COAL CARBONIZATION: CURRENTAND FUTUFIE APPLICATIONS

R Menendez and R Ahrarez.

Instituto Nacional del Carbon y sus Derfvados.
"Francisco Ptntado Fe" (CSIC).Apartado 73.33080 Ovledo. Spain.

INTRODUCTION
Carbonization is deflned as 'The destructive distillation of organic substances in the absence of
air. accompanied by the production of carbon and liquid and gaseous products". The coke
produced by carbonization of coal is used in the iron and steel industry and as a domestic
smokeless fuel.

Only a llmlted range of coals produces acceptable metallurgical cokes. These coals are in the
bituminous rank range but not all bituminous coals are caking coals. Prlme coking coals are
expensive and not always available nationally. It is predicted that remaining indigenous coals
available for coke making are poorer in coking quality (1). In addition. coke ovens need to be
rebuilt and , in most parts of the world. proflts from the steel and iron business are Insumclent to
.
provide the necessary capital. In future years we will have to extend our technology even further
and flnd new blends or raw materials and optimum operating conditions in order to reduce costs.
This will only be possible with a better understanding of the fundamental aspects of the coking
process. &. properties of coals and their functions in the coal-to-coke conversion. This
understanding is also necessary because of the gradually increasing stringency of requirements
made on coke by modem industrial practices. 1.e.maximum output with maximum elllclency.

In this paper. the authors attempt a preview of the future of coal carbonization from the
viewpoint of past and current experience.

COAL'PFIROLOGY
Greatest use of coal petrology has been made In the area of coke making. Most steel companies
have adopted petrographic relationships. based on coal rank (reflectance) and type (maceral
composition). for use them for preliminary evaluation of coals and for coal-blend design. Coal
macerals have their o w n carbonization behaviour. some of them, part of semifusinite and
most of the micrlnite and fusinlte. remain relatively inert whilst others, a. vitrlnite, resinite
and part of semifusinite, gasify, soften and become porous. hardening ultimately into coke (2. 3).
However, maceral behaviour is more complex than originally thought and a s Kaegi u. (4)
showed, they behave quite dmerently depending on what other macerals are in contact with
them. Quick u. (5) proposed the use of a tandem system of fluorescence and reflectance
microscopy for the recognition of reactive v i t m t e and lnertinite to provide a better assessment
of carbonlzatlon behaviour.

FWEOu)(;ICAL PROPERTIESOF COAL

Several tests are available to evaluate the sultabfllty of coals for coke production 16). C o w coals
become plastic when heated: consequently. a wide variety of tests have been introduced to
measure the plastic and swelling properties of coal (7). The most common are the free-swelling
index test to determine the agglomeratlng and swelling characteristics of heated coal, the
Gieseler plastometer for assessing the plastic properties and the Audibert-Amu dilatometer to
record volume change a s a function of time.

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CHEMlSTRY OF COAL CARBONIZ.ATION
A sigdicant development in understanding carbonization processes was made with the
discovery of mesophase in the plastic stage of carbonlzation leading to graphitizable carbons, as
observed by optical microscopy (8). The development of spherical mesophase particles (Figure 1)
from an isotropic mass and their progressive growth and coalescence eventually to form
anisotropic structures is well established for pitch-like precursors (9-11). Essentially. during the
carbonization process. dehydrogenative polymerization of aromatic molecules occurs, with a
consequential increase in average molecular weight (12). The final coke structure (Figure 2) is
related to the properties of mesophase at the time of solidification and these, in turn. are
dominantly dependent upon the chemical properties of the parent material. Coke quality
improvements are dictated by the quality of the parent feedstock which predetermines the optical
texture of the resultant coke.

In contrast to pitch-like materials, carbonlzation of coal produces mesophase in the form of very
distorted spheres which do not show observable coalescence because of their high viscosity.
These differences In behaviour could be attributed to inhibiting effects of elements such as
nitrogen. oxygen and sulphur and to the influence of particulate inert matter in the coal (13).

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COMMERCIAL CARBONIZATION
The coals selected for blending for blast furnace coke give the highest coke physical strength with
acceptable chemistly. acceptable reactivity and at a competitive cost. The coke must contract
sufficiently for easy removal from the oven and swelllng pressures must be acceptable.

The chemical composition of coke can be controlled within desirable llmits by coal selection and
control of carbonizing and quenching conditions (14). The desirable physical properties of coke
are less defined in that furnace operation is still not completely understood. The physical quality
of coke is usually defined in terms of its she and by empirical parameters representative of its
resistance to breakage and abrasion. The classical strength tests (shatter test or drum tests,
Micum. Irsid) are size dependent and it is difficult to derive relationships linking the results of
one test to another (15).

Conventional strength indices are being supplemented by new coke heating procedures which
provide a better simulation of the behaviour of coke in the blast furnace. These include various
"solution loss" reaction tests and hot strength tests (16). A major objective of modem coke
making is to Improve the properties of coke at high temperatures, especially its strength aRer
reaction with C02 and its reactivity (17. 18). Table 1 shows the BSC coke specifications for large

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blast furnaces. Many tests have been developed to measure coke reactivity and a large and diffuse
amount of literature is available on this subject. A synoptic report describing the high
temperature properties of coke has been published by the Commission of the European
Communities (19).

It is established that some coals can damage coke oven walls because of either excessive pressure
developed during carbonization or insufficient coke contraction at the end of the coking process.
This problem has lately become a matter of importance due to coal preheating and the widespread
acceptance of tall batteries which increase the bulk density of the coal charge. so decting coking
pressure. contraction and coke oven life. The Spanish National Coal Institute (INCAR) has

264
developed (20)a laboratory method of predicting expansion and contraction behaviour during
carbonlzation. based on a modincation of the early Koppers laboratory test.

&diction of cokine urouerti@

Much effort has been made to predict coke strength based mainly on measurements of vitrinite
reflectance and maceral analysis. These predictive techniques have two common premises: 1) for
any glven coal there Is an optimum blend of reactives and inerts which will give the best coke, ii)
percentages representlng this optimum blend or ratlo vary with rank. Different approaches have
been followed in terms of analysis and treatment of coke conditions and of the particular index of
coke strength determined (21-23). The Japanese assessed the suitablllty of a single coal to be used
In a blend from maximum fluidity values and Ro (24).CRM Belgium developed a new prediction
method (25)applicable only to the conventional wet charge process which relates coke strength
indices to inert content of coal, caking ability of the reactive components and the maximum
Gieseler fluidity of the blend.

Predictions for volume charge and carbonization pressures based on petrographic data have also
been formulated.

CURRENT COKING TECHNIQUES

As mentioned before, producers of metallurgical coke are experiencing a shortage of prime coking
coals and suitable high volatile coals at a time when more stringent coke quality demands are
being made as iron is being produced in larger, faster-driven blast furnaces. The conventional
wet charglng process of making good quality coke is very dependent on coal quality. To solve this
problem several techniques have been tested.

P
The aim of this process is to produce metallurgicalcoke of good quality by adding reformed non-
coking coal or petroleum heavy residue to coal. This technical approach does not produce any
particular problems in the coking process itself and Its success depends upon maklng inexpensive
binders. Major binder manufacturing processes that have already been industrlalised or are in
the pilot plant stage are in Japan. Coal tar pitch has been found to be a satisfactory substltute for
medium volatile coking coal in blends in coke oven tests conducted in West Germany (26).

Selective crushing
It is known that selective crushing of many types of coal and blends can produce a n improvement
of coke quality (27)but commercial development has been obstructed by the non-avaflability of
suitable equipment to screen wet flne coal with large throughput. Nippon Steel Corporation has
developed a large wet coal screening equipment (110t wet coal/hour) which i s efficient and
commercially available (28).The process mlnimlzes the productlon of very flne coal particles
and, at the same time. selectively crushes inertinite-rich particles into smaller sizes than the
vltrinite-rich particles. In this way, the inertinite-rich particles are evenly distributed in the
coking blend, the bulk density is increased and coke quality is improved (29).

in
Briquette blend c o w process (BBCP) Is most commonly used in Japan a s a technique to use low
grade coals (301.Non-caking and poorly caking coals can replace coking coal gMng coke with a
suitable strength. However. blending conditions must still be optimized and briquette
manufacturingcosts reduced.

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Stamr, charfzlng
This technology is applied in China. Czechoslovakia, Poland, East Germany. Rumania, FTance
and West Germany. In India a plant is being built and the USSR recently decided to implement it.
This process has been used for many years in Europe to produce coke from hlgh volatile coals and.
at the present time it has been successfully incorporated into the new hlgh ovens (31). The coke
Oven feed is compacted in a stamping machine and is charged Into the ovens horizontally.
Stamping increases bulk density of the charge and improves coke strength,especially resistance
to abraslon.

Eormed coke
Formed coke processes (32-33) conslst of manufacturing briquettes from non-caking or weakly
caking coals which. after suitable carbonization. can be fed dlrectly into blast furnaces. Thls
avoids the construction and maintenance of expensive coke oven batteries. The briquetting may
be hot or cold and the binder Is usually a pitch. Several tests have been carried out in the blast
furnaces with formed coke replacing conventional coke b u t , at the present time, the process does
not have signincant appllcation.

Preheating
Preheating is a technique which substantially improves coke quality from low rank coals. It also
produces an increase in oven and battely throughput (as much as 50%for the lower rank coals).
Other advantages derived from the elimination of the water from the charge include more
uniform heating and a reduction in the thermal shock. Applications of preheating also provide
more effective smokeless charging. elimination of routine mechanical levelling and a decrease of
pollution during the pushing operation. These effects of preheating may be due to modifications I
of the plastic properties or possibly to a permeable plastic layer which allows tar and other
pyrolysis products to react with the coal (341.

The disadvantages of the preheating process are related to the ditriculties of handling fine hot
coal and the increased carryover of fines. Coking pressure during carbonization must also be
closely controlled and. in general. coking batteries charged with preheated coals have more
technical problems (351.

DEVELOPMENT OF MODERN COKE MAKING ?ECHNOLOGY

In recent years, the productivity of coke ovens has been increased by using higher coking
temperatures. silica bricks with higher thermal conductivity and coking chambers of larger
volume. In past decades, the use of wide ovens was controversial because the correlation between
coking time and chamber width was not clear. In this respect, Bergbau-Forschung (BBF) carried
Out a large scale testing operation (36)in oven chambers of 450, 600 and 750 mm width in the
range of temperature of 1300-135OoC. It was assumed that the increase in residence t h e . at these
temperatures. was not significant and in any case It could be compensated for by increasing bulk
density. As a result. a n increase in productivity could be achieved by building wider oven
chambers. From this research. such plants were built in Germany and operational experiences
indicated that the operation of coke ovens with an eEective volume of 8Om3 and more. and a coke
production of about 50 t per charge is possible without too much rlsk.

However the controversy about coke ovens width still continues. Recently, Centre de Recherches
Metallurgiques (Belgium1 carried out coking tests in its experimental oven in order to determine
1
I

266
 the effect of chamber width on coke quality and on coke oven productivity (37). It was concluded
that it is malnly dependent upon coal blends used. With wider chambers. good coking blends
showed a n improvement in fissuring resistance. significant improvements in the abrasion
resistance indices and a n increase in the mean diameter of coke pieces. With poorly coking
blends. the mechanical strength indices and coke piece mean diameter decreased.

FUlURE OF COAL CARBONlZATION

From the above discussions it is evldent that, despite considerable effort, there is a s yet no
practical alternative to traditional coke making. Three different approaches to coal
carbonlzation may be adopted in the future: i) improvement of coke production by introducing
modifications. U) the building of a new coking system, M) the development of new carbon
materials with different specifications and new functions.

Improvement in eldsting technology Includes the construction of new heating systems which
reduce NOx formation. the automation of the coke oven battery and the use of computers to
control the working schedule. Automation could be extended to the characterization of coking
coal blends in order to save time. 1.e. techniques such as neutron activation elemental analysis
are being assessed (38).

The second approach. to build a new coking system, was taken Into consideration by the German
i coking industry. in collaboration with Ruhrkohle AG and BBF CmbH. They developed a new
concept in coke maklng technology on the basis of ecological problems, cost-effective production
of coke with high productivity and specilic output. To achieve this. some constraints must be
considered (39): maintenance of the present coke structure. establishment of independence from
the raw materials. minimization of the energy consumption. reasonable solutions to problems of
environmental protection. improvement of process control and monitoring and production of
by-products adapted to prevailing conditions. Noting these constraints. a research programme
called 'gumbo Coking Reactof' was developed (39).

From the studies carried out. the productivity would be hlgher than those currently operating.
The operation of only 55 reactors will be of major benefit to the environment. The length of the
sealing surfaces that require daily cleaning is 60% less than those for the large capacity ovens
that are now in service. The number of opening processes is reduced to only 110. agalnst 1200 in
one of the new German plants (Prosper). From the economical standpoint. this plant will reduce
the total coke costs by between 10 and 20%.

ALTERNATIVES TO COAL CARBONIZATION

One of the functions of coke In the blast furnace is to provide heat in the hearth of the furnace for
melting the reduced ore. In the mid-fifties oil was injected at the furnace tuyeres to provide heat
to the hearth and reduce the coke rate. When oil prices rose, a number of systems were developed
to Inject pulverlsed coal. 'At least 16 countrles have blast furnace coal injection systems. This
has been one of the most rapidly expanding iron-making developments world-wide (Figure 3) (40).

Ironmakers are now considering coal WJection to reduce the coke rateof blast furnaces. Reasons
given are: coal is cheaper than purchased coke: for those ironmaking plants which are
considering bullding or rebullding coke ovens. the capital cost of coal inJection equipment is less
I
than coke Oven plant: a wide range of coal types can be inJected including non-coking coals. Coal

267
injection results In smoother blast furnace operation with less hanging and slipping than the
comparable all-coke operations.

Injected coal can reduce the fuel and reductant roles of coke in the blast furnace but the provision
by coke of a solid permeable bed from stockhe to the hearth cannot be replaced by coal injection.
As coke rate reduces, the pressure drop across the furnace increases and It is thought that the gas
and liquid flow wlll decrease and, consequently. the iron production rate.

SPANISH APPROACH
The availability of coking coals in Spain is Ilmited. ENSIDESA. the most important Spanish
iron and steel industry has a coking coal consumption of about 3 x 106 t/year. 70-8046 is foreign
coal and only 20-3036 Spanish coal. The wide diversity of Spanish coal mines and the need to
import coking coal from all over the world causes major difficulties in coal blending.

ENSIDESA is using a very sophisticated blend of 15 to 20 different coals and owns a large yard for
coal blending and homogenizing with a handling capacity of 8.5 Mt/year and a stockpiling
facility of 800,000tons. To,predict the coke strength and to optimlze the blending from an
economical stand-point, a mathematical model has been developed and successfully applied by
ENSIDESA (41). The Spanish Research Council (CSICI has two Institutes for coal research. One of
them. the National Coal Institute (INCAR) has a n Experimental Coking Test Plant (Figure 4). The
battery contains four ovens. The oven dimensions are 2.8 m in height. 6.5 m in length and 300.
350. 400 and 450 mm. respectively, in width. The heating system is independent for each and
their capacity is 4-6 tons. INCAR co-operatesvery closely with ENSIDESA.

Some of the research carried out by INCAR Is related to coking pressure, preheating. coal
weatherlng effects on coke quality. coal blending and the use of dlfferent additives to improve
coke quality. INCAR h a s developed and patented (20) a laboratory method for predicting
expansion and contraction behaviour during carbonization. based on the Koppers laboratory
test. The Koppers-INCAR laboratory test was successfully applied to the problem of Spanish coals
which have dangerous swelling behaviour during coking. The contraction behaviour data
obtained are related to the chemical properties of coal. Is.volatile matter. mean vitrinite
reflectance and softening point. A 2 t / h preheating pilot plant, Precarbon process. owned by
ENSIDESA and built on line with the INCAR Coking Test Plant, is being used for preheating
research. It has been used to study effects of adding a high volatile coal and semi-anthracite to an
industrial base blend which had given good quality coke by the conventionalwet coking process
(42). Studies were also carried out on the effect of petroleum coke addition to coals with high and
low volatile matter content and the deet on the productivity and the pressure exerted during the
coking process. The improvement of coke quality from coals with a high volatile matter content
by using different additives is also being studied. It was observed that aluminium additions up to
3.0 wt% of aluminium considerably improved coke strength (43).

ACKNOWLEDGEMENTS
R.M. is grateful for support from the American Chemical Society to attend the April 1989
meetings.

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 REFERENCES
1. Elliot D.R (1971). Coke Oven Managers' Year-book. Mexbomugh. U.K p. 196.
1 2. Schaplro N.. Peters J.T. and Gray RJ.. (1962).Transactions of AIME. p. 1.
3. Schapiro N. and Gray RJ. (1966).A Guidebook for the Geological Society of America and
Associated Societies. Utah Geology and Mlning Survey,Salt Lake City. Utah, Bulletin 80,
P 55.
4. Kaegi D.D.. Valia H.S. and Harrison C.H. (1988).47th Ironmaking Conference
Proceedlngs, 47.p. 339.
5. Quick J.C. Davis A. and Lin R. (1988). 47th Ironmaking Conference
Proceedtngs.42.p. 331.
6. Zimmerman R.E. (1979). Evaluating and Testing the Coking Properties of
I Coal. Miller Freeman. San Francisco.
7. Brewer RE. (1945). Utlllzation of Coal, vol. 1. p. 170.
8. a,
Tay1orG.H. (1961).Fuel. 465.
9. Davis A,. Hoover D.S..Wakely L.D. and Mitchell. G.D. (1983).J. of Microscopy.
m, 315.
10. Menendez R. and Marsh H. (1987). F'yrolysis of Pitch Materials, Colloque
International du C.N.RS.. Metz (France) Fuel Procesing Technology. To be published.
11. Marsh H. (1973).F u e l s , 205.
12. G r e w R A. (1986). a.
Carbon 677.
13. Patrick J.W. (1975). The Coke Oven Managers' Year Book. Mexborough. U.K. p. 201.
14. Graham J.P. and Wilkinson H.C. (1978).AIME 37th Ironmaking Conference.
Chicago, p. 421.
15. BCRA. Investigation Report, 27. 1976.
16. Nakamura N. Togino Y. and Tateoka T. (1977)."Coal. Coke and the Blast Furnace.
The Metals. Society. London. p. 1.
17. Nakamura N.. Toglno Y. and Adachi T.. (1977).ibld. p. 93.
18. BCRA Annual Report 1978.p. 17.
19. Wilkinson H.C. (1986).Commission of the Euopean Communitles.Technica1
coalResearch EUR 10430EN.
20. Procedimiento o sistema para evaluar el empuje de 10s carbones. Patente No.
524.258.1983.
21. Schapiro N.. Gray R.J. and Eusuer G.R. (1961). AIME Proceedings. Blast
Furnace. Coke Oven and Raw Materials Conference, Vol. 20,p. 89.
22. Simonis W.. Gnuschke G. and Beck K.G. (1966).Gluckauf Forsch.-H. 27. p.
105.
23. Steyn J.G.D. and Smith W.H. (1977).Coal, Gold and Base Minerals. September.
24. Miyazu T.. Okuyama Y., Suzuki N.. Fukuyama T. and Mori T. (1975).Nippon
Kokan Technical Report-Overseas, December. p. 1.
25. a,
M U M I XR (1984).lronmaklng Proceedings p. 19
26. Rohde W. (1983). Gluckauf 119.no. 18,Trans. p. 25.
27. Burstlein E. (1971). Revue de Metallugie. Janvler. p. 39.
28. Yamaguchi T. (1980).68th Tech. Meeting on Coke Making. The Fuel Society
Of Japan, April.
29. Matsouka H. (1980). Seminar Rourkela Steel Plant and Indian Institute of
Metals, September.
30. Yoshinaga M. (1976). Ironmaking Proceedings. Vol. 35.p. 256.
Fuel Processing Technology. z. 91.
1
31. Leibrock K and Petak H. (1983).

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32. Warren LH.(1980). CIM Bulletin. January.p. 147.
33. United Nations. Economic Commission for Europe. Coal Committee
ECEfCoalf32.12 April,, 1978.
34 Gray R.J. (1988). Short Course: Introduction to Carbon Science, Newcastle
upon w e . September 12-16th.To be published by Buttemorths.
35. Guerin J.P. and Ebwness M.M. (1984). Ironmaking and Steelmaking. Vol. 11. no. 4. p. 186.
36. Rohde W. (1986), lronmaldng Proceedings. 113.
37. Munnix R.. Steyls D. a n d Vidal R. (1988). 47th Ironmaking Conference
Proceedings. 47. 145. ,
38. Taylor R and Massey W. (1988). Coke Oven ManagersYear Book Mexbomugh U.K. p. 152.
39. Nasham G. (1987). 1st International Cokemaking Congress. Essen. Vol. 1. A2.
40. International Iron a n d Steel Institute Committee on Technology. Techco-20.
AprU 26. 1988.
41. Sirgado M. and Verduras J.L. (1978). International Iron and Steel Congress,
Chicago, p. 404. I
42. Alvarez R (1987). 1st International Cokemaking Congress. Essen. vol. 1. E5.
43. Menendez R. Alvarez R. Miyar EA. Canga C.S. and Marsh H. (1988).Carbon 88. Institute of
Physics. Brlstol p. 522.

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I
I
F i g u r e 1. Mesophase development from F i g u r e 2 . O p t i c a l m i c r o g r a p h of p o l i s h e d
isotropic pitch material. s u r f a c e of a m e t a l l u r g i c a l coke.

Blast furnaces with

coal injection
60'

I
40.

L &dddf
20
20.

ke
1980 1982
1984

Year
Ii
986 1988

F i g u r e 3. Development of c o a l i n j e c t i o n . F i g u r e 4. INCAR Coking T e s t P l a n t

(Oviedo, S p a i n ) .

, T a b l e 1. The new BSC s p e c i f i c a t i o n f o r

l a r g e b l a s t furnaces (18).

Mean size 50 nirn

Size range 30-75mni
Japanese DI :io a82
Japanese reactivity 6 30%
Japanese post-reaction strength 253%
Ash. d.b. e 10%
Sulphur. d.b. e1.1%
h140 niicuni index 380
I
All0 niicuni index e7
Extended-mirum slope c0.8
/

I 271