The Sorptive Behavior of Organic (Üompounds on Retortcd ()iI Shale by Adi] Noshirwan (iodrej Gregory D. Boardman, Chairman (Zivil lingineering (ABSTR1\(ZT) Oil shale is a valuable natural resource of oil. The United States has only 5% of the known world reserves of recoverable crude oil and about 73% of the known world reserves of recoverable oil shale. Before there can be full-scale commercial development of oil shale, the problems associated with the large amounts of wastes generated by the processing of the shale must be solved. The wastcs have a complex eheinical matrix. lt is felt that the spent shale can be used as a sorbent to either treat or pretreat the contaminated process waters or could be codisposcd with the process waters, Quite extensive work has been done in exploring this altemative with respect to inorganic constituents, but that with organic constituents has been mainly restricted to the measurement of total orgauie carbon. This study was done to base the analysis of the suitability of the spent shale as a sorbent upon individual compounds so that a more fundamental understanding could be ob- tained as to how familics of conrpounds behave. Single- and multisohite batch sorption isothcrrn experirnents performed on Antrim spent shale from Michigan indic.;¤ted a consistcnt sor‘;‘—live behavior by the shale with respect to the four sorbates used in the study Y——- Pl:·.·nol. 2·~liydroxynaphthalene (HN), 2,3,5—Trimethylphcnol (TP) and l,2,3.4-Tctrahydroquinoline (”l”llQ). The sorptive capacity of the spent shale was least for Phenol and greatest for Tll(_), with the order being Phenol ·< TP < [IN <Tl](_). Single-solute continuous- flow column expcrirncnts on shale could not be better analyzed because of a lack of proper kinelic daisy but the order in which the coinpoundte would reach a 50% breakthrough, as well as the soipläve order (from least to largest amounts sorhed) of the four study compounds in batch multi- componcnt experiruenls, could be piedicted based upon the single-solute experimental data. The order of breakthrough at l0% of intluent in the continuous~llo·„v column experiments cannot be predicted with the same degree of clarity. Averagcs of the ratios of the amount sorbed of any one component to the total sorbed amount of all components in multisolute systems were calculated and indicated the panitioning of the com- ponents as ll% (Phenol), 32% (TIN), 37% (TIIQ), and 20% (TP) in a four—componcnt system. Average ratios for bi- and trisolute systems computed from the tetrasolute system agreed to within l l% for those compounds that sorb to larger extcnts (HN and THQ) and to within l9% for those that sorb to a smallcr degree (Phenol and TP). A comparison with singlc—eomponent batch isotherm experiments performed on Filtrasorb 300 granular activated carbon (GAC) showed that the shale had a sorptive capacity of about two orders of magnitude less than that of the GAC. The multicomponent shale data could not be adequately modelled with any one of three models —- a multicomponent Freundlich type model, the multicomponent Iangmuir model, and the sim- plitied ideal adsorbcd solution theory model. Among the three phenolie compounds studied, the effects on sorption due to ascending a homologous series (from Phenol to TIN) are more pronounced than t.hose associated with branch- ing (from Phenol to TP). No relationship was found to exist between the amounts sorbed and the octanol—watcr partition coeflicient. Acknowledgements I owe a deep debt of gratitude to my committee chairman and good friend, Dr. Gregory Boardman. Not only did he offer me the chance to work with him, but maintained his usual good Irurnor throughout the long period that it took me to perfomr and report upon my research. I shall not forget his honesty, gentleness, encouragement, open-heartcdness and irrdulgence of my more whimsical moments. I was favored with a very helpful and caring committee. My many thanks and respect go to Dr. Robert Iloehn (who was instrumental in convincing me to obtain the doctoral degree), l)r. William Knocke (whose clear sense helped me focus my research a little better), Dr. .lohn Novak (for his down—to—earth explanations of theory), Dr, I,ncian Zelazny (for his accommodation of urgent meetings and for getting surface analyses perforrned), and Dr. Daniel Gallagher (who helped me understand modelirrg and statistics much better than I did before, and whose friendship eased a lot of my anxieties). I also obtained considerable insights into sorption from Dr. Menahern Rebhun, who, although not on my committee, took time during his sabbatical at Virginia Polytcclrnic In- stitute and State Ilrriversity to discuss technical (and other) subjects with me. Aclmmxlevlgcrrtcnts iv Tlrroughout my stay here at Virginia Polytechnic Institute and State University I have received ti- nancial support from the Environmental Engineering Division of the Department of Civil Engi- neering, and also from the ll. S. Department of Energy through a research project. I wish to thank these institutions and the people that represcnt tlrern. These institutions and these people are part of a country that has been most welcoming and encouraging. I have met many people, both in oflieial and social situations, in my many years in the United States, and certainly the people of the Il. S. have paid for my education through their tax dollars. Very few countries and peoples have such a generous and friendly character, and I wish to acknowledge a debt of gratitude to the United States of America and her people for helping a guest who had so little to offer in return. Aeknowledgements w Aeknmvlcrlgemcnts vi Acknowlertgcnrcnts viii Table of Contents Introduction ...,........................................................ I Research Objectives ...................................................,.. 6 Literature Review — ()il Shale ............................................... 7 i llistory of the l)evelopment of ()il Shale ....................................... 8 The Scottish Industry ........................,.......................... 9 The Australian Industry ........................................,........ l7 The United States Industry .............................................. I9 The Iaramie Energy Technology Center ...............,.,..,.,............ 25 ()perations in the Eastern United States ................................... 26 Oil Shale Developments in Other Countries 26 Fomration, Composition and lixtent of I)eposits ...................,............ 27 Genesis and Composition of ()il Shale ..................,................... 27 The Fischer Assay and the TOSCO Modified Fischer Assay ..................... 33 Iixtent ot ()il Shale Deposits ..........................................,.. 39 Methods of Processing Oil Shale ...........,..,............................. 49 li'x Sim or Surface Retorts ..............,.......................,........ 52 Turrrc or tinntcncs ix The Retort ................................................... 52 The Kiviter Reton ...................,............................... 54 The Petrosix Process .......,................,........,............... 54 The Paraho Process .,......,.....................................,... 57 The IGT IIYTORT Process.....................................,...... 57 The Lurgi—Ruhrgas Retort ............................................. 60 The TOS(I() II Retort ..,......................,...................... 60 The Galoter Retort .....................,............................ 63 In S'im Retorting Techniques ........,.................................... 63 The Retort ................................................... 63 Modified In Sim Retorting Techniques ..,................................... 66 The ()ccidental Retort ................,............................... 66 Amounts and (Äharaeteristics of Products a.nd Wastes Produced from Oil Shale ...,...... 69 Elemental (Öomposition of Raw Shale ..............................,....... 69 Retorting (Iharacteristics, Products and Energy Balance for a Westem and an liastem Shale 71 (Iomposition of Shale Oil .....,...,..............................,...... 82 (Öharacteristics of Spent ()il Shale .......................................... 82 (Äharacteristics of Retort Water .......,..,................................ 93 Air I’ol1utants ..........,................,.,......................,.. 104 Ieachates from Spent Shale ............................................. 111 Ilealth Problems Associated with the Oil Shale Industry ........................ 113 Environmental (Öoncerns Related to the Oil Shale Industry ..,..................,.. 114 Amount of Waste to be Treated .......................................... 117 Potential Uses for ()il Shale \Vastes ......................................, 119 Treatment of Oil Shale Wastes ,,.................................,,....,. 122 R eclamation and Revegetation of Spent ()il Shale ..............,.......,...... 123 Literature Review —— Sorption .....,....................................... 124 Table of ('ontents x Ilistory ........................,............,..........,............. 124 Some Terms Related to Sorption .............................,............. 127 Interfaces ......,..................................................... 127 Types of Sorption .....,..,,..............,......,..................,... 128 Factors That Influence Sorption .......................................,... 130 The Rate-Limiting Step ...................................,......,..... 130 The Rate of Diffusion 'Through