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Commercially interesting deposits of zeolite rich tuffs and amorphous silica have been discovered recently in the Taupo Volcanic Zone (TVZ), North Island, New Zealand. This paper reviews them and comments on the potential for further discoveries. Potential markets for these unusual industrial minerals are discussed.

Jan 1, 1997

By D Hill

In the Ngakuru area zeolite deposits occur in late Quaternary lacustrine vitric tuffs of the Ngakuru Formation and two of the deposits are being mined. The Ngakuru Formation overlies the Ohakuri Ignimbrite dated at c. 240 ka, and is overlain by younger alluvial sands and gravels. Individual zeolite deposits contain 50 - 80 per cent zeolite over a thickness of up to 45 m in thinly stratified vitric tuffs and are localised along NE-trending normal faults. Glass shards in the tuffs are replaced by the silica-rich zeolites mordenite and clinoptilolite. Amorphous silica (opal A), opal-CT, Kfeldspar and smectite are also present. The zeolites and other minerals are very fine grained (<10 8m), with open meshes of crystals that result in high porosities (52 - 70 per cent) in mordenite-rich tuffs. Zeolitic tuff samples typically have cation exchange capacities of 80 to 110 meq/100 g and internal surface areas of 25 - 58 m2/g, which combine to give high liquid and odour absorption capacities. The first zeolite deposit (Mangatete) was found in 1992, and this and the Twist Road deposit are worked by quarry benching into the side of hills. The zeolitic tuffs are dried and crushed to produce a variety of products including adsorbents for soaking up oil/chemical spills and animal wastes, animal feed supplements, water treatment, and sports turf and slow release fertiliser. The Ngakuru zeolite deposits formed at shallow depth (<100 m) along fault zones from reaction of glass-rich tuff beds with groundwater-diluted geothermal water during the late Quaternary, and are as young as 8500 yr BP from 14C dating of plant material in sinter associated with the Mangatete deposit.

Jan 1, 2005

By R. M. Bricka, T. J. Olin

Heavy metals contamination is an environmental problem at Army installations engaged in firearms training and munitions production. At these facilities, weathering and corrosion of expended munitions and leaching from wastewater lagoons, landfills and burn pits have resulted in heavy metals contamination of the soil. The principal metals encountered in firing-range soils are lead, copper and zinc. Cadmium and other metals, such as antimony, that are often incorporated in the munitions are sometimes seen in lesser concentrations. Mercury is associated with various propellants and, while present in much smaller concentrations, is of concern because of its acute toxicity. Chromium is primarily associated with plating operations. The transport of metals into groundwater has been confirmed at some locations, which has required treatment of the soil and groundwater at these sites. Certain treatment processes for contaminated soil produce metals-laden extracts, which also require treatment before reuse or disposal. Ion exchange is generally quite effective for removing metals from aqueous streams. However, resins are expensive and must be regenerated, and activated carbon is generally less effective for most metals and also requires regeneration. Therefore, alternative effective and economic sorbents are needed. Twelve sorbents were screened in initial batch testing. These included activated carbon, bark, chitosan, crown ether, corn cob, xanthate, clay (kaolinite and montmorillonite), peat moss, seaweed and reagent-grade zeolite (aluminosilicate, Sigma Product No. Z3125). Of these, zeolite demonstrated the highest capacity for Pb, Cr and Cd. For this reason, zeolite was selected for further testing in batch, kinetic and column studies. Materials and methods Zeolite. The zeolite used in the second-phase batch and column studies was obtained from a natural deposit of clinoptilolite-rich rock located in South Dakota (Rocky Ford SDH) (Desborough, 1996). Large blocks of the material were crushed and sieved into the following three particle size ranges: 0.5 to 1.0, 1.0 to 4.0 and 2.0 to 4.7 mm. This material demonstrates high structural stability in acidic solutions (pH 2.5) (Desborough 1996) and has a measured surface area of 30 m2/g. The measured total cation-exchange capacity (TCEC) was approximately 10 meq/100 g. This is well below what has been indicated for commercially available zeolite, which has been reported to be about 180 to 220 meq/ 100 g. The TCEC test was repeated (Method 9081, SW 846) using sodium acetate. The test resulted in a TCEC of 54.5 meq/100 g. The difference between values obtained for this material and published values for zeolites may be attributable to the greater heterogeneity in the material used in this study, compared to commercially available materials, or to the effect of the relatively large particle sizes utilized. Batch studies. Seven batch studies were conducted using synthetic metal solutions and soil extracts (Table 1). Extract composition: The P-extract was prepared by sequential surfactant extraction of organics from a burnpit soil followed by acid extraction of metals. The pH of this solution is approximately 1.1. A number of metals and organic compounds were present in the soil. Analysis of the extract was restricted to Pb, Zn and Cu concentrations for this study. The FBH extract was produced from a firing-range soil that was oxidized with a 0.01 M CaO solution and then extracted with 0.1 M acetic acid. This was filtered through 0.5-µm Whatman No. 5 filter paper and stored at room temperature. The pH of the FBH extract was approximately 4.5. pH Control: Calcium carbonate (CaCO3) may be present in the zeolite horizon or bed. Calcium ion (Ca") is released from the exchange sites when in contact with solutions containing ions for which it is more selective, such as lead. This results in a rise in solution pH over time. Acid washing removes most of the carbonates, eliminating the need for a buffer. Batch studies were conducted using both acid-washed zeolite (AW) and unwashed zeolite (UW) for performance comparison. The UW zeolite was rinsed with distilled deionized (DDI) water to remove fine soil particles. Both materials were dried at 105°C (220°F) overnight, so that the dry mass could be determined. Column studies. Ten column studies were conducted. Because it was expected to have the best hydraulic properties, the largest particle

Jan 1, 1999

By Richard H. Olson

"Rarely in our technological society does the discovery of a new class of inorganic materials result in such a wide scientific interest and kaleidoscopic development of applications as has happened with the zeolite molecular sieves." The foregoing, the opening sentence in a landmark volume on zeolite molecular sieves by D. W. Breck (1974), is, if anything, an understatement. Zeolites were recognized as a new group of minerals in the 1750s, but it was not until 1930 that the first analysis of the crystal structure of a zeolite mineral was made. In the late 1940s research workers at Union Carbide Corp. began a program of zeolite synthesis and study which has resulted in one of the major research achievements of all time. Naturally, with the vast research and development efforts devoted to the synthetic molecular sieves, Union Carbide became concerned in the mid-1950s about its position should minable deposits of natural analogues be discovered. Zeolite minerals have diverse origins, and even a brief discussion of these is beyond the scope of this paper. The early work on zeolites was confined to igneous rock occurrences (e.g., amygdules and veins) which were formed by "space-filling;" these crystals tend to be euhedral, thereby rendering them appealing to both mineralogists and collectors. During the first year or so of Union Carbide's exploration (which began in mid-1957) attention was devoted solely to such igneous occurrences. A landmark paper by Bramlette and Posnjak (1933) heralded the potential significance of the occurrence of zeolite minerals as alteration products of vitric ash and similar materials. In the summer of 1958, full attention was directed by Union Carbide to the search for deposits of this type in the western United States. Since then, such exploration has been continu-

Jan 1, 1975

By David A. Holmes

Zeolites are crystalline, hydrated aluminosilicates of the alkali and alkaline-earth metals. Their crystalline framework is based on a three dimensional network of SiO4 tetrahedra with all four oxygens shared by adjacent tetrahedra. The alkali and alkaline-earth cations are loosely bound within this framework structure and may be exchanged, to varying degrees, with other cations or molecular water. Most zeolites can be reversibly dehydrated. At present, close to 40 natural zeolite minerals have been identified and over 100 zeolites have been synthesized. Zeolites are a family of hydrous aluminosilicate minerals whose physical properties provide unique features for a wide variety of practical applications. Zeolites have been known for more than 200 years, but it was not until the middle of this century that their economic potential and widespread occurrence in sedimentary rocks were known. Since 1950, literally thousands of articles and patents have appeared in technical literature, and commercial pro¬duction of natural zeolites may now exceed 1 Mt worldwide an¬nually. In the past 40 years, the zeolite mineral group has changed from that of a museum curiosity to one of an established industrial mineral commodity. According to Breck (1974), zeolites are characterized by the following properties: 1) High degree of hydration, 2) Low density and large void volume when dehydrated, 3) Stability of the crystal structure of many zeolites when dehydrated, 4) Cation exchange properties, 5) Uniform molecular-sized channels in the dehydrated crys¬tals, 6) Ability to adsorb gases and vapors, 7) Catalytic properties. All zeolites are molecular sieves, but not all molecular sieves are zeolites. Activated carbon, activated clays, alumina powder, and silica gels are also molecular sieves. Molecular sieves are materials that can selectively adsorb molecules on the basis of their size, shape, or electrical charge (Clifton, 1987). Commercial application of zeolites is based on the following physical properties: molecular sieving, ion exchange, adsorption, and catalysis. Potential commercial utilization includes hundreds of possible applications. The principal uses at this time, however, are as fol¬lows: -Ammonium-ion removal in waste stream treatment, sewage treat¬ment, pet litter, and aquaculture, -Odor control, -Heavy metal ion removal from nuclear, mine and industrial wastes, -Agricultural use, such as soil conditioner and animal feed supplement. An estimated 800 kt to 1 Mt of natural zeolites were produced and consumed worldwide in 1991. Eight small operators reported collective production and consumption of an estimated 18 kt of natural zeolites in the United States during 1991, mostly for feed additives and for odor control, aquacultural, agricultural, catalytic, and ion exchange applications (Eyde, 1992).

Jan 1, 1994

By Frederick A. Mumpton

For more than 200 years zeolites have been familiar minerals to geologists and mining engineers as minor, but ubiquitous constituents in vugs and fractures of most basalt and traprock formations. More than 35 different species have been recognized including several, such as chabazite, erionite, mordenite, and faujasite, whose adsorption properties rival those of many synthetic molecular sieves. Igneous occurrences of this type have never been mined on a commercial scale; they are generally small and low grade, and they commonly contain as many as four zeolite minerals, along with small quantities of calcite, quartz, and other silicate minerals. Their economic beneficiation to monomineralic zeolite products has also not been achieved and, for the most part, industrial applications of zeolites have relied primarily on synthetic molecular sieves that were crystallized from hydrous aluminosilicate gels. During the middle 1950s, when Union Carbide Corp. and other groups were developing processes and markets for their fledgling synthetic zeolite businesses, natural zeolites

Jan 1, 1975

By Richard H. Olson

"Rarely in our technological society does the discovery of a new class of inorganic materials result in such a wide scientific interest and kaleidoscopic development of applications as has happened with the zeolite molecular sieves." That opening sentence in a landmark volume on zeolite molecular sieves by D. W. Breck (1974), is, if anything, an understatement. Zeolites were recognized as a new group of minerals in the 1750s, but it was not until 1930 that the first analysis of the crystal structure of a zeolite mineral was made. In the late 1940s research workers at Union Carbide Corp. began a program of zeolite synthesis and study which has resulted in one of the major research achievements of all time. Naturally, with the vast research and development efforts devoted to the synthetic molecular sieves, Union Carbide became concerned in the mid-1950s about its position should minable deposits of natural analogues be discovered. Zeolite minerals have diverse origins, and even a brief discussion of these is beyond the scope of this paper. The early work on zeolites was confined to igneous rock occurrences (e.g., amygdules and veins) which were formed by "space-filling;" these crystals tend to be euhedral, thereby rendering them appealing to both mineralogists and collectors. During the first year or so of Union Carbide's exploration (which began in mid-1957) attention was devoted solely to such igneous, occurrences. A landmark paper by Bramlette and Posnjak (1933) heralded the potential significance of the occurrence of zeolite minerals as alteration products of vitric ash and similar materials. In the summer of 1958, full attention was directed by Union Carbide to the search for deposits of this type in the western United States. Since then, such exploration has been continuous by both commercial firms and private parties. The future economic potential for natural zeolite deposits seems to be restricted to those of the "open-and-closed system" types as described by Sheppard (this chapter). Therefore, this and the following discussions will concentrate upon these types; the other types of zeolites in sedimentary rocks (e.g., deep-sea sediments, burial metamorphic, and hydrothermal) will be, for the most part, ignored. Despite the relative cheapness of natural zeolite deposits as compared with the cost of synthetic molecular sieves, there has been minimal development of zeolite mining in the US over the past 25 years or so. Mumpton (this chapter) discusses the present commercial utilization of natural zeolites and their future potential in detail, but perhaps the following will serve as useful background. In the early days of synthetic molecular sieve research and production, the efforts were concentrated largely upon such high-value applications as physical separation of components in a stream (based upon molecular size and geometry) and in catalysis. Due to a number of reasons (some of which are difficult for an outsider to understand), natural zeolite ores (beneficiated or not) have not made substantial inroads upon the use of the higher-priced synthetic molecular sieves for the foregoing applications, but this is not to say that such a condition will exist forever. Furthermore, in view of the many other uses which are now known, or which loom in the future, the competitive position of the natural zeolites vs. the more expensive

Jan 1, 1983

By D. W. Breck

Zeolites were first recognized as a new group of minerals by Cronstedt with the discovery of stilbite in 1756. The word zeolite was coined from the two Greek words meaning "to boil" and "a stone" because of the loss of water when heated in the mineralogist's blowpipe (Breck, 1974). In 1845 it was discovered that certain soils lave the power of retaining ammonium salts Way, 1850). These were the first ion exchange experiments. Later it was discovered that it was the hydrated silicates in the soil that produced this phenomenon. Several years later a paper was published dealing with the action of dilute salt solutions on silicates which showed that this base-exchange principle, which we now call cation exchange, is reversible. The quantitative cation exchange behavior of zeolite minerals, such as chabazite, was studied. As a result any aluminosilicate which exhibited the property of ion exchange was referred to as a "zeolite," even today the term has been applied to clay minerals as well as synthetic organic ion exchange resins.

Jan 1, 1975

By Richard A. Sheppard

Zeolites-crystalline hydrated aluminosilicates of the alkalis and alkaline earths-are important rock-forming constituents in sedimentary rocks and are potentially valuable industrial minerals. They have a framework structure that encloses interconnected cavities occupied by the relatively large cations and water molecules. The cations, chiefly sodium, potassium, and calcium, and the water have considerable freedom of movement within the structure and give the zeolite their cation- exchange and reversible-dehydration properties. Some zeolites have essential contents of barium, strontium, or magnesium. The basic structure

Jan 1, 1975

By D. Eyde

The zeolites review arrived too late for the June issue. The natural zeolite industry continues to grow even as some companies look for the exits. Production for 1993 was estimated at between 42 and 44 kt (46,000 and 48,000 st). That is between 7 and 9 kt (7700 and 9900 st) above 1992 production. GSA Resources, Saint Cloud Mining, Steelhead Specialty Minerals, Teague Minerals, UOP and Zeotech all reported continued growth last year. At the same time the East-West Minerals' Eastgate mordenite mine, and American Resources' Ash Meadows clinoptilolite operations both shut down their processing plants and are attempting to sell the mines and facilities. In addition, Tenneco Minerals continued its attempt to sell the Mud Hills clinoptilolite deposit. Unimin entered the natural zeolite industry through its acquisition of several properties of Aimcor. The properties included the Ben-Jel bentonite and Castle Creek clinoptilolite deposits and processing facilities near Caldwell, ID

Jan 1, 1994

By Zeynep Aktuna

In this study, the formation of zeolites around Kizkapan and Karlikoy villages (Sothwest Kesan) were investigated. In this region, stratigrafically, Upper Eocene Kesan Formation, i.e. sandstone and rarely shale are observed at the bottom. Early Middle-Oligocene Yenimuhacir Formation is composed of sandstone, marl and tuffs. The zeolitisation is determined in the dasitic tuffs of the Yenimuhacir Formation. In this tuffs' zone, alteration had primarily resulted in zeolites, mainly mordenite, heulandite-clinoptiIolite. Silicification and alteration to clay minerals are also common. The Miocene-Pliocene Ergene Formation and alluvium deposits are the top units in the area. In the studied area, zeolite occurences have economic importance. The results show that successively rapid and short term periods are responsible for the clinoptilolite-heuylandite formations. The homogene chemistry of the solutions may be evaluated for a possible successive zeolitisation period. Multi-periodic vocanic activity and also circulation of thermal water had resulted in a continous dissolution of volcanic glass; moreover, resulted in the formation of suitable conditions of zeolite formation. The mineral crystallization sequences and alteration products as zeolites within the wall-rock, circulated solution reaction depends on a serie of parameters such as chemical composition of both initial materials and volcanic solutions during rock¬solution interaction period. The previous researches and the chemical studies support our results and observations in the studied area. The aim of this study is to investigate the presence of zeolitisation and to explain the formation steps of zeolitisation in Kesan Area by considering the content and distribution of major and minor elements determined in zeolite bearing tuffs. The chemical structures of both zeolite bearing volcanics and zeolite minerals are compared to the results of previous studies. Two dimentional behaviours of major and minor elements were discussed in order to caracterize zeolitisation development and to postulate a probable formation type of zeolitic alteration.

Jan 1, 2005

This paper examines the integration of risk management into the design philosophy of a project to produce a æzero baseÆ design, which targets a minimum capital cost without adversely impacting upon the operating costs of the resulting plant. The concept of zero base design is similar to zero base budgeting and the desired outcome is to improve the economy of the design. Design requirements are questioned in an attempt to distinguish preference, prejudice and myth from necessity. Where doubt remains a risk management approach is adopted. The key to risk management is not risk elimination, but risk mitigation. Risks can be managed by designing them out, but often this involves considerable capital cost penalties and it is more attractive to accept the risk and design an operating strategy to deal with it. The paper discusses this with some examples of real world risk mitigation strategies that resulted in substantial capital cost savings. The paper concludes that as much as a quarter of project capital costs can be eliminated by a combination of zero base design and carefully crafted risk mitigation strategies.

Jan 1, 2004

By D. Eriksen

Zero Emission Gas power, ZEG, is a novel concept where a high temperature solid oxide fuel cell (SOFC) is integrated with a reforming reactor producing hydrogen from natural gas through Sorption Enhanced Steam Methane Reforming (SESMR). The SOFC is used as a high temperature heat source for regeneration of the CO2-absorbent. Moreover, by using part of the produced hydrogen as fuel for the SOFC, the waste heat of the process is considerably reduced. Thus, the process has a very high thermal efficiency and produces both electricity and hydrogen from natural gas. In addition, a stream of pure CO2 is produced in the regeneration step and can be deposited or used commercially. Initial cost estimates indicate a cost of electricity and a cost of hydrogen well below today's prices. A small (1kWel + 1kW H2) demonstration set-up is under construction and experimental results and related research will be presented. This set-up comprises one 2.5kWth H2 SESMR-reactor (about 0.85 Nm3/h H2) operating batchwise with dolomite as the CO2-sorbent. The reactor developed is designed like a parallel plate heat exchanger where the mixture of sorbent and reforming catalyst is packed between the heat exchanging plates. The demonstration set-up includes a 1kW SOFC operating in a continuous mode. The set¬up will therefore demonstrate continuous simultaneous hydrogen- and electricity production, but cannot demonstrate simultanuous electricity- and CO2-production. The set?up is well equipped for on-line monitoring of gas composition, flows and temperatures. This important part of the demonstration set-up is developed and provided by Christian Michelsen Research (CMR). A minor part of the project is the development of a continuous circulating fluidized bed SESMR-reactor system and in another related project the focus is on the development of more suitable sorbents. In these two projects co-operation with University of British Columbia and Lousianna State University, respectively, is highly appreciated.

Jan 1, 2005

By A. Taylor

This paper considers mineral processing in zero gravity dry environments typical of asteroids or comets. The electro-dynamic separation technique using pneumatic flow systems is explored. Pneumatic delivery of solids is used because of extreme temperature changes and the possible scarcity of water. The present earth-based process and how it can be modified for these conditions is examined.

May 1, 2001

By A Dal-Corobbo, R Zick

The coal mining industry is now faced with new regulatory requirements that limit the discharge of chlorides into receiving streams. To meet these new regulatory standards for treated mine water, a zero liquid waste approach was developed using advanced treatment technologies. The approach described in this paper will generate clean water for reuse in various energy endeavours or discharge to the environment, with no substantial liquid or solid waste from the treatment process leaving the site.CITATION:Dal-Corobbo, A and Zick, R, 2013. Zero liquid discharge in coal mining operations, in Proceedings Water in Mining 2013 , pp 221-226 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Nov 26, 2013

In view of the increasing environmental regulations that have been promulgated all over the world in the last 30 years, non-ferrous smelters and refineries have learnt and adapted to treat effectively metals'-containing process waste streams that need to be bled from the plant. However, anions such as sulfates, chlorides and fluorides-presently not a major problem ?are coming under increasing scrutiny and need to be addressed in the near future. The current paper reviews options for waste water treatment with reference to: a) types of waste streams processed b) process chemistry c) discharge options d) recovery and reuse of water and e) solids disposal. Methods to obtain zero liquid discharge ?a possible solution to eliminate discharge of above anions and residual heavy metals- are discussed with case studies. The long term goal of any non-ferrous smelter plant should be to have a zero liquid discharge philosophy-an approach that would become an epitome of water reuse and conservation.

Jan 1, 2009

By J. Bostjancic

As wastewater discharge regulations become more stringent, power plants, manufacturing plants and other industrial sites are looking for ways to reduce makeup water requirements and to recycle and reuse as much wastewater as possible. In some cases, environmental regulations require zero liquid discharge, meaning all wastewater must either be retained on site or reduced to solids for disposal off site. Zero liquid discharge or "closed-loop" wastewater treatment systems using evaporators and other process equipment have been well-accepted in recent years. Often overlooked is the fact that zero discharge is not just the latest fashion--many commercial zero liquid discharge systems have been in operation since the mid-70's. This paper will give specific examples of zero liquid discharge operations from 1974 to the present, showing how evaporation equipment and processes have changed to meet the requirements of industry and environmental regulations.

Jan 1, 1996

By V. K. Gupta

The phenomenon of zero order production of fines associated with the batch comminution of monosize feeds in tumbling mills has been examined in the context of the size discretized population balance model. It has been shown that the model admits zero order production kinetics only in an approximate sense. The necessary and sufficient conditions for approximate zero order production of fines have been obtained. As these conditions cannot be expressed in terms of the model parameters Sj and Bi,j alone,. several examples have been used to illustrate some of the important characteristics of the zero order production systems. One of the important characteristics of these systems has been identified as a "weak necessary condition", and the other as a " favourable condition ".

Jan 1, 1985

By J. Borlee, F. Sorrentino, A. Fleischanderl, M. Gimenez, W. Gebert, U. Gennari

Large quantities of solid by-products are generated by the steel industry and other important activity sectors in Europe (power plants, car dismantling companies, urban incinerators) with no or very limited potential for direct recovery. In the frame of a multi¬national project supported by the European Union, a consortium has been created to develop a treatment process able to turn these by-products into valuable metallic and mineral products. VAI has been responsible for the design, erection and start-up of the pilot plant for the new metallurgical process and for the execution of the test campaigns, with the targets defined together with the partners. Up to now, 9 campaigns comprising 60 heats have been performed successfully. By-products from C-Steel and stainless steel plants, as well as fly ash and auto shredder residues, have been used and defined products such as hydraulic binders for cement, metallurgical powders for De-S practice and recycled metal phase have been produced. The mineral products were positively assessed under industrial conditions. Results from cement tests and secondary metallurgy are reported, as well as a detailed characterization. The economic value of the products, credits from avoiding dumping and significant savings on CO2 emissions make the new process economically very attractive.

Jan 1, 2004

By Henry C. Knight

A number of improvements in the techniques of budgetary control have been developed in the 1970's. The most significant of these is zero-base budgeting. This procedure is a marked improvement, because it overcomes some of the key weaknesses inherent in most traditional approaches to budgeting. It incorporates techniques and disciplines which improve the quality of both the budgeting effort itself and the documents that most senior managers will need to evaluate. The end result is a budget that establishes and improves cost effectiveness. This budget is based on resource allocations using cost-benefit criteria and on a system of prioritization for making funding choices. Zero-base budgeting is applied only to costs and expenses that are not conducive to control using industrial engineered standards. Therefore, the benefits attributed to zero-base budgeting will only hold true for administrative, selling, exploration, safety, fire protection and overhead, and other indirect types of costs and expenses. It is in this context that the question of its attractiveness for the mining industry is dealt with.

Jan 1, 1978