PHASE CHARACTERIZATION OF UNMODIFIED

PETROLEUM COKE AND COAL GASIFICATION SLAGS

Mihi S. Najjar
Texaco Research Labs at Beacon (TRCB), P. 0. Box 509,
Beacon, N Y 12508
John C. Groen and James R. Craig
Department of Geological Sciences, Virginia Polytechnic Instituteand State University
Blacksburg, VA 24061-0420
Keywords: coal-ash,petroleumcoke, slag, phase characterization
ABSTRACT
The slags produced in gasifiers using petroleum coke as a feedstock differ compositionally
and texturally from the ash and slag formed during combustion of coal. Hence, the chemical and
slagging behavior of petroleumaike ash under gasification conditions must differ markedly from the
behavior of coal ash. Whereas the latter is reasonably well understood, the former has been much
less well studied. The present work is pan of an ongoing study aimed at understanding the physical
and chemical characteristics of the phases formed in the slags that are produced during petroleum
coke gasification.
INTRODUCTION
The partial oxidation of liquid hydrocarbonaceous fuels such as petroleum products and
slurries of solid carbonaceousfuels such as coal and petroleum coke to form alternative fuels is now
a common practice. An evolving trend in the feedstocksfor such processes is that they are becoming
increasingly heavy and of poorer quality. To compensate for this a n d , refiners must employ more
"bottom of the barrel" upgrading to provide the desired light products. The current industry
workhorse to provide this upgrading is some type of coking operation (either delayed or fluid). A
good deal of c m n t refinery expansion includes the installationor expansion of coker units, and this
coking will be a process of general use for some time to come.
The production of light hydrocarbon fuels from coal or petroleum feedstocks results in the
formation of ash or slag which concentratesmost of the contaminantsoriginallypresent in the coal or
petroleum. Coals contain significant amounts of clays, quartz, pyrite, and carbonates, along with a
broad range of less abundant solid mineral phases (Jenkins and Walker 1978). Petroleums contain
less solid mineral matter but may contain significant amounts of other contaminants such as iron,
nickel, vanadium and sulfur. Consequently, the residual concentration of elements is significantly
different depending upon the feedstock materials. The resulting phases affect gasifier operation and
the ultimate use or disposal of the ash or slag.
PROCESS DESCRIPTION
The Texaco Gasification Process is a partial oxidation reaction to produce mixtures of CO
and Hz,known as synthesis gas. A carbon containing feedstock is reacted with a controlled, sub-
stoichiometric quantity of oxygen in a fuel rich, exothermic reaction. The process is carried out in a
pressurized reaction chamber with the temperature maintained above the melting point of the coal or
petroleum-cokeash, thus making a slag (molten ash), by controlling the individual feed rates of the
reactants. The feeds are introduced together, through the top of the gasifier, and pass through it
concurrently with the product gases transporting the solids, making it an entrained flow gasifier. It
is fundamentally a simple system that leads to high reliability, and it can be adapted readily to fit
many applications economically.

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 The chemical reaction path is quite complicated, and includes many simultaneous and
sequential reactions such as devolatilization, combustion and interactions between the feeds and
intermediate or final products. The chemisuy is depicted in a schematic sense in Figure 1. The
conversionof feedstock slurry to synthesis gas is normally in excess of 95% and can be over 99%.
The use of coal as a feedstock, either in direct combustion or as a gasifier feedstock results in
most of the ash being converted to slag, a nearly carbon-free, inorganic material. After water
quenching, the slag is normally a glass-like solid, with a maximum size of one-half inch. In all cases
evaluated to date, the slag from coal gasification, including the fine fractions that are co-mingledwith
carbon-rich char, have been classed as a non-hazardouswaste.
The high temperature gases, char and molten ash, or slag, produced in the gasifier are nor-
mally cooled prior to cleanup, by either of two methods: quenching, Le., direct contact with water,
or indirect heat exchangeto make high pressure steam in a special syngas cooler.
The molten slag is cooled with the gas and is collected in a water pool either in the bottom of
the radiant cooler or in the quench vessel located under the gasifier. The slag is removed from the
system by means of a water-filled lockhopper system. The carbon-rich char can be disposed of with
the slag or separated for recycle.
The cooled gas is scrubbed with water to remove the remaining fine particulates. Following
particulate scrubbing, gas purification is completed by sulfur removal. A variety of subsequent
processes can then be used, with the choice made to fit the overall project needs. The cleaned gas
can be used for many purposes, such as fuel for power generation or process heat, synthesis of
ammonia or other chemicals, or as a reducing gas.
SAMPLE PREPARATION AND ANALYSIS
The slag samples examined in this study occur both as fragmental materials that are dis-
charged routinely from the gasifiers and as solid incrustations that build up on the interior walls of
the gasifier. Megascopically,most samples appear as dark brown to black, porous to solid, irregular
masses ranging from less than one-fourth to more than several inches across. The samples removed
from the gasifier walls are commonly layered, apparently reflecting episodic buildup.
Representative portions of slags were cast in a low viscosity, cold-setting epoxy resin.
Porous samples were vacuum impregnated by placing them in a vacuum desiccator in which vacuum
was alternated with normal air pressure. This procedure removed trapped air and forced the epoxy
into pores and cracks. Samples were then polished using standard techniques employed for optical
microscopy and electron microprobe analysis as described in Craig and Vaughn (198 1).

GASIFIER SLAGS
Characterizationof slags produced in gasifiers is important in determining the ultimate use
and/or disposal of the slags. Furthermore, a prior knowledge of the nature of the slag phases is
necessary if it becomes desirable to alter slag properties that adversely affect the operability of gasi-
fiers. To these ends, we have been canying out investigationson the physical and chemical proper-
ties of slags produced both from coal and from petroleum coke feedstock. The slags produced from
the different feeds are markedly different,as evidenced in the data presented in Table 1,2, and 3.
The conditions under which coal and petroleum-coke ash and slags form are similar in that
they all involve partial to full combustion. The principal difference is that direct combustion is
generally more oxidizing and hence will permit formation of more oxidized phases (eg. ferric rather
than ferrous phases). Coal bottom ash, fly ash, and slags have been examined by numerous
investigators in recent years as noted in Table 2 and by a wide variety of techniques (eg. Huggins
and Huffman, 1979; Weaver 1978; Voina and Todor, 1978; Eriksson et al. 1991). Typical coal ash
as noted i n Table 1 is rich in Si@ with major but variable amounts of Al2O3. Fe2O3, and CaO. Coal
slag are generally dominated by glass phases which, though highly variable, are always rich in Si02
and contain significant Al2O3. Some glasses are also sufficientlyrich in reduced iron to be referred
to as "ferrous glasses" (Huffman et al. 1981). The number and variety of other mineral analogous

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phases are considerable (Table 2) but often constitute only small proportions of the bulk material.
Furthermore, several percent unreacted or panially reacted carbon-char are commonly present.
The glass phases display flow, banding, indicating some flow of compositionally distinct
zones. Crystalline phases range from skeletal to fibrous laths (commonly mullite or anorthite; Hulett
et al. 1980; Huggins et al. 1981) to skeletal and cruciform spinels (Chen et al. 1986).
Petroleum-coke slags are also highly variable in composition but generally contain less SiOz,
less A1203 and less CaO but greater amounts of Fez03, VzOs, NiO and sulfur (included in "others"
Table 1). The iron and vanadium contents are reported as given by ASTM analytical procedures;
however, iron and vanadium actually occur in lower oxidation states in these slags. These gross
compositional differences reflect the nature of the source materials. Coals contain abundant included
clays and carbonate minerals, whereas petroleum contains less discrete fragmental mineral matter but
often contains significant amounts of organic sulfur and porphyrins that hold iron, nickel, vanadium,
and chromium.
A general result of these differences in composition is the fusibility of the ash. Typical coal
ash has initial deformation (ID) temperatures of 2120'-2140' F, softening temperatures (ST) of
2150"-2210°F, and fluid temperatures (IT )2250'-2430' F. In contrast, typical petroleum coke
of
ash remains undeformed and does not melt until temperatures exceed 2700' F.

PETROLEUM COKE SLAGS

The present study has concentrated especially on slags formed during gasifier operation using
petroleum coke without any additives to alter constituents or behavior, and are part of an ongoing
study to characterize the physical and chemical characteristics of such slags (Craig et al. 1990; Craig
and Najjar 1990; Groen et al. 1991).
The investigators have found that the slags formed, display a variety of textures and phases;
these apparently reflect differing locations and hence conditions within the gasifiers as well as
differences in the feedstock. In general, the types of slags may be summarized as (1) glass-rich, (2)
V-oxide rich, (3) sulfide-rich, (4) CaMgFe-silicate-rich. These no doubt represent end members of a
continuum, but most samples extracted from the gasifiers conveniently fall into one of these
categories. The total of the wide variety of phases that the investigators have found to date are listed
in Table 3. Below briefly described are each of the major types of slags noted above:
Glassv Slw - These generally range from black to brown glasses that occasionally exhibit well
developed flow textures evidencing their slow flow down the sides of the gasifier. Typically, they
contain significant quantities of very fine spherical iron sulfide droplets. The droplets greater than 1
mm in diameter appear to have been formed along with the glass. Finer droplets, down to less than
1 micrometer, appear to have formed primarily through exsolution on cooling. Glassy slags
commonly contain dispersed skeletal to cruciform spinels which also appear to have formed on
cooling as the liquidus boundary was intersected.
V-oxide-rich s l a a - These slags are relatively SiOz-poor and represent slag formation within the
gasifier where vanadium phases crystallize as relatively coarse crystals (-100 micrometers). The V-
oxide phases occur as interlocking laths with interstitial spinel crystals and droplets of glass and
sulfide-oxide intergrowths. The coarseness of the crystals and the absence of flow structures and
exsolution features indicate that the V-oxide phases were stable and forming directly under the
conditions of gasifier operation.
Sulfide-rich Slaes - Many chunks of slag consist primarily of intimate iron sulfide-iron oxide
intergrowths. The iron sulfide ranges from pure FeS (troilite) to Fel.,S (hexagonal pyrrhotite) and
the iron oxide is FeO (wustite). The intergrowths are symplectic in nature and are often so fine (1
micrometer and less) that they are barely resolvable with an optical microscope. The textures are
characteristic of the unmixing of phases from a homogenous melt on rapid cooling. Nickel may
substitute on a minor scale for the iron in the pyrrhotite and may, in nickel-rich areas, occur as Ni3S2
(heazlewoodite) or as (Fe, Ni)gs8 (pentlandite). The iron sulfide-iron oxide masses commonly
contain dispersed drop-like to cruciform crystals of free iron-nickel alloy. Also scattered throughout

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 the sulfide-oxidemamx are droplets of glass and euhedral to skeletal iron aluminum spinels which
may cowenpate significantamounts of vanadium and chromium
- These occur as local segregations within sulfide-rich slags. The sulfide
e%
%
t$%
%a$ Ca, Mg, or Si within its structure, hence these elements concentrate
sufficiently to form a variety of CaMgFe silicates.
SUMMARY
It is apparent that the differences in the bulk chemismes of the petroleum coke and coal slags
are reflected in the behavior and nature of the phases withiin each. The high silica and alumina con-
tents of the coal slags result in lower melting temperatures and the development of predominantly
glassy products. In contrast, the low silica and alumina contents of the petroleum coke slags,
coupled with high transition metal contents, result in the development of a variety of crystalline
phases. Most notable are aluminate spinel phases that concentrate iron, vanadium, chromium and
nickel, and sulfide-oxide intergrowths in which nickel becomes concentrated in both sulfide and
accessory alloy phases.
REFERENCES
1. Chen, T.T., Quon, D.H.H., and Wang, S.S.B.(1986) Compositions and micro structures of
furnace-bottom deposits produced from beneficiated western Canadian bituminous coals.
. Canad. Mineral. 24,229-237.
2. Craig, J.R. and Nadar, M.S. (1990) Elemental partitioning in Coke gasification slags. in
W. Petruk, et al. eds., Process Mineralogy M,The Minerals, Metals and Materials Soc.,
473-483.
3. Craig, J.R., Najjar, M.S., and Robin, A.M. (1990) Characterizationof Coke gasification
slags. in W. Petruk, et al. eds., Process Mineralogy IX,The Minerals, Metals and
Materials Soc., 473-483.
4 . Craig, J.R.and Vaughan, D.J. (1981) Ore Microscopy and Ore Petrography, Wiley
.hterscience, New York, 406pg.

5 . Groen, J:C., Craig, J.R.,and Najjar, M.S. (1991) Chemical phases in petroleum coke
gasificahon slag. Amer.Chem.Soc.Preprints Div. of Fuel Chem., 36,207-215.
6. Eriksson, T., Zygarlicke, C., Ramanathan, M.. and Folkedahl, B. (1991) Composition
and particle size evolution of Kentucky #9 Preprints Fuel Chem. Div.,
36, 158-164.
7 . Fessler, R.R., Skidmore, A.J., Hazard, H.R., and Dimmer, J.P. (1980) Composition
and Microstructure of a furnace ash deposit from a coal-fired utility boiler. Jour. Engin.
for Power 102,692-697.

8. Huffman, G.P., Huggins, F.E.,and Dunmyre, G.R. (1981) Investigation of the high-
temperature behavior of coal ash in reducing and oxidizing atmospheres. Fuel 60,585-
597.
9 . Huggins, F.E. and Huffman, G.P. (1979) Mossbauer analysis of iron-bearing phases in
coal, coke, and ash, in C. Karr ed.,Analytical Methods for Coal and Coal Products,
Academic Press,New York, Vol.III, pp. 371-473.

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10. Huggins, F.E., Kosmack, D.A., and Huffman, G.P. (1981) Correlation between ash-
fusion temperaturesand ternary equilibriumphase diagrams. Fuel 60,577-584.
11. Hulett, L.D. and Weinberger, A.J. (1980) Some etching studies of the microstructureand
composition of large alumino silicateparticles in fly ash from coal-burning power plants.
Envir. Sci. and Tech 14,965-970.
12. Hulett, C.D., Weinberger, A.J., Nonhcutt, K.J., and Ferguson, M. (1980) Chemical
species in fly ash from coal-burning power plants. Science 210, 1356-1358.
13. Jenkins, R.G. and Walker, P.L. (1978) Analysis of mineral matter in coal, in C. Karr ed.,
Analytical Methods for Coal and Coal Products, Academic Press, N.Y. Vol.lI, 265-292.
14. Quon, D.H.H., Wang, S.S.B., and Chen, T.T. (1984) Viscosity measurements of slags
from pulverized western Canadian coals in a pilot-scale research boiler. Fuel 63,939-
942.
15. Raask, E. (1982) Flame imprinted characteristicsof ash relevant to boiler slagging,
corrosion and erosion. Jour. Engin. for Power 104,858-866.
16. Voina, N.I. and Todor, D.N. (1978) Thermal analysis of coal and coal ashes, in C. Karr
ed., Analytical Methods for Coal and Coal Products, Academic Press, N.Y. Vol.I1,619-
648.
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oils, in C. Karr ed., Analytical Methods for Coal and Coal Products, Academic Press,
N.Y. V01.1, 372-401.

G AS IFI cAJI o N R EA CTIo N S c H E MAT I c

REA CTAN TS:
OXIDANT ( OXYGEN, 02 )
+
SLURRY COKE ( C,H,S, N, 0,ASH, H 2 0 )

PRODUCTS:
f co

TRACE cos
-
( 1 1OOOppm) : (CN-
Figure 1. Simplified schematic diagram of the partial oxidation reaction occurring in a
petroleum coke gasification.

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Table 1.' Typical ash composition in wt % of coal and
petroleum-coke generated ash.

Coal Petroleum Coke

Eastern Western T p A TypeB

52.1 42.0 4.4 40.6

15.4 25.0 . 1.5 9.6
7.3 20.9 23.0 6.3
17.4 9.5 7.5 1.4
3.7 -- 2.4
-- __ 20.9 14.0
-- __ 40.3 16.6
4.1 2.6 2.5 9.1
9.5 9.7 0.5 0.9

2120 2140
2150 2210 __ __
2250 2430 >2700 >2700

1798
I

1199
 t
..
-:s-_
f

1800
1801