ENVIRONMENTAL & WASTE MANAGEMENT

IN IRON & STEEL INDUSTRIES

Proceedings of the International Workshop

E
Editors

TCDC International Workshop Sponsored by United Nations Development Programme (UNDP) under Govt. of India-UNDP Umbrella Programme
December 2-3, 1999 Jamshedpur, India

AMITAVA BANDOPADHYAY N. G. GOSWAMI P. RAMACHANDRARAO

NATIONAL METALLURGICAL LABORATORY (Council of Scientific & Industrial Research) Jamshedpur - 831 007, India THE INDIAN INSTITUTE OF METALS Jamshedpur Chapter

JSSN . 097! 9-407 Environmental & Waste Management

t:rlr ::t. 1lrrrrdop,i,11nan. .t' G. Gos arni and P. Ronrac/tandra Ran ti'11- la nched;'u, X 3/007. India. 1999, pp. 1.10

Environmental aspects of the direct reduction route to steel making

B. R. NIJHAWAN f x- Senior Interregional Adviser & Senior Consultant, UNIDO Kokomo, IN 46902, USA

ABSTRACT

Whilst the environmental aspects of the integrated iron and steel industry have been given significant emphasis, the .stone cannot be claimed for the direct reduction route to steel inakint;. Environmental aspects of gas and coat based direct reduction plants have been outlined including ISO Certification thereof. Directly reduced iron (DRI)HB! production worldwide exceeded 37 million tonnes in 1998 with India being the second largest sponge iron producer globally. having risen from scratch since the eighties. The need to study all environmental aspects of Direct Reduction and app/v remedial measures is imperative.
Key Words : Environmental aspects. Direct reduction, Steel making.

INTRODUCTION
The direct reduction-electric are furnace (DR -EAF) produetioti route to steel making is an alternative to the conventional blast furnace/LD oxygen steel making route, especially in the low capacity ranges where the availability of low cost natural gas and/or solid/fossil reductants (non-coking coals, lignite, anthracite etc.) offers favourable technical and economic advantages. Another factor in favour of direct reduction processes in many locations is that it does require coking coal, an increasingly scarce commodity in the world. For these reasons, many developing countries, as also some developed countries, are basing their steel industry expansion or new plants based on the direct reduction-electric arc furnace route.

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ENVIRONMMENTAL ASPECTS OF DIRECT REDUCTION ne of the attractive katures of the direct reduction route to iron making is that the processes can he effectively controlled to prevent major emissions to the environment. The following discussion outlines several potential pollution problems each of which may he eliminated by good process design and control. Gas reduetant systems The shafl furnace gas reductant systems produce some particulate material. The origin of the particulate material is feed deterioration brought about by abrasion and reduction reactions.Thc gas exiting the shaft furnace contains unreacted CO. H. CH,. reacted products. CO.. HO and dust particles. This gas is normally treated in wet scrubbers and the cleaned gas is recycled to the gas reforming unit and subsequently back to the reactor furnace. The particulate solids in the scrubber water are recovered and then briquetted, pelletized or disposed of in solid waste storage areas. It is important to note that the gas reductant systems operate under conditions that are unlivourahle for formation of polynuclear aromatic hydrocarbons (PAM), for example:
(1) LOW order hydrocarbons are used in the reforming process (CH,) which are

unlikely to combine to form high order PAHs. (2) Reforming is conducted by surface catalyst techniques that do not promote formation of higher order molecules. (3) The reduction reactor is operated at temperatures around 950C below which PAUs form. Even if PAUs are formed in the reduction furnace, in all probability they will be effectively removed from the gas streams along with the scrubber sludge. The fate of PAUs in the scrubber water is not known. It is suspected that some of the PAM material will dissolve in the aqueous phase (the low molecular weight compounds) and some will remain with the solids either as condensed particulate organic solids (the high molecular weight compounds) or as adsorbed species on the solids. The fraction of the PAM material that is not removed by scrubbing should not pose a problem because the gas stream is either recycled to the reduction furnace or is combusted in a separate chamber. Even if PAUs are formed and removed by scrubbing, they would most likely not present a problem at those facilities that recycle their solids to the direct 'Compiled from data of the Environmental Protection Agency (EPA). USA.

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reduction furnace and their water to the scrubber system. Some facilities do not recycle the sludge solids but dispo c them of in solid waste storage areas. The final fate of any PAH material Of exist,) in the solid ssaste is not known. As is true at alt facilities that have ure storage. wind blown dust is a potential pollution problem The .: onge iron produced do not fpo^c pollution problems because it is normally placed in protective enclosures fnr covered with canvas to prevent reoxidation by exposure to moisture. Pelletiration is another associated source of potentialpollution which also needs to he considered. It is estimated that 90-150 million tonnes per year of ore, with an acceptable chemical composition for use in direct reduction, is available. However, about 70 percent of this material is fine grained. The fine grained material is useful for fluid-bed applications hut the sire range necessary for use in the fluid-bed reactors is fairly natTow, Therefore, a significant fraction of the ore will likely have to be agglomerated before it can he used, Emissions from iron ore mining, heneticiation, and pellcti,ing have heen studied by Midwest Research Institute for the EPA. Solid reductant systems The gas from a rotary kiln coal reductant system could contain CO. CO,. H2 , H,Q, SO/NO, hydrocarbons, trace metals and particulate matters. The effluent gas phase composition from rotary kiln reactors is very much dependent on the coal chemistry and mineralogy. Stringent requirements must be imposed on the coal to limit both the sulphur and trace metal content. The particulate matter from these reactors is usually high in fly ash and char. Some systems must combust the exit gas in the afterburner chamber to reduce the concentration of CO, H 3 , char and hydrogens in the exit stream;. The afterburner is normally followed by a wet scrubber device. The collected scrubber product may be dewatered and the solids pelletized or briyuetted and recycled to the kiln, hut usually they are simply disposed in the solid waste areas. The product from the kiln is screened and the iron is magnetically seperated from the char and other svaste solids. The other waste solids are calcium sulphate (if the feed contains some sulphur. it can he controlled by adding lime to the charge) and a slag like material from the coal. The larger size char material is recovered and recycled to the kiln. The fine char material is disposed of along with the slag and gypsum in solid waste storage area,.
The potential pollution problems are:

(1) The sun'iral of PAH.c formed in the eon/-ore bed

It has heen well documented that PAH material is created and/or evolved

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during pyrolysis and combustion of coal. Coalfired heating and power generation plants are estimated to contribute over 30 percent of the l3enio-alpha-pyrene (BAP) emitted to the air environment of USA each year and over 45 percent to the world's air. BAP, a member of the PAH group of chemicals, is known to he carcinogenic. It is, therefore, reasonable to suspect the rotary kiln processes as being potential polynuclear aromatic hydrocarbon (PALL) emitters. The gas phase above the rotary kiln bed is normally oxidiiing and will. therefore, he expected to combust the organic material if the retention tittles are long enough. The entrance region of the kiln appears to he an ideal place for the formation of PAH compounds i.e., the material is being preheated and volatile constituents are being evolved: soot is also being evolved (in effect the material is smouldering). The PAIl compounds evolved into the ,as phase will he oxidised if the retention times in the oxidizing zone above the bed are sufficiently long. However, near the feed end of the kiln the retention times will he very short. Also, it appears likely that PAH compounds readily adsorb on fine particulate matters. in particular soot, and that the PAIL compounds are protected and would survive if the retention times are short.
(2) The survival of PA Hs from the comhrr.lstion oef oil elite/ oral above the coati

ore mixture
The survival of organic compounds evolved during the combustion of the fuel is expected to be very low. The kiln gas temperature varies from approximately 1200C at the burner end to 5(H)(' at the gas exit end. An exposure at greater than 900 C for at least 0.3 sec is necessary for destruction of the PAH material. The gas flow rates generally allow an average residence time in the reactor from 5 to 9 sec. Therefore, the destruction of most PAH material formed by combustion is expected to occur during steady state operation. However, emission of PAH compounds during start-up and shut-down periods is expected to be considerable. As stated earlier, some rotary kiln processes treat the kiln gases in an afterburner and then scrub the gas in wet scrubbers. Therefore, the PAH material that survives the combustion is most likely he collected in the scrubber sludge. It's fate in subsequent processing or in solid disposal sites is uncertain at this time.

(3) Trace element and sulphur oxide emissions franz the coalfired Tractors
Reactors (only one in US at present) that combust coal above the surface of a coal/ore mixture emit some of the sulphur and most of the trace elements from the rotary kiln. A portion of these elements are removed by the attached control devices.

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The sulphur content in the feed coal is specified to he low; i.e., usually less than 0.5 percent. Calculations using the operating data for a coal fired rotary kiln (assuming 0.5 percent sulphur in the feed coal and it heating value of 10,000 Btu/ lb coal) yield a sulphur emission factor of 0.5 lb sulphur/MM Btu. In terms of sulphur concentration, emission is 0.6 grams per cubic metre. New Source Performance Standards (NSPS) have not been considered for direct reduction reactors. However, if it k assumed that regulations similar to the proposed NSPS for electric utility steam generating units would apply to a coal fired direct reduction reactor, then emission levels above 0.2 lb sulphur/MM Btu would have to be controlled to meet an 85 percent reduction in input sulphur content. About 20 percent of the inlet sulphur will be associated with the slag phase exiting the reactor and should he effectively removed from the gas stream by most particulate control devices. A portion of the sulphur will be 'gettered" from the gas stream while still in the reactor by lime in the ore bed. The fraction extracted by this mechanism cannot be estimated because the reaction is dependent on such kinetic factors as efficient gas/solid contact and residence time. It is anticipated. however, that sulphur oxide emissions can he controlled without special add-on sulphur removal equipment. Sulphur content in the coal used as a reductant in the coal/ore bed has been effectively controlled by the addition of lime or dolomite to the charge mixture. Gypsum is formed and can be separated from the sponge iron and disposed of in a solid landfill site. The partitioning behaviour of [race elements during coal combustion has

heen studied. The fate of trace elements falls into three general cIa'" those normally partitioned to the slag phase are Al. Ba, ('a, Ce, Co. Fu. ie, Hl', K, La. Mg, Mn, Rh. Sc. Si. Sin, Sr. Ta. Th, and Ti: those normally partitioned to the fly ash are As, Cd, Cu, (in. Ph, Sb, Sc. and Zn; and those normally remaining in the gas phase are Hg. Cl and Br. As and Cd are usually more concentrated in the fly ash particles 1 7es of less than l() micrometers, so concentration occurs in the
size fractions that are at least effectively removed by control devices. The concentration of trace elements varies in coals and the release of trace elements during combustion varies greatly. lt is certain, however, that great care should be exercised in designing a control system to include good removal of fly ash particles which most likely, will contain ioxic material. National Emission Standards for Haiardous Air Pollutants (N1SHAP) are being considered for As, Cd and Ph in the USA. For example, if one assumes that the normal concentration of trace elements are representative of coal fuels, then uncontrolled emissions of As, Cd, Pb and Be can be calculated.

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The concentrations of trace metals in low sulphur coals are:

As 9.3-13 ppm
Cd 0.1-2.4 ppm

Pb 8,3-12 ppm Be 1.2-2.8 ppm

The process feed rates air.

Combustion coal Air (at Standard Conditions 0'C, I Atm)

0.7 tonnes/hr 4990 mVhr

The calculated trace metal uncontrolled emission values are:

Constituents As
Cd

Emission rates (1g/m') 1085-1517 12-21) 968-1400 140-326

Ph Be

Control devices will decrease these concentration levels and dispersion dilution further decrease the concentration of trace elements emitted to the atmosphere.

Recommendations The gas reductant systems appear to he environmentally clean processes, particularly those that recycle the reductant gas. It is recommended that samples of scrubber effluents be collected and characterized at least through the EPA Source Assessment Sampling System (SAAS) Level I analytical scheme. The rotary kiln solid reductant systems are of particular interest because of the large US coal reserves. All systems that involve coal and oil combustion have been shown to be potential PAM, sulphur oxide and trace metal emitters. It is recommended that an initial sampling he made to ascertain the uncontrolled and controlled emission rates for PAM. SO and trace metals. As an initial effort, a preliminary sampling programme should he performed to provide mass balances on these effluents from the rotary kiln scrubber system.

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STEEL MAKING USING METALLIZED PROI)U('T Direct Reduction-Electric Arc Furnace (DR-EAF) Steel Making The major use of sponge iron produced by direct reduction processes i,, as a source of iron for electric arc steel makine furnaces. Tsso mini milli in the I S Georgetown Steel and Oregon Steel - use a substantial fraction of sponge iron in their charge. Both use a charge of sponge iron and scrap. about SO percent of

each.
The literature quotes a number of advantages for the DR-FAF combination process. Several quoted advantages are presented below: (1) A variety of excellent processes have heen developed and proved in coinmercial operation. These are based upon the moving bed shaft furnace, the fixed shaft furnace, flu idiied beds and the notary kiln. All represent good technology for tonnages of 900 to I S+t ?Q tonne/day. Additional plants can he added as needed, and they can he used with no initial over capacity as would occur for a modern blast furnace-coke plant-I30IF complex. (2) For socio -economic reasons, developing nations desire domestic steel industries. Limited initial tonnages are the guideline and direct reduction provides moderate scale production at moderate capital investment. Moreover, many of these nations with reserves of high-grade iron are deficient in metallurgical coals, but have abundant supplies of natural gas and petroleum. These latter forms of reluctant and energy can he used in only limited quantities in blast furnaces but are ideal for many direct reduction prt^cesses.

(3) In developed nations, opportunities occur for mini- and ntidj-steel mills with direct reduction product supplementing local scrap. These applications will he hampered in the future by high costs and shortages of natural gas or petroleum from which reducing gases can he produced. But economic processes for gasifying coals will doubtless he a favourable factor for the

future.
(4) The gross consumption of energy per tonne of liquid steel is comparable for the method of combining direct reduction and the electric furnaces leitil the
blast furnace and the basic oxygen furnace.

(5) The time required for commissioning a DR-EAF steel plant is about two to three years compared to five to seven years for an integrated steelworks. (6) An IBRD study comparing DR-EAF to the blast furnace-basic oxygen furnace (BF -BF) has found that: (a) the quality of common steels produced by DR-kAF and 13k-I3(.)1b practices is approximately equal:

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(h) the estimated capital costs of facilities for pelletizing. iron making. steel making and continuous slab casting of 3-4 million tonnes/year at Matanzas suggest that a DR-I:AF plant will he nearly 40 percent cheaper than a comparable BF -BOF installation; (e) The production cost, excluding fixed charges and income taxes, for a tonne of carbon steel slabs is approximately 20 percent lower when produced by DR-EAF operation than when made by the BF -BOF route; (d) The average rate of return on investment is from 2.5 to 3 times greater for the DR-EAF compared with the RF-BOF route, (7) Steel production at an EAF plant becomes independent of scrap, a raw material that is volatile in pricing. quality and supply. (8) A number of qualities are quoted for the use of sponge iron (versus scrap) as a feed material to electric arc furnaces: (a) chemical composition is known exactly (h) chemical composition is uniform (c) contains no undesirable impurities (d) permits dilution with low cost (more available) scrap (e) easy to transport and handle (f) permits automatic continuous charging (g) increases furnace productivity (h) less noise during melt down (i) more predictable price structure (9) Air pollution problems are minimised in a closed cycle gas based direct reduction plant because all gases are cleaned and recycled. Effective control of electric arc furnace steel making is possible but care must he exercised to ensure a non-polluting operation. (10) In rotary kilns the exit gases are combusted in an afterburner to reduce the concentration of reduction gases and hydrocarbons. This can he followed by wet scrubbing or by an electrostatic precipitation. Where briquetting and pelletizing equipment is available, the collected scrubber products can be recycled to the kiln, but usually they have to be simply dumped in solid waste areas. Materials recovered from the seperation of the reduced ore from char (ash and other solid wastes) can contain calcium sulphate and slaglike materials. Large char particles are recycled. The smaller char particles and the other solids pass to waste storage areas.

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Effluent from the scrubbing in the afterburner also contains sulphur compounds and has pH 2.3 to 4.5 which has to be ncutraliied. This results in about 600 kg of sludge per tonne of DR!. while the dust emission in the as slack is about 145 mg/Nm

Other Uses of Metallized Product

The major use of metaili,ed product is as a feed material to the electric arc steel making furnace as noted in the previous section. Other uses have been proposed and tested on, at least, a pilot plant scale. These are: (I) To increase production and decrease coke requirements in a blast furnace. It has been reported that blast furnace productivity is increased and coke rate decreased by 5-6 percent for each 10 percent increase in furnace burden metallization. (2) To serve as a coolant source in the BOF process for temperature control. (3) To replace the use of scrap in FAF steel making processes, in cast iron foundry electric furnaces and cupolas and in the 130F process. Integrated steelworks may have a direct reduction capability. It's product could be used in one of the ways listed above. It's utility would be to supply prereduced iron wherever it is required. It's source of feedstock would be steel plant fines, dusts from pollution control devices and supplemental ore. Its reductaft would be coke oven gas, blast furnace gas, gasified coal gas or for a rotary kiln process, coke, coal or coke hreeic.

Recommendations
(1) It is recommended that the sponge iron and steel industry based on direct reduction technologies should make every effort to keep the natural environment as clean as possible. particularly in relation to atmospheric pollution, water contamination and dispersion of solid wastes. (2) It is further recommended that atmospheric pollution control Standards should he established to ensure that the daily average atmospheric concentration of nitrogen oxides (NO) should be within or below the range of 0.04-0.06 percent. (3) Improved combustion methods including fluidized bed combustion should he applied. The application of high-performance electro-static precipitators, changing to low sulphur fuels and raw materials should be promoted. (4) The increase of water recycling rates and installation of various water treatment facilities should be promoted to reduce water pollution.

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(5) As for problems of residual solid wastes, the steel industry should make the maximum use of all types of dust and sludges fi oill sponge/steel making processes as well as endeavour to reduce the generation of these wastes themselves.
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(6) Sponge iron and steel makers should continue to promote the afforestation programme around sponge iron and steelworks. The DRI/H131 production worldwide exceeded 37 million tonnes in 199 with India being the second largest producer globally, having risen from scratch since the eighties. The need to study all environmental aspects of Direct Reduction and apply remedial measures is imperative.

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