Lime in the limelight

Accepted Manuscript Lime in the Limelight Aideen Dowling, Jean O’ Dwyer, Catherine C. Adley PII:

S0959-6526(14)01343-2

DOI:

10.1016/j.jclepro.2014.12.047

Reference:

JCLP 5018

To appear in:

Journal of Cleaner Production

Received Date: 1 May 2014 Revised Date:

11 December 2014

Accepted Date: 13 December 2014

Please cite this article as: Dowling A, Dwyer JO’, Adley CC, Lime in the Limelight, Journal of Cleaner Production (2015), doi: 10.1016/j.jclepro.2014.12.047. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

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Lime is one of the most versatile chemicals in the world. There are two main types of lime produced, quicklime and hydrated lime. Quicklime is formed during the calcination of limestone. Hydrated lime results from subsequent hydration of quicklime where required. Lime has been innovatively rediscovered to be a more

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environmentally sustainable product aiding in the implementation of new cleaner systems from, remediation of acid mine draining to key uses in water source

treatment. Further research has been undertaken to investigate new roles for lime as an antimicrobial compound and environmentally friendly biocide. The uses of lime

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have evolved steadily over time; this is thought to be due to its ease of acquisition,

affordable price and unique versatile properties. The aim of this literature review is to

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provide an informed view on the current application of lime and its potential novel

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uses in the future.

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Authors: Aideen Dowling*, Jean O’ Dwyer, Catherine C. Adley

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Title: Lime in the Limelight

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Name and Address of Institute at which the work was preformed: Microbiology Laboratory, Centre for Environmental Research;

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Department of Chemical and Environmental Sciences, University of Limerick,

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Limerick, Ireland.

*Correspondent footnote: Aideen Dowling,

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Department of Chemical and Environmental Sciences

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University of Limerick Limerick Ireland

Email: [email protected] Phone: +353 61 202646

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Keywords: Uses of Lime; Trade; Lime industry; Environmental remediation; Healthcare solutions; Metallurgy applications.

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Abbreviations: REACH: Registration, Evaluation, Authorisation and Restriction of Chemicals IPPC: International Plant Protection Convention

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BAT: Best Available Techniques BREF: BAT Reference Document

AMD: Acid Mine Draining LCA: Life Cycle Assessment CCS: Carbon Capture and Storage CCU: Carbon Capture and Utilisation

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FGD: Flue Gas Desulphurization

NP: Nanoparticles

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IPCC: Intergovernmental Panel on Climate Change

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EU ETS: EU Emissions Trading System PCC: Precipitated Calcium Carbonate

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EINICS: European Inventory of Existing Commercial Chemical Substances VCAS: Vitrified Calcium Alumina-Silicate EULA: European Lime Association

1. Introduction Lime is one of the most versatile chemicals in the world with numerous industrial, environmental and chemical uses. It is a white alkaline substance consisting of calcium oxide (CaO), which is obtained by heating limestone; it is also used in the production of hydrated lime [Ca(OH)2]. Due to its different geological origins and the various circumstances

ACCEPTED MANUSCRIPT surrounding its production, there are several differences as regards physical and chemical characteristics. There is evidence that illustrates the use of quicklime and hydrated lime in construction was widespread as early as 1000 B.C., among many civilisations, including the Greeks, Egyptians and Romans. It is suggested that the Romans were aware of its chemical properties and used it medicinally as limewater and for bleaching linen (European

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Commission, 2013). Uses of lime began to expand with the arrival of the industrial revolution, although it remained primarily a construction commodity in most developing countries (Miller, 2013). However, the production of lime decreased at the end of the 1980s as one of the main users of lime, the iron and steel industry, dramatically reduced its specific

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consumption of lime (Miller, 2002). The rejuvenation of lime occurred around the mid 1990s with the growing use of lime in environmental protection. Lime has been paramount in improving industrial application through the development and usage of “environmentally

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friendly” technologies. Lime is used in a wide range of products and applications, each suited to particular market requirements. Lime and its derivatives are used as a fluxing agent in steel refining, as a binder in construction. Key uses for lime have been found in several areas of pollution prevention and abatement; some of these include treatment of drinking and waste water, remediation of air emissions and treatment of hazardous waste (Domke et al., 2004).

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The aim of this literature review is to provide an informed view on the current application of lime and its potential novel uses. The conservation of this commodity, the lime industry and its sustainability will be examined.

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2. Methods: Search strategy and selection criteria The database Thomson Reuters Web of Science (V5.15) was used to search for the topic “lime” with the publication dates between 1950 and 2014 returned 101,185 hits (Thomson

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Reuters Web of Science, 2014a). When this search with the topic is further refined with the term “environment” it returns 8,055 hits (Thomson Reuters Web of Science, 2014b). On review this illustrates that only 8% of the lime literature between 1950 and 2014 pertains to use in the environment.

Original research articles were retrieved from Thomson Reuters Web of Science. The search strategies submitted combined the concepts “lime”, “calcium oxide” “quicklime”, “hydrated lime”, “burnt lime”, “dolime”, “dolomitic lime”, “dead burnt lime”, “slaked lime”, calcium hydroxide”, “calcium hydrate”, “caustic lime”, “hydrated dolime”. In conjunction with “types of lime”, “lime industry”, “trade”, “energy use and emissions”, “use of lime”, “industrial

ACCEPTED MANUSCRIPT applications of lime”, “non-environmental uses”, “metallurgical industry”, “construction industry”, “soil stabilisation”, “nutrient in fertiliser”, “chemical industry”, “environmental uses”, “potable water sources”, “wastewater treatment”, “sludge treatment”, “Flue gas treatment”, “acid mine draining”, “mediation of waste”, “lime as a disinfectant” and “lime innovations” etc.

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Keywords of the concepts used in the search strategies included articles in all languages from January 2012 to November 2014. Research reports from international organisations and grey literature were also included in our literature review

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3. Types of lime The term “lime” is often used incorrectly to describe limestone products. This is a frequent

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cause of confusion (Stork et al., 2014). Lime includes quicklime and slaked lime and this term ‘lime’ is synonymous with the term ‘lime products’.

Quicklime is calcium oxide (CaO) produced by the decarbonisation of limestone (CaCO3). Slaked lime is produced by reacting or ‘slaking’ quicklime with water and consists mainly of calcium hydroxide (Ca(OH)2) (Oates, 1998). Characteristics of various forms of lime are

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summarised in Table 1.

There are many qualities of lime products. These factors are influence by: The presence of magnesium in the raw material, and thus the product;

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The temperature of the kiln;

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A slaking step.

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•

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Different types of lime are used for an extensive variety of applications. A clear distinction is made between calcium limes, dolomitic limes and hydrated limes. Calcium limes are by far the largest category and are supplied in lump, ground and hydrated forms. Dolomitic limes are more specialised products and are usually supplied in smaller quantities in lump, ground, hydrated and dead burned forms. Hydraulic limes are partially hydrated and contain cementitious compounds, and are used exclusively in building and construction. Quicklime is the most widely produced lime product (Stork et al., 2014). Throughout the rest of this report, the term lime products will be used to refer to all products mentioned above.

4. The lime industry

ACCEPTED MANUSCRIPT The lime industry is characterised by several large European Union (EU) and International producers that operate on an international stage. This gives them access to global best practice, technology and markets for a wide range of lime applications. With the exception of some industrialised nations, accurate lime production data for individual countries is difficult to obtain. Aside from production by large commercial lime companies, lime productions in

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small scale manufacturing units operate simple kilns to supply local demand. These variations and the frequent confusion with limestone data, make accurate collecting of

international lime figures difficult and incomplete. In some cases, lime sales data has been used to give an indication as to amount of lime produced (Crump et al., 2000, European

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Commission, 2001b). The current estimated figures demonstrate that in 2012 there was 346 million tonnes of lime produced worldwide, of which China produced 220 million tonnes, 43 million tonnes was produced in the EU and 19 million tonnes was produced in the United

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States (including Puerto Rico) (Miller, 2013). In Figure 1, the worldwide production of quicklime and hydrated lime (including dead-burned dolomite) is broken down by country; China has been removed so that a visible scale can be used.

Lime production technology and efficiency has evolved over several thousand years. It now represents the best possible outcome in terms of environmental performance. The extraction

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and processing generally happens on site, this avoids unnecessary transportation costs and associated environmental damage.

The lime industry is capital and energy intensive, the energy costs usually account for up to

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half of the gross production costs (European Commission, 2014a). Lime kilns are long lasting; and are productive for approximately forty years, which means it is difficult for producers to comply in the short term with updated legislation, which for example could

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affect energy or emissions. The most common fuels used to produce lime are coal, oil and natural gas (EMEP & EEA, 2013). Emissions generated in the combustion of coal and other fuels make the lime industry subject to regulation under the Clean Air Act (European Commission, 2001a). In European member states this act has introduced a number of concerns for the lime industry. The major concern is the cost of production, which greatly increased due to the necessity of additional monitoring, reporting and the control of the production of hazardous air pollutants. Such as hydrogen chloride, and greenhouse gases, particularly carbon dioxide. The EU Emissions Trading System (EU ETS) is the largest multi-national, greenhouse gas emissions trading scheme in the world. It is a cornerstone of the EU’s policy to combat climate change. It is a key tool for reducing industrial greenhouse

ACCEPTED MANUSCRIPT gas emissions cost-effectively; it works on the ‘cap and trade’ principle. A ‘cap’ or limit is set on the total amount of greenhouse gas that can be emitted from power plants, commercial airlines and a wide range of energy-intensive industry sectors, such as the lime industry. The cap is reduced over time so that total emissions fall. In 2020, emissions from sectors covered by the EU-ETS will be 21% lower then in 2005. Within the cap, companies receive or buy

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emission allowances, which they can trade with each other as needed. After each year companies must surrender allowances to cover its emission, otherwise heavy fines are imposed. By having a high price on carbon, the EU ETS is acting as a major driver in

investment in clean technologies and low-carbon solutions (European Commission, 2014b).

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Notwithstanding the successful implementations and the popularity of the cap and trade

system as a policy tool in the EU, a national trading program in the US proves elusive. In 2009 the American Clean Energy and Security Act H.R. 2454 a greenhouse gas cap and trade

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bill was passed by the House of Representatives, but later died in the Senate in 2010. Since that time the debate over climate change has grown louder but carbon monitoring is looked upon as at state level rather than national level issue in the US (EPA, 2009 and EPA, 2010).

4.1 Trade Lime is a heavy product with a relatively low selling price; the transport cost usually dictates

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the distance it can be transported on a regular basis under viable economic conditions. Due to the transport cost of delivering lime, long distance exportation is rare; except to supply lime products of a superior quality not locally available. Only a very small percentage of the total

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product is exported, and this is mainly to neighbouring countries (ECORYS, 2009). The majority of the value data for lime are reported by type of lime produced: high-calcium quicklime, high-calcium hydrate, dolomitic quicklime and dolomitic hydrate. The value for

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dead-burned dolomitic has been included in the averages for all types; this has been done to avoid revealing company proprietary data. The prices for all types of lime have increased in 2012 when compared with those of 2011, as outline in table 2.

4.2 Energy use and emissions The lime production process is energy intensive and results in CO2 emissions from both mineralogical transformation process and energy used. The production of one tonne of lime entails the emission of around 1.2 tonne of CO2 (Ochoa George et al., 2010; Sagastume Gutiérrez et al., 2012). This makes lime one of the products with the highest specific

ACCEPTED MANUSCRIPT emissions of CO2 when compared to other energy intensive industries such as power plants and commercial airlines. When seeking to determine the extent of emissions from an activity it is not always practical to measure the mass of emissions directly. Thus emissions are calculated from a known quantity such as fuel burned or units of electricity consumed. As combustion of a fuel is a stoichiometric chemical reaction, the mass of CO2 emissions can be

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directly related to fuel burn. Hence in a power plant for every kWh of energy supplied by gas or fuel oil, the CO2 emissions are approximately 0.206 or 0.281 kgCO2 respectively (DEFRA, 2008). In the aviation industry calculating the amount of CO2 will depend on a number of factors, for example the plane type, the engine type on the plane, seating configuration and

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freight load. Bearing these factors in mind emission factors of 0.180, 0.126 and 0.11

kgCO2/km travelled for short, medium and long haul flights have been generated (Jardine,

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2009).

The majority of the CO2 emissions occur during the decarbonation of the limestone to lime and the remainder (30 to 40%) from burning of fossil fuels. While processes are being explored to sequester CO2, none eliminate it (Licht et al., 2013). Using Novel innovative research has shown that new molten salt chemistry allows solar thermal energy to drive calcium oxide production with minimum carbon dioxide emission (Licht et al., 2012). This is

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based on anomalies of oxide solubilites, where electrolysis of molten carbonates form oxides, which precipitate as calcium oxide when mixed with calcium carbonate. This would result in a cost effective, high throughput and environmentally friendly solution to producing calcium oxide quicklime, if proven successful at an industrial scale (Licht et al., 2012). Without

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breakthrough technologies at the production stage, the level of performance standards the industry has reached, cannot be improved upon. The industry has every incentive to reduce its

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energy consumption and environmental concerns and compliance are of paramount importance to the industry. The lime industry falls within the scope of several pieces of environmental legislation, the most notable of these are the Directive on Greenhouse Gas Emission Trading (Council Directive 2003/87/EC, 2003), Industrial Emissions Directive (Council Directive 2010/75/EU, 2010), the Management of Waste from Extractive Processes (Council Directive 2006/21/EC, 2006), and Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH) (Council Directive 2006/1907/EC, 2006). Other emissions from the lime industry can be NOx, SO2, CO and dust. Measures have been put in place by the lime industry to minimise emissions and improve product quality including scrubbers and filters (EPA, 2008). The quantity of biomass waste that can be used as a

ACCEPTED MANUSCRIPT substitute for fossil fuels and raw materials is limited due to quality and supply reasons, as well as kiln suitability. The waste products that are generated during the lime production are usually in the form of unburnt or overburnt products. However in a modern kiln, very little product out of specification is produced, but when it does it mainly constitutes of dust, which has been collected from the exhaust gases.

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In 2001 the EU Commission under the provisions of the International Plant Protection

Convention (IPPC) Directive adopted the Best Available Techniques (BAT) reference

document. This document has to be taken into consideration when the permit conditions

based on best available techniques are determined (European Commission, 2001b). At the

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IPPC Information Exchange Forum meeting in April 2009 the revised cement, lime and magnesium oxide BAT Reference Document (BREF) was adopted (Council Directive

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2010/75/EU, 2010).

5. Uses of lime While traditionally lime has been used as a core material in the steel and building industry, it has many innovative roles in an environmental capacity. Using lime for environmental abatement further improves the overall image of the industry. The expansion of the lime

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industry encourages further research and innovations into specialised products with ecofriendly applications. The antimicrobial properties of lime have been an attractive source of potential non-chemical disinfectants. This is an area with increasing interest in a world that is so heavily dependent on antimicrobial compounds (Dowling et al., 2013). The various uses of

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lime have been highlighted in table 3.

The reactivity of the lime product determines the intended end-use of the lime product. For

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example, lime products with a low granulometry (small particle size distribution) and a high reactivity are used for drinking water treatment. Lime products with a higher granulometry and reactivity are used in soil stabilisation. The reactivity of the lime product results from the burning temperature and time, the crystalline structure of the limestone, the impurities of the limestone, the fuel and the kiln type. Reactivity is a measure indicating the speed at which temperature rises from 20 to 60°C in a mixture of lime and water under standard conditions. A reduction of the surface and the porosity of the lime can decrease the reactivity of the lime product. The reactivity of the lime is commonly referred to as soft burnt (high reactivity), medium burnt (medium reactivity), hard burnt (low reactivity) and dead burnt (no reactivity) (Stork et al., 2014).

ACCEPTED MANUSCRIPT 5.1. Non- Environmental Uses Metallurgical industry Steel production requires vast quantities of lime to form slag to prevent the steel from oxidising. The melted slag is also used to remove impurities. Quicklime is extensively used as a flux in purifying steel. Dolime or dolomitic lime is also used as it has additional benefit

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of prolonging refractory lining of the steel furnace or converter. This increases the life span, which is a crucial parameter from a financial viewpoint. In basic steelmaking with oxygen, the molten iron is transferred from a blast furnace into a refractory lined steel-making

furnace. Then oxygen is injected at high speeds in the molten iron, resulting in oxidation of

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carbon and impurities. As electric arc furnaces are more economical to build and operate, they have become more popular. The impurities that are removed are phosphorus, sulphur

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and silica, and to a lesser extent manganese. Whether the steel is produced in a basic oxygen or electric arc furnace it often requires secondary refining to transform it into a saleable product. Key functions of the secondary refinery use lime to preform key function, namely adjustment of steel temperature, removal of additional impurities and prevent the reabsorption of impurities from slag. Quicklime may also be used in conjunction with other materials, such as alumina or fluorspar to form a synthetic slag. This slag can be used to

Lime Association, 2014).

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remove additional phosphorous and sulphur in a secondary steel refining process (National

Hydrated lime also has a number of uses in the manufacture of steel products; it is used as a lubricant in wire drawing and in pig iron casting to prevent the molds from sticking.

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Furthermore it plays a role in neutralisation of sulphuric acid (Singleton Birch, 2014). With regards the nonferrous ores, lime is used in the copper ore beneficiation process. Lime

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acts as a depressant and maintains proper alkalinity in the flotation circuit. It aids in the removal of sulfur during the recovery of mercury from cinnabar. Furthermore it is used in the flotation of zinc, nickel and lead bearing ores. Finally it is used in the metallurgical processes that extract uranium, gold and silver (Habashi, 1969). Construction industry The use of lime as a building material can be dated back throughout the last 10,000 years (Ventolà et al., 2011). However, the introduction of cement in the middle of the 19th century led to a decrease in its importance. The revival of lime occurred in the 1970’s when developments on the harmful effect of cement on historical buildings emerged. The benefits

ACCEPTED MANUSCRIPT of lime are that it is highly porous and has high permeability; this allows the material beneath the lime to ‘breath’. Masonry cement mortars that include lime display good workability coupled with appropriate strength and low water permeability (Baltazar et al, 2014). Lime aids in the reduction of rot and the dispersion of condensation due to its flexible nature. This flexibility plays a fundamental role in the elimination of cracks and minimises shrinkage. The

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wide variety of lime available means that a myriad of building applications can be chosen from, some of these include plastering, rendering, foundation, mortars for blocks, grouting, washes, paints, floor slabs and stucco (Holmes and Wingate, 1997).

The importance of old building restoration is growing in the construction sector. Grouting is

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currently a repair technique for strengthening and consolidating old masonry buildings

(Baltazar et al, 2014). Grouts can be seen as mixtures of binders with water, these should present low viscosity and high penetrability. In many cases the use of cement mortars for the

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replacement of old render does not respect the features or traditional methods of application (Lanas and Alvarez, 2003). Furthermore problems such as detachments, cracking and crystallisation of soluble salts can appear. Grouts must be compatible with the original coating as it is an irreversible technique. It is very important to achieve a composition that is deemed compatible and consistent with the original render at both chemical and physical

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levels (Margalha et al, 2011). Traditional air-lime mortars for rehabilitation of buildings resulted well and constitute a suitable solution for the rehabilitation of old building renders (Azeiteiro et al, 2014). Limewater with a dispersion of 5% ethyl silicate and a commercial alcoholic dispersion of nanostructured calcium hydroxide, also proved to be very effective at

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improving cohesion of weak lime mortars (Borsoi et al, 2012). Pozzolans are a well know material additive with the purpose of ensuring greater durability,

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strength and density of renders. Pozzolans are silica-based materials that, though not cementitious react with calcium hydroxide generated by hydrating cement to form additional cementitious materials. Typically pozzolans are used as cement replacements rather then cement additives (Boffey and Hirst, 1999). Adding pozzolans to a mix change the proportions, replacing some of the cement with pozzolans preserves the mix proportions and hence replaces the cement, having important environmental dimensions (European Commission, 2013; Gartner, 2004). It is important to note that chemical composition, particle size, dosage and different pozzolans will affect the concrete strength differently. Typical pozzolans include metakaolin, silica fume, fly ash, slag and VCAS (Vitrified Calcium Alumina-Silicate). Silica fume is the most reactive of these, with a particle size averaging 0.3

ACCEPTED MANUSCRIPT microns. Many pozzolans are waste products from industrial processes. Silica fume and slag comes from steel refineries and fly ash comes from coal-fired power plants. VCAS and metakaolin are purposefully manufactured pozzolans (Veiga et al, 2007). Soil stabilisation Clay soil can be stabilised by the addition of small percentages, by weight, of lime, this

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enhances many of the engineering properties of the soil. It produces an improved

construction material that is less likely to condense under pressure (Locat et al, 1996). Soils treated with lime results in an increase in optimum moisture content while undergoing a

decrease in maximum dry density. Cementation bonds between soil particles that are brought

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about by lime-soil reactions can resist the forces applied, this results in the reduction of compression of the soil (Rajasekaran and Narasimha Rao, 2002). Hydrated lime and

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quicklime are used in subgrade stabilisation to add stability to fine-grained soils in place of materials that are required as sub-bases, such as hydraulic clay fills and other poor-quality clay and silts obtained from cuts and borrowed pits. Lime is also used in base stabilisation, which includes upgrading the strength and consistency properties of aggregates that may be judged as instable (Cai et al, 2006).

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Nutrient in fertiliser

The importance of an acceptable supply of nutrient elements and lime in the soil is now universally recognised as one of the key factors of crop production. Lime is applied to fields to neutralise acid soils, offset acidity created by nitrogen fertilisers, improve soil structure

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and add nutrients (calcium and magnesium) to the soil. The ideal pH for soil is from 6.0 to 6.5 because most plant nutrients are in their available state. Limestone is usually added to soil

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to increase the pH of the acidic soil (Beach et al, 2000). Chemical industry

The paper and pulp industry also uses lime in the Kraft pulping process. In this process wood chips and an aqueous solution (called liquor) of sodium hydroxide and sodium sulphide are heated in a digester. After cooking the wood chips and the liquor are discharged, it is then screened and washed and sent to either the paper machine or the bleaching plant. The bleach for the paper pulp is calcium hydroxide; lime is sometimes used to produce this chemical. After processing the liquor is passed through a recovery furnace, where the dissolved organics are burned to recover waste heat, sodium sulphide and sodium carbonate. Following this the recovered sodium sulphide and sodium carbonate are diluted with water and slaked

ACCEPTED MANUSCRIPT lime. The sodium carbonate is recausticised to sodium hydroxide by the slaked lime. With the by-product calcium carbonate is recalcined in a lime kiln to recover lime for reuse (Shen et al, 2011). High purity lime is used in making Precipitated Calcium Carbonate (PCC), this is specialty filler used in premium-quality coated and uncoated papers, paints and plastics (Kemperl and Maček, 2009).

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In the sugar refining industry, milk-of-lime is used to elevate the pH of the product stream and precipitating colloidal impurities in both sugar cane and sugar beets. Sugar cane is

processed with water and hydrated lime. The lime raises the pH and reacts with the impurities to form insoluble calcium organic compounds that can be removed. Sugar from sugar beet is

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similar but more lime is required. This process can be repeated numerous times depending on the purity of the final produce required. Excess lime is then reacted with CO2 or by the addition of phosphoric acid to precipitate out the calcium carbonate (Xu and Cheng, 2011;

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Loginova et al, 2012). 5.2. Environmental uses

In the environmental sector, lime is used in remineralisation and softening of potable water sources. It aids in neutralisation, flocculation and hygienisation of wastewater and sludge treatment. Lime plays a valuable role as a biocidal agent. It is used for the control of SO2

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emissions at coal-fired generating stations. Lime is consumed in the Flue Gas Desulphurization (FGD) process. Furthermore lime can be used to control acid mine drainage in the vicinity of metal mine tailings deposits (Lu et al., 2013).

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Potable water sources (softening and remineralisation) Hydrated lime is used to remove carbonate hardness from the water. This hardness is caused by magnesium and calcium salts; for the most part it is treated by means of the lime-soda

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process. This entails the precipitation of magnesium by lime. The calcium salt that is coproduced reacts with the soda ash to form a calcium carbonate precipitate. Lime enhanced softening can also be used to remove arsenic from water (Greenleaf et al., 2006). Hydrated lime is also used in the Nalgonda technique of defluoridation and is based on combined use of alum and lime in a two-step process and has been claimed as the most effective technique for fluoride removal (Meenakshi and Maheshwari, 2006). Wastewater treatment (neutralisation and flocculation) The tertiary process of lime precipitation is used in many wastewater treatment plants. Phosphorous is precipitated as complex calcium phosphates alongside other dissolved and

ACCEPTED MANUSCRIPT suspended solids. Activated carbon treatment is often added to the lime precipitate for a final clarification step before the effluent is discharged. The high-pH of lime, around 10.5-11, plays a valuable role in the reduction of the pathogenic microorganisms in municipal wastewaters (Grabow et al., 1978). The high pH aids in the removal of nitrogen and phosphorus. Hence the removal of phosphorus and nitrogen aids in the prevention of

Sludge treatment- sewage biosolids (hygienisation)

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eutrophication (build-up of algae) in surfaces waters (National Lime Association, 2013).

Treatment of organic biological wastes using quicklime and calcium hydroxide has been in use for more than 100 years. The treatment has been described in the US Environmental

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Protection Agency (EPA) regulations (EPA, 2012) and European regulations (European Committee for Standardization, 2013). Environmental issues concerning wastewater

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treatment are numerous. Legislation is continually being amended to refine the requirement of the removal of various pollutants and pathogens from sludge treatment. Landfill regulation are getting more and more stringent in Europe regarding dumping of organic waste, with it total prohibited in Europe by 2015 (Renou et al., 2008). Incineration continues to face strong opposition in countries such as Italy, Finland, France and the UK (Renou et al., 2008). Lastly, 40% of European sludge is being recycled as fertiliser on agricultural soil. This is being

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questioned more and more by farmers.

The various economical, technical and environmental questions related to sewage management, wastewater and sludge treatment processes tend to be extremely diverse. It is

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thought that to assess the overall impact on environmental wastewater systems, rigorous methods to evaluate and compare environmental performances of wastewater treatment plants must be put in place. These must be multi-criteria based as they deal with many

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aspects: toxicity and ecotoxicity of sludge and treated water, energy consumption, greenhouse effect, eutrophication etc. Life Cycle Assessment (LCA) is a ‘cradle-to-grave’ method which evaluates several potential environmental impacts of a process; methodological rules have been noted in ISO 14040 standards (Hauschild et al., 2013; ISO 14040, 2006; ISO 14041, 2004; ISO 14042, 2000). Mediation of waste With legislative re-evaluation of various pollutants and pathogens from sludge treatment the monitoring of pathogens entering into the environment is a fundamental concern. Another potential route of transmission is the spreading of animal derived wastes onto farmland, such

ACCEPTED MANUSCRIPT as faecal and abattoir wastes (Avery et al., 2009; Heinonen-Tanski et al., 2006; FSAI, 2008). Resulting from increased numbers of infectious disease outbreaks year on year, Regulation (EC) 142/2011 implementing Regulation (EC) No 1069/2009 of the European Parliament and of the Council laying down health rules as regards animal by-products and derived products not intended for human consumption (Council Directive 2011/142/EU, 2011) was

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implemented. This directive lays down health rules as regards animal by-products and derived products not intended for human consumption. It is now illegal to spread untreated ruminant blood or waste containing ruminant blood onto agricultural land in Europe. It must be pre-treated by rendering or incineration. Lime application could provide a more cost

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effective and alternative option for reducing pathogen loads in abattoir waste, integrating such treatment methods with specific land application techniques, such as sub-surface injection may provide a means of coupling a bio-secure and economical method of utilising

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essential nutrients from a waste product (Avery et al., 2009). Further studies are needed to elucidate the potential effect on other pathogens and different types of abattoir waste, but if successful it may warrant the inclusion of lime treatment within the Animal By-Products Regulation as a method for treating abattoir waste (Avery et al., 2009). Lime as a disinfectant

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Lime is registered in the EU Biocide Regulation for product Type 2 (Private area and public health area disinfectants and other biocidal products) and Product Type 3 (Veterinary hygiene biocidal products). Moreover it is advised to use quicklime and hydrated lime that complies with the CL90 (Calcium lime) or DL85 (Dolomitic lime) grade as described in building lime

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European standard EN 459-1:2010 (Council Directive 98/8/EC, 1998). The use of lime to treat influenza has been around for hundreds of years, during the 1918-

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1919 global influenza outbreak; local governments took a series of measures to control the pandemics, one of these was that “houses should be sprayed with limewater or lime powder” (Cheng and Leung, 2007). Calcium hydroxide [Ca(OH2)] has been used in the prevention and control of avian influenza virus (Alphin et al., 2009), foot and mouth disease and Aujeszky’s Disease (Pseudorabies Virus) (Turner et al., 2000 and Turner & Burton, 1997). Lime is listed as an effective disinfectant in numerous national regulations and guidelines (Germany, Austria, Switzerland, France, UK and Ireland (EuLA, 2009)) and is used on a regular basis as in situ disinfection. Lime is commonly used to disinfect animal houses, in the case of an outbreak; the treatment of manure, soil, floor and walls is common practice. Practical guidelines on the use of lime for prevention and control of avian influenza, foot and mouth

ACCEPTED MANUSCRIPT disease and other infectious diseases have been drafted by the European Lime Association (EuLA, 2009). A number of new studies and applications for the use of lime are being investigated as a cheaper alternative to chemical disinfectants in cattle housing. Kristula et al concluded that when comparing five different bedding types that, ‘hydrated lime was the only treatment that

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significantly reduced bacterial counts on both the bedding mattress and teat ends’ (Kristula et al., 2008). A study conducted by Gleeson supported this finding (Gleeson et al., 2009). Both studies noted some skin irritation to teats; these cases were predominately transient in nature. Quicklime, hydrated lime and milk of lime are irritant products and protective measures

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should be used at all times when using these products. The CAS-number (a division of the American Chemical Society) Registry numbers and their EC numbers found in the EINICS

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Inventory (European Inventory of Existing Commercial Chemical Substances) for calcium oxide is CAS # 1305-78-8 and EC # 215-138-9 and calcium hydroxide is CAS # 1305-62-0 and EC # 215-137-3 (European Commission, 2013). The classification is: Xi R37/38, R41. These code letters denote, Xi- Irritant; R37/38- Irritating to respiratory system and skin; R41Risk of serious damage to eyes.

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However, it should be noted that lime may not be a suitable biocide for all microorganisms; a scientific review has illustrated new evidence that suggests exposure of anthrax spores to calcium may aid in their survival and viability (Himsworth, 2008). Flue gas treatment (acid gas removal)

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In Flue Gas Desulphurization (FGD) serving industrial plants, electric utility and incinerators, lime is used to react with sulphur and chlorine oxides in the flue gas. It is used to stabilize the

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resulting sludge before disposal (European Commission, 2002; Lu et al., 2013). Lime is also considered a feasible sorbent for CO2 capture and is mentioned in early Intergovernmental Panel on Climate Change (IPCC) Special Report (Zeman, 2008; IPCC, 2005). In the simplest form the technology alternates between the forward (calcination) and the reverse (carbonation) applications of reaction. The carbonation reaction takes place in the flue gas stream and the calcination reaction occurs in a separate kiln (Abanades, 2002). Acid mine draining The most common method to mitigate acidic effluents is an active treatment process that involves the addition of a chemical-neutralising agent. This alkaline agent when added to the Acid Mine Drainage (AMD) site will raise its pH and accelerate the rate of chemical

ACCEPTED MANUSCRIPT oxidation of ferrous iron (Coulton et al, 2003). It also causes many of the metals present in the solution to precipitate as hydroxides and carbonates. The result is the production of an iron-rich sludge that may contain various other metals depending on the chemistry of the mine water treated. There are a number of neutralising agents that have been used, including lime (calcium oxide), slaked lime, calcium carbonate, sodium hydroxide, sodium carbonate,

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magnesium hydroxide and magnesium oxide (Johnson and Hallberg, 2005). These vary in effectiveness and cost, for example sodium hydroxide is one and a half times as effective but is approximately nine times more expensive then lime. Additionally removal of sulphate (as gypsum) is achieved when calcium-containing neutralising reagents are used. Although the

problem of bulky sludge disposal (Matlock et al, 2002).

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6. Novel innovations of lime

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chemical- neutralising treatment can provide an effective remediation of AMD, it poses a

The role of lime is continually adapting and a modern innovative approach to drug development is the use of calcium oxide (CaO) nanoparticles (NP) as antimicrobial agents. The nanoparticles consist of well-dispersed agglomerates of grains with a narrow size distribution of 14-24 nm (Roy et al., 2013). The cell structure integrity of all microbial strains was affected after treatment with CaO-NPs (Sawai et al., 2001). There have also been

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numerous reports that slurry composed of powder oxides for example CaO and MgO generate superoxide (O2-) and have antibacterial and antifungal activity (Sawai, 2003; Sawai et al., 1996; Yamamoto et al., 2000). In addition to high pH, active oxygen also helps the antibacterial activity of CaO and MgO powder (Roy et al., 2013). These initial finding are

action.

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extremely promising and further work has been initiated to examine the mechanisms of

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Lime producers have developed new innovations and a number of patents have been secured. On analysing lime patents between the years 2005 and 2011, some of the most notable of these are hemp concrete with reduced CO2 impact (Hirst et al, 2010); dust minimisation from lime products; enhanced metal recovery and application of lime in the Ecoloop process. The Ecoloop process was started by a German lime company and in 2012 won the prestigious German Innovation Award for climate and environment and the Hugo Junkers Innovation Prize of Saxony-Anhalt. The Ecoloop project aims at producing syngas without flue gas emissions. Unprocessed shredded material from the automobile industry, sorting residues and rubber parts are used to produce the gas. Lime is used in the process as the transport medium, pollutant-bonding material and catalyst. After the purification the gas is available for thermal

ACCEPTED MANUSCRIPT or electrical production. It can also be used in place of natural gas and produces a high quality lime product. The entire process is a closed system, which is both efficient and economical; hence this is where the name ‘Ecoloop’ is derived (Ecoloop, 2012; Stork et al, 2014). These novel applications illustrate the diversity and variations in use for lime products.

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7. Share of lime used by application

Although lime value data is not collected by end-use, an overview of customer markets has been drafted; shares are tonnage based for the year ending 2012. The EuLA indicated the largest share of lime produced is used in the metallurgical industry. This industry accounts

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for 39% of lime sold in Europe, in the US the figure is very similar with 38% of lime

produced being used. The chemical and industrial applications of lime made up 21% of lime

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sales in Europe and 22% within the US. The construction industry in the US makes up approximately 8% of lime consumed. In Europe this figure is slightly higher at 11%. The environmental sector makes up 16% of the customer market in Europe. In the US this is nearly double with 31% of the market share of lime used in environmental abatement. (Despotou, 2014, Stork et al, 2014, Miller, 2013). The data is rounded to, no more than one significant digit to avoid disclosing company proprietary data. This results in 1% in US and

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3% in Europe’s lime market share not being accounted for, it is suggested that this could be exported lime (Despotou, 2014). 8. The future for lime

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The uses of lime are extremely diverse and versatile as outlined above. This affordable commodity has many roles in both non-environmental and environmental settings. Lime in its various forms has been around for thousands of years but is still finding use in today’s

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society; this is thought to be down to its affordable price, ease of acquisition and unique versatile properties.

Lime sales in markets such as chemical and industrial, steel and construction are expected to increase with the overall improvement in the global economy. This will increase lime demand and emissions, namely CO2. It will become more important for the lime industry to monitor its energy use and emissions and highlight areas where improved abatement measures can be implemented. Mitigation measures for CO2 include fuel switch, kiln switching or possible carbon capture and storage. As only one third of the emissions are generated during burning of fossil fuels, this would only lead to minimal reductions if switched to fuels with reduced carbon intensity, such as natural gas or biomass. Switching to

ACCEPTED MANUSCRIPT natural gas may have a positive impact on the quality of the produced lime, but in many cases it is more expensive then solid fossil fuel-based production. Switching to biomass required additional investment, which can prove costly. The impact of complete fuel switches to gas or biomass only applies to the energy generated emissions and not the process emissions. Improving energy efficiency is another important option to reduce energy related emissions.

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Vertical lime kilns preform close to their thermodynamic minimum energy use and are highly efficient. The biggest possible reduction is replacing horizontal kilns, which are less efficient than vertical kilns. This is a sizable investment and this must be earned back by saved energy purchase costs. The biggest part of the emissions in lime manufacture come from the

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calcination of the limestone, the potential reduction of the carbon intensity could come from Carbon Capture and Storage (CCS) or Carbon Capture and Utilisation (CCU). While the cost of CCS and CCU are already high, the cost for transport to a suitable storage location and

place without external incentive.

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storage of the CO2 could add to these costs. This is not a viable option and is unlikely to take

On examining the outlook for the lime industry the current carbon emission legislation must be assessed. The European Commission published a roadmap in 2011 aimed at moving to a competitive low carbon economy, namely ‘Low Carbon Economy Roadmap’ (European

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Commission, 2011). This document sets out the main factors shaping the EU’s climate action to enable Europe to develop into a low carbon economy by 2050. As the lime industry is dependent on other energy intensive industries, the development in those sectors has a direct correlation on the lime industry. The energy and carbon price development shown by the

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European Commission modelling will affect investment in the sector more than emissions. If the modelled global action scenario doesn’t become a reality, it could force lime investment

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out of Europe. Moreover, if future EU climate policies impose a uniform carbon price across the economy regardless of the reduction potential of CO2 that is currently available to the lime industry. Then pressure that would be exerted onto the key customer sectors of the lime industry may as a consequence move large parts of the manufacturing process out of Europe. There is a wide range of parameters to be considered when examining the lime industry and the products it provides. This paper has been written primarily to review the current literature both scientific and grey and to stimulate further debate, to achieve a wider interchange of information from policy markers, producers and end users of lime products and to ensure ‘lime remains in the limelight’.

ACCEPTED MANUSCRIPT References 1. Abanades, J.C., 2002. The maximum capture efficiency of CO2 using a carbonation/calcination cycle of CaO/CaCO3. Chemical Engineering Journal 90, 303-306. 2. Alphin, R., Johnson, K., Ladman, B., Benson, E., 2009. Inactivation of avian influenza virus using four common chemicals and one detergent. Poultry Science 88, 1181-1185.

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5. Baltazar, L.G., Henriques, F.M.A., Jorne, F., Cidade, M.T., 2014. Combined effect of superplasticizer, silica fume and temperature in the performance of natural hydraulic lime grouts. Construction and Building Materials 50, 584-597.

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ACCEPTED MANUSCRIPT 26. EPA, 2012. A Plain English Guide to the EPA Part 503 Biosolids Rule, Land application of Biosolids. http://water.epa.gov/scitech/wastetech/biosolids/503pe_index.cfm Date accessed: 11/12/2014. U.S. Environmental Protection Agency. 27. EPA, 2010. EPA Analysis of the American Power Act in the 111th Congress. http://www.epa.gov/climatechange/Downloads/EPAactivities/EPA_APA_Analysis_6-1410.pdf Date accessed: 11/12/2014. U.S. Environmental Protection Agency.

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29. EPA, 2008. BAT Guidance Note on Best Available Techniques for the Production of Cement and for the Production of Lime in a Kiln. http://www.epa.ie/pubs/advice/bat/bat%20guidance%20note%20cement%20&%20lime.p df Date accessed: 11/12/2014.

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30. EuLA, 2009. Practical guidelines on the use of lime for prevention and control of avian influenza, foot and mouth disease and other infectious diseases, http://www.eula.eu/sites/eula.eu/files/documents/Influenza_UK_web.pdf Date accessed: 11/12/2014. European Lime Association, Rue des Deux Eglises, 26-B-1000, Brussels. 31. European Commission, 2014a. Energy Prices and Cost Report. SWD (2014) 20 Final/2. http://ec.europa.eu/energy/doc/2030/20140122_swd_prices.pdf. Date accessed: 11/12/2014 32. European Commission, 2014b. The EU Emissions Trading System (EU ETS). http://ec.europa.eu/clima/policies/ets/index_en.htm Date accessed: 11/12/2014

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ACCEPTED MANUSCRIPT 38. European Committee for Standardization, 2013. CEN/TS 13714:2013 Characterization of sludges- Sludge management in relation to use or disposal. http://standards.cen.eu/index.html Date accessed: 11/12/2014. 39. FSAI, 2008. Food Safety Authority of Ireland (FSAI) Food safety implications of landspreading agricultural, municipal and industrial organic materials on agricultural land used for food production in Ireland. ISBN 1-904465-59-5

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80. Shen, J., Fatehi, P., Soleimani, P., Ni, Y., 2011. Recovery of lignocelluloses from prehydrolysis liquor in the lime kiln of kraft-based dissolving pulp production process by adsorption to lime mud. Bioresource Technology, 102(21), 10035-10039. 81. Singleton Birch, 2014. A-Z uses of lime. http://www.singletonbirch.co.uk/lime/uses Date accessed: 11/12/2014. 82. Stork, M., Meindertsma, W., Overgaag, M., Neelis, M., 2014. A competitive and efficient lime industry cornerstone for a sustainable Europe. ECOFYS Netherlands B.V. www.ancade.com/files/.../165/.../LimeRoadmapFinalJune4th2014.pdf Date accessed: 11/12/14 83. Thomson Reuters Web of Science, 2014a. Lime Search. https://apps.webofknowledge.com/Search.do?product=UA&SID=P1KbMoFPePNeqlOFq qC&search_mode-GeneralSearch&prlD=9a6e6900-3d57-40bd-b251-f45517428774 Date accessed: 16/11/2014 84. Thomson Reuters Web of Science, 2014b. Lime and environment search. https://apps.webofknowledge.com/Search.do?product=UA&SID=P1KbMoFPePNeqlOFq

ACCEPTED MANUSCRIPT qC&search_mode-GeneralSearch&prlD=bbad6352-16d0-41ea-b84b-a77d2bfbbdb9 Date accessed: 16/11/2014 85. Turner, C., Williams, S., Cumby, T., 2000. The inactivation of foot and mouth disease, Aujeszky's disease and classical swine fever viruses in pig slurry. Journal of Applied Microbiology 89, 760-767. 86. Turner, C., Burton, C.H., 1997. The inactivation of viruses in pig slurries: A review. Bioresource Technology 61, 9-20.

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87. Veiga, M.R., Velosa, A., Magalhaes, A., 2007. Experimental applications of mortars with pozzolanic additions: Characterization and performance evaluation. Construction and Building Materials 23, 318-327

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88. Ventolà, L., Vendrell, M., Giraldez, P., Merino, L., 2011. Traditional organic additives improve lime mortars: New old materials for restoration and building natural stone fabrics. Construction and Building Materials 25, 3313-3318. 89. Xu, J., Cheng, J. J. 2011. Pretreatment of switchgrass for sugar production with the combination of sodium hydroxide and lime. Bioresource Technology, 102(4), 3861-3868.

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90. Yamamoto, O., Shimura, T., Sawai, J., Kojima, H., Sasamoto, T., 2000. Effect of CaO doping on antibacterial activity of ZnO powders. Journal of the Ceramic Society of Japan 108, 156-160.

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91. Zeman, F., 2008. Effect of steam hydration on performance of lime sorbent for CO2 capture. International Journal of Greenhouse Gas Control 2, 203-209.

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Table 1. Lime Nomenclatures.

Formula

Magnesium

Hydrated

Quicklime

CaO







Kiln Temperature

900-1200°C

Synonyms

Calcium oxide, lime

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Name

and burnt lime.

Dolomitic lime,

Slaked lime

Hydrated

Ca(OH)2

CaMg(OH)4

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dolime

CaO MgO











900-1200°C

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dolime






Up to 1800°C

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Sintered

CaOMgO

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Dolime





N/A

N/A

dolime and calcium magnesium oxide.

Dead burned dolime

Calcium hydroxide, calcium hydrate, caustic lime and hydrated lime Calcium magnesium tetrahydroxide

ACCEPTED MANUSCRIPT Table 2. The cost of lime1. The data for lime is reported by type produced: high-calcium quicklime, high-calcium hydrate, dolomitic quicklime and dolomitic hydrate. The value for dead-burned dolomitic has been included with the averages of all types. The prices for all types of lime increased when compared with those from 2011. (Miller, 2013) 2012

Dollars per metric ton

Dollars per metric ton

(US)

(US)

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Type

2011

Sold and Used: 108

Hydrate

131

Average all types2

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Sold:

119.5

115 137

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Quicklime

126

105

112

118

124

111.5

118

High-calcium Hydrate

130

135

Dolomitic Hydrate

142

157

Average Hydrate

136

146

Average all types2

122

130

High-calcium Quicklime Dolomitic Quicklime

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Average Quicklime

Average value per ton, free-on- board plant, including cost of containers.

2

Includes dead-burned dolomite.

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Table 3. The applications of lime. (European Commission, 2013.) Application details

Steel and non-ferrous metals

Construction and civil work

Environment - water

Environment - gas Environment - waste Environment - disinfectant

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Chemical and industrial applications

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Agriculture

• Used to reduce sulphur and phosphorus in the steelmaking process. •To protect refractory lining life of the furnace, from the slag and modify slag viscosity. • Used in the smelting of copper, lead, zinc and other metals as a flux. • Used to extract uranium, gold, nickel and silver. • Plaster mixes and masonry for building facades. • Used in the production of bricks. • Soil stabilisation and road binders. • To adjust the pH of the soils to give optimum growing conditions and increase crop yield. • Used to treat industrial and mining wastewater (pH adjustment, removal of phosphates and nitrogen and water clarification). • Used to soften and remove impurities of potable water. • Used in wastewater treatment. • Used to neutralise flue-gas pollutants such as sulphur and chlorine. • Blended with additives, it captures heavy metals. • Treatment of hazardous waste. • Treatment of organic and inorganic sludge. • Treatment of disease contaminated areas, e.g. walls, floors and bedding. • Paper – manufacturing process; pulp and raw material for Precipitated Calcium Carbonate (PCC). • Used in the sugar industry to precipitate out impurities from beet and cane extracts. Also used to neutralise odours generated by beet washing and transport. • Acid neutralisation. • Used in the manufacture of food and drink additives.

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Application sectors

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Quicklime and hydrated lime, including dead-burned dolomite: world production, by country1 in 2012. (In thousand metric tons)

0

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Ireland ᵉ United Kingdom ᵉ Spain (sales) ᵉ Canada ᵖ, ² Belgium ᵉ Iran ᵉ France ᵉ Turkey ᵉ, ⁴ Republic of Korea ᵉ Italy ᵉ, ³ Germany ² Japan (quicklime only) Brazil Russia ᵉ India ᵉ U.S. (inc. Puerto Rico) ⁴

2000 4000 6000 8000 10000 12000 14000 16000 18000 20000

Figure 1. World lime production by country 2012. Quicklime and hydrated lime production including dead-burned dolomite. China the top producer of lime (with approximately 220* metric tons) has been removed in order to not skew the graph (Miller, 2013). estimated, p preliminary

1

World totals, US data, and estimated are rounded to no more than three significant digits; may not add

to totals shown.

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Reported figure

3

Includes hydraulic lime

4

Production estimate based on sales only; data may be incomplete.

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Highlights: • The current lime industry. • Illustrating the extensive uses of lime in both an industrial setting. • Examining lime usage in environmental applications.