COMPARISON 

### OF

### FZTELPROPERTIES 

### OF PETROLEUM 

### COKES 

### AND COALS

### USED IN POWER GENERATION
James J. Baker, Jefiey 

### G. Rolle, Robert Llerena, k J. Edmond Co. 1530West 16th Street,Long Beach, CA 90813 Keywords: INTRODUCTION petroleum coke, coal, fuel properties

U.S. petroleum coke production 

### is projected to continueto increase, reaching 90,000 dcd (short tons per calendar day) by the year 2002, primarily due to refining heavier and higher sulfur content crudes 

### [I]. In 1996 the coke production was 86,805 dcd and 65.7% of the annual I
production was exports. Green (raw) petroleum cokes are mostly used as utilityfuels (about 73% for fuel grade) combining with coal to make fuel 

### in processing industries. Petroleum cokes are produced at refineries using three different types of coking processes: delayed, fluid, and flexicoking. The delayed coker 

### is mostly used at forty-eight refineries. The other fluid coker (4 units) and fledcoker (2 units) are lessutilized. Coke products fiom a delayed coker are classilied as shot, spongeorneedle coke depending on their chemical and physical characteristics. Utility companies used 3,852 dcd

### of petroleum coke 

### (less than 5% of 

### annual production) as 

### a powerplant supplementalfuelblending with coal 

### in 1996,because petroleum coke has advantages of low price (36% lower at Wst or 46% lower at %/MMBtu), high heating value, and low ash content [I]. The disadvantages of petroleum coke as a fuel are expense of a dual solid 

### bel handling and crushing system, high sulfur, high nickel and vanadium content. Normally cokes are blended with coals at 10-20% before burning 

### in boilers because of their low volatile matter and 

### high sulfur content. Average quality of coke bumed 

### is: 

### on as-received basis, 13,930-14,820 Btdlb, 5.5% sulfur, and 0.5-3.8% ash. Some refineries consume a portion or all of the coke they produce as a solid fuel to generate steam, and more recently, 

### as fuel for cogeneration facilities. 

### An average of 1,767 st/cd of petroleum coke was used within reheries 

### in 1996. Texaco cogeneration power pht at El Dorado refinery, 

### Kansas gasifies a delayed coke to produce syn-gas for a combustion turbine fuel [2]. Typical composition of the delayed coke is: on 

### dry basis, 90% carbon, 4% hydrogen, 4% sulfur, 1.5% nitrogen, 

### 0.5% oxygen, and 0.5% ash. Other coke-fueled cogeneration plants bum 100% delayed coke [3] or 100% fluid coke 

### [l] in a circulating fluidized bed (CFB) steam generator. Delayed coke 

### fines sized to 0.25 in. (6 

### mm) is fed to the CFB hacealong with crushed 

### limestone. Typical compositionofthe delayed coke feed 

### is: on 

### drybasis, 89.2% carbon, 3.7% hydrogen, 5% 

### sulfur, 1.8% nitrogen, 0.3% ash, and 

### 15,050 Btu/lb of high heating value 

### (HHV). The coke containsapproximately 10.6% 

### moisture. Cement industry consumes a large portion of fuel-grade petroleum coke (35.5% of world demand) to combust 

### in 

### kilns [l]. 

### The addition of cokes can constitute up to 50% of the fuel mixture and 

### is carellly controlled conducting test bum due to detrimental 

### effects of high sulfur and vanadium content to concrete quality. 

### Sulfur contamination can cause cement cracking and preheater plugging-fouling due to combination with alkalies, and high vanadium content above 

### 500 ppm can cause cement to 

### lose strength. The cement kilns operate as scrubbers, absorbing sulfur and other contaminantsintohished cement. U.S. utility companies consume about 80% of annual coal production (approximately 1,000 million 

### short tons 

### in 1995) burning 

### in boilers to generate electricity 

### [4]. The coal production consists 

### of 60% bituminous, 30% subbituminous, 8% lignite and small percentage of anthracite. U.S.exports annuallyabout 90-1 10millions tons (9-1 1% oftotalproduction). Coalgasification process technologieshave been extensively tested 

### in conjunction with integrated gasification combmed cycle (IGCC) systemsto improve efficiency, environmental performance, and overall cost effectiveness

### in electric power generation [5]. Several successll demonstration projects are: British GaslLurgi gasifier, Texaco Cool Water gasification plant, Shell Coal Gasification Process, Dow Coal Gasification Process (Destec), etc. Full-scale projects are now proceeding 

### in The Netherlands, Germany, Spain and Italy on a commercialbasis. Utah 

### (SUFCO) coal, an export western bituminous coal, was the predominate coal gasified at the Texaco Cool Water plant 

### [6]and also tested 

### in the 

### Shell demo-plant 

### [5]. Typical coal properties are: 0.4% sulfur, 8.8% 

### ash, 12,360 Btu/lb

### (HHV),and 2,200 deg 

### F of ash fusion temperature. 

### The SUFCO 

### Utah coal has low sulfur, low 

### iron and high sodium content. 

### Shell demo-plant tested a delayed coke which has low ash, high 

### sulfur, low oxygen, low calcium, high vanadium, and high nickel 

### 1
I 

## I

80\

\ Content. 

### Feedproperties of 

### the delayed coke are: 

### on dry basis, 10.6% volatile matter, 0.5% ash, 5.2% sulfur, 89.3% carbon, 3.6% hydrogen, 1.35% nitrogen, 0.03% chlorine, 0.1% oxygen, 15,350 Bru/m 

### (HHV), and 61 hardgrove grindability index (HGI). The coke contains 9.3% 

### moisture and ash mineral analysis shows 0.8% lime, 1.2% sodium oxide, 71.8% vanadium pentoxide, and 7.4% nickel oxide. Texaco and 

### Kellogg (KRW) gasification processes also extensivelytested petroleum cokes asraw material to gasifier [7,8]. Coal ash 

### is classifiedinto two categories:lignitic ash 

### is defined ashaving more (CaDtMgO)than ferric oxide; and 

### bituminous ash is defined as having more femc oxide than the sum of CaO and 

### MgO. The Utah coal is classified a western high volatile bituminous coaL but has lignitic ash. 

### Ash characterization methods such as slagging and fouling indices are different in calculation depending upon bituminous or lignitic ash [9]. Chemical composition of coal ash affects dag viscosity, which 

### is an important criterionfor determining the suitabC7 of a coal ash for 

### use in a &%-tap cyclone fumace. Slag flow readily at 

### or below a viscosity of250 poise. The temperature at which 

### this viscosity of ash occurs is called T,,, temperature. The preferred maximum 

### TzJo for wet-bottom applicationsis 2,450 deg F. 

### The alkali

### metals, sob andpotassium,have 

### long been associatedwith the foulingtendencies of coal ash. Correlations in fouling index have been developed using various parameters such as 

### strength of sintered 

### tly ash and total 

### alkali content for bituminous ash, and sodium content done for lignitic ash.

### AU bauminous coals contain enough sulfur and alkali metals to produce corrosive ash deposits on superheaters and reheaters, and those containing more than 3.5% 

### sulfur and 0.25% chlorine may be particularly troublesome. The elementsin coal ash corrosion are sodium, potassium, 

### aluminum,sulfur and iron, which are derived ffomthe mineral matter in cod Fouling observed in a CFBC boiler firing coal and petroleum coke was attriiuted to agglomeration of sulfate and carbonate, not due to high concentrationofnickel and vanadium present in petroleum coke (306 and 870ppm, respectively)[lo].
The objective of 

### this study 

### is to evaluateand compare various fuel properties ofpetroleum cokes and bituminous coals used in power generation,comparing different cokes produced ffom several refineriesin U.S. and export western coals 

### sampled at 

### the 

### LosAngelesExport Terminal (LAXT). 

### Four fluid cokes, fourteen delayed cokes and &e export coals are included for evaluation based 

### onrecent analysisdata accumulated for the past two years (1997-1998). 

### SAMPLING, PREPARATION

### AND ANALYTICALMETHODS Representative samples ofpetroleum cokes and coalshave been obtained 60mvarious refineries located in California, Texas, Louisiana, 

### Kansas, Illinoisand other states, and storage facilities at numerous national ports. Laboratory samplesare prepared for fuel properties analysis following the proceduresand principles in handling listed in the

### ASTM Methods D 346, D 2013 and D 2234. Laboratoly test methods using various advanced analytical instruments are described in the QualityAssurance Manual of k 

### J. Edmond Company [lI].


### RESULTSAND DISCUSSION Important fuelproperties ofthree significantly different types, delayed coke, fluid coke and export 

### western coal 

### are presented for comparison in Tables 1-3. Petroleum cokes evaluated for 

### this study are produced in various U.S. refineries located in west coast (WC), 

### Gulf coast 

### (GC),mid west 

### (MW), and south east (SE), which are phadyconsumed in export to foreign countries (65.7%) and in der extent 

### (less 

### than 10%)used m domestic power generation and cement 

### kiln fuelmix. Export western coals sampled at the LAXT are high volatile bituminouscoals with low 

### sulfurand iron content. They are primarilyproduced in Utah and Colorado forpower generation. The throughput capacity of LAXT 

### is 10 

### million metric tons per year, which is correspondentto about 10%of current coal export to foreign countries. Based 

### on data presented m Tables 1-3, 

### five different arbitrary groups of concentration or value of several primary fuelproperties areused asindicatorsof different levels ofproperties as follows: 

# -
ywLQWr-Q= 

### MediumHigh 

## xa-mh sulfur,wt% 1-2 2-4 4-6 Asb,wt% 0.5 1-2 9-10 Volatile Matter, wt% 2.5-6.1 9.5-13 40.2-4 1.1 Btu/lb 12600-13400 14200-14600 15200-15600 Nitrogen, wt% 1.2-2.2 2.8-3.2 

### Vanadium,PPm 270-400 500-800 900- 1400 2300-2900 Nickel, ppm 25-200 400-500 700+

81

### -fuel properties of petroleum cokes used in power generation. 

### Three fluid cokes (WC-1, WC-2 and WC3), one bed coke (WC-4) and 

### six delayed cokes (WC-5, SW/MW-1, SWiMW-2, SE, 

### SUGC, 

### E/MW) are mcluded for comparison. Fluid and bed cokes (WC-I to WC-4) have been extensively used m circulating fluidized bed combustors at cogeneration power plants. WC-2 and WC-3 fluid cokes 

### also represent export qualityto foreign countries. Fluid coke generated

### fiom a fluidized bed reactor is a solid, spherical particulate normalty smaller than 8 me& (98%for WC-2 and WC-3, and 74% for WC-4, as 

### shownin Table 1). The coke is very hard and abrasive, suitable for direct use m a circulating fluidiz,ed bed combustor, and generallyhave lower 

### HGI than delayed coke and cod Typical moisture content 

### is very low in the rangt of 0.3to 1.2%except for export cokes having 7-11.5% which increased to control dus! during transportation. 

### Sulfur content for fluid cokes, WC-1, WC-3 and WC-4, 

### is low mthe range of 1.0 to 2.1%; and WC-2 coke 

### has medium 

### sulfur with 3.3%, somewhat 

### lower than other delayed cokeslisted in Table 1 (4-6%). 

### A& content 

### ofWC-1 and WC-2 cokes 

### is very low m the range of 0.35to 0.46%, and WC-I and WC-2 cokes have a 

### little higher ash fiom 1.1 to 1.5%. 

### These ash values 

### are significantly lower comparedto coals (9.2-lo%), which 

### is normally claimed as an advantage as heL Calorific value for all fluid cokes studied 

### is 

### medium m the range of 14,200-14,400 Btuilb 

### (dry basis), relatively 

### high compared to coals (12,600-13,400 

### BWlb 

### dry basis). Volatile matter content 

### is low in the range of 2.5 to 6.1% for 

### all fluid cokes, compared to delayed cokes (9.5- 13%) and coals (40.2-41.1%). Power plant startup is easier with fuels having higher volatile matter. However, serious operationalproblems m burning petroleum cokes as 100% or 10-20% blend mix have not been reported. Fluid cokes, WC-2, WC-3 and WC-4, have relatively low nitrogen content m the range of 1.4to 2.2%,while WC-1 has a higher nitrogen of 3%, 

### similarly ,observed with 

### some delayed cokes (2.8-3.2%). Coals evaluated for 

### this study have a low nitrogen of 1.2to 1.5%. 

### Vanadium content for WC-1 and WC-2 

### is medium m the range of 650 to 850 ppm, near concentrationused m the cement 

### kiln fuel mix (530-760 ppm for SW/MW-1 and SW/MW-2), but higher than that for good anode-grade cokes (270-400 ppm). WC-3 and WC-4 cokes show the highest 

### V content 

### in the range of2300 to 2900 ppm among petroleum cokes and coals evaluated for 

### this study. Detrimental affects with 

### this 

### high V content (as much as 10,000ppm) have not been reported m the operation of 

### steam generating combustors [12]. 

### Sodium content for WC-I andWC-2 cokes 

### is low mthe range of 80 to 180ppm, which 

### is 

### similarly observed m good anodegrade sponge cokes (25-200 ppm). WC-3 and WC-4 cokes have a higher Na content of 480 to 500 pprn compared to WC-1 and WC-2. 

### Most of delayed cokes studied have a low Na content (50-160 ppm) except forWC-5 and WC-E4 (380-450 ppm).



### Six delayed cokes m Table 1 (WC-5, SWm-I, SW/MW-2, SE, SUGC, E/MW) have been used as 

### fuel blend mix m pulverized coal combustors for steam generation and cement 

### kilns. These cokes are 

### &el grade, green (raw) cokes with high ash, 

### high sulfur and 

### high metal content ranging spongeto shot coke. Typical ash content 

### is m the range of0.25 to 0.65%;

### sulfur content in the range of 3.1 to 6%; vanadium 

### fiom 530 to 1700 ppm; nickel ftom 190 to 600 ppm; and sodium ftom80 to 380 ppm Calorific value 

### is 

### high m the range of 15,000 to 15,580 

### Btu/Ib 

## (m, dry basis), producing more heat during combustion than fluid cokes and coals. 

### Size distribution covers wide range ofparticle

### size fiom-6

### mmto +40 

### mm dependingon 

### fines,lump or ROC 

### (run of coker) delivered &om refineries. Typical 

### HGI 

### is in the range of 35 to 60, mostly higherthan coal

### HGI (49,with shot content varying fiom 0 to 80%. Typical moisture content 

### is in the range of5to 9%, and volatile

### mattervaries fiom 9.5to 13%. Two delayed cokes, SW/Mw-1 and SW/MW-2 have been fiequentiy used in cement 

### kiln operation, as fuel mix (up to 50%). Typical 

### sulfur and vanadium content (controlled quality parameters for cement application)ofthese cokes vary mthe range of 3.1to 3.8% and 530 to 760 ppm, respectively. 

### Sulfur and vanadium content are higher than those required for good anodegrade sponge coke (3% and 400ppm, respectively).

Table 2 presents analysis results ftom eight export delayed cokes. 

### These cokeshave been mostly used as utilay 

### helscornbigwith coal to make fuel m processing industries. Fuel property data in the table update export quality analysis 

### ofpetroleum cokes previously reported [I I]. Export qualdy criteria 

### of green (raw), fuel-grade cokes are dependent upon buyer's requirements of coke specifications. 

### As shown m the following for west coast cokes, ptimary criteria hquentlyused
82

### L

\ 

## i

1 

# t

\ are: Size 

### distribution, moisture, 

### sulfur, a&, volatile matter, fixed carbon content and calorific value; and 

### secondary are: nitrogen, vanadium and sodium content. 

### In addition, complete ash mineral analysisis sometimes required to report. Ox6,OxlO 01 -2 & +25 Moisture, wt% 8-12,9-12 

### or 9 max 

### sulfur,wt% 1max, 2 

### max or 3 max Ash, wt% 0.5 max, 1 max or 1.5max VolatileMatter,wt% 9-13, 11-12.5 or 14 max Fixed Carbon, wt% 88-90 or 87 min HGI 45-50 or 50 min 

### Bdlb 15,000 min 

### Nitrogen, wt% Vanadium, ppm Soh PPm 

### b=wmx size,

### mm (drybasis)

2,253.5 or 2.9 max 500-800 or 700 max 200-300 or 700 max Eight delayed cokes 

### in Table 2 (WC-E1 to WC-E8) are produced 

### in relineries located 

### in west coast. 

### These cokes are good quality, fuel-grade green (raw) cokes, which generallyhave lower ash, 

### sulfur and metal content than six delayed cokes 

### in Table 1 used in domestic power generation. Typical ash content 

### is in the range of 0.18 to 0.45%;sulfur content m the range of 0.8 to 4%;vanadium6om270 to 1150 ppm; nickel fiom 180 to 550ppm; and 

### sodium 6om 50 to 450 ppm Calorific value 

### is high 

### in the range of 15,300 to 15,520 Btuilb 

### (HHV,

### dry basis), as 

### ely observed with delayed cokes m Table 1. Size distribution covers wide range of particle size fiom -6 

### mm (30-99%)with 

### hes, to +40 

### mm (3-47%) with 

### lump or ROC 

### (runof coker) dependingon delivery 60mreheries. Typical HGI 

### is inthe range of35 to 80,mostly higher than coal HGI (49,withshot content varying fiom 0 

### to 60%. Typical moisture content 

### is in the range ,of7 to 12%,andvolatilemattervaries fiom 10to 12.5%.

Table 3 

### summarizes analysis results &om five export westem coals (type I to 

### V). These coals sampled at the 

### LAXT are high volatile bituminous coals with low sulfur and 

### iron content. They areprimady produced in Utah and Colorado and used 

### as utdity

### fuelsfor power generation. Coal 

### quality specifications for export were previously reported [1

### I]. 

### primary fuel propehes 

### of coal are: proximate, ultimate, calorific value, HGI, 

### size distribution, ash mineral analysis and ash fusion temperatures. Typical ash 

### content of export western coals is high 

### in the range of 9.2to 10%; sulfur content 

### is very 

### low in the range of 0.45 to 0.6%. These coals are classified as western high volatile 

### bituminous coal, but have lignitic ash having more (CaWMgO) than ferric oxide [9]. F?imary constituentsof coal ash are silica (52.3-58.6%),alumina (11.6-21%) and lime (5-13.1%). Ferric oxide content m ash 

### is low 6om 4.4 to 5.9% compared to eastern bituminouscoal (20-30%); 

### sodium oxide content 

### is high fiom 1.8to 4.2%. Calorific value 

### is low in the range of 12,640to 13,360

### Btdb 

### (HHV,

### dry basis), compared to fluid cokes and delayed cokes 

### in Tables 1 and 2. Size 

### distribution showstop Size of 2 inches having 92-100%50

### mm x 0 

### mm and 11.6-33%2 

### mm x 0

### mm Typical HGI 

### is 

### in the range of 43 to 46. Typical moisture content is 

### in the range of 7.7 to 10.3%, andvolatilemattervaries~om40.2 to41.1%. Data for coal ash characteristicsused for selection offeed coal and boiler design criteria are also presented 

### in Table 3. 

### Ash and slag 

### Viscosity plot parameters are: silica ratio, base-to-acid 

### (B/A) ratio, Tzm and slagging mdex Foulingplot parameters are: 

### alkalies as sodium oxide and fouling index 191. Typical silica ratio ism

### the range 

### of 0.712

### to 0.828;

### BIA ratio fiom 0.2to 0.386;T,, 6om2,420to 2,760 deg 

### F; and slagghg index 

### is mediumto high m

### the range of 2,114 to 2,263. Typical 

### alkaliesas sodium oxide 

### is high 

### in the range of 2.5 to 4.5;and fouling mdex is high 6om 1.8to 4.2. Very low sulfur content

### with theses coals may lower corrosive ash deposits caused by reacting with 

### sodium,potassium, 

### aluminumand iron, but addition of

### high sulfur petroleum cokes as fuel mix 

### may maease corrosion reactions with 

### alkali metals. Coal type 

### El and V 

### with 

### high B/A ratio of 0.386 and 0.372 have low T,,, (2,420 and 2,450 deg F, respectively) meeting requirementfor operation ofslag-tap cyclone fiunace. 

### SUMMARY Various 

### &elproperties offour fluid cokes, fourteen delayed cokes and five export western coals were an+d and are compared for use 

### in power generation. Important fuel quality parameters (typical and range) are tabulated for comparison, using recent analysis data accumulated for the ,

83past two years (1997-1998). Primaryproperties evaluated are: heating value, sulfur, nitrogen, ash, 

### moisture, volatile matter content, hardgrove grindability index, Size disaibufon, and mineral analysis. In addition, coal ash characteristics

### such as silica ratio, base-to-acid ratio, ash 

### fusiility, alkalies, 

### TZJoI slaggingindex, foulingindex, etc. are discussed.
Petroleum cokes as 100%fuel or 10-20%fuel mix with coal have been used 

### in power generation without serious operational problems reported, even burning with some cokes of high vanadium content (1,000-3,200 ppm). Some cokes have high sulfur content up to 7%. high nitrogen content up to 3.5%, and low HGI down to 25 (for delayed coke). Typical sulfur content ofmost cokes studied variesin the range of 0.8to 4.1%; nitrogenvaries 

### in the range of 1.3 to 3.2%; and HGI vanes from 40 to 80 (for delayed coke),

### mostlyhigher than coal HGI (45). Petroleum cokes asfuel mix (up to 50%)have been used in cement 

### kiln operation. Typical sulfur and vanadium content (controlled quality parameters for cement application) of delayed cokes mixed m

### kilnvary mtherange of 3.1 to 3.8%and 530 to 760 ppm, respectively. Export delayed cokes are good quality, fuel-grade green (raw) cokes, which generally have lower ash, sulfur and metal content than delayed cokes

### used m domestic power generation. Typical ash content is in the range of 0.18 to 0.45%; sulfur content fiom 0.8 to 4%; vanadium fiom 270 to 1,150 ppm; nickel 

### fiom 180to 550pprn; and sodium

### fiom 50to 450 ppm Calorific value is 

### high in the range of 15,300to 15,520 Btdb(HHV,

### drybasis). Price of fuel grade petroleum coke is normally below 5 $/ton at refinery, however, transportation cost si&cantly increases the price at power plant (21 $/ton, 1996 

### annual average delivered). Demand and supply of petro(eum coke are dictated by three important factors such as refinery cost, coke quality and transportation cost. Location of refinery and power plant seems an important factorto be considered. Export westem coals are high volatilebituminous coals with low sulfur and iron content, and are used as utility

### helsfor power generation. Typical ash content 

### ishigh 

### in the range of9.2 to 10%; sulfur content 

### is very low in the range of 0.45 to 0.6%. 

### Ash 

### fiom these coals are defined as lignitic ash having more (CaDtMgO) 

### than femc oxide. Ferric oxide content in ash 

### is low 

### fiom 4.4 to 5.9% compared to eastern bituminous coal (20-30%); sodium oxide content 

### is high 

### fiom 1.8 to 4.2%. Calorific value 

### is low 

### in the range of 12,640 to 13,360 BMb (HHV, 

### drybasis), compared to petroleum cokes. Coal ash characteristics

### used for selection of feed coal and boiler design criteria are discussed relatingto slagviscosity, fouling, and corrosion. Coal fype 

### JII and V have low 

### TZ5@ meetingrequirementfor operation ofslag-tap cyclonefurnace.
The SUFCO Utah coal, one ofhe export 

### westem bituminous coals evaluated for 

### this study, was extensively tested at several gasification demonstration plants for IGCC systems m addition to variety ofpetroleum cokes asfeed materialto gasifiers.


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VOL38,NO.4, 1237-1244 (1993).

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88Table 3. FUEL PROPERTIESOF EXPORT WESTERN COALS USED IN POWER GENERATION

a9