UNITED STATES DEPARTMENT OF THE INTERIOR Harold L. Ickes, Secretary GEOLOGICAL SURVEY W. E. Wrather, Director Bulletin 928-C ADSORBENT CLAYS THEIR DISTRIBUTION, PROPERTIES PRODUCTION, AND USES 'BY P. G. NUTTING Contributions to economic geology, 1941-42 (Pages 127-221) . UNITED STATES GOVERNMENT PRINTING OFFICE WASHINGTON : 1943 For sale by thelSuperintendent of Documents, U. S. Government Printing Office, Washington, D. C. Price 20 cents CONTENTS Page Abstract-..------.-------.----.--._-.---....-- ......_...-_ 127 Introduction _-__-__-_-_-_---________-__-_-_-_-_---__._.-._-_.__--_ 128 Purpose of the report._____. _________._.__.____________.__.___ 128 Production of adsorbent clays.___.______._____-___._.___.__.___ 128 Early uses.-----_--------------_--------_----------.__------ 128 Naturally active versus activated clays___---____-__._____._____ 129 Recent advances in the study of adsorbent clays___-_.___-___-.__ 120 Acknowledgments -_-_-----_-_----____--_-_---_-_-___________-_ 131 Miscellaneous activable materials___-__-_---__-__-..__._.______ 131 Synthetic materials and special treatments______________________ 133 Nature of adsorbent clay___--_-_----__-_ _--__--.____._._._____ 133 Subclasses of montmorillonite clays._________________________ 134 Nature of the adsorbing action._________________________________ 136 General occurrence and character of deposits-.___---_--_--.-__.-__.__- 137 Distribution by areas___----_-._.._-___________-___-________________ 139 New Jersey and Maryland.------.-.-..____-___._________..____. 131 Virginia and North Carolina____-_-____-______-__.__-______-____ 142 South Carolina._-_-----_---____---_--_-____.--___^_____.__.__. 142 Georgia --_---_-__-_----_---____--_-_-_.._-__--._-_---_-_-____-- 142 Florida___-_.____.__-.--..-_.--..-__.___.__-.__..._.______.. 144 Alabama -._.-_-.._------_--_-_--__-__._--_._-_.------_..-___- 145 Mississippi- _----_-----_-_-_---_--__-..__________-______________ 146 Tennessee.______._-_--_--__.-_-:.__-_____-_---._--________-____ 147 Illinois---.-----------...-----!-----.-.-..----.---.---.---..-- 148 Missouri_ _ _--_____--_l_-_-_---_---.______ __--_______._____._ 148 Arkansas. _.___.:__-___ ._______ _______________-________________ 148 Louisiana_ . _-___'__-____-_____-______________________________ 149 Oklahoma._-_.-_-_-..--_..._-__._._.._._-.__-.._.__.._...___. 140 Texas.--._.----_------_-----_-.-.-.-.._----.--.-...-...-.... 149 New Mexico..__--__--___--______-_-_____-___-_-___-__________ 141 Colorado.__-______.__-_-_______._______._.__.__________'______ 151 Utah..__---_---.._-_------..-..-.--._-..--.--.-----_.......--- 152 Nevada._.________._--____-____________.__._.__.__.___.______ 152 Arizona -___--___._----_------_.-_-_-_____._-_-_-_._..._-_____. 152 California.___-__-_-_-_--_-_--_____-_-_-_-._.-._-__-___-___-__ 152 Wyoming and South Dakota......._____________________________ 153 North Dakota.-.--.--------_- --._..._...._._.._.__.._.._._ 154 Minnesota._--_-___-__--_-_-_-__-__-_-__----___-__--_________. 154 Montana.___________--_-__-_-_-_-_.___._____-_.____________._ 154 Canada.____________________.__________'_____.________________ 154 Mexico_ -_-_---_-.__-\_---_-_---_-_--___----_------__-.-_... 154 England.-.____-___-_-_-____--_-___-_____-_---________________ 155 Faeroe Islands-___--_---_-----___-_-_-___---_-_____-_-_.______ 155 Germany.____________________________________________________ 155 Other countries__-__--._-_-------_..__._-.__--_-._-._..____._ 155 in IV . CONTENTS Page Distribution by geologic ages__ _____________________________________ 156 Ordo vician__ _-_______________-___-_-____-__________-___'-______ 156 Mississippian ________-_____-_-_-___-_-_-_-___-___-________ T ___ 156 Permian (?)..___..__...__..-._.._...__....._..._...___.__...... 156 Upper Cretaceous._________-_-___-__.__-_____-_.________.._.__ 156 Eocene._-____-__-___-__--__--_-_---_-----__----_-_--__-______ 156 Oligocene__ _ _________________-_-_-_____-_ ___'-_'_-______________ 156 Miocene.._ __---_-_-_-----_--------__-----__--_-------_-______ 156 Pliocene._____________________________________________________ 157 Physical properties of adsorbent clays._______________________________ 157 Field and laboratory identification____________-__ ________________ 157 Texture and color.____--______---_---_----__----_-_._.___._.__ 157 Slaking.........._.._-.-....------._---....__._......._..... 158 Density _____-_-___-..-___-_-_-_-____--_-_---_-_-_-_-_-_-_-_-__ 158 Refractive indices.___-_-_-_---_--_----_--__-----_____-_-____-_ 158 X-ray patterns.-______-__-__-_--___-_-_-_-__-_-____________-__ 159 Clay-water relations.__--___---_-_-_---______--_---___________. 159 Lattice water_____________________________________________ 160 Adsorbed water____________________________________________ 160 Free-pore or capillary water._______________________________ 161 Adsorbed and lattice water. ____________________________________ 162 Adsorption and hydration of montmorillonite__ ___________________ 164 Vapor pressure of water in clays________---_____-________________ 166 Thermal analysis of clays_____-_--______--______-_______________ 170 Adsorbent clays and oils______________________________________ 175 Chemical properties of adsorbent clays----------------.-.....-.-.^... 177 Composition and structure___-_--------__-_ T ___---______________ 177 Lattice, spacings... _ _____---_____---_-_--_-___-__.__________ 180 Alteration by natural processes_-_-_-----_-_-_-__----____________ 182 Base exchange._____________________--_--___--_--__-----_----- 184 Slaking_______-______-_-___.----_----------------------------- 184 Derivation of adsorbent clays.__--___----_--__--_--_____________ 185 Acid solubility and activation.___________________________________ 186' Experiments on solubility of adsorbent clays._ _ __________________ 188 Slow alteration with time___------_----_-_____---________:____ 196 Adsorption potential and activation ______________i.___-_____-_- 199 Processing and testing of adsorbent clays__ __________________________ 201 General conditions_______ -___--_____-__--_-_------------------ 201 Drying..... _________-______-________-_.._____---___- _______-_. 201 Acid treatment of activatale clajrs_____________.__-_-___-_-_--_.-. 203 Testing adsorbent power.______.___.__-_______._________....___ 204 Contact method.._______-__-_______-_-_------___--_---_--- 204 Percolation method--____-----.___.___._______________.____ 204 Preliminary tests of c]ays__________.___----___-----_------_-.--- 206 Color curves________________--..-_-_-____-_-_--_--_______------ 2OO Work tests...........-_----..___________________________.__._. 207 Economics of production of adsorbent clays__--_.__-_------------------ 208 General conditions......-----_---------_-----------__----..----_ 208 Transportation___-___---------_--------- r --------------------- 2O9 Active clays-..-----_-----.--..--__---___-___--..__-_._.______ 209 Activated clays____________---_-_-_-___-i__-_-.__.__________ 209 Import duties._-___-________--_-____--_-_____--_____-_________ 210 Mapping and mining--.---...--------------____________________ 210 Cost of drying.--..---.-__-__-__-_-_-_-_____--___-.-_-_-..__ 210 OONTE'NTb ' Eeomomrcs of production of adsorbent clays Continued. Cost of acid activation________.__________---------------------- . 211 Uses of adsorbent clays. _ _ _ - -_- _- ---- 211 Treatment of oils . - ------------------- 211 Renovating dry-cleaning fluids._______-._--_-----__--------- 212 Catalysts---.------.---.-----------.-.------------------- 212 Treatment of water solutions.______-._-_-_-_--------------- 213 Bleaching crude sulfur______-__ _ ---_.-- --------------- 213 Fungicides.. -______ _-.---------_----------------------- 313 Supplying adsorbed food to plants.- _ - ------------- 214 Increasing bonding power of sands___------------------------ 214 In drilling muds. - -- ------- 214 In ceramics._________ ________._________-_----_--_--------- 215 In portland cement-.----.--------------------------------- 215 Waterproofing___ ______ _- - - _ - 215 Summary _ _._ _- ____ _ ----- -- 215 --- ---------- - - ---------- - -------- 219 ILLUSTRATIONS PLATE 13. "Solubility of two clays in alkaline solutions___._._..______ 194 8. Heat of wetting and adsorption potential in the film of water adsorbed on silica.__________________________________ 162 Q. Adsorbed water and adsorption potentials for powdered quartz and weight-temperature, curve for powdered Pyrex glass._ ____---____----_-------____..-_____._______-_ 164 10. Weight-temperature and log C (1/T) curves for normal bentonite. --_----.-- - - _---- - - 165 11. Weight of various adsorbent materials at different humidi­ ties and constant temperature (26° C.)------- ---- 168 12. Energy of hygroscopic water._______________ ___________ 170 13. Weight of various clays and related minerals at different temperatures and constant humidity____-___._______... 171 14. Weight of various clays and of pyrophyllite at different temperatures and constant humidity.-._-_-_._._.._____ 172 15. Thermal dehydration curves for coarse and fine constituents and for acid-leached, dry-aged, and moist-aged adsorbent clays _ _ _ _ _ ____ 173 16. Energy of association of water with clay._______________ 174 17. Relative bleaching power of various clays at different tem­ peratures.- ---__-___----_-----__-___________..______ 177 18. Relation of moisture" content and spacing between lattice planes in montmorillomte._ ____- _ _ ______ __ . 181 19. Relative loss of bases on acid treatment-________ _ 187 20. Relation between refractive indices