ANALISYS OF POSSIBILITIES FOR THE UTILISATION OF WASTES FROM ELECTRODES MANUFACTURING

MIHU GRJOAB*, LIVIU DRAGO*, NICOLAE SCARLAT*, SILVIU MRUNELU*, GRIG MOLDOVEANU*, LIVIU UGULAN** *S.C. OVM-ICCPET S.A., Vitan 236, Sector 3, 031301 Bucharest, Romania, mihu@ovmiccpet.pcnet.ro **S.C. ELECTROCARBON S.A., Silozului no. 9, Slatina, jud. Olt, Romania Keywords: fluidized bed combustion, coke, waste ABSTRACT Electrocarbon S.A. is a company producing carbon electrodes for use in metallurgy. Carbon waste resulting from the technological process has been deposited for many years in a nearby landfill, amounting to about 1.2 million tons. In spite of its high calorific value, because of the low volatile content and the grinding difficulties, little use was found for this material. Investigations are currently carried out to burn the waste in a fluidized bed boiler located near the site, that would replace two existing heat recovery steam generators producing electricity for the internal consumption, and a preliminary evaluation of the costs for electricity generation was performed. Several fuel types have been taken into consideration for combustion in a 65 t/h steam boiler: electrode waste, Romanian lignite, imported bituminous coal and petroleum coke. INTRODUCTION S.C. ELECTROCARBON S.A. Slatina is an important company in the field of metallurgy, but also the second greatest atmospheric polluter in the Olt County. Residues from manufacturing of carbon electrodes have been stored nearby, and over the years a dump was formed, containing more than 1.2 million tons of so-called secondary coke. The company is currently under pressure from the local authorities to reduce its environmental impact and to remove completely the waste dump. Measures have been taken and the modernisation of the technological process allowed the reduction of resulted waste down to 50-60 tons/month, with the whole quantity being sold to cement factories. However, the programme for conformation included in the environmental authorisation imposed that all measures should be taken for the elimination of the existing waste dump (see Fig. 1). Currently the secondary coke is sold to cement and steel factories, but the rate is very slow - about 200.000 tones in 2 years. Tests have been made for co-combustion of this material in pulverised coal fired boilers, but its poor grinding characteristics and low volatile content led to a very low combustion efficiency. Investigations are currently carried out to verify the feasibility of economically burning these wastes in a new fluidized bed boiler integrated in Electrocarbons existing power plant.

Figure 1. The secondary coke landfill at Slatina

CURRENT SITUATION Existing equipment The existing power plant is equipped with two heat recovery steam generators of 30 t/h, 40 bar, 450C; two more were initially planned. The design fuel is residual gas resulted from petcoke calcination, with natural gas as auxiliary fuel; characteristics are presented in table 1. The steam was initially required for a 12 MWe turbogenerator, for heating and for industrial use. Because of the insufficient flow rate and fluctuant characteristics of the residual gases, the natural gas consumption was much higher than estimated, making electricity production uneconomical. Consequently, the boilers planned for the next stage were no longer built, and the turbine never functioned after the commissioning tests. During 1999, one of the boilers was modified to operate at reduced parameters, with the steam exclusively used for heating and technological necessities. After commissioning three new hot water boilers, the power plant was completely shut down. Table 1: Characteristics of residual gas Name CH4 CO H2 CO2 N2 Water Coke dust content Lower heating value Available fuels The main fuel for combustion in the fluidized bed boiler would be the carbon waste (secondary coke). Apart from the fuels already used in the existing power plant residual gas and natural gas petroleum coke is also available, which is used as main fuel in the technological process. The main characteristics are presented in table 2. Unit % % % % % % g/ m3N kJ/m3N Value 5 3 10 6 51 25 20,85 3.224

Table 2: Main characteristics of the fuels Secondary coke sort 0-40 sort 0-10 sort 10-40 mm mm mm 8,5-9,5 8-10 2,5-5,0 35-45 35-40 25-30 1,3-1,7 1,1-1,5 1,0-1,5 54-65 55-65 65-70 17-25 19-20 15-17 8-10 9-10 6-7 3 3 3 11,3-14,65 11,3-14,65 11,3-12,56 Petroleum coke 8-9 0,3-0,7 9-10 87,5-90,5 1,0-3,5 35,586

Characteristic Water Ash Volatile matter Fixed carbon SiO2 SiC Sulfur, max. LHV

Unit % % % % % % % MJ/kg

The analysis revealed several aspects of the electrode waste that can pose problems. The very low volatile content less than 2% - will require a longer burnout time, and a high ignition temperature. The graphite and SiC makes it very difficult to grind, but since 80% is less than 10 mm in diameter, after sieving no crushing will be required. The sulfur content, although the maximum value is 3%, is usually less than 0.5%. Coal could also be an option; bituminous coal and lignite are available locally. The analysis of some Romanian coal types is presented in table 3. Table 3: Technical and elementary analysis of several Romanian coal sorts [1] Characteristic Unit Type no.1 Water % 33.40 Ash % 33.20 Carbon % 20.95 Hydrogen % 1.83 Total sulfur % 1.20 Comb. sulfur % 0.80 Oxygen % 9.22 Nitrogen % 0.60 Volatile % 22.10 Volatile (d.a.f.) % 66.20 HHV kJ/kg 7,621 LHV kJ/kg 6,365 Lignite Type no.2 35.60 27.10 23.70 2.23 1.00 0.60 10.12 0.65 23.45 62.85 9,087 7,688 Bituminous coal 9.70 9.50 64.15 4.85 2.10 2.00 8.84 0.96 33.30 41.20 26,281 25,481

Type no.3 44.10 20.40 21.76 1.94 1.05 0.80 10.29 0.71 22.50 63.38 9,388 7,461

If, from technical reasons, combustion of secondary coke alone could not be achieved, petroleum coke should be used for support. It is preferred to use coke rather than coal, since a petroleum coke depot is already existing in the area; coal would require additional storing areas. Limestone will be used for desulfurisation, and sand will serve as inert material during startup, until the ash from the fuel accumulates. Because of its low availability, residual gas will not be considered as a fuel, but the new boiler will provide the possibility to burn it too, from environment protection reasons. Natural gas will only be used during startup.

DESCRIPTION OF THE PROPOSED SOLUTION The solution proposed is to demolish the existing HRSG, and implement a new fluidized bed boiler, adequate for combustion of secondary coke, but also petroleum coke and coal. Besides the new equipment, this will also require a series of modifications to the existing power plant. Adaptation of the power plant Since steam for heating purpose is no longer required, the two heat exchangers for district heating and the corresponding piping and pumps will be removed; all other components will be maintained. As a result, the turbine will operate with only 65 t/h steam at inlet (from a maximum of 120), keeping the steam flow at the maximum value in the low pressure part, and reducing down to minimum the steam flow extracted from turbine outlets S and L, while maintaining the electric output at 12 MWe. The scheme of the modified power plant is presented in Fig. 2.

Figure 2. Scheme of the modified power plant ASF FB steam boiler; TA steam turbine; GE - 12 MW electric generator; Cd - condenser; IRR 1, IRR 2 pressure reduction 39/12 bar, respectively 12/1,5 bar; PIP, PJP heat exchanger; D deaerator; RAD demineralised water tank; PAD water preheater; PAA feeding pumps; PCB condensate pumps; PCR cooling circuit pumps; TR cooling tower

New equipment The new CFB boiler will use secondary coke and petroleum coke as main fuels, with the possibility to burn coal too. When available, residual gas from calcination kilns will be introduced in the furnace, by means of an ejection system. Startup will be performed with natural gas burners. The boiler is fitted with a sand feeding system, to provide the necessary inert material when using low ash fuels or during startup. The main parameters are presented in table 4.

Table 4: Main parameters of the CFBC boiler Parameter Steam flow (nominal/min.) Nominal steam pressure Nominal steam temperature Fuel LHV Feed water temperature Max. flow secondary coke Max. flow petroleum coke Max. flow limestone Outlet ash temperature Primary air flow Secondary air flow Flue gas flow Flue gas temperature Estimated thermal efficiency Unit t/h bar C kJ/kg C kg/h kg/h kg/h C m3N/h m3N/h m3N/h C % Value 65/30 40 450 sec. coke, petcoke, bit. coal 17.958; 32.395; 25.937 140 12.000 6.000 1.300 150-200 45.000 19.500 70.000 150 91

Other ancillary equipments are required, such as: solid fuel feeding system, limestone feeding system, bottom ash and fly ash extraction systems. The fuel feeding system, composed of belt conveyers and two storage hoppers, allows the operation of the boiler using two solid fuel types in the same time. The limestone is unloaded from the trucks with a pneumatic system, and stored in a 200 m3 silo, with capacity for 3 days. From the silo, the limestone is brought to the boiler hopper also by pneumatic transport. A similar system is provided for sand handling and storage. The resulting ash is stored separately (bottom ash from fly ash) in silos having enough capacity for several days. From here, the ash is transported by truck to the waste dump, if no other use is found. ECONOMIC CONSIDERATIONS From the available data, an estimation was made for the cost of electricity production. This estimation is presented in table 5, but does not include depreciation. Local lignite and bituminous coal have also been considered, but the high fuel cost made these options not economical. The price of electric energy for industrial consumers is currently in Romania 60 EURO/MWh. Considering that all the electricity produced will be consumed internally, an economy of about 4 mil. EURO/year will be achieved; with an investment of 7 mil. EURO, at a depreciation rate of 12%, the payback period would be less than six years. Although preliminary calculations indicate a profitable investment, the current conditions on the Romanian energy market are not favourable. At the moment, Electrocarbon purchases electricity at a very low price about 40 EURO/MWh being an eligible consumer; however, as soon as the liberalisation of the energy market will occur, the company may be forced to buy energy at a much higher price.

Table 5: An estimation of the costs for electricity production using secondary coke (case 1) or a mixture of secondary coke and petroleum coke (case 2): Parameter Secondary coke flow Petroleum coke flow Limestone flow Secondary coke price Petroleum coke price Limestone price Transport costs Fuel costs Raw water costs Personnel costs Operation time Maintenance costs Total operation and maintenance costs Net energy production Energy production cost Unit kg/h kg/h kg/h EURO/t EURO/t EURO/t EURO/h EURO/h EURO/h EURO/year hours/year EURO/year EURO/year MWh/year EURO/MWh Value Case 1 10.760 0 260 21,622 48,649 6,757 3,514 237,919 0,373 326.919 7.000 75.800 2.070.762 73.500 28,174 Case 2 5.100 3.125 800 21,622 48,649 6,757 40,372 308,074 0,373 326.919 7.000 75.800 2.561.850 73.500 34,855

CONCLUSIONS Measures have to be taken for the elimination of a 1.2 million tons electrode waste dump located near the town Slatina, in Romania. The electrode waste, or so-called secondary coke, is a high calorific value granular material, with low water and volatile matter content. Since co-combustion tests with coal in existing PC boilers proved to be technically not feasible, selling of secondary coke to cement factories should continue, but for the more rapid elimination of the existing waste dump, fluidized bed combustion should be considered. From the technical point of view, for the fluidized bed combustion of electrode waste the following elements should be considered: startup burners should have enough power to bring the temperature up to the ignition point; the low reactivity of the fuel demands a long residence time in the combustion zone, thus requiring a high furnace and an efficient cyclone; fuel crushing should be reduced to minimum possible; limestone feeding should be dimensioned for the utilisation of high sulfur petroleum coke, in case the waste is no longer available or it needs co-combustion. Since until liberalisation of the Romanian energy market Electrocarbon has the possibility to purchase electricity at a low price, the economic opportunity of investing in a CFB boiler for secondary coke combustion might be questionable. However, if considering the actual electricity price for industrial consumers in Romania of about 60 EURO/MWh, the investment would be recovered in about six years. REFERENCES
1. Dragos, L., Girjoaba, M., Macavescu, M., and Savu, A., Compared CFB Combustion of Lignite and Bituminous Coal, In: Process Efficiency and Environment Quality in Thermal, Chemical and Process Engineering, Zlatibor, 1997.