Mercury Emission Scenario World and Indian Cement Industry

TIWARY, N. K.; SELVARAJAN, M.; BOHRA, A; NATH, K R P; and MISHRA, A. K.

NATIONAL COUNCIL FOR CEMENT AND BUILDING MATERIALS

ABSTRACT Mercury hazards are being studied for few sectors in India. The awareness to hazards caused by mercury pollution is increasing among Indian public. Industries such as Chloralkali, Thermal power plants, steel and cement plants are some of the major source of mercury release to atmosphere and in some cases to surface water. Out of around 600 million tonnes every year of coal consumption in India, Cement industry consumes around 5% of coal. Coal contains mercury, hence, during its combustion mercury emission may take place due to its semi-volatile characteristics. The Indian cement industry is the second largest producer in the world. The possible sources of mercury from Cement Industry includes raw materials like limestone, clay, bauxite, iron ore; blending materials like fly ash, slag, fuels like coal, petcoke, alternate fuels etc. Raw Materials used for Cement production are one of the major sources for mercury emissions from Cement industry. Cement plants have a wide range of fuel inputs mainly coal resulting in mercury emissions because of the high temperature in pyro-processing. Heavy metals such as mercury contained in conventional or alternate raw materials and fuels are mainly incorporated in clinker. Mercury, being the only metal which can be emitted with the clean gas in gaseous form, the input of mercury with raw materials and fuels has to be carefully controlled. The present paper discusses the status of Mercury emissions from cement plants worldwide, techniques and technologies adopted to control mercury emissions, emission norms available, if any for mercury emissions in other countries and future approach for Indian cement industry regarding mercury emissions. Keywords: Cement Industry, Mercury, Coal, Mercury Emissions, Biosphere 1.0 INTRODUCTION The average level of mercury in the atmosphere is around 1.1 1.7 nanograms/m3 (UNEP 2008), which is largely due to Anthropogenic activities. There is a growing level of concern about mercury emissions from various industrial sources. Exposure to Mercury at higher concentrations may result in nervous system disorders, reproductive and developmental problems, kidney and liver damage, and other health effects. The global anthropogenic mercury emissions to atmosphere from different regions of world is given in table 1.1. Asia is the largest emitter of mercury emissions contributing 1281 tonnes (i.e. upto 66.5% of the total emissions) to the atmosphere.

Table 1.1 : Global anthopogzonic mercury emission to atmosphere in world S.NO. 1. 2. 3. 4. 5. 6. 7. Continent Asia Europe North America South America Russia Oceania Africa Emissions, Tonnes 1281 150 153 133 74 39 9.5 %, Emissions 66.5 7.8 7.9 6.9 3.9 2.0 5

(Source: The global atmospheric mercury emission; sources, Emissions and transport UNEP, 2008)

The leading countries among emitters of mercury to atmosphere are China and India (Fig 1.1). The mercury hazards are being studied for few sectors, including cement world over. Due to global awareness to hazards caused by mercury pollution concern is increasing among Indian public towards mercury emission from industry. In India, major source of mercury to atmosphere are fossil fuel combustion in thermal power emissions plants, chloralkali, cement plants, metal production (ferrous and nonferrous), gold production, waste incineration etc as shown in figure 1.1. The proportion of Global Anthropogenic Mercury Emissions from different sectors is given in figure 1.2 and table 1.2.

Figure 1.1 The global atmospheric mercury emission

(Source: Emissions and transport UNEP, 2008)

India consumes around 600 million tonnes of coal every year in various industries like thermal power plants, steel, cement and others, where coal is used either to generate power or as thermal energy input. Coal contains mercury hence during its combustion mercury emission takes place due to its semi-volatile characteristics. It is evident that thermal power plants using fossil fuels are the major source of the mercury pollution to Atmosphere. Cement plants have a wide range of material as well as fuel inputs mainly coal, resulting in mercury emissions because of the high temperature in pyro-processing. Cement industry contributes around 10% of the total global anthropogenic mercury emissions as shown in table 1.2 and figure 1.2. However, the current level of mercury emissions from Indian Cement Industry due to various types of fuel, technology, geographical location, Pyroprocessing, raw material etc is not studied in detail. Table 1.2 Global anthropogenic mercury emissions from different sectors Sectors Thermal Power Plants Metal Production Large Scale Gold Production Small scale gold prod. Cement Industry Chlor-Alkali Waste Incineration Dental Amalgam Emission, Tonnes 878 200 111 350 189 47 125 26 Emissions% 45.6 10.4 5.8 18.2 9.8 2.4 6.5 1.3

Figure 1.2 Global anthropogenic emissions from different sectors

mercury

(Source: The global atmospheric mercury emission; sources, Emissions and transport UNEP, 2008)

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MERCURY CYCLE Mercury is bio-accumulative. Once released into the environment, mercury deposits on soil, air, groundwater and surface water where it accumulates and moves up the food chain. In water bodies, mercury is taken up from the sediment by small organisms, which are eaten by increasingly larger organisms until it ends up in fish that is eaten by humans. At each step of the process, mercury levels increase in concentration, which makes large food fish that exist at the top of the food chain, especially dangerous to eat. Mercury emissions are regulated based on concern for mercury entering the food chain and bio-accumulating to significant levels that can 3

impact people eating fish. Cement kilns mercury emissions fall back to earth in a process known as deposition. As it is an element, mercury does not decompose but persists indefinitely in the environment once it has been released

Figure 2.1 Mercury cycle in food chain 3.0 STATUS OF INDIAN CEMENT INDUSTRY The Indian cement industry is the second largest producer of cement in the world comprising 185 large cement plants and 365 mini cement plants. The installed capacity and cement production during the year 2012-13 are 349 Mn.t and 240 Mn.t respectively. By the year 2020, it is expected that the installed capacity of Indian Cement Industry will be increased to 600 Mn Tonnes per annum. Today, it is by and large comparable to the best in the world in respect of quality standards, fuel & power consumption, environmental norms, use of latest technology and capacity etc. Cement being one of the six core sector industries, plays a vital role in infrastructure development especially in a developing country like India. The per capita cement consumption in India is approx 200 Kg, against the world average of approx 500 Kg. It is lower than several developing countries like Thailand (366). Sustainable growth of the industry for enabling sustainable growth of infrastructure calls for leveraging pollution control measures with rapid growth of the industry. The main clusters of cement industry in India are shown in Figure 3.1.

Figure 3.1 : Clusters of Indian Cement Industry 3.1 Pyro-Processing Technology used in Indian Cement Industry Wet Process Semi-Dry Dry Pre-Heater (PH)/ Pre - Calciner (PC) - Single/Double/Triple string - 4 stage PH - 5 stage PH - 6 stage PH Inline Calciner (ILC) Separate Line Calciner (SLC) 5

3.2

Process Profile of Indian Cement Industry The technological spectrum in the cement industry is very wide. At one end of the spectrum are the old wet process plants, while at the other end, are the new state-ofthe-art technology plants presently being built by the Industry. The Cement Industry today comprises mostly of Dry Suspension Preheater and Dry Precalciner plants and a few old wet process and semi-dry process plants. Today, there are 178 kilns in operation comprising 165 dry process kilns, 5 wet process kilns and 4 semi-dry process kilns. In addition to these, there are more than 300 mini cement plants. Figure 3.2, shows the percentage variation in process profile (i.e. Dry, Wet or Semi-Dry) of Indian cement industry in terms of no. of kilns and kiln capacity in TPD respectively.
Wet 1.0% SemiDry 0.4%

Wet 5.1%

Semi-Dry 2.2%

Dry 98.6%

Dry 92.7%

Wet

Semi-Dry

Dry

Wet

Semi-Dry

Dry

Fig 3.2 : Process profile on Indian Cement Industry

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SOURCES OF MERCURY EMISSIONS IN CEMENT INDUSTRY The possible sources of mercury from Cement Industry includes raw materials like limestone, clay, bauxite, iron ore; Blending materials like fly ash, slag, fuels like coal, petcoke, alternate fuels etc. Raw Materials Limestone Clay Bauxite Iron Ore Blending Materials Gypsum Fly Ash Slag Fuels Coal Petcoke Imported Coal Alternate Fuels like Hazardous waste Lignite

The mercury content in various raw materials and fuels used in Cement Industry for other countries was published in a study of CEMBUREAU CSI (2010) and is shown in Table 4.1. However, for Indian cement industry, no study has been carried out yet for estimation of mercury content of various raw materials, fuels used and its impacts on the biosphere. Table 4.1: Mercury Content of Materials & Fuels used for Cement Production S. No. Mercury Content Raw Materials Limestone Clay Sand Flyash Iron ore Blast furnace slag Gypsum (natural) Gypsum (artificial) Range mg/kg <0.005 0.40 0.002 0.45 <0.005 0.55 <0.002 0.8 0.001 0.68 <0.005 0.2 <0.005 0.08 0.03 1.3 0.1 13 0.03 0.11 0.01 0.71 0.006 <0.06 0.22 <0.07 2.77 0.01 0 0.4

1. 2. 3. 4. 5. 6. 7. 8.

Fossil Fuels 9. Coal 10. 11. 12. 13. 14. 15. Lignite Petcoke Heavy Oil Alternative fuels Liquid-waste derived fuel Solid-waste derived fuel Tyre-derived fuel

(Source: Mercury in the Cement Industry, University of Lige, CEMBUREAU-CSI, 2010)

Raw Materials used for Cement production are one of the major sources for mercury emissions from Cement industry. Limestone is major raw material for cement industry. India is having limestone reserves of 109703 Mn.T. During year 2010-2011, 232 Mn.T of Limestone is consumed for cement production in India. Cement plants have a wide range of fuel inputs mainly coal resulting in mercury emissions because of the high temperature in pyro-processing. Out of around 600 million tonnes every year of coal consumption in India, Cement industry consumes around 5% of coal. Coal contains mercury hence during its combustion; mercury emission may take place due to its semi-volatile characteristics. Table 4.2 shows the growth of major cement industry and its limestone and coal consumption during the last four years.

Table 4.2 Growth of Indian Cement Industry during last five years (In Million Tonnes) Captive Coal Coal Power Installed Total Coal Year Production* Consumption Consumption Generation Capacity* Consumption* in Process* CPP* Capacity$ (MW) 2007190.11 174.29 18.92 6.14 27.33 2545.99 08 2008217.56 187.61 19.52 7.64 29.57 2791.11 09 2009250.92 207.56 16.04 6.90 25.80 2676.74 10 2010310.96 228.30 17.51 8.50 28.06 2697.34 11 2011325.78 246.70 17.70 8.81 28.37 2688.14 12

*Source: Working group on cement industry for XII five years plan. Cement Statistics 2012. $DG set included

In 2020, the estimated cement production capacity of Indian Cement Industry may reach around 600 Million Tonnes. As per Mercury Emission factor for global cement production given in UNEP 2008 report, 0.1 gm mercury per tonne of cement production is emitted in the environment (Table 5.1). Hence, the mercury emission from Indian Cement Industry is estimated to be: At present, 33 Tonnes per year By 2020, it may be around 60 Tonnes per year

Future Growth in Indian Cement Industry

700 600 500 400 300 200 100 0
Grow th of Indian Cem ent Industry 600 414 318 61 133 220 98

Mn.T

29

21

49

Year 2001 2011 2020(E)

1981

1991
Installed Capacity (M n.T)

Cement P roduction (M n.T)

5.0

MERCURY HOTSPOTS FROM CEMENT INDUSTRY Mercury present in raw materials and fuels used as inputs in cement industry comes out in the form of entrapment in clinker, emissions from stacks as shown in figure 5.1. Sources of Mercury Emissions to atmosphere from Cement Industry Entrapment in Clinker Emissions Kiln and Raw Mill Stack Cooler Stack
Hot Gases (E)

Fuel (S)

Pyroprocessing System
Raw meal (S) (S) Source; (E) Emission, (En) - Entrapment Clinker (En)

Figure 5.1 Mercury sources and emission points from Cement industry Heavy metals contained in conventional or alternate raw materials and fuels is mainly incorporated in clinker. Mercury, being the only metal which can be emitted with the clean gas in gaseous form, the input of mercury with raw materials and fuels has to be carefully controlled. Table 5.1: Mercury Emission Factors from different sectors Category Coal Combustion in 1. power plants 2. Oil Combustion 3. Cu Smelters 4. Pb Smelters 5. Zn Smelters 6. Cement Production 7. Steel Production 8. Gold production Municipal Waste 9. Incineration (Source :UNEP 2008 report) 9 S.NO. Unit g/Tonne coal g/Tonne oil g/Tonne Cu produced g/Tonne Pb produced g/Tonne Zn produced g/Tonne Cement g/Tonne Steel g/ g gold mines g/Tonne waste Emission factor 0.1 - 0.3 0.001 5.0 3.0 7.0 0.1 0.04 0.025 - 0.027 1.0

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MERCURY EMISSION LIMIT VALUES IN DIFFERENT COUNTRIES Due to high awareness and concern to mercury hazards for flora and fauna countries world over have either evolved or in the process of evolving limit of mercury concentration in the environment. Standards and guidelines for some countries are presented in Table 6.1. Table 6.1 : Mercury Emission limit values in different countries Hg Concentration (mg/Nm3) for existing facilities for new ones mg/Sm3 0.10 0.07 0.05 0.24 0.05 0.05 0.05 (8) At reference O2 % 0.012 mg/Nm/43 (21.5 mg/tonne) 0.004 mg/Nm/14 (7 mg/tonne) 0.15 mg/Sm3, 10% O2 for Hazardous Waste only. at 7% O2 at 10% O2 Sum of Hg and Cd; at 10% O2 at 11% O2. at 10% O2. under review; reference value: 0.05 at 10% O2. Sum of Cd, Hg, and Tl: 0.2 or 0.28 (at 7% O2). at 10% O2 0.2 @ 7% O2 @ 13% O2 @ 12% CO2 @ 7% O2 (for waste incinerators) (permit limit)

USA

Canada Morocco (1) Mexico El Salvador Costa Rica Colombia Venezuela Ecuador Brazil

No limit Argentina 0.109 Chile 0.2 Bangladesh 5 Indonesia 0.1 Korea 10 Malaysia 5 Philippines 0.10 Thailand 0.5 Vietnam 1.0 mg/Nm Australia 0.05 mg/Nm3 Europe (Source : UNEP 2008 report) 7.0 7.1.

MEASURES FOR MINIMISATION AND CONTROL OF MERCURY EMISSIONS Input control Mercury enters the kiln system as a trace element through naturally present in raw materials and, to a lesser extent, in fuels. Best environmental practice is to carry out a 10

careful selection and control of all substances entering the kiln in order to reduce mercury input. 7.1.1. Raw materials A. Raw Materials from Quarries

Mercury concentrations in raw materials (limestone, marl or clay) vary significantly from quarry to quarry. There are even cases where mercury concentrations vary significantly within a single deposit, thereby sometimes requiring selective mining. In those cases, after exploration and analyses of the quarry, it is possible to define specific parts of the quarry with higher mercury concentrations and to continue exploitation in zones where the concentration is lower (selective mining) . It has to be highlighted that such a procedure is complex to manage and cannot always be carried out . If mercury is present in all quarry layers, other options have to be considered. B. Other Raw Materials and Waste Materials

Corrective materials such as bauxite, iron ore or sand may be required to adapt the chemical composition of the raw mix to the requirements of the process and product specifications. To a limited extent, alternative raw materials are used to substitute natural raw materials and correctives. This consists of selecting materials with a low mercury content as well as in using a quality assurance system to guarantee the characteristics of the materials used. In cases where alternative raw materials lead to a significant increase in the mercury intake into the system they may have to be replaced by another alternative material. 7.1.2. Fuels The cement production process usually uses fossil fuels such as coal, petroleum coke, oil and alternative fuels (tyres, wastes derived fuels, etc.). Fuels are not usually the dominant source of mercury in cement kiln input. Nevertheless, it can be necessary, in specific cases, to also monitor the mercury content of the fuels (more particularly alternative fuels). Literature review has shown that petroleum coke has lower Mercury (0.01 0.20 ppm), coal (0.01 0.43 ppm) In principle, for alternative fuels, best environmental practice is to apply quality assurance systems to guarantee the characteristics of the waste and to analyse and control the mercury content if necessary. 7.1.3. Process integrated measures In order to avoid an undesired increase of mercury in the kiln system, the periodic purging (bleeding) of cement kiln dust from the system is an efficient way to control mercury emissions. Many preheater-precalciner kiln systems have raw mills in-line. 11

Adsorption is favoured due to the very high dust loadings of up to several 100 g/m present in the raw mill gas streams from preheater-precalciner kilns. This purging process is more efficient in the mill-on mode than in the mill-off mode due to the higher mercury concentrations in the dust. During the mill-on operation mode, the finely ground raw material in the raw mill retains mercury from the flue gases. This leads to lower mercury emissions in the mill-on mode compared to the operating periods without raw mill (mill-off). About 80 to 95% of the overall operating hours are carried out in the mill-on mode. Furthermore, the temperature of the flue gas plays an important role. In general, the adsorption capacity for mercury increases with lower temperature. For controlling mercury emissions, bleeding of the kiln dust system, whereby cement standards allow for the incorporation of the collected dust into the cement, is suitable. This is a proven and safe procedure in many regions of the world, neither the environment nor the product quality is affected. 7.2 Other techniques tested in the cement industry 7.2.1. Adsorption on activated coke, Polvitec The Polvitec system (CEMBUREAU, 1999) consists of several packed beds of activated coke. The dedusted kiln exhaust gas is passed across the activated coke whereby compounds like heavy metals (and mercury), VOC, SO 2 and NH3 are adsorbed. The cleaned gas is then released into the atmosphere. The spent activated coke is periodically extracted to a separate silo and replaced with fresh adsorbent. Since volatile and semi-volatile heavy metals are effectively adsorbed on activated coke and since the clean gas dust content downstream of the activated coke device is down to a few mg/Nm, the emission of heavy metals is virtually equal to zero. Adsorption on activated coke is not economically viable. In the case of a Polvitec system installed in a Swiss cement plant, the project was only made economically feasible through the financial contribution of the communities burning their sewage sludge in the kiln, the fees for burning other alternative fuels in the kiln and the complex problem related to different emission components. 7.2.2. Activated Carbon Injection Activated carbon injection systems are well established as commercial air pollution control processes for a variety of volatile organic compounds, dioxin-furan and mercury controls in waste incinerator applications (Richards 2005). Activated carbon injection processes are being considered in the US for widespread use in the coal-fired utility boiler industry. For many reasons, the possible application of activated carbon injection systems in cement kilns is considerably more challenging than in the case of coal-fired power stations. Cement kilns must recycle a major portion of the collected dust. Some kilns use the fabric filter system as an integral part of the raw material processing system. 12

The temperature of this system would have to be carefully controlled to less than 200C to ensure proper mercury adsorption and reduce the risk of activated carbon fires in the fabric filter or solids handling system. If all other measures fail, installation of a powdered activated carbon injection system and a further dedusting device (fabric filter) downstream of the main kiln filter may be thought of. This last control option would be extremely expensive. The high costs are due to the need for a second fabric filter system, a new fan and an activated carbon injection system. The operating costs depend heavily on the cost of the adsorbent. Dust management is a subsequent issue. This is the reason why, so far, there are only a few applications of such a technique in the cement industry. 7.0 ROLE OF NCB National Council for Cement and Building Materials (NCB) has been engaged in R&D activities for cement and construction industries. It has given support services in different spheres of these industries. It has excellent environment management facilities and experienced team working in the area like air quality monitoring, EIA/EMP studies, LCA studies, carbon accounting and climate change studies, pollution load studies, noise & ground vibration studies etc. The organization has state of the art instruments for air emission quality monitoring like ICP spectrophotometer, FT-IR, spectrophotometer, XRD/XRF, PSD analyser etc. The environment management group has completed projects in the area of environment management for organizations like MoEF (India) UNFCCC, NATCOM etc. With such expertise and experience, NCB can play important role in creating mercury data base for Indian Cement Industry. 8.0 CONCLUSION Mercury emission is an important global issue as the persistent pollutant remains in the eco-system and enters the human food chain. Mercury consumption is hazardous to human health and especially prenatal development. The UN has led an international coalition to measure and reduce global mercury emissions. The cement manufacturing process directly accounts for approximately 10% of global mercury emissions. Developed countries like USA and Europe have taken steps to curb emission from cement industry. In view of projected potential of mercury emission and lack of data on mercury emissions from Indian cement industry, a detailed study is required for different elements of input, output, process, so that a suitable strategy can be designed for curbing the catastrophic impact of mercury on flora & fauna. NCB can play a pivotal role on estimation of mercury emission from Indian cement industry to make a reliable data base. ACKNOWLEDGMENT This article is being published with the permission of Director General, NCB.

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10.0 1. 2. 3. 4. 5. 6. 7. 8.

BIBLIOGRAPHY Annual Report 2011, Ambuja Cement Ltd. Annual Report 2011, ACC Ltd. Cement statistics 2011, Cement Manufacturers Association, India Report on Mercury in the Cement Industry April 2010, University of Liege, Independently Commissioned by Cembureau CSI The Global Atmospheric Mercury Emissions: Sources, Emissions and Transport, UNEP, 2008 Linda M. Hill (2006) PCA R&D, serial no. 2944, summary of PCA projects on mercury topics. Rechards John, capabilities and limit hour of available control technology for Mercury Emission from Cement Kiln, SN27 48 a, PCA, USA, 2005. NCB reports

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