INVESTIGATION OF BONDING MECHANISM OF COKING ON SEMICOKE FROM LIGNITE WITH PITCH and TAR

Assoc. Prof. Dr. Vedat ARSLAN Dokuz Eylul University Engineering Faculty Mining Engineering Department, 35160 Buca, Izmir, Turkey. e-mail: vedat.arslan@deu.edu.tr

ABSTRACT In coking, bonding ability of inert macerals by reactive macerals is dependent upon various parameters and also related to the wettability of inert macerals. In this study, the effect of carbonization temperature on the wettability of semi cokes produced at various temperatures has been investigated. Soma and Yataan semicokes represent inert macerals and pitch was used as reactive structure in the experiments. The briquetted pitch blocks were located on the semi cokes and heated from the softening temperture of pitch (60oC) to 140oC for observing wettability. In addition, liquid tar was also used to determine wettability of semi cokes. From the point of wettability the temperature of 900OC was found to be the critical point for coke produced from sub-bituminous coals.

Keywords: semicoke, surface wettability in coking

1. INTRODUCTION Coals having 18% to 38% volatile matter in dry ash free (daf) basis can be used in classic coke making process. Other processes especially briquette charge methods and form coke methods can widen the coal range.1, 2, 3, 4 However using high volatile coals in metallurgical coke production has caused several problems. Especially, using high volatile bituminous coals and sub bituminous coals in coal blends for making metallurgical coke, parameters that have to be taken into account have changed. In coking process reactive macerals are softened and fluidized between 350 and 500oC and these liquefied materials can bond inert macerals. Maceral types related with coalification are found to be very important for this bonding mechanism 5, 6, 7.

Main factors affecting the bonding mechanism during coking are fluidity of reactive macerals and surface wettability of inert materials. Fluidized reactive macerals spread on the inert coal particles forming coke walls between them. Insufficient wettability of inert particles can weaken the coke structure. Good wettability of inert materials and sufficient quantity of reactive macerals that cause caking of coal is necessary for strong coke structure 6, 8, 10.

Surface wettability in coking differs from the wettability of solid materials in liquids. There is no liquid phase in coking process. Thus, behavior of carbonized inert coal particles and fluidized materials are usually examined in coking9, 10, 11.

Wettability of carbonized coal surface by various oils (originated from fossil fuels) provides important data on coal coking properties. In coking, plasticity occurs between 350 and 500oC and reactive macerals are fluidized and swollen and they cover inert materials. At approximately at 500 OC, this matrix resolidifies again. The strength of this matrix (coke) is strongly dependent on the wettability of inert matrix elements. Decreased wettability of the inert materials necessitates more fluidity from the reactive macerals.10, 11, 12.

Wettability of inert materials is also important in the blends of coking coal. Generally, subbituminous coals are added in the blend in the form of semi coke. Semi coke is an inert substance in a blend for a strong coke structure; it must be well wetted by the fluidized reactive macerals. When reactive macerals do not posses enough fluidity, pitch is added to the blend for supporting the proportion of fluidized reactive macerals9, 13, 14.

For good bonding between the inert materials and fluidized reactive macerals, there must be a balance between the wettability of inert materials and fluidity of reactive macerals. Decreasing wettability should be compensated by increasing fluidity and also the amount of reactive macerals11, 12.

Kemal et al. tested a serious of coking coal and lignite blends and concluded that above 900oC coking temperature, the strength of coke and the wettability of lignite cokes were decreased. It was also deduced that these high temperature lignite cokes absorb more coal oil as pitch than normal carbonized coking coal9.

2. MATERIALS AND METHODS 2.1. Materials For the investigation of the bonding mechanism the coal pitch was used as reactive material in these tests. Two different lignite semi cokes obtained from 2 different pits were used as inert substances. These are Soma lignite and Yatagan lignite. Short analyses of these coals are presented in Table 1. Sample of Soma coal was taken from raw coal by hand sorting; therefore its ash ratio is very low. The moisture content is also low in air dried basis. Yatagan lignite sample was taken from the coal seam carefully as a clean part. Considering their general characteristics and analysis given below, Soma coal can be classified in the group of sub bituminous-A coal and Yatagan coal in the group of sub bituminous-B coal stated by ASTM standarts.

Table 1 The results of analysis of samples received from Yatagan and Soma coals. Moisture % (ar) Soma 10.38 Yataan 27.59 ar: as received Ash % (ar) Sulphur (dry) Volatile Matter. % (daf) 41.16 52.30 AID kcal/kg (ar) 5966 3604

1.72 1.12 6.45 1.26 daf: dry ash free

Due to high moisture ratio, Yatagan coal dries rapidly in atmospheric conditions resulting cracking. Yatagan coal sample was, therefore, preserved in the form of lumps. Coal pitch representing the reactive macerals was used to investigate the wettability of coke surface under various temperatures. Coal tar was also used to determine wettability in a

different type of tests. Characteristics of pitch are given Table 2. The tar used in these tests had %60 pitch ratio after distillation.

Table 2. The results ofpitch analyses used in tests. Moisture (%) Sulphur (%) Gross Calorific Value (kcal/kg) Density (g/cm3) Softening temperature (OC) 3 1,32 9662 1,18 60

2.2. Methods 2.2.1. Wettability Tests with Pitch In new coking technologies where noncoking coals are used in blends, coal is added to blend as carbonized coal. Soma and Yatagan coal samples were therefore carbonized separately a various temperatures from 100C to 1000C. In carbonization process with Soma coal controlled heating was used below 400C for hindering excessive fissure occurrence. This limit is 150C for Yatagan coal because of its higher moisture ratio.

For carbonization, the samples were heated in a drying oven with stainless steel box below 200C. Above 200C specially designed retort and jenkner retort were used. Nitrogen gas was used for producing inert atmosphere in the retort.

In wettability experiments, small pitch tablets about 1 gram each were prepared by a small hand press and they were placed on the top of the semicokes (Picture 1a). For every semi coke produced at various temperatures, 14 pieces were prepared for wettability tests. The tests were carried out at 7 different temperature intervals ranging from 60oC to 140oC. In these tests, pitch tablets were melted and spread on the surface of semi cokes. Due to fluidity, some melted pitch filled the cracks of samples depending on the wettability of the semi cokes.

Picture 1.a Melted pitch tablets formed at various oven temperature of 60C, 70C, 80C and 90 C.

Picture 1.b Melted pitch tablets formed at various oven temperature of 100C, 120C and 140C.

Semi cokes treated with pitch at various temperatures were taken from oven after 30 minutes cooled in atmospheric conditions and placed in polyester molds. These molds were then cut perpendicularly to form surfaces and they were polished for microscopic observation. A Leitz Wetzlar Orthoplan Polarized Light type microscope was used for observations (Picture 2).

Picture 2 Instrument used for computer supported investigation. 2.2.2. Wettability Tests with Tar For producing numerical values on surface wetting of semi cokes, a different type of wettability test was performed using only Soma coals. Semi cokes and cokes were produced at various temperatures (100oC to 1000oC) as before. After producing semi cokes and cokes, all samples were crushed under 2 mm by controlled crushing and sieved with 0.5 mm sieve to obtain 2-0.5 mm and -0.5 mm fractions. These samples were put into separate glass tubes of 10 mm diameter with their bottom covered with 0.5 mm sieve opening. They were dipped in the tar and maintained a contact for certain period of time. After a certain time, the tubes were taken out of the tar, cleaned and weighed.

3. TEST RESULTS 3.1. Results of Microscopic Observation

A system was prepared for detailed microscopic observations. A multimedia camera was placed on the top of microscopes ocular and images were transferred to a computer by a camera (Picture 2). Wetting of semi coke surfaces by heated pitch were investigated on the monitor of the computer. All results were evaluated by observing about 400 images. Some interesting sample images (Pictures 3 a, b, c, d, e) and their evaluation are given below.

Explanation of the samples. S 400 100b S Coal name

400 Carbonization

100 b Reheating temperature Sequence number of image of semicoke and pitch on the same sample

(S:Soma, Y:Yatagan) temperature(OC) k: represents coal, z.: represents pitch.

Picture 3 a) S 400-100b

Picture 3 b) S 800-120c

Picture 3 c) Y 400-100a

Picture 3 d) Y 1000-14a

Picture 3 e) Y 900 -120c

In the first step, the structure of fissures occurring during the carbonization process was examined. Next, the contact structure between semi coke surfaces and melted pitch were observed. Spreading conditions of the melted pitch on the semi coke surfaces and the tendency of melted pitch to fill the fissures and cracks were investigated. The results of macroscopic and microscopic observations are evaluated below; The behavior of Soma and Yatagan coals shows different carbonization characteristics due to their different coalification degrees. It was observed that during the carbonization temperature of Soma coal up to 500oC, few fissures were occurred. Increasing the carbonization temperature resulted in macro fissures, further heating caused enlarging these cracks. In the case of Yatagan coal, crack occurrence started at 300oC and above this temperature semi cokes broke easily and more surface area were occurred. As a result of these observations, it can be concluded that semi cokes produced from these coals

require more reactive macerals in the blend because of unfavorable increase in their specific surfaces. Strong coke structure is primarily related to the ability of wetting the inert materials by melted reactive macerals. It was also observed from the experiments that wetting of semi cokes of both type by the heated pitch was well accomplished especially above 100oC. A decrease in wettability of semi cokes of Soma coals was noticed by 900 0C carbonization temperature. This critical temperature therefore, should be watched in making metallurgical coke with blends of Soma semi cokes. In the case of Yatagan semi cokes, wettability decreased at 400 0C, for semi cokes produced above 5000C fluidized pitch easily entered in to the cracks indicating an increase on the wettability of semi cokes. It can be deduced from the experiments and observations that coalification is an important parameter for the surface wettability of the carbonized coal. If semi cokes are to be used in blends for metallurgical coke production, original coalification of the semi cokes becomes important for the resulting coke strength. During carbonization, more pores and cracks were observed with temperatures above 500oC. Fluidized pitch could penetrate into small cracks as fine as 25 microns on the semi cokes with well wettability. During the process of heating semi cokes with pitch, new cracks developed especially in the semi cokes produced below 500oC carbonization temperature. Therefore the final metallurgical cokes obtained from such blends will probably develop weak coke structure due to the new cracks occurring in semi cokes.

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3.2. The Results of Investigation of the Semi Coke Surface Wettability with Tar The result of these tests performed with semi cokes of 2-0.5 mm fraction is given in figure 1. As seen from the figure, at the initial 3-4 minutes periods, semi cokes and cokes absorbed tar rapidly in different ratios. Initial maximum tar absorptions were seen in semi cokes produced at 500oC and 1000oC , minimum initial absorptions on the other hand took place at 100 0C, 300 0C and 800 0C. Tar absorptions ratios were decreased after 4 minutes from the beginning of the test and eventually stopped after about 1 hour.

The same procedure was carried out with semi cokes below -0.5 mm fractions. By evaluating these results (Figure 2) similarly, it was seen that, the results were very close with the previous tests, except with a slight decrease in the total absorbed tar. In figure 3 the results of previous tests are combined to see the effect of carbonization temperature on the wettability of semi cokes. It is clear that there is no linear correlation between the carbonization temperature and wettability. But, it can be seen that, wettability changes with the carbonization temperature. The results showed that, two important zones appeared on figures. These are the intervals of 300-400 0C and 800 0C carbonization temperatures. The wettability of semi cokes produced at these temperatures decreased rapidly. On the contrary the wettability of semi cokes produced at the temperatures of 200 0C, 600 0C and 1000 0C were better than the others.

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6 2-0,5 mm 5 4

100 C 200 C 300 C

Adsorbed tar (%)

400 C 3 2 1 0 0 10 20 30 Time (minute) 40 50 60 1000 C 500 C 600 C 700 C 800 C 900 C

Figure 1 The results of wettability tests performed with semi cokes of 2-0.5 mm fraction with tar.

6 0,5- 0 mm 5 100 C 200 C 300 C Adsorbed tar (%) 4 400 C 500 C 600 C 2 700 C 800 C 1 900 C 1000 C 0 10 20 30 Time (minute) 40 50 60

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Figure 2 The results of wettability tests performed with semi cokes of 0.5 - 0 mm fraction with tar.

6 5 Adsorbed tar % 4 3 2 1 0 0 200 400 600 800

o

2-0.5 mm fractions 0.5-0 mm fractions 1000 1200

Carbonization temp C

Figure 3 The results of wettability tests with tar.

4. CONCLUSION The results of this investigation with two types of coals showed that young coals like Yatagan coal have more risk than the coals like Soma for using in the blend as semi coke to produce strong metallurgical coke. In carbonization of Yatagan coal, higher surface area, porocity and cracks were observed. Semi cokes produced from Yatagan coal in low carbonization temperature will show more shrinking stress when subjected to high temperature carbonization in blends for producing metallurgical coke. As a result, the coke strength will be negatively affected.

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Tests performed with both tar and pitch showed that about 900 OC carbonization temperatures are critical for wettability of semi cokes derived from Soma coals.

In this study, some data about wettability of inerts in coking mechanism was obtained. The effect of coalification on the new surface area development and resulting increase in the requirement of the reactive maceral was also investigated.

The results of this study clearly show that, classical reactive/inert ratio is not always sufficient in the calculation of the coke strength. The origin of the inert material should be considered, especially in the utilization of high volatile coals.

Currently in Turkey, metallurgical coke production is directly obtained from coking coals by classical method. As practiced through the world form coke methods, which utilize the addition of certain amount of non-coking coals in the metallurgical coke production might be a new choice for Turkish iron and steel industry in the near future. In the form coke processes the wettability of semicoke briquettes is utterly important in deciding the strength of cokes to be produced. It is hoped that the present study will shed some light on the form coke production method.

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13. Maroto-Valer, M.M., Andresen, J.M., and Snape, C.E.; In situ IH NMR study of the fluidity enhancement for a bituminous coal by coal tar pitch and a hydrogen-donor liquefaction residue, Fuel, Vol. 77, N.9/10, 1988. pp. 921-926 14. Bujnowska, B. and Collin G.; Co-carbonization of coals with coal-tar pitch. Cokemaking International, Vol.6, No: 2, 1994. pp 25-32. 15. Hower, J. C., Lloyd, W. G.; Petrographic observations of Gieseler semi-cokes from high volatile bituminous coals. Fuel, Volume 78, 1999. Number 4, pp. 445-452

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