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FuelVol. 75, No. 6, pp. 659-663, 1996 Copyright 1996ElsevierScienceLtd Printed in Great Britain. All rights reserved 0016-2361/96 $15.00+ 0.00

New materials by agglomeration of petroleum coke fines

Nilo Cornejo, Alberto Isidro, Juan C. Ruiz, Fernando Garcia, Inocente Gbmez* and Ignacio Covi&n*
Centro Nacional de Investigaciones Metal6rgicas, Avenida Gregorio del Amo 8, 28040 Madrid, Spain *Repsol Derivados S.A., Orense 34, 28020 Madrid, Spain (Received 27 October 1995; revised 19 December 1995)
The agglomeration process is of broad potential use in revaluing fine-sized petroleum coke wastes and waste products known as impalpable fines. These materials were agglomerated in a disc pelletizer with binding agents to obtain pellets with high carbon content, good reactivity and good consolidation in hot and cold environments. Pellets formed with the addition of carboxymethylcellulose and oven-dried at 100C possess adequate compressive strength and may be used as carburizers, e.g. in steel manufacturing. In steel melting tests the pellets had a high resistance to thermal shock. High levels of steel carburization were obtained, to a carbon content of ~6.1 wt%. Copyright 1996 Elsevier Science Ltd. (Keywords:petroleumcoke; agglomeration;carburizers)

The oil industry produces high-molecular-weight hydrocarbon wastes which are heat-treated at high temperatures, 600C, to volatilize the greatest possible fraction. The solid product of this process is known as green coke, which has a volatile matter of 10wt%. If green coke is calcined at high temperature, 1300C, calcined coke, which is almost free of volatile matter 1'2, is produced. The following waste products of petroleum coke arise: RF: Refinery fines of calcined coke, obtained by a drift process within the refinery. SF: Slag fines or foaming fines, from the sieving of green coke after grinding and drying. This product has a high volatile matter. The sieving process leaves this product with a coarse particle size. CC: Fines produced in the sieving of calcined coke. This product is of higher quality and contains less sulfur and volatile matter. IF: Impalpable fines from dust scrubbing in the dryers of the mills and the sieves. The generation of these fine fractions, mainly CC, has led to the development of a process of agglomeration and heat treatment which allows the fines to be used in favourable conditions as carbon additives or to be recycled in a calcining oven, producing pellets by coking or to be sold directly. It is sought to obtain pellets with a good degree of consolidation that is maintained at high temperature and with a low emission of gases, properties which are of interest in metallurgical applications as carburizing material in steel manufacturing (electric are furnaces) 3'4. It is also of interest to produce pellets with low ash and sulfur contents. Accordingly, the binding agents 5-7 that are used must comply with these conditions.

EXPERIMENTAL

Materials
Four samples of the fines described above were used. Their particle sizes and chemical characteristics are shown in Table 1. Refinery fines of calcined coke are the finest of the first three materials. These materials have low ash and sulfur contents. The following binding agents were studied 8'9. A. Carboxymethylcellulose (CMC) (Hoechst) and starch. These additives were used in an attempt to provide a good degree of consolidation in cold environments without increasing the ash content. B. Pitch. With this additive it was sought to obtain pellets which remained consolidated in both cold and hot environments. C. Oil (Extensoil-4). The aim was to achieve a degree of waterproofing that would allow storage of the pellets in all weather conditions.

Agglomeration trials
The samples were agglomerated in a disc pelletizer I m in diameter and 0.2 m deep. The green pellets were ovendried. Some of the dried pellets were subsequently heattreated in a reducing atmosphere (in a metallurgical coke bed).

Compressive strength testing

The resistance of the pellets was established by determining the breaking load under compression of a standard-size pellet. The compressive strength (CS) was recorded in kg/pellet. Pellets with diameters of 1015 mm were produced to facilitate the study of their mechanical properties.

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New materials by agglomeration of petroleum coke fines: N. Cornejo et al.

Table 1 Particle size distribution and composition of the petroleum cokes tested (wt%)

CS, kg/pellet

Type of fines Particle (am) >425 425-300 300-200 200-63 <63 Composition Organic C S Moisture Ash Volatiles

RF 3.8 2.7 6.0 37.5 50.2 98.0 1.0 0.1 0.3 0.5

SF 9.1 13.3 21.4 55.2 1.0 88.5 1.0 0.1 0.3 10.0

CC 0.3 22.3 26.4 48.0 3.0 99.0 0.3 0.1 0.1 0.5

IF 1.8 12.7 85.5 -

1GI

i4-.

i
4 i

IO0 200 Drying temperature, C

300

Figure 1 Effect of drying temperature on compressive strength of Table 2 Compressive strengths of RF pellets with CMC

pellets 5
Table 3 Compressive strengths of pellets of petroleum coke fines

Test no. Binding agent (wt%) CMC solid CMC liquid CMC total Extensoil Moisture content of green pellet (wt%) CS (kg/pellet) Green Dried at ll0C Cured Dried at 200C Dried at 300C

1 1.0 0.2 1.2 1.0 21.9 0.8 15.1 1.9 0.3

2 0.0 0.2 0.2 0.0 21.8 1.1 0.9 1.0 . .

3 0.5 0.2 0.7 0.0 19.6 1.1 4.4 4.3 . .

4 1.0 0.2 1.2 0.0 23.7 1.2 14.8 20.1 . .

2.0 0.2 2.2 0.0 25.0 1.3 25.5 26.0

Moisture content of green pellet (wt%) With 1.2wt% CMC RF unground SF unground CC unground IF unground CC ground 15 min CC ground 60min 10% IF+90% CC With 1 wt% CMC + 5 wt% pitch RF With 10wt% pitch RF
a

CS (kg/pellet) Green Dried (110C) Cured 1.20 0.30 0.16 1.40 0.21 0.43 0.20 14.8 3.2 6.3 6.9 12.0 16.0 8.0 20.1 9.1 10.0 14.5 10.9

23.7 21.6 27.7 22.5 22.2 22.5 22.3

. .

Steel melting tests

Melting tests using steel (F-151) with the addition o f carburizing pellets (obtained according to the formula established, 10% I F + 9 0 % C C with 1.2wt% C M C ) were carried out in an induction furnace at 1500C, maintaining these conditions for 20 min. F o r comparison, calcined coke p o w d e r was also used (size 0.5-1 mm). The following designations were used to identify the materials and carburizing treatments: initial steel material with low c a r b o n content molten metal with carburizing pellets on the surface o f the bath Pell-2: molten metal with carburizing pellets placed at the b o t t o m o f the bath Powd-1: molten metal with the addition o f coke powder p o u r e d on the surface Powd-2: molten metal with the addition o f coke powder placed at the b o t t o m o f the bath. F-151: Pell-l:

20.0 20.0

1.47 0.70

30.7 12.5a

0.5

Dried at 200C

with Extensoil shows that the presence o f the oil does not inhibit the consolidating effect. Consolidation can be achieved by oven-drying or by curing. Pellets cured at r o o m temperature show a similar degree o f consolidation to that obtained with oven-dried pellets. Owing to the characteristics o f C M C , these pellets are destroyed when submerged in water, and therefore must be kept in protected storage. The pellets p r o d u c e d tend to lose compressive strength when they are heated. At temperatures o f 100-200C C M C is destroyed and the compressive strength o f the pellets diminishes (see Figure 1). The oven-drying process reduces the a m o u n t volatile substances, whose release at high temperatures m a y lead to the destruction o f the pellet.

RESULTS AND DISCUSSION

Tests with carboxymethylcellulose Refineryfines (RF). Carboxymethylcellulose ( C M C )

was added to the mixture in solid form. The atomized water in the disc pelletizer contained a concentration o f 1 w t % C M C . In the first test the oil Extensoil-4 was added ( l w t % ) . The results obtained are given in Table 2. The more C M C was added, the m o r e the moisture content rose. It is seen that the addition o f C M C has a clear effect on the compressive strength o f the dry pellet. C o m p a r i s o n o f test 1 without Extensoil and test 4

Coarse raw materials (SF and CC). Tests were carried out with the addition o f 1.2 w t % C M C in conditions identical to those described above for refinery fines. The results are shown in Table 3. Calcined coke fines are the materials most difficult to pelletize. There is a considerable difference between the particle size o f these coarse products and that o f refinery fines, and therefore their compressive strength is low, 0.3kg/pellet c o m p a r e d with 1.3 kg/pellet for RF. Oven-dried pellets also have a low compression strength. Cured pellets have a greater compression

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New materials by agglomeration of petroleum coke fines." N. Cornejo et al.

coke is reground, to 16 kg/pellet. This may be due to a favourable mixing effect of the mill, as the CMC was added before regrinding.

.... ....

80*(2

100'~C

......... A. ........ 1 4 0 " C

CS, kg/pellet lo

,.7...,..,,. ''l ~...... ............ . ..........

30

60

90

120

Time, rain

Figure 2 Compressive strength at different temperatures and drying times

Mixture of IF and unground CC. The results (Table 3) for a 10:90 (w/w) I F - C C mixture demonstrate that it is possible to obtain similar CS values for the pellets to those obtained for the individual fines of the mixture. Figure 2 shows the CS of the green and dry pellets at several different temperatures (80, 100 and 140C). It can be observed that the compressive strength increased as the water content decreased during drying. A reduction in the compressive strength was obtained on oven-drying at 140C, possibly due to the fact that CMC starts to deteriorate at this temperature. Oven-drying at 80C was found to require > 120 min. The most suitable temperature for oven-drying was 100C. The dry compressive strength is in the region of the values obtained with the calcined coke fines and impalpable fines. The green strength is, rationally, an improvement on the value obtained with calcined coke fines. Final considerations. It has been demonstrated that the green strength of the pellets is dependent on the particle size of the coke fines. The highest green strengths correspond to pellets with impalpable fines, giving values of 1.4 kg/pellet, followed by pellets with refinery fines, with values of 1.2 kg/pellet. The value of the dry compressive strength with the addition of 1.2wt% CMC is greatest for pellets with refinery fines (14.8kg/pellet). For pellets of very fine impalpable fines it is 6.9kg/pellet and for pellets of calcined coke fines it is 6.3 kg/peUet. For coarse material the dry compressive strengths are lower. Tests were carried out using refinery fines and 1 wt% carboxymethylcellulose (CMC) to produce minipellets. Highly homogeneous pellets were obtained without difficulty, the majority (91 wt%) between 0.5 and 2.88 mm. Tests with the addition of starch Starch was heat-treated at 180C for 60 min and 4 wt% of the treated starch was added to the refinery fines for pelletization. The green pellets had a CS of 1.1 kg/peUet. Only slight hardening was obtained, giving pellets with a CS of 6.8 kg/pellet after drying at 100C and 1.9 kg/pellet after drying at 200C. It is considered that petroleum coke inhibits the consolidating effect of heat-treated starch demonstrated in other systems9. Tests with the addition of pitch Pellets were produced with the addition of pitch, a somewhat fragile product which facilitates shredding and grinding and makes for easy mixing. By adding pitch, with coking of the agglomerate, it was hoped to achieve a consolidating effect that would persist at high temperatures. The moisture content of the pellets with pitch was ~20 wt%. The tests were carried out using 10 wt% pitch with refinery fines. The green strength of the pellets was 0.7kg/pellet. These pellets were not consolidated by curing, which gave a very low consolidation of 0.5 kg/ pellet (Table 3). The pellets were consolidated at 200C for 30 min in an oxidizing atmosphere, giving a CS of 12.5 kg/pellet. The consolidated pellets were used for heat-treatment testing

strength than oven-dried pellets, and this seems to recommend that drying be undertaken at temperatures <100C. Comparison of the results achieved for the three particle sizes of CC with the same addition of CMC shows that the coarsest material has the lowest strength. The lowest CS value is given by the dry pellets with slag fines (SF). This may be due to the fact that the superfine fraction (<0.063mm) in SF is 1.0wt%, while in the calcined fines it is 3.0 wt%.

Impalpable fines (IF). The pellets prepared with this fine material showed a green strength similar to that of the RF pellets (see Table 3). The functioning of the pelletizer was observed to be laborious in the initial stages of pelletizing, due to the tendency to form minipellets. The pellets were also observed to have an irregular surface due to the agglomeration of minipellets. Another effect observed was the production of pellets with excessively moist surfaces, due to the rearrangement of their structure. This rearrangement of the internal structure of the pellet gave rise to migration of the water from the interior of the pellet towards the surface. The green strength of the pellets obtained with impalpable fines was greater due to the finer particle size. Tests with calcined coke and impalpable fines showed that the dry compressive strength of the pellets was lower than that of pellets obtained with refinery fines. Effect of regrinding of coarse products. An attempt was made to study the effect of a finer particle size by regrinding calcined coke with a load of 2 kg for 15 and 60 min, producing a relatively low fraction of superfine particles. The results obtained with ground calcined coke are shown in Table 3. The pellets dried at room temperature (curing) have greater compressive strength than those oven-dried at l l0~'C. These pellets were manufactured with 1.2wt% CMC. It can be seen that in spite of the grinding, their green strength reaches only 0.4 kg/pellet compared with 0.16 kg/pellet for the unground calcined coke fines. The value of the dry CS increases when the calcined

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New materials by agglomeration of petroleum coke fines."N. Cornejo et

(X) CS, kg/pellet
-

al,

40 -

(m) Weight lost, %

Table 4 Pelletswith ideal composition(wt%) to ensure high quality 9,5

1.2% CMC (10% IF + 90% CC) Moisture Ash Volatiles C H N S 0 0.4 1.0 97-98 0.08 0.8 0.2

1% CMC+5% pitch (RF) 0 0.5 0 98-99 0.09 0.8 0.3

30----

20

................................ i ........

2,5
i 300 Table 5 Chemicalcomposition (wt%) of the initial and carburized 400 1200

1O0

200

steels
C S

Temperature, *C Figure 3 Effect of consolidation by heat treatment at different

Si 0.02 0.08 0.10 0.17 0.10

temperatures in a reducingatmosphere (metallurgicalcoke bed) at different temperatures in a reducing atmosphere (a metallurgical coke bed) for 60min. The consolidating effect of the pitch began at 100C, reached a maximum at 300C and remained acceptable at 1300C (Figure 3). The weight loss indicated that 85wt% of the pitch was vaporized at 1300C.

F- 151 Pell-1 Pell-2 Powd-1 Powd-2

0.09 3.45 6.10 2.13 4.30

0.020 0.020 0.020 0.021 0.023

Mixed additions of pitch and CMC. Tests with refinery fines showed that pitch and CMC were compatible and the mixture gave high compressive strength, 30.7 kg/pellet (Table 3). In all the tests, atomized water with 1 wt% CMC was used. The moisture content of 20 wt% was somewhat lower than in other tests carried out with refinery dust, which was the finest material. This lower moisture content is due to the presence of the pitch, which can reduce the amount of water necessary for pelletization. This work demonstrated that it is possible to dry-grind mixtures of 5wt% pitch and 95wt% refinery coke, obtaining a light reground product and a homogeneous mixture using conventional equipment. Effect of oil on the agglomerates
An attempt was made to render the pellets consolidated with CMC waterproof and inert by the use of oil. Accordingly, dry pellets with refinery fines and 2 w t % CMC after consolidation were subjected to double immersion in oil for several minutes. Subsequently, these oil-treated pellets, and other pellets that had not received this treatment, were submerged in water for 5 min. The compressive strengths of the pellets with and without oil were 5.0 and 0.6 kg/pellet, respectively. This clearly shows that it is possible to obtain a waterproofing effect by immersing the dry pellet in Extensoil-4. If the immersion is prolonged, the consolidating effect of the CMC disappears in pellets with or without oil.

and 14.4kg/pellet after 7 d storage. Pellets produced using a mixture of 10 wt% impalpable fines and 90 wt% calcined coke fines gave values of 8 kg/pellet at the end of drying, 6.7 kg/pellet after 7 d storage, and 10.9 kg/pellet after curing and 7 d storage. This indicate that the storage of the oven-dried and cured pellets for periods of several weeks does not seriously affect the consolidation achieved. Dried pellets were obtained with the composition indicated in Table 4 from the mixtures defined, using a CMC with low ash content. When pitch was added the pellets were calcined at 900C, which eliminates the volatile matter.

Experimental evaluation of pellets as carburizing mater&l

No bursting of the pellets was observed during the melting tests, despite the working conditions involving superheated steel baths and a hot melting pot. The C, S and Si contents of the carburized steel are shown in Table 5. Carburization levels can be seen to be greater when coke pellets were used. Much greater levels of carburization, reaching a carbon content of 6.1 wt%, were obtained when the pellets were placed at the bottom of the bath and the molten metal was poured on top of them. This indicates that the pellet is a better carburizer due to the fact that it comprises finer particles. Addition of the pellet at the bottom means that it passes through the molten metal, thus facilitating contact with the bath and providing better carburization. The silicon originates from the refractory in the bath during the carburizing process. The results indicate that this effect is small and is not related to the carburization of the bath. An industrial carburizer is prereduced material which has a low carbon content (2.6wt%), much lower than that of the pellets studied (98wt%), indicating the advantages of the pellets as a carburizer. However, the prereduced material has a density close to that of the bath, favouring carburization since it remains partially submerged in the bath. The tests carried out clearly show that carburization is possible and that the carburized steel may in turn be used as a carburizing material. Microstructural analysis of the carburized steel revealed that the carbon was present in the form of cementite and graphite.

Effect of storage on consolidation of pellets

After > 15 d in storage, the compressive strengths of the dry pellets were determined. The values obtained seemed to indicate increased consolidation. The pellets with the greatest resistance, those produced using refinery fines with the addition of 1.2 wt% CMC and 5 wt% pitch and oven-dried at 110C, gave values of 30.7 kg/pellet at the end of drying and 41 kg/pellet after 15d storage. Dry pellets obtained with calcined coke fines reground for 15min gave values of 12kg/pellet at the end of drying

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New materials by agglomeration of petroleum coke fines. N. Cornejo et al.

The use of these pellets as carburizers in steel baths can be improved if the coke fines can be agglomerated with additives that could become incorporated in the slag or in the molten steel. Such additives of metallurgical interest include iron from ground prereduced products and MgO fines. Both additives, particularly the iron, facilitate densification of the product, which assists incorporation into the bath. CONCLUSIONS 1. Petroleum coke fines pelletize without difficulty. In principle, a formula has been established consisting of 90 parts calcined coke, 10 parts impalpable fines and 1 part C M C (carboxymethylcellulose) by weight. The formula is dry-mixed. The material is pelletized with 25 w t % atomized water containing 1 wt% dissolved CMC. The addition of impalpable fines enables pellets with better mechanical characteristics to be obtained. 2. The addition of C M C produces a consolidating effect only after drying (100C, 90min). The curing of pellets with C M C gives results similar to those obtained by oven-drying at 100C. Prolonged storage of the pellets with C M C does not impair their compressive strength. 3. These pellets as carburizing material show high resistance to thermal shock. No decrepitation was observed when the coke pellets with C M C were added to a molten steel bath. A high degree of carburization of the steel bath was observed. 4. The carburized steel is a material which may in turn be used as a carburizer, being of better quality than prereduced materials. It has a less cooling effect and its density is sufficient to ensure greater contact with the molten metal, even in the presence of slag.

REFERENCES 1 Alvarez,R., Alvarez, E., Barriocal, C., Pis, J. J., Suarez, C., Sirgado, M. and Verduras, J. L In 'El Coque de Petr61eo como Aditivo en la Coquizaci6n', Congreso Nacional de Ciencia y Tecnologia Metalfirgicas,Vol. 1, Madrid, 1990, pp. 11-20 Koshkarov,V. Y., Danil'yan, P. G., Vdovichenko, N. S., Kosbkarova, M. E. and Zhitnikov, P. N. Coke Chem. USSR 1982, (3), 43 'The JUPITER Project: CFB Reduction of Coal-Ore Mixtures', ECSC Workshop on Developmentsin Alternative Ironmaking Processes, EUR 15582, 1994, p. 63 De Carvalho, R. J., Quariguasi, P. G. and D'Abreu, J. C. Can. Met. Q. 1994, 33, 217 Antolii,D. Z. In 'Adhesion of Dust and Powder', Plenum Press, New York, 1982 Patrick,J. W. and Stacey, A. E. Fuel 1978, 57, 258 David,L. D. and Skagerberg,W., Minerals Eng. 1992, 5, 1469 Davidson,R. L. 'Handbook of water-soluble gums and resins', McGraw-Hill, New York, 1980 Ayala, N. 'Mejora de la fabricaci6ndel silicio metalflrgicopor J. reciclado de productos residuales', Ph. D. Thesis, Universidad Polit~cnica de Madrid, 1991

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