Department of Petroleum Engineering and Applied Geophysics TPG4140 NATURAL GAS

DIRECT REDUCTION OF IRON ORE USING NATURAL GAS

Written by:
Roohollah Ashrafian Mahla Rashidian Mandana Amiri Gaukhar Urazgaliyeva Milad Khatibi

Supervisor:
Jon Steinar Gudmundsson

Trondheim November 2011

ABSTRACT
In the given report, the advantages of using natural gas to produce steel is considered from technical, economic and environmental points of view. The major processes that have been developed to facilitate this production are reviewed as well as the availability of the associated raw materials. It was found that of the multiple processes investigated for steel production, Direct reduction of iron (DRI) based on natural gas was relatively economically viable with considerably low greenhouse gas emissions. Furthermore, our considerations with regard to DRI method were organized in terms of providing a qualitative business case for decision makers. To do that, we considered business opportunity for developing iron industry in Norway, analyzing the iron market, capital and operational expenditures and environmental impacts. By considering the European market for steel and also the available natural gas resources in Norway, there is a special opportunity for using natural gas to produce iron with lower cost per ton in comparison with other producers worldwide. This market opportunity as well as lower environmental impacts by using natural gas can compensate the potential investment and operational cost overruns with respect to other methods.

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TABLE OF CONTENTS
ABSTRACT .....II 1. INTRODUCTION ....... 1 2. IRON MAKING DEVELOPMENT HISTORY ..... 3 2.1. History of Iron Production in the world ....... 3 2.2. Methods of Iron Ore Reduction ......3 2.2.1. Direct Reduction Iron (DRI) processes ............ 4 2.2.2. Blast Furnace ........ 5 3. BUSINESS CASE FOR BUILDING A DRI PLANT IN NORWAY.. 6 3.1. Business Opportunity ...... 7 3.2. Market Analysis ...... 7 3.3. Business Networking Opportunities ..8 3.4. Capital Expenditures ....... 9 3.5. Operational Expenditures ......... 10 3.6. Location of the plant ..... 11 3.7. Environmental Advantages ....... 11 3.8. Technical Advantages ... 13 4. DRI PRODUCTION... 14 4.1. Process Flowsheet ..... 14 4.2. DRI Process basis ..... 15 5. CONCLUSION ........ 16 REFERENCES ..... 17 LIST OF TABLES ....... 19

LIST OF FIGURES ........ 20 APPENDICES Appendix I: DRI (Direct Reduction of Iron) Furnace ....I Appendix II: Process Gas and Cooling the Reduced pellet ..IV Appendix II: DRI Production in Norway ........VIII Appendix IV:Technology in producing Reduction Gases .....XIII

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1. INTRODUCTION
The iron and steel production sector is the second-largest industrial consumer of energy after the chemical sector. It accounts for about 20% of industrial energy consumption and is one of the largest industrial emitter of CO2, including all the process emissions from coke ovens, blast furnaces, etc. To emphasize more on the later issue, the increasing greenhouse effect on Norways average temperature in the 20th century has been shown in Figure1. (Norwegian Meteorological Institute, 2010)

Figure 1: Norways mean temperature change during 20th century (Norwegian Meteorological Institute, 2010)

As it is obvious, any improvements in iron-making process could contribute great improvements in both industry and environment. Within this industrial context, DRI - making (Direct Reduction of Iron) is a process through which iron is produced without using a blast furnace. As it is shown through 2008 World Direct Reduction Statistics (Figure 2), the use of this method is increased dramatically during the recent years. (Midrex , 2008)

Figure 2: DRI statistics worldwide (Midrex, 2008)

The following items provide the industrial background for DRI to develop so fast worldwide: The cost per unit of produced iron could be reduced either for those countries with limited resources of coke or scrap iron or for those with great resources of natural gas. Natural gas could be considered the most environmentally friendly fossil fuel, because it has the lowest CO2 emissions per unit of energy. So, by using natural gas to produce reducing agent, DRI process will be a better choice with respect to previous technologies. In this report we are going to consider the business, technical and environmental requirements of DRI route for iron making to see whether its compatible with Norwegian industrial background.

2. IRON MAKING DEVELOPMENT HISTORY 2.1. History of Iron Production in the world Iron production is one of the most important inventions and it returns to 2000 BCE in ASIA. Iron became replacement instead of the bronze in the war weapons. The main features of the iron with combination of carbon in comparison with bronze are harder, more durable and it can obtain sharper edge than previous metals. Later this invention became the basis of the civilization is other continents too. In the nature, It is infeasible to find pure iron itself because it has a high tendency to react with oxygen. In general, you can find iron as iron oxide with other materials like: silicon, sulfur and phosphor, manganese. Iron oxide with all other materials which exists in the nature calls iron ore or iron stone and is usually found in the form of magnetite (Fe3O4), hematite (Fe2O3), goethite (FeO(OH)), limonite (FeO(OH).n(H2O)) or siderite (FeCO3).(Figure 3) Iron ore is one of the main raw materials used in different iron making processes. Crude iron ore needs to be pretreated before fed into DRI plant. Details for iron reduction procedures are discussed through the following sections. 2.2. Methods of Iron Ore Reduction There are different methods of iron ore reduction and we consider new methods to develop technologies of steel making by electric arc furnace. The main goal of the process development has been to avoid coke formation and by this process reduce the operating costs. In general, in direct reduction process the oxygen is removed from iron, the process is happened in a furnace by reducing gas, if cooling zone in the furnace will be eliminated, the DRI can be immediately briquetted into hot briquetted iron (HBI). The reducing gas for the process can be generated from two different ways: externally to the reduction furnace or from hydrocarbons such as natural gas. Processes that are used for this general producer are as followings:

DRI, which includes o Midrex direct reduction o HYL direct reduction o SL/RN direct reduction

Blast furnace

2.2.1 Direct Reduction Iron (DRI) processes Direct reduction iron (DRI), also called sponge iron, is produced from direct reduction of iron ore (in the form of lumps, pellets or fines) by a reducing gas produced from natural gas or coal. The reducing gas is a mixture majority of hydrogen (H2) and carbon monoxide (CO) which acts as reducing agent. This process of directly reducing the iron ore in solid form by reducing gases is called direct reduction. In the following paragraphs we explain briefly different methods of the production. First of all, Midrex direct reduction is a more common method of Iron reduction and the furnace has two main stages which are reduction zone and cooling zone. The process is based on natural gas. The details of the process description referenced at part (3.2) of the report. The second method is HYL direct reduction, which is a less common than Midrex, but the source for HYL is the same as for Midrex, although in HYL the reducing section of this process includes four reactors. The reduction charge is taking place in main reduction stage and other three stages are used for cooling, carburization, and the final regulation of metallization. The third method is SL/RN direct reduction, which is coal-based rotary kiln reduction process. This is used mainly in India and South Africa. In this method the feed is preheated up to 1800F by counter flowing gas, which is usually contain ore coal, recycle char and flux if sulphur should be removed from the coal. Due to increase kiln efficiency, the preheat zone should be 40 to 50% of total kiln length. Another way to have a uniform temperature in the reduction zone is to put all the coal at the feed end of the kiln. Reduction is started when temperature reach roughly 1650F. Then, the solids are discharged from rotary cooler, which is cooling by spray water to the cooler shell and down temperature about 200F. The cooled material is separated by screen and magnetic separator. The fines are briquetted to be used later with the DRI. (Iron and Steel
Engineer, 1995) 4

2.2.2 Blast furnace A blast furnace is a type of metallurgical furnace used for melting to produce industrial metals, generally iron. Fuel, ore and flux (limestone) are continuously used through the top of the furnace, at the same time into the bottom of the furnace fuel is injected by air (with oxygen enrichment), so that the chemical reactions take place throughout the furnace as the material moves downward. The end products are usually molten metal and slag phases tapped from the bottom, and flue gases exiting from the top of the furnace. (Wikipedia., 2011)

3. BUSINESS CASE FOR BUILDING A DRI PLANT IN NORWAY

In this section of our report, we are going to dig the reasons behind initiating a project to build a DRI plant in Norway. This is important because these kinds of projects require huge amount of money to invest in. So, government organizations, private companies, suppliers and subcontractors, financial institutions, public media and other stakeholders should be convinced by a go/no go decision made by authorities. As a model to our analysis we reviewed US Department of Energy research report (DOE, 2010), on different iron making processes. In this study, different iron making processes were compared and prioritized based on the following criteria: Capital Cost (CAPEX): The relative capital costs per unit production Operating costs per unit production Simple Internal Rate of Return (I.R.R.) Total Cumulative Electric Power Consumption Total Cumulative Process Emissions

The results of this study are presented through table 2 by a simple ranking method. It could be seen that Midrex Direct Reduced Iron process, has a good rank among other iron making technologies. Consequently, it is a good candidate for establishing an iron making plant in Norway. Weve considered two different alternative routes for iron making process in order to apply a similar systematic approach to our business case review. The first one is blast furnace rout which has a vast usage all around the world and the second one is DRI followed by EAF route. We chose the former as our baseline project and the later as our scenario project. We try to compare qualitatively these two different alternatives through next sections. To do that, we analyze the subject from the following perspectives: Business opportunity Market analysis Capital expenditures Operational expenditures Location of the plant Environmental impacts
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Technological advantages

3.1 Business Opportunity

Geographically, Barents region is rich in terms of diverse natural resources including natural gas, metal ore and mineral deposits. So, by taking this fact into account, Norwegian government is going to exploit this opportunity to create value with close cooperation with neighboring countries, such as Sweden, Finland and Russia. (Kirkenes Seminar, 2010). Metal industry, one of the largest Norwegian industries, can benefit largely regarding this opportunity. The potential for creating value from coexistence of natural gas and metal ore resources depicted in figure 7 in the Barents region.

3.2 Market Analysis

Steel industry plays a vital role in the economic growth of the world. Thus, developing the steel industry in each country might be perceived as an indicator to show its economic growth. The World Steel Association report, on world steel forecast for 2011 and 2012, shows that world steel demands will grow by 5.4%. The amount of steel demand in different world regions through 2011 and the forecasted growth for 2012 is shown in Table 3.

Table 3: Worldwide iron demand (World Steel Association, 2011)

China India USA Central & South America EU Japan

2011 mmt 643.2 67.7 88.9 47.8 154.9 61.8

2012 mmt 686.1 73.1 93.8 52.4 158.9 62.3

Growth % 6.0% 7.9% 5.2% 9.8% 2.5% 0.8%

As it could be seen from the Table 3, iron and steel industry are highly influenced by the worlds economic, political and environmental conditions. For example, while the industry trend analysis

had high growth forecasted in 2008, the world economic crisis lead to decrease in the steel demand and consequently the steel price fell down. ( Arica, Vuvunikian, 2009) Political turmoil in Middle East and North of Africa also affected the forecasts for the 2011 demand for steel in this region. Japans earthquake is another example showing how environmental accidents can influence the industry progress in a special region. (World steel association, 2011) In spite of economic crisis, potential price increase could be expected for the market in the European iron market. This fact can potentially lead to business opportunities for producers with competitive advantages within this market. The trend analysis of the European iron industry in terms of forecasted price has been shown in Figure 8.

Figure 8: European iron price trends (Ulf Holmqvist, 2010)

In Norway the iron industry is not well developed with respect to aluminum industry. The main part of the domestic consumption is imported from other countries. The world market as well as domestic market conditions provide great opportunity to develop iron industry in Norway to create value.

3.3 Business Networking Opportunities

There are some special features concerning Barents region that makes it vulnerable for being developed in terms of iron industry. By taking into consideration the active industrial companies as well as the available natural resources in this region, great potentials could be perceived for multilateral cooperation. According to SINTEF report (2011), there is a developed plan of

GeoNor project, where processes and strategies of the project are clearly illustrated in Figure 9.

Figure 9: The concept of industrial cluster through GeoNor project (SINTEF, 2011)

This concept provides special business opportunities for active companies in this region. For example, according to Hgans report (2009), Swedish iron ore is significantly cheaper for European consumers due to lower shipping costs compared to other importing iron ore sources. LKAB is one of the largest Swedish companies widely recognized as a leading producer of upgraded iron ore pallets. Hgans is another company with great competencies in using and sale of metal products. In addition, Statoil has well-established skills in energy generation and gas refining. The potential business cooperation between active companies in this region depicted through Figure 10.

3.4 Capital expenditures

Capital investment is the most sensitive factor in analyzing the financial model of iron making processes. According to Grobler and Minnitt works (1999), the estimated capital investment for building a DRI plant is about US$200/ton to US$300/ton. In more recent estimate, investment costs for our baseline project (Blast Furnace) is approximately US$211/ton. For our scenario project (DRI and EAF combination), the investment costs is approximately US$220/ton. (IEA, 2010)
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Available infrastructures such as transportation facilities, natural gas pipelines, ports and harbors have great contributions on capital investment costs. Therefore, it could be concluded that selecting a right location for building a DRI plant can affect its financial viability (Grobler and Minnitt , 1999). This factor is discussed in more detail in section 5-6. Another important economic factor is related to the capacity of the plant. It is obvious that the more the capacity of iron production, the more capital investment requirements. The rough order of magnitude estimate of capital investments required to build a DRI plant in terms of the plant capacity has been shown in Figure 11.

Figure 11: Required capital expenditure in terms of DRI plant capacity (Metal Consulting International Report, 2010)

3.5 Operating expenditures

Among operational cost factors, raw material play more vital role in financial model of the plant lifecycle. Main raw materials used in our scenario project include iron ore and natural gas. As it was mentioned, our baseline project uses coal and iron ore as a raw material. Barents region have the competitive advantage of available resources for both iron ore and natural gas. So, instead of importing iron ore from other counties and paying CIF prices for them, building the plant at Barents region might lead to decrease in operational cost. On the other hand, vast resources of natural gas in Norway, makes it available for cheaper prices. This fact partially compensates for higher natural gas prices compared with coal prices.

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3.6 Location of the plant

As it could be seen from previous sections, determining the proper location for building a DRI plant has a great impact in terms of both capital expenditures and operational expenditures. Generally speaking, the following factors can affect the decision making about location of the plant (Gobler and Minnit 1999): Proximity to consumer market Proximity/availability of iron ore Proximity/availability of cheap and abundant natural gas or coal sources Favorable local socio-political situation

The intended location is close to the industrial facility at Tjeldbergodden, south of Trondheim, offering good links to existing infrastructure such as an incoming natural gas pipeline, methanol plant and harbor. As it could be seen from Figure 12, proximity to the market might result in 10% to 20% reduction in the production cost. (Hgans, 2010) The impacts of other factors are discussed in the previous sections.

3.7 Environmental Advantages

Steel making industry has great effects on both releasing greenhouse gases and dust production, therefore, all the efficient improvements in different process steps to make it more environmentally friendly, are welcomed by producers worldwide. To achieve this goal, the following factors should be considered: Producing less dust particles Generating less noise pollution Reducing the energy consumption of the steel making process Reducing the GHG emissions Using steel waste products as a feedstock to produce salable products

In gas based DRI plants, the plant dedusting system is done by using special scrubbers and filters (Bhawan and Nager, 2007). In general, because the plant uses natural gas and pelleted iron ore, the overall dust produced in this process is much less than the other iron making processes.

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Among iron making processes, gas based DRI produces less noise with respect to older technologies such as blast furnace. In gas based DRI plants, briquetting units and compressors are the most important sources of noise.(ibid.) In addition to dust and noise generation, CO2 emission as well as energy requirements should be analyzed and compared to each other. In 2000, U.S Department of Energy in cooperation with Carnegie Mellon University conducted an investigation on CO2 and energy consumption of different iron making processes. They calculated theoretical minimum energy requirements to produce iron with different processes. Their findings provided great information in terms of potential improvements in the energy consumption of the iron making processes. The results of the study have been shown in Table 4. It should be mentioned that we take just our baseline and scenario project here in this report.
Table 4 : Minimum energy requirements for different iron making processes (DOE, 2000)

Process BF-BOF EAF-(50% DRI) Thin slab EAF-(50% DRI) Billet

Product Hot Rolled Sheet Cold Rolled Sheet Bar

Rolling Direct Reheat Direct Reheat Direct Reheat

Energy (MJ/t) 7878 8703 6081 6906 6068 6893

In addition, the calculated energy values will be converted to CO2 emissions in order to determine the CO2 emission opportunities in different processes. (DOE, 2000) Greenhouse gas emission can be analyzed based on the CO2 taxation which has been placed from 1991 by the Norwegian government as one of its tools for reaching countrys target on the GHG reduction. This kind of taxation as well as investment in new energy sources are to get the following national targets which the parliament set in 2008: Reduce greenhouse gases by 9% from their 1990 levels over the 20082012 period emissions by 2020. Become neutral by reducing global greenhouse gas emissions by the equivalent of 100% of Norways emissions by 2050. (IEA 2011 Norway review)
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Reduce global greenhouse gas emissions by the equivalent of 30% of Norways 1990

Based on Hgans report (2010) the total amount of CO2 emission in the whole iron production process will be decreased by 75%. This could result in CO2 emission reduction up to 1.5 million ton/year. Figure 13 compares the amount of CO2 released in EAF route and DRI route per ton of produced iron. Thus, assuming the 4 NOK/ton of CO2 as the current CO2 tax for manufacturing processes like basic iron production, it might be seen that around 4.5 million NOK/annum might be saved if a gas based DRI plant is built instead of our base case, that is ablast furnace.

Figure 13 :The CO2 emission in different iron making processes (source???)

3.8 Technical Advantages

All the technical aspect and the process for our scenario project have been discussed in previous sections. The following list includes some of the known technical advantages of DRI route in comparison with blast furnace route: Lower operational pressure Much more energy efficient Higher quality products in terms of carbon content flexibility and high degree of metallization Single reformer instead of reformer heater combination No need to pre cool the reformed gas No need to a separate CO2 removal system No need to further treatment to lower the carbon content of the products
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4. DRI PRODUCTION 4.1 Process Description In this method the feed is continuously fed from the top of furnace and crossing uniformly into preheat, reduction zone and at the end cooling zone of the furnace. The reducing gas contains about 95% hydrogen and carbon monoxide. The gas flow is injected to furnace counter currently which will result in increasing the solid-gas contact. At the top of the furnace, the partially spent reducing gas (approximately contains 70% hydrogen plus carbon monoxide) exists and is recompressed. After contacting with natural gas, it is preheated to approximately 750F and then will be sent to reformer. So, reformer reforms the processing gas containing 95% of hydrogen and carbon monoxide. This gas is ready to use by the direct reduction furnace again. In the cooling zone, the cooling gases flow counter currently to the DRI. The cooling gases exit from the top cooling zone and sent to recycling from the bottom. The cooled direct reduced iron is discharged from the bottom of the furnace. Afterwards screening is done to remove fines. Then, for minimizing the hazards associated with storage of these fines, further treating is necessary. The reduced fines are briquetted to produce a usable DRI product. ("Iron making Process Alternatives Screening Study", 2000) More detailed technical aspects of DRI production could be found in Appendix I.

Figure 4: Process Flow sheet of DRI

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4.2 Main Parts of DRI: The main parts of Direct Reduction Iron are listed below: Furnace Charge hopper Reduction Zone (bustle Zone) Cooling Zone Reformer (Primary and Secondary) Stack and Blower Top Gas Scrubber ( Washing with hot water and Cooling Process gas with cold water ) Cooling gas Scrubber (Cooling refrigerant gas with cold water) Natural Gas Tank ( 95% methane) Recuperator (Heat Exchangers for preheating Air, Natural Gas and Process gas) Complete details can be found in Appendix I. (KOBE STEEL, 2011)

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5. Conclusion
In this report we reached a qualitative analysis based on the industrial, economic, environmental and geographical background of Norway. Developing iron industry in Norway can lead to optimum deployment of the country strengths in terms of natural gas and iron ore resources to seize the European iron market opportunities. Although the mentioned DRI route for developing iron industry will cost more in terms of capital expenditures, it might be seen that other factors, such as lower operational costs, lower environmental impacts, can compensate this disadvantage. Based on our studies the following issues and recommendations should be taken into ones consideration: To reduce the uncertainty of decision making process, it is recommended that a quantitative sensitivity analysis to be conducted with respect to supply and demand for the internal and external markets. Using mega module DRI modules may make this project more economically viable, because the concept of economy of scale can potentially decrease the overhead costs.. As the main parts of the Midrex DRI plant should be imported, it is recommended to negotiate more in terms of technology transfer. It is recommended that further development plans for producing more pelleted iron ore inside the Norway to be considered.

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References
1- Antonio Mouer ,Fredrick Mah The Lion Group and Midrex Experience, Operational Aspects of Lionss Midrex Plant 2- Birat, J.-P. "Steel and CO2 the ULCOS Program, CCS and Mineral Carbonation using Steelmaking Slag." ArcelorMittal, Maizires-ls-Metz, France. 3- Central Pollution Control Board (Ministry of Environment & Forests, Govt. of India) 4- Chris Parr, G. A. (2008). Low Cement Castable Wear Mechanisms in DRI Rotary Kilns. St Louis, USA(Kerneos, France). 5- Comsigua c.A. , C. F. O., JSC Lebedinsky GOK , matesi s.A. , Orinoco Iron S.C.S. , Venprecar c.A. (2009). "Direct Reduced Iron Fines High Moisture." Guide for Handling, Maritime Carriage, and Storage (HBI Association Ltd. ISBN 0-615-33698-5). 6- Direct Reduced Iron and Iron ore. (1999). ACTED consultants http://www.chemlink.com.au/iron.htm (Chemlink Pty Ltd ACN 007 034 022. Publications1997). 7- DRI Midrex Statistics worldwide (2008). Retrieved from www.midrex.com 8- Drogin, "Carbon Black", Journal of the Air Pollution Control Association, 18:216-228, April 1968. 9- Energy & Fuels 2001, 15, 1227-1232 Solar-Thermal Processing of Methane to Produce Hydrogen and Syngas 10- Hot briquetted Iron Association (HBIA),Hot Briquetted Iron (HBI), guide for handling, maritime carriage and storage 11- Iron and Steel Engineer(1995) Retrieved from www.heattreatcosortium.com) 12- Ironmaking Process Alternatives Screening Study (2000), LG Job No. 010529.01 Volume I: Summary Report. 13- Kobe Steel, L. "Midrex Process." Retrieved from http://www.kobelco.co.jp/p108/dri/e/dri04.htm. 14- MPT-Metallurgical plant and technology (2011) Retrieved from http://journalseek.net 15- Norwegian Meteorological Institute(2010). Retrieved ftom www.environment.no 16- Optimization Models For The Integrated Steel Plant Within The Gas-Mat Research Project Emrah Arica & Milena Vuvunikian. Number of pages: 115, Molde, (2009)

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17- Parivesh Bhawan, East Arjun Nager Delhi 110 032 e-mail : cpcb@nic.in Website : www.cpcb.nic.in 18- Patent, U. S. (1988). Method and Apparatus for producing Hot Direct Reduced Iron. Science Direct. 19- The Barents Region Where Gas Meets Ore Kirkenes, 22 23 June 2010 Seminar Paper 20- The increasing role of direct reduced iron in global steelmaking, F. Grobler and R.C.A. Minnitt March/April 1999, The Journal of The South African Institute of Mining and Metallurgy 21- U. Ortiz, J. A., J. Berrn, R. Viramontes"Development of Iron Layers on The Internal Wall of Reduction Reactors." A.P. 076 "F", Monterrey, N.L. 66450, Mxico (Universidad Autnoma de Nuevo Len, Facultad de Ingeniera Mecnica y Elctrica,Doctorado en Ingeniera de 22- UIF Holmqvist, H. A. (2010). Gass som reduksjonagent for jernmalm med potential til forbedre utslippsituasjonen for europeiske stlindustrien. Gasskonferansen I Bergen (Ironman)

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LIST OF TABLES
Table 1 reaction, enthalpy changes and temperature range Reaction C+2H2=CH4 C+1/2O2=CO C+O2=CO2 H2+1/2O2=H2O CO+1/2O2=CO2 Fe 0,947 +1/2O2=Fe0,947O 3Fe+2O2=Fe3O4 2Fe+3/2O2=Fe2O3 H KJ/mol -91 -114,4 -395,3 -247,3 -280,9 -263,7 -1102,2 -814,1 S J/mol K -110,7 85,8 0,5 -55,9 -86,3 -64,3 -307,4 -250,7 25-1371 25-1597 25-1500 G J/mol -91000+110,7T -114400-85.8T -395300-0.5T -247300+55.9T Temperature range C 25-2000 25-2000 25-2000 25-2000

Table 2: Scoring table for ranking different iron making processes (DOE report, 2010)

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LIST OF FIGURES

Figure 3: Iron ore in the nature (Wikipedia, 2011)

Figure (5) - DRI (Direct Reduction of Iron) Furnace (DRI Midrex Statistics worldwide, 2008)

Figure 6 - Christmas Tree (Iron and Steel Engineer, , 1995)

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Figure 7: The coexistence of natural gas and iron ore resources in Barents region (Ulf Holmqvist, 2010)

Figure 10: Multilateral cooperation among active companies in Barents region, 2011

Figure 12: The location of the proposed DRI plant in Norway ( Arica, Vuvunikian, 2009)

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Figure 14: Relation between CO/CO2 and H2/H2O with Temperature SOURCE

Figure 15: Firebrick Refractory

Figure 16: HBI shape (Wikipedia, 2011)

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Figure 17:DRI production in Norway (Arica, Vuvunikian: 2009)

Figure 18: DRI production in Norway (Arica, Vuvunikian: 2009)

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Figure 19: Autothermal Reformer (Uhde, 2008)

Figure 20: Schematic of thermal aerosol flow reactor.( Energy & Fuels, 2001)

Figure 21: Comparison of DIR Production Methods (Energy & Fuels, 2001)

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Appendix I: DRI (Direct Reduction of Iron) Furnace

Main Part of Furnace The main parts of Direct Reduction Furnace are Charge hopper Reduction Zone (bustle Zone)

Charge hopper The Pellets are transferred by conveyor from Day Bin (Daily Storage Tank) to the Charge hopper. The Charge hopper should always be full of pellets and the minimum and maximum amount is controlled by Load Cell. The Load Cell is in relation with Feeder to control the amount of pellets in the charge hopper. If the Charge Hopper becomes empty, the Load Cell will send the alarm to the sliding gate to be closed automatically, so the H2 and CO cannot penetrate to the environment. (Comsigua C.A., C. F. O., JSC Lebedinsky Gok, Matesi S.A. , Orinoco Iron S.C.S. , Venprecar C.A. 2009) Seal Leg exists bellow the Charge Hopper which inserts the seal gas to prevent syngas to go out Furnace by making the positive pressure. The combination of seal gas is CO2 and N2 that also keep Process Gas to be burned. Process Gas Fuel after compression and cooling by Seal Gas Compressor and Seal Gas Cooler will be used as Seal Gas for this purpose. Seal Gas also uses in Discharge Area which will be describe later. The pellets will be transferred to the Reduction Area and separated uniformly by Octopus Pipes. ("Ironmaking Process Alternatives Screening Study.", 2000 & KOBE STEEL, L. "MIDREX Process." Reduction Zone Reduction Zone is between Input Syngas and Output (Top Gas) as be shown in the Figure(5); The syngas insert to the reduction are with Bustle Ports and the direction of them are 45 degree down, so the gas will go down a little and then goes up to reduce pellets. The syngas passes through the pellets and causes to produce Sponge Iron. The reduced gas will exit from Top Gas to the Top Gas Scrubber to be washed and become cold to be used again in the reformer.

The Furnace Temperature controls with 10 thermocouples which are in three thermosets. The quality of input pellets, size of pellets, pellets porosity and the parameters of reduction effect on the temperature control. (ACTED , 1999) Permeability in Reduction Furnace: Permeability in reduction furnace means the resistance of pellets against the syngas flow which passes through them. The permeability can be measured by pressure drop in constant flow velocity. (Birat, J.P.) P/L=A(V/d2)(1-e)2/e3+B(V2/d)(1-e)/e3 P: Pressure Drop L: Reduction Length e: Fraction of bed spaces : Dynamic Viscosity V: Fluid Speed d: Pellets diameter A, B: Correction Factor : density of Syngas Chemical Reduction Reaction in the Furnace: According to the particles forming of Iron Ore, approximately the highest fraction in one pellet is hematite (Fe2O3). So the chemical reaction of hematite at the first stage with hydrogen and monoxide carbon can be the same as below:

3 1 1 Fe3 O4 + H 2 O Fe2 O3 + / H 2 2 2 2 3 1 1 Fe2 O3 + / CO Fe3 O4 + CO2 2 2 2

In both reaction the ratio of H2/H2O and Co/CO2 is so important and should be more than 1,5E-5 and 1,3E-3. Both functions are exothermic, so it is changed to the magnetite so easily by syngas, but it causes to increase the temperature at near the bustle when the syngas insert to the furnace.
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In the next step the magnetite Fe3O4 will be changed to the Wstite (Ferrous oxide FeO) and this reaction are endothermic, so the temperature should be high and the ratio of CO/CO2 and H2/H20 are so important and should be 0,6 and 0,7 to have the best result, so this ratio should be check each time by some instrumentation from furnace. (ACTED, 1999) Fe3O4+H23FeO+H2O Fe3O4+CO3FeO+CO2 The last step is the reaction of wstite (ferrous oxide FeO) by hydrogen to produce Reduced Iron. This reaction with H2 is endothermic. The ratio H2/H20 should be equal or more than 2. The highest temperature is in the reduction area, the lowest syngas ratio needs to have a high reaction velocity in the furnace, so it causes less syngas needs for the same reaction than low temperature.

FeO + H 2 Fe + H 2 O
The reaction of wstite (ferrous oxide FeO) by CO is exothermic and it means that at high temperature in the Furnace, the reaction should be with hydrogen and at the low temperature in the Furnace as shown in Figure (14) the reaction should be with monoxide, so:

FeO + CO Fe + CO2
The reaction of wstite (ferrous oxide FeO) with syngas controls the speed of chemical reaction and the velocity of production of reduced iron. Chart (1) shows the each reaction with enthalpy changes and temperature range. (Patent, 1988)

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Appendix II: Process Gas and Cooling the Reduced pellet

Cooling Zone Refractory with Firebrick Burden Feeder, Charge and Discharge Feeder Reformer Recuperator HBI (Hot Briquetted Iron)

Cooling Zone After reduction of pellets in reduction zone, the Sponge Iron likes to have reaction with oxygen or steam to be burned, it means that Sponge Iron is self-burning with oxygen when it wants to be discharged from furnace to storage tanks by conveyor belts, so it should been cold less than 45C before discharging in cooling zone. (Patent & UIF Holmqvist , 19882010) The cooling process is operated by combination of gases with 75% CH4. The refrigerant is the mixture of N2, CO2, Co, H2, H2O, and CH4. The Cooling gas (refrigerant) after cooling in the Cooling Scrubber will be compressed and added fresh CH4 to be concentrate, also it passes the filter to reduce its water, then insert to the Christmas Tree as shown in the figure (6). The Christmas Tree causes to distribute the cooling gas through the pellets uniformly. However, the Sponge Iron become cold in the Cooling Zone, the Insitu Reforming reaction also happens on it, so in this area two functions are happened cooling and Insitu Reforming. Insitu Reforming is also called decarbonized reaction, this reaction is endothermic and helps in cooling process and also increase the amount of process gas. (Holmqvist, . 2010) CH4+H2OCO+3H2 CH4+CO22CO+2H2 Burden Feeder, Charge and Discharge Feeder: There are three burden feeders to prevent forming bridge of pellets in the furnace. Upper Burden Feeder, Middle Burden Feeder, Lower Burden Feeder are shown in the Figure (5). These burden feeders have periodically movement like Pendulum with big segments, so they cause to break the
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clusters in the furnace and let the pellets to move in the furnace. The speed of charge feeder on the top of furnace and discharge feeder under furnace to charge and discharge the furnace is so important not to form bridge or empty in the system. Empty happens when the speed of feeder is low and forms a hole in reduction zone so it causes the temperature goes up in the furnace and convert the pellets to cluster and block the furnace. (. ACTED ,1999 ) Refractory with Firebrick: According to the Heat Transfer in furnace surface, the inside of the reduction furnace is refactored and insulated against heat transferring to keep the reduction zone at constant temperature. The firebrick should be resistance against erosion with less than 5% Iron and resistance against heat shock, so refractory in the reduction furnace is an important part of the furnace and in each shut down it should be repaired by special methods, because the loose of firebrick in each part or low quality of refractory can cause Hot Spot and next problems. As you can see in the figure (5) and figure (15) the conical area in upper Top Gas is not done refractory because in this area the temperature of pellets are low, but the line of bustle as an input gas line does refractory. (Chris Parr et.al. 2008) Reformer Reforming Process Gas happens in two steps, first in Primary Reformer (with inactive catalyst, active and super active catalyst) which is steam reforming with inactive catalyst for remain steam after miss eliminator and CO2 reforming with active and super active catalyst that are based aluminum and covered by Nickel, and second in Secondary Reformer which is Partial Oxygen reforming(POX). More detail is mentioned in Appendix II. (KOBE STEEL, 2011) Recuperator One of the advantages of Reformer in Midrex is recovering the exhaust gas of flame in Reformer to the stack. This recovery happens in Recuperator Box which is shell and tube heat exchanger for preheating air, Natural Gas and Process gas in three separate Tubes. (Patent, 1988)

HBI (Hot Briquetted Iron) Sponge Iron is produces by elimination of oxygen from iron in temperature lower than melting point of iron .sponge iron is completely porous with microscopic cavities as the result it has a high specific area about 1 cubic meters per gram which is 10000 times more than specific area of the DRI .this high specific area cause fast oxidation, So the solution with compacting DRI after discharging from blast furnace in high temperature of 650 C with high pressure density of the particles increased and then it would become less porous that adsorbs 75 percent less water in comparison with DRI. This is called briquette. (Figure 16) Briquetting means to compact by pressure in specific type of moulds in order to make high strength, high quality of the DRI particles with the same sizes. Main reason of Briquetting DRI segments is avoiding ignition of fine particles of iron and make it easy for storage and shipment. (MPT, YEAR !!!??? DRI is completely porous with microscopic cavities and it has a high specific area about 1 cubic meter per gram. Its clear that fine particles have specific areas even more than DRI leading higher tendency to oxidation. The problem is that these fine particles can easily ignite. So, these fine particles need further treatments for safety and storage considerations. This treatment is called Briquetting. This process is to convert fine particles into compact segments for easier transportation and storage. (MPT, YEAR !!!??? For briquetting, special equipment with large diameter of 1400mm is used. The diameter of the roller is large because the size of particles must be between 40 to 130 cubic centimeters. For achieving required particles size, large rollers are required. The presses are in hinged frames type which can be slide for roller removal. One of the rollers push the another one by hydraulic pressure in order to provide uniform pressing force .There is another important aspects of crews and roller cores that they have affective cooling system so that there is no risk of danger of ignition for DRI particles with temperature of 700 degree or more. The application of the screws and rollers are in the way that they keep the surface of the particles in 200 C to 300 C. The presses speed can be controlled according to the operational conditions. Any smaller particles recycle times and times by the hot recycle system. Density of the HBI is more than 5 grams per cubic centimeter .higher density and pillow shape of the particles cause superior handling, shipping and storage ( HBIA, YEAR !!!)

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There is a new system with name of Briquetting system design for LION. This new system has the specific feature as increase of 40% in diameter of the roller machines in comparison of previous briquette machines which causes higher production rate up to 70 t/h per machine. (Mouer and Mah, 2011) Cold briquetting is not as important of the hot briquetting just in case of long time keeping of briquettes and it improve the molding factor.

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Appendix III: DRI Production in Norway

Today there is no particular plant for DRI technology in Norway. However, there are several feasible projects are going to be realized to construct DRI plant in Norway using the existing raw materials from the different industries. Regarding the production of DRI based on natural gas, there is a new research project of steel production, Gas-Mat project, in Norway cooperating between SINTEF, NTNU, and the companies StatoilHydro ASA, Celsa Armeringsstal AS, Sydvaranger Gruve AS and LKAB. (Arica, Vuvunikian: 2009) The projects main objective includes: to make an assessment of potential utilization and industrial processing of natural gas to make an assessment of ore/minerals deposited in the Barents /Northern Region to consider environmental issues. This project based on the gas industrial clusters where carbon dioxide (CO2) is captured and rejected back in to oil/gas reservoirs causing zero emissions to the environment.(ibid.). The following figure illustrates the interrelated chain between various plants (Figure 12): The industrial cluster may contain following plants (ibid.), as it is demonstrated in Figure 17. Separator plant; Air Separation Unit (ASU) plant; Partial Oxidation (POX) plant; Methanol plant; Direct Reduction Iron (DRI) plant; Steel plant; Gas Power plant; Carbon Black plant. As we can see, in the technological scheme above the DRI technology is considered to produce steel using the natural gas as a main source. In general, according to Sustainability Report (2008), steel is produced by the following methods (ibid): Combination of the blast furnace (BF) and basic oxygen furnace (BOF). In this process the following raw materials are used, such as iron ore, coal, limestone and recycled scrap steels.

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 Electric arc furnace (EAF) method based on the recycled steel scrap and/ or DRI and electricity input. Nowadays, in Norway the first method is in process on the existing plants where iron is produced from iron ore by blast furnaces, e.g. Corus steel production technology as it was indicated before. It is clear that in the Gas-Mat project the latter method is considered to be implemented, that is iron and steel will be produced based on the DRI technology (ibid.). The DRI plant produces direct-reduced iron from iron ore using gas based or coal based process, as can be seen in Figure 18. DRI production process is described very shortly as following: iron oxide is preheated and reduced by reducing gas (H2+CO) in the shaft. The inputs to DRI plant is syngas from POX plant, hydrogen from Carbon Black and electricity from Gas fired power plant. The outputs are reduced iron, heat and gases. Some of the gases are recycled again to produce reducing gas. (ibid). According to the SINTEF report (2011), there is a developed plan of GeoNor project, where processes and strategies of the project are clearly illustrated (Figure 9): As it was reported (2009), Swedish iron ore company LKAB is studying plans to build a direct reduced iron plant at Tjeldbergodden in Norway (Steel Business Briefling, 2009). Moreover, according to the Hgans report (2009), companies such as Hgans AB, LKAB and StatoilHydro made an agreement to implement ironworks study outside Trondheim, Norway and also to test the possibilities of DRI production in Norway. This collaboration unites the parties technological know-how with the benefits of LKABs iron ore pellets, Hgans usage and sale of metal products and StatoilHydros skills in energy generation and gas refining. (Hgans: 2009) The planned location of this study works is close to the Tjeldbergodden industrial facility, where there are good links to existing plant and infrastructure such as natural gas pipeline, methanol plant and harbour. In addition, there is an important reason for using Tjeldbergodden which refer to the CO2 emissions that can be significantly reduced by using natural gas. The ambition of the project is to manage the worlds most CO2-neutral DRI plant an ironworks with the lowest CO2 emissions technologically possible. (ibid.).

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Appendix IV: Technology in producing Reduction Gases

As it was mentioned before, there are several new projects in Norway that are considered to use Direct Reduced Iron (DRI) technology to produce steel, iron and other materials. Based on the facts, DRI unit will receive synthesis gases from the existing methanol plant, such as Tjeldbergodden and hydrogen produced from Carbon black plants (Arica, Vuvunikian: 2009).

Syngas technology (Tjeldbergodden) In general, all commercial methanol technologies based on the following process sections: synthesis gas preparation (reforming), methanol synthesis, methanol purification(AasbergPetersen, 2011). Moreover, producing synthesis gas can be implemented by several reforming technologies available nowadays (ibid.): One-step reforming with fired tubular reforming Two-step reforming Autothermal reforming (ATR) The design two-step reforming was first used in Norways methanol plant with 2400 MTPD production rate. As it was reported, this methanol plant was built at Tjeldbergodden, Norway and was officially inaugurated on 5 June 1997 (Hansen, 2005). The plant is constructed to produce methanol by using the natural gas from the Heidrun field off the West Coast of Norway (Statoil, 2011). Tjeldbergodden is considered as the biggest methanol plant in Europe. Moreover, it is the first large-scale industrial production using the natural gas as a raw material in Norway (Statoil, 2011). As far as its known, Statoil has an 81.7 percent of ownership in the plant, and ConocoPhillips possess the rest 18.3 percent respectively. (Statoil, 2011). The process technology of the two-step reforming combines both fired tubular reforming (primary reforming) and oxygen-fired adiabatic reforming (secondary reforming). Figure 4 illustrates a process flow diagram for a plant with two-step reforming technology (AasbergPetersen, 2011). In primary reforming, the synthesis gas is produced by the following reaction which takes place without using of oxygen (ibid.):

Basically, the synthesis gas produced by primary reforming will typically contain a surplus of hydrogen of about 40% (ibid.). According to the report, it is likely to achieve the most suitable composition for the synthesis gas by combining the two reforming technologies (Aasberg-Petersen, 2011). The given block scheme in Figure 4 describes the more detail process ways of these two reforming technologies. In general, the amount of produced synthesis gas generated by the tubular reformer, that is primary reforming, between 35 to 45%. The rest amount of syngas is achieved in the oxygen-fired reformer, which is secondary reforming. Consequently, the primary reformer operates at low S/C ratio and low temperature, but high pressure. These conditions lead to a reduction in the transferred duty by about 60% and in the reformer tube weight by 75 to 80% compared to one-step reforming (Aasberg-Petersen, 2011). In addition to the steam reforming, the following reaction occurs in the secondary reforming (Uhde, 2008): CH4+0.5O2 CO + 2H2

However, in Tjeldbergoddens methanol plant Autothermal reforming (ATR) used as a secondary reforming (Statoil, 2011). In Figure 19 the autothermal reformer design is shown, which consists of a burner, a combustion zone, and a catalyst zone.(Uhde, 2008). As it is pointed out in Figure 19, there are three different reactions occurring in ATR: first - combustion of natural gas with oxygen, second reaction between natural gas and steam producing the syngas, and third conversion of syngas to carbon dioxide and hydrogen. The last two reactions take place in thermal and catalytic zones from which synthesis gas can be taken as a product. Carbon black technology Regarding the production of DRI by using natural gas the main part of process is producing syngas. There are several methods to obtain syngas such as Steam reforming plant, Dry reforming, Partial-Oxidation (POX). Whereas in our production plant which is located in Norway for this part of project we have POX plant and also before DRI furnace for making more hydrogen a carbon black plant is considered. Furthermore, to compare carbon black with CO2; that stock of solid Carbon need less amplification rather than storing gaseous carbon dioxide.

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As we can see, in scheme below of our DRI production plant this is going to build in Trondheim. POX and Carbon black plants are used simultaneously due to produce extra syngas, since conversion of DRI is dependent on amount of syngas, so the key point for our plant is produced syngas as much as possible. Now two processes are used for manufacturing carbon black in the U.S. Oil furnace process and Thermal furnace process which are describing at below:

Description of thermal furnace process: In thermal process Methane is dissociated thermally into carbon particles and hydrogen: CH4C+2H2 H= +74.9 Kj/mol

Generally for this process two furnaces are used that the first one is cracking the Natural gas and producing carbon black and hydrogen. Then waste gas from the first reactor will be cooled by water up to approximately 125 C. Afterwards amount of black grain is collected in a filter. Gas produced is containing 90 percent of hydrogen, 6 percent of Methane and 4 % of higher hydrocarbons. In our case hydrogen is added to DRI furnace and carbon black send out from cycle to applicant plants, using as a reinforcing in base material of tires, black pigments of inks, paper and plastic. Structure of thermal furnace is given in Figure 20.

Description of Oil furnace process In oil furnace process aromatic liquid hydrocarbon feed stock heated by heat exchanger and will be injection to combustion area of natural gas furnace and is decomposed to carbon black. Carbon black is cooled by primary quench water up to 500C. Exhaust gases which are contain carbon black particles cooled to approximately 230C by heat exchanger and water spray. Then finally the gas stream and carbon black would be separated by fabric filter from each other. In result, we can mention about some advantages of the Thermal furnace rather the oil furnace in this plant: raw material in thermal process is natural gas that is cheaper than aromatic and also to consider Hydrogen; Methane is an appropriate choice because of its high hydrogen to carbon ratio and rather low cost.
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