Petrographics of Marls-Chalks-Shells
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PETROGRAPHIC CHARACTERISTICS AND PHYSICAL PROPERTIES OF MARLS, CHALKS, SHELLS, AND THEIR CALCINES RELATED TO DESULFURIZATION OF FLUE GASES CONTENTS Page Ab stract l Introduction 3 Definitions of sample tYIJeS and other terms 3 General sample processing and methods of analyses 5 Gr ain size by image analysis . 5 Particle-size analysis by sedimentation 6 Methods of mineral and chemical analyses 6 Experimental methods of calcination and determination of pore structur e and surface area . .7 Pore structure by mercury porosimetry . 7 Apparatus for calcination and surface ar ea measurements 9 Surface area measurements lO Calcination conditions ll Experimental procedure ll Obs ervations on calcination of samples l2 Marl Investigations l4 Uses and production of marl l4 Sources and samples of marl l4 Illinois marl deposits and samples l7 Characterization of marl samples l8 Grain size and particle size 2l Mineral and chemical analyses 27 Moisture-density relations of marls 30 Results and discuss ion of pore structure and surface ar eas of marls and their calcines 3l Pore structur es and surface areas of marls 3l Pore structure and surface area of calcined marl 3l l6xl8-mesh particles 31 l70x200-mesh particles 40 Chalk Investigations . 43 General characteristics of chalks and their origin 43 Sources of samples of chalk and chalky limestone 43 Niobrara Chalk 45 Greenhorn Limestone 45 Austin Chalk 46 Other chalk st.rata in Texas 47 Annona Chalk 47 Saratoga Chalk 47 Selma Group 47 Tertiary formations containing chalk and chalky limestone 48 Page Characterization of chalk and chalky limestone samples 49 Petrographic description . • 49 Bulk density and crushing characteristics ...• 50 Mineral and chemical analyses . 55 Results and discus sion of pore structures and surface areas of chalks, chalky limestones and their calcines 55 Chalks . 61 Chalky limestones 66 Shell, Coquina, Caliche, and Sludge Investigations 71 Sources of samples . 71 Characterization of samples and their calcines 72 Investigat ion of Carbonate Rocks Related to Previous Fluidized Bed Desulfurization Tests 78 Samples and their·relative decrepitation 79 Characterization of samples 80 Discuss ion of results 84 Su mmary and Conclusions 84 Marl ....... 84 Chalk and chalky limestone 85 Shell , coquina, caliche , and waste sludge 86 Conclusions regarding carbonates studied in relation to fluidized bed desulfurization 87 References 87 TABLES 1. Textural analyses of marls 24 2. Mineralogy of marls 28 3. Chemical analyses of marls 29 4. Harvard miniature compaction test result s of marls 30 5. Pore volumes and mean pore sizes of marls 32 6. Pore structures and surface areas of marls and their calcines ( 16xl8 mesh particles) . ... 33 7. Effect of calcination conditions on calcine pore structure and surface area of 16xl8 mesh particles of marl 38 8. Comparison of test results on 16xl8 and 170x200 mesh part icles of marl . • . • 41 Page 9, Petrography and bulk densities of samples 52-53 lO . Median particle sizes of pulverized samples 56 ll . Mineral analyses of chalk· and chalky limestones 57-58 l2 . Chemical analyses of chalks and chalky limestones 58 l3. Pore structur es and surface areas of chalks , chalky limestones , and their calcines 60 l4. Chemical and mineral analyses of shell and other carbonat e samples 73 l5. Pore structures of shell and other carbonate samples and their calcines (l6xl8 mesh particles ) l6. Petrography , pore structures , and decrepitation test results . 79 l7 . Chemical and mineral analyses 83 APPENDIXES l. Annotated bibliography on marls in the northeastern quarter of the United States . 93 2. Sources of samples and remarks on the deposits l02 ILLUSTRATIONS Figure Page l. Examples of penetration-volume curves for (a) a single particle , (b) l6xl8-mesh particles , and (c) l70x200-mesh particles of marl . • . • . 8 2. Schematic diagram of apparatus used for calcination and for measurement of surface area . • . • . • . • . • lO 3. Typical calcination recorder traces for (a) marls calcined at 8500 C, (b) marls calcined at 950° C, and (c) chalks , limestones , and shells calcined at 850° C. l3 Page Figur e 4. Marl production pit . 15 Localities of marls and other rocks sampled and the 5. q outcrop areas of principal chalk and chalky limestone strata 16 6. Particle-size distribut ion of selected marls 25 7. Particle-size distribut ion of marl samples 26 8. Particle-size distribut ion of marl samples 26 9. Particle-size distribution of marl samples 27 10 . Pore-volume curves for 16xl8 mesh particles of bog marl 7132D and its calcine . 35 11 . Pore-volume curves for 16x18 mesh particles of bog marl 7149A and its calcine . 35 12 . Pore-volume curves for 16xl8 mesh particles of bog marl 7137 and its calcine ......... 35 13 . Pore-volume curves for 16xl8 mesh particles of tufaceous bog marl 7133 and its calcines . 39 14. Pore-volume curves for 16xl8 mesh particles of lake marl 7150 and its calcines . 39 15 . Pore-volume curves for 16xl8 mesh particles of bog marl 7162c and its calcines . 40 16 . Pore-volume curves for 16xl8 mesh particles and penetration volume curves for 170x200 mesh particles of tufaceous bog marl 7133 and their calcines . 42 17 . Pore-volume curves for 16x18 mesh particles and penetration volume curves for 170x200 mesh particles of lake marl 7150 and their calcines . • . 42 18 . Geologic time-rock classification of carbonate rocks studied 44 19 . Pore-volume curves for sample of chalk of the Mar ianna Limestone (7201 ) and its calcine . • . 64 Page Figur e 20. Pore-volume curves for samples of the Selma Group and their calcines : Prairie Bluff Chalk (7206), Arcola Limestone Memb er of the·Mooreville Chalk (7204) , and Demopolis Chalk (7230) . .... 21. Pore-volume curves for samples of the Fort Hays Limestone Memb er of the Niobrara Chalk and their calcines . 67 ' 22. Pore-volume curves for samples of th� Austin Chalk (7221A and 7222B) , the Pecan Gap Chalk (7225 ), and their calcines . 68 23. Pore-volume curves for samples of the Annona Chalk (7226A and 7227B ), the Saratoga Chalk (7228) , and their calcines . 69 24. Pore-volume curves for samples of chalky limestones and their calcines : Crystal River Formation (7120 ); Dessau Member , Austin Chalk (7219); Greenhorn Limestone (7210B) . 70 25. Pore-volume curves for 16xl8 mesh particles of clam shell 7124 and its calcine .... 26. Penetration-volume curves for 170x200 mesh particles of carbonat e sludge 7153 and its calcines ..... 27. Calcine pore-volume curves for samples studied related to fluidized bed desulfurization . 82 Plate 1. Common mollusks from Pleistocene marls 19 2. Characteristic textural features of lake marls 20 3. Characteristic textural features of bog marls 22 4. Selected types of particles that occur in marls 23 5, Typical textural features of lime in calcined marl 37 6. Texture of chalk and a chalky limestone (F), coarse sparite in micrite 51 Plate Page Texture of micritic calcite in chalk samples 54 8. Texture of calcined (lime ) samples of chalks shown in plate 7 . • . 62 9, Textur e of the calcine (lime) from three types of calcite in chalks lO . Characteristic textural features of shells 74 ll . A. Relatively smooth and coarse grains, of lime in calcined shell material ; B. Relatively smooth and fine grains of lime in calcined sludge • . 78 l2. Typ ical textural characteristics of samples studied related to fluidized bed desulfrrrization • . PETROGRAPHIC CHARACTERISTICS AND PHYSICAL PROPERTIES OF MARLS, CHALKS, SHELLS, AND THEIR CALCINES RELATED TO DESULFURIZATION OF FLUE GASES Richard D. Harvey , Robert R. Frost , and Josephus Thomas , Jr . ABSTRACT Thirty-seven operating and other pits in fresh-water marl in the northeastern quarter of the United States and twenty-four de posits of chalk in chalky limestone, four deposits of shell and co quina, two deposits of cal iche , and a large carbonate sludge refuse pile, all in the eastern part of the United States , were sampled and studied in relation to their potential use in limestone (Caco l pro 3 cesses for control of emission from fossil fuel combustion. so2 Earlier studies had suggested the superiority of these materials over denser limestones in these processes. Each sample and its calcined product (lime ) were investigated for their petrography , mineralogy , chemistry, pore structure, and surface area. The occurrence of marl containing 80 percent or more Caco3 is restricted largely to Pleistocene age sediments that occur in the states around the Great Lakes and in Virginia . Annual production of marl in recent years has been approximately 2 million tons; it is at present us ed entirely as agricultural limestone and for related soil conditioning . Production could be vastly increased if demand in creased . Chalk and chalky limestone are generally restricted to the sedimentary rocks of Upper Cretaceous and Tertiary age in the Kansas Nebraska-Colorado area and in the southeastern states from Texas to Florida. Currently chalks and chalky limestones in most of these states are used primarily in the manufactur ing of cement . - l - - 2 - Marls are composed principally of equant calcite grains , most of which are less than 4µ in diameter , that are weakly ag glomerated and also of mollusk shells, which cons ist of aragonite. Together these minerals provide a Caco content that is most fre 3 quently between 80 and 90 percent . Impurities are mainly quartz silt and organic matter. The pore volume of marls averages about 0.50 cc/g, which corresponds to a porosity of ab out 57 percent. Calcina tion of marl at 85 0° C for 5 to 10 minutes under high gas flow in creases the pore volume about 0.2 cc/g marl�slightly more than the theoretical increase calculated from the Caco3 content because of the presence of organic matter. The phys ical characteristics of high pore volume and fine grain size in marls and their calcines indicate that they should have high reactivities with so2 • Such character istics of solids are of major importance in most gas -solid inter actions .