . The success of those f i r s t experiments then encouraged extension of t h e work t o i n v e s t i g a t e t h e influence of other parameters. w i t h which t h i s paper i s p r i m a r i l y concerned. theory has been covered extensively i n previous reviews and papers ( 4 . and i t w a s a l s o assumed t o b e f i r s t order w i t h r e s p e c t t o t h e oxygen p a r t i a l pressure adjacent t o t h e s o l i d surface. 7-9) only t h e s a l i e n t p o i n t s w i l l be quoted i n summary here. kept constant. at-and-with t h e s o l i d surface. 2. together w i t h a comparison between t h e experimental and p r e d i c t e d behaviour. t o r e p o r t t h e r e s u l t s of t h e s e f u r t h e r experiments on t h e i n f l u e n c e of oxygen c o n c e n t r a t i o n on t h e burn-out times of t h e coal p a r t i c l e residues. The o b j e c t of t h i s p r e s e n t paper is. D i r e c t work on c o a l has. was t h e oxygen concentration. With t h e s e l i m i t i n g cond i t i o n s . f o r k i n e t i c s t u d i e s . t o check proposed k i n e t i c equations. K i n e t i c a l l y . and t h e v a l i d i t y o f e x t r a p o l a t i n g such r e s u l t s d i r e c t l y t o c o a l r e s i d u e s has g e n e r a l l y been then taker. INTRODUCTION J' \ h I S i n g l e p a r t i c l e s of c o a l burn i n two stages.

. a t an e f f e c t i v e l y constant temperature of about 1000°C. f o r t h e reasons o u t l i n e d i n t h e Introduction. w e assumed t h a t v a l i d a t i o n on a s i n g l e c o a l chosen a t random should be s a t i s f a c t o r y . and 1. M . The p a r t i c l e s were burned i n a i r . The value of t h e burning c o n s t a n t KD had.t. burning times (of both v o l a t i l e s and residues) of p a r t i c l e s i n t h e s i z e range 4000 t o 300 microns were measured a s a f u n c t i o n of diameter. under r e l a t i v e l y quiescent ambient conditions. and t h e two a d d i t i o n a l v a r i a b l e s : oxygen concentration and temperature. T h i s set of equations t h e r e f o r e provided u s w i t h r e l a t i o n s between burning time. i n t h e f i r s t i n s t a n c e % (4) j u s t as i t s t a n d s using only a few coals. but subsequently(5) t h e number and rank range o f c o a l s w a s i n c r e a s e d t o determine t h e i n f l u e n c e of c o a l rank. K.p. Do i s t h e s. and a l l were found t o obey t h e eqn.t. T i s t h e a b s o l u t e temperature. The experiments were then c a r r i e d o u t by measuring burning time as a f u n c t i o n of oxygen p a r t i a l pressure. To do t h i s . of course. were found (5) t o b e i n good agreement w i t h the following p r e d i c t e d r e l a t i o n s h i p between K and KD where Cf i s t h e f i x e d carbon percentage. (1). using f i v e d i f f e r e n t s i z e s of p a r t i c l e taken from t h e s i n g l e c o a l . w e only used a s i n g l e c o a l since. as the q u a n t i t a t i v e i n f l u e n c e of rank is given bY eqn.values were found by measurement t o be: u n i t y f o r c o a l s of V. T h i s equation was t e s t e d i n t h e previous experiments.to be a d j u s t e d t o allow f o r t h e e f f e c t s of v o l a t i l e loss and swelling.thus ‘ I where i s a p r e d i c t a b l e burning c o n s t a n t that i s a f u n c t i o n of temperature and oxygen p a r t i a l pressure. g r e a t e r than 10%. less than 5%. and then swelled by the l i n e a r f a c t o r f . t h a t of Our choice of v a r i a b l e f o r t h e experiments r e p o r t e d h e r e was t h e f i r s t : I n doing this. d i f f u s i o n c o e f f i c i e n t of where p i s t h e s.M. ranging in v o l a t i l e percentage from 5 t o 40. oxygen concentration. but t h q experimental values of t h e burning constant.p. as described i n t h e s e c t i o n following. The b a s i s of t h i s p r e d i c t i o n was t h e assumption t h a t t h e c o a l s f i r s t l o s t v o l a t i l e s a t constant diameter.21 f o r a i r ) . and po is t h e ambient f r a c t i o n a l oxygen c o n c e n t r a t i o n (of value 0. t o be checked by comparison w i t h measurement i n f u r t h e r experiments. po) ln(l - (34 d e n s i t y of air. between two s m a l l h e a t i n g c o i l s of r e s i s t a n c e w i r e . 10 c o a l s w e r e u l t i m a t e l y t e s t e d . T h i s then provided a c o r r e c t i o n f a c t o r t o t h e s o l i d d e n s i t y Q t h a t appears i n t h e t h e o r e t i c a l r e l a t i o n f o r % %= 1 J / 3 p ~ D ~ ( T / T ~ ) ~ * ~ ~ .5 for c o a l s of V . (2). oxygen ?hrough n i t r o g e n . and f i s a swelling f a c t o r whose. o r burning constant. I n all.

by Fereday and F l i n t (11) e q u a t i o n ) . w i t h t h i s . The two h e a t i n g units were then mounted h o r i z o n t a l l y w i t h t h e i r f a c e s about 1. t h i c k former. 0.75 cu. The c o a l used w a s Winter (ex-Grimethorpe). a s m a l l combustion u n i t w a s used i n s i d e a l a r g e perspex ( p l e x i g l a s s ) box s o t h a t t h e ambient atmosphere could be c o n t r o l l e d a t w i l l . t h e oxygen concent r a t i o n was checked by Orsat a n a l y s i s .0% V. using t h e s t o p watch which w a s found t o be p e r f e c t l y s a t i s f a c t o r y f o r these. Burning times were measured w i t h a s t o p watch i n p l a c e of t h e p h o t o c e l l and pen recorder u n i t s used previously. 5.f. f t . a medium bituminous coal. oxygen or n i t r o g e n was metered i n as required. T h i s s t r i p was about 112 cm.6% H20. by means of a c o n t r o l rod extending o u t s i d e t h e box.5 cm. t h a t used i n t h e previous experiments ( 4 .M. No. The h e a t i n g was e l e c t r i c a l . 4 9 .. The oxygen atmosphere i n s i d e could be a d j u s t e d a s r e q u i r e d over t h e range 3% t o 70% 0 2 . 8. However. The p h o t o c e l l w a s abandoned because of l i g h t s h i e l d i n g and o t h e r d i f f i c u l t i e s experienced w i t h t h e l a r g e r h e a t i n g elements. wound from 18-gauge Nichrome resistance wire. by 3 f t . Proximate 36. The combustion u n i t w a s . spacing on a 112 cm. 5 by 1. w i t h t h e 'main stream' o r ambient oxygen c o n c e n t r a t i o n c o n s t a n t d u r i n g t h e r e a c t i o n thus meeting t h e s p e c i f i e d boundary c o n d i t i o n s r e q u i r e d by t h e t h e o r e t i c a l a n a l y s i s . This m e a n t t h a t v e r y s h o r t v o l a t i l e burning times could n o t be measured those l a r g e r ones t h a t were.. a s and when required. The h e a t i n g In p l a c e of the 2-cm diameter f l a t c o i l s were l a r g e r than t h o s e used previously. subs t a n t i a l l y covered by t h e r e t u r n s t r i p s on t h e o t h e r s i d e s o t h a t t h e whole f a c e a r e a w a s r a d i a n t . In f a c t . could be reached. high. Most measurements were t h e r e f o r e r e s t r i c t e d t o t h e r e s i d u e burning t i m e s alone. of course. - I I .7% ash. c o n t r o l l e d by a v a r i a b l e transformer u n i t . 7 of the set prepared and used p r e v i o u s l y (5). t h e r e f o r e . wide. element temperatures of up t o 1O6O0C. EXPERLMENTAL To burn t h e p a r t i c l e s i n v a r i a b l e but c o n t r o l l a b l e oxygen atmospheres. a r a i l c a r r y i n g 18 c a r r i a g e s was mounted i n t h e box. i n p r i n c i p l e .0%C.3%OJ 1. T o make up t h e r e q u i r e d atmosphere. and t h e a n a l y s i s t h e n checked by Orsat. w e r e measured w i t h a second s t o p watch. 2. 5). and w a s wound w i t h 112 cm. t h e v o l a t i l e measurements t h a t were made were found t o e x h i b i t such c o n s i d e r a b l e v a r i a b i l i t y i n t h e d i f f e r e n t oxygen atmospheres t h a t t h e i r v a l u e was g r e a t l y reduced.f a s h i o n . c a n t i l e v e r . i n which t h e c o a l p a r t i c l e s were cemented t o s i l i c a f i b r e s and h e l d by these. as measured by an o p t i c a l pyrometer. A f t e r burning. i n plan s e c t i o n . of f a c e a r e a about 5 x 5 cm. a s before.8%NJ 0 . To take advantage of t h i s . t h e box was l a r g e enough f o r a number of p a r t i c l e s t o be burned without having t o open and r e c h a r g e the box f o r each p a r t i c l e . a p a r t . s p i r a l s . 3. S (d.5 f t . ) . and t o each c a r r i a g e could b e a t t a c h e d one s i l i c a t h r e a d w i t h i t s c o a l p a r t i c l e cemented on ready f o r burning. of analysis: U l t i m a t e 84.77% C02.227. (6. 1.m. t h e gaps between t h e set of s t r i p s on one s i d e of t h e former were. The r e a s o n f o r making t h e box so l a r g e w a s t h a t t h e oxygen dep l e t i o n during combustion of a p a r t i c l e would not t h e n be s i g n i f i c a n t . - I - The perspex box used t o house t h e combustion u n i t had dimensions: 1 . made of Nichrome s t r i p . t h e new heaters were s q u a r e elements. be taken as being e f f e c t i v e l y i n f i n i t e . The p a r t i c l e s on t h e c a r r i a g e s were moved i n t o p o s i t i o n between t h e c o i l s . and w i t h o u t s i g n i f i c a n t change i n t h e box's atmosphere.5%H. and t h e atmosphere could. midway between two h o r i z o n t a l h e a t i n g elements of e l e c t r i c a l r e s i s t a n c e w i r e .

1 \ A t t h e o t h e r end of the s c a l e . Where t h e v o l a t i l e s d i d i g n i t e in reduced oxygen. t h i s a l s o r e q u i r e s f u r t h e r d e t a i l e d study. Fig. This happened whether t h e c o i l s were already up t o temperature before t h e p a r t i c l e was i n s e r t e d ( a s was t h e case i n g e n e r a l i n t h e s e experiments). as w a s t o b e expected. The p a r t i c l e s d i d n o t i g n i t e immediately. I n c o n t r a s t .i n v e s t i g a t i o n . and burned i n e f f e c t i v e l y i n f i n i t e atmosphere. 1300. they required t i m e t o heat up t o i g n i t i o n . t h e p a r t i c l e s showed i n c r e a s i n g tendency t o d e c r e p i t a t e o r explode. t h e g e n e r a l r e s i d u e behaviour i s f a r b e t t e r understood. a t an approximately constant temperature of 1000°C. t o show t h a t t h e s l o p e s of t h e l i n e s o b t a i n e d are. a t high oxygen concentrations. w i t h t h e v o l a t i l e s (when they burned a t a l l ) i g n i t i n g f i r s t and burning w i t h t h e c h a r a c t e r i s t i c l u m i nous.T h e g e n e r a l behaviour of t h e p a r t i c l e s was a s observed before ( 4 . by t h e ambient T h i s would seem t o imply t h a t t h e oxygen causes some oxygen concentration. 5): t h e p a r t i c l e s burned i n two stages. (1) and (3b) w e have for I . and t h i s i g n i t i o n time increased v i t h decrease of oxygen concentration. t h i s suggests t h a t t h e v o l a t i l e s g e n e r a t i o n must be influenced. A t t h e low oxygen concent r a t i o n s . f l i c k e r i n g f l a e .2 I n f l u e n c e of Oxygen Concentration burn-out of t h e residues: - By combining eqns. before t h e v o l a t i l e s i g n i t e d i n flaming combustion. below 6%.228. 4. and t h i s was then followed i n t h e burn-out s t a g e by the much s t e a d i e r glow of r e s i d u e combustion. t h e v o l a t i l e s of t h e smaller p a r t i c l e s o f t e n f a i l e d t o i g n i t e because of their s m a l l q u a n t i t y and t h i s f a i l u r e increased.kd2 o/ln(l - po) (4) I To t e s t t h i s equation.1 RESULTS g u a l i t a t i v e Behaviour . or whether t h e p a r t i c l e was already i n p o s i t i o n ( a s i n the previous experiments) before switching o n t h e h e a t i n g current. 928. I f d e c r e p i t a t i o n i s due t o too r a p i d g e n e r a t i o n of v o l a t i l e s before t h e coal becomes s u f f i c i e n t l y p l a s t i c . t h e experimental d a t a obtained have. 4. The p a r t i c l e s were derived from t h e s i n g l e c o a l . 4. and 388 microns. w i t h i n - . t h e burning times a l s o s t a r t e d t o become very s c a t t e r e d . t h e r e f o r e . been l o g l o t b against presented i n two graphs. 649. t h e p a r t i c l e s f a i l e d t o i g n i t e a t a l l . and a t 3%. a s described i n t h e s e c t ions following 1 ! . 1 and 2. Figs. as the oxygen was reduced. f o r each of t h e following p a r t i c l e sizes: 1870.)]. s i g n i f i c a n t and r a p i d change i n the c o n s t i t u t i o n of t h e p o t e n t i a l v o l a t i l e m a t e r i a l before generation. With t h i s apparatus. A s i n t h e previous experiments. but s i g n i f i c a n t o x i d a t i o n may be occurring. This may i n d i c a t e t h a t preliminary. 1 is a p l o t of: loglOlln(l p. and more p r e d i c t a b l e . w i t h s i g n i f i c a n t h e a t generation. T h i s r e q u i r e s closer. c o n t r a r y t o previous expectation. though how it should do t h i s is by no m e a n s c l e a r . I tb = ~(Cf/loO)/f]. the r e s i d u e burning times were measured a t d i f f e r e n t l e v e l s of oxygen concentration as t h e p r i n c i p a l v a r i a b l e . t h e usual f r a c t i o n a l l a g i n time between f i n i s h of t h e v o l a t i l e flame and s t a r t of t h e r e s i d u e combustion was o c c a s i o n a l l y i n c r e a s e d t o a long delay ranging from two t o t h i r t y seconds.

3. Po i s For t h e Winter coal. (3b) and ( 3 c ) .cm.4 Now. 4. it is considered t o s u b s t a n t i a t e eqn. Within t h e l i m i t s of accuracy of the measurements. (Z).7. 0. but chosen a t random. which i s value of M 2 is 225. t h e t h e o r e t i c a l a l t e r n a t i v e s a r e compared i n t h e two eqns. Here again t h e p l o t i s reasonably l i n e a r . (127390. and f o r ln(l This i s lower than of 957 sec/sq. w e t h e r e f o r e have for M(calc.21. but t h e l a t t e r was used i n t h e previous paper (5). Since t h i s agreement w a s obtained by using t h e rank-influence equation (2). and U i s 1. thus: - 4 \ / For a i r .d: (5) This equation has i n t u r n been t e s t e d by p l o t t i n g (m)"' a g a i n s t doJ as shown i n Fig. 3. With t h e s e values. (4) it i s c l e a r t h a t t h e s l o p e s of t h e l i n e s i n Fig. 2 ( w r i t t e n as m) are r e l a t e d t o p a r t i c l e s i z e by - m = [(Cf /loo) If 1k. as i n t h e previous experiments. (3a) and (5). Do f o r oxygen d i f f u s i n g through n i t r o g e n a t temperature To 1. t h e c a l c u l a t e d a v a l u e of 15. t h e r e f o r e . and i s g e n e r a l l y accepted as being v a l i d f o r - - . so t a b u l a t e d v a l u e s (as i n From eqns. t h e s e p l o t s are. which i s t h e e s t i p a t e of t h e o v e r a l l e r r o r i n both experimental and c a l c u l a t e d values. (4).cm) but t h i s may be accounted f o r same coal (previous value: po)] and t h e i n p a r t by t h e d i f f e r e n c e b e p e e n t h e logarithmic term [ l n ( l f i r s t term of i t s expansion [ p o l s i n c e t h e former has been used i n . Cf i s 60.po) - (7) 2 po) of 0. Use of t h e f i r s t term expansion as i n eqn.t h i s paper. Again w i t h i n t h e limits of accuracy of t h i s p l o t . (5). 4. 2 i s t h e a l t e r n a t i v e p l o t of t b a g a i n s t t h e r e c i p r o c a l of ln(1 po).3 Influence of P a r t i c l e S i z e From eqn.) p r e c i s e l y the experimental v a l u e obtained from t h e s l o p e of F i g . (3). o r 1 .cm/sec. c l o s e t o 45". (1).235 when po is Hence w i t h a v a l u e for: M of 225.181 sq. This e x a c t agreement i s c l e a r l y f o r t u i t o u s . t h i s g i v e s a value f o r K (talc 1 (though c l o s e t o ) t h e value o b t a i n e a i n t h e previous experiments (5) f o r t h i s 1095 sec/sq.5 Burning Constant This i s t h e c o n s t a n t KD o r K of eqn. and a l s o passes through t h e o r i g i n . and ( 6 ) .5. but w i t h i n an e r r o r o f 5%. (3c) i s very cornon. It i s c a l c u l a t e d almost u n i v e r s a l l y from measurements made i n a i r . (l). it Reviews 7. g / c c . Fig. t h e s l o p e of Fig. 8) a r e given f o r po = 0. reason. t o show t h a t t h e p l o t s obtained a r e again acceptably l i n e a r and passing through t h e o r i g i n . t h i s a l s o supports t h e assumption macle t h a t v a l i d a t i o n of t h e t e s t e d equations using a s i n g l e coal. - 4.229. it i s c l e a r t h a t agreement i s s t i l l s a t i s f a c t o r y . considered t o s u b s t a n t i a t e eqn. would probably be s a t i s f a c t o r y .21. f i s 1. is clear that - 2 K = M /h(l .3 x The p a r t i c l e temperature i s taken a s 1000°C (273OK) i s 0. 3 ( w r i t t e n a s M) i s an Comparison w i t h P r e d i c t i o n experimental q u a n t i t y whose value i s p r e d i c t e d from t h e a p p r o p r i a t e terms i n eqns.25.

i n equivalent Fig. Now. Now.230. however. but again only w i t h a s t a t i s t i c a l l y s i g n i f i c a n t i n t e r c e p t . because of t h e adjacent d i f f u s i o n layer. Agreement. i n equivalent Fig. convincingly s t r a i g h t lines could be run through the points. To do t h i s w e assume some a p p r o p r i a t e v a l u e f o r the s u r f a c e order of r e a c t i o n and then deduce what net. a s t r a i g h t l i n e could again be run through t h e points. Just how widely t h e two terms d i f f e r a t enriched concent r a t i o n s . 1 . Superimposed on t h i s p a t t e r n i s t h e oxygen supply by boundary l a y e r diffusion. similar p l o t s were prepared (not reproduced) with po i n p l a c e of l n ( 1 po). but the p l o t s then showed marked i n t e r c e p t s on t h e oxygen-function axis.235 compared w i t h 0. followed by desorption. t h a t under t h e s e quiescent conditions is r a t e . 5. and the displacements from t h e o r i g i n were found t o be s t a t i s t i c a l l y s i g n i f i c a n t . 4 i n which t h e logarithmic term i s p l o t t e d a g a i n s t po. and t h e new v a l u e of 957 is w e l l w i t h i n 5% but can i n any c a s e b e a t t r i b u t e d t o unc e r t a i n t y in t h e p r e c i s e temperature i n t h e two cases. a i r o r v i t i a t e d a i r . i s regarded as acceptable. when t h e temperature is high enough f o r t h e sequence of chemisorption. 2. one of t h e p r i n c i p a l reasons f o r c a r r y i n g o u t t h e work described was t o provide a more d i r e c t check on t h e assumed order of r e a c t i o n a t t h e s o l i d surface. however.The p l o t s were found t o vary s i g n i f i c a n t l y as follows: i n e q u i v a l e n t Fig. What is y e t undetermined. but even i n a i r i t s e l f the d i f f e r e n c e amounts t o n e a r l y 1% (0. To check t h e i r s e n s i t i v i t y t o the f i r s t expansion term i n p l a c e o f t h e f u l l expression. Use of t h e Ln term i n p l a c e of po i n t h e previous experiments would therefore. o v e r a l l . f i n a l l y . - 5. when t h e temperature is low enough f o r t h e s u r f a c e chemisorption sites t o be f u l l y s a t u r a t e d a t a l l times. is shown by Fig. t h i s i s considered b r i e f l y in t h e next section.f i l m theory of r e a c t i o n . 2. t b = Kcdo where Kc is t h e high-temperature chemical burning constant. A t intermediate temperatures t h e r e a c t i o n approximates t o a f r a c t i a n a l order. w e have (7) two extreme l i m i t i n g values: (1) zero. t h e p l o t s showed s l i g h t but d e t e c t a b l e curvature i n s p i t e of t h e f a i r l y considerable scatter. and 3.c o n t r o l l i n g . o r ' g l o b a l ' o r d e r of r e a c t i o n should then follow. F i r s t of all. I f i n t e r n a l or pore r e a c t i o n a l s o t a k e s place. In v i t i a t e d a i r t h e two are c l e a r l y resonably comparable. This agreement w i t h t h e logarithmic term thus provides by f a r t h e b e s t s u b s t a n t i a t i o n of t h e o r i g i n a l Nusselt a n a l y s i s i n terms of t h e d i f f u s i o n .21). i f t h e temperature i s h i g h enough f o r f i r s t order r e a c t i o n to p r e v a i l then w e get the burning time equation t h a t combines both t h e d i f f u s i o n a l and a d s o r p t i o n r e s i s t a n c e (91. and - (8) % is the . a r e t h e limits of a p p l i c a b i l i t y of t h e Nusselt equation and a n a l y s i s . t o be e f f e c t i v e l y instantaneous. 1.1 DISCUSSION Reaction Order As s t a t e d i n t h e Introduction. t h e lower l i m i t i n g o r d e r is then r a i s e d from zero t o 112. and (2) unity. The f u r t h e r d i f f e r e n c e between this. i n t h e f i r s t place. reduce t h e value of 1095 t o 978. The s i g n i f i c a n c e of t h e l o g a r i t h m i c term also showed up i n t h e graphs of Figs.r a t e c o n t r o l . 3. i n choosing an order f o r t h e s u r f a c e reaction. i t is only p o s s i b l e t o check t h e s u r f a c e o r d e r of r e a c t i o n i n d i r e c t l y .

I n c a l c u l a t ing heat and mass t r a n s f e r t o spheres i t i s almost u n i v e r s a l t o use Nusselt's concept of t h e . t h e n i f t h i s w a s important t h e p l o t of t b a g a i n s t l / p o would not have been so poor i n comparison w i t h the p l o t of Fig. t h e r e fore. i f t h e a d d i t i o n a l chemical t e r m i n eqn. 5. o f a l i n e a r equation. (3) There i s f i n a l l y t h e e x c e l l e n t agreement between t h e experimental and c a l c u l a t e d v a l u e s of the burning c o n s t a n t ( w r i t t e n a s K i n s t e a d o f KD a f t e r c o r r e c t i o n f o r c o a l rank and s w e l l i n g by eqn. w e have a l t o g e t h e r three confirmatory p o i n t s provided by t h e experimental r e s u l t s .2 Boundary Layer Thickness . I d i f f u s i o n a l burning constant. This c l e a r l y has l i m i t s . - - - S i n c e t h e r e a c t i o n i s e v i d e n t l y d i f f u s i o n c o n t r o l l e d .5.e f f e c t i v e o r ' f i c t i t i o u s ' boundary l a y e r t h i c k n e s s . r e s p e c t i v e l y . I f t h e oxygen c o n c e n t r a t i o n a t t h e s o l i d s u r f a c e of t h e p a r t i c l e of r a d i u s .a d s o r p t i o n r e a c t i o n must be f i r s t order. according t o whether d i f f u s i o n i s unimportant o r dominant. a v a l u e of 2 f o r n i s q u i t e unambiguous i n implying t h a t t h e r a t e of boundary l a y e r d i f f u s i o n dominates the reaction control: and t h e s i g n i f i c a n t c o r o l l a r y of t h i s i s t h a t t h e s u r f a c e r a t e . f r o m t h e c e n t e r of t h e p a r t i c l e i s given approximately by Since p r i s e s t o t h e main-stream v a l u e po only when r becomes i n f i n i t e . obvious t h a t d e t e r m i n a t i o n of t h e power index n i n any burning t i m e experiments w i l l g i v e a c l e a r g u i d e t o t h e r e l a t i v e importance of t h e t h r e e f a c t o r s considered: (i) r a t e of d i f f u s i o n . as d i s c u s s e d i n sec.231. 4. A t i n t e r m e d i a t e temperatures t h e burning time i s p r o p o r t i o n a l t o some intern mediate power of the diameter. t h e .5. and ( i i i ) r a t e of oxide-film decomposition. S i n c e Kc i s i n v e r s e l y p r o p o r t i o n a l t o po (9). 4. i s zero. I n concluding t h a t t h e r e a c t i o n i n our experiments was i n t h e h i g h temperature region. t h e burning t i m e e q u a t i o n i s l i n e a r only (9) tb - Ktdo (9) where Ki i s t h e low-temperature chemical burning c o n s t a n t . (1) The f i r s t i s t h e 'square-law' agreement i l l u s t r a t e d by t h e square-root p l o t of Fig. the l i n e would be curved w i t h a tendency t o an i n t e r c e p t on the t a x i s . i t s v a l u e a t any o t h e r r a d i u s . Other checks such as p l o t t i n g ( t / d ) a g a i n s t do confirmed t h a t Kc was n e g l i g i b l e under t h e c o n d i t i o n s of b o experiment. 2) a s described i n sec.po). 2 a g a i n s t l/ln(l po). and d i f f u s i o n c o n t r o l l e d . do.A secondary p o i n t of i n t e r e s t t h a t a l s o emerges from t h i s i s a r e f l e x i o n on t h e q u e s t i o n of boundary l a y e r t h i c k n e s s .o f . 3 . r . when t h e r e a c t i o n o r d e r i s zero. i t follows t h a t t h e s u r f a c e r e a c t i o n must be f i r s t order. I n p a r t i c u l a r . where n l i e s between 1 and 2. A t t h e o t h e r extreme of l o w temperatures. It is. (2) W e a l s o have t h e agreement between t b and t h e oxygen f u n c t i o n l n ( 1 . o r a s q u a r e law equation. 8 Kcdo w a s a l s o important. (ii) r a t e of chemisorption. a .

t h e actual. W '(physical) = lOOa 3 'OoS( fictitious) The s i g n i f i c a n c e of t h i s becomes immediately apparent when considering t h e behaviour of d u s t flames s i n c e t h e i n t e r p a r t i c l e d i s t a n c e a t a s t o i c h i o m e t r i c concentration i s g e n e r a l l y of the order only of 30 p a r t i c l e diameters. over t h e range of oxygen concentraiions used i n our experiments. This. t h e r e a c t i o n order was expected t o drop p r o g r e s s i v e l y from u n i t y t o zero. t h a t a t r = 2a. This was estimated. however. If. An e f f e c t i v e f i l m t h i c k n e s s can s t i l l be defined. p = po/2 (from eqn. p h y s i c a l boundary l a y e r must c l e a r l y be of i n f i n i t e thickness i f it i s defined as t h e d i s t a n c e r e q u i r e d f o r p t o reach t h e main-stream value. - - 5. infinity). (10)-which po) . even f o r purposes of c a l c u l a t i o n . a s opposed t o f i c t i t i o u s film-thickness terms. a t 1200°C. say. 999. Now. i t means t h a t eqn. (10) i s replaced by an e q u i v a l e n t behaviour such t h a t p i s a s s k d t o r i s e l i n e a r l y t o po and then t o remain constant w i t h r. p h y s i c a l rise i n p is only h a l f t h e f i c t i t i o u s value. being abaut 200° lower than t h e expected value of t h e 'higher c r i t i c a l temperature'. and t h e oxygen function l n ( 1 i s also approximated by po ( a s shown i n Fig. - Now. what w e have e s t a b l i s h e d so f a r is t h a t t h e s o l i d s u r f a c e r e a c t i o n i s f i r s t order a t a temperature a s low as 1000°C. t h a t d i r e c t e x t r a p a r t i c l e o r another in t h e flame. The explanation f o r t h i s apparent c o n t r a d i c t i o n would appear t o be a consequence of t h e i n f l u e n c e of the . o r p h y s i c a l f i l m thickness. It should be r e a l i s e d .232. (following Nusselt (10)) t h e r e a l behavfour i n d i c a t e d by eqn. po) could not be Because our range was high. r e a l . B e l o w t h a t . w r i t i n g the boundary l a y e r thickness a s 8. This can be defined w i t h p h y s i c a l realism as t h e d i s t a n c e w i t h i n which p rises t o . This means t h a t i n r e a l . of the main stream v a l u e ( t h i s is a standard s o l u t i o n t o continuum problems i n which some r e l e v a n t parameter reaches i t s l i m i t i n g v a l u e only a t e then have t h a t . o r one r a d i u s o u t from t h e s u r f a c e of the p a r t i c l e . i n a d d i t i o n t o t h e p o i n t s made above. but t h e expression for i t i s s o complex a s t o be v a l u e l e s s as i t is then e a s i e r t o s o l v e t h e i n i t i a l d i f f e r e n t i a l equation and n o t t o bother about t h e ' s h o r t c u t ' of using an e f f e c t i v e o r f i c t i t i o u s f i l m thickness. p o l a t i o n of the r e s u l t s i n t h i s paper t o p a r t i c l e s i n dust flames should b e made w i t h caution. however. i n o t h e r words. by assessment (7) of t h e a v a i l a b l e l i t e r a t u r e . through t h e t r a n s i t i o n range down t o 800"C. physical terms. t h e main stream value i s then reached a t t h e Nusselt f i c t i t i o u s f i l m thickness a t r = 2a. therefore. This can be represented i n another way by r e l a t i n g t h e f i c t i t i o u s f i l m t h i c k n e s s t o a d e f i n a b l e r e a l . 1 0 ) . 4 ) . a f u r t h e r complication t h a t emerges i s t h e a d d i t i o n a l inadequacy of t h e f i c t i t i o u s f i l m concept.3 The f i n a l p o i n t t o be considered a s a consequence of Range of A p p l i c a b i l i t y t h e s e r e s u l t s i s t h e i r range of a p p l i c a b i l i t y : t h e temperature range of a p p l i c a t i o n i s of p a r t i c u l a r importance. was unexpected. however. most of t h e oxygen i s already w e l l i n s i d e t h e boundary l a y e r of one It i s c l e a r .i s a l s o inadequate to based on t h e same approximation of po f o r l n ( l d e s c r i b e t h e behaviour of t h e oxygen concentration over our f u l l experimental range.

It would t h e r e f o r e seem t h a t p r e v i o u s l y published experiments t h a t were a s s e s s e d a s showing a f i r s t o r d e r r e a c t i o n only down t o 12OO0C. s i m i l a r t o t h a t observed previously w i t h c o a l p a r t i c l e s burning i n a i r . combustion f a i l u r e tended t o i n c r e a s e as t h e oxygen c o n c e n t r a t i o n w a s reduced. and can drop p r o g r e s s i v e l y t o z e r o as t h e ambient v e l o c i t y a l s o increases. 6. but t h e a n a l y t i c a l f u n c t i o n r e l a t i n g t h e two i s s t i l l unknown. m . This means t h a t t h e t r a n s i t i o n range of temperature between t h e two extreme r e a c t i o n c o n d i t i o n s i s v e l o c i t y dependent.233. a r e increased. b u t they showed i n c r e a s i n g tendency t o d e c r e p i t a t e o r explode. because of low l i m i t requirements. I n i t i a l l y . and t h e r e f o r e r e a c t i o n rate. tended t o produce too s m a l l a q u a n t i t y of v o l a t i l e s The frequency of t h i s f o r t h e i r combustion. and a t t h a t p o i n t t h e coverage of the s o l i d s u r f a c e by t h e chemisorbed f i l m must i n c r e a s e . with t h e r e s u l t t h a t both oxygen t r a n s f e r . The e f f e c t of ambient v e l o c i t y i s t o promote such i n c r e a s e d speed of mixing of the ambient gases t h a t t h e t h i c k n e s s of the boundary layer.r e l a t i o n between temperature and v e l o c i t y is now. . t h e s y f a c e r e a c t i o n o r d e r then becomes f r a c t i o n a l .c o a l p a r t i c l e s i n s i d e t h e s i z e range 350 microns t o 2 m . up t o t h e p o i n t t h a t t h e rate of chemisorption exceeds t h e r a t e of r e a c t i o n . i s p r o g r e s s i v e l y reduced. Burning times of t h e r e s i d u e s ( t b ) were found experimentally t o obey t h e r e l a t i o n p r e d i c t ed from t h e Nusselt d i f f u s i o n t h e o r y of r e a c t i o n c o n t r o l : t where po i s t h e ambient oxygen c o n c e n t r a t i o n . CONCLUSIONS F o r . w h i l s t o u r s were i n e f f e c t i v e l y quiescent systems. Davis. a t about 1000°C. i n general. even t h e r e s i d u e s f a i l e d t o i g n i t e . under quiescent ambient conditions. ambient g a s v e l o c i t y o n t h e boundary l a y e r thickness. followed by ( i i ) i n two s e q u e n t i a l s t a g e s : r e s i d u e combustion. i n our opinion. . A t 3% oxygen. and m is a p r e d i c t a b l e constant. t h i s must s t e e p e n t h e oxygen c o n c e n t r a t i o n g r a d i e n t . b u t t h i s i n t e r . (3) Q u a n t i t a t i v e l y . (2) P a r t i c l e s b e l o w 1 m . A t high oxygen c o n c e n t r a t i o n s t h e p a r t i c l e s i g n i t e d and burned s a t i s f a c t o r i l y . however defined. The i n c r e a s e d f i l m t h i c k n e s s t h a t must have e x i s t e d i n our experiments can account q u a l i t a t i v e l y f o r t h e f i r s t order r e a c t i o n down a s low as 1000°C. . This dependence i s shown very c l e a r l y by t h e s i n g l e s p h e r e experiments of Tu. m . burning i n v i t i a t e d and enriched O2 atmospheres (3% t o 7 0 % ) . and H o t t e l (12). This i n c r e a s e can proceed j u s t so f a r . combustion proceded (i) v o l a t i l e e v o l u t i o n and combustion. t h e combustion behaviour was found t o b e a s follows: (1) Q u a l i t a t i v e behaviour was. t h e most outstanding problem of t h e combustion system r e q u i r i n g t o be resolved by f u t u r e work. cannot y e t be d i r e c t l y c o r r e l a t e d w i t h t h e r e s u l t s of our experiments because t h e previous ones were c a r r i e d o u t i n flowing systems. only t h e r e s i d u e combustion was examined i n d e t a i l . f o r p a r t i c l e s l a r g e enough.

(T/T. although t h i s exact agreement was f o r t u i t o u s it i s s t i l l e n t i r e l y s a t i s f a c t o r y w i t h i n the expected limits of e r r o r . and t h a t .s. England. The work w a s c a r r i e d out i n t h e Department of Fuel Technology and Chemical Engineering.234. t h e r e s u l t s t h a t the r a t e of d i f f u s i o n i s t h e slow s t e p t h a t dominates t h e r e a c t i o n r a t e . The p r e d i c t e d and experimental v a l u e s of M2 were in f a c t i d e n t i c a l . (6) The burning c o n s t a n t K i n t h e Nusselt square-law equation was a l s o calculated.t. This g e n e r a l agreement w i t h p r e d i c t i o n t h e r e f o r e s u b s t a n t i a t e s t h e primary (7) assumption of t h e t h e o r e t i c a l a n a l y s i s : t h a t t h e o r d e r of r e a c t i o n a t the s o l i d It a l s o follows from p a r t i c l e s u r f a c e with r e s p e c t t o oxygen c o n c e n t r a t i o n i s unity. the chemisorption process i s l i k e l y t o become s i g n i f i c a n t . sponsored by the E l e c t r i c i t y Supply Research Council of Great B r i t a i n . Qo i s t h e s. Do is t h e s. f is t h e swelling f a c t o r (of value 1. a t 2 2 5 .t. This i s now the outstanding p o i n t r e q u i r i n g i n v e s t i g a t i o n in any subsequent work. and i n c r e a s i n g l y so w i t h i n c r e a s i n g v e l o c i t y . . and t h i s is i n adequate agreement w i t h values obtained previously f o r t h i s same c o a l under s i m i l a r (though n o t i d e n t i c a l ) experimental conditions. however. ( 5 ) The experimental v a l u e of t h e second constant M w a s a l s o found t o be i n good agreement w i t h the p r e d i c t e d value.p r e v i o u s experiments.) 0 -75 ! 3= [(cf/l0o)/f] . and t h a t t h e importance o f t h e chemisorption process i s n e g l i g i b l e under t h e conditions of experiment.g. The authors are indebted t o t h e ESRC f o r f i n a n c i a l support o f t h i s work and f o r permission t o p u b l i s h t h i s paper.5 f o r density of a i r . being g i v e n by K = M /ln(l 2 - po) I The v a l u e was 957 c. i n a v e l o c i t y f i e l d a t these temperatures. There is background evidence from o t h e r . f 4 . c o e f f i c i e n t of oxygen d i f f u s i n g through n i t r o g e n . 4 The work described i n t h i s paper formed a p a r t of a g e n e r a l program of research on Pulverized Fuel F i r i n g .p. where Cf is t h e f i x e d carbon of t h e coal. T i s t h e absolute temperature and To is t h e r e f e r e n c e temperature of 273°K. '. as c a l c u l a t e d from t h e r e l a t i o n i i ~ /p 3 D . bituminous c o a l s ) . i n d i c a t i n g t h a t t h i s i s t r u e only f o r t h e f u l l y quiescent system. (4) The r e s u l t s a l s o showed good agreement w i t h t h e following p r e d i c t e d r e l a t i o n between t h e constant m and t h e i n i t i a l p a r t i c l e diameter G: m = Ido 2 2 where M i s another p r e d i c t a b l e c o n s t a n t . u n i t s . U n i v e r s i t y of S h e f f i e l d . @ i st h e s o l i d p a r t i c l e density.p.

1958 p.S. G ( l 9 2 9 ) 808. h u a l Meeting.M. General Discussion on "The P h y s i c a l Chemistry of Aerosols" B r i s t o l . J. Godbert. 65. A. Ind. I n s t . M Davis. Essenhigh. Tu. 24. London. R. p. 1932. "Safety i n Mines Research Board". W. and F l i n t .D. Frank-Kamenetskii. R. L . 73 H. Winter 5.M. 64(1942) 497. L. i b i d . A. Essenhigh. t o be p r e s e n t e d a t A. and Smith. No. S h e f f i e l d . H.S. . Proc.M. Proc. Essenhigh. &ori. 11. Orning. T . 6. 10. C.) i 8. D. g ( 1 9 3 4 ) 749. J. K. Essenhigh. Paper 29 p. "Diffusion and H e a t Exchange i n Chemical K i n e t i c s " 1 . D1: 1958. . 1958. Adams. A . Fereday. C. H. Conf. M. and H o t t e l . "Science i n t h e Use (of Coal" I n s t i t u t e of Fuel. and Wheeler. V. 1955) Ch. F u e l 29(1950) 283. H. R. A. 7. I n t r o d u c t o r y Survey "Combustion and G a s i f i Essenhigh. 1960. 9. 1 pp. and Perry. 208: Faraday Society. Chem.I. A. 1961. Eng. London. R. H. W. Ind. P r i n c e t o n U n i v e r s i t y P r e s s (Trans. F u e l z(1930) 57. H. H.z ( 1 9 5 0 ) 591. D21: I n s t i t u t e of Fuel. - 4.E. G r i f f i n . R. D. Trans. 1958.. R. Conf. 68(1924) 124. A. F. R. Paper No: 62-WA-35. Nusselt. A. V.O. Eng. M. Paper No. "Science i n t h e Use of Coal". I. D. Nov. H. F u e l (Lond. 1962. 3.235- REFERENCES 1. F. 2. J .E.. and F e l l s . Chem.S. London. G. . 12. A. and Thring. S h e f f i e l d . and Orning. 34(1961) 239. cation". 64. Paper Godbert. H. London.

Llneor plot of burning tune.0gainsl the oxygen p r t d pressure function. [ Ine(l-h)] FIG I .236. lnJ-& FIG 2.Double logarithmic plot of burning time.agoinst the reciprocal of the oxygw. tb . dartlol preSSure function Ine( I-PO ) 1 i . i VdUeS of o lg . tb.

Variation of square root of fig 2 slopes ( m ) as a function of initial diameter of particle ( d o ) ' Enrched '* /linear oppr to logorith function lotion 1 Values of oxygen penentage (IOOp. 4-Voriaticm of oxygen function In&-pO) with oxygen putial pressure po. FIG.Values of Initial particle dlometer do(mccrons) FIG 3. .

Essen-Bay The theory of heterogeneous reactions' ' 2 ) is applicable to the combustion and gasification of solid fuels.0. the speed of the reaction 'fixed 1 . Thus. the decomposition of the carbon monoxide 1 2 co = c + CO2 (3) does n o t play any part.e.c t = reaction time (set1 m = quantity of coke (g) * 2 0 = sum of the external and internal surfaces cm / g c = concentration of C02 L/. The rapidity constant of the chemical reaction The gasification of fixed carbon with carbon dioxrde(Boudouard's reaction) is a reaction of the'first order(6). The Theory of Gasification and its Application to Graphite a n d Uetallurgical Coke Bergbau-Forschmg GmbH. . + co2 = 2 CO is governed by the equation: dx E where = k.m..m3? k = reaction speed constant (cm /cm sec) x = quantity of converted carbon (g) In the range of the technically interesting temperatures the back reactior) i. In connection herewith the passage of 1. ( 238.1. 1 i .

m.:/here in 1 c(x) r:x) = C atoms transferred = quantity of coke = height scf the layer = C O concentretion at point x = voluminal velocity at point x (cm) ( d c m 31 (cm3/sec) Let u s assume that the stream of C02 having a speed vo and a concentration c o penetrates f n t o a c o k e layerof equal c r o s s sectional area at any goint. is S O small t%at the stream of gas can reach the reactive surface c-uickly enough.239. Higher CO. the quantity of CO converted in the unit of tiae along e layer of infinitely small &ickness is determined by the equation d x = -d [v(x) n (4) (5) . Eoreover. concentrition.c 0 co + c(x) Substitution of equation ( 5 ) into equation (4) and integration over x from zero to 1 leads to 3 After integretion between the lixits indicated equatiorz ( 6 ) adogts the Zollowing ? o m : xhere c1 = the concentration of C 0 2 in the outsoing gas (g/’cm’) Often the differentiation plays a great part in the experimental determination of the reaction speed. 3quLtiOn (2) indicates the effective conversion in such ceSeS where k. c can be determined bjr gas analysis. as in 1 .. 1 ) ) . require a very high accuracy of enslyzis.. by contrast.le come into a range where the concentration of SO idibits Boudouard‘s reaction ( 1 0 .i t & t the required apparatuses do not becoze too expensive. which is due $ 0 the increase of the nuzber of molecules engaged in Boudouard’s reaction.1 3 ) . 71th lower Co concentrations . co and vo c a n be fixed in such a :“le. At sufficiently low temperatures this will always be the case. In these conditions. its value sholild range between 4b and 80 $.fornation of co leads to a continuous decrease in the CO concentration. . the speed of flow nil1 increase. For 30udouard’s reaction 08 industrial coke the upper temperature limit is situated at about 1100 C. then the speed vo at ulg point of this layer is 2v0 v (x) = . : & e n the reaction gas flows through a bed of coke (Fig.

to determine the surface of reaction 0.02 . whilst the CO. t h e ictivation energy E can be de- 1. differs only slightly from its concentration co when errtering the reaction chamber. C' / k' = reaction speed constant ( 1 sec c' = concentration of CO. their range even great changes of the rsaction speed entail only siight modifications of the C 0 2 concentration. = gas constmt T = the a b s o l i l t e tengerature 3 (cm / e set) (kcal/Mol. k a n d 0 are combined to form the reaction speed constant based upon the weight unit instead of the unit of surwhich is face : km = k . If the method used for the determination of the reactivity involves direct weighing of the loss of weight of the coal. however. or l o g k' agaicst the gradient 5. As. 7ith the experiaental conditions as described and the values of C02 concentration found in the outgoing g z s . it is easier to use equation ( 2 ) in the form: dx = dt where k'. 10'~ k . (10) 1. cl. 0 can be calculated quite simply. ) under the existing conditions concentration of C 0 2 (g/cm 3 ) under standard conditions ~~~~~ 4 ) In this case the loss of weight during gasification is indicated by k'. 8 me obtain a straight line with T 3rom this greaieDt.itsdimension is cm3/g sec. e (11) where H = the frequency factor E = activation energy 3.240.concentration in The outgoing gas.. Beactivity as a function of temperature The dependence of the reactivity ugon temperature is expressed in Arrhenius's forinula: E. it is difficult . m . -2T km = 3 .0 This value km is called nreactivityn in the following chagters.) (kcal/mol degree) (degrees Kelviq) 3y >lotting log k .2. . (g/cm . the groduct k. and the following nuinerical relation exists between kn and k': k' = 5. .

as expressed in equation dt dx = * q to Seyond a zone of transition the utilization coefficientTis proportionalA the reciprocai value of the catalyser coefficientQ(1. termined. Substitution of equations (14) and (15) into equation (2) leads to .2).241.the slowest step of a whole chain of physical and chemical reactions. With rising temperatures._ (cm /sec) 2 ( cm2/sec 1 D = diffusion speed Do = diffusion speed constant As k rises much more sharply than D. becoraes the dominant factor (1. where L = length of pores r = dianeter of pores (cm) (cm) For coke it is admissible to replace the length of pores by half the diameter of the l m p d/2. tie chemical reactivity will increase to such a degree that tke diffusion of the gasifying agent in the carbon and towards the carbon.3. as compared with its concentration in the ambient gas. z-s. Figure 2 shows schematically the 'runof this straight line within range I. This means that the conversion can utilize the internal surface only to a lesser degree. 1. the concentration of the gasifying agezt in the pores of the fuel begins to darease.2). The validity of 2 . 1. however. beyond a certain temperature limit. 1 1 the foregoing considerations is unrestricted only as long as the problems of molecular passage of materials during the gasification process d o not yet come into play.4. Pore diffusion 3ith rising temperature the reaction speed increase? in conformity with eouation and the diffusion speed according to equation: D = Do where . The influence of diffusion upon the reaction speed constant and the energy of activation.

242. the reaction speed k rises D with the temperature. 1. according to equations (12) and (IS). In figure 2 this is schematically represented by the straight line within range 11. Boundary film diffusion If the reaction speed continues to increase with rising temperature.the conversion is restricted to the external surface of the fuel.cO s CY$ S Substitution into equation ( 1 8 ) leads to . F . As.D F 9 2C F = external surface of the coke 9 = distance f r o m the coke surface dc - (cm2 (cm) In the boundary layer the concentration shows a linear decrease: = . much more rapidly than the diffusion speed a This is to say that in the case of pore diffusion the activation energy is reduced to half its value.5.ch can be solved as follows: The transfer . of heat on surfaces is governed by the general law: where q = quantity of heat' (Gal o( = coefficient of heat transfer C)cal/cm2 sec°C) .cO The determination of $ is an aerodynamic problem whi. Around the piece of coke forms a boundary film through which the gasifying agent will diffuse towards the place of the reaction.E = D i . .. Under these conditions the reaction speed mainly depends on this diffusion process which is governed by Pick's first law: ax at where = .

a s a rule the following basis is assumed: 9ea Bu = b (25) . Using a sha-oe factor I". thus. On the other side the flow of heat in a layer can be expressed as follo~vs: dq= 1 dt where . the external sur- .d?ry lager substituted into equation (20'): 6 whose velue i s (26) 71th sufficient accuracy the kinematic viscosity4 c a n be assumed to be equal to the diffusion speed D. 6 3rom m m j measurements the ratio is known for pieces of coke in a R free stream of gas. P .243. whose dependency upon the temperature is expressed b y eguation (13). as well as for coke grains in layers and fluidized beds. 3y substituting irto ?quation (24) the value of d 2 obtained from equa- tion(25). we get the thickness of the bour. dT Tf = thermal conductivity (cal/cm sec OC) A According to equation ( l g ) . dS 9 is constant Division of equation ( 2 3 ) by equation.(21) leads to the next equation from which the thickness of the boundary layer can be determined. the temperature gradient as ael-1 as & .

and (30). 1..16 f b Do 1 -a ' I T p daT2 To. (27) and ( 2 8 ) 'we obtain from equation $26) the final formula: m dx dt = 2. in fact.6. The proportionality to I/d'rS reflects the great importance of the piece size in gasification processes at very high temperatures.arches. the straight lines are shifted. viz. i. whereas the transition zone between range I a n d I1 is shifted to the left. In the irrhenius diagram LFig. the three straight sections being linked together by shorter or widec. . 2 ) . 3) the straight lines show a garallel upward dkglacenent with decreasing particle size in the range I1 and 111.244.' m d t = 2.16 f b Do ' N P 1 d P fl 1 *0. face of the mass of coke (m) can be calculated fromthe equation 6 f m F = kd where F = shape factor @ ( 0 . Dependency on the conditions of gasification I Practically. applicable to the three ranges. If the conditions are changed. as aDpears from the homontal str t h of the curve in rvlge I11 ?see fig. : ) = apparent density of the piece of coke (g/cmj) To derive co from the standard concentration cao. each range of reaction is characterized by a straight line in the Arrhenius diagram.5. in renge I1 the may of diffusion up to tbe internal surface is reduced. ( 1 9 1 .e. the power a is about 0. cases reads as follows: .8 - 1. In the other ranges crushing of the coke leads to a higher intensity of gasification.1 In the range of boundary film diffusion the dependency upon the temperature 'P is almost negli ible. In the range of chemical reaction the particle size d is not influential upon the intensity of gasification. the temperature T and the pressure p have to be taken into account as-usually: 0 ' - ' N o 273 P T 760 Takin into account equations (IS). whereas in range 111 the reactive external surface is enlarged. as will be shown in detail in the light of the three final equations.8a F s o that the final formula i n most In practice. 7 2 ) . towards higher tenperatures.

in stronger boundary film diffusion a n d in a greater intensity of gasification (Big. The measuring method (20) may be briefly described as follows: Analytically pure C02 flows at a speed of 2. through a reacticn tube 20 m in diameter. Xecent exgeriments of Dahme end Junker (18) as well as of Hedden have confirmed the usefulness of thiszrangement and ha. Here. In the Srrhenius di-agram (Fig. cm3 /see. . Through the tube a platinum-rhodium couple is introduced into the coke sample.1. Measurements 2.7) which is not based o n the principle of gas analysis but on the gravimetric determination of the l o s s of weight.sification.1.ve made it possible for conclusions to be drawn from the results with regzrd to the kinetics of reaction (19). In range 111.In ranges I a n d I1 the increase in the internal surface 0 entails a proportional intensification of g5. The temperature is measured 10 mm above the frit with a platinum-rhodium couple. which has been adapted to the special puroose. The gas flows downstream through the layer of coke and leaves the reaction zone through the frit. 2. The samples used in this method. Ueasurements on lumns of coke For the determination of the intensity of gasification of lumpy coke up to temperatures of 1500 O C an apsaratus has been developed (see Pig. This tube is blown from quartz.5. Gas-analytical method ?or determining the reactivity of fine-grained coke we have used an apparatus (Fig. haaaratuses 2. via. This arrangement makes it possible to continuously observe the temperature of reaction in the coke samgle during .1. In our tests the weight of the coke in the tube was 2. or 5 g.5. the speed of flow does influence the thickness of the adhering boundary layer. are coke cylinders 40 mrh high and 20 m in diameter. The oven is designed in such a way that the reaction tengerature is rexhd after 10 minutes and the first measurement can be carried out after 15 minutes. and the transition ~m range I1 to I11 is shifted to the right. 2. however. where C02 is completely converted on the external surface the internal surface does not play any Dart. 5). thdoke sample is resting upon a frit. 6) which differs only slightly f r o n thit designea by Kop9ers and Jenkner (15-17).1. Only for %his . In range 11. The speed is influential upon the decrease in CO concentration during the passage through the layer of coke. re&son.245. r : i t hincreasing surfece 0 in ranges I and 11.2. 4) the straight lines show a parallel upward displacement . a decrease in the boundary layer thickness results in a steeper gradient of concentration. an azotometer. Through a pipe the outgoing gas f l o w s into the analyser. In many cases an infra-red analyser mas used.not directly the intensity of gasification is influenced by the speed of f l o w in ranges I and 11. A ceramic tube is suspended from a -balancewhich records the time and the l o s s of weight.

The sampling method mas as follows: A representative sample was taken from about 150 kg of coke. its ash content mas 8. It is well homn that coke will lose weight in inert atmosphere at temperatures higher than the carbonizing teqerature. The throughput of gas is 400 l/h for each measurement. In fact. Particularly careful sapling was required for the metallurgical coke n a semi-industrial coke oven at a heating flue which had been made A n the properties of temperature of 1300 C.2. wide fluctuations i the individual pieces of coke have to be expected even if they come from the same charge. weighing. the values found varied withm/the following limits: Po rositg: Average pore size: Number of pores per mm: 19. and these cylinders =ere grouped.2. according to their position The number of utilizable cylinders was rather limiin the big l m ~ s . however. :#7eightloss during high-teagerature treatment in nitroqene.. ted on zccount of the cracks and fissures in t & coke. 2 . 40 mm long. this temperature differs from the temperature of the gas. Because of the endothermic reaction.3 to 29. revealed significant differences from which an influence upon the reactivity was to be expected. Material used and sampling method The electrode graphite used in our tests was ash-free. at high temperatures the difference may reach values of some 50 C. - 2-2. extending fro= the wall of the coke oven up to its center.entration of CO in the outgoing gas is only small and negligible in the calculation. 1 . and thanks to its high graphitizing temperature it could be looked upon as a g o o d primary material for the measurements intended. by means of a 20 mm hollow drill. It was necessary for us to determine the amount of this loss in order to estimate the weight of the error introduced into the gravimetric measurements. and well-preserved at both ends.16 14 to 1 9 k 12 to 16 The electrode graphite samples were received from the producer in form of cylinders 20 m in diameter. this sample was crushed and screened into two fractions 3 2 mm and 1 .0. This means that the conc. 2 . The granular samples were obtained by grinding several cylinders. The coke mas dry-quenched in an air-tight chamber.From the remaining lumps cylindrical samples were prepared. Ueasuring results Our reactivity measurements were preceded by investigations intended to determine the influence of different factors upon the measuring accuracy.08 $. For the tests they mere gut to size. in fact.3 . Part of these lumps mere cut into pieces so that the outer. Eicroscopical determination of the pore volume and the pore structure. In . the middle and the inner ends vr5re separately available and could be ground a n d screened inta the same fractions as the mean sample.246.5m Prom the remaining coke long lumps were selected. 2.

3. The loss of weight reaches considerable values. This is to be explained by the large differences of the pore volume.2.-no fluential upon the gasification reaction. Setween 900 C and 1500 C the curves are similar. however. seems hardly possible. the differences of burn-off were still larger in the tests on coke cylinders. After a steeprise during the first 3 0 minutes they becomGlatte6. and a perature difference radiation will be sufficient to make up for the heat consumed by the gasification reaction.volafile inorganic ash components are distillated. . Beyond 1400 C the curve is flattening out which indicates that the reaction has reached range I11 where the gasification intensity becomes a fun+ tion of the boundary film diffusion and is. as the heat required-for the reaction at the given temperature is supplied by radiation. no matter whether the smples had been taken from the middle of the chamber or from the wall of the oven. The qualitative explanation of this phenomemn is very simple.eratures. Fig. This fact is due to the endothermic character of the gasification reaction which consumes more heat than the quantity supplied to the coke by radiation from-thewallaf the oven and. Temperature difference between gas and coke In the course of our preliminary tests we found out that the temperature of the coke which had been attained in nitrogene fell off when carbon dioxide was fed to the apparatus. as mentioned above.In range I11 l o n g e r inwhere the internal structure of the graphite cylinders is. these differences disappear. e. to a lesser degree. we could observe the trend that at high temperatures the burn-off after the same lapse of time was constant. adsorbed gases are liberated. FTith decreasing temperat a certain temture of the coke.2. But h e r e . however. 10 $ at 1500 C after 20 hours. S before. altnough to a lesser degree.4. and oxides in the ash are reduced by the surrounding carbon. especially at high tem.according to equation ( 3 0 ) . A quantitative determination of these different concomifant phenomena. . 2. It was found that at the same temgerature and after the same time the l o s s of weight of the graphite cylinders differed very much.247. 8 the l o s s of weight & s plotted vainst the time for different tesperatures. IYith rising temperature. practically independent of the temperature. by convection. Apart from after-carbonization at temperatures beyond the carbonization temperature. Up tolloo C no perceptible difference is to be observed. 0 Surn-off as a function of time The burn-off in C02 as a function of time was determined o n cylindrical samples. As expected. the reaction speed increases rapidly and the heat consumption of the reaction ivill increase to such a deg6ee that a considerable temperature difference does appear. 2. Fig. 9 gives the resultsof measurements which show the difference of temperatures reigning in the ambient gas on the one side a n d in the core of the coke pieces on the other at different reaction temperatures. the heat transfer is improved. At lower tsmperatures it is always the samples taken from the middle of the chamber that sbmthe highest l o s s of weight.g. using only the gravimetric method.

ranging betBeen 1 0 and 50 $. as calculated f r o n . beyond 1350 C all points are close together and differences caused by the position of the samples in the coke oven are no longer noticeable.248.is a straight line. This is to be explained by the fact t h t the final carbonization temperature reigned much longer near the wall of the oven which entails a higher degree of gas emission and a decrease in reactivity. In the pore dhffusion range whose starting point for electfode graphite is about loo C higher than in the caxe of metallurgical cokg. In case of coke. The upper curve of Pig. t is interesting to note that but we come back to this question later on. In Pig. up to 1200 C. As for the conditions in the range of boundary film diffusion. the ratio of the gasification intensities goes down to 1 . After a short arsh the curve adopts again the form of a straight line starting at 1400 C with a flat gradient. I this wrae dispersion of the individual values disappears more and more. Vith rising temperature &he wide dispersion of the values measured disappears. Beactkvitg of lumps between 900 and 1500 OC. . I most of all the coke samples taken from the middle of the chamber that show this trend. In the lower part the individual values found by this method are so widely dispersed that nothing can be said about the activation e n e r . whereas structure and external surface become the dominating factors. the lumps taken from the middle of the oven show a higher reactivity than those taken from the wall.5 on the average. 6 at 1300 C. a slow-down of the loss of weight per unit of time Eith prot is gressing combustion is clearly evident. Above 1300 C the ratio of the gasification intensities of both materials is about 1. In fact. the gradient of this second straight part.5. from which it is to be expected that the activation energy in this range should be 50 $ of what it amounts to in range I. lo shows the results of measurements made o n coke. From the burn-off curves the reaction speedcan be calculated using equation (9). The activation energy in the range of pore diffusion. A comparison of the burn-off curves of graphite and coke leads to the result that for graphite the loss of weight per unit of time remains almost constant even after gasification of 5 0 $ of the material. its value is 65 kcal/Mol. the upper one o n coke. differs very much. This proves that the chemical reactivity of the coke samples. l o ? the values calculated in this way have been marked on a n Arrhenius diagram similar to that shown in the first part of this paper.2. From the gradient we cac calculate the activation energy f o r the purely chemical reaction in range I. c y . which corresponds to the difference. At this temperature the internal structure of the coke becomes the decisive factor. the measurements made do not permit any conclusions to b e drawn. This statement is confirmed by a comparison of the graphite and the coke curves which approach with rising temperature. The lower curve represents the measurements made on graphite. taken from the different parts of the oven. The lower section of the grzphite curve. The conclusion to be drawn from this observation is that with rising temperature the importance of the chemical properties decreases more and more. at least up to 1200 C. amounts to 34 kcal/Molc This value agrees fairly well with the theoretical postulates according to equation (17). 2. The diagram shows the reaction speed at different stages of burn-off.

1 0 we have marked o n the graphite curve the results obtained from both cylindrical samples and the grandlar samples 3 2mm. In the preceding chapter it was already said that this is due to the final temperature of the coke. It is understandable that the values obtained from these mean samples do not show the dispersion which was observed with the cylindrical samples. even o? different diameter. Above this temperature the cylindrical samples show the influence of the pore diffusion which. are o n l y valid for coke originating from the chamber wall. Relation between reactivit. range I. irrespective of the position of the coke in the oven. it finds its explanation in the treatment after sampling.5mm. I’t seems that the measurements were carried out not yet entirely within the limits of range 111. These results. 1 1 we have also given the results oT measurements made on granular coke of different size. however. For metallurgical coke Fig.2.0. the activation energy is the same for all measurements. diffusion need not be taken into account.y and coke size The theoretical considerations have made it clear that in the range of purely chemical reaction. values of the fine-grained mean samples from the three zones of the oven as determined by the coincide gas-analytical method. 12 shows that the reactivihy measured on lumps a n d on granular samples is the same up to 1050 C. 12) that the coke size does not matter. 2.e. - In Zig. Here all the values measured coircide with the Arrhenius lines. In the range of temperatures examined (1000 . of their apparent densities. and to the length of time during which the final temperature has been effective. The results obtained from the sample representing the whole of the charge do not agree with the sean value of the samples representing the three different zones of the coke oven. the zone Of pure boundary film diffusion. The finerfcaction will always be composed .7. In both cases the reactivity increases from the wall of the oven towards the centre.2. In Pig. because below a certain temperature the gasifying agent (CO ) will reach the whole reactive surface of the coke pieces.249. donot show the same reactivity as the 3 .6.2 mm fradtion.e. 2. 1 1 we have reproduced the reactivitj. i.1 1 0 0 C) the values agree perfectly. Reactivity in dependency upon the position of the co$e in the oven In Fig. This leads to the conclusion that there is no linear relation between reactivity and the position of the coke in the oven. this is true of the 3 to 2 mm as well as of the 1 t o 0. From the wall of the oven up to its centre line the reactivity increases by more than loo $. namely 67 kcallYo1 . This observation is no argument against the theory. i. Similar measurements on lumps from the centre of the oven led to a wider dispersion of the results so that it is not possi’sle to draw exact conclusions from them. This is to say (Fig. The experimental values confirm the conclusions reached on theoretical grounds. without any perceptible decrease in concentration as compared with the ambient gas.5 mm size fraction. As the Arrhenius lines are parallel. in the case of granular material would only appear after a further rise of temperpture. Here the finer size fraction 1 .

304 0. Further investigations have shown that to all appearance the ash content is an important factor.8. at 1 0 5 0 0 C Very pure coke W Si02 0. Very clean coal (ash content under 0. with or without addit&ons.55 For the time being we are not able to sag whether the large differences between these values are due to catalytic or other influences. and differences are unavoidable. The $allowing table shows the first results of reactivity test2 mzde onovery clean coke.250. whereas Si0 will slightly inhibit the reaction.485 0.5 $) was coked with selected additions. The influence of ash on reactivity. 2. i In a large series of tests which are still going on.2.825 2. Mat eria1 dddition k . of unhomogeneous material. Crushing and grinding leads to a concentration of high-ash and weaker particles. Very efficient i5 Ea CO .at a temperature of 1050 C. the coking temperature was 1150 C in all cases. .78 11 Fe304 CaC03 n W Na2C03 7. we are studying the influence of the ash content and the ash components on the reactivity of the coke. It was found that Boudouard's reaction is accelerated by iron oxides and CaCo .

F i f t h Symposium on Combustion. 651 (1922) 17) H 18) A. 2. Koppers. (London) A 193. Hinshelwood.) 14) W. Philadelphia. SOC. Springer-Verlag (1943) (1955) C a t a l y s i s Vol. G. W. 19) W. 6 ) K. K. Coke Oven. Roy.-W. Eisenhuttenw. 158-170. J. 323/328 (1961) .-W. 193/224 (1960) 10) C . K. Wien. Philadelphia. N. Sykes. Arch. Roy. H. Gadsby. Literature 1) Handbuch d e r Katalyse I. W. Wicke. K. P e t e r s .251. Koppers. (London) A 193. 377/99 (1948) 13) K. Proc. Co. Brennstoff -Chem. Koppers-Mitt. 84/90 (1961) 15) H. Jenkner. New York the ECONOMIC C O M M X S X O NF O R EUROPE COAL C O I 4 M I T l m 3) Placed t o t h e Meeting of E x p e r t s on t h e R e a c t i v i t y of Coke and semi-coke of (1962) 4) H. V o l .. Gluckauf 96. Echterhoff. J. Third Conference on Carbon. 57. Lang. A. Wicke. Lask. Beck und W. G. Dahme. Hedden. Echterhoff. Proc. 20 (1961) S. Blast Furnace. Vol. Lask. Co. 245/52 9). of P i t t s b u r g h . P a u l H. 1954. Koppers. and Raw Materials Proceedings. Coke Oven. Brennstoff-Chem. 41. Roy. P e t e r s . 403-414. SOC. Jenkner. 2) Schwab. Elax Materials 5) W. 2. Buffalo (1957. a . Gadsby u E) F. P e t e r s . and Proceedings. I. Hedden. Elektrochem. Hedden. Reinhold Publ. J. 357/76 (19484 1 1 ) J. G. Proc. 997/1006 (1960) 20) W. Emmett. Sykes. (London) A 187. B l a s t Furnace. SOC. 193/224 (1955) 42. K. Wicke. 20 (1961) S. Hedden. A. New York. . 636/41 (1953) 8) E. Proc. 543/547 (1931/32) 16) H. 5. Brennstoff-Chem. P e t e r s . Reinhold Publ. Brennstoff-Chem. 1955. U n i v . K. VDI-Zeitschrift 66. D i s s e r t a t i o n Ghttingen (1954) 7) E. G. 15/16 (1922) .-M. 129/51 ( 1946) . Junker.. 42. E. 36. P e t e r s und H.

t v. I I P C L 67 Figure 2 Intmsiiy of gasification (kefflos a function of temperature (TI .252. \ Schematic drawing coke frit of the coke layer through wich the gas is f/OWiIIg Figure 1 IC.

253. m 1 1 1 I Figure 4 i Influence of &e apvssaknoction surk 0IA-B) on the ~ntmsityof psiticobon (k 01 rwng tempemlure iT ) III II I Figure 5 Figure 6 j. .

1 Figure 7 ACpomtus lor thec*ArminotiOn of the gmifiwtion mfensilyof lumpy coke I LcIu Figure 8 lb ‘C I I I I Al Figure 9 .

t Figure 10 i Intensity of gasjfikation ( k e r f ) a s a function d the tempMfure \ F i g w e 11 &qPou .Forrrhung Reactivity Figure 12 f m n the wall) PCL ob .

J. Also.A 256.s t e e l e l e c t r i c furnace in an i n e r t cylinders. United S t a t e s S t e e l Corporation Applied Research Iaboratory Monroeville. Ecperiment al The laboratory cokes used i n this study were prepared by carbonizing a variety Of different-rank coals used in various c o a l blends i n U. These coal samples were crushed t o minus 8 mesh and placed in 1-1/4. 1 4 Previous investigations''') have evaluated q u a n t i t a t i v e l y the s t r u c t u r a l properties of coke i n t e of i t s c h a r a c t e r i s t i c s and behavior in s p e c i f i c uses.by 1-1/2-inch s t a i n l e s s . a l l t h e s e properties are. After the carbonized c o a l s a t t a i n e d t h e temperature of t h e cylinder a t 1850 FI t h e y w e r e soaked f o r an a d d i t i o n a l two hours and t h e n cooled i n nitrogen gas. t h e i n t e n s i t y of t h e reflectance from a w a l l i s dependent on t h e rank of c o a l from which t h e p a r t i c u l a r coke was produced and on t h e a s produced. Also. 1. These o p t i c a l p r o p e r t i e s a r e r e l a t e d t o t h e stages i n c r y s t a l l i n i t y of t h e carbon . studies were conducted t o determine whether a s i g n i f i c a n t . S t e e l operations. S. and r e a c t i v i t y of coke are c e r t a i n l y important p r o p e r t i e s that should c' be considered as c r i t e r i a of coke q u a l i t y . both of which properties are concerned with structure. * See-references . s ) have been made of differences i n t h e o p t i c a l properties of t h e vaLL material of cokes. I ) * porosity. s t r e n g t h .c o r r e l a t i o n could be obtained with. Imrestigations conducted a t t h e Applied Research Laboratory have shown t h a t coke s t r u c t u r e as well a s t h e order of c r y s t a l l i n i t y of t h e carbon in t h e coke can be determined by reflectance measurements. qualitative o b s e n r a t i o n s . from amorphous t o graphitic forms. Reactivity w a s chosen as t h e parameter because various workers i n t h e fieidg-=J have reported it t o be a function of surface area and/or porosity. a m u a l method of t m v e r s i n g coke WES used temperature a t which it w t o obtain Quslitative measurements of pore and w a l l areas.m c e use has never been s a t i s f a c t o r i l y nor completely answered. Since coke-sample preparation is a r a p i d routine procedure and t h e reflectancescanning microscope is automated. t i o n s in t h e transmission or r e f l e c t i o n of polarized l i g h t (anismtropism). it m a y be possible t o obtain much valuable information On t h e p r o p e r t i e s of cokes i n a s i n g l e operation. which permits t h e scanning of a specimen a t a constant rate and thus makes possible quantitative measurements.It i s not w i t h i n t h e scope of this paper t o discuss t h e r e l a t i v e importance of t h e various p r o p e r t i e s that. Formerly. Schapiro and R. however. related t o t h e s t r u c t u r e of coke. which were then put i n t o a preheated (1850-~) atmosphere. and a constant speed could not be msintained. The size. I n carbon t h e c r y s t a l structure causes d i r e c t i o n a l varia-.t h e instrument between coke s t r u c t u r e a s indicated by pore volume and t h e reactivi y of coke. . a r e a s representing the coke walls are high i n reflectance compared wfth t h e filled pore areas of low r e f l e c t a n c e . These d i f f i c u l t i e s were eliminated by t h e construction of t h e automatic t r a v e r s i n g device. affect t h e p e r f o m c e of coke i n t h e b l a s t furnace. Gray . EELATTON OF COKE S ' I ' R U m TO REACXIVITY N. T5is time-consuming method required t h e continuous presence of t h e operator. As p a r t of a general program t o i n v e s t i g a t e t h e various properties of coke that could be delineated by t h e use of t h i s t r a v e r s i n g device. Introiuction The question of what c r i t e r i a should be used t o determine the r e l a t i v e Q u a l i t y of coke for b l a s t . Pa. When t h e polished surface of a p i e c e of epoxy-impregnated coke i s scanned with a reflectancemeasuring nicroscope.

The x motion or p r i n c i p a l d i r e c t i o n of t r a v e l was set t o move t h e a s set a t specimen a t the r a t e of 5 microns per second (18 mm per hour). ( 3 ) p a r t i c l e s i z e . .3 mm on t h e recorder chart. T h e @ o ~ m u l t i p l i e r photometer i s used i n conjunction with a recorder t h a t charts t h e reflectance differences. impregnated. A . and ( 4 ) sample weight. was considered t o be t h e most significant. Because t h e i n i t i a l portion of the weight loss-time curve.1 P I 257The cokes s o produced were cut i n t o halves. it can be observed t h a t the coke produced from -side c o a l contains very t h i n walls and large pore area. Thus each millimeter . S t e e l coal blends f o r metallurgical-coke production a r e shown i n Figure 2 t o il-hmtrate structural differences i n t h e cokes. However. Photomicrographs of t h e various forms of carbons i n these same coke * The u. whereas the cokes from higher-rank coals such as Pittsburgh and P r a t t contain t h i c k e r walls and less pore area. The weight l o s s was calculated on t h e dry. . s. Fromthese fingers. The platinum basket was suspended from t h e l e f t pan of an Ainsworth balance. Fingers were selected because they represented the extremes i n the t i m e and temperature conditions under which t h e cokes were produced. The stage of the microscope i s driven automatically and the number and length of traverses i s automatically controlled.0050 gram). However. The individual coke specimens prepared f o r t h e microscope study were placed on t h e stage of t h e microscope and levelled o p t i c a l l y t o assure uniform focus throughout.048 mm per hour). r e a c t i v i t y data used i n this presentation were supplled by K. The low-reflecting r e s i n f i l l e d t h e coke pores. cokes produced from Pocahontas Ao. Each crushed coke sample was placed on a basket with an 80-mesh platinum screen bottom and suspended i n the uniform-temperature zone of t h e platinum-rhodium-wound furnace. Results and Discussion photomicrographs of surface sections of t h e laboratory cokes prepared from four d i f f e r e n t ranks of coal used i n various U. The commercial cokes used i n the study were obtained from U.! a t a controfied temperature i s defined a s r e a c t i v i t y .000 F. ( 2 ) atmosphere. The instrument arrangement used i n t h e automatic recording of coke microstructure i s shown i n Figure I. c i r c u l a r area with a diameter of 12 microns. K. f o r future work an i n t e g r a t o r w i l l be i n s t a l l e d t h a t w i l l make this calculation automatically. The chart moves a t the speed of 0. and the inner end were removed. t h e weight l o s s i n 30 minutes was used a s a parameter of reactivity. and polished i n t h e manner described f o r t h e laboratory-produced cokes. The microscope f i e l d of view exposed t o t h e p h o t o m l t i p l i e r i s a . This method i s adequate t o demonstrate t h e technique i n t h i s stage of development. In t h i s study t h e B w a l l and pore areas and t h e r e l a t i v e height of the reflectance peaks a r e measured by counting the a c t u a l areas from t h e recorder graphs. t h e center.5 l i t e r s per minute. The balance sensed t h e changes a t the conditions i n t h e furnace. 1 . A thermogravimetric u n i t was used t o determine t h e r e a c t i v i t y of t h e coke samples. * The conditions used f o r each d e t e r minstion were (1)temperature. which were then impregnated with epoxy resin containing an opaque pigaent. and t h e y motion w 4. S. ash-free basis ( d a f ) and corrected f o r the incremental loss of v o l a t i l e matter. minus 4 plus 6 mesh. whiFh i s e s s e n t i a l l y linear. S t e e l Corporation ccke plants a s complete fingers (one-half oven pieces) from one oven push.5 degrees. ! z \ I The measurement o f the extent of reaction (weight-loss) of t h e solid coke with CO. 5 grams ( 2 0. S. The coke surface impregnated with the r e s i n was then polished f o r microscopic examination. portions representing t h e w a l l . 3 coals approach Sunnyside i n pore volume. 2.85 mm per second (3. A photomultfplier tube i s attached t o t h e monocular tube of t h e micro'scope and i s used t o sense reflectance differences. on the specimen surface i s represented by 169. Kappmeyer of t h e S t e e l @plied Research Laboratory. and a B r i s t o l recorder connected t o the balance recorded the weight change a s a function of time. providing contrast with the high-reflecting coke walls. 100 percent CCQ a t 2.

258.
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samples at higher magnification a r e shown i n Figure 3 t o indicate- t h e relation of carbon forms i n coke t o t h e rank of t h e c o a l used i n its preparation. The cokes from high-rank c a ' a s Pocahontas No. 3 under polarized reflected l i g h t show extreme anisotropic e f f e c t s Kith t h e appearance of a sinuous structure and high reflectance. The cokes from lower-rank coal such a s Sunnyside show carbon forms that areikotropic and have low reflectance.

I n t h e Laboratory cokes, t h e degree of anisotropism was d e d as a measure of the types of carbon present. O p t i c a l l y anisotropic substances transmit or r e f l e c t l i g h t i n unequal v e l o c i t i e s i n d i f f e r e n t d i r e c t i o n s . Cokes dispLaying d i f f e r e n t degrees of anisotropism appear smooth, granular, or sinuous in polarized U g h t . Therefore, t h e degree of anisotropism and t h e surface texture of t h e coke are used t o i d e n t i f y t h e stage of coalificat i o n of t h e c o a l from which t h e coke was produced.
Since organic Fnerts do not become f l u i d during carbonization, they remain virtually I s o t r o p i c in coals of all ranks. Thus t h e amount of o r g m i c i n e r t s can be determined by t h e isotropism i n cokes produced from c o a l s of a l l ranks except t h e marginal-coking high-volatile coals. F'igure 4 shows photamicrographs of i n e r t s incorporated i n t o t h e coke walls.
A graph o f t h e r e f l e c t a n c e and r e l a t i v e anisotropism of t h e p r i n c i p a l carbon form

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from each of t h e seven laboratory cokes i s shown i n Figure 5. The samgles are arranged i n t h e order of increasing rank of t h e coals from which they were derived. The maximum and
minimum r e f l e c t a n c e o f t h e subject material was measured by revolving t h e sample on a micro-

scope stage through 360 degrees with t h e p o l a r i z i e r s e t a t 45 degrees. The anisotropism of t h e carbon materials increases as t h e spread between the maxhm and minimum reflectance increases as shown by t h e peabs and troughs. Thus, t h e reflectance measurements provide a q u a n t i t a t i v e determination of anisotropism. Furthermore, t h e graph shows t h a t t h e maximum reflectance i s proportional t o t h e amount of anisotropism. When polished surfaces of t h e various cokes are traversed a t a constant r a t e v t t h a continuously recording r e f l e c t a n c e microscope, a p a t t e r n i s obtained that shovs t h e lowr e f l e c t i n g pore areas and t h e high-reflecting w a l l area. The Fntensity or magnitude of the r e f l e c t a n c e i s dependent upon t h e rank of t h e coal and carbonization conditions. Exanrples of t h e p r o f i l e s obtained i n t r a v e r s i n g t h e coke surfaces of two cokes produced from highand low-rank coals are sham i n Figure 6. The approximate d i v i s i o n between t h e w a l l and t h e pore area i s displaced t o t h e r i g h t of t h e v e r t i c a l base line because of the occurrence of portions of both w a l l and pore a r e a i n t h e same f i e l d of view. These two p r o f i l e s show t h e 4 1 differences i n s t r u c t u r e and i n t h e rank of t h e coals used t o produce t h e cokes. The coke produced from Sunnyside c o a l has l a r g e pore areas, indicated by t h e l a r g e v e r t i c a l spaces 1 between t h e peaks. T h e refLectance i s low, as indicated by t h e r e l a t i v e l y short horizontal 1 peaks. I n c o n t r a s t , t h e coke f r o m Pocahontas No. 3 c o a l show qmaller but numerous pore I areas, 8 8 indicated by t h e short v e r t i c a l distance betveen t h e peaks. The reflectance is high, as indicated by t h e g r e a t e r l e n g t h of t h e h o r i z o n t a l peaks. The p r o f i l e s thus obtained
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verif'y q u a n t i t a t i v e l y t h e d i f f e r e n c e s i n s t r u c t u r e s observed i n Figure 2 and t h e differences i n t h e forma of carbon observed i n F i g u n 3. Since t h e objective of this phase of t h e program of characterizing coke w a s to e s t a b l i s h whether relationship could be obtained between coke r e a c t t v i t y and t h e coke structure and carbon forms as obtained by reflectance measurements, seven samples of laborat0 Produced coke that had p r s i o u s l y been t e s t e d for r e a c t i v i t y were analyzed for structure. Fromthe graphic calculated; and this value cokes. This p l o t i s shown curve obtained by p l o t t i n g p r o f i l e s obtained, t h e pore volume of each of the cokes was was t h e n p l o t t e d against t h e rank of t h e CodL6 used t o produce t h e i n Figure 7. The curve obtained w a s almost i d e n t i c a l with the t h e rank of t h e coals from W c h cokes w e r e produced against t h e

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259r e a c t i v i t y of t h e s e same cokes as s h m i n Figure 8. Since both t h e r e a c t i v i t y of coke and t h e s t r u c t u r e of coke a r e r e l a t e d i n t h e same m e r t o c o a l rank, it was l o g i c a l t h e r e f o r e t o assume t h a t t h e s t r u c t u r e of coke, as defined by pore volume, would be r e l a t e d t o t h e r e a c t i v i t y Of t h e coke. The pore volume of t h e s e cokes w a s then p l o t t e d against t h e r e a c t i v i t y of t h e same cokes; t h e r e s u l t i n g curve i s shown i n Figure 9. This curve demonstrates that a strong r e l a t i o n s h i p exists between t h e r e a c t i v i t y of coke and t h e s t r u c t u r e of the coke as defined by pore volume, and t h a t t h e r e a c t i v i t y is g r e a t e s t i n cokes from low-rank coals, least from medium-rank coals, and intermediate from high-rank coals.

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This r e l a t i o n s h i p between s t r u c t u r e and r e a c t i v i t y was established on t h e b a s i s of cokes produced from individual coals of d i f f e r e n t rank. To determine, therefore, whether t h e same relationship held for cokes produced from blends of diffdrent-rank coals (such a s are normally used in making metallurgical coke), samples of U. S. S t e e l coke-plant cokes t h a t a r e made from blends of two o r more coals of d i f f e r e n t rank were analyzed. Photomicrographs of sections of t h e four cokes analyzed f o r structure a r e shown i n Figure 10. Examination of t h e s e photographs indicates t h a t plant coke A contains t h i n coke walls and l a r g e void a r e a s and i s similar t o t h e coke from low-rank coals, which comprises 76 percent of t h e t o t a l c o a l blend a t Plant A. In contrast, plant coke D shows t h i c k c e l l walls and much less pore area. ,The carbon forms present i n t h e commercial cokes a r e similar t o those of t h e cokes made from individual coals making up t h e blends; they a r e shown i n Figure U,.
Graphic p r o f i l e s of t h e s e same four cokes obtained with t h e reflectance microscope a r e shown i n Figure l.2. Examination of t h e s e p r o f i l e s i n d i c a t e s t h e difference i n both s t r u c t u r e and carbon forms of t h e various cokes. I n general, t h e s t r u c t u r e and carbon forms follow those of t h e cokes made from individual coals. For example, t h e c e l l s t r u c t u r e of plant coke A i s characterized primarily by t h i n walls and l a r g e pore area because of t h e large amount of low-rank coal i n t h e blend.

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When t h e reflectance i s measured i n a t r a n s e c t of a prepared coke surface, t h e 'carbons derived from t h e individual coals remain d i s t i n c t s o t h a t t h e d i s t r i b u t i o n , t h e s i z e , and t h e s t r u c t u r e of t h e individual carbon p a r t i c l e s can be determined. I n addition, t h e e f f i c i e n c y of t h e blending with reference t o amount, s i z e , d i s t r i b u t i o n , and fusion c h a r a c t e r i s t i c s of t h e individual carbon s t r u c t u r e s i n the coke can be assessed. P l o t t i n g the pore volume as obtained f r o m t h e graphic p r o f i l e against t h e r e a c t i v i t y of t h e s e same cokes, a r e l a t i o n s h i p similar t o t h a t found f o r cokes from individual coals of different rads w a s obtained, see Figure 13. The data i n d i c a t e t h a t t h e cokes made from a preponderance of low-rank coals have t h e g r e a t e s t pore volume and a l s o t h e highest r e a c t i v i t y . Plant coke B exhibits both high r e a c t i v i t y and l a r g e pore volume because t h e coal blend c o n s i s t s of 4.0 percent low-volatile coal, which i s of high rank and when used alone produces coke of r e l a t i v e l y high r e a c t i v i t y . Plant coke C shows r e l a t i v e l y l o w r e a c t i v i t y and smaller pore volume primarily because of t h e l a r g e amount of medium-volatile c o a l i n t h e blend.

It i s t h e opinion of t h e authors t h a t an even b e t t e r c o r r e l a t i o n would be obtained between pore volume and r e a c t i v i t y i f t h e temperature a t which t h e cokes were carbonized were taken i n t o consideration. Plant coke D i s carbonized a t temperatures higher than those used a t other U. S. S t e e l coke plants, whereas plant coke A i s carbonized a t t h e lowest temperatures. High f i n a l coke temperatures reduce r e a c t i v i t y , increase t h e reflectance of t h e coke walls, and may a f f e c t t h e r e l a t i v e proportion of the dense wall and more porous inner oven coke. For example, coke taken from t h e inner and outer portions of an oven a t Plant D were analyzed f o r r e a c t i v i t y and pore volume. The inner oven coke, which i s exposed t o lower temperature and time a t a given temperature than t h e cokes from t h e outer o r w a l l portion of t h e oven, showed both higher r e a c t i v i t y and g r e a t e r pore volume than t h e outer portion sample. The e f f e c t s of temperature and time on coke s t r u c t u r e t h u s appear s i g n i f i c a n t and warrant f u r t h e r investigation.

260.

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This investigation has established a relationship between t h e r e a c t i v i t y prope&y of coke and i t s s t r u c t u r e a s defined by pore volume. The s t r u c t u r e and hence t h e r e a c t i v i t y of coke a r e dependent upon t h e rank of t h e coal from which t h e coke vas produced. Lov-rank c o a l produces coke having t h e highest pore volume and thus t h e greatest reactiv€ty. As t h e c o a l rank increases, t h e pore volume and therefore t h e r e a c t i v i t y of t h e coke decreases t o t h e ntinhum. High-rank c o d a produce coke of intermediate pore volume and r e a c t i v i t y . Blends of coals produce coke with pore volumes and r e a c t i v i t i e s dependent upon t h e rank and amount of t h e individual coals n d d n g up t h e blend.
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%e temperature and t i m e a l s o a f f e c t t h e pore volume and t h e r e a c t i v i t y of a p a r t i c u h r coke. These e f f e c t s w i 3 l be studied and reported Fn t h e future.
References
1 . C. G. Thibaut, "French Research on Coke i n t h e Iron and Steel Industry," I n s t i t u t e de Recherches de La Sidenrrgie, 1957; pp. 1-13.

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2. 0. 0 . m e i s , "9s-product Coke C e l l Structure," Industrial and m g b e e r i n g a & t r g ,
Pol.

16, 1924; pp. 901-904.

. 3. E

J. Rose, "The Study of Coke Macrostructure,"

s, Vol. 5, 1926; p.

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4 . H. J. Rose, "Selection of C o a l s 1926; pp- 600-639.
5. H. Hoffman and F .

f o r t h e Manufacture of Coke,"

AIME Trans., Vol. 74,

Kuhlwein, "Rohstoffliche und verkokungstechnische Untersuchungen und Saarkohlen," Gluckauf, Val. 71, 1934; pp- 625, 657-

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Icrajewski, ''Microscopic Research on t h e Structures of Coke Produced from Various P o l i s h C o a l s , " WansLated f r o m Polish, Builetyn I n s t y t u t u Iiaukowo-Badavczego Przemyslu Weglowego, Report no. 3 7 ,1 9 . 9 4 8 ;pp. 1-25.

. AbramskL, "Zusarrrm%nhange zwischen Kohlenpetragraphie and Verkokung, " Truiseme Cangres 7- C Pour L'Avancement des Etudes de Stratigraphie e t de Geologie du Carbonifere: Compte Rendu, Pol- 1 , 1952; pp. 1-4-

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8 . C. AbramskL and 9-

M. Th. Mackuwsky, "Methoden und Ergebnisse d e r Angevandten Koksmilrroskopie H . Freund, Handbuch der Mikroskopie i n der Technik, Bank 1 1 , T e i l I, ubnschau Verlag Frankfnrt Am. Main, 1952; pp. 311-410.

OnusaLtis and Yurevskaya, Zvest. Akad. N a u k USSR, Otdel, "e%, Nauk

1949, 519.

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19 161, (19.960).
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2524 (1955), Cap.

243, 1764 (1965), J.

Chem. phys.

2, '

97 (1961).

X5O.261. whereas coke from h i a e r .r a n k coals such a s Pittsburgh and Pratt has t h i c k e r walls and l e s s pore a r e a . an Ortholux microscope ( C ) . Figure 1. an automatic stage-drive unit ( D ) and controls ( E ) . Coke from Sunnyside coal has v e r y t h i n coke walls and much pore area. Coke produced from t h e low-volatile Pocahontas No. Surface sections of coke. Polarized reflected l i g h t . a photomultiplier sensing u n i t ( B ) . and a s t r i p . SUNNYSIDI PITISBURGH Figure 2.c h a r t recorder ( F ) . The equipment f o r automatic photometric scanning of coke specimens consists o f a photometer ( A ) . 3 c o a l approaches t h a t from t h e Sunnyside coal i n t h a t it contains m c h pore area. .

3 c o a l is highly r e f l e c t a n t and shows extreme ribbonlike anisotropism. Inorganic i n e r t s (11) a r e e a s i l y recognizable i n coke. The coke f'rom t h e low-volatile Pocahontas No. . ' ' / x350. Polarized r e f l e c t e d l i g h t . Polarized r e f l e c t e d l i g h t . . Sumgside coke i s low-reflecting and i s o t r o p i c (smooth). r . X350. M E D I U M VOLATILE L O W VOLATILE Figure 4. Surface sections of coke.262. Organic i n e r t s (01) do not fuse during carbonization and remain v i r t u a l l y i s o t r o p i c i n coals of a l l ranks. /' Figure 3. whereas higher-rank coals such as Pittsburgh and Pratt produce cokes with high r e f l e c t a n c e that show pin-point e f f e c t s of anisotropism.

~ a r y Lee 2. arranged i n order of increasing r a n k 1. Pittsburgh 6.nl Figure 6. Pratt 3.nl Figure 5. REFLECTINCE IN OIL.rs. p.263. Pocahontas Nos.rc. Pittsburgh 5. Graphic p r o f i l e of i n d i c a t e d cokes showing (1) v a r i a t i o n s i n r e f l e c t a n c e of d i f f e r e n t carbon forms and ( 2 ) w a l l and pore areas = . I 0 2 4 6 8 1 0 1 2 1 4 REFLECTINCE I N OIL. Sunnyside 4. 3 & 4 7. 3 I SUNNYSIOE POCAHONTAS NO 3 CELL WALL CELL WALL 0 5 1 0 1 4 0 I 1 0 1 4 . p. Reflectance i n p o l a r i z e d l i g h t f o r one 360-degree revolution on a s i n g l e carbon form i n t h e following coke samples. Pocahontas No.

Relation of r e a c t i f i t y and coal rank for laboratory cokes.264. SUNNISlOE I Figure 8. Figure 7- Relation of coke pores t o t h e rank of t h e c o a l from which t h e coke was produced. L .

whereas t h e cokes from Plants B. PLANT C PLANT D Figure 10. X50. and D show thickening coke walls and decreasing pore area. . Polarized r e f l e c t e d light. The coke from P l a n t A contains t h i n coke w a l l s and much pore area. i \ b I 4 \ Figure 9 . Relation of weight l o s s t o coke pores a t indicated conditions f o r laboratory cokes.265. C.

The p l a n t cokes were produced from blends of e i t h e r high. The coke from high-volatile c o a l i s i s o t r o p i c (smooth). medium-. The carbon forms representing the d i f f e r e n t coals a r e i l l u s t r a t e d by t h e anisotropic e f f e c t s . . Polarized r e f l e c t e d l i g h t .266. and t h e coke from low-volatile coal shows ribbonlike anisotropism. PLANT 0 PLANT C PLAN1 D Figure 1 1 . a d low-volatile coals. Figure 12. the coke from medium-valatile coal shows pin-point anisotropism. X350.and low-volatile coals or high-.. Graphic p r o f i l e s of p l a n t cokes showing (1) v a r i a t i o n s i n reflectance due t o d i f f e r e n t carbon forms and (2) w a l l and pore a r e a s - J .

p. C O I E PORES.loss t o coke pores a t indicated conditions f o r p l a n t cokes. Relation of weight . \ 49 s5 60 65 .~c.267.nt Figure 13. .

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