Coal Science: Volume 2

Coal Science

VOLUME 2

MARTIN L. GORBATY

Corporate Research-Science Laboratories, Exxon Research and Engineering Company, Linden, New Jersey

JOHN W. LARSEN

Department of Chemistry, The University of Tennessee, Knoxville, Tennessee

IRVING WENDER

Chemical and Petroleum Engineering Department, The University of Pittsburgh, Pittsburgh, Pennsylvania

Table of Contents

Cover image

Title page

CONTRIBUTORS

Copyright

Contributors

Preface

Contents of Volume 1

Chapter 1: The Science of Mineral Matter in Coal

Publisher Summary

I INTRODUCTION

II MINERAL MATTER IN COAL: ORIGIN, CHARACTERIZATION, AND IMPLICATIONS FOR COAL-PROCESSING TECHNOLOGIES

III COMBUSTION

IV GASIFICATION AND LIQUEFACTION

V SILICATE CHEMISTRY AT ELEVATED TEMPERATURE AND ITS RELEVANCE TO ASH FUSION PHENOMENA

ACKNOWLEDGMENTS

Chapter 2: Chemistry of Hydrogen Donor Solvents

Publisher Summary

I INTRODUCTION

II SOLVENT EFFECTS ON DISSOLUTION RATES AND YIELDS

III SOLVENT EFFECTS ON PRODUCT QUALITY

IV CHEMICAL MECHANISMS OF THE ACTIONS OF LIQUEFACTION SOLVENTS

V EVALUATION OF DONOR SOLVENT QUALITY

VI CONCLUSIONS

Chapter 3: The Role of Noncovalent Bonding in Coal

Publisher Summary

I INTRODUCTION

II HYDROGEN BONDING

III CHARGE TRANSFER INTERACTIONS IN COALS

IV RELATED STUDIES ON PETROLEUM PRODUCTS

V EFFECT OF HYDROGEN BONDING AND π-π INTERACTION ON THE PHYSICAL PROPERTIES OF COAL AND COAL-DERIVED LIQUIDS

VI CONCLUSIONS

ACKNOWLEDGMENTS

Chapter 4: Solvent Extraction of Coal

Publisher Summary

I INTRODUCTION

II SOLVENT PROPERTIES AND COAL SOLUBILITY

III PHYSICAL ASPECTS OF DISSOLUTION

IV CHEMISTRY OF COAL-SOLVENT INTERACTIONS

V CATALYTIC EFFECTS DURING COAL CONVERSION

VI EFFECTS OF COAL CHARACTERISTICS ON COAL CONVERSION

VII SOLUBILIZATION OF COAL

VIII SUPERCRITICAL GAS EXTRACTION

IX SOLVENT EXTRACTION TECHNOLOGY

X CONCLUSIONS

Index

CONTRIBUTORS

Richard J. Baltisberger

Zeinab Baset

Bradley C. Bockrath

John P. de Neufville

Howard Freund

Martin L. Gorbaty

Stephen C. Mraw

Kundan M. Patal

Janet R. Pullen

Krishna Raman

Virgil I. Stenberg

Neil F. Woolsey

Franklin J. Wright

Copyright

COPYRIGHT © 1983, BY ACADEMIC PRESS, INC.

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Contributors

Numbers in parentheses indicate the pages on which the authors’ contributions begin.

Richard J. Baltisberger,     (125) Department of Chemistry, University of North Dakota, Grand Forks, North Dakota 58202

Zeinab Baset¹,     (1) Exxon Research and Engineering Company, Linden, New Jersey 07036

Bradley C. Bockrath,     (65) U.S. Department of Energy, Pittsburgh Energy Technology Center, Pittsburgh, Pennsylvania 15236

John P. de Neufville²,     (1) Exxon Research and Engineering Company, Linden, New Jersey 07036

Howard Freund,     (1) Exxon Research and Engineering Company, Linden, New Jersey 07036

Martin L. Gorbaty,     (1) Corporate Research-Science Laboratories, Exxon Research and Engineering Company, Linden, New Jersey 07036

Stephen C. Mraw,     (1) Exxon Research and Engineering Company, Linden, New Jersey 07036

Kundan M. Patal,     (125) Department of Chemistry, University of North Dakota, Grand Forks, North Dakota 58202

Janet R. Pullen,     (173) IEA Coal Research, London SW1W 0EX, England

Krishna Raman,     (125) Department of Chemistry, University of North Dakota, Grand Forks, North Dakota 58202

Virgil I. Stenberg,     (125) Department of Chemistry, University of North Dakota, Grand Forks, North Dakota 58202

Neil F. Woolsey,     (125) Department of Chemistry, University of North Dakota, Grand Forks, North Dakota 58202

Franklin J. Wright,     (1) Exxon Research and Engineering Company, Linden, New Jersey 07036

¹Present address: Exxon Research and Engineering Co., Baytown, Texas 77520.

²Present address: Energy Conversion Devices, Inc., North Branch, New Jersey 08876.

Preface

The ultimate need to replace liquid and gaseous fuels now derived from petroleum and natural gas resources with synthetic fuels from coal is generally recognized. Although technological bases already exist for utilizing coal directly in combustion and for converting it to liquid and gaseous fuels, we feel that considerable improvements in these technologies (such as greater overall thermal efficiency, hydrogen utilization, and selectivity to specific products) are needed. These improvements, along with new, more efficient routes to coal utilization, will only come about if we are able to gain more fundamental knowledge of coal in terms of its structure and reactivity.

Because coal is such a heterogeneous material, coal science in its broadest sense embraces many scientific disciplines—including chemistry (organic, inorganic, and physical), physics, and engineering (chemical and mechanical). Consequently, the literature of coal science is vast and complex, containing a great deal of information—but only rarely in such a form that this information is logically assembled, reviewed, and evaluated. Because of the current interest in coal, we felt that critical reviews written by experts and aimed at the professional chemist or engineer now working (or contemplating working) in coal science would be both timely and useful. These reviews would not only pull together what has been reported in the past into a coherent picture, they would also point out the original reports’ significance as well as areas where more research is needed. Ultimately, coal science should furnish data and clues for solving or bypassing many of the problems now associated with coal conversion technologies.

This is the second in a series devoted to presenting and evaluating selected fundamental scientific areas involved with our understanding of coal structure, reactivity, and utilization. Reviews describing current state-of-the-art knowledge of coal’s inorganic structure and reactivity and the role ionic bonding plays in coal’s chemical and physical structure and reactivity are included, as well as contributions on hydrogen donor chemistry and solvent extraction, both relating to coal conversion and utilization. It is our hope that this and subsequent volumes will not only be a valuable source of information and a guide to the coal literature, but will also stimulate research and serve as a basis for further advances in science and technology.

The editors would like to thank the contributing authors for their time and diligence in helping to make this volume a reality. We may have acted as catalysts, but the major share of the credit belongs to them.

Contents of Volume 1

Coal Plasticity Mechanism: Inferences from Liquefaction Studies

Richard C. Neavel

The Physical Structure of Coal

Warren R. Grimes

Magnetic Resonance Studies of Coal

H. L. Retcofsky

Molecular Structure of Coal

Robert M. Davidson

The Reductive Alkylation Reaction

Leon M. Stock

Index

The Science of Mineral Matter in Coal

STEPHEN C. MRAW and JOHN P. DE NEUFVILLE*

HOWARD FREUND and ZEINAB BASET†

MARTIN L. GORBATY and FRANKLIN J. WRIGHT,     Exxon Research and Engineering Company, Linden, New Jersey

Publisher Summary

This chapter discusses the modes of occurrence of inorganic elements in coal, both as mineral phases and as organically bonded elements. The effects that highly dispersed elements may have on coal processing are also reviewed in the chapter. Mineral matter plays a variety of important roles in all coal utilization processes. Inorganically bound elements in present-day coals are the result of at least five mechanisms operating at or from the time of initial peat deposition: (1) incorporation of elements from the original plant material; (2) precipitation of elements from aqueous solution; (3) accumulation of airborne detritus; (4) accumulation of waterborne detritus; and (5) epigenetic mineralization, that is, minerals that have formed in cleats and fractures of the coal deposit. Accumulation of detrital mineral particles and the chemical precipitation of dissolved species from aqueous solution are the major processes by which inorganic elements are introduced into the peat deposit from external sources.

I. Introduction

II. Mineral Matter in Coal: Origin, Characterization, and Implications for Coal-Processing Technologies

A. Introduction

B. Origin of Mineral Matter in Coal and Resulting Mineralogical and Chemical Variations

C. Identification and Characterization of Mineral Matter in Coal.

D. Role of Chemical Bonding of Inorganic Matter in Coal Conversion or Combustion

III. Combustion

A. Introduction

B. Pulverized Coal Combustion Overview

C. Particulate Formation

D. Slagging

E. Fouling

F. Attempts to Combat Slagging and Fouling

G. Reduction of SO2 Emissions via Ca-S Reactions

IV. Gasification and Liquefaction

A. Introduction

B. Sintered Deposits Formed in Gasification of Coal Liquefaction Residues

C. Inorganic Components of Gaseous Streams

D. Catalytic Effects of Mineral Matter in Gasification

E. Catalytic Effects of Mineral Matter in Liquefaction

V. Silicate Chemistry at Elevated Temperature and Its Relevance to Ash Fusion Phenomena

A. Introduction

B. Sintering Phenomena—Combustion or Gasification of Coal in a Bedded Unit: Relevance of ASTM Ash Fusion Test (Initial Deformation Temperature)

C. Slagging Phenomena—Conventional Combustion of Pulverized Coal in a Nonslagging Boiler: Relevance of ASTM Ash Fusion Test to Actual Slagging Behavior

D. Summary Comparison of ASTM Test versus Sintering and Slagging

References

I INTRODUCTION

In this article we give a general overview of the area of mineral matter in coal and a critical review of many specific aspects which are most intriguing scientifically. We consider the term mineral matter in its widest sense, that is, all of the inorganic material found in coal as mineral phases and the elements in coal that are considered inorganic (Gluskoter et al., 1977). Such a broad area as mineral matter in coal would be extremely difficult to review totally in all of its complex scientific and technological aspects. It is our intent in this article to concentrate in detail on specific portions of the total picture which are particularly intriguing to us on a scientific basis, because complex and poorly understood chemical and physicochemical mechanisms appear to be operating to produce the observed results. Throughout the article, we shall often go beyond merely reviewing the literature, in that we shall attempt to analyze the reported results further and even speculate upon their significance, as a means of indicating where further research is needed and would be most fruitful.

Our discussion of these questions will include mineral matter in what can be thought of as before, during, and after processing, that is,

(1) The modes of introduction of mineral matter into coal and the chemical and physical nature of the mineral matter in a present-day coal

(2) The effect of coal combustion or conversion on the mineral matter and, conversely, the effect of the mineral matter on these high-temperature processes

(3) The final chemical and physical state of the mineral matter or ash after processing, and whether it is potentially hazardous or potentially useful

In this vein we present, in Section II, a critical review of the modes of occurrence of inorganic elements in coal, both as mineral phases and as organically bonded elements, and we examine the effects that highly dispersed elements may have on coal processing. Section III deals with the role of mineral matter in the high-temperature process of coal combustion, including discussions of the chemical and physical processes responsible for ash particle formation and of the mechanisms of slagging and fouling. Some specific examples of the role of mineral matter in coal gasification and liquefaction are highlighted in Section IV. Finally, in Section V, we discuss in detail the relationship between high-temperature silicate chemistry and the mechanisms of ash fusion and ash sintering.

We hope to convey in the present article some flavor of the many intriguing aspects which this area presents to the research scientist. Our goal is to highlight specific examples of instances where scientific questions of a physical and chemical nature pervade the technologically important discussions of mineral matter.

II MINERAL MATTER IN COAL: ORIGIN, CHARACTERIZATION, AND IMPLICATIONS FOR COAL-PROCESSING TECHNOLOGIES

A Introduction

Mineral matter plays a variety of important roles in all coal utilization processes. These roles have traditionally been dealt with in terms of ASTM or other engineering specifications, thereby hiding their physical and chemical origins. However, to understand, control, and assess opportunities for modification of these roles, it is necessary to know how the mineral matter is spatially distributed within the coal, and how it is chemically bound, in as much detail as possible.

It is our primary objective in this section to critically review what is and what is not known about the distribution and structural chemistry of the mineral matter in various coals and to see how this chemistry is affected by coal processing. In order to achieve this objective, we first review the mechanisms by which mineral matter can be introduced into the coal. We then review the methods which have been established to characterize the mineral matter and elucidate its distribution and bonding. Finally we summarize the structural and chemical effects of coal processing on mineral matter and provide an initial assessment of the inverse question, How can mineral matter affect coal processing?

Of particular interest in this section will be two intriguing classes of inorganic constituents: microscopic mineral phases intimately mixed with the organic constituents (macerals) of the coal and inorganic elements actually bonded to the organic matrix (which contribute a major portion of the total mineral matter primarily in low-rank coals and lignites). These classes have received much less attention than the bulk inorganic mineral phases, but, owing to the high degree of dispersion, they are potentially reactive and could be expected to significantly affect most coal utilization processes. In the later sections of this article, more emphasis will be given to the role of gross mineral matter chemistry, especially as it affects the tendency of certain coal ashes to cause sintering, slagging, or fouling problems during gasification or combustion.

The theme that will emerge is that the characterization of mineral matter in coal is necessary to achieve an improved understanding of the structure and properties of coal. The state of mineral matter in coal is incompletely known, especially with respect to the highly dispersed elements. However, the application of a wide variety of recently developed analytical and structural probes promises much greater understanding in the near future. Such studies would benefit the exploitation or modification of mineral matter to improve coal processing. As the spectrum of coal-processing technologies under consideration for commercialization continues to grow, control over the role of mineral matter could provide the margin of feasibility for some of these new technologies.

B Origin of Mineral Matter in Coal and Resulting Mineralogical and Chemical Variations

1 Introduction

The precursor of all coals is generally assumed to be peat, an organically rich deposit that forms in marshes and bogs under both freshwater and saltwater (marine) conditions (Given and Dickinson, 1975). The geology and geochemistry of coal, therefore, might be understood by combining the geology and geochemistry of peat with the physical and chemical changes believed to occur during the metamorphism of peat into the various ranks of coal, including lignite. This process of metamorphism is termed coalification.

It is possible to understand the origin of certain forms of mineral matter in coal without reference to the organic structure of the coal, since the processes by which this mineral matter is incorporated into coal operate independently of the organic chemistry of peat formation and coalification. The other forms of mineral matter are incorporated via organic bonding, either as the consequence of plant biochemistry or via reactions between certain organic functionalities, such as acids and chelating ligands, and ground waters. These major processes of mineral matter introduction are described in the following sections in terms of their chemistry, their role in controlling gross mineral matter composition, and their probable impact on the mechanisms of mineral matter bonding in coals as they occur today. A close correspondence can be established between the present bonding of the mineral matter in lower rank coals and its mode of introduction into the peat or coal. Therefore in these cases the interplay between plant chemistry, peat chemistry, and coal chemistry will be highlighted. In higher rank coals, many of these subtle connections between the present structure and the geological origin of the mineral matter tend to be destroyed by the coalification process.

2 Introduction of Inorganic Mineral Phases into Peat and Coal

Inorganically bound elements in present-day coals are the result of at least five mechanisms operating at or since the time of initial peat deposition (Finkelman, 1982): (1) incorporation of elements from the original plant material, (2) precipitation of elements from aqueous solution, (3) accumulation of airborne detritus, (4) accumulation of waterborne detritus, and (5) epigenetic mineralization (i.e., minerals that have formed in cleats and fractures of the coal deposit). Accumulation of detrital mineral particles and the chemical precipitation of dissolved species from aqueous solution generally are the major processes by which inorganic elements are introduced into the peat deposit from external sources. These same processes account for the generation of most of the purely inorganic sediments which accumulate in shallow bodies of water, and thus the inorganic matter in coal often has a mineralogical composition akin to that of the sedimentary layers which are found interbedded with coal seams.

The precipitation of pyrite (FeS2) is somewhat of an exception to this statement, in the sense that this process is intimately connected to the low oxidation potential in the peat layer, which results from the presence of decaying plant matter. The pyrite precipitation is generally believed to occur as a consequence of the reduction by anaerobic bacteria of soluble sulfate ions to sulfide or bisulfide ions which precipitate any ferrous ions available, leading to the formation of pyrite. The sulfate ions appear to have been derived from marine or brackish environments (Renton, 1978), while the ferrous ions may have been leached from detrital minerals. Thus coals containing large amounts of pyrite are assumed to have been affected by a marine influence at some state of coalification.

Since both the detrital and the chemical precipitation mechanisms for the introduction of mineral phases into coal operate in the same time domain as the deposition of the peat itself, there exists, in general, a correlation between the nature of the inorganic minerals in coal and the geological environment under which the original peat deposit formed. This point is further developed in Section II,C,2. An additional but volumetrically less important class of mineral phases in coal are the epigenetic minerals. These are minerals, such as calcite, which have precipitated from migrating solutions at some later stage of coalification, when the coal is sufficiently brittle to form cracks into which these precipitates can be deposited. When such fractures are perpendicular to the bedding plane, they are called cleats, which are a characteristic feature of most coal beds. In general, the remaining discussions on the occurrence of mineral matter in coal presented in this article will exclude the epigenetic minerals.

3 Introduction of Organically Bound Mineral Matter into Peat and Coal

The structural chemistry of the plant matter which is reconstituted to form a peat deposit plays two important roles in the introduction of organically bound inorganic elements into peat and low-rank coals. In the first place, the actual mineral matter content of the plant matter, averaging around 2%, is incorporated directly into the peat as it forms. The major inorganic elements in plants are Si, Al, K, P, Ca, Mg, Na, Fe, and Ti. The percentage of each element varies widely from one species to another. Grasses, for example, contain larger amounts of silicon; modern representatives of the lycopods, a species which is a precursor of the carboniferous bituminous coals, contain large amounts of aluminum (Watt, 1968). While this source usually contributes only a minor portion of the total mineral matter in coal, it can be the major source of mineral matter within individual coal macerals, for example, vitrinite. These inorganic constituents of the coalified plant material can remain organically bound, but normally would be expected to transform to a greater or less extent to very fine-grained inorganic mineral grains.

In addition to introducing the organically bound elements derived directly from plant mineral matter, the organic structure of peat contains structural sites including acidic and chelating functionalities which can trap metal ions and atoms via ion exchange, chelation, or another reaction. For example, Ca²+, Na+, Ba²+, Sr²+, and other ions dissolved in ground water can exchange with the H+ of the humic acid constituents present in peat and very low-rank coal. A significant portion of the mineral matter in certain low-rank coals and lignites consists of ion exchangeable cations whose origin can be traced to this process.

4 Chemical Analyses of Mineral Matter in Coal

a Introduction

Chemical analyses of mineral matter in U.S. coals, usually expressed in terms of oxides as the weight percent in the high-temperature ash, have been widely available for years. For the most part such analyses have usually emphasized the major (> 1% of ash) and minor (> 0.1% of ash) constituents in eastern and midwestern coals (e.g., Abernethy et al., 1969). Relatively few data are available on the trace elements in these coals, although recent studies are changing this situation (Swanson et al., 1976; Zubovic et al., 1979). Furthermore, although analyses of low-rank coals and lignites from the western and Gulf Coast regions of the United States, which are of increasing scientific interest, have appeared in recent years (Swanson et al., 1976; Morgan et al., 1981; Finkelman, 1982), these coals are still not as well investigated as the eastern coals.

Emphasizing first the major inorganic elements in coal, one can initially be struck by the diversity of coal ash compositions. For example, it will be shown in Section III that the correlations between ash fusion and ash chemistry defined for eastern U.S. coals do not apply to western U.S. coals owing to gross chemical differences. However, on closer inspection, a great many similarities among ash compositions, at least within a given region, become apparent. In the United States, a large group of Appalachian coals will show many similar trends in their mineral matter contents, while, similarly, a large group of western coals will show a different but internally consistent set of trends. Even in comparing eastern versus western coals, there are many similarities in the mineral matter contents if the alkali and alkaline-earth constituents are excluded. Thus the observed diversity in mineral matter compositions is not random, but arises as a natural consequence of the various mechanisms by which mineral matter can be introduced into peat or coal. Furthermore, once the mineral matter is present, further changes can occur, depending on the geological setting of the peat formation (Renton, 1978). Thus, although the detrital constituents occur to a greater or lesser extent in most coals, pyrite is generally significant in coals where there has been a marine influence, while the organically bound ion exchangeable constituents are significant only in low-rank coals. This helps to account for the great regional differences in inorganic coal mineralogy and ash chemistry. For example, in the many coals analyzed by O’Gorman and Walker (1971), all coals with a Fe2O3/(SiO2 + Fe2O3) molar ratio > 0.15 are pyritic eastern or midwestern bituminous coals which have seen a marine influence, while all coals with a CaO/(CaO + SiO2) molar ratio < 0.15 are low-rank western or Gulf Coast coals containing a substantial portion of calcium on ion exchangeable sites.

Thus many of the extreme variations in the geochemistry of the major elements in different coals can be understood by reference to the accepted mechanisms for mineral matter introduction into coal. However, the variations in minor and trace element geochemistry from one coal formation to another, or from one coal sample to another within a given coal formation, are not so easily correlated with the origin of these constituents in the coal. Recent evidence suggests that these variations are also not random (Finkelman, 1982). Such information, if available for a broader spectrum of samples, would be useful in understanding and extrapolating chemical trends within coal formations, in prospecting for desirable coals, and in assessing the stability of these elements during coal processing. One method by which the introduction of trace and minor elements in coal and the variations in their concentration can be analyzed is based on the correlations between elemental analyses of different samples of a given coal formation.

b Correlation-Coefficient Analysis of Coal Chemistry

Illinois Coals. As an example of such an approach to inorganic coal chemistry, we shall consider the study of Gluskoter et al. (1977) performed at the Illinois State Geological Survey. This study reports a comprehensive set of analyses, including major, minor, and trace inorganic elemental analyses for 172 raw coal samples, with 114 samples from the Illinois Basin coal field. These results are listed in Tables 3–7 of Gluskoter et al. (1977), and the cross-correlation coefficients for every possible pair of elemental analyses for the 114 Illinois Basin coals are listed in their Table 11.

When the occurrence of any one element is plotted versus the occurrence of another, the magnitude of the correlation coefficient between the two elements can vary between 0 (uncorrelated) and 1 (perfectly correlated). This coefficient reflects the degree to which a least-squares fit to the points provides a description of the data. The sign of the correlation coefficient is given by the sign of the slope of each such fitted line. Examination of these data suggests that correlation coefficients above about +0.2 may have some significance in the sense that such element pairs tend to be well correlated in some subset of the entire data base. Correlation coefficients above about + 0.5 tend to indicate a relatively good correlation between such element pairs over the entire data base. Significant negative correlations were not encountered. It is important to remember that there could be some instances where significant statistical correlations may mean nothing geochemically and, conversely, that a significant geochemical mechanism may be operating which does not show in the statistics. Given this caveat, a summary of the results and their probable significance in terms of the geochemistry and structural chemistry of Illinois coal is given below. Many of these correlations were pointed out by Gluskoter et al., while others were derived from a careful examination of the tabulated results coupled with a speculative assessment of their significance.

• Most lithophile (rock loving) elements, such as K, Al, Mg, Si, Ti, Sr, Cs, Rb, Th, Cr, and the rare earths, are correlated with each other and with certain chalcophile (copper loving) elements, Cu and Ag. Excellent correlations exist between Si and the major rock-forming elements Al (4-0.76), K (+ 0.68), and Mg (+0.58) and between Si and the minor element Ti (+ 0.76). Ca, Na, and Fe are not well correlated with Si. Since Si (or Al) can be considered as a tracer for the detrital silicate constituents of mineral matter in these coals, the elements correlating with Si presumably were introduced into the coal either bonded within or adsorbed onto the detrital silicate minerals. Evidently the Na, Ca, and Fe in Illinois coal were not introduced in this manner.

• Fe is correlated highly only with pyritic sulfur (+ 0.72) and with the trace element Tl (+ 0.78). The lack of correlations between Fe and any major or minor elements confirms the picture that Fe is directly formed in the coal as pyrite (or a lower sulfide) and thus acts essentially as an independent constituent of the mineral matter. The Tl is presumably coprecipitated with the Fe, possibly in solid solution within the pyrite lattice.

• The analyses for organic sulfur are correlated with a number of metallic elements in the Illinois coals such as Mo (+ 0.52) and, to some extent, with U and pyritic sulfur analyses (+ 0.26). It may be plausible that the coals with high organic sulfur contents preferentially incorporate these metals, either in direct association with the organic sulfide groups or within inorganic sulfide minerals precipitated in a sulfur- or H2S-rich environment.

• The elements Zn, Cd, Ba, Zr, and Ca have interesting cross-correlations which are understandable, in part, from accepted processes of mineral matter genesis:

    For example, the high correlation between Zn and Cd might be expected simply as the result of the similar chemical properties of these two elements. Both of these elements have been found in cleat-filling postdepositional sphalerite (ZnS) crystals (Hatch et al., 1976; Gluskoter and Lindahl, 1973). Calcite is commonly associated with sphalerite in these cleats, which may account for the correlation between Ca and Zn or Cd.

We have noted other correlations among the analytical results in the same Table 11 of Gluskoter et al. (1977). These observations, and their possible significance, are indicated here.

• The correlation of Na with Cl is only 0.48, much less than unity. Presumably these elements sometimes occur together in Illinois coal, perhaps as the result of being absorbed or precipitated as NaCl during deposition of the coal beds. However, Gluskoter and Ruch (1971), based on a neutron activation analysis of 35 samples of Illinois coal, concluded that there was a clear lack of correlation between sodium and chlorine, and they repeated earlier suggestions of an organic association for the chlorine that does not occur as NaCl.

• Mo, Tl, U, V, and Se tend to be correlated with each other, but only Tl is correlated with Fe. Analytical data indicate that only Tl is commonly associated with pyrite (FeS2) in a reducing environment (Finkelman, 1980), so the cross-correlations of these trace elements with each other are as yet unclear.

• The chalcophile elements, As, Co, Ni, Sb, Pb, and Cu, are correlated with each other and with the lithophile elements Ge and Ga, and, to a lesser extent, Be. These elements may have a common origin in Illinois coals, possibly involving chelation by the organic host of trace ions introduced into the coal seams by percolating solutions at a particular stage in the coalification process.

Note that in an effort to explain these correlations, we have focused primarily on the origin of each inorganic element in the coal, whether it be present in major, minor, or trace quantities. To go beyond this point, to derive specific information about how each element is bound in the coal, it is necessary to separate the coal constituents either physically or chemically in one way or another. Such techniques, and the information that has been derived from them, are discussed in the following sections.

C Identification and Characterization of Mineral Matter in Coal

1 Introduction

A variety of techniques have been utilized to identify and characterize the mineral matter in coal that go beyond the mere determination of the bulk mineral matter (or ash) composition. The two questions which have been most frequently asked are the following:

(1) What is the mineralogical analysis of the true mineral phases, that is, what minerals are present and in what proportions? This information has been sought, in part, to account for the variations in gross mineral matter chemistry from one coal to another and, further, to help interpret the geological history of the coal, based on models for the formation or introduction of certain minerals in coal.

(2) Which inorganic elements are organically bound in a given coal and how are they held? This information has been sought for much the same reasons as the information regarding the occurrence and concentration of inorganic mineral phases in coal, that is, to understand gross mineral matter chemical variations, to gain a clearer picture of the detailed geological and geochemical history of a given coal formation, and to predict and interpret the changes in mineral matter structural chemistry accompanying coal processing.

In this section we shall first review the techniques that have been developed for concentrating and analyzing the inorganic minerals in coal and then review the current state of knowledge concerning the identification and structure of organically bound mineral matter in coal. Some emphasis will be placed on the relationship between the observed bonding tendencies of mineral matter in coals of different ranks and the origins of these coals. The behavior of the highly dispersed mineral matter constituents during coal processing will be introduced in Section II, D, while the role of gross mineral matter chemistry during coal processing will be deferred to Sections III–V.

2 The Identification, Characterization, and Significance of Inorganic Minerals in Coal

a Low-Temperature Ashing Technique

Studies of the inorganic mineralogy of coal received a substantial impetus from the development of the low-temperature ashing technique (Gluskoter, 1965). Low-temperature ashing involves subjecting a pulverized and mildly heated coal sample (100-150°C) to a radio frequency-induced glow discharge in an oxygen atmosphere at reduced pressure. The oxygen atoms thus created facilitate the combustion of the organic macerals without seriously affecting the inorganic minerals, which are recovered as a residue. Most of the published information regarding the inorganic mineralogy of coal is derived from the x-ray diffraction of this low-temperature ash (LTA) (see, for example, O’Gorman and Walker, 1971; Rao and