Luke Bird Thesis

QUT SCIENCE AND ENGINEERING FACULTY

Coal Seam Gas BrineDisposal

Investigating Bromide Removal Using StrongBase Anion Resin and the Commercial Disposalof Brine in the Queensland Chlor Alkali Market

Semester 2 2013

Luke Bird | n4413679 Bachelor of Mechanical Engineering

Professor Graeme Millar

TABLE OF CONTENTS 1 Introduction ............................................................................................................................................. 6

2 Concentrate Management ........................................................................................................................ 7

2.1 Brine Containment........................................................................................................................... 9

2.2 Commercial Brine Production ........................................................................................................ 10

2.3 Chlor alkali industry ....................................................................................................................... 12

2.4 Brine Pre-Treatment ...................................................................................................................... 13

2.5 Chlor Alkali Membrane Cell Process ............................................................................................... 14

2.6 Brine Requirements for CA Process ................................................................................................ 15

3 Removal of Bromide Using Strong Base Anion Resins .............................................................................. 17

3.1 Bromide in Water .......................................................................................................................... 17

3.2 Impurities in CA Feed ..................................................................................................................... 17

3.3 Bromide in CA Feed ....................................................................................................................... 18

3.4 Strong Base Anion Resins ............................................................................................................... 19

3.5 Conclusions of An Alternative Experimental Study.......................................................................... 20

3.6 Other Methods of Bromide Removal .............................................................................................. 21

4 Bromide Removal Using Chloride Loaded Dowex Marathon A ................................................................. 22

4.1 Results of Lab Based Experiments .................................................................................................. 22

5 Commercial Viability of Brine Disposal .................................................................................................... 28

5.1 Brine Processing ............................................................................................................................ 28

5.2 Commercial Salt Production ........................................................................................................... 29

5.3 Chlor Alkali Products ...................................................................................................................... 30

5.3.1 Chlorine..................................................................................................................................... 31

5.3.2 Caustic Soda .............................................................................................................................. 31

5.4 Toward an Industrial Symbiosis Network ........................................................................................ 32

6 Literature Review.................................................................................................................................... 35

6.1 Coal Seam Gas ............................................................................................................................... 35

6.2 Ion Exchange ................................................................................................................................. 35

6.2.1 Halide Removal ......................................................................................................................... 36

6.2.2 Bromide .................................................................................................................................... 36

6.3 Chlor Alkali .................................................................................................................................... 36

6.3.1 Industry ..................................................................................................................................... 36

6.4 Forward Osmosis ........................................................................................................................... 36

7 Conclusion .............................................................................................................................................. 38

Appendix A: Effects of Impurities on CA Process Using Membrane Technology and Brine Specifications Required by Membrane Cells .......................................................................................................................... 39

Appendix B: Dow Marathon A......................................................................................................................... 41

Appendix C: CSG Treatment Processes ............................................................................................................ 42

Appendix D: Original Literature Search Regarding Forward Osmosis................................................................ 43

Bibliography ................................................................................................................................................... 48

Works Consulted ............................................................................................................................................ 50

TABLE OF FIGURES FIGURE 1: WATER MANAGEMENT SCHEME ...................................................................................................... 6 FIGURE 2: SANTOS PRODUCED WATER ESTIMATES ........................................................................................... 8 FIGURE 3: QGC MONOCELL SCHEMATIC.......................................................................................................... 10 FIGURE 4: PRECIPITATION OVERLAP DURING EVAPORATION........................................................................... 11 FIGURE 5: USES OF CHLORINE IN INDUSTRY AND COMMERCE......................................................................... 12 FIGURE 6: PURIFICATION STAGES IN THE CHLOR ALKALI PROCESS ................................................................... 13 FIGURE 7: MEMBRANE CELL PROCESS OVERVIEW ........................................................................................... 15 FIGURE 8: CHLOR ALKALI PRE-TREATMENT ..................................................................................................... 15 FIGURE 9: BROMIDE STRIPPING DURING IN THE CHLOR ALKALI INDUSTRY ...................................................... 19 FIGURE 10: ISOTHERMS SHOWING BROMIDE REMOVAL USING MIEX ............................................................. 20 FIGURE 11: LANGMUIR VAGELER FIT OF ISOTHERM DATA FOR EXCHANGE OF 187 MG/L BROMIDE (FROM

SODIUM BROMIDE) WITH DOW A CHLORIDE EXCHANGED RESIN ............................................................ 22 FIGURE 12: COMPETITIVE LANGMUIR FIT OF ISOTHERM DATA FOR EXCHANGE OF 187 MG/L BROMIDE (FROM

SODIUM BROMIDE) WITH DOW A CHLORIDE EXCHANGED RESIN ............................................................ 23 FIGURE 13: FREUNDLICH FIT OF ISOTHERM DATA FOR EXCHANGE OF 187 MG/L BROMIDE (FROM SODIUM

BROMIDE) WITH DOW A CHLORIDE EXCHANGED RESIN .......................................................................... 24 FIGURE 14: TEMKIN FIT OF ISOTHERM DATA FOR EXCHANGE OF 187 MG/L BROMIDE (FROM SODIUM

BROMIDE) WITH DOW A CHLORIDE EXCHANGED RESIN .......................................................................... 25 FIGURE 15: DUBININ-ASTAKHOV FIT OF ISOTHERM DATA FOR EXCHANGE OF 187 MG/L BROMIDE (FROM

SODIUM BROMIDE) WITH DOW A CHLORIDE EXCHANGED RESIN ............................................................ 26 FIGURE 16: BROUERS SOTOLONGO FIT OF ISOTHERM DATA FOR EXCHANGE OF 187 MG/L BROMIDE (FROM

SODIUM BROMIDE) WITH DOW A CHLORIDE EXCHANGED RESIN ............................................................ 27 FIGURE 17: COST OF SALT BASED ON PURITY .................................................................................................. 28 FIGURE 18: AUSTRALIAN PRODUCTION OF SALT USING LINEAR EXTRAPOLATION ............................................ 30 FIGURE 19: CHLOR ALKALI MEMBRANE ........................................................................................................... 30 FIGURE 20: BAYER PROCESS DIAGRAM ........................................................................................................... 31 FIGURE 21: SUSTAINABILITY FRAMEWORK AROUND INDUSTRIAL SYMBIOSIS .................................................. 33 FIGURE 22: GLADSTONE INDUSTRIAL SYMBIOSIS NETWORK ........................................................................... 34

TABLE OF TABLES TABLE 1: BRINE MANAGEMENT COSTS ............................................................................................................. 7 TABLE 2: COMPARISON OF PRECIPITANT QUANTITY ....................................................................................... 10 TABLE 3: INDICATIVE VALUE OF PRECIPITANTS................................................................................................ 11 TABLE 4: COMPARISON OF CHLOR ALKALI TECHNOLOGIES .............................................................................. 13 TABLE 5: RECENT ADVANCEMENTS IN MEMBRANE CELL TECHNOLOGY ........................................................... 14 TABLE 6: CHLOR ALKALI QUALITY FEED SALT COMPOSITIONS .......................................................................... 18 TABLE 7: COMPARISON OF MARATHON A WITH OTHER RESINS ...................................................................... 21 TABLE 8: COMPARISON OF SELECTIVE BROMIDE REMOVAL METHODS ............................................................ 21 TABLE 9: NON-LINEAR LEAST SQUARES (NLLS) FIT OF LANGMUIR VAGELER ISOTHERM DATA FOR BROMIDE ION

EXCHANGE FROM SODIUM BROMIDE SOLUTION WITH DOW A CHLORIDE LOADED RESIN. NUMBERS IN BOLD INDICATE MINIMUM ERROR VALUES AND MINIMUM SUM OF NORMALIZED ERROR VALUES. ........ 22

TABLE 10: NON-LINEAR LEAST SQUARES (NLLS) FIT OF LANGMUIR ISOTHERM DATA FOR BROMIDE ION EXCHANGE FROM SODIUM BROMIDE SOLUTION WITH DOW A CHLORIDE LOADED RESIN. NUMBERS IN BOLD INDICATE MINIMUM ERROR VALUES AND MINIMUM SUM OF NORMALIZED ERROR VALUES. ........ 23

TABLE 11: NON-LINEAR LEAST SQUARES (NLLS) FIT OF FREUNDLICH ISOTHERM DATA FOR BROMIDE ION EXCHANGE FROM SODIUM BROMIDE SOLUTION WITH DOW A CHLORIDE LOADED RESIN. NUMBERS IN BOLD INDICATE MINIMUM ERROR VALUES AND MINIMUM SUM OF NORMALIZED ERROR VALUES. ........ 24

TABLE 12: NON-LINEAR LEAST SQUARES (NLLS) FIT OF TEMKIN ISOTHERM DATA FOR BROMIDE ION EXCHANGE FROM SODIUM BROMIDE SOLUTION WITH DOW A CHLORIDE LOADED RESIN. NUMBERS IN BOLD INDICATE MINIMUM ERROR VALUES AND MINIMUM SUM OF NORMALIZED ERROR VALUES. ................. 25

TABLE 13: NON-LINEAR LEAST SQUARES (NLLS) FIT OF DUBININ-ASTAKHOV ISOTHERM DATA FOR BROMIDE ION EXCHANGE FROM SODIUM BROMIDE SOLUTION WITH DOW A CHLORIDE LOADED RESIN. NUMBERS IN BOLD INDICATE MINIMUM ERROR VALUES AND MINIMUM SUM OF NORMALIZED ERROR VALUES..... 26

TABLE 14: NON-LINEAR LEAST SQUARES (NLLS) FIT OF BROUERS SOTOLONGO ISOTHERM DATA FOR BROMIDE ION EXCHANGE FROM SODIUM BROMIDE SOLUTION WITH DOW A CHLORIDE LOADED RESIN. NUMBERS IN BOLD INDICATE MINIMUM ERROR VALUES AND MINIMUM SUM OF NORMALIZED ERROR VALUES..... 27

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1 INTRODUCTION The experimental use of ion exchange (IX) resin takes place in the context of coal seam gas (CSG) produced water treatment and its commercial implications for the chlor-alkali (CA) industry via production of salt from effluent brine streams. Based on the assumptions stated in the introduction the discussion is therefore concerned around the importance of IX for CSG water management as it relates to brine disposal and the particulars of CSG water and brines as they relate to the CA industry. This report discusses the importance of high quality treatment in Australia and the use of IX to facilitate this. It introduces IX resins and examines previous experimental research concerning halide removal using these resins as well as other novel techniques. It then discusses experimental findings using Dow Chemical’s proprietary Marathon A resin and compares its properties and results to existing literature on the topic. Using literature on brine disposal and environmental controls discussion is also made on the importance of adequate management of brine which does not meet the beneficial use or reprocessing requirements stipulated in Australian CSG operator water management plans. The discussion concludes with the reuse of such brine in the CA industry by considering the pre-treatment requirements, particularly with respect to bromide, as well as the commercial implications in an Australian context focusing on the state of Queensland.

Using data collated from CSG operators and regulatory authorities it can be determined that CSG water production will be in the order of 61 gigalitres per year or higher for Queensland projects to at least 2030. The options indicated for beneficial end-use as part of CSG operator comprehensive water management plans (WMPs) are in various stages of implementation and include aquaculture, coal washing, industrial operations, irrigation, feedlots watering and use as potable water [1]. All uses require some form of treatment, also known as amendment, with treatment options in a continuing state of improvement and capacity increase. Re-use of water is considered beneficial as it makes use of the water in-line with CSG processing albeit at increased cost of operations. This is opposed to surface discharge and deep re-injection which make the water unrecoverable as well as inviting environmental considerations [2]. An established pre-amendment desalination method currently in practice and being expanded is reverse osmosis (RO). This produces an amendment ready desalinated water for beneficial use and a concentrated effluent stream comprising anywhere from 25% to 10% of the original RO feed stream (depending on technology). RO and its use of ion exchange IX are currently the only technologies deployed in Australian CSG production for the treatment of produced water [1]. Figure 1 below gives a brief process diagram of these WMP elements [3].

FIGURE 1: WATER MANAGEMENT SCHEME

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2 CONCENTRATE MANAGEMENT Early studies performed by consulting firm URS Australia determined that the management of water and related operations, given as “drilling, well construction, extraction and excess water disposal” would amount to over 30% of total operating costs [4]. It was also predicted that the number and quality of specialist personnel required to carry out the water management activities was insufficient within Australia and would face demand from other burgeoning water management projects across the world. In the case of the main RO stage of treatment of CSG water at QGC, representatives from French water giant Veolia manage an operation cost break down similar to other brackish RO facilities: 54% fixed costs (capital amortisation and insurance), 11% electricity, 9% maintenance, 7% membrane replacement, 9% labour and 10% consumable chemicals [5]. The largest cost centre of fixed costs also includes the challenge of disposing the reject concentrate stream resulting from the RO process. This is because it must be safely sequestered from the environment as determined by local regulations and best practice. In addition, where seawater RO plants can strategically reject to the ocean, this isn’t an option for CSG producers at large distances from the coast. In advice given to the public, Santos estimated that to dispose just its own concentrate in the ocean would take 200 tankers operating 24 hours a day driving 500km to keep up with production rates over the life of the project and thus determined this option non-feasible [6]. The lack of this option’s availability is even more disappointing when recognising that evaporation ponds and brine concentration technology are considered to be some of the most expensive methods of in situ brine disposal. This is due to the large volumes involved, the energy required for processing and the strong regulations regarding pond management. Table 1: Brine management costsbelow gives an estimate of costs for RO brine disposal [2].

TABLE 1: BRINE MANAGEMENT COSTS

The literature is in broad agreement that a limiting factor for inland RO treatment is the challenge of concentrate disposal [7]. Several papers have outlined possibilities for effective in-situ management however consensus has not yet been achieved for the most applicable solutions. This lack of consensus is due to the variability of feed stream composition, the variability of local factors which impact on re-use and storage as well as the pace of technological development in finding a solution. In this context, indefinite brine storage is considered a temporary solution and unsustainable for global inland RO industry growth. A number of possibilities have therefore been considered in order to achieve what the industry labels ‘zero liquid discharge’, or ZLD, whilst minimising water loss via evaporation and injection. Examples of the technologies

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currently in place include the proprietary SAL-PROC system as well as evaporative processes such as: falling film, circulation, spray dryer, fluidised bed, mechanical vapour compression, solar pond and scraped surface. In all cases the technology integration with the RO process is still undergoing refinement and is unproven in terms of complete efficiency and reliability [1]. In Queensland brine concentrators supplied by GE are currently in place in the form of three tall towers as part of its Kenya Water Treatment Plant project. In this case the water management contract has been awarded to Veolia for a period of 20 years at a project cost of $800 million. This is in addition to the capital cost of $920 million required to construct the plant which is projected to come online in June 2014 with a treatment capacity of 200 megalitres per day at 97% recovery [8].

QGC, Santos and ConocoPhillips (Origin partnership) represent the ‘big three’ of Australian east coast CSG production [9]. In the case of Santos, a capacity of 2 gigalitres has been constructed as ‘brine containment ponds’ to effectively sequester the concentrated brine effluent originating from the RO process. This capacity is designed to contain a salt mass of 27.5 thousand tonnes in a brine volume of 1.1 gigalitres to 2014 in line with environmental requirements. Beyond this date Santos expects to manage the brine balance using deep saline aquifer injection and solar/wind evaporation to reduce the geographic footprint of the landfill. It has commissioned a series of studies to investigate this possibility using the Timbury Hills Formation as a starting point however recognises the environmental challenges this presents. Commercial salt production has been a consideration however this has currently been rejected on the basis of logistics and commercial viability. The result is that Santos will publish a revised WMP by the end of 2014 with the admission that brine containment capacity will very likely increase to meet project requirements. Figure 2 shown below gives a projection from Santos of its total produced water volumes (top line) across all three production sites to 2040 [3].

FIGURE 2: SANTOS PRODUCED WATER ESTIMATES

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The projections show that 2014 RO brine effluent volumes start at 4.78 megalitres per day from 44.1 megalitres of produced water and double to a peak of megalitres per day in 2020. Even with costly improvements in RO efficiency a brine volume reject rate of 10% will create up to 3 gigalitres of brine effluent in 2020 alone. When considering that volumes are increasing to this value from their 2014 start point before declining with the same slope until 2028 it is obvious that without deep injection or commercial alternatives Santos will need to actively manage upwards of 30 gigalitres of brine effluent with a salt mass of 735 thousand tonnes. This estimate ignores the impact of evaporation/rainfall balance and the long-tail contribution of a following 15 years of continued CSG water production to 2040, albeit with exponentially decaying volumes. This therefore represents a brine containment pond capacity increase of over ten times the current value and the management of said brine into perpetuity. This is a very conservative estimate for one operator however the ABC, using data collated from a variety of sources, has published a nationwide figure of 31 million tonnes of salt resulting from the Queensland CSG industry over a thirty year period. This it is of relative magnitude with the Australian Petroleum Production and Exploration Association figures of 21 million tonnes and ‘big three’ (Santos, QGC, ConocoPhillips) estimates of 7.8 million tonnes [9].

2.1 BRINE CONTAINMENT Brine containment ponds are manmade structures designed to safely store brine in line with regulations. They function similarly to evaporation ponds which use solar energy to evaporate water from the brine, leaving the precipitate in situ. Evaporation ponds are used extensively in the commercial art of solar production where seawater is reduced to greater concentrations with staged precipitation to improve harvesting efficiency [7]. When applied to desalination effluent the concentrate is pumped into shallow sealed ponds and allowed to evaporate using the sun, thus making them suited to hot and dry climates. Due to the reliance on the sun for this process ponds therefore require a large surface area to be effective, with contingent cost and environmental considerations [2]. As a result that are preferred for smaller concentrate flows when discharge back to the ocean is not an option.

With respect to Australian CSG production, operators are forced to establish a brine management network which simultaneously separates brine from the immediate environment whilst evaporating water to the atmosphere with consideration to regulations and weather. To this effect operators are investigating novel processes such as wind aided intensified evaporation in order to reduce the geographic footprint of these evaporation methods in a variety of different configurations. This form of brine management is creating a variety of challenges to CSG operators not engaged in salt production as their core business. Industry analysts predict that with competition from other unconventional operations the type of experience required to profitably manage water will become progressively more difficult to secure [10]. This experience must also include the perpetual management of the brine containment pond itself, given as at least thirty years, with consideration of natural disasters and land remediation through and concluding that period [2]. A final criticism of concentrating precipitate via evaporation as a brine management strategy is that the water is not recovered [11]. Despite this and due to operational necessity CSG producers have proceeded with individual technologies for brine containment. Figure 3: QGC Monocell Schematic shown over the page demonstrates a schematic of one of QGC’s twelve containment monocells with approximate dimensions of 1km2 each to store 200 thousand tonnes of salt waste per annum for the thirty years of the project [12].

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FIGURE 3: QGC MONOCELL SCHEMATIC

2.2 COMMERCIAL BRINE PRODUCTION Considering the extensive financial implications of brine management it is prudent to examine the disposal of brine from a commercial perspective. This means understanding the market value of market quality brine from an in-line commercial perspective rather than as a waste product of growing magnitude and perpetual concern. This requires learning lessons from commercial salt/brine producers and harnessing novel processes to meet the peculiarities of inland brackish water composition as well as the tightening regulations regarding water use and storage. The recovery of commercial products from CSG brines accomplishes two objectives: improving the economy of the complete treatment process which currently operates as a total loss and minimising the capital and operating expenditures of brine containment [13]. The commercial possibilities of using the sodium chloride rich and mineral poor produced water in order to offset the costs of CSG development have also been established by literature reviewed in 2011 [1].

Effective brine production can be assisted with information from the solar salt industry. The industry operates in production cycles of at least a year between pond in-take to salt harvest due to natural dynamics and variations imposed by weather [14]. The industry uses a sequence of fractional crystallisations to obtain precipitates in a controlled manner. In the example of solar salt production using seawater direct crystallisation would produce the following composition of precipitants.

TABLE 2: COMPARISON OF PRECIPITANT QUANTITY

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In practice the harvesting of various precipitates including magnesium, salt of the form NaCl and calcium, takes places in overlapping stages. The way in which this occurs and the optimisation of this process is considered to be part of the art of solar salt production, evidenced by the curves below.

FIGURE 4: PRECIPITATION OVERLAP DURING EVAPORATION

As a result, commercial salt production via evaporation continues until a brine density of 1.25 is reached corresponding to 75% of NaCl. It is due to this reality that solar salt on the commercial market often contains significant amounts of magnesium compounds. The presence of extensive pre-treatment and concentration in the CSG industry means that both the size and operation of evaporation ponds will be radically different when compared to those for solar salt production from seawater. QGC and Santos are pursuing an allied research project to identify whether a selective salt recovery (SSR) method of brine management is economically feasible based on the composition of their concentrated brines [12]. No details are publicly available on this effort however the proprietary SAL-PROC method described earlier has been assessed to determine the commerciality of its by-products. The 2003 study concluded that under an optimistic best case scenario the method could produce US$1.1 million (converted to 2012 dollars) commercial salts from 405 megalitres of water per year. Table 3 shown below was used to demonstrate the breakdown of value in USD although market prices have certainly changed since it was published [15].

TABLE 3: INDICATIVE VALUE OF PRECIPITANTS

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However regardless of the method applied to achieve a final NaCl precipitate the primary consideration is finding a market for the consumption of such large salt volumes and the quality demanded by that market. After this it becomes necessary to understand how to deliver those volumes at a cost which doesn’t exceed available options such as injection and storage.

2.3 CHLOR ALKALI INDUSTRY The chlor alkali (CA) industry is the term given to the industry that uses brine or solids composed of sodium chloride to create chlorine and sodium hydroxide (caustic soda) via electrolysis [16]. It is a significant industry due to both chlorine and sodium hydroxide being in the top ten chemicals produced worldwide. They are critical as precursors in the manufacture in everyday products as well as pharmaceuticals, detergents, deodorants, disinfectants, herbicides, pesticides, and plastics. It is also the case that chlorine and caustic soda are extensively used as process chemicals facilitating the production of other items or services [14]. As stated, the production of these chemicals is facilitated by electrolysis of sodium chloride meaning that with appropriate plant and equipment the only raw materials required are power, water and salt. Industry analysts predict that the industry will have a value of over US$86.6 billion in 2017 with production volumes of 79.8 million, 74.2 million and 58.1 million tonnes of caustic, chlorine and soda ash respectively [17]. Although local factors in Queensland mean that the production of caustic is of greater importance, the physics of the CA process mean that the chemicals of chlorine and caustic are produced in almost equal volumes. To this effect the image below indicates the range of potential uses which can be derived from chlorine produced using the CA process [14].

FIGURE 5: USES OF CHLORINE IN INDUSTRY AND COMMERCE

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2.4 BRINE PRE-TREATMENT As a high volume power intensive electro-chemical process, CA manufacture has historically taken place where both power and salt are plentiful. During the process salt of the form sodium chloride combined with water and energy undergoes the following reaction:

Impurities need to be removed from the brine before efficient industrial CA electrolysis can occur. These impurities include sulphate, calcium carbonate, potassium chloride, chloride and bromide The graphic below provides a simple overview the stages where purification takes place in the CA process [16].

FIGURE 6: PURIFICATION STAGES IN THE CHLOR ALKALI PROCESS

Historically brine purity was less of an issue due to the use of mercury cell and diaphragm cell CA technologies. For various reasons, including the regulatory challenges around chemicals such as mercury and asbestos, these technologies have lost favour to more modern membrane cells. Although membrane cells have far more stringent requirements on brine purity for commercial outcomes, the relative benefits and challenges of each technology are provided in

Table 4 below [16].

TABLE 4: COMPARISON OF CHLOR ALKALI TECHNOLOGIES

Without providing a complete history of the technology or discussing the relative merits of each cell, there are several reasons why it is prudent to only consider membrane cell technology within this report. Firstly, CSG development and water management is an environmentally sensitive topic in Australia without adding legacy technologies which reduce environmental credentials. Additionally, the CA industry and its products are the target of regulation and environmental concern globally, despite as previously discussed being essential to a modern economy. Finally, best practice and existing Australian operations indicate that membrane technology is the most suitable for use thereby increasing longevity and improving factors such as maintenance and interoperability if implemented. The outcome of these factors and the essentiality of the CA process to

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modern manufacture is the continuing innovation of technology and management within the CA process. Table 5 shown over the page gives an indication of recent technology developments as a demonstration of the continuing improvements in efficiency and effectiveness of what is essentially a more than 100 year old industry [18].

TABLE 5: RECENT ADVANCEMENTS IN MEMBRANE CELL TECHNOLOGY

The most promising and fast-developing technique for the production of CA is the membrane cell process and this will undoubtedly replace other available techniques. Membrane cells require highly pure and very concentrated brine which often requires costly IX purification steps prior to electrolysis. Due to this, different research projects have started evaluating alternative CA precursors derived from IX treated brines [19]. For these reasons this report focuses on the process and requirements of IX treated brines for membrane technology.

2.5 CHLOR ALKALI MEMBRANE CELL PROCESS The pre-processing of brine for mercury and diaphragm technologies is simplified to basic precipitation and filtration before electrolysis. In the case of membrane cells this processing is further extended by the requirement for secondary treatment with IX resins [20]. The illustration below describes the CA process with system inputs and outputs using a membrane cell operation to separate anode and cathode in the containment vessel [18].

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FIGURE 7: MEMBRANE CELL PROCESS OVERVIEW

The position of this schematic in the overall process of typical membrane cell CA production can be understood when considering Figure 8 below [16].

FIGURE 8: CHLOR ALKALI PRE-TREATMENT

2.6 BRINE REQUIREMENTS FOR CA PROCESS Before the brine can be used in membrane cells the hardness must be reduced to a magnitude of parts per billion such that multivalent cations such as magnesium and calcium do not travel into the containment vessel. This would lead to damage caused by scaling and fouling forcing plant shutdowns and increased maintenance costs. Therefore softening for sensitive membranes operating at high current efficiencies takes the form of IX resins which replace mineral ions with ions like sodium and potassium. This is made more complex by the competition for available sites in the IX process bed and the relative selectivity or affinity between the relevant ion and resin [14]. This complexity involves discussion of the IX process in an industrial context and the

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diversity of impurities/resins which might undergo this form of in-line treatment are sizeable. As part of the body of research being conducted around CSG water management, this discussion is therefore limited to the experiments undertaken by the author on bromide recovery using strong base anion resin. Further data on preferred brine composition for CA production using specific membrane technology and the consequences of using various impurities is provided in Appendix A [14].

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3 REMOVAL OF BROMIDE USING STRONG BASE ANION RESINS There are two key factors when assessing the removal of bromide from CSG brines. The first is understanding the guidance regarding its concentration due to the danger posed to humans and the environment. The second is understanding what effect it has on the CA membrane process and what its required concentration is to maintain process efficiency. Studies investigating bromide removal using resins are discussed and results of the experiments undertaken is given in the subsequent section.

3.1 BROMIDE IN WATER The literature on the effects of bromide in produced water is rare for a number of reasons including the fact that it is only in recent history that operators are considering concentrated brine disposal from inland RO as a primary concern. Due to changing geology across CSG production sites, water composition is also highly variable. In this concern the concentrations of other solids, particularly those resulting from the chemically diverse hydraulic fracturing (fracking) operations, have received a large amount of regulatory and media attention where bromide has not. In addition, bromide concentrations in produced water are typically regarded as ‘trace’ quantities well below the safety thresholds which arise in waste water treatment.

Most literature on bromide draws upon its history as an anticonvulsant and sedative in the first half of the 20th century. The experiments undertaken to write this report consider initial concentrations of 10 parts per million (ppm) processed into a concentrated effluent stream of approximately 200 ppm before consideration of IX treatment. The literature advises that for the inorganic bromide ion the empirically evaluated no-observed-effect level of consumption is 4mg/kg body weight per day and gives the acceptable daily intake evaluated as 0.4mg/kg per day with a safety factor of 10 applied for diverse populations. This represents 24 mg for a 60kg and is equivalent to 6 ppm for 2 litres water consumption per day [21]. There has been one case reported where an investigation was undertaken in Angola based on widespread but localised somnolence, ataxia and co-ordination impingement in the human population. The study concluded a chemical leak of bromide into the water supply was responsible with differential diagnosis supporting a similar GABA affecting toxic origin [22]. The key public concern with bromide is its potential to form carcinogenic brominated disinfection by-products when used as an industrial water disinfectant during waste water treatment. This context is applicable to brominated water being assessed before surface discharge after amendment but is otherwise not considered in this report [23].

3.2 IMPURITIES IN CA FEED The RO water treatment and evaporative process of brine storage result in progressively greater concentrations of total dissolved solids (TDS), assuming that there is no addition of extra solvent such as rainfall. As discussed with regards to solar salt production, these TDS concentrations increase until they exceed their solubility in the evaporating volume of solution. To prepare crude salt for use in the CA process the industry standard is for a certain degree of pre-treatment by the salt provider rather than the CA processor. This pre-treatment is comprised of salt washing, brine evaporation and salt recrystallization which is extensively covered in the literature on the subject. For membrane cell technology the chief concern is purity and therefore after the well-established industrial process of impurity removal the IX process is undertaken by the CA processor to further refine the feed before alkalinity-reducing acids are added to mixture. The table over the page describes the typical impurity concentrations across source salt which is purchased by CA processors for use.

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TABLE 6: CHLOR ALKALI QUALITY FEED SALT COMPOSITIONS

3.3 BROMIDE IN CA FEED There is very little literature on bromide in CA brine feed despite most salts containing a small quantity of the chemical. When considering membrane cell technology bromide may form part of the spectrum of impurities (including iodide and barium) which must be reduced so as to enhance membrane life and improve electrolysis efficiency. Historically some membranes were challenged with the more reactive chlorine located in the feed brine however as purity and membrane technology have improved this has become less of an issue. As a diverse group, combinations of these impurities behave differently and necessitate different management techniques. In this regard the literature on brine pre-treatment for the CA process is well established however operator manuals stress the importance of precise brine analysis and continuous in-line testing to assure accurate treatment and improved membrane life. Given the highly diverse quality of CSG water it is presumed for this report that CSG operators maintain a comprehensive program to ensure consistent CA brine feed composition to a downstream CA operator. With that considered the solution used for the experiments which inform this report used a bromide concentration of 175-200 ppm based on averaged produced water concentrations of 10 ppm before RO processing.

When assessing the effects of bromide as a solitary impurity there are three relevant factors for CA feed. Consulted literature does not report any adverse effects of bromide ions on membranes, indicating that when taken in isolation fouling is not a risk factor for this class of impurity. There is some published material on the possibility of bromide adversely affecting proprietary DSA electrodes however this is not mentioned in relation to CA applications. Of most relevance is the twin processing of bromine with fellow halide chlorine leading to its overabundance in the chlorine gas arising from the electrolysis. There are chemical and thermodynamic steps taken to prevent the commercial production of chlorine gas being impacted by this unwanted bromine. Steps such as pH adjustment and control of the oxidation reduction potential which prevent the further oxidation to bromate assist in air stripping the bromine from the solution. Sources consulted indicate a reduction in bromide levels during commercial operation from 50 ppm to less than 0.5 ppm using the method which is indicated in the schematic over the page.

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FIGURE 9: BROMIDE STRIPPING DURING IN THE CHLOR ALKALI INDUSTRY

With the addition of temperature, which is stated as above 65 degrees Celsius, the result is a bromine off gas with chlorine impurity. The next opportunity in the CA process to remove bromine occurs post-electrolysis via partial condensation during chlorine gas compression. It is determined from these facts that the CA industry has an established treatment method for controlling bromide in feed brine at concentrations below 50 ppm. As a result the analysis of bromide removal in this paper will only be concerned with achieving a bromide in brine concentration of 50 ppm or better so as to commence this established process. In addition, there are few industry applications where the presence of bromine in the chlorine gas product causes a negative impact during use. This means that there is a lack of research available on bromine removal technologies for this application and the industry accepted value of 50 ppm is not investigated further [14].

3.4 STRONG BASE ANION RESINS The objective during IX for bromide is to provide a commercial method of extracting monovalent monoatomic anions of bromine (Br-) from a solution. For the chemical compound sodium bromide (NaBr) dissolved in water, the hydrated cations of sodium become disassociated with the anions of bromine forming the aqueous solution of both. Insoluble strong base anion resin (SBAR) is added to the solution which facilitates anion exchange based on equivalent charge and selective affinity. The SBAR itself is comprised of polymer beads whose porous matrix is design loaded with fixed cations and mobile counterions in a process of chloromethylation and amination. The principle dynamics of the ion exchange after the SBAR is added are based on ion quantity and selectivity: quantity being determined by the number and charge of fixed ions in the resin bead and selectivity being determined by the chemical affinity (itself influenced by the physics of electron affinity) between two ions. In the case of SBARs, different cations (most are quaternary amine groups) will display different affinities to different anions such as bromide. The resins also perform differently under various conditions and this is due to the effect of proprietary factors such as bead size, pore size and resin material comprising the ion exchange matrix. The large number of interactions derived from the IX matrix used, the composition of solution being evaluated, the environment of interaction and the outcomes being tested underpins the basis of IX experimentation. The resin used in the experiments performed by the author is the proprietary DOWEX Marathon A manufactured by the Dow Chemical Company. The resin’s product data sheet is provided in Appendix B [24].

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3.5 CONCLUSIONS AN ALTERNATIVE EXPERIMENTAL STUDY The literature indicates that SBARs have previously been used as to reduce bromide concentrations in the case of the MIEX resin manufactured by ASX-listed Orica. The Australian research indicated that the removal of bromide was “highly dependent on the alkalinity of the water and competing ion concentrations”. When conditions were optimal the resin was able to “reduce bromide concentrations by approximately 93%” however this dropped to 60% when conditions were less suitable. The study also demonstrated that regeneration, the process by which the capacity of the resin is restored to its original state, resulted in significant reductions in resin performance. By referencing other literature the study concluded that “any strong anion-exchange resin could be expected to display some bromide and iodide adsorption capacity under favourable conditions”. Other polystyrene resins which were compared and found a favourable result were Ionac-641 and Amberlite IRA910 [25].

Results of bromide removal using MIEX resin lead to the following experimental conclusions [26]:

MIEX resin can be used as an effective adsorbent for bromide removal from aqueous solutions. The uptake of bromide on MIEX resin increases with increasing the initial bromide concentration. The removal rate of bromide increases with increasing adsorbent dosage. The agitation speed of 100 rpm is appropriate. The high removal efficiency of bromide is obtained at the pH range of 4–9. The uptake of bromide decreases with increasing temperature of solution. The coexistent anions have significant effect on bromide removal, and the following sequence is

given: SO4 2 > CO3 2 > Cl . The equilibrium adsorption of bromide on MIEX resin at 303 K can be well fitted by both Freundich

and Redlich Peterson isotherm models. The kinetics process of bromide on MIEX resin can be well described by the pseudo second-order

model. The diffusion simulation shows the intra-particle diffusion is not the only rate limiting step.

Isotherms indicating the performance of MIEX resin were published in a separate study as shown in Figure 10 below [26].

FIGURE 10: ISOTHERMS SHOWING BROMIDE REMOVAL USING MIEX

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In a further study, data was published comparing bromide removal across a variety of resins and conditions as shown below [27].

TABLE 7: COMPARISON OF MARATHON A WITH OTHER RESINS

3.6 OTHER METHODS OF BROMIDE REMOVAL There are few techniques discovered during research which are effective at removing bromide from industrial brine. Most of the research on bromide removal techniques has been focused on drinking water applications and waste water treatment systems. These methods include aluminium coagulation and adsorption using silver-doped carbon aerogels [28], [29]. It is a recurrent issue across all removal methods that the other halides (binary halogen compounds) of chloride and iodide which flank bromide in terms of reactivity compete for its removal [30], [31]. Due to high concentrations of these halides in CSG brines relative to bromide the applicability of these novel techniques is questionable. When considering competing halides and the costs of bromide selection using traditional filtration techniques there is strong opportunity for further study to validate the possibility of selective bromide removal using SBARs when preparing commercial brine for the CA industry [23]. In consideration of bromide removal using other methods, a comparison table is provided below [26].

TABLE 8: COMPARISON OF SELECTIVE BROMIDE REMOVAL METHODS

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4 BROMIDE REMOVAL USING CHLORIDE LOADED DOWEX MARATHON A A solution of ca. 187 mg/L bromide ions (from sodium bromide) in pure water was equilibrated with various masses of chloride loaded DOW A strong base anion resin at 30 degrees Celsius. The resultant isotherm profile was then subjected to fitting by a variety of sorption models as shown in the following section.

4.1 RESULTS OF LAB BASED EXPERIMENTS Figure 11 shows the Langmuir Vageler fit of the isotherm data and this plot suggests that the maximum exchange capacity for the DOW A resin is ca. 2.5 mol Br per kg resin (equates to 200.5 g/kg resin) [Table 9]. Visually the plateau in the bromide uptake appears closer to 2.1 mol Br per kg resin (167.8 g per kg resin). The Langmuir Vageler fit seems to overestimate the loading capacity of the resin as the fit rises above the region where the loading has stabilized.

FIGURE 11: LANGMUIR VAGELER FIT OF ISOTHERM DATA FOR EXCHANGE OF 187 MG/L BROMIDE (FROM SODIUM BROMIDE) WITH DOW A CHLORIDE EXCHANGED RESIN

TABLE 9: NON-LINEAR LEAST SQUARES (NLLS) FIT OF LANGMUIR VAGELER ISOTHERM DATA FOR BROMIDE ION EXCHANGE FROM SODIUM BROMIDE SOLUTION WITH DOW A CHLORIDE LOADED RESIN. NUMBERS IN BOLD INDICATE MINIMUM ERROR VALUES AND

MINIMUM SUM OF NORMALIZED ERROR VALUES.

SSE HYBRID MPSD ARE EABS

qmax 2.47 2.53 2.59 2.58 2.51

KLV 1.843 2.055 2.234 2.232 2.009

SSE 0.15 0.16 0.2 0.2 0.16

HYBRID 0.6 0.49 0.55 0.55 0.49

MPSD 9.11 6.46 5.78 5.8 6.81

ARE 6.77 5.24 4.79 4.74 5.4

EABS 1.52 1.48 1.61 1.6 1.46

SNE 4.66 4.44 4.66 4.54 4.36

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The Competitive Langmuir fit of the experimental equilibrium data given in Figure 12 fits the data reasonably well and from the optimal ARE error function the maximum loading of bromide ions on the resin surface was predicted to be 182.8 g/kg.

FIGURE 12: COMPETITIVE LANGMUIR FIT OF ISOTHERM DATA FOR EXCHANGE OF 187 MG/L BROMIDE (FROM SODIUM BROMIDE) WITH DOW A CHLORIDE EXCHANGED RESIN

TABLE 10: NON-LINEAR LEAST SQUARES (NLLS) FIT OF LANGMUIR ISOTHERM DATA FOR BROMIDE ION EXCHANGE FROM SODIUM BROMIDE SOLUTION WITH DOW A CHLORIDE LOADED RESIN. NUMBERS IN BOLD INDICATE MINIMUM ERROR VALUES AND MINIMUM

SUM OF NORMALIZED ERROR VALUES.


qmax 182.34 182.53 182.19 182.85 183.84

KL 2.612 2.579 2.588 2.557 2.505

SSE 431.49 433.41 434.47 435.9 447.17

HYBRID 14.04 13.89 13.91 13.94 14.42

MPSD 3.22 3.18 3.18 3.2 3.34

ARE 2.36 2.2 2.21 2.16 2.24

EABS 64.2 61.67 62.02 60.51 59.68

SNE 4.9 4.84 4.86 4.82 4.94

On the other hand, the Freundlich fit which is based upon the premise of an exponential decrease in the heat of sorption as a function of increasing coverage of the resin surface in Figure 13 does not appear to fit the experimental isotherm points as well as the Langmuir equation [Table 11]. The magnitude of the error values using the Freundlich fit is consistently higher than those obtained for the Langmuir fit.

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FIGURE 13: FREUNDLICH FIT OF ISOTHERM DATA FOR EXCHANGE OF 187 MG/L BROMIDE (FROM SODIUM BROMIDE) WITH DOW A CHLORIDE EXCHANGED RESIN

TABLE 11: NON-LINEAR LEAST SQUARES (NLLS) FIT OF FREUNDLICH ISOTHERM DATA FOR BROMIDE ION EXCHANGE FROM SODIUM BROMIDE SOLUTION WITH DOW A CHLORIDE LOADED RESIN. NUMBERS IN BOLD INDICATE MINIMUM ERROR VALUES AND MINIMUM SUM OF NORMALIZED ERROR VALUES.


KF 7.319 6.091 5.415 5.019 7.451

nF 1.5951 1.5027 1.4465 1.4089 1.603

SSE 1109.68 1223.21 1430.41 1732.55 1113.67

HYBRID 55.64 45.47 49.36 57.98 58.26

MPSD 9.84 6.83 6.23 6.49 10.3

ARE 6.98 5.65 5.22 5.12 7.12

EABS 127.1 130.44 138.02 145.37 126.28

SNE 4.41 3.84 3.96 4.34 4.51

Similarly, the Temkin fit which makes the assumption that the heat of sorption linearly decreases as a function of increasing surface coverage, shown in Figure 14, does not fit the data as well as the Langmuir expression.

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FIGURE 14: TEMKIN FIT OF ISOTHERM DATA FOR EXCHANGE OF 187 MG/L BROMIDE (FROM SODIUM BROMIDE) WITH DOW A CHLORIDE EXCHANGED RESIN

TABLE 12: NON-LINEAR LEAST SQUARES (NLLS) FIT OF TEMKIN ISOTHERM DATA FOR BROMIDE ION EXCHANGE FROM SODIUM BROMIDE SOLUTION WITH DOW A CHLORIDE LOADED RESIN. NUMBERS IN BOLD INDICATE MINIMUM ERROR VALUES AND MINIMUM SUM OF NORMALIZED ERROR VALUES.


A 0.108 0.119 0.13 0.114 0.111

bT 7838.9 8287.9 8918.9 8179.3 7935.8

SSE 1269.54 1456.92 2515.4 1415.75 1285.54

HYBRID 101.68 87.44 107.49 89.71 94.87

MPSD 15.54 12.49 11.48 13.37 14.3

ARE 9.34 8.68 9.33 8.49 8.79

EABS 141.44 150.21 197.04 144.97 140.26

SNE 4.17 3.96 4.81 3.97 4.04

Application of the Dubinin Astakhov expression as in Figure 15 indicates [Table 13] that the resin surface is actually heterogeneous in character as indicated by the “n” value close to 1. In comparison activated carbon normally exhibits a value for the heterogeneity factor “n” close to 2 and zeolites which are highly ordered and homogeneous are characterised by values of n of 4 to 5. The Dubinin Astakhov theory relates to movement of species through the pore structure of the material in question, and thus the resin may be heterogeneous in terms of porosity but homogeneous in terms of the nature of the active exchange sites. This latter statement relates to the fact that the Langmuir equation appears to fit the isotherm data best and this theory assumes a homogeneous surface. Notably, the value for “E” the sorption energy is relatively high at 40.0 kJ/mol which suggests strong interaction between the bromide and the resin surface sites.

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FIGURE 15: DUBININ-ASTAKHOV FIT OF ISOTHERM DATA FOR EXCHANGE OF 187 MG/L BROMIDE (FROM SODIUM BROMIDE) WITH DOW A CHLORIDE EXCHANGED RESIN

TABLE 13: NON-LINEAR LEAST SQUARES (NLLS) FIT OF DUBININ-ASTAKHOV ISOTHERM DATA FOR BROMIDE ION EXCHANGE FROM SODIUM BROMIDE SOLUTION WITH DOW A CHLORIDE LOADED RESIN. NUMBERS IN BOLD INDICATE MINIMUM ERROR VALUES AND MINIMUM SUM OF NORMALIZED ERROR VALUES.

SSE HYBRID MPSD ARE EABS qmax

(mg/g) 205.06 192.4 176.7 190.16 205.33

E (J/mol) 40970.4 40040.5 39888.3 39559.3 40104.3

n 1.224 1.271 1.312 1.298 1.222

SSE 1857.056 2258.72 4091.324 2689.785 1871.071

HYBRID 182.882 149.835 188.313 167.046 191.628

MPSD 22.056 17.139 15.428 16.284 22.859

ARE 12.259 11.846 11.938 11.296 12.309

EABS 169.898 201.945 260.439 208.147 166.688

SNE 4.02 3.82 4.63 3.96 4.1

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The Brouers Sotolongo isotherm below supports the conclusion that the resin surface is relatively homogeneous as the value for is 0.933 (close to the value 1 which suggests a homogeneous surface site distribution).

FIGURE 16: BROUERS SOTOLONGO FIT OF ISOTHERM DATA FOR EXCHANGE OF 187 MG/L BROMIDE (FROM SODIUM BROMIDE) WITH DOW A CHLORIDE EXCHANGED RESIN

TABLE 14: NON-LINEAR LEAST SQUARES (NLLS) FIT OF BROUERS SOTOLONGO ISOTHERM DATA FOR BROMIDE ION EXCHANGE FROM SODIUM BROMIDE SOLUTION WITH DOW A CHLORIDE LOADED RESIN. NUMBERS IN BOLD INDICATE MINIMUM ERROR VALUES AND MINIMUM SUM OF NORMALIZED ERROR VALUES.


qmax 200.03 208.25 217.84 229.26 223.67

Kw 0.0118 0.0129 0.0134 0.0133 0.0131

1.001 0.962 0.933 0.916 0.929

SSE 368.18 377.7 400.72 433.31 415.53

HYBRID 13.69 12.87 13.27 14.22 13.72

MPSD 3.68 3.11 3.01 3.07 3.06

ARE 2.7 2.2 1.96 1.89 1.91

EABS 64.63 60.35 57.85 56.88 56.21

SNE 4.81 4.56 4.46 4.57 4.5

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5 COMMERCIAL VIABILITY OF BRINE DISPOSAL Assessing the commerciality brine disposal to the CA industry in this context implies that treated CSG water is an environmental requirement and that concentrated brine or crude salt management is unavoidable. Therefore the CA industry can offset treatment and management costs by absorbing this core business externality and repurposing it to productive use. The value of commercial salt production to CSG operators lies on a quantum between the sale at market value of all appropriately treated brine concentrate and the cost of regulation-compliant brine management into perpetuity. It is further implied that effectively sequestering this concentrate into deep saline aquifers or freighting it for disposal into the ocean are environmentally and commercially untenable for the volumes being considered. Therefore the determination of commerciality of producing brine for the CA industry from CSG water is made by estimating the achievable market value of processed brine for local CA operators and comparing this to the cost of indefinite storage.

An assessment is not made on the cost of indefinite storage due to the inaccessibility of commercially sensitive data, a lack of agreement about valuation figures, the dynamic changes within the CSG industry and the required effort to provide reliable conclusions. For similar reasons it is also impractical to estimate a cost for effectively processing water to generate a useful brine outside of the broad cost centres discussed earlier. Therefore this commercial consideration is confined to the domestic market potential for membrane technology grade CA feed brine.

As can be assumed, the market price of sodium chloride increase exponentially with its purity. The table below gives an illustration of this principle [32].

FIGURE 17: COST OF SALT BASED ON PURITY

5.1 BRINE PROCESSING The viability of commercial brine disposal has been assessed a variety of times in the literature when considering seawater desalination. It is established that no single silver bullet exists and that a mixed technology approach is required with an overview of these assessed technologies available in Appendix C [33].

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Taking into account produced water source, types of contaminants and final use requirements the feasibility of commercial brine processing from concentrate streams is further determined by consideration of the following factors [15]:

Composition and concentration of chemicals used during the production and treatment process. Climatic conditions which indicate pond sizing when considering evaporation and crystallisation. Commercially sensitive data regarding flow rates, compositions and resultant efficacy of proprietary

technology (e.g. SAL-PROC, concentrators, membranes). Cost of electricity and accessibility of waste heat or cheap energy sources. Availability of land and regulations regarding water treatment and land use. The synergy achieved by private industry contributing entrepreneurship and capital, government

agencies providing ‘public good’ assurance and universities providing access to technological insight.

Based on these factors and a review of existing technologies the study concluded that novel treatment of inland brines to produce commercial salt is feasible if conditions are met for the specific case. The feasibility is enhanced by the market value of the by-products from the treatment process which can include gypsum, salt, magnesium hydroxide, calcium chloride, calcium carbonate and sodium sulphate. The conclusion regarding collaboration between industry, regulators and researchers is supported by symposium comments which provide lessons from US gas development. These comments advise operators to “consider a multitude of options and keep as many of these open as possible - particularly in Australia, where the volume of water produced is very difficult to predict”, where beneficial outcomes are enhanced by “planning the entire life cycle of a CSG project from permitting to reclamation .. Engage and build strong and open relationships with all stakeholders” who include “soil scientists, environmental scientists, agronomists, biologists, hydro geologists - keep data available and credible” and finally to “perform self-assessments so that audits become an exercise of verification. Most importantly, be honest and do the right thing” [34]. During the writing of this report the extensive data available from operators and its context as part of industry-funded research demonstrates that the current industry approach agrees with the recommendations.

5.2 COMMERCIAL SALT PRODUCTION Taking into account the next step of viability assessment requires assessing the value of processed brine in a local context. The value of the brine is a function of demand by local industry and the economics of supply. These factors are affected by potential salt customers, CA process customers and the locations of each with respect to the location of CSG production. Trade data reveals that Australian production of salt was 11.4 million tonnes in 2011 and in Queensland production has recently tripled from 50 thousand tonnes to more than 168 thousand tonnes in the same period. Salt production is driven by a number of factors: in the food industry recent local investments include the $150 million acquisition of Cheetham Salt for soy sauce manufacture by Hong Kong’s CK Life Science International [35]. This is an indication of Australia’s global position as a salt exporter with 11.3 million tonnes in 2012 valued at $254 million. Industry news also reported that Australia’s only producer of soda ash (Penrice Soda Products based in South Australia), manufacturing 315 thousand tonnes in 2012, will phase out production and rely on imports in 2013. Penrice is the company working with CSG operators on SSR (selective salt recovery) technology as a possible revenue stream into the future. Another insight is that Australia is a poor consumer of salt: with negligible imports of 57 thousand tonnes Australia consumes just 190 thousand tonnes of salt a year [36]. Despite this the chart over the page projects production growth over the life of CSG production in Queensland using historical data provided by the Australian Government.

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FIGURE 18: AUSTRALIAN PRODUCTION OF SALT USING LINEAR EXTRAPOLATION

That the CA process uses a significant amount of salt but Australian consumption of salt across all industries is relatively small indicates that the commercial recovery of salt may not be viable compared to more competitive methods of salt extraction. However the production by the CA industry of chlorine and caustic leads to other commercial avenues of exploration.

5.3 CHLOR ALKALI PRODUCTS There are two key outputs from the CA process, chlorine and caustic soda, with a small quantity of hydrogen produced also [37]. For every 40 tonnes of caustic soda produced, 35.5 tonnes of chlorine and 1 tonne of hydrogen is co-produced. Required inputs are 2,200 kWh of energy and 1.6 tonnes of salt for each tonne of caustic, as shown below.

FIGURE 19: CHLOR ALKALI MEMBRANE

0.002000.004000.006000.008000.00

10000.0012000.0014000.0016000.0018000.0020000.00

1969

1972

1975

1978

1981

1984

1987

1990

1993

1996

1999

2002

2005

2008

2011

2014

2017

2020

2023

2026

2029

2032

2035

2038

Kilo

tonn

es o

f Sal

t

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5.3.1 CHLORINE Without a vibrant chemical industry by global standards, the usefulness of chlorine as an industrial product in Australia is limited. According to a study published in 2008, Australia’s chlorine needs are met by imports and the operations of four main producers: Orica, Nufarm, Coogee Chemicals and Kiwi Brands. In 2011 only $261 thousand worth of chlorine was imported comprising 186 thousand tonnes, down from $1.5 million the year before and a more stable $767 thousand in 2009 [38]. Production of CA chemicals in Australia comprised 10% of the inorganic chemicals industry in 2012-13, accounting for $290 million of revenue in the industry [39].

Chlorine is produced in Australia for applications such as water treatment and herbicides with approximately 110 thousand tonnes of caustic are produced each year as a by-product. Orica produces 9,000 tonnes per year of chlorine in Yarwun, near Gladstone in Queensland, using membrane cell technology [40]. This capacity represents a salt feed of approximately 16.2 thousand tonnes, or roughly 500 B-Double truckloads. Outside of a small facility run by Coogee Chemicals at the Port of Brisbane, this is the only information that could be found on CA production in Queensland.

5.3.2 CAUSTIC SODA By contrast to the figure for chlorine, in 2010 Australia imported over US$432 million worth of aqueous caustic. This is the largest value imported compared with every other nation, ahead of the US (US$321 million), Brazil (US$229 million) and Canada (US$177 million). Other nearby significant importers of caustic soda include Malaysia (US$57 million), Singapore (US$52 million), Philippines (US$44 million), South Korea ($34 million), Thailand (US$30 million), Indonesia (US$26 million) and Vietnam (US$25 million) [41]. Australian export values for the chemicals produced in the CA process are negligible and these trade values don’t address the utilisation of chlorine or caustic in a domestic capacity for manufactured goods. Despite this it is obvious that Australia is importing a significant quantity of caustic soda despite having a small but established CA industry.

The reason for Australia’s large caustic imports is its position as a globally significant producer of alumina, the precursor for the manufacture of aluminium. Australia uses vast quantities of nationally sourced bauxite ore and imported caustic to produce the precursor compound. This production makes ahead Australia the world’s largest producer of alumina, edging ahead of China priming it to be the world’s fifth largest producer of aluminium. Australia is also the world’s largest producer of bauxite outstripping its nearest rival Brazil by nearly three times with 62.4 million tonnes produced in 2007. The vast quantities of bauxite are mixed with the caustic soda as part of the digestion phase in a thermodynamic sequence known as the Bayer process. A process diagram is shown below with the location of caustic soda addition indicated as NaOH [42].

FIGURE 20: BAYER PROCESS DIAGRAM

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The Bayer process produces sodium aluminate which is precipitated to aluminium hydroxide before decomposing to aluminium oxide (alumina). Production of alumina in Australia was 21.9 million tonnes in 2012-13 with the industry meeting local demand of $1.91 billion and export demand of $6.42 billion. This was achieved with the expansion of production facilities at Yarwun in Queensland and Worsley in Western Australia. Rio Tinto’s facility in Yarwun has a post-expansion production capacity of 3.4 million tonnes of alumina with 90% utilisation in 2012 and overall Australia generates one quarter of global alumina output. By 2018 industry revenue is expected to reach $9.94 billion with Alcoa of Australia, Rio Tinto and BHP Billiton dominating production across seven facilities, six of which rely on natural gas for steam-raising. In addition to Rio’s Yarwun, Queensland Alumina Ltd (QAL) operates a refinery 80% owned by Rio Tinto in Gladstone with a capacity of 3.8 million tonnes and production of 3.69 million tonnes in 2012. Overall, 27.6% of alumina production occurred in Queensland in 2012 for a total volume of 6.75 million tonnes.

An advantage of the limited number of operators and the concentration of operations (Gladstone for Queensland) makes negotiation of long-term high-volume contracts a more straightforward exercise. The supply factors resulting from reliance on caustic soda imports and fluctuating energy prices mean that operators have a strong demand for supply arrangements which reduce volatility. In addition, the majority of aluminium smelting occurs in Queensland with 30.7% of national production. Despite a declining aluminium smelting industry in Australia exports of alumina are based primarily on demand from China and expected to remain stable.

Using broad based figures and practicalities of the Bayer process, it is estimated that to produce 1kg of alumina requires 3.76 kWh of energy, 3kg of bauxite, 2.6 kg of process water and 100g of caustic soda for high-quality bauxite or up to 750g for high silica bauxite [43]. This implies that to manufacture 6.75 million tonnes of alumina in Queensland approximately 675 thousand tonnes to 5 million tonnes of caustic is required, depending on bauxite quality (typically taken as 40 to 60% in Queensland) and technology/process employed. However industry researchers place the nationwide usage of caustic soda as 1.5 million tonnes, with the split being 80% to alumina production, 5% to sodium cyanide and 15% to other uses, thereby approximating 1.2 million tonnes per year for alumina production [44]. It is highly relevant to note that Gladstone is within 50km of the CSG terminal located at Curtis Island and 500km of the gas fields themselves therefore increasing its desirability as a destination for CSG by-products. To completely meet annual alumina industry demand for caustic would require approximately 1.9 million tonnes of salt and almost ten times the CA production capacity in Australia as well as 100 times the CA production capacity in Queensland.

5.4 TOWARD AN INDUSTRIAL SYMBIOSIS NETWORK It is challenging to create an economic argument for the sale of industrial salt to the CA industry despite world-leading demand for its products in Australia due to the disparity between produced volumes and CA production capacity. Despite this an arrangement which suits the known data is collaboration between several large members of industry to create shared economic benefit. This collaboration, as previously discussed, must also involve regulators and researchers to achieve the required outcomes. A strong incentive for this collaboration and its acceptance with regulators lies within the field of industrial ecology in what are termed ‘industrial symbiosis networks’. The term has been defined as “the process whereby a waste product in one industry is turned into a resource for use in one or more other industries. It is the essence of a well-functioning ecosystem. The Kalundborg experience shows that cooperation among different industries in the use of waste increases the viability of the industries. At the same time, the demands from society for resource conservation and environmental protection are met” [45]. Figure 21: Sustainability framework around industrial symbiosis

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displayed over the page gives an overview of how industrial symbiosis fits into the nomenclature of environmentally focused sustainability [46].

FIGURE 21: SUSTAINABILITY FRAMEWORK AROUND INDUSTRIAL SYMBIOSIS

The concept of industrial symbiosis is already proposed and in effect with CSG production through the beneficial use of water supplied to nearby communities. In these formative stages of the industry the reality of large produced water volumes has led to anecdotal comments from CSG employees that CSG isn’t a gas business so much as a water business. With the issue of brine disposal and the volumes being managed as well as consideration of commercial end users it certainly has the capacity to be considered a salt business too. This report proposes that a likely outcome of a functioning industrial symbiosis network based in Gladstone would involve the CSG operator, a water contractor such as Veolia (consuming process chemicals), a novel technology partner such as Penrice, a CA and chemicals leader such as Orica (who may also re-process and supply water treatment chemicals/resins) and a CA output consumer such as Rio Tinto. The mentioned businesses are highly concentrated major players with established commercial links to the CSG industry or are currently based in the port city of Gladstone, the industry’s downstream terminus.

With capital costs of CA production facilities in the order of $100 million for a 30 thousand tonne per year membrane plant and preferential access to raw materials such as water, power and salt, the potential economics and industry benefits of processing CSG brine make compelling consideration. They also make a cheaper proposition than the almost $2 billion being spent by QGC to treat its own produced water. It is worth noting that currently the largest customers for natural gas in Australia are alumina kilns and ore smelters followed by the chemical industries centred around fertiliser and plastic manufacture [47].

Gladstone has already been the subject of research when considering the concept of industrial symbiosis networks [48]. These studies highlight Gladstone’s growth as a centre for heavy industry, its opportunity for reliable cheap environmentally friendly energy via the CSG pipeline and its proximity to export locations with deep water port infrastructure. Also highlighted in relation to this are the Queensland Alumina and Rio Tinto alumina refineries, Australia’s largest aluminium smelter Boyne Smelters, chemicals manufacturer Orica and Cement Australia’s reuse of alumina and aluminium waste streams [49]. One study goes on to mention that “many other new regional resource synergies could be identified by a more detailed outlook on regional material/energy/water balances, and specific industries wastes and material flows analysis … emerging industries could bring more options to enhance the industrial symbiosis development”. The symbiosis network is currently being strengthened by the addition of the Gladstone Pacific Nickel refinery occurring in Yarwun,

34

which may combine acid effluent streams with the alkaline alumina reject to broadly neutralise pH. Once again Orica has been included as a local partner with chemical expertise. The need for another partner such as Veolia would also be required as water consumption for the proposed nickel plant and soon to be commissioned Boulder Steel plant will exceed 42.5 million cubic metres per year by 2020, exceeding current infrastructure [49]. The study produces the following illustration as an analysis of existing industrial symbiosis opportunities in Gladstone.

FIGURE 22: GLADSTONE INDUSTRIAL SYMBIOSIS NETWORK

The study concludes that the only barriers to this implementation are a lack of information sharing between industry and regulators as well as those which have an economic and community basis. None of the studies reviewed as yet proposed the development of CSG waste brines as precursors for the CA industry in Queensland.

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6 LITERATURE REVIEW There has been some variation in project focus before the decision was made to focus on commercial brine disposal in the CA industry. As a result a wide of literature has been consulting across the themes below.

6.1 COAL SEAM GAS This establishes the importance of the research topic by introducing the industry and its strategic value to stakeholders as a long-term reality whilst recognising the need to manage brine produced in the process of developing CSG resources

The importance of coal seam gas development to industry and Government in Australia as an ongoing industry

Water produced as a by-product of CSG development – quantity produced and composition Treatment options - reverse osmosis and brine management

Example Boolean string used: (CSG OR “coal seam gas” or CBM or “coal bed methane”) AND water AND (quantity OR composition OR properties OR quality)

Hamawand et al., Alley et al., Santos and Hancock were the key contributors to background information helping to frame the research. Peer reviewed works led by Hamawand and Alley were used to establish the credibility of Hancock’s electronic article and Santos’ regulatory conformance document. There is a large amount of literature available on CSG produced water and the important factors were gaining enough empirical and anecdotal insight into the Queensland example. Hancock offered a national overview of the critical factors facing the industry with a focus on water and the use of Santos’ WMP document offered detail on volumes and regional challenges for a major CSG operator.

There was significant overlap in the area of CSG produced water and factors regarding brine. At least nine academic papers were directly regarding brine disposal with a number of papers mentioning it as a consideration of RO or IX technology. It was the relating concepts of brackish water, RO, IX, disposal and brine which yielded the most relevant results and therefore required the most specialised search filters. Specific information that was sought was therefore based on commercial use of brine resulting from water treatment. Only one paper was found that directly linked RO desalination to the chlor alkali industry, however this was based in the Canary Islands. Most others helped inform the literature search on salt production.

6.2 ION EXCHANGE This search examines current research on ion exchange resins in the context of halides (specifically iodide and bromide where possible) and their removal from water. It is an exploratory review to determine whether similar laboratory experiments have already been undertaken and what can be learned from them. It is also therefore useful to understand the novelty and value of the project topic. The search was initially limited to brines however was later expanded to include wastewater treatment due to a greater amount of literature being available as well as the process of chelating using silver.

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Example Boolean string used: ion exchange AND (brine OR water) AND (iodide OR bromide) AND removal AND strong base anion OR resin

6.2.1 HALIDE REMOVAL Studies involving silver doped carbon aerogels were referenced insofar as they indicated such research had occurred. As this wasn’t the focus of the paper very little detail was given of the studies except to explain that they were a novel method being pursued as a means of bromide removal. There were a total of five papers consulted in relation to primary research on novel methods and three summary papers which collated the research in comparison with other methods. As the research and the paper progressed it became clear that an industrial scale production process was required to meet the needs of the chlor alkali industry and therefore these methods were not given as much attention as established methods of in-line bromide removal.

6.2.2 BROMIDE Research on bromide was deliberately limited to its relevance to the chlor alkali industry. Despite uncovering literature on factors such as world production and Australian imports the relevance was considered minor compared to the report objectives. Where discussion of the effects of bromide on humans was concerned, the use of Hsu and Singer’s research paper on selective removal as well as two reports regarding the World Health Organisation’s previous research were referenced. In consideration of the influence of bromide on the chlor alkali process the relevant texts are reviewed in the following section.

6.3 CHLOR ALKALI Discovery of information on the chlor alkali industry started later in the research as the paper’s direction took shape. It also accelerated after a general understanding of the process and its position in the commercial world was increased. The most useful work in this area was Obrien et al.’s Handbook of Chlor Alkali Technology published in 2005. The work is comprehensive handbook regarding every element of CA technology in the world including inputs and outputs. It also served as a vital resource for discovering new references in the area.

6.3.1 INDUSTRY Information on the local CA industry in Queensland was obtained via IBIS World industry reports as well commercial data from industry members. Global data was obtained from online sources such as CNBC and IndexMundi. Many of the conclusions reached were based on extrapolations from existing data sources and made simpler by the highly concentrated nature of the industry and its local customers.

6.4 FORWARD OSMOSIS A literature review of the topic was initiated by searching technical databases under the following Boolean strings:

(Reverse osmosis OR water purification) AND (coal seam gas OR CSG) AND (cost OR limitations)

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Forward osmosis AND water purification AND (technology OR cost OR commercial) Forward osmosis AND concentrat* AND reverse osmosis AND brine* AND dilute Forward osmosis AND (magnetic nano*) Forward osmosis AND (energy consumption OR water flux OR osmotic agent OR output

quality OR (membrane AND quality OR fouling)) Forward osmosis AND reverse osmosis AND compari* AND (cost OR effectiveness OR

maintenance)

The literature review first pass results indicate that the majority of technical research in the field is occurring around membrane performance and draw fluid characteristics. Technical articles relating to membrane performance total 19 potentially relevant articles. Those relating to draw fluid comprise 11 articles. There are 7 articles generic enough to be considered in the overview category, providing information general enough to place the role of forward osmosis in the field of water purification. Maintenance generally concerns the fouling and upkeep of membranes and totals 4 articles. The CSG category contains 3 articles considered directly relevant to oil and gas operations and generally authored by industry representatives. Under the umbrella term forward osmosis are 17 articles which either take a global view of the process itself or lean toward a particular technical element without that being its focus. There are 3 other articles which are relevant but don’t fit in other categories. An overview of the literature consulted during this research effort is given in Appendix D.

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7 CONCLUSION This report has taken a high-level approach to determining whether the possibility exists for commercial disposal of concentrated brine in Queensland by local CSG producers. It has also considered the experimental use of IX resin to remove bromide in the context of CSG produced water treatment. The experiments undertaken over a semester of lab work have indicated that bromide can be effectively removed from a sodium bromide solution using a strong base anion resin in the conditions specified. This research is limited by its exploratory nature which only considers the possibility of this process and the lack of competitive halides to test the relative selectivity of bromide using the resin.

The report has also indicated that Gladstone offers the potential to play a more active role in the CSG industry if certain industry conditions are met. Research is required to determine whether the treatment and haulage costs of concentrated brine from Central Queensland to Gladstone can be economically achieved beyond the costs of indefinite storage. A high-level feasibility study is also required to determine if an industrial symbiosis network could be established to support two-way flows of precursors and production between the CSG fields and Gladstone heavy industry. If completed this would confirm the possibility of an expansion in Orica’s CA production capacity to produce caustic soda for alumina refineries in Yarwun. The research indicates that these industrial parks have experienced success in other areas and that Gladstone is currently the subject of research exploring such possibilities.

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APPENDIX A: EFFECTS OF IMPURITIES ON CA PROCESS USING MEMBRANE

TECHNOLOGY AND BRINE SPECIFICATIONS REQUIRED BY MEMBRANE CELLS

APPENDIX B: DOW MARATHON A

APPENDIX C: CSG TREATMENT PROCESSES

APPENDIX D: ORIGINAL LITERATURE SEARCH REGARDING FORWARD OSMOSIS

Overview

Al-Rawajfeh, A. & Zarooni, M. (2008), 'New processes in seawater desalination', Recent Patents on Chemical Engineering 1(2), 141--50.

Elimelech, M. & McGinnis, R. (2009), 'Energy-efficient water purification made possible by Yale engineers', Membrane Technology 2009(4), 10--11. Field, R. W. & Wu, J. J. (2013), 'Mass transfer limitations in forward osmosis: Are some potential applications overhyped?', , --. Huehmer, R. & Wang, F. (2009), Energy in desalination: Comparison of energy requirements for developing desalination techniques, in '2009 AWWA Membrane Technology Conference and Exposition', American Water Works Association, Memphis, TN, United states, pp. American Membrane Technology Association--. Mcllvaine, R. (2008), 'Reverse osmosis [water purification]', Chemical Engineering 115(8), 20--22. Shaffer, D. L.; Yip, N. Y.; Gilron, J. & Elimelech, M. (2012), 'Seawater desalination for agriculture by integrated forward and reverse osmosis: Improved product water quality for potentially less energy', Journal of Membrane Science 415-416, 1--8. Zhao, S.; Zou, L.; Tang, C. Y. & Mulcahy, D. (2012), 'Recent developments in forward osmosis: Opportunities and challenges', Journal of Membrane Science 396, 1--21. Forward Osmosis

Altaee, A. (2011), Forward Osmosis: Potential use in desalination and water treatment, in 'AIChE Annual Meeting, Conference Proceedings', American Institute of Chemical Engineers, Minneapolis, MN, United states, pp. --. Alturki, A. A.; McDonald, J. A.; Khan, S. J.; Price, W. E.; Nghiem, L. D. & Elimelech, M. (2013), 'Removal of trace organic contaminants by the forward osmosis process', Separation and Purification Technology 103, 258--266. Cath, T. Y.; Drewes, J. E. & Lundin, C. (2009), A novel hybrid forward osmosis - Reverse osmosis process for water purification and reuse, using impaired water and saline water, in '2009 AWWA Membrane Technology Conference and Exposition', American Water Works Association, Memphis, TN, United states, pp. American Membrane Technology Association--. Choi, Y.-J.; Choi, J.-S.; Oh, H.-J.; Lee, S.; Yang, D. R. & Kim, J. H. (2009), 'Toward a combined system of forward osmosis and reverse osmosis for seawater desalination', Desalination 247(1-3), 239--246. Coop, T. & Lampe, L. (2009), Future water supply desalination technology: Forward osmosis co-located with power generation, in 'Proceedings of World Environmental and Water Resources Congress 2009 - World Environmental and Water Resources Congress 2009: Great Rivers', American Society of Civil Engineers, Kansas City, MO, United states, pp. 5472--5477. Kim, C.; Lee, S.; Shon, H. K.; Elimelech, M. & Hong, S. (2012), 'Boron transport in forward osmosis: Measurements, mechanisms, and comparison with reverse osmosis', Journal of Membrane Science 419-420, 42--48. Lay, W. C. L.; Chong, T. H.; Tang, C. Y.; Fane, A. G.; Zhang, J. & Liu, Y. (2010), Fouling propensity of forward

44

osmosis: Investigation of the slower flux decline phenomenon, in 'Water Science and Technology', IWA Publishing, 12 Caxton Street, London, SW1H 0QS, United Kingdom, pp. 927--936. Lee, S.; Boo, C.; Elimelech, M. & Hong, S. (2010), 'Comparison of fouling behavior in forward osmosis (FO) and reverse osmosis (RO)', Journal of Membrane Science 365(1-2), 34--39. Li, Z.-Y.; Yangali-Quintanilla, V.; Valladares-Linares, R.; Li, Q.; Zhan, T. & Amy, G. (2012), 'Flux patterns and membrane fouling propensity during desalination of seawater by forward osmosis', Water Research 46(1), 195--204. Lundin, C.; Cath, T. & Drewes, J. (2009), A novel hybrid forward osmosis process for drinking water augmentation using impaired water and saline water sources, in 'Water Quality Technology Conference and Exposition 2009', American Water Works Association, Seattle, WA, United states, pp. 2705--2738. McCormick, P.; Pellegrino, J.; Mantovani, F. & Sarti, G. (2008), 'Water, salt, and ethanol diffusion through membranes for water recovery by forward (direct) osmosis processes', Journal of Membrane Science 325(1), 467--478. Martinetti, C. R.; Childress, A. E. & Cath, T. Y. (2009), 'High recovery of concentrated RO brines using forward osmosis and membrane distillation', Journal of Membrane Science 331(1-2), 31--39. McCutcheon, J. R.; McGinnis, R. & Elimelech, M. (2005), Desalination using a novel ammonia-carbon dioxide forward osmosis process: Evaluation of process performance, in 'AIChE Annual Meeting, Conference Proceedings', American Institute of Chemical Engineers, Cincinnati, OH, United states, pp. 2094--. Yangali-Quintanilla, V.; Li, Z.; Valladares, R.; Li, Q. & Amy, G. (2011), 'Indirect desalination of Red Sea water with forward osmosis and low pressure reverse osmosis for water reuse', Desalination 280(1-3), 160--166. Zhao, S. & Zou, L. (2011), 'Effects of working temperature on separation performance, membrane scaling and cleaning in forward osmosis desalination', Desalination 278(1-3), 157--164. Zhao, S.; Zou, L. & Mulcahy, D. (2012), 'Brackish water desalination by a hybrid forward osmosis-nanofiltration system using divalent draw solute', Desalination 284, 175--181. Zhou, A.; Zhang, T. C. & Yuan, Y. (2012), Performance of forward osmosis processes under different operating conditions and draw solutes, in 'World Environmental and Water Resources Congress 2012: Crossing Boundaries, Proceedings of the 2012 Congress', American Society of Civil Engineers (ASCE), Albuquerque, NM, United states, pp. 808--817. CSG

Averina, A.; Rasul, M. & Begum, S. (2008), Management of coal seam gas (CSG) by-product water: a case study on spring gully mine site in Queensland, Australia, in 'Proceedings of the 2nd International Conference on Waste Management, Water Pollution, Air Pollution, Indoor Climate (WWAI'08)', WSEAS Press, Athens, Greece, pp. 169--74. Hutchings, N. R.; Appleton, E. W. & McGinnis, R. A. (2010), Making high quality frac water out of oilfield waste, in 'Proceedings - SPE Annual Technical Conference and Exhibition', Society of Petroleum Engineers (SPE), Florence, Italy, pp. 4991--5000. Willis, M. J. & Conrad, G. A. (2010), Reverse osmosis compatible chemical foamers for gas well deliquification and production enhancement, in 'Society of Petroleum Engineers - SPE Asia Pacific Oil and Gas Conference and Exhibition 2010, APOGCE 2010', Society of Petroleum Engineers, Brisbane, QLD, Australia, pp. 1096--1111.

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Draw Fluid

Bai, H.; Liu, Z. & Sun, D. D. (2011), 'Highly water soluble and recovered dextran coated fe3o 4 magnetic nanoparticles for brackish water desalination', Separation and Purification Technology 81(3), 392--399. Chanukya, B.; Patil, S. & Rastogi, N. K. (2013), 'Influence of concentration polarization on flux behavior in forward osmosis during desalination using ammonium bicarbonate', Desalination 312, 39--44. Elimelech, M.; McCutcheon, J. & McGinnis, R. (2006), 'Desalination by ammonia-carbon dioxide forward osmosis: Influence of draw and feed solution concentrations on process performance', Journal of Membrane Science 278(1-2), 114--23. Ge, Q.; Su, J.; Chung, T.-S. & Amy, G. (2011), 'Hydrophilic superparamagnetic nanoparticles: Synthesis, characterization, and performance in forward osmosis processes', Industrial and Engineering Chemistry Research 50(1), 382--388. Kim, Y.; Han, S. & Hong, S. (2011), 'A feasibility study of magnetic separation of magnetic nanoparticle for forward osmosis', Water Science and Technology 64(2), 469--476. Li, X.-M.; Xu, G.; Liu, Y. & He, T. (2011), 'Magnetic Fe3O4 nanoparticles: Synthesis and application in water treatment', Nanoscience and Nanotechnology - Asia 1(1), 14--24. Ling, M. M. & Chung, T.-S. (2011), 'Desalination process using super hydrophilic nanoparticles via forward osmosis integrated with ultrafiltration regeneration', Desalination 278(1-3), 194--202. Ling, M. M.; Wang, K. Y. & Chung, T.-S. (2010), 'Highly water-soluble magnetic nanoparticles as novel draw solutes in forward osmosis for water reuse', Industrial and Engineering Chemistry Research 49(12), 5869--5876. McCutcheon, J. R.; McGinnis, R. L. & Elimelech, M. (2006), 'Desalination by ammonia-carbon dioxide forward osmosis: Influence of draw and feed solution concentrations on process performance', Journal of Membrane Science 278(1-2), 114--123. Stone, M. L.; Rae, C.; Stewart, F. F. & Wilson, A. D. (2013), 'Switchable polarity solvents as draw solutes for forward osmosis', Desalination 312, 124--129. Xu, Y.; Peng, X.; Tang, C. Y.; Fu, Q. S. & Nie, S. (2010), 'Effect of draw solution concentration and operating conditions on forward osmosis and pressure retarded osmosis performance in a spiral wound module', Journal of Membrane Science 348(1-2), 298--309. Membranes

Bui, N.-N.; Lind, M.; Hoek, E. & McCutcheon, J. (2011), 'Electrospun nanofiber supported thin film composite membranes for engineered osmosis', Journal of Membrane Science 385-386, 10--19. Cath, T. Y.; Hancock, N. T.; Lundin, C. D.; Hoppe-Jones, C. & Drewes, J. E. (2010), 'A multi-barrier osmotic dilution process for simultaneous desalination and purification of impaired water', Journal of Membrane Science 362(1-2), 417--426. Chu, B. & Hsiao, B. S. (2009), 'The role of polymers in breakthrough technologies for water purification', Journal of Polymer Science, Part B: Polymer Physics 47(24), 2431--2435. Coday, B. D.; Heil, D. M.; Xu, P. & Cath, T. Y. (2013), 'Effects of transmembrane hydraulic pressure on performance of forward osmosis membranes', Environmental Science and Technology 47(5), 2386--2393. Croll, B. (1992), Membrane technology: The way forward?, in 'Journal of the Institution of Water and

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Environmental Management', pp. 121--129. Dumee, L.; Lee, J.; Sears, K.; Tardy, B.; Duke, M. & Gray, S. (2013), 'Fabrication of thin film composite poly(amide)-carbon-nanotube supported membranes for enhanced performance in osmotically driven desalination systems', Journal of Membrane Science 427, 422--430. Han, G.; Zhang, S.; Li, X.; Widjojo, N. & Chung, T.-S. (2012), 'Thin film composite forward osmosis membranes based on polydopamine modified polysulfone substrates with enhancements in both water flux and salt rejection', Chemical Engineering Science 80, 219--231. Jia, Y.-X.; Li, H.-L.; Wang, M.; Wu, L.-Y. & Hu, Y.-D. (2010), 'Carbon nanotube: Possible candidate for forward osmosis', Separation and Purification Technology 75(1), 55--60. Jin, X.; She, Q.; Ang, X. & Tang, C. Y. (2012), 'Removal of boron and arsenic by forward osmosis membrane: Influence of membrane orientation and organic fouling', Journal of Membrane Science 389, 182--187. Kim, H.; Choi, J.-S. & Lee, S. (2012), 'Pressure retarded osmosis for energy production: Membrane materials and operating conditions', Water Science and Technology 65(10), 1789--1794. Liu, C.; Fang, W.; Chou, S.; Shi, L.; Fane, A. G. & Wang, R. (2013), 'Fabrication of layer-by-layer assembled FO hollow fiber membranes and their performances using low concentration draw solutions', Desalination 308, 147--153. Liu, L.; Wang, M.; Wang, D. & Gao, C. (2009), 'Current patents of forward osmosis membrane process', Recent Patents on Chemical Engineering 2(1), 76--82. Nayak, C. A.; Valluri, S. S. & Rastogi, N. K. (2011), 'Effect of high or low molecular weight of components of feed on transmembrane flux during forward osmosis', Journal of Food Engineering 106(1), 48--52. Tang, W. & Ng, H. Y. (2008), 'Concentration of brine by forward osmosis: Performance and influence of membrane structure', Desalination 224(1-3), 143--153. Teoh, M. M.; Wang, K. Y.; Bonyadi, S.; Yang, Q. & Chung, T.-S. (2011), 'Emerging membrane technologies developed in NUS for water reuse and desalination applications: Membrane distillation and forward osmosis', Membrane Water Treatment 2(1), --. Tiraferri, A.; Kang, Y.; Giannelis, E. P. & Elimelech, M. (2012), 'Highly hydrophilic thin-film composite forward osmosis membranes functionalized with surface-tailored nanoparticles', ACS Applied Materials and Interfaces 4(9), 5044--5053. Tiraferri, A.; Yip, N. Y.; Phillip, W. A.; Schiffman, J. D. & Elimelech, M. (2011), 'Relating performance of thin-film composite forward osmosis membranes to support layer formation and structure', Journal of Membrane Science 367(1-2), 340--352. Wang, H. L.; Chung, T.-S.; Tong, Y. W.; Jeyaseelan, K.; Armugam, A.; Duong, H. H. P.; Fu, F.; Seah, H.; Yang, J. & Hong, M. (2013), 'Mechanically robust and highly permeable AquaporinZ biomimetic membranes', Journal of Membrane Science 434, 130--136. Wang, R.; Shi, L.; Tang, C. Y.; Chou, S.; Qiu, C. & Fane, A. G. (2010), 'Characterization of novel forward osmosis hollow fiber membranes', Journal of Membrane Science 355(1-2), 158--167. Maintenance

Baoxia, M. & Elimelech, M. (2010), 'Gypsum scaling and cleaning in forward osmosis: Measurements and mechanisms', Environmental Science and Technology 44(6), 2022--2028.

47

Mi, B. & Elimelech, M. (2013), 'Silica scaling and scaling reversibility in forward osmosis', Desalination 312, 75--81. Sewell, M. (2010), 'Combating fouling in membrane separation systems', Water and Wastewater International 25(2), --. Valladares Linares, R.; Yangali-Quintanilla, V.; Li, Z. & Amy, G. (2011), 'Rejection of micropollutants by clean and fouled forward osmosis membrane', Water Research 45(20), 6737--6744. Other

Juby, G. J.; Shih, W.-Y.; Zacheis, G. A.; James, W.; Nusser, M. D.; Mortazavi, B. & Ravishanker, P. (2008), Getting the most from your brackish groundwater: Treating RO brine to increase recovery and reduce volume for disposal, in 'American Water Works Association - American Water Works Association Association Annual Conference and Exposition, ACE 2008', American Water Works Association, Atlanta, GA, United states, pp. 788--844. Manolakos, D.; Kosmadakis, G.; Kyritsis, S. & Papadakis, G. (2009), 'On site experimental evaluation of a low-temperature solar organic Rankine cycle system for RO desalination', Solar Energy 83(5), 646--656. Peng, N.; Widjojo, N.; Sukitpaneenit, P.; Teoh, M. M.; Lipscomb, G. G.; Chung, T.-S. & Lai, J.-Y. (2012), 'Evolution of polymeric hollow fibers as sustainable technologies: Past, present, and future', Progress in Polymer Science 37(10), 1401--1424.

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