Kinetic Studies on the Thermal Cracking of Middle Distillate Using a Helical Coi1 Reactor

Sean Vernon Cuthbert




MAY 2001

O Sean Vernon Cuthbert 200 1

uisitions and "9. Bib mgraphii Services

Acquisitions et services bibl'iographiques

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A helicai coi1 reactor to thermaIly crack heavy hydrocarbons was designed and

constructed according to the criteria oE varying feed properties (including bihunen); large volumes of liquid product produced; gas and liquid phase cracking; varying residence times; using either steam or inert gas during the experiment; minimizing the axial dispersion; and full characterization of the heat transfer effects inside the reactor. The system was designed to process flowrates fiom 240 mWhr to 6820 m L k , with pressures up to 10000 kPa. The reactor was constructed using a two-zone design, with the srnaller
tube able to attain heating rates of 1400 Wm and 495 Wrn for the larger diameter.

Products collected fkom experiments completed in the 435-700°C range agree well with the data by Dong [1O4], except for the runs completed at temperatures >550°C. The four-

lump kinetic mode1 developed by Dong 11041 was used to conficm the operation of the


From conception to completion, a project of this size requires the involvement, ideas, and efforts of many good people, al1 experts in their respective fields. Unfortunately, I am unable to thank al1 those that have been involved with this project in some way. However,
1 would like to thank the following colleagues and fiiends who made this project a reality:

Mr. D. Verhegge, Mr. M. Grigg, Mr. M. Hancock, Mr. R. Scorey, Mr. B. Miles, and Mr.
1. Mikalson for their extensive practical advice and reality checks.

Dr. N. Okazawa and Ms. E. Zalewski for theu analytical chemistry advice and
analysis of the liquid and gas samples.

Dr. C.L. Hyndman, Dr. B. Pruden, Dr. A.A. Jeje, Dr. R.G. Moore for their theoretical and

practical advice and help in maintaining focus.

Mr. D. Dong for completing the initial runs and adding the gas phase cracking collection

Mr. M. Misunis of HP (now Agilent) and Ms. C. Cumow for the many fmstrating hours

of GC setup.

Ms,B. Crickmore of Syncmde Canada Ltd. for providing the detailed characterization of
the gas oil feed.

Mr. H. Albourwarej, Mr, D .Mallory, Mr. S. Gupta, M r .R. Jakher, Mr. N. Koak for their
fnendship and support during the most difficult stages.

for sarah
you introduced me COa new ~vorid

and gave me the courage to face the old

Approval Page . . .............................................................................................. ii


... . . . .iii Acknowledgements ................................................................................ iv ....................... . . . . .. vi Dedication ..-....-..............-...-....-.-.---..-.-.--..*... Table of Contents .......................................................................................................... vil List of Tables ......-..-..........-....S.-. . ..................................................................................... x List of Figures ........................--..-....--....... .........................................xi . . Nomenclature and Abbrewations ..................................................................................... xv .-. Epigraph ......... . ..... . . ....... . ............ - .................................... .......... xxiii
Abstract ................................... . . . ...........................................

CHAPTER ONE: lNTRODUCTION ................................................................................. 1
1.1 Introduction ................... .......

1.2 1-3

...-....--. ............................. . . . .1 Thennal Cracking Kinetics of Heavy Hydrocarbons ....................................... 2 Project Description ...........................-......-......--.*-.....-......................-...--.---..-. 2

CHAPTER TWO: LITERATURE REVIEW ......... .......................................-.. ..*. ............4
Thermal Cracking Kinetics ..................................... ...-.-.-.. .-.-.-........ - .-.... ..........4

.-. ..-.-. -........ .....16 Reactor Modeling ........... . . . ............ . ................................................... 19 Reactors Design Evaluations ........ .... ............. .......-*.... ................-.. ..............19 2.4.1 Wire mesh . -.20 2.4.2 Taylor-Couette .................... . .................................................... ...2 1 2.4.3 Batch .............................................................................................. 23 2.4.4 Helical Coi1 .................................................................................... 23 Lumped Component Kinetic Models ................... . . ........................................ 28 Themodynamics ......... ................. ......... . . ....... ... . .. . .....3 1 Thermophysical and Thermodynamic Properties ............................... . . . . . . . . .-35
vi i

Heavy OiVBitumen Molecular Structure ...................

.................. ..............1....................3 3. 4.. ............... .. -45 3................... ...... ............................ ...... ........................ 73 .........................................................46 Reactor ... CHAPTER FOUR: RESULTS AM) DISCUSSION..................1 Conclusions . ................... 5............................ 51 Control and Data Acquisition .................... ....................CHAPTER THREE: EXPERIMENTAL APPARATUS AND METHODS ...... .1 3......2 Kinetic Mode1................. ......................1.......... ............. .............. ............ APPENDIX B: Reactor Reynold's Number.......1 Experimental Apparatus .......................................................... ...............................1.. 57 4......... ...................3...... 1 3 5 APPENDIX C: Liquid Feed to Nitrogen Mass Ratio Calculation .2 ........................................ ........................... .......... ....5 Process Overview. ......................... 3 9 ... ......4 3........................ -73 5.1 Product Analysis and Mass Balance........................... ........ 65 ......................... ..... ..........................66 CHAPTER FIVE: CONCLUSIONS AND RECOMMENDATIONS ............... and Heat Transfer ..............................3 Product Analysis.........................2 Recommendations ...........................................1 3.......56 Product Liquid ..................*............. 4........................... 75 APPENDIX A: Milton Roy Pump Calibration Curves .........1.... ..............................133 Coefficient Calculation ................3 Cornparison with Mode1 Predictions .................. .......................................... -74 REFERENCES .......................................... 3.....2 3. 3 3 -35 3......... ......... ...... 49 Product Collection .................151 ............................................................................................................................ .......................... ..... 3 4 3......................... 149 APPENDIX D: Electrical and Process Instrumentation Drawings ............. 45 Feed System and Utilities .......... ......................... ...... ..................................3...56 Product Gas .....1............ .. ... .... ... Pressure Drop..............44 3......... .....................2 Feed Characterisation ...................

......................182 APPENDIX G: Product Gas Primary Condenser Heat Transfer Calculations ................. APPENDIX J: Reactor Residence Time and Axial Dispersion Calculations ............. ................... ................................................226 APPENDIX M: Mass Balances................................ ...................... .................... 193 ...*........ ............................ .......-223 APPENDK L: Thermocouple Calibrations and Locations .. ......... .....................APPENDIX E: Reactor and Process Equipment Drawings ............ ................. APPENDUC P: Summary of Successfûl Experiments .......... ........... .......................................................................... ... APPENDIX 1: ........................... ................. ...-200 Reactor Inlet Feed Vapouriser Calculations .................. .......304 308 APPENDIX Q: Surnrnary of Unsuccessfûl Experirnents ..........216 APPENDIX K: Operating Manual ....................... 234 .... .............. 154 161 APPENDIX F: Pressure Vesse1 Mechanical Calculations........... ................... ............................. .263 APPENDK N: Reactor Temperature Plots ............................. APPENDIX H: Nitrogen Preheater Heat Transfer Calculations ..... 291 APPENDIX O: Simulated Distillation Plots ........

............ 02-22-0 1-02 Mass Balance Summary . .. 308 .. .. .. 66 Thennocouple Calibrations ............LIST O F TABLES Physical Properties of Light Gas Oil (LGO) Feed .60 Lump Mass Fractions and Feed Conversion ... 231 National Instruments Data Acquisition System Board . ............. ......02-2 1-01-02 Mass Balance Summary ......... ..........02-22-0 1-04 Mass Balance Swnmary ........ ... ....... ............ ..............65 Surnmary of Activation Energies and Frequency Factors (Dong [104]) ............260 Table M.......3 Table 4... 02-2 1-01-01 Mass Balance Summary ..4 Table L.1 Table 4........................ 256 ..... ..........2 Table M...................4 Table M....1 Table O.........02-22-0 1-03 Mass Balance Summary ......................240 Expenment No ..... 02-2 1-O 1-03 Mass Balance Summary ....... .......... ..........7 Experiment No . Table 3................... -304 Summarv of Unsuccessful Ex~erimentai Runs .5 Table M................2 Table 4..1 Table L... Experiment No . .... 236 .....*....... .......... Table P...........-227 Therrnocouple Locations and Channel Numbers ....... Experiment No . 03-27-0 1-0 1 Mass Balance Summary .. ........ 55 Sumrnary of Experimental Conditions for Successfùl Runs................... ............. . ...............1 Table M... .......3 Table M... ......6 ................ .. .... .1 Table 4... 252 Experiment No ............... .............3 Table M.......2 Table L............................ .... . ......-244 -248 Experiment No .................... 58 Surnmary of Mass Balances for Successfùl Experiments ............... .........1 Summary of Successful Experimental Runs ... 233 Expriment No ....... .. ..

................3 Figure F.....5s .... 181 ....171 Flange Design Drawing for the Glycol Tank for the Condenser ................................ 70 Figure 4........................................................1 Flange Design Drawing for the Bitumen Accurnulator Glycol Tank Flange...1 Reactor System Schematic for Gas Phase Cracking Experiments............. .................. . Residence Time at 500°C .. .......................2 Comparison of Simulated Distillation Curves for Various Reactor ......8 Comparison of Experimental Data and Model Developed by Dong [ 1041 Component Yield vs........................... .7 Comparison of Expenmental Data with Model Developed by Dong Cl041 Component Yield vs............. 45 Expriment Comparison of Product fiom First and Second Condenser Pots ..........02-22-0 1-02 Shulated Distillation Boiling Point Curve .......2 Figure F.. Residence Time at 436°C Figure 4.............4 Flange Design Drawing for the Product Gas Condenser Flanges....................69 Figure 4...........1 Milton Roy Metering Pump Calibration Curves.....4 Comparison of Experimental Data and Model Developed by Dong [104] Component Yield vs.......... 61 Figure 4...................6 ....1 Figure 4............ 176 Flange Design Drawing for the Heat Exchanger Shell Flange .................. No . Figure 4.......... 62 Four Component Lumped Kinetic Model for Middle Distillate Thermal ........... .............67 Figure 4..................3 ..........134 Figure F........ Figure 4................ Residence Time at 462OC ..LIST OF FIGURES Figure 3...............71 Figure A.. Temperature for a Residence Time of 0......... Temperatures.....65 Cracking ........................................................68 Comparison of Experimental Data with Model Developed by Dong [104] Component Yield vs............................5 Comparison of Experimental Data with Model Developed by Dong (1041 Component Yield vs......Temperature for a Residence Time of 1s.. 166 Figure F...........

.... 02-22-0 1-04 .9 Filtered Data Experiment No ........................................... 02-2 1-01-02 . 02-22-0 1-02 ........................16-01-01 ...............-273 Unfiltered Data Experiment No ... 02-2 1-01-0 1 ................................................... ..........................02-22-0 1-04 .....4 Figure N.Figure N......02-2 1-01-03 ............... ................ ...2 Figure N. ....02-22-0 1-01 ...02...............266 Figure N.. .............. .......................... 270 Filtered Data Experiment No . 02-22-0 1-01 ................... ...18 Filtered Data Experiment No ..........-280 Figure N.. Figure N................................................. ............ ....16 Filtered Data Experiment No .........................285 ...................... ................................ 284 Figure N...................7 Figure N......1 (Filtering Not Required) Experiment 02...20 Filtered Data Experiment No ............................16-01-02 ..................................6 Figure N.....02-2 1-O 1-02 ................ -269 Unfiitered Data Experiment No ..............02-2 1-01-02 .. 267 Unfiltered Data Experiment No ............8 Figure N..... ..................15 Unfiltered Data Experiment No ....... 279 Figure N............ ...17 Unfiltered Data Experiment No ....10 Filtered Data Experiment No ..02............5 Figure N... ............11 Unfiltered Data Expriment No ......2 1 Unfiltered Data Experiment No .... 272 Filtered Data Experiment No ........12 Filtered Data Expriment No ........................ 274 275 Figure N . 02-2 1-01-02 ...... 278 Figure N........ Figure N ......19 Unfiltered Data Experiment No ................ 276 Figure N ....268 Filtered Data Experiment No .16-01-01 ................02-22-0 1-02 ...................02-22-0 1-03 .........02............. ... ................... 286 ...02-22-0 t -03 ................. 271 Unfiltered Data Experiment No ........... .. 283 Figure N.............13 Unfiltered Data Experiment No .....3 Figure N........ 277 Figure N ...................................281 Figure N ....13-0 1-0 1 Using Bulk Steel Temperature as the Controlled Variable .02...02-2 1-01-01 ............. 282 Figure N ......16-01-02 .14 Filtered Data Experiment No ............. ..... 02-2 1-01-03 ....

..... . .. .. 02-22-0 1-0 1 Simulated Distillation Boiling Point Curve .. ....... ... ..... Figure 0........................ 03-27-0 1-01 ..3 Experiment No. .. ... ..... .....-----.... ...... .-.-................. ...... .....~. .--....... .. .6 Expriment No...9 Experiment No...23 Unfilterad Data Experiment No.-........... . ........25 UnfIltered Data Experiment No. .... ............ ......-.. ........... .............. ..... ...296 Figure 0... ..... ..5 Experiment No... 02-22-0 1-02 Simulated Distillation Boiling Point Curve ASTM D2887 Extended Method .. .........-.. .--295 Figure 0..-... ... 03-27-0 1-02 ......-..-i m . ... . .-...1 Experiment No.... Figure 0............... ASTM D2887 Extended Method .... ..... ........4 Experiment No. r ..... 02-2 1-01-01 Simulated Distillation Boiling Point Curve ASTM D2887 Extended Method .... 02-22-01 -04 Simulated Distillation Boiling Point Curve ASTM D2887 Extended Method .8 Experiment No.--... ...22 Filtered D a t a Experiment No.... . ........ Figure N. .rim. .... ..... ......rim.. 02-2 1-0 1-03 Simulated Distillation Boiling Point Curve ASTM D2887 Extended Method . ..... .--.... a ............... ....... ...........24 Filtered Data Experiment No. .......... ............... ...16-0 1-02 Simulated Distillation Boiling Point Curve ASTM D2887 Extended Method ... .. ..-. 02-20-0 1-01 Simulated Distillation Boiling Point Curve ASTM D2887 Extended Method ... . .-. ...... .........-...... 02-2 1-01-02 Simdated Distillation Boiling Point Curve . . ...294 Figure 0... 02-22-0 1-03 Simulated Distillation Boiling Point Curve 299 ASTM D2887 Extended Method ............ .... ........ 03-27-0 1-01 ...... ..........-.. ... ... .. ........... Xlll ..--. ......... 292 Figure 0.. .-. 293 Figure 0......---.. .... .. . ...-.. ............ .. ....... ... ......... 287 288 Figure N.........7 -. 02.. .......-------..... ..... ..... 290 Figure 0......-.... ...---.. .. 289 Figure N. 03-27-0 1-02 . ASTM D2887 Extended Method .... ... ...2 Expriment No..... ..297 298 Experirnent No.... Figure 0.................... -.. .... ...... . ... .. .Figure N...

...11 Expriment No..Figure 0. ... ......... -301 Figure O. ... .. ..03-27-0 1-02 Simulated Distillation Boiling Point Curve ASTM D2887 Extended Method ....10 Experiment No... ............ ....... Faculty of Engineering Tar Sands Research Group ASTM D28 8 7 Extended Method . ............. . .. .................... .. ............. ..... 302 Figure 0...... ... ........ ... .... . . . ..12 Light Gas Oil Feed Boiling Point Curve University of Calgary......... . .. ..... .... ........ ... ... 303 xiv ..... .........03-27-0 1-01 Simulated Distillation Boiling Point C u ~ e ASTM 02887 Extended Method . ... .....

JI(mo1. m flange factor activation energy. rn equivaient diameter. in flange factor reactor diameter. in2 tube outside surface are& r n ' effective gasket seating width. J/mol friction factor frac mass fiaction of component . m2 frequency factor. in corrosion allowance. s" outside diameter of flange. m2 total required cross-sectional area of bolts.K) constant for turbulent natural convective flow reactor tube diameter. m bolt diarneter. in correction factor constant for laminar natural convective flow heat capacity of substance at constant pressure. in actual cross-sectional area of bolts. in2 flow area. in inside diameter of flange. m diarneter of helical coil. in bolt circle diameter.NOMENCLATURE AND ABBREVIATIONS cross-sectional area of tube. in2 root area of bolts for coarse thread series.

in local heat transfer coefficient. m theoretical bolt spacing. in reactor section height. r n total hydrostatic end force. lb. s-' thermal conductivity.flange factor gravitational constant. total outer joint-contact surface compression load. and I. in buik heat transfer coefficient. in flange factor radial distance fkom bolt circle to H . gasket load. in fluid mass flux. in thickness of hub at small end. tota1 joint-contact surface compression load. bolt spacing based on Nb. gasket load. m xvi . in radial distance fiom bolt circIe to outer gasket load reaction. W/(m-K) ratio of flange OD to ID reactor length.. rate constants. Ib. Ib. lb. in dif5erence between the flange O. w/m2-K radial distance fiom gasket load reaction to bolt circle. Ib.8 1 m/s2 thickness of hub at back of flange. kg/(m2s) gasket load reaction diameter. 9. outer gasket load.D. in heat exchanger shell length. w/(m2-K) hub length. in and d. lb.D..

psi mass flowrate. 8. w/m2 radial distance from bolt circle to intersect hub and back of flange. w/m' maximum power available. psig standard pressure.3 14 J/(molK) xvii . in-lb. component of moment due to HG. W heat flux. m heat exchanger tube length. W heat flux at the wall. psig MAOP based on flange dimensions and material. in universal gas constant.twisted tape flow length. . 101-325kPa heat transferred. in-lb. psig MAOP based on bolting pattern. psig reactor operating pressure. in maximum allowable operating pressure of vessel. order of reaction total number of bolts axial dispersion number design pressure. m gasket factor. calculation factor total component acting on flange at operating conditions. in-lb. inlb component of moment due to H .. kPa outside diameter of vessel. g/s nitrogen maximum mass flow. kPa atmospheric pressure. g/s calculation factor for operating conditions or gasket seating component of moment due to H.

psi calculated radial stress in flange. s tube wall thickness. psi calculated longitudinal stress in flange. psi calculated tangential stress in flange. psi maximum tensile strength of flange material at arnbient conditions. psi maximum tensile strength of bolting material at design conditions. K critical temperature. in 'as-built' flange thickness. . K flange design temperature. K standard temperature. psi maximum tenule strength of bolting material at arnbient conditions. K outlet temperatwe. 294 K fluid velocity. d s flange factor reactor volume. psi reactor residence tirne. K temperature with natural convection. K normal boiling point. O F inlet temperature. in assumed flange thickness. d s fluid velocity through the vapouriset. in flange factor temperatwe. rn3 xvi i i v. m3/min volume of gas evolved during reaction at standard conditions. m3 Vair volumetric flowrate of air at standard conditions.critical Reynold's number greatest total stress. psi maximum tensile strength of flange material at design conditions.

lb. m3 flange design bolt load for the operating conditions. J/mol-K differential pressure. psi mole fkaction of component twist ratio flange factor flange factor gas compressibility heat of vapourisation. minimum required bolt load for gasket seating. Ib. Ib. kPa Subscripts O initial concentration.flange factor volume of liquid. m a s hction gasket or j oint-contact-surface unit seating load. temperature. or pressure at tirne zero lower reaction section upper reaction section air linear average bulk 1 2 air coii cooling water gas oil feed l w gauge pressure product gas at reactor outlet xix . required bolt load for the operating conditions.

K" flange stress factor flange stress factor volumetric charge ratio. % friction factor for a straight tube friction factor for turbulent flow in a helical coi1 temperature rise per unit length of reactor. or ithexpriment in this study liquid 1 LGO liq mix nap surn of LGO and HG0 mass fractions product liquid extracted from condenser pots fluid mixture naptha component niîrogen outside dimension standard conditions reactor sensible heat heat exchanger shell straight tube nit O O r S shell str SW twisted tape wall W Greek Lerters a a flange stress factor thermal diffisivity.1 1 inside dimension ithcomponent in product gas or liquid. rn2/s coefficient of thermal expansion. K/m flange stress factor P P Y r 6 E 6 0 .

W/(mK) fluid viscosity.inclination angle residence tirne. Pa-s kinematic viscosity.Webb-Rubin Cold Junction Compensation Chain o f Rotators Equation of State Gas Chromatograph Hydrocarbon Hydraulic Oil Inside Diameter ASTM BWR CJC COR EOS GC HC HO ID LGO Light Gas Oil Linear Solvation Energy Relationship Mu1 tiplexer LSER MUX MW Molecular Weight xxi . moVs correction factor A bbreviat ions ABC API Atoms and Bonds in the Conjugate American Petroleum Institute American Society for Testing and Materials Benedict. dynes/cm2 molar flowrate. kg/m3 surface tension. m2/s variable in pressure drop equation by Gnielinski [144] fluid density. s flange stress factor thermal conductivity.

NMR OD Nuclear Magnetic Resonance Outside Diameter ODE PHCT Ordinary DiRerentid Equation Peturbed Hard Chain Theory Peng-Robinson Pressure-Volume-Temperame Residence Time Distribution Statistical Associating Fluid Theory Supercritical Fluid Extractive Fractionation Soave-Redlich-Kwong Thennocouple Universal Quasi-Chernical Watet Column Wet Test Meter Correction Factor PR PVT RTD SAFT SFEF SRK T/C UNIQLJAC WC WTMCF Dimensionless Nwnbers De Nu Pr Pe Ra Re St Dean Nurnber Nusselt number Prandtt number Peclet number Rayleigh number Stanton number ~e-(d~lD~)O-' hL/k pCfi Re-Pr gp~Td3/va Nu/(Re-Pr) Reynold's number pud/p xxii .

speech and action derived by the confonnants fiom study of themselves.Mad. this present (and illustrious) lexicographer is no firmer in the faith of his own sanity than is any inmate of any madhouse in the land. The Devil S Dicfionav xxi ii . adj. instead of the Io@ occupation that seems to him to be engaging his powers he may really be beating his hands against the window bars of an asylum and declaring himself Noah Webster. AfTected with a high degree of intellectual independence. . It is noteworthy that persons are pronounced mad by officials destitute of evidence that themselves are sane. at odds with the majority.Arnbrose Bierce. unusual. not conforming to standards of thought. in short. For illustration. yet for aught he knows to the contrary. to the innocent delight of many thoughtless spectators.

Particular interest is. and have proven track records for . Sanford and Xu [425]. Both processes are described elsewhere. Although difficult to extract. Srinivasan and McKnight [464] and Trasobares et al. reliable lcinetic models for optimizing the thermal cracking.m. particularly the effect of asphaltene content on the yield of the desirable components . [140]. Nandi et al.coke. have been highly successfid in developing and optimising the heavy residuurn. Ozum et al. or 'bottom of the barrel'. [363]. and Suncor Energy Inc. [l 1. hydrocracking1hydrohPater and hydrogen donor processes for bitumedheavy oil upgrading. [262]. Companies and countries with the end goal of s a t i s m g the population's energy demand are constantly seeking new sources and methods of extracthg petroleum-based energy.CHAPTER ONE: INTRODUCTION 1. The choice of many refining companies when deciding on the type of heavy oilhitumen upgrading technology has k e n the coking technologies . Srinivasa and Sastry [463]. In addition. [346]. can be found in the papers by Deutscher et al. portion of the topped bitumen rnined fiom the sands. and oil sand bitumen have a requirement for accurate.eiadoe. Although not described in this thesis.fluid cokinghlexicoking and delayed coking (Dong 11041). Jeong [2 1O]. Abbas et al. shale oil.and the undesirable component . In this environment of increasing energy demand and economic growth. M e r information on visbreakhg can be found in the works of Conesa [72] and Giavarini et al. and has ken.1 Introduction According to Statistics£ltrend-2. 14881.naphtha and g?soil . Laxminarasimhanet al. a d o r hydrotreater units that upgrade the heavy oil/bitumen to a synthetic crude oil. [97].. petroleurn refiners processing heavy residues. conventional crude oil reserves continue to decline with each year as the energy demands for Canada and the world continue to grow (http:f/-. companies such as Syncrude Canada Ltd. in the development of Athabasca oil sand bihunen discovered in the early part of the 2om century. visbreaker. Koseoglu and Phillips [243].

2 operation and reliability (Fuertes et al. and Speight [461]). 1.2. Inherent dificulties do exist.2 Thermal cracking kinetics of heavy hydrocarbons Obtaining reliable and accurate kinetic models requires the inclusion of the thermophysical and thermodynamic properties and transport phenornena characterization of the system under investigation. although many researchers have developed techniques that will be described in more detail later in section 2. which are dificult if not impossible to define (Allen et al. Reduction of the complexity of the modeling can be achieved via the use of pseudo-cornponents or lumping. construction and . With more accurate intrinsic kinetic models.naphtha and gas oil . Selucky et al. commission. 13 Project Description Initially. and metai porphyrin complexes (nickel and vanadium. however. nitrogen. 14391 14401and Speight [46 1J). The text by Sapre and Krambeck [427] provides an excellent review of lumping in complex petroleum mixtures. Even with downstream hydrotreating and M e r upgrading. specifically). The complexity of the study becomes apparent very quickly. Nguyen and Watkinson [353]. Di Carlo and Janis [199]. Khorasheh and Gray 12291. [l 11. [132]. McCaRey et al. Although the design. Schabron and Speight [435]. for biturnedheavy oil feedstocks consist of millions of components. Mansfield and Barman [3 121 and Mehrotra [326] provided an excellent review on the various techniques. for the heavy feedstock that contains a high concentration of catalyst poisoning sulfur. the synthetic crude diesel fraction still falls short of the ASTM specification for cetane nurnber (Dong [104]). of which there are many references. construct.with the minimum sulfùr and nitrogen content. the coking operations c m be optimized to yield the desirable fractions . the primary focus of this thesis work was to design. 13201. and generate kinetic data from a pilot plant reactor system with a wide operating envelope with regards to bitumen feedstocks and flowrates.

modeling and conclusions are described in chapters three. and. A review of the pertinent literature on the topics encompassed by this project is provided in the following sections. experimental procedure. Much of the literature on bitumen thermal cracking kinetics and structural considerations applies only in that the review was a requirement at the onset of the thesis work. complete with the required utilities. . to determine the yield of olefins and naphtha at each temperature. The review of the various reactor types considered prior to the construction of the helical coi1 reactor is also provided to highlight the benefits of the reactor chosen for this project. in particular. Coker2000 reactor kinetics study and completed under the financial assistance of the Natural Sciences and Engineering Research Council of Canada. A sirnilar lumped reaction kinetics model to that employed by Dong [IO41 was used to calculate the kinetic parameters and the effect of temperature on the optimal production of naphtha and the minimization of low carbon number olefins. Detailed descriptions of the pilot plant. Al1 experiments were designed to obtain measurable quantities of the products of interest. Obtaining the necessary data and devetoping the ensuing model required the development of a pilot plant-scale reactor system. This work was initiated as part of the Syncrude Canada. four and five. the final step of operating with bitumen feedstock was never realized. A wide range in temperatures for a constant feed and inert gas I-lowrate was chosen for this study. For the purposes of reactor confirmation.3 cornmissioning of the unit was completed. Ltd. kinetic descriptions of the thermal cracking (pyrolysis) of Syncrude Canada Plant 18 Light Gas Oil (middle distillate) based o n data collected fiom a helical coi1 reactor becarne the secondary objective.

more detailed. in turn. increases with a more technologicaily dependent society. been applied to the problern of optimization and control of pyrolysis units used in the production of ethylene. highly theoretical models.ethylene. The importance of the thermal cracking of hydrocarbon feedstocks is becoming more apparent as our dernand for the main products . and Shah [442]). reactor design. the pnmary component in many important plastics. some resulting in seminal works on the subject such as the work by Kossiakoff and Rice [244]. These main olefinic products must be economically maximized. etc. and other monomers with the goal of minimizing the coking reaction (Abdulaev et al. [484] found that acetylene is a precursor to coke formation.CHAPTER TWO: LITERATURE REVIEW Hydrocarbon feedstock thermal processing has been the focus of many research groups for the past century. and heavy oiVbitumen structural characteristics. synthetic rubbers. Froment 11291. propylene. Plehiers et al. Tesner et al. Some older references are included for their significance as seminal works on the subject. . The following sections provide a detailed review of the most recent literature on the topics of hydrocarbon thermal cracking. Murata and Saito [342] compared the thermal cracking products of alkanes and alkenes and detemined that alkanes have a self-inhibition effect that the alkenes lack. 131. and new technologies that are closely Iinked with new kinetic models are achieving that goal (Heyndenckx et al.1 Thermal Cracking Kinetics The kinetic study of the thermal cracking of low carbon number saturated hydrocarbons has k e n studied extensively as a means of developing and testing new. [186]). etc. 2. [380]. butadiene. Simple psraffins such as n-butane and n-pentane were studied in the early part of the 2othcentury with the goal of producing a higher valued product or products (Frey and Hepp [128]). Some reseanihers developed highly theoretical models detailing the intricacies of bond scission and hydrogen abstraction. kinetic and thermodynamic modeling. whereas Pramanik and Kunzru [385] . These models have.

waste management. Due to their simplicity. thermal cracking processes have found widely varied applications . Di Blasi p8]presented results of wood pyrolysis in the heat transfer controlled regime. The environmental concerns that have become more focused in the present day have lead researchers to investigate the kinetics of the pyrolysis of hydrocarbon-based waste materials. Murphy et al. Mixtures of hydrocarbons are also of industrial importance. Shah et al. the effect of H2S surface treatment of the reactor wall on coking rates was presented with the rate data described by severity factor type correlations. oil shales. Haraguchi et al. 15641 conducted a kinetic study on a used tire particle and developed a cornprehensive twodimensional mode1 that includes both transport and kinetic phenomena. [434] investigated the effect of small amounts of oxygen on the cracking reactions of Cz to CI normal alkanes at 500°C resulting in both positive and negative effects on feed decomposition. [343] found that the aromatic content of the Iiquid products fiom the cracking of ethane and similar feedstocks accounted for 98+% of the total composition. and proposai that acetylene may be the required precursor to its formation. Doue and Guichon [105] also completed cracking studies in the C6 to C9 range and included branched alkanes with similar results as Shah et al. [443] investigated the coking phenomena during the cracking of n a t a n e in a tubular reactor with space times up to one second. Scacchi et al. and biomass. FinalIy.5 determined that ethylene was one of the coke-forming species in the pyrolysis of nhexane. adiabatic reactors using ethylene and propane to more closely sunulate industrial units. Yang et al. 11741and Koyama and DranofF [250] completed modeling studies employing non-isothermal. Applicable to this thesis is the study of wood particle pyrolysis of sufficiently small particle size that the kinetic regime is controlling. [443]. i n Shah et al. Albright and Marek 1 9 9 1 detennined that reactor geometry and various metals catalyze the undesired coking mction. cod. [443]. Biomass pyrolysis is another area of environmental interest. confinning that secondary reactions invalidate the simpler pyrolysis . and the shidy of binary and temary mixtures of light hydrocarbons gives a preliminary look at the complexity that is inherent when modeling thermal cracking of the heavier hydrocarbons (Froment et al. 11301).

Results obtained match well with the complex reaction scheme developed. and modeled the results using a fkst-order kinetic model similar to the model by Dong Cl041 for light gas oil. in a fluidized bed (Sarnolada and Vasalos [42 Il). Orfao et al. cracking mechanisms. [198] studied the pyrolysis of canola oil in the presence and absence of stearn at temperatures and space velocities sirnilar to that used in this thesis and by Dong [104]. Fookes et al. and can be applied to the shale pyrolysis directly or to the produced bitumen pyrolysis. and a cone reactor (Wagenaar et al.6 models. but is only applicable to oil shales of the sarne kerogen type. Skala et al. Used oil recycling is also of concem fiom an environmental viewpoint: Kress [253] provides an overview of thermal cracking applications in the used oil recycling industry. As reactor technology improved.with results similar to Di Blasi [98]. fluidized bed pyrolysis of oil shale particles proved to be an effective apparatus for the study of vapour phase cracking kinetics studies as evidenced by Carter and Taulbee [59] and Levy et al. Koufopanos et al. Udaja et al. and described an extemal to intemal alkene ratio that couid be useful for the indication of coking vs. Other applications of industrial importance include the thermal cracking of oil shale kerogens to bitumen. Extension to middle distillate cracking is a good possibility given that the feed W C ratio is similar. 14531 described a highly complex kinetic model for the non-isothermal kinetics. Idem et al. [516] [Slv). [ 1231 proposed three causes of shale oii alteration when the shale oil is thermally . Other authors have studied wood pyrolysis in pellet form (Hastaoglu and Berruti [175]). [359] pyrolyzed lignocellulosic materials in nitrogen and air. [499] studied shale cracking kinetics using a moving bed reactor. 12461 [247] determined that biomass particles of less than 1mm in diameter would be considered controlled by pyrolysis kinetics and provided both transport and kinetic phenomena models for larger particles. Behar et al. [35] developed a unique model for the secondary reactions. McKee and Lyder [322] provided an authoritative description of oil shales and the challenges faced by cesearchers at the beginning of the 20Ihcentury. The produced biturnen is then pyrolyzed in a secondary reaction scheme to the products typical of synthetic crude. [274].

determining that at high temperature and low pressure. Williams and N d [545] presented a very detailed study of the polycyclic aromatic compounds in the products fiom fluidized bed pyrolysis of oil shale particles in the temperature range 400-620°C. Mushrush and Hazlett [344] hypothesized that long. Coal is also of industrial importance. with recoverable oil reserves declining worldwide. [85] investigated the secondary reactions associated with the heavy oil recycle process in oil shale pyrolysis and developed a four component lumped model similar to that used in this thesis. Wen and Yen [534] and Luss [300] provided excellent optimization studies on the pyrolysis of oil shales with the goal of maximizing pyrolytic bitumen. These authors used nine model compounds to test the hypothesis. However. Shih and Sohn 14461 described a mathematical model for the pyrolysis of a large oil shale particle. coal is again gaining popularity as an ' Theory based on the isomerization reactions occuring at a higher rate than the decomposition rates.Su and Yang [471] presented sirnilar results to Dogan and Uysal[100] for similar particle size and temperature range. In this model. However. the resulting products were best modeled using the FabussSmith-Satterfield theory2 (Fabuss et al. Dave et al. 1421 developed four models of varying complexity to adequately describe the twoet a step oil shale pyrolysis under investigation.7 cracked. 11171). Rates of decomposition were also found to change at critical temperatures (-300~~).6mm) in a temperature range equivalent to this thesis and detemineci that first-order kinetics fit the data. the authoa incorporate intrinsic kinetics for the decomposition of kerogen with the heat transfer effects inside the particle that is rigorous and more accurate than the shrinkingcore model. the ~ossiakoff-Rice'fiee-radical mechanism was valid (Kossiakoff and Rice [244]). Bissel1 l . Dogan and Uysal[100] pyrolyzed small oil shale particles (Q. and presented a method for diagnosing the oil yield loss due to cracking in the shales. although its importance has waned in the latter half of the 2othcentury due to the exploitation of less expensive oil reserves. . Much of the focus of this paper was on the coke formation-promoting sites on shale ash and sand. at low temperature and high pressure. unbranched alkyl groups are one of the main components in shale crudes. The compounds detemiined are very similar to that found in the middle distillate used in this thesis. 'Theory based on the pyrolysis reactions proceeding according to a molecular mechanism.

Savage [430] provided an excellent description of the use of model compounds to sirnulate the thermal cracking of more complex hydrocarbons such as asphaltenes.8 alternative for hydrocarbon-based hels. and n-hexadecane. Thermal processing of coal tar pitch and cod solutions is a more common method of extracting more saieable products from the coal. Li and Nelson [276] described the reaction pathways of aromatic ring systems based on the thermal cracking of coal tars in a fluidized bed reactor at 400-700°C. Detailed theoretical studies on the pyrolysis of model compounds are provided in Zhai et al. but have linle applicability to this thesis work and will not be reviewed here. but are beyond the scope of this thesis.C20and compared the detailed model with other literatwe data with good agreement. In an early paper on higher parafin thetmal cracking. iso-dodecane. These papers are very comprehensive. these engineers and scientists gained substantial insight into the reaction mechanisms of more complex feedstocks. Blouri et al. and Bounaceur et al. Voge and Good [5 131 thermally cracked n-dodecane. researchers began to investigate the thermal cracking of heavier pure hydrocarbons. Julien et al. Correlations are provided for the C dCJ2carbon number range. and . 1431 studied the pyrolysis of n-tetracosane. The primary goal of the study was to determine devolatization rates of each coal type. There are many references to work in the areas of coal liquefaction kinetic models (Rantell and Clarke [392]). 6-methyleicosane. [49]. [572]. Building on the reaction network models developed for the srndler hydrocarbons. high molecular weight hydrocarbons that are similar in molecular weight and other physical characteristics to heavy oils. Walter and Klein [523]. Liliedahl and Sj6str6rn [286] separately introduced a small quantity of four different coals into a micro-scale pyrolysis reactor attached to a gas chromatograph equipped with an FID detector. and compared the results with the kinetic model based on the radical chain theory with good results. 12141 studied l o w .the reaction rate decreased with decreasing rnolecular weight. and RTD studies are provided for the reactor. Woinsky [546] simulated the thermal cracking of C . Most notable is the effect of molecular weight on the overall reaction rate . Using complex.r d coal pyrolysis using I3c NMR studies and provided a simple kinetic model describing semicoke formation and gas evolution.

Most notable in this p a p a is the assertion that steam does not affect the product yield and quality. Although the authors stated clearly that the TGA technique carmot clearly describe the kinetic mechanism. and the product compositions agreed well with that predicted by the fiee radical theory. [252] published a theoretical paper on hydrocarbon pyrolysis with a focus on detenninistic models. 12651. Kopinke et al. [366] provided a kinetic analysis of the pymlysis of long-chain polymen using the thermogravimetric technique. researchers used n-hexadecane as a model compound coupled with the of use steam instead of nitrogen to more closely resemble industrial cracking furnaces. and theoretical papers on the subject can be found in works by Belohlav and Horak [3 81 [39] . high pressure. [93]. [479] developed a detailed reaction mechanism for the decomposition of normal alkenes. Parameswaran et al. and Van Damme et al. The literature on the thermal cracking n-hexadecane is extensive. As a close approximation. [242] completed similar work as Tanaka et al. [479] with the exception that the eEect of vapourised sodium and zinc on the kinetics was also investigated. Kravtsov et al. Kumar and Kunzni [256] and Lee et al. the authors develop a dynarnic model that was able to describe the necessary kinetic parameters. The authors reported kinetic data similar to that for lighter hydrocarbons. Gerasicheva and Botinikov [1381 described the production of higher value a-olefuis fiom parafins of varying carbon nurnber. provided the reactor pressure is less than 3 atm: if the reactor pressure exceeds 3 atm. [507]. References to naphtha cracking results can be found in the works by Belohlav and Fiedler [37].9 dodecylbenzene in a passivated tubular reactor in the temperature range 550-700°C. Dente et al. [2411.10% of the fumace charge will be necessary to maintain the same product yield and quality as at atmospheric pressure. In addition. [44] studied other pure heavy hydrocarbons under low temperature. Korzun et al. Tanaka et al. Chowdhury and Kunzni 1 711. Many authors have chosen this alkane as it most closely approximates the complex naphtha cracking systems that are typically found in the European ethylene industry. and long residence time conditions with the intention of simulating visbreaking of heavy o h . Blouri et al. Bartekova and Bajus [33] employed a steam tc hydrocarbon . then a steam feed of 5. 13651. Park et al. Kumar and Kunzru [257].

provided a highly detailed model [95] with accompanying kinetic data 1941 using an Inconel 800 and a quartz tube reactor. and the reaction rate was substantially limited by the rate of k t transfer. the decomposition kinetics agreed well with the Fabuss-Smith-Satterfield mechanism. whereas more addition products are formed in liquid phase cracking. the authors . the studies by Wu et al. however. These authors determined that the fiee-radical theory is only applicable at temperatures less than 650°C. above 5% conversion. With application to industrial cracking furnaces. Depeyre et al. In a more recent paper. Khorasheh and Gray [228] conducted experiments l . Ford [132] deterrnined that at conversions of less than 5%. Furthering the work on liquid phase cracking. Fabuss et al. [528] presented results from batch-type n-hexadecane pyrolysis for 400-500°C. Doue and Guiochon [1051 reported an interesting observation that inert gas severely reduces the formation of alkanes during the pyrolysis of n-hexadecane. In a simple variation of the heated tube reactor. Results obtained indicate liquid phase kinetics is dominant as the temperature decreases. [547] presented a cornparison between gas phase and liquid phase thermal cracking of n-hexadecane. Vranos [5 141 used a heated plate with a constant purge of nitrogen to determine the decomposition of vapourishg n-hexadecane. also describe a kinetic model that is valid for a wide range of alkanes (CIO Closely linked with the studies on n-hexadecane pyrolysis are the studies on gas oil pyrolysis. The authors note that the amounts of coke were much less than that reported in the literature at that time. [Il61 investigated the thermal cracking of n-hexadecane in a flow reactor at 590-700°C and 200-1000psig. Unfortunately. Watanabe et al. Wu et al. [Il61 at lower temperatures and higher pressure and described a similar to Fabuss et a model based on the fiee-radical theory. The Fmt-order rate constants were also found to be independent of pressure. Although the quantity of these studies is not as extensive and the reactor .10 ratio of 3:1 at 700-780°C. In that paper. Results were similar to that obtained by convective and conductive coupled heat transfer. In the study.Czs). [548] 15491 investigated the effect of radiation thermal cracking. the authors determined that more alkenes are produced in gas phase cracking. branched chah alkanes formed that were not predicted by theory. this observation could not be explored fùrther in this thesis.

The model agreed well with experimental data. Henderson and Weber [183]. the overall order of decomposition. Despite the work on simple hydrocarbon systems and the development of detailed kinetic models as described in previous paragraphs. Su et al. The model best suited to the conditions of the study was the mechanistic. non-isobaric tubular reactor. (1891 [190] provided a study on the pyrolysis of gas oil using a feedstock of similar properties as that used in this thesis. The residence time in this work is similar to that of the work by Dong [104]. researchers have stniggled wi th developing a kinetic model that adequately describes heavy oil and biturnen system. [472] developed a simple kinetic model for the pyrolysis of a light gas oil of similar properties as that used in this thesis. The product collection train used in this thesis is based on that used by Geniesse and Reuter [136]. Zhou et al. The temperature and residence t h e ranges are also very similar. Tominaga and Kunugi [486] provided an excellent review of the thermal cracking of petroleum residues up to the early 1970's. Most notable about this early paper is the conclusion that an increase in reactor temperature of 17°C halves the time necessary to produce the sarne results at the lower temperature. [36] and Karacan . Hirato et al. Depeyre et al. Geniesse and Reuter Cl361 described pioneering work on the thermal cracking of gas oils. [575] determined that ethylene and aromatics are the primary coke precursors when themally cracking atmospheric gas oil at atrnospheric pressure. consisting of 138 reactions. 15061 thermally cracked kerosene using conditions similar to industrial units.II conditions not as applicable as n-hexadecane simply due to the complexity of the feedstock and the dificulty in developing a detailed kinetic model. descnbed in detail by Depeyre et al. with the resulting system of equations solved numerically for n. Illes and Hocvath 11 991 investigated the overall kinetic rate constants for the themal cracking of naphthas in a non-isothermal. and developed a sophisticated kinetic model with applicability over a wide range of temperatures and residence tirnes that is also applicable to this thesis work. the results presented are valuable for kinetic modeling. [96]. The model was based on nth order decomposition kinetics. Van Camp et al. [96] developed and compared several detailed kinetic models on the modeling of stearn cracking of atmospheric gas oil. Belgrave et al.

Parkash and . Coke production is more pronounced when thermally cracking heavier hydrocarbons. and developed a feed-specific correlation for thermal cracking reactivity. The results for the nonhomogeneous kinetic model agreed well with published results. The characteristics of the distillate product collected compared well with that predicted by first-order kinetics. Kawai and Kurnata 12241 employed model cornpounds similar to that described earlier to model the thermal cracking mechanism of heavy oil and the influence of hydrogen partial pressure. Billaud et al. The introduction of this parameter raised the order of reaction by a constant and negated the use of the Arrenhius Law in the rate equation. [240] used "C tracers to investigate the mechanisms of coke formation in the steam cracking of naphtha at 8 10°C with specific emphasis on the coke production for various reactor materials.12 and Okandan [22 1] conducted experiments on the pyrolysis of heavy oi l as it applies to reservoir engineering. The authors concluded that hydrogen partial pressure did not affect fiee radical recombination. Del Bianco et al. Takatsuka et al. Overend and Chomet [360] introduced the concept of tirnevarying rate constant as opposed to assuming first-order kinetics. [261] presented results of coke formation in terms of a function of the metastability of the colloid disperse phase and its transition from sol to gel. [478] employed kinetic lurnping strategies to develop an eight lump model for the thermal cracking of residual oil that has wide application in laboratory and industrial settings. but only described a semiquantitative kinetic model. Kopinke et al. Kemp and Wojciechowski [226] introduced an "Extent of Reaction Effect" for heavier mixed feed systems that included a catalyst. 0941 studied the thermal reactivities of eight vacuum residues and deoiled asphalts obtained by supercritical fluid extraction. 1901 studied the thermal cracking of petroleum residues using a batch reactor and long residence times. Liu et al. [41] studied the thermal steam cracking of vacuum distillates using a tubular reactor. whereas Laux et al. Heintz [182] provided a highly detailed characterization study of petroleum coke. The determination of coke formation kinetics is an important aspect in the optimization of naphthdgas oil production fiom heavy oilhitumen upgrading processes in order to minimize the negative effect on naphthdgas oil production rates and reactor reliability.

Lee [267] developed a theoretical model to describe the reduction of coke formation when additives . Wiehe 15401concluded that an induction period exists prior to the formation of coke during pyrolysis of heavy oils due to the separation of phases within the oil. 15631 focused on the non-isothermal kinetics.such as phosphorous compounds . [149] used statistical analysis on the data for the coke formation during pyrolysis of vacuum residues. Song et al. Hüttinger Cl971 developed a general theoretical model for the coke yield during liquid phase pyrolysis of hydrocarbons. Menendez et al. [426] also studied the mesophase behaviour of heavy crudes and its influence on semi-coke production: the mesophase king defmed as the intermediate solid-like phase that Forms just prior to the formation of solid coke during thermal cracking. [82]. Hall et al. and ranked the feedstocks on the basis of severe coking to low coking for residence times of 70-340ms at 8 15-943OC. 13971. [3O6J and Raud et al. fiom light naphtha to vacuum gas oil. the activation energies matched that of the . Lin 12921 described the effect of induction periods on the coke production in the thermal cracking of shale oils. [39 11 investigated the effect of operating conditions and various inorganic additives on coke yield for Athabasca bitumen. Leftin and Newsome [268] investigated the coking propensity of 14 feedstocks. Nohara and Sakai [356] studied the early stages of coke formation using mode! components as the feed. Dalai et al. and developed a new model based on those provided in the literature.are added to the heavy oil during pyrolysis. [330] also presented experimental work on the pyrolysis of coal tar pitches with similar results as found by Hüttinger 11971. Reyniers and Froment [40 11 presented a similar study on sulfür addition to reduce coke production. [460] and Yang et al. and found that coke yield correlated well with WC ratio and vanadium and nitrogen content. al1 with positive effects on the reduction of coke.13 Berkowitz 13671and SantarnariaaRamirezet al. [297]. 15631 presented similar data on five Chinese vacuum residues: although Yang et al. Magaril et al. The authors determined that butadiene was one of the main contributors to the growth of aromatic ring size. Three studies on the effect of coke production on industrial-scale cracking units and the kinetics of coke deposition that confirmed the lab-scale Findings are presented by Lott et al. Simulation results compared well with experimental results fiom the pyrolysis of coal tar binder pitch at 600°C. [169] [170] [171] [172] and Rahimi et al. Gracia et al.

[320 1. whereas Banej e e et al. However. and the parameters of the equation Vary linearly with the aromaticity of the feedstock. and k are constants. to use model compounds. The solution to the kinetic model presented is dificult and computationally intensive. It is far easier. Andersen et al. b. [2 151 used long residence times and low temperatures in the development of a detailed kinetic model for asphaltene coking. Savage and Klein [43 11 and Yasar et al. tailored to conform to the asphaltene structural probability density fiinction. 13961 confirmed the findings in Banarjee et al.000 species. and concluded that the models are only approximate due to the inexactness of the group separation. [565] provided detailed theoretical models based on Monte Carlo simulations that incorporated up to 10. Khulbe et al. [171 constnicted a high temperature/high pressure filtration system to achieve good separation of the asphaltene molecule. Kaganov et al. [32] determined that fmt-order kinetic descriptions are adequate. [272] [273] investigated the mechanism of coke formation by thermally cracking the component groups of the petroleum residue. Magaril and Aksenova [304] [305] built on the work of Levinter et al. - The Robertson curve is defined using the general form: y = a / [ I + e):p(b -akT)] where a. as presented by Jess [2 111. Asphaltenes found in large quantities in heavy crude oils and biturnens have been generally accepted by the oil indutry as one of the major precursors to coke production (Speight [46 11). [32]. [23 11 [232] determined that the dipole moment of the organic solvent used during experiments has an inverse exponential effect on coke production. however. Schucker 1436) recommends the use of activation energy distribution functions similar to that described by Lin et al. and is the preferred method for thermal cracking studies of the components of bitumen. Wakabayashi [5 181correlated coke yield versus temperature fiom the pyrolysis of topped crudes using the Robertson curve3 as a basis. Levinter et al.14 isothennal case described by Song et al. [460]. The coke yield correlated well. [272] [273] and presented a mode1 of coking kinetics based on a limiting concentration of asphaltenes. Raud et al. . asphaltenes are very complex high molecular weight molecules that are difficult to characterize.


hence coke production . have determined that the asphaltene content is a good indicator of coking propensity (Kirchen and Sanford [233]. respectively). but were only able to achieve analysis on approximately 60wt% of the bitumen sample (up to 700°C cut point). [390]. Boduszynski [46] also provided results of the characterization of an atmospheric residue up to a cut point of 760°C using short-path distillation. Ehrmann and Izquierdo [ 1 131 performed characterization studies on vacuum residues and asphaltenes using a Curie-point-like pyrolyzer coupled to a GC with a FID and FPD detector (hydrocarbon and sulhir detector. Satou et al. [473] extended the ASTM D2887 standard (ASTM [ investigate the fractions boiling above 538*C. [390] employed supercritical fluid extraction techniques to obtain 10 narrow cut fiactions of the 52S°C+ fiaction of Athabasca bitumen. which were then studied for the appearance of the mesophase under various conditions. [4411).16 kinetic model with a Gaussian distribution of activation energies to accurately describe the pyrolysis of heavy oil upgrader pitches with good results. Selucky et al.and asphaltene content of the fiaction. The author presents a detailed molecular model in the second paper of the series (Boduszynski [47]). [428] correlated the aromatic ring size distribution in heavy oil with the boiling point and molecular weight distributions generated from simulated distillation studies. [. [332] and Suzuki et al.2 Heavy OiüBitumeo Molecular Stmcture DeveIoping kinetic models capable of closely approximating the thermal cracking reaction mechanisms of complex hydrocarbons such as bitumen requires understanding of the complexity of the feed. [1531 reviewed the analytical techniques available up to 1989 and the work completed on heavy oil characterization. Gray et al.Michon et al. similar to Rahimi et al.Other researchers have also conducted coking studies with bitumen. Rahimi et al. and. 2. The authors described a direct relationship between mesophase formation .F75] determined the chernical structure of various oil sand bitumens using "C NMR and "C I . Z 1) to Subramanian et al. Hydrocarbons such as bitumen consist of many different molecule types: quantifjing the types in such a way as to adequately describe the fluid at a low cost that can still be meaningfbl for kinetic studies is dificult.

W C KH.and pst-thermal cracking. Alexander et al. Both research tearns proposed structural models. Sane et al. and cryoscopic measurements to obtain the necessary data required for the estimation of thermodynamic properties. [153] completed analyses on Middle East and topped Athabasca bitumen. The mode1 predicted the group concentrations within *20%. [205] and Gray et al.17 'H NMR spectroscopy. [420] conducted experiments on the diffusion of asphaltene within a catalyst pellet to infer molecular structure. Khorasheh et ai. Jain et al. whereas Calemma and Rausa 1541 studied the structural characteristics of asphaltenes using pyrolysis/GC/MS. [462] employed continuous distribution functions . Hayes et al. [13] charactenzed the vacuum gas oil distillates (360-525OC) fiom various Kuwait crude oils according to ASTM standards. and provided results that show there is little difference in structure characteristics. [1771 [1781 presented a cornparison of analytical rnethods that could be applied to bitumen characterization. Sportisse et al. Groenzin and Mullins [158] detemined the molecular diameter and weight of various asphaitenes fiom crude oil. Al- Zaid et al. Mojelsky et al. similar form to the UOP K factor. IR. [229] developed the Structurai Group Analysis technique to adequately charactenze heavy gas oils. aithough Suniki et al. [IO] focused on the characterization of distillable heavy fractions (u)50°C) using NMR. Modeling the structure of the complex heavy hydrocarbons is markedly more difficult than lighter hydrocarbons due the limitations of analytical chemistry tools and computational power required to compute the billions of combinations and permutations of molecular structure. Y a n g and Wang [562] used supercritical fluid extractive fiactionation to characterize heavy oils and residues. and corre!ates well with the residues studied. 13381 [339] presented the results of ruthenium (VIII) ion catalyzed oxidation methods to determine the structural details of asphaltene molecules from Athabasca bitumen. respectively. The which has a results obtained were used to develop a new characterization factor. The advantage of the technique employed is that a very detailed anaiysis of the n-alkyl chains can be completed without the aromatic carbons affecting the results. respectively. but requires a data set similar to that developed by the authors. (4751 presented more data on the structure of bitumen pre.

Goossens [ 1471 developed a predictive mode1 for determining the hydrogen content of petroteum fractions. utilized the more expensive Ru (VII1)-cataiy zed oxidation reaction analytical technique to determine the structural features of Athabasca bitumen that have the rnost effect on the thermal cracking reaction pathways. respectively. respectively. 14701. Holmes [1941. with a focus on the nitrogen compound distribution. Matsubara [3 171 proposed another statistical method based on pattern similarity and p ~ c i p a l component analyses with good results. [344] analyzed Utah and Athabasca oil sand bitumen. Another modeling method is the Monte Car10 algorithm proposed by Trauth et al.e. [558] and Mushrush et al. Le. inorganic minerals and diamondoids. These findings were confi~rmed by Kubo et al. [329] described a simple method of utilizing structural group fiactions as a means of quickly and cost-effectively approximating heavy hydrocarbon feedstocks for pyrolysis Wiehe [542] described a method of approximating residue macromolecules. Strausz [468]. [352]. and Strausz et al. Rudnick and Gaiya [417] and S d o r d [423] used thermal cracking and hydrotreating. The authors found that the heaviest sub-fractions consisted of primarily condensed polyaromatic ring molecules that were associated with nitrogen-based heteroatoms and nickel and vanadium porphyrin complexes. [573] investigated topped Athabasca bitumen to determine its core structu. to determine the structural and chernical changes pst-reaction. [489] and Neurock et al. using two building blocks and thermally labile bonds that correlated well with Conradson carbon residue values. The research teams concluded that the indole-type nitrogens . which then leads to coke formation. Other important aspects of the structure of biturnen are the hydrogen content and solids and heteroatom fractions. Vazquez and Mansoori [5 101 identified a number of procedures to assist in the detemination of the inorganic precipitates fiom petroleum fiuids . Zhao et al. however.18 based on fmilies of n-dkanes. n-alkylbenzenes. 12541. Both research teams conclude that the absence of hydrogen results in the domination of the condensation reactions to form aromatics. Strausz and Lowe [469]. Men'shchikov et al. and polyaromatics to accurately characterize the heavy fiaction of petroleum.g. asphaltenes. Yamamoto et al.

[447] described the vanadyland n i c k e i p o r p h y ~ complexes within petroleum residues. lumped analysis (Ho [19 11). To properly . 14901 would be recommended.19 were the most comrnon. the numerical method descnbed by Font and Fabregat [122] or Trnka et al. differential and integral (Ans [19]. but the primary methods are. Although the focus of the work by Kotlyar et al. and residence times. respectively. Shiraishi et al.Jain et al. [245] was on the separation of bitumen from oil sands. Reactor-specific modeling techniques are discussed for each reactor design considered in the next section. [204] presents a detailed description of a spreadsheet program that employs nonlinear regression methods to calculate the kinetic rate constants. Sieniutycz [449] [450] and Tsoi [493] proposed the use of variational or matrix f'unctions to describe the transport equations for the unsteady-state system within the reactor. Ma et al. For the system of ordinary differential equations that describe the pyrolyis of the heavy hydrocarbon feed. and suggested a method of removal. 13011 detennined the structures and concentrations of 100+ sulfiir cornpounds in the non-polar fiaçtion of vacuum gas oils.4 Reactors Design Evaluations From the onset. 2. Denbigh and Turner [92] and Hougen and Watson [195]). 11453 and Conesa and Font [72] describe an approach similar to that described in the text by Hougen and Watson [195] on the kinetic severity tùnction as it applies to oil s t e m cracking and polyethylene pyrolysis. activation energies. which accounts for approximately 73wt% of the total sulfur.3 Reactor Modeling Methods for the determination of kinetic parameters are varied. Golombok et al. pressures. 2. a good description of the inorganic constituents remaining in the bitumen d e r separation is provided. and fiequency factors as it applies to the thermal transformation of sedimentary organic matter to hydrocarbons. the goal of the experimental apparatus was to obtain accurate kinetic data over a wide range of temperatures. and non-isothermal data analysis (Vyazovkin 15 151).

and heat transfer and fluid flow have been described by Levey [271] and Amour and Cannon (221. Carrica et al.20 incorporate that kinetic data into an instrinsic kinetic model that would later be used in a hydrodynamic mode1 for fluid coking. [209] presented simulation results for the surface temperature oscillations on electrically heated wires supplied by alternating current.1 Wire mesh Initially. 2. this design was not considered technically feasible due to many disadvantages that will be described in the fol10wing paragraphs. the transport properties of the system would have to be known. However.4. the reactor hydrodynamics (if a flow type reactor were used) would need to be defined. The temperature deviations were significant enough to consider changing the apparatus preliminary design. One of the first challenges with properly designing a wire mesh reactor is the determination of the thermal conductivity and fluid flow of the wire mesh. Isothennality was also a requirement. Jeglic et al. [56] presented results of the electric field effects on boiling heat transfer. using direct current power would severely affect the thennocouples considered for the reactor. Chang [64] described the calculation of the porosity and thermal conductivity of wire meshes. [142] was considered as a possibility for thermal cracking studies. Finally. then the method of Malloy and Seelig [308] could be used to convert the non-isothermal temperature profile to isothermal. Additionally. the system would be required to handle feedstocks in the OAPI 15-50 range. such that two-phase flow patterns similar to that describeci by Frankwn et al. However. Hot wire probes could be applied as a replacement. however. using the calibration model provided by Wu and Bose [SSO]. [127] and other phenornena can be removed fiom the kinetic analysis. should the chosen reactor temperature be slightly non-isothermal. a wire mesh reactor similar to that described by Gibbins et al. but not a necessity. .

[328] and de Kee et al. if not impossible. [508] calculated the melting of an ice shell around a cylinder that could be extended to this problem. hydropyrolysis of tan (Guell and Kandiyoti 11631). When the liquid surface ruptures. the gas film pressure increases dramatically. to quanti@. and polyethene/polypropene l . However. However. The advantage of the wire mesh reactor is (Westerhout et a the high heating rates. A reactor of this type is constructed of two concentric cylinders. The structure of the flow strearnlines through the annular space between the two cylinders has been extensively studied under conditions of no axial flow and with axial flow by Gu and Fahidy [160] [16 11 [162]. with either the inner or outer cylinder rotating. transport phenornena effects will be negligible. [1881 and Jie et al.2 Taylor-Couette The second reactor design considered was the Taylor-Couette flow reactor. [1411. kerogen (oil shale) pyrolysis (Madrali et ai. [88]. It was concluded that the wire mesh reactor would not meet the requirements described at the begiming of this section. coal devolatization (pyrolysis) (Gibbins et al. and coupled with the small sample size. ultimately exceeding the surface tension of the liquid.21 The wire mesh reactor has k e n used for studies on. [303]). The surface tension of the bitumens could be predicted fiom the correlations provided by Mehrotra et al. 15361) studies at 300-900°C. 2. sugar cane bagasse pyrolysis (Drumrnond [108]). Vargas et al. Taylor vortices that form as a result of the . droplets of unreacted and partially reacted components leave the surface with the escaping gas. Once this temperature is exceeded. [2 121). Hindmarsh et al.4. The loss of unreacted or partially reacted liquid fiom the surface would be very dificuit. the additional complexity of the Leidenfiost point would make the problem solution unmanageable. but instead a thin film of gas foms in the annular space (Rohsenow [4 161). the most apparent disadvantage is the Leidenfiost point: the temperature at which the liquid is no longer contacting the metal surface. but the system would be difficult to control. Another disadvantage would be the inability to uniformly coat the wire surface and maintain that uniform thickness for the duration of the reaction. on the order of 5000 Ws.

However. . The concentric cylinder design was re-visited minus the rotating seal to detemine if such a system was technically feasible. RTD studies by Pudjiono and Tavare [386] confirm the assumption by Campero and Vigil 1551.Reynolds et al. [299]. Pant and Kunnv [364] investigated the stearn pyrolysis of methylcyclohexane in an annular tubular reactor of similar dimensions to that proposed for this thesis work. this reactor type was rejected based on the hypothesis that if the annular space was too small it would plug quickly with coke. The authors ernphasized that neither the reference time nor the equivalent reactor volume technique were used in evaluating the kinetic constants. Lundberg et al. provided the conditions set out by Molin and Gervais [340] have k e n met. derived the necessary heat transfer models for single-phase flow in the and Leung [225] annular space. and determined that each vortex could be modeled as a perfectly mked CSTR comected in senes to the vortex on each side. a very detailed model could be developed for the kinetic study of hydrocarbon pyrolysis (single phase only). the dificulty in constructing a high temperature mechanical seal capable of withstanding the conditions without fail rnakes this design technically infeasible. and if it was too large. Experimental data matched well with the first-order Heaton et al. Upon further consideration. [402] and Kays kinetic model. in which case the reactor could be modeled as a plug flow-type reactor. however. the temperature gradient would not be steep enough. however.22 rotating cylinder advance in the direction of flow (when axial flow exits). therefore the residence time of the reacting fluid would be dificult to determine. [ 1 7 9 ] . For specific conditions. 5 5 1 studied the axial dispersion of low Reynold's number TaylorCampero and Vigil 1 Couette flow. under the conditions of flow and temperature proposed. Coupled with the conduction equation of El-Shaarwi and Mokheimer [ I lSI. This is the main advantage of this reactor. there is little m a s and heat transfer between the vortices. there wouid be diffusion between the cells. Although few researchers have utilized this type of reactor for hydrocarbon pyrolysis studies and kinetic modeling.

if the batch reactor was made sufficiently small to negate heat transfer effects. the batch-type reactor proposal was shelved in favour of a coiled tubular flow reactor for reasons that will be explained in section 2. and non-negligible errors can result fiom such an assumption. Nauman 13471 discussed the errors associated with conventional residence time analysis . a tubular reactor will not achieve ideal plug tlow. Trombetta and Happe1 [4911 proposed an approximation method for analyzing kinetic constants and residence times that accounts for the transverse concentration and temperature gradients in the tubular pyrolysis reactor. Al1 kinetic models would then be constructed on the basis of a combination of secondary and primary reactions. such as that used for the Curie-point pyrolyzer apparatus. the heat transfer effects become significant.4 Helical Coil Straight tubular reactors have been the subject of much study. and. However.4. are a preferred choice of reactor when high temperature continuous flow conditions apply.4. however. The analysis. In addition.this process negates the possi bili ty of investigating the prirnary cracking reactions. the arnount of product collected would not meet the requirements of at least lOOmL of Iiquid product set out in the initial design parameters. like the batch reactor. is its simplicity of operation.4. the latter of which was most important to the industrial partner in this thesis. Finally.The advantage of the batch reactor is its simplicity. The advantage to applying tubular reactors. Researchers have worked around the problem of heat transfer effects by extending the residence times . based on the paper by Ishigaki and Goto [200]. Helically coiled tubular reactors closely approximate the ideal plug flow model due to the development OF secondary flows in the radial direction (Koutsky and Adler [249]). Thus. 2. In an early paper. unless the batch reactor volume is sufficiently small. as a result. can becorfie rather cornplex should the reactor not be able to approximate the ideal plug flow model.

[295]. ' and describes the tortuosity o f the flow in the tube . and van den Berg and Deelder [89] presented results of the measurement of axial dispersion in capillary coils. Although the theoretical works described above provide an excellent bais fiom which to understand the intricacies of secondary flow effects in helical coi1 flow. The results of the study by Kao [220] indicated that the secondary flow patterns became highly distorted when the ratio of curvature to the torsion approached unity. In an earlier paper. and Adler [492] presented a detailed mode1 with a numerical solution up to Dean numbers4 of 200 that compared well with literature data. Shetty and Vasudeva (4451 examined the effect of Schmidt number on the laminar axial dispersion in tube coils and presented a correlation to determine the effective dispersion coefficient. the predicted values did not agree well with systems with large Schmidt numbers. Daskopoulos and Lenhoff 1831 also presented data and a correlation for the determination of the dispersion coefficient for laminar flow in curved tubes.24 as applied to helical coils.low Dean numbers are characteristic o f laminar flow and highly detined secondary flow ce11s. Jr. the complexity of the problem formulation and subsequent solution is more ngorous than required for this study. and Truesdell. Yamamoto et al. Gennano [139] extended the Dean equations to helical pipe flow and compared the results with similar theoretical works on torsion effects in different systems of coordinates. however. Experimental data on the pressure drop in helical coils. 4 .and the correlations developed by the researchers presenting the results are the most easily incorporated into the analysis of the transport phenomena with the iowest overhead. Wang 15241 presented similar conclusions with the numerical solution to the Navier-Stokes equations. [557] experirnentally determined the effect of torsion on the flow in helical tubes. The results of van den Berg and Deelder [89] clearly show the minimization of axial dispersion in a coiled tubed. Ito [20 11 published one of the first works summarizing the Dimensionless nurnber that is characteristic o f helical flow: De = Re-(di 1 D ~ O . and determined a direct relationship between the torsion and the destabilization of the flow. such as that presented by Liu et al. Kao 12201 rigorously described the torsion effect on lamina hilly developed flow in a helical coi1 by numerically solving the full Navier-Stokes equations.

[559][560]15611 completed a similar study with the slight dfierence that the effect of substantial coil pitch was theoretically investigated. Rzaev et al. This work was shown to give results that were approximately 20 percent lower than experiniental results in the paper by Xin and Ebadian [556].heat transfer fiom the tube wall to the bulk fluid is enhanced over that of a similarly dimensioned tube. However. Rogers and Mayhew 14151 d s o presented correlations for detennining the heat transfer and pressure &op for turbulent water flow through a steam heated coil. Yang et al. Gnielinski [144] summarized the pressure drop correlations available in the literature and recommended the set of equations presented by Mishra and Gupta [333]as the most accurate for the widest range of operating conditions. [368]1 3 6 9 1 provided a numerical solution to problem of determining the laminar and turbulent flow and temperature fields in threedimensional parabolic flow based on the procedure described Patankar and Spalding [370]. due to the secondary flow characteristics of the helical coil reactor (Koutsky and Adler [ 2 4 9 ] ) . [IO71also described a rigorous solution to the laminar heat transfer problem in helical tubes. .2). although the correlations are only applicable in the low Dean number range (c0. Dravid et al. respectively. Patankar et al. with accurate results for the system studied. The problem of quantitfjing the heat transfer coefficient for various Reynold's and Dean nurnbers has been studied fiom both a 'fint-principles' and empirical viewpoint. Fortunately. [289]solved the three-dimensional parabolic transport equations to determine developing turbulent convective heat transfer and the laminar thermal entrance region for helical tubes. One of the largest influences on the kinetic mode1 is the heat transfer fiom the wall. Lin and Ebadian [287][288) and Lin et al. 1 4 191 presented correlations for single-phase incompressible flow pressure drop through helical tube coils. Seban and McLaughlin 14381 presented pressure drop and heat transfer correlations for the laminar flow of oil and turbulent flow of water in coils with a coil to tube diameter ratio of 17 to 104.25 experimental detemination of fiction factors for various flows.

[5>4] [SSS]. . Watanabe et al. Austin and Seader [27]studied the entry region velocity profile development for helical coils with viscous fluid flows. and provided a method of calculating the inversion point Many other research tearns have investigated pressure drop and heat transfer for Mo-phase air-water flow in helical tubes. [407]). Acharya et al. Srinivasa and Sastry [463] presented the results of experiments on the turbulent heat transfer for viscous gas-liquid flows in a tube coil using combinations of air-glycerol and air-water two-phase fluids. Whalley [537]. Kalb and Seader [2 171 presented the theoretical solution to the problem of viscous flows in tube coils. One of the considerations for the design of the reactor for this thesis is the effect of not only viscous flows. Il641 presented an excellent study on the effect of pulsatile 80w on the turbulent heat transfer in tube coils. al1 producing similar results (Xin et al. Banerjee et al. that indicate a separation of the phases for increasing length down the tube. Guo et al. Chen and Guo [66] and Herm-Stapelberg and Mewes [185] presented the results of. three-phase air-water-oil emulsions flowing through straight pipe and helical coils. In a more comprehensive study. Finally. Manlapaz and Churchill 13 111 provided an excellent review of applicable correlations for fiilly developed laminar forced convection heat transfer. respectively. and presented an accurate correlation for the nurnber of degrees around a pipe coil must be traversed before the establishment of fully developed curved-pipe flow. for pulsatile flows are typical of the metering pumps used in this thesis. [6] and Kalb and Seader [217] investigated the thermal entrance length for helical tubes and provided experimentd data to support the developed models. Guo et al. Rippel et al.26 Al1 the theoretical papas descnbed provide numerical results only and are not compared to experimental data. [32] described the gas velocities at which the liquid film would invert in the tube due to the secondary flows of the vapour. 11641 determined that the effect of pulsatile fIow is significant and presented correlations for the average Nusselt number calculation for both steady state and pulsatile flow conditions. but also two and three and phase flows that would result fiom liquid phase experiments with a helical coil reactor. [529] 15301. and relations for.

[448] presented data and a mode1 on particle velocities of air-coal mixtures in vertical helical coils. [422] presented RTD studies on air-water and non-Newtonian suspensions. 136 11 presented experimental results of the forced convection boiling of water at near atmospheric pressure. [433] and Sandeep et was there that the vapour flowrates were too low to properly correlate with the remaining data. Kaji et al. The RTD for the helical coil was found to be nmower in the helical coil than for the straight tube. respectively. 5 . and correlated the average Nusselt number and fiction pressure drop values with the ~ a r t i n e l lparameter. [n the work by Sandeep et al. i~ The exception to the correlation presented was where the nucleate boiling regime existed .27 With the consideration of multiphase flow in the helical coil. the authors compare the RTD for the suspension flowing in a vertical helical coil with the same suspension flowing in a straight tube of identical length and tube diameter. parameter used widely in the calculation of two-phase flow pressure drop and is defined by the following: X = [(d P/dz). heat transfer and pressure drop for boiling flow within the reactor proposed.7mrn tube. Owhadi et al. [422]. D191 investigated the condensing heat transfer and pressure drop characteristics of refngerants passing through a vertical helically wound 12. Jayanti and Hewitt [208] developed a set of equations to predict the onset of nucleate boiling. and presented correlations for both the heat transfer coefficient and the pressure drop. Saxena et al. where the mode1 has its basis in the saltation velocity correlation for straight pipes. Rzaev and Filatov [418] developed~correlations for the deterrnination of the heat transfer coefficient fur low to high pressure boiling flow in helical coils. 1 (d P/dz)d]"( l D) where the term 'dz' is the differential eleinent along the length of the tube. [216] and Berthoud and Jayanti [40] studied the phenornena of dryout in het ical coils and presented a correlation and 'dryout maps'. and the critical heat flux for coils. Shu et al. respectively. the next consideration would be the deterrnination of residence time. point of net vapour generation. Finally. In an early paper on the subject. Kang et ai.

[134] compared various nonlinear equation fits that could be applied to the analysis of kinetic data using the differential method. would then be collapsed ont0 a single line for analysis. 1211). Another method is the kinetic polynomiai technique described by Lazman and Yablonskii found in the text by Ans et al. developrnent of a kinetic network model to describe al1 the species and interaction would be an impossible task with very M e benefit Feinburg provided an excellent review of the state-of-the-art in chemical reaction network theory up to 1991 (Aris et al. Another method of kinetic modeling is termed "lurnping" . Petzold and Zhu [378] described an optimization technique to simplify the large . Galaviin et al. Using the method of lumped pseudocomponents.the division of the feedstock into pseudocomponents that are treated as a single molecule with the themodynamic and thermophysical properties calculated based on the correlations described in section 2. Blowers and Masel [45] proposed a unique application of quantum mechanical calculations and Buckingham potentials with the kinetic data. though.5 Lumped Component Kinetic Models Given the large numbers of molecule types within heavy oil and biturnen. Generally. using a stochastic technique similar to that described by Marcoulaki and Kokossis [3 141 or the adaptive model reduction technique of Briesen and Marquardt [SOI. Wang and Homiann [526] descnbed kinetic modeling fiom a qualitative viewpoint. the treatment of kinetic data and derivation of the reaction rate equations becomes a manageable task. data sets of the size required for neural network modeling are not available.7. The importance of considering thermodynamicl effects in the development of the kinetic model is emphasized in Section 2. 11331 used computer neural networks to model complex kinetic schemes fiom a very large data set.2. such that the activation energies for a series of hydrocarbon reactions. Garcia-Ochoa et al.6 and by Holiastos and Manousiouthakis [I93]. [21]. Happe1 and Sellers [173] presented a method to characterize a complex reaction system based on the initial definition of the elementary reactions. stressing that the model should represent the data not the mechanism. for example. There is also the advantage of the ability to optimize the reaction mechanism.

Ranzï et al. Farkas [120] generalized the result of Hutchinson and Luss 11961 in this theoretical work. [126] presented an automatic method for reducing the number of p h a r y reaction equations. and tested the mode1 using the combustion of a single. and detailed a 10-lump model for fluid catalytic cracking that is also descnbed by Jacob et al. Weekman [532] provided the first comprehensive survey of the application of linear lumping analysis in kinetic modeling. the only di fference k i n g the number of lumps was reduced to five fiom 10. although there are different mecfianisms for aromatics as described by Kirk and Sorensen [234]. Lee [266] described a procedure to synthesize and analyze a kinetic structure for a system of irreversible firstorder reactions. [203]. partial oxidation. An example of both types of analysis to a system of many paralle1 fvsforder reactions is provided by Hutchinson and Luss 11961. LI871 to generate several hundred rate equations for the thermal cracking of a light hydrocarbon. [16] also developed kinetic models for fluid catalytic cracking. [553] employed density functional theory equations to develop a detailed model of the thermal cracking of a light hydrocarbon. [1871. or lumped component descnbed by group contribution theory. respectively. In a series of theoretical papers. or non-linear lumped component. The authors summarized the results in terms of three main steps in the thermal cracking mechanism. and combustion. Li and Rabitz [277] [279] [28 1] rigorously derive the equations necessary to describe approximate lumping analysis. or continuous mixture. pure hydrocarbon. Xiao et al. pyrolysis. after which the authon described algorithm to calculate the fiequency factors and activation energies. Ancheyta-Juirez et al. [393] also provides an exhaustive explanation of lumping procedures for the kinetic modeling of gasification. Fournet et al. Willems and Froment 15441 used a similar technique as Hillewaert et al. Sapre and Krambeck [427] presented an excellent summary text on describing a complex chemically reacting system using either lumped component. Pioneering works in the study of lumped component kinetic models using exact and approximate analysis was completed by Kuo and Wei 12581 and Wei and Kuo [533].29 numbers of rate equations that can be generated based on fiee-radical theory through the use of computer code similar to that described by Hillewaert et al. general lumping analysis of a .

Nigam and KLein [355] applied lumping analysis fbndamentals coupled with a quantitative structure-reactivity relationship constraint to the modeling of heavy hydrocarbon pyrolysis. Li and Rabitz [280] modified the constrained lumping schemes fiom a previous paper to be applicable for the non-isothermal case. . and demonstrated the infiuence of radical behaviour on product selectivities and apparent kinetics. Quann and JafSe [429] described a mode1 system very similar to Nigam and K l e i n [355]. provided the criteria for non-isothennality is met. Robbins et al. [409] demonstrated the differential and integral methods using non-linear least squares regression. The numerous papers of Urbanovici and Segal [500] [50 11 [502] [503] [504] detailed the determination of kinetic constants fiom non-isothermal data using classical and non-classical techniques and constant and variable heating rates. Should the reactor system produce kinetic data while operating non-isothermally. and constrained lumping. respectively. and compared the resulting kinetic parameters with results fiom isothermal experiments with good agreement. the method of Malloy and Seeling [308] could be used to determine the equivalent isothermal temperature. Savage and Klein 14321 incorporated lumping strategies into their detailed study of pentadecyibenzene pyrolysis. Martinez [3 151 and Coxson and Bischoff [79] [80] also provided rigorous mathematical descriptions of geneml lumping analysis. Agrawal and Sivasubramanian [7]. The example provided was based on the processing of polymer melts. If the non-isothemality is such that an equivalent isothermal temperature cannot be determined.30 reaction system coupled with diffwion. Li 12751 and Popescu and Segal13821 [383] proposed an integral method of analysis and described in detail the necessary approximations and assurnptions and errors associated with those assumptions. Nauman [347] described the solution of kinetic models in terms of the thermal time distribution and its relationship to the residence time distribution. The Mobil 10-lump cracking mode1 described by Weekman [532] was used as an example. there are several methods of analyzing the data to obtain the kinetic parameters.

The model provided good cornparisons to the data. first-order. Astarita and Ocone [24]. lumped kinetic models for the unconstrained and constrained lumped cases. [282] and Tomlin et al. Li et ai. The model agreed well with the experimental data. respectively. 12371 also applied the theory of continuous mixtures to the hydrocracking of asphaltenes. 2. and then use asymptotic solutions for the rate constants. [505] applied identifiabilit. Alberty [8] illustrated the power of coupled thermodynamic and kinetic models in fülly describing a constant temperature and pressure reaction system consisting of polycyclic aromatic hydrocarbons. [285]. Koukkari et al. non-linear lumped kinetics models. Biturnen mixtures wouid be a good exarnpk. thermodynam prïnciples must be included to descnbe the molecular and phase changes that occur.6 Thermodynamics To adequately understand the mechanisms of thermal cracking. Wiehe [54 11 presented a solvent-residue phase diagram for determining the extent of residue conversion. nonlinear. described by Liddell et al. would be to construct the kinetic mode1 assurning non-linear reaction kinetics. 12481developed a method to combine the overall reaction . Kodera et al. Li and Rabitz [278] presented a rigorous solution to the exact. Krambeck [25 11 proposed a detailed thermodynamic and kinetic analysis to hilly explain the phenornena occurring in polymerization systems. McCoy [321] applied the theory of continuous mixtures to the pyrolysis of coal in a flow reactor. the reaction scheme is generally assumed to follow first-order kinetics.31 When thermally cracking heavy hydmcarbons. where the fluid in question is so complex that the number of pseudocomponents required to accurately define the physical properties gives an wunanageable result. Vajda et al. analysis to determine qualitatively and quantitatively the uniqueness of the parameters fiom the solution to the set of differentiai equations. Astarita [23] and Chou and Ho [69] 1701 provided a framework for the determination of kinetic constants when the lumped components are defined by continuous distribution functions of concentration. 14871developed a general analysis procedure for the first-order. Aris [20] discussed kinetic modeling in tems of continuous mixtures. A better approximation.

a review of applicable thermodynamic models was necessary. The authors noted that due to the vapourisation of the coal liquid. The reaction scheme was asswned to follow the Arrenhius rate law. Given the complexity and colloidal nature of the feed (Li et al. [459] compared the PR EOS. Walas [52 1 ] recommends against the use o f the PHCT EOS for the assumption o f rigid spheres is often unrealistic. Andersen and Speight 1181.32 kinetics with the minimization of the Gibbs free energy. the P H C EOS ~ (a derivative of the PR EOS). Walas [521] and Speight [4615] are excellent texts on the application of thermodynamics to hydrocarbons systems. . Yermakova and Anikeev [567] used the Soave-Redlich-Kwong (SRK)equation of state (EOS) to model the multiphase processes in the Fischer-Tropsch synthesis reactor. the residence time of the s l m y changed significantly. and the COR' EOS to determine the best prediction of the PVT properties of 34 hydrocarbons. condensed polyaromatic species typical of the products fiom thermal 9 11 presented thermodynarnic probability cracking of hydrocarbons. De Song [86] [87] conciuded that the coke formation within a trickle bed reactor during heavy oil processing is strongly related to the vapour-liquid equilibria of the fluid at the catalyst particle. but only a qualitative analysis is provided. Finally. 7 Chain o f Rotators EOS has its bais in the van der Waals EOS but is rnuch more coinplex and contains many more parameters than the other cubic equations o f state such as the SRK or PR €OS. The COR EOS is not common in industry due to its computational complexity. thus the model allowed for the effect of temperature on the kinetics. [284]. Solimando et al. Demirel and Wiser 1 values for the conversion of multiring aromatics to isoparaffins and cycloparaffhs to detemine the optimal reaction conditions for the production of high-octane gasoline. Gopal and Shah [148] described the role of thermodynamic phase equilibria on the study of coal liquefaction kinetics. The COR EOS proved to give Perturbed Hard Chain Theory (also referred to as the Perturbed Hard Sphere EOS) is modification o f the van der Waals and Redlich-Kwong equations of state and assumes that the molecules o f the fluid arc rigid hard spheres. Stein and Fahr [466] examined the high temperature stabilities of many hydrocarbons to determine the thermodynamically favoured pathways that lead to large. Montel [341] also gives an excellent review of thermodynamic models for the reservoir engineering industry. Lam et al. [260]) and the possibility of the localized existence of vapourliquid and vapour-liquid-solid equilibria within the reactor (particularly for the TaylorCouette reactor).

Sim and Daubert [45 1] evaluated the procedures for predicting the vapour-liquid equilibria of undefined mixtures of light fractions. whole crudes. 13721 [373] [374] [375] compared the PVT predicted properties of heavy oils using the PR EOS and SRK EOS. Universal Quasi-Chemical equation o f state originally developed by Abram and Prausnitz as described in the text by Walas [52 11. and is further elaborated upon in the works by Wang et al. respectively. The authors concluded that the accuracy of the critical properties is crucial for good prediction of phase behaviour. 9 Statistical Associating Fluid Theory has its basis in statistical mechanics and is commonly used for simulating the thennodynamic behaviour o f complex polyrneric systems. This model was compared to a less detailed. as illustrated by Gregonvicz and de Loos [155]. The model compared well with bitumen-diluent systems measured at atmospheric conditions. Coutinho [78] developed a predictive UNIQUAC~ model for the description of solid-liquid equilibria in complex parafnnic hydrocarbon systems. and heavy residua to determine the best predictive model. Chao and Seader [65] derived a general correlation for the vapour-liquid equilibria of hydrocarbon mixtures based on Pitzer's modified correspondhg States model. Neau et al. whereas the PR and PHCT EOS's are described in detail by Walas [S2 11. James and Mehrotra [206] developed a multiphase flash algorithm for the prediction of vapour-liquid-liquid-solid equilibria for biturnendiluent systems.33 the most accurate prediction. 15271 and Pults et al. simpler model with negligible improvement in efficiency. with experimental data on various North Sea cmdes with good results. Sheng and Lu [444] used the volume-translated PR EOS to predict the behaviour of gas-bitumen systems with positive results. The authors found that the original SRK EOS gave the best prediction. Gregorowicz and de Loos [155] compared the predictions of PR and SAFT~ EOS's with liquid-liquid-vapour phase equilibria data. whereas the size of the error involved with the mixing rules terms has a minimal effect. Jaubert et al. The SAFT EOS contains an attractive parameter along with a molecular segment volume and number that i s coupled with the Boltzmann constant. The SAFT EOS has proven to be one o f the more accurate therrnodynamic models. Soave [457] coupled the theories of group solutions and cubic EOS to predict phase equilibna of highly non-ideal hydrocarbon systems. [349] and Pedersen et al. 8 . [207] performed detailed and costly NMR analyses on Indonesian crude oil and incorporated the data in the group solution/EOS predictke model. The correlation gave good predictions for hydrocarbon mixtures of alkanes through aromatics. 13871.

[298] developed a novel optimisation algorithm for the determination of multiphase equilibriurn. Heidemann and Fredenslund [l8 11 presented an excellent review of the application of cubic EOS 's to complex mixtures. Vidal [5 121 provided a summary of the application and limitations of cubic EOS's for chemical process design and reservoir engineering. and macromolecules in heavy oilhitumen systems. Gupta et d. Cotteman and Prausnitz 1771 based their model for flash calculations on continuous or semi-continuous mixtures of hydrocarbons. [52] and Chien [68] described a threephase algorithrn for the multiphase flash calculation in multicomponent mixtures. . and Lucia et al. Wiehe and Liang 15431 provided an excellent review o f phase equilibria. Jr. The component most often studied when researching heavy oil systems is asphaltene. Taylor [48 11 studied the electrodeposition of asphaltenes in residual oils and concluded that thermal treatment reduces the peptizing agents sumunding the asphaltene core. The stability of the asphaltenelresin system is important in al1 aspects of the heavy oiVbitumen upgrading process. Nelson 13511 formulated a rapid search algorithm for the determination of multiphase equilibria. Heidemann [180] and Olivera-Fuentes [357] presented procedures for determing the excess properties and fbgacity coefficients. [l 1 I l proposed themodynarnic consistency tests for the deterrnination of correctness of vapour-liquid equilibrium data. Cl671 and Rijkers and Heidemann [406] investigated the single stage flash calculation for criteria for optimal search algorithms and convergence. respectively. Zhvanetskii and Platonov [574] correlated the phase equilibriurn constants of petroleum cuts in ternis of volatility of the petroleum cut and constants for heptane and ethane.A requirement for understanding and applying the above models to heavy oilhiturnen systems is a grasp of the algorithms involved. [298] demonstrated the flexibility of the algorithm using model hydrocarbon systems. leading to flocculation. asphaltenes. The reduction of peptizing agents alters the electrical charge balance. Edminster and Robinson.[1661 developed a method for the phase and stability calculations within reacting systems and tested using a reacting mixture typical for methanol synthesis. Gupta et al. Bünz et al. Lucia et al.

Dukhedin-Lalla [IO91 stated that the mixture described previously closely resembled the whole biturnen and the criticai temperature of ndodecane was in tempera2. and compared the data to the PR EOS with favourable results. Thermophysical and Thermodynamic Properties In developing the reactor design and kinetic model for this thesis. The . and Yaws 15661. [192] reported on phase behaviour and solids formation in hydrocarbons systems. The most comprehensive publicly available databases on the subject of thennophysical properties for pure liquids and gases are presented in the texts by Reid et 13991. thus allowing for modifications to the reactor design to minimize or eliminate the problems associated with coke build-up. and will thus be summat-ized in the following paragraphs. Cartlidge et al. Cl251 developed an experimental apparatus capable to detecting the onset of asphaitene precipitation using electrical conductivity measurements. The model predictions compare favourably with field data Holder et al. Gray et al. [IO11 suggested a relationship between rheologicai properties . viscosity . Cl541 reviewed the problems of heavy oil property prediction and the pitfalls in EOS modeling. property correlations specific to petroleum and bitumen fractions and parent fluids are treated in detaii in the texts by Reid et al. The surfactants used in the study that exhibited the greatest degree of inhibition were the ethoxylated nonylphenols and hexadecyltrimethyl ammonium bromides. it was imperative that accurate correlations for the therrnodynamic and thennophysical properties of the feed and products be determined. 13771.i. Perry et al. Knowledge of the colloidal structure of the feedstock would give an indication of coking propensity. [399] and Perry et al. However. [3341 investigated the reversibility and inhibition of asphaltene precipitation in a Brazilian crude oil. [601 1611and Dukhedin-Lalla [log] described the complex phase behaviour of topped Athabasca bitumen + n-dodecane + hydrogen based on experimental observations.7 range of industrial bitumen upgrading processes.35 Mohamed et al. Fotland et al.e.of petrolewn residues and the col~oidal structure. 13771. For example. Victorov and Firoozabadi 1 5 11] proposed a therrnodynamic rnicellization model for the precipitation of asphaltenes using the PR EOS. Dolomatov et al.

[29]. [399] 1 0 . 13891 completed sunilar work using a two- parameter model that achieved good agreement with the literature on pure components. The models are applicable to pure hydrocarbons as well as undefined petroleurn fractions. With the varying feedstocks that would be typical of a reactor system as described in this thesis.1. and J. hydrocarbons. and refiigerants. Gomez 1146) described a simple correlation for the prediction of the viscosity of undefined hydrocarbon vapours that has been incorporated in this thesis. and are used extensively in the Appendices B. Results of the model for temary hydrocarbon systems of octane + tetradecance + hexadecane clearly show its superïority to corresponding states models such as that described by Moharam and Fahim [337]. and Twu 14951. Mode1 modifications for mixtures were not attempted. The theory is described in the text by Reid et al. Guo et al. Aboul-Seoud and Moharam [ 5 ] based their model for the kinematic viscosity-temperature behaviour of undefmed petroleum fractions on the Theory based on the assumption that the fluid consists o f hard spheres that collide at a rate proportional to a calculated radial distribution function. models capable of accurately predicting the viscosities of undefined petroleum and bitumen fractions and whole fluids are necessary.36 compilation of Yaws [566] is focused primarily on the correlation of the properties of organic and inorganic pure components using simple polynomial relationships. Xiang et al. The correlations available for the viscosity of hydrocarbons and their mixtures are extensive. [165] developed a viscosity equation of state model based on the three-parameter Patel-Teja and two-parameter PR equations of state. but has yet to be developed for mixtures. [552] presented a simple three-parameter viscosity-temperature correlation with applicability to nitrogen. thus enabling the model to be more predictive for hydrocarbon mixtures. developing a two-parameter model their new model on the ~ n s k o ~ with predictive capabilities but lirnited to pure organic liquids. Baltatu et al. GyH. Nhaesi and Asfour 13541 modified the McAllister three-body interaction model to a more generalized form. Chhabra [67] extended the correlation in Mehrotra [325] to include mixtures. Qun-Fang et al. Mehrotra [323] correlated 273 heavy hydrocarbons using a generalized oneparameter equation and is predictive in nature. Yücel and 0zdogan 15681 based hard " sphere theory. F.

Mehrotra [325] generalized a one-parameter viscosity correlation equation to include oil sand bitumens that have k e n diluted with light gases or liquids. Mehrotra et al. Wakabayashi [5 19] developed a simpler correlation of the kinematic viscosity of crude oil fractions that required only the specific gravity and molecular weight of the oil. and is accurate for the range 5-120°C. [520] and Rastorguev et al. Wakeharn et al. Eigenson [114] provides a model equation plus a nomograph for calculating the viscosity of sulfiir-containing crude oils typical of the oils produced in Western Siberia Miadonye et al. and concluded there was M e effect. Baltatu et al. [395] studied the effect of high pressure on the thermal conductivity of hydrocarbon mixtures. and provides results comparable to established and inorganic . simple correlation for the thermal conductivity of undefined petroleum and coal-liquid fractions applicable up to 500°C. [269] modeled the thermal conductivity of many compounds . Singh et al. [522] conducted viscosity measurements on various solvent-bitumen mixtures and employed the Cragoe equation to predict the experimental results. Amin and Beg 1141 developed a similar kinematic viscosity-temperature correlation based on measurements of 45S°C+ fractions of Arabian cmde oils that is applicable in the 100-200°C range. This model requires viscosity data as input.37 Walther equation. accurate correlation for crude oil fractions in the mid-boiling range 80-550°C and within a temperature range of 40-200°C. Burg et al. Comparisons with more complicated models show better results with the simpler model. Klaas and Viswanath [235] and Lei et al. Aboul-Seoud and Moharam [4] derived an accurate. Similarly. 133 1] and Wallace et al. 13351developed a simple.using a semi-theoretical approach. [452] presented a simple absolute viscosity correlation for bitumens and heavy oils that requires one viscosity measurernent to ensure accuracy. [327] determined that a two-parameter correlation was best suited to accurately predict the viscosity of various western Canadian bitumens and their fractions. however. Another thermophysical property that is necessary for the accurate modeling of the reactor system is the thermal conductivity of the fluid. Mohanun et al. 1531correlated the kinematic viscosity of cmde oils with data generated by gas chromatography and the LSER equation. [30] used a more complex .

hence only data is presented. The model required many more constants than that defined by Aboul-Seoud and Moharam 141 and gave less accurate predictions. Lin and Daubert [290] components to predict the activity coefficients for binary hydrocarbon mixtures. Teja and Tardieu [482]used the Effective Carbon Number method to predict the thermal conductivity of organic liquids and their mixtures for a temperature range up to 200°C. order of 20% lower than experimental values. G u ~ n et viscosity. and vapour pressure of several Venezuelan heavy oils and bitumens. Povarnin and Kurbandberdyev [384] and Teja et al. Similarly. Robinson [410]described a simple correlation for the thermal conductivity of Athabasca bitumens that predicts values on the h al. solubilities and dipole correlated critical constants and accenttic factors of pure moment. respectively. Latini et al. Obtaining the thermal conductivity of hydrocarbon vapour mixtures required the mixture rules developed by Lindsay and Bromley [293]. The thermal conductivities of the mumires were calculated using a quadratic mixing d e . 8 . [4l2] correlated . Soave [458] denved expressions for the critical constants of the C+ fiaction using the normal boiling point and specific gravity at 60°F. [168] evaluated the density. 1 4 8 3 1 employed the gened corresponding states principle to develop a complex model for the prediction of thermal conductivity and viscosity of petroleum products and coal liquids. [259]presented simple predictive models for the detemination of thermal conductivity and dynamic viscosity for heavy hydrocarbons for a reduced temperature range up to 0 .38 corresponding states method for the thermal conductivity of coal-liquid and petroleum hctions. normal boiling points. Riazi and Faghri [405] correlated liquid and vapour C+ hydrocarbons at low pressures to a simple equation based on the calculated values of three parameters. and in the case of crude oil fractions. Grigor'ev and Svidchenko [156] developed a method of calculating the thermal conductivity of consumer-grade petroleum products containing additives. Rogalski et al. The authors determined that a correlation could not be constructed that related the physical properties to the API gravity. the oil was divided into pseudocomponents. thermal conductivity. specific heat. Equally important in the process engineering of heavy oiVbitumen systems are the correlations that define critical constants.

Rochocz et al. [13 11 developed very sirnilar models for the prediction of petrolewn and coal-tar liquid critical properties. Riazi and Al-Sahhaf [404] proposed a generai equation for the calculation of many physical properties of n-alkanes and n-alkylhydrocarbons. [4 111 rigorously derived the expressions necessary to determine the critical constants for semi-continuous mixtures. enthalpy. and normal boiling point are other physical properties on which researchers have focused. such as petroleum fluids and bitumens. Dolomatov et al. [53 11 developed correlations based on nomal boiling point. accentric factor. 80th models are cornplex in the number of constants required. Gray et al. 12961 employs a unique approach to calculating the critical pressure of hydrocarbon mixtures by reversing the Reidel equation. Watanasiri et al. specific gravity. Twu [494] also included molecular weight determination in the model. Redelius [398] used a threedimensional solubility parameter model to refute the classical description of bitumen as a fluid consisting of a dispersion of asphaltene micelles and predict the stability of bitumens subject to various processes.39 critical properties with experimentally determined vapour pressure and density data. An equation of state-type relationship is recommended to calculate the liquid . Liu et al. and dipole moment of model coal compounds. The prediction of other properties such as density. and molecular weight to predict the critical constants. Zhou [575] defined correlations for the average boiling points of various petroleum fhctions using pseudo-critical constants fiom industry-recognized sources. [102] developed a relationship between specific gravity and Conradson carbon residue number for a number of vacuum residues. molecular weight. Extending the model. and is described in Ri& and Al-Sahhaf [403]. The authors suggest that the equation could be extended to heavy petroleum mixtures. Twu 14961 modified the BWR equation of state to give predictions for the thermodynarnic properties of alkanes while only requiring the normal boiling point as input. [15 11 [152] experimentally detemined the liquid density and other physical properties for coal tar liquids. Twu [494] and Fu et al. The resulting simple expression is applicable to pure hydrocarbon mixtures only. but are easily prograrnrned on a computer. The complexity of this model lends itself to application in the reservoir engineering field.

and recommends either the API method or the Kesler-Lee equation (Lee and Kesler [264]). be used as confirmation that the correlations used in this study are valid. and gas oïl Fractions which requires only the characterization factor as input. Walas [S2 11 is an excellent text describing many equations of state. St. and the best source of data and correlation parameters is found in Hepler and Hsi [184] for bitwnens and heavy oils and in the API handbooks for conventional crude oil fractions. [3 161. [119] tabulates the results of the vapour heat capacity measurements for various petroleum fractions. 13761presented the molecular weight and specific gravity distributions of various fractions of Athabasca biturnen. Moharam et al. but did not present correlations. Gilyazetdinov [143] developed a method for calculating the . however. Rao and Bardon [394] completed similar work by developing a correlation to estimate the molecular weight of gas oil fiactions using the ASTM distillation cuve and the specific gravity. the equation developed by An et al. in the opinion of this author. Enthalpy of vapourisation correlations have been developed for pure components. though not as flexible. [15] is superior to that developed by Xiang [55 11 and less cornplicated.40 density of heavy oils at a specific temperature and pressure. Cholakov et al. are limited simply due to the uniqueness of the fluid involved. The data could. such as described by Kokal and Sayegh [2381 and Mathias et al. kerosene. specific heat. Correlations and models for other properties. for these relationships best describe the complex fluid behaviour at the elevated conditions typical of a reservoir or processing operation. accurate method for calculating the enthalpy of naphtha. [465] or Wessel and Jurs [535]. [429]. [336] can be found in the paper by Lenoir and Hipkin [270]. Fang et al. and molecular weight. the normal boiling point of the fluid could be estimated in turn using the correlation developed by Satou et al. [103] and Peramanu et al. and. such as nomial boiling point. Liquid and vapour heat capacity data for petroleurn fractions is difficult to obtain. as that developed by Zabaloy and Vera [571]. A data set that can be used as check of the calculation method described by Mohararn et al. If the molecular structure of the fluid is known. Dornin et al. Altgelt and Boduszynski [12] developed correlations that related normal boiling point and molecular weight for atmospheric residue fiactions of heavy oil. 13361 presented a simple.

Abdoul et al. 121 to polycyclic heavy hydrocarbons by defining new groups and evaluating new interaction parameters. 12631 extended the mode1 developed by Abdoul et al. which describe the thermophysical and themodynarnic properties of the homologous series of hydrocarbons only. Kontogeorgis et al. This method should not be confûsed with the Asymptotic Behaviour Correlations of Marano and Holder [3 131.41 liquid heat capacity of petroleum factions using a summation of group contributions method. Whitson 15381 15391 described the effect heavier fractions of petroleum fluids have on the PR EOS. This method is specific to acyclic hydrocarbons and gives better accuracy than the group contribution method with less parameters. The method is valid for temperatures up to 200°C and heteroatom content not exceeding 10%. enthalpy. The calculated critical constants and accentric factor could then be used with the PR EOS to calculate various thermodynamic properties. Coniglio and Daridon [73] proposed a group contribution method for calculating the ideal gas k a t capacity. Coniglio et al. heats of vapourisation. . [76] developed the method of contributions of Atoms and Bonds in the Conjugate (ABC) f o m s of a molecular structure. Constantinou et al. saturated liquid heat capacities. and speed of sound in a large number of hydrocarbons. and Poling et al. with the exception that this method is specifically developed to determine the critical constants and accentric factor for heavy . [2] and Avaulle et al. [239] described a method for estimating the critical properties of heavy hydrocarbons up to a molecular weight of 394 using the group contribution method. saturated liquid densities. 1751 extended the method by developing group contribution parameters for the PR EOS. 1291 also developed a group contribution rnethod. Le Roy et al. oils. the method is able to adequately describe the vapour pressures. Although cornplex. [38 1] described a method for avoiding the trivial roots and spurious derivatives when determining themodynarnic properties using a cubic equation of state such as the PR EOS. and entropy of pure light hydrocarbons for wide temperature and pressure ranges.

ALI the models described below can be compared to the experimental data on vapour pressures and boilîng points of n-alkanes with carbon number fiom 2 1 100 presented by Kudchadker and Zwolinski 12551. Soave [456]. accurate mode1 for the calculation of vapour pressure and volumetric and thermodynamic properties. Smit 14541developed a highly cornplex Monte Car10 simulator to predict thermodynamic properties of long-chain alkanes. have been developed based on vapour pressure and extended to predict other physicd properties. although Zabaloy and Brignole [570] have raised concerns on the use of volurnetranslated equations of state. Coniglio et al. [412] used a modified version of the volume-corrected PR EOS to predict the vapour pressures of various hydrocarbons fiom the triple point to the critical point. and Bond and Dawe [48] proposed new expressions for the SRK EOS specific to heavy oils and petroleum fluids. [57] to more accurately calculate the therrnophysical properties of heavy hydrocarbons using the PR EOS. [497] developed a generalized vapour pressure equation for heavy hydrocarbons based on the Pitzer expansion described in the text by Walas [52i] that proved to be accurate fiom the triple point to the critical point for pure hydrocarbons up to n-C19. giving better extrapolation of vapour pressures below the boiling point than the original EOS. Chandar and Singh [63] applied the extended Smith-Winnick-Abrams-Prausnitz correlation to a large number of vapour pressure data points for nitrogen and sulfur heteroatoms. Jr. and Pitzer 198 1 developed a simple. Carrier et al. Maxwell and BonneIl [3 181derived a new vapour pressure correlation for petroleum fractions that has withstood much scrutiny and is - . [498] also extended the Twu-Coon-Cunningham cubic equation of state to better represent vapour pressures of heavy hydrocarbons and petroleum fractions. Wang and Gmehling [525]. Kudchadker and Zwolinski [255] also correlated their data using the simple Antoine fonn with excellent results. Cul.42 The vapour pressure of a fluid is one of the more important properties: numerous models. Twu et al. providing a sirnplified calculation procedure and better accuracy than the unmodified SRK and PR EOS's. Gareev and Arslanov [135] derived the equation for calculating the vapour pressure of hydrocarbon systems from a first-principles concept. Twu et al. 1741 modified the form of the temperature dependent parameter determined by Carrier et al. correlative and theoretical. [57]and Rogalski et al.

Zuliani et al.43 generally accepted by industry. The authors concluded that the Perturbed Hard Chain Theory gave the best fit. [577] measured Henry's constants for the light alkanes in mode1 petroleum fractions and compared the results to that predicted by various equations of state. Rogalski et al. . [4 131 reviewed the problems of developing equations to represent the vapour pressures of hydrocarbons and devised a general method for fonnulating the necessary equations.

Both nitrogen and partially vapourised feed then entered a comgated tube vapowiser that provided the heat flux necessary to completely vapourise and heat up the nitrogedfeed cornbined flow to close to the reactor temperature. Al1 glassware and tubing in the condenser train were cleaned with >99. where hydraulic oil was metered into the cylinder using two Milton Roy Mode1 No. 3. and product yield.'^ 007 128 and 006940) positive displacement metenng purnps. Although there is the flexibility to use a feed preheat section to reduce the heat load on the reactor (Dong [104]). In this study. the helical coil reactor was the best solution to satisQ al1 the requirements of flow. 920 15003 (serial no. and isothermal operation was assumed for the length of the reactor. 1 Experimental Apparatus The helical coil reactor designed and constructeci for the pyrolysis of heavy hydrocarbons is outlined in this sectioa A simplified schematic of the reaction system is provided in Figure 3. Once at the inlet to the reactor. residence time. Typical temperature rise rates were calculated to be 1400 Wm and 495 Wm. and was preheated in the nitrogen fumace to a typical setting of 35O0C.1 Process Overview As described in Section 2.1. Detailed electrical and process flow drawings are located in Appendix D.44 CHAPTER THREE: EXPEMMENTAL APPARATUS AND METHODS 3 .5% purity dichlorornethane (Anachernia Canada Inc. respectively (see Appendix B). the preheaters were not necessary for the flowrates used in this study. and afler the expriment to ensure that oxygen did not enter the system. Nitrogen was used as a purge gas for before.1. hydrotreated light gas oil &GO) was fed into the reactor via a hydraulic oil transfer cylinder.4. the gas entered a two-section reactor with different tube sizes in each section. . Detailed drawings for the process equipment are located in Appendix E.) after each experimental run and thoroughly dried. dwing.

1 Reactor System Schematic for Gas Phase Cracking Experiments .To Gas Sampling & y 'l Wet Test - Secondarv Condenser Demister Condenser Pot #I Condenser Pot #2 I Primary Condenser N2/Air Furnace Reactor Hydraulic Oi1 Reactor Feed Figure 3.

DM3C. a Parker Hydraulic Oil Accumulator (Model No. the amount of condensed product was minimized. The vapours then exited condenser pot #2 and entered the demister unit. the feed system was designed to accommodate widely various heavy hydrocarbons from n-hexadecane to biturnen. it was circulated through the holding tank prior to being transferred to the accumulator using a variable speed Moyno pump.2m iong single tube stearn heat exchanger with the glycol circulating on the shell side. Serial No. Model No. When steady flow was . Afier exiting the g l a s condenser. two. Steam pressure was maintained at satwated conditions at 200kPa. the vapours entered the second condenser pot. or three A R 0 diaphragm pumps (Model No. Once at a temperature at which the bitumen could flow. single tube heat exchanger before e n t e ~ the g f m t condenser p o t Vapours fiom the condenser pot #1 then passed through another water-cooled g l a s heat exchanger where some of the vapours condensed. 0456 10) wet test meter and periodically sampled using a 1. By angling the g l a s heat exchanger in the downward direction. A7K0578D 1KUUUU) with a 9500 mL liquid capacity was placed in a pressurized hot glycol bath heat exchanger. For handling the bitumen. The scrubbed gas was then metered using a (G H Zeal Ltd. 3 . 2 Feed Systcm and Utilities Due the requirements of feed flexibility. The hot glycol also passed through the copper coi1 of the open-air tank that was used to pump the bitumen to the accumulator without opening the system. 666054-444 (old number) 666057-444 (new stock number)). Hot glycol was circulated using one.2L environrnentally sealeC plastic gas bag supplier. The detailed drawing of the accumulator and glycol exchanger shell is provided in Appendix E. the system was designed for quick replacement of the coi1 should it be necessary. The glycol was heated using a 1. Although copper is not recommended for bitumen service due to corrosion problems. This unit consisted of a flanged glass vesse1 packed with cosmetic grade rayon andor cotton balls typically found in local pharmacy stores. 1 .The products exiting the reactor passed through a water-cooled.

the three-way valve was switched to direct the flow to the accumulator. The capacity of this transfer cylinder was approximately 2 100 mL. the Moyno pump pressurized the bitumen side of the accumulator suficiently to push the hydraulic oil to the hydraulic oil reservoir.Milton Roy Model No. Either the small transfer cylinder or the large Parker accumulator could be fed hydraulic oil from a combination of three positive-displacement hydraulic oil pumps.LINC electric chernical injection pump Model No.7mm).47 established.'s 007128 and 006940) metering units . the piston could not travel M e r . Again. A second transfer cylinder that was manufactured locaily was also used for relatively lighter feedstocks that did not require heating to easily flow. with the smailer transfer cylinder came the flexibility to flow the feedstoçk into the preheaters or directly to the inlet of the feed vapouriser.000 kPa. Once connected to the reactor system.Le.1 1 1.82 Lhr. A third hydraulic oil pump . a pressure relief valve was used as an indication that the transfer cylinder was completely full.the pressure increased until the relief valve downstream of the Moyno purnp opened and the bitumen flowed back into the holding tank.1 1-41 .4mm and 12.were used in this study. Finally. 86-1 2 1. 92015003 (serial no. All the pumps and process piping is capable of delivering the specified flowrates at also available. With the hydraulic oil system open to the recirculation loop. This transfer cylinder was of a similar floating piston design as the Parker unit with threaded caps for easy disassembly.02 L h r to 6. This pump has two different head sizes available (6. The latter setup was used in this study. When the bitumen side of the accwnulator was full . however. the system is protected using spring-type pressure relief valves for 700 kPa. the transfer cylinder did not have to be disassembled for via a vahing system that allowed for the transfer refilling: a vane pump was c o ~ e c t e d of the feed to the cylinder in the same manner as for the bitumen. Detailed pump specifications and calibration curves are located in Appendix A. . The smaller two pumps . which gives a flow capability range from 1. The maximum volume fiow the Milton Roy pumps can supply is 460 m L h per pump.

When the feed is introduced directly to the feed vapuiser. The nitrogen is fed fiorn a high-pressure gas cylinder fiom Praxair. Once an estimate of the preheater size was established. Detailed calculations for the heat transfer coefficient with the twisted-tape insert are in Appendix 1. Inside the 75mm stainless steel tube. a stainless steel twisted-tape was inserted to improve the heat transfer to the gas. If necessary. DB 1V-3024-FOS0 solid-state power relays used to reguiate the 120/240VAC eiectrïcal feeds to al1 heaters. The PID control loop was auto-tuned at the time of installation for a typicai nitrogen flow. M e r metering. the nitrogen then entered the bottom tube of a three-tube radiant heat-type furnace manufactured by Applied Test Systems Inc. Adequate sizing of the feed preheaters for widely varying feed types was difficult. and was the Ultra High Purity-grade nitrogen (99. A check valve was placed between thr: furnace and the mixing point to ensure hydrocarbons did not enter the îùmace. instead a general heat balance was used for design purposes. thus providing a theoretical power requirement specific to the feed type and flowrate. for changes in thermophysical properties would change the transport phenomena characteristics dramatically. [227].998~01%pure) that is widely sold. it is partially vapourised by the hot nitrogen gas that mixes with the feed upstream of the vapouriser. The nitrogen was metered using a Matheson Model No. The controllers described herein sent the 4-20mA signals to the Watlow DIN-a-mite Model No. a feed preheat section was installed to reduce the heat load on the inlet vapouriser. A simulation was not completed for this thesis. 7631T-604 variable area fiowrneter equipped with a g l a s and steel bail. After exiting the furnace. the preheaters #l and #2 were arranged in series and a Yokogawa UT350 controller was attached on each unit to separately control the power to the heaters. Contrary to design . the nitrogen was directed to the inlet of the reactor vapouriser where it mixed with the incoming feed. The temperature of the nitrogen is controlled using feedback control on the fumace power using a Yokogawa UT350 digital indicating controller. Solution of this problem would involve the development of a preheater simulation similar to that described by Khandhadia et al.

The valve w and the transfer cyiinder was attached at this point for al1 experimental runs in this study. Detailed drawings for each preheater is provided in Appendix E. 3 Reactor Once the nitrogedsteam rnixed with the gas oil feed.49 heat balance. the steam passed through a check valve and mixed with the incoming feed at the same location as previously described for nitrogen. both components entered the comgated tube reactor inlet vapouriser. Once the distilled water was vapourised in the exchanger using the s m e steam as used for the hot glycol system. depending on the flowrates required. Based . preheater #l should be given a steady low power input. At the exit of preheater #2 there was a high-temperature needle valve and an a t t a c h e n t to connect the a s closed second transfer cylinder and feed directly to the inlet vapouriser. See Appendix I for detailed heat transfer calculations. Finally. upon exiting the fumace. For additional flexibility. This heat exchanger was of al1 stainless steel construction. Generally. 3 . the reactor steam was superheated in the top two 75mm stainless steel tubes of the three-tube fumace. Both the nitrogen and steam sides of the fumace were protected with relief valves. stainless steel twisted-tape inserts were placed in the tubes to improve heat transfer. Again. A shell-and-tube heat exchanger (TEMA AEL-type with steam shell-side) was designed and manufactured to initially vapourise the metered water. 1 . Moving the thermocouple connector fiom the nitrogen side to the steam side could control the exiting reactor steam temperature. Metering of the distilled water w a s accomplished using needle valves with one of two variable area flowrneters. and detailed heat transfer calculations are provided in Appendix 1. A detailed drawing is provided in Appendix E. while preheater #2 should be in automatic control. The Yokagawa convoiler settings were adequate for the steam flows used during cornmissioning. experience showed that preheater #1 did not require the calculated power input due to the influence of preheater #2. a steam generation system was also installed to study the effects of hydrogen donor reactions (fiom the water) on the pyrolysis of heavy hydrocarbons.

The outside cylinder was grooved to accommodate the two main 1 1 TGO(M0D) Inconel 600 sheathed 9. vertical conduction in the reactor. Aithough the. The tube was coiled around stainless steel bar stock with grooves cut in the surface to allow for the tube to sit in the groove flush with the bar surface.AR1 Mode1 No. the reactor inlet temperature measurements show that the feed w completely vapourised prior to entering the reactor proper (see Appendix 1). The lower section of the reactor was constmcted with a smaller tube diameter than the upper section to achieve the high heat transfer rates that would ensure an isothermal .5 electric heaters . The tube and bar stock combination was then placed inside a thick-walled stainless steel cylinder machined to tight tolerances on the inside diameter. Detailed drawings are located in Appendx E. 6 mm type K Inconel 600 sheathed thennocouple w a s inserted into the tube for a linear distance of 457 mm to provide accurate measurement of the gas temperature while minimizing heat conduction effects. VXX25B 129- mm diameter by 1200 mm long capable o f supplying 7200W with 240VAC and a power density of 1 13. .2 k w/m2. a tube sarnple cut from the exchanger after completion of the runs showed no residue on the tube wall. In this section the average heat transfer coefficient for al1 the runs was approximately 1280 w/(m2 -K) with a temperature rise per unit length of 1400 Wm (see Appendix B for calculation details). The hot gases exiting the vapouriser entered the first section of the helical coil reactor.was concem about contamination o f new feeds fiom residue left in the exchanger corrugations. naturd convection at the insulation surface.50 on the heat transfer calculations for the inlet vapouriser with the light gas oil feed used a s in this study. A third heater (1 000W) was added to the bottom half of this first section to compensate for the heat lost through the base plate. Typical Dean nurnbers for the flows studied ranged fiom 3900 to 4900. A 1 . and to the inlet vapouriser. This heater was typically operated at 50% power levels whereas the main heaters were operated at 5% power levels for the duration of the experiment. 3 4 mm (ID) Inconel 600 tubing wrapped in Ths first section comprised of 8950 mm o f 3 a mean coil diameter of 95 mm with a coil pitch of 1 0 mm.

3. The heavy wall cylinder was placed over the bar stock and the A M heaters were wrapped around the outside.1. the tube was coiled around stainless steel bar stock with grooves cut so that the tube was flush with the bar surface. the gas entered the product collection system. one simplifjhg modification was made to the collection system used by Dong [104]: the second condenser pot was removed and the two condensers were directly connected. The prïmary condenser located approximately 600 mm downstream of the reactor (al1 tubing was well insulated between the units but not heated). giving an overall condenser .51 temperature in the upper section.75 mm (ID) stainless tube surrounded by a 38 mm (OD) by 400 mm long copper pipe in which cooling flowed in a countercurrent direction. Typicai Dean numbers for the flowrates studied ranged nom 360 to 820. This thermocouple was a dual-type: one side was connected to the data acquisition system. The average heat tranfer coefficient for this section for d l the flowrates studied was approximately 235 w/(m2K) with a temperature nse per unit length of 495 Kim (see Appendix B for calculation details). After the concentric reducer transition piece. 457 mm of a 1. Downstream of the tirst pot.4 Product Collection Gas and liquid products fiom the gas oil pyrolysis experiments were collected in a g l a s collection train similar to that previously described by Dong [1041. At the outlet of the reactor. m e r temperature measurement. the upper section of the reactor comprised of 8650 mm of 6. As described for the lower section. The cooled and partially condensed products collected in the tirst condenser pot.6 mm type K Inconel sheathed thermocouple was inserted into the flowstream to accurately measure the gas temperature while minimizing the effects of sheath conductance. and consisted of a 7. and other attached to the Yokogawa UT-350 controller. The entire assembfy was thickly coated in a hydrocarbon-based copper powder anti-sieze lubricant manufactured by Jet-Lube (SS-30 Copper Base Anti-Seize Lubricant) to minimize the losses due to thermal contact conductance as discussed in the text by Madhusudana [302].1 6 mm (ID) Inconel600 tubing wrapped in a mean coi1 diameter of 92 mm with a coi1 pitch of 10 mm (see Appendix E for drawing details).

Introduction of air to the reactor is necessary to remove the carbon deposits and extra-heavy hydrocarbons that could collect in the tubes. Liquid samples from condenser pot # l were taken irnmediately and stored in the freezer until analysis was completed. the cleaned gas volume was measured using a G H Zeal Ltd. The reactor burn was conducted by increasing the temperature of the reactor and adding air at the same flowrate and pressure as nitrogen. Upon completion of an experimental run.Mode1 No. DM3C-25 (serial no. Thus product gases not condensed by the primary condenser continued through the secondary condenser. Finally.5% dichloromethane. Liquids nom the secondary condenser collected in the second condenser pot. the collection train was disconnected from the reactor outlet and disassembled for product collection and cleaning. The solvent and liquid product mixture was then placed in a multistage distillation unit that operated at 34t°C. Gas samples were taken on a periodic basis using vacuumed 1 . The distillation unit was left to operate until it was observed that the flow of clear fluid from the condenser had ceasedWhile the condenser was being ckeaned. 0456 10) wet test meter.52 length of 685 mm. There is also the additional flexibility of collecting a sample of the cooled gas to determine the quantity of carbon removed from the system. The levels of carbon residue produced during the experiments in this study were not determined -qualitative observations and an explanation of why the coke production was not quantified are included in the next . The packing for the demister consisted of cosmetic grade cotton balls purchased fiom the local phannacy. and gases not condensed were passed through a rayon andlor cotton bal1 demister unit. 2 L plastic sample bags. This modification was done as a result of the observation that the third condenser pot did not improve actual condensate collection. and passed through a 0 . 0 3 N zinc acetate solution to absorb the HrS without affecting the COz levels. the tubing for the reactor bum cooling coi1 was connected. The gases that passed through the demister were assumed to be completely scrubbed of condensable Iiquids. The washed units were then lefi in the fiune hood to dry. The nitrogen was shut off during the reactor burn. The liquid products in the condensers and condenser pot #2 was collected by washing the units with >99.

preheater #1.53 chapter. Since one of the critieria in the design of the reactor was also to investigate liquid phase kinetics. then stainless steel wire mesh Although not comrnissioned at high pressures.)% output accuracy on span). a sixth controller/relay pair could not be installed to accommodate the heat tracing attached to al1 the bitumen feed iines. preheater #2. Liquid product that is not condensed on the plate must pass through a section of the vessel packed with 75rnm OD x lOmm wide stainless steel rings. see the work by Dong [104].1. *O. Unfortunately due to space limitations. These controllers individually fed the Watlow solid-state power relays that controlled the electrical power to the heaters. However. control of the furnace. main reactor. 1% input accuracy and +O. As with the study of any reaction systern. For a detailed investigation of the quantity of coke produced during middle distillate pyrolysis. The glycol is circulated using one of the A R 0 diaphragm purnps described earlier through two ice baths then to the collection vessel. To achieve the fast quench times required. a high-pressure collection system was designed and installed The high-pressure collections system consists of one pressure vessel that is surrounded by a pressurized cold glycol bath. the speed at which that system is quenched at a certain point determines the accuracy of the residence tirne for the reaction. and reactor bottom temperatures were achieved using Yokogawa UT350 cabinet mounted controllers (250ms sampling time.5 Control and Data Acquisition As described in the above. It should be noted that the product collection system described above is for gas phase cracking only. 3. the mechanical calculations provided in Appendix F describe the maximum pressure rating for the vessel. the reacting gas is directed ont0 a glycolcooled impingement plate located in the pressure vessel. the heat tracing that was installed is of the self-regulating type that has the capability of being fed directly from a . The plate that is sloped to promote liquid run-off to the bottom of the vessel. Detailed drawings of the high-pressure condenser and the overall assembly with the reactor is provided in Appendix E.

and the physical properties are described in Table 3. and then sent to two channels on the National Instnunents board. determined from the volwnetric boiling point calculated from the simulated distillation data from Syncrude Canada Ltd. Results of thermocouple calibrations can be found in Appendix L.. The nitrogen components determined by Syncrude Canada agreed well with the study on nitrogen complexes in middle distillate oils by Mushnish et al.1.. The characterization factor was determined from the mean average boiling point that was. AT-MIO-64E-3 with 32 differential. 12-bit analog inputs sampling at a rate of 500 kHz). The volumetric (normal) boiling point was calculated from the relationship given by Zhou [575]. The mean average boiling point was calculated by interpolation using the industry-recognized charts of Smith and Watson that can be found in any text on petroleum processing.1. in turn. Based the characterization factor. Reactor temperatures were read directly by the NationaI Instruments data acquisition board (Mode1 No.1 graphitai programming system developed by the National Instruments Corporation. [344]. See Appendix L for a list of the thermocouple locations within the physical and data acquisition systems. 2 Feed Cbaracterization The heavy hydrocarbon feed used in this study was Plant 18 hydrotreated Iight gas oil supplied by Syncrude Canada Ltd. A simulated distillation curve for the feed is provided in Appendix O. Measurement of the temperatures was accomplished using standard type K thennocouples. whereas al1 other y p e 304 sheathed. 3 . . and is summarized in Table 3. the aromaticity of the feed is high and highly unsaturated: this observation is confirmed by the data provided by Syncrude Canada Ltd. process thermocouples are Stainless Steel T Data acquisition and storage of the temperatures for the pilot plant were achieved using the Labview v4. A11 thermocouples used on the reactor are Inconel 600 sheathed. whereas the temperatures associated with the utilities were first read by a custom-built multiplexer system.54 120VAC source.

Each method is similar to that completed by Dong [104].? API gravity Volume Average (Normal) Boiling Point Conradson Carbon 30 291°C C 15 84H28.8 LV% l 1 UOP K Factorf. respectively.8725 1 Hydrogen Sulfur Nitrogen 1 I 12.34 219 t determined fiom the correlation developed by Dolomatov et al.1 Physical Properties of Light Gas Oil (LGO) Feed Feed Reaction Density (15/4) Density (20/4) Bromine No.79 25.Table 3. Flash Point Correlation Index Light Gas Oil Neutra1 0.8760 0. The quantity of coke for each run was not measured due to its small quantities and the inaccuracies imposed by the coke collection system.8 ppm 36.3 Product Analysis The gas and liquid products collected from each experimental run were analyzed for individual components and general carbon number distribution.Sg/l OOg 88°C 44 1 WC Aromatics Naphthalenes Experimental Formula Mean Molecular Weightz 1 1.8 LV% 64.43 ppm O. [IO21 $ calculated using the paraffin carbon n m b e r method detailed in Appendix M tt mean average boiling point calculated fiom correlation by Rao and Bardon 13941 3.97 wt% 248. A recommendation for design changes that would facilitate more .

2. Appendix M provides a summary of the component analysis for each successfil experimental nui- 33. 0. Errors inherent with the Appendix O for al1 runs completed except Run #02use of simulated distillation are presented in Section 4.1 Product Cas The gas analyses were performed by Dr.2 Product Liquid Al1 simulated distillations were performed by Ms. Inc. Simulated distillation plots are provided in 16-0 1-01.56 accurate. The GC was prograwned according to the ramping rates described in Appendix M. Elizabeth Zalewski of the 0i1 Sands Research Group using a Hewlett-Packard 6890 GC with a Separation Systems. Gas samples were collected in 1-2 L plastic gas sample bags complete with an integral sampling valve fiom Fisher Scientific.D. A detailed procedure for completing an experimental run is provided in Appendix K.53 mm bonded phase column (SM 289216) using the ASTM D2887 Extended Megabore method (ASTM [25]). Nancy Okazawa of the Oils Sands Research Group at the University of Calgary using a Hewlett-Packard 6890GC with Porpak Q and Molecular Sieve packed columns with 28 ml/min helium carrier flow and a TCD detector. In addition. 10 m x 0. . the limitations of the method regarding the ability to characterize the heavier components of the feed are described in the work by Satou et al.9 p n I. simpler quantitification of the coke yield is descrïbed in Chapter Five. 3. [429].

the controlled variable (reactor temperature) was measured on the outside surface or inner bar stock of the reactor. .CHAPTER FOUR: RESULTS AND DISCUSSION The design criteria changed fiom a focus on operating with various feedstocks and studying liquid and gas phase thermal cracking to strictly gas phase thermal cracking of middle distillate and pure hydrocarbons in the Cm and under range.13-0 1-0 1) and p s t . With the change to a strictly gas phase unit. was replaced with the low-pressure gas phase system of g l a s vessels and condensers described earlier. the high-pressure condenser would not be used for high-pressure experiments. therefore there was not an accurate method of determining the temperature of the cracked gas exiting the reactor. Previously (Dong [l O4]). and the progression towards improved control is illustrated in Appendix N. Dong Cl041 added a number of design modifications to the feed and product collection systems that were again modified or removed to complete the nuis in this study. With this change in focus. Another modification was the removal of the extraneous tubing and collection tanks used for measuring the flowrate of the LGO to the reactor. as such.1 6-01-0 1) modification nins (see Appendix N).(Run No. 02. The dual thermocouple was heat stationed to minimize errors that could result due to heat conduction through the therinocouple sheath. One of the major modifications completed for this study was the removal of the reactor outlet thermocouple and the installation of a dual thermocouple unit to achieve both data acquisition and better control of the reactor temperature.1) and a cornparison of the reactor temperature plots for pre.(Run No. for the process of d i s m d i n g the pressurized system was eliminated. and. This change allowed for f a t e r tumaround of experimental runs. 02. since flow measurement for caiibration purposes was conducted directly fiom the discharge of the transfer cy linder. The results of this author's modifications are illustrated by the simplicity of the collection train (Figure 3. The removal was justified on the basis that the amount of liquid collected in the last two pots of the condenser was minimal compared with the first pot. Another modification was the removal of the middle condenser pot from the product collection train.

Table 4. for that day. the preheaters were not necessary and were thus bypassed for al1 experiments conducted. With al1 the modifications in place. based on the inlet vapouriser calculations in Appendix 1. and seven were successfùl.58 Finally. gas. and the model was correlated to data in the 500-550°C range only. . respectively. The basis for the kinetic model was that the LGO lump decomposed into naphtha. and coke lumps following first-order kinetics.1 Summary of Experimental Conditions for Successfbl Runs Expriment Number Temperature LGO Mass Flow Nitrogen Mass Flow Nz/LGO Mass Ratio Residence Time (s) The data generated fiom the above experiments was compared to the four-lump kinetic model for middle distillate thermal cracking developed by Dong [104]. The mass ratios and the residence times are calculated in Appendices C and J. respectively. Table 4. a total of 12 experiments were conducted. The expriment number follows the format of Day/Month/Year/Run No. Surnmaries of the successfül and unsuccessfid runs are tabulated in Appendices P and Q. Intermediate compounds were not considered.1 provides a surnmary of experimental conditions investigated.

particularly during the experiments with the temperature >600°C (see Appendix M). A Paraffins-OlefinsNapthalenes-Aromatics (PONA) analysis method was attempted using gas chromatography. Therefore the liquids collected from the condenser pots were not mixed: the liquid sarnple that was analyzed was fiom the f m t condenser pot only. the quantity of liquid absorbed ont0 the demister packing increased with increasing temperature. but could not be completed within the time frame of this thesis. the liquid was analyzed from the second pot and proved to be slightly higher in low boiling (496OC) and high boiling (>343OC) components. This can be explained by the large increase in the quantity of gas evolved. hence the velocity of the gas traveling through the condensers was able to carry more condensed liquid through the condensers pots into the demister. the distribution of liquid fractions from condenser pot #1 to the demister packing was assumed to not be significantiy different for this study. for there was not a significant difference in the naphtha (<196OC). and heavy gas oïl (>343*C) fractions of the liquid collected fiom the primary and secondary condenser pots as illustrated in Figure 4. As a final note. [428]). therefore accurate determination of the extent of aromatic and napthenic ring formation . and liquid samples fiom the first condenser pot were analyzed according to the analytical techniques described in the previous chapter. The liquid that absorbed onto the packing in the demister was also weighed and added to the total liquid mass.1 Product Analysis and Mass Balance Ail liquid and gas products from the reactor were measured for mass and volume. based on the liquid absorbed ont0 the demister packing k i n g qualitatively similar to that collected in the second condenser pot. The simulated distillation curves for the product liquid for various reactor temperatures are compared in Figure 4. light gas oil(196-343"C).2. 02-22-0 1-02 only. This is contrary to the assurnptions by Dong [104].1. For Experiment No. Additionally.4. respectively. and it is clear that the thermal cracking process changes the molecular structure of the LGO significantly: the step-type curve is indicative of an increase in the aromaticity of the liquid (Satou et al.

60 could not be completed. Table 4.- - Due to the limitations of the GC simulated distillation method. Std.21 Component Mass (g) Gas Liquid Feed 4. In addition. Typically. " . the molecular weight calculation is based on the carbon number and boiling point for paraffins (see Appendix M) instead of using a correlation for molecular weight such as that developed by Rao and Bardon [394].2.5 348 ~ecoveq l (wt %) 99.2 Summary of Mass Balances for Successfbl Experiments Expriment Nurnber Temp. Dev. Thus pseudocomponent lwnping based on boiling points were used in the kinetic analysis.the range did not exceed *5%. Temp. The ASTM D2887 method (ASTM [25]) does account for this discrepancy. However. a check was perfomed using the correlation by Rao and Bardon 13941 to determine the magnitude of the error introduced by the aromatic and naphthenic components in the feed . The mass difference is assumed to be the coke produced (coke production was not quantified for reasons provided later in this chapter). and a summary is provided in Table 4. (OC) 3. The molecular weight determination based on parfin boiling point is preferred when the calculation is based on data fiom the simulated distillation method. the boiling point curve in Figure 4. as the method is based on a close correlation between parafin boiling points and elution times. the correlation of Rao and Bardon [394] gave a value of molecular weight for the liquid products that was less than that predicted by the paraffin carbon number rnethod.2 will be slightly skewed due to the elution of heavier aromatics and napthenics with a lower molecular weight p6n (ASTM 1251). Detailed mass balances are provided in Appendix M for al1 successfûl runs.09 340.0 --- - . as illustrated in the work by Satou et al14281..

1 Cornparision of Product fiom First and Second Condenser Pots Experiment No.O 20 40 60 80 1O 0 Weight Percent Off (wt%) Figure 4. 02-22-0 1-02 Simutated Distillation Boiling Point Curve .

I -Feed (Syncrude) 40 - .2 Comparison of Simulated Distillation Curves for Various Reactor Temperatures . i O 20 60 80 1O 0 Weight Percent Ot'f (wWO) Figure 4.

As illustmted in Appendix G. the mass balance for each lump. but did give the wall conditions necessary for the induction period to be satisfied. The light gas oil feed is considered a low coking feed (Lefiin and Newsome [2681)3.3. hence. the primary condenser did not provide the quenching expected. Thus the " Ta detemine the mass o f product gas. as defined by Dong [104]. 2.63 For the purposes of comparing the results o f the experimental runs fiom this study with the mode1 developed by Dong [1041. The coke production was not quantitfied in any of the experimental runs for the following reasons: 1. The majority of condensed polyaromatics that lead to coke formation require an induction penod prior to their formation (Wiehe [540]). . Conversion - 1 - LGO LGO~ A summary of the mass fiactions for each component lump is provided in Table 4. was detemined using the following relationshipsI2: and the conversion of the feed LGO lump to either gas or naphtha is based on the amount of LGO Iost during the reaction. This period coincides with a change in operating conditions that results in a thennodynarnic instability of the fluid and a change in phase that occurred at the inlet to the primary condenser only. The product collection train was not designed for quantiQing the coke collection after a pyrolysis run. the mass o f nitrogen gas was subtracted from the m a s of gas calculatcd using the results frorn gas chroinatography. Absent fiom the table is the mass fraction for produced coke.

the change in the quantity of this lump with changing reactor conditions gives a reasonable indication of the dominant kinetic mechanism . for cornparison reasons. Previous efforts to measure the quantity of coke produced (Dong [104]) would not have been able to determine the coke deposited at the inlet of the primary condenser. a measureable quantity of coke was physically removed fkom the inlet of the pnmary condenser and for a short length into the condenser. The negative feed conversion for the lowest temperatures is consistent with the kinetic model of Dong [104] and will be illustrated in the following sections.02-22-0 1-04. this lump was added to the LGO lump fiaction. Since H G 0 is the heavy gas oil fraction of the feed and product liquid that boils at temperature >343OC. Instead. and 03-27-0 1-0 1. The majority of coke was removed fiom the inlet of the primary condenser. Thus the reaction rate constants calculated in the work by Dong [104] will be in error. which supports the hypothesis that a suficient change in temperature to cause the heavier components to condense resulted in the Iargest quantity of coke formation. which cannot be included in the coke collection procedure defined by Dong [104]. In addition. The hypothesis that coke formation will not occur until sufficient levels of condensed polyaromatics exist at a point of phase change was proven during the >600°C experiments conducted in this study. and this mass is thus not quantified in the mass balance. During those experiments.3 does not introduce any error in the model by Dong [104] since it is included in the LGO lump. . A summary of the lump mass fractions and the feed conversion is provided in Table 4.either the primary decomposition or secondary polymerization reactions. However. the coke produced is assumed to be the mass difference required to achieve 100% m a s balance for each successfùl experimental run. but due to the 'rodding' technique of removal. there were also some losses of coke. but it is important for inferring the kinetic mechanisms for the pyrolysis of gas oil.64 majority of coke produced was at the primary condenser inlet. the omission of the lump termed "HG0 in Table 4.3. A combined total of 15g of coke were recovered fiom the condenser after runs 02-22-0 l-O3.

8 -1. Dong [104] assumed the helical coi1 reactor closely approximates an ideal plug flow reactor. and coke .063 0.093 YO -2. 02-21-01-01 02-21-01-02 02-2 1-01-03 03-27-0 1-0 1 Temp.3. The model is based on four lumps . (OC) Gas Lump Mass Fractions 0.006 0. In the development of the four-lump model.65 Table 4.3 Four Component Lumped Kinetic Model For Middle Distillate Thermal Cracking .6 1 1 1 Feed 1 O 1 1 0. This assumption was confirmed to be valid according to the axial dispersion calculations for each section of the reactor provided in Appendix J.3 Lump Mass Fractions and Feed Conversion Experiment No. 178 0.747 0.1872 1 4. the kinetic model developed by Dong 11041 was used to compare with the data generated fiom the experiments performed in this study. LGO.2 Kinetic Model As described earlier.070 0.75 1 0. gas. and is illustrated in Figure 4.1 78 0.166 LGO 0.744 0.010 0.012 0.068 0. 4 /u\ LGO kt Figure 4.7187 1 I 0.2 -1.and is assumed to follow firstorder kinetics.171 0.131 Feed Conversion 436 462 503 54 1 Naphtha 0.0609 1 I 1 0.608 HG0 O.naphtha.8 22.

3 Cornparison with Model Predictions The correlated values of activation energy and Frequency factor determined by Dong [104] were used to calculate the mass fractions of the LGO.4 components) detennined from the above system of noniinear equations. naphtha.. ki (i = 1. Dong 11041 then detennined the activation energies and fiequency factors for each lump reaction path by using the Arrenhius relationship. and gas at various reactor temperatures and residence times.4-4. Results are presented in Figures 4.4 Sumrnary of Activation Energies and Frequency Factors (Dong [104]) Activation Energy Reaction Pathway Ei (J/mol) Frequency Factor Ai (s-') LGO + Naphtha Naphtha + Gas LGO + Gas LGO + Coke 4.8. Table 4. .. Table 4.Using the rate constants.4 summarizes the activation energies and fiequency factors for the thermal cracking of rniddle distillate in the temperature range 500-550°C..

4 Comparison of Experimental Data with Model Developed by Dong [104] Component Yield vs.Residence Time (s) Figure 4. Residence Time at 436OC .

Residence Time (s) Figure 4.5 Cornparison of Experimental Data with Model Developed by Dong 11041 Component Yield vs. Residence Time at 462OC .




6 and 4.72 It is clear from Figures 4.8 illustrates the extent of the deviation when the temperature is allowed to increase whiie holding the residence time constant at the best fitting value of 0. Dong [104] assumed the reactor volume was constant based on the equivalent volume theory described in the text by Hougen and Watson [195]. even though the authors expressed that the method was not accurate when applied to systems with many simultaneous reactions. nor was it achieved in the study by Dong [1041 (values were similar to that calculated for this thesis). Although a residence time of 0. [95] and Geniesse and Reuter 11361 that the mechanism of thermal cracking of hydrocarbons changes significantly at temperatures >650°C. Figure 4.7 clearly show that the model predictions begin to deviate significantly fiom the experimentai data From the figures. An additional source of discrepancy centers on the heat transfer and axial dispersion effects in the helical coil. However. the axial dispersion is less than that for an equivalent straight tube reactor and thus more closely approximates that of an ideal plug flow reactor (see Appendix J for calculation details). it is clear that another reaction mechanism is becoming more dominant as the temperature exceeds 5S0°C. The explanation for the mass fraction discrepancies at the higher temperatures goes back to the main assurnption upon which the model is based .5s.the assumption that the reactor is isothermal and the volume is constant. then. A more appropriate term for the kinetic model would have k e n space-time. however. in the development of the model. the value was chosen to illustrate the reactor conditions necessary to achieve the best fit to the model of Dong [104]. Due to the secondary flows that evolve in the helical coil (Koutsky and Adler [249]).5 that the model developed by Dong 11041 fits the data well for the temperatures and residence times determined for nuis where Tr<5000C.5s was not achieved in this study (Table 4. The equivalent reactor volume does change.4 and 4. a kinetic model based on time and m a s fraction could be applied to describe the reaction mechanism. Figures 4.1 ). as evidenced by the change in residence times listed in Table 4. With the constant volume assumption.1. This observation c o n f h s the conclusion of Depeyre et al. Dong [104] assumed that ihe Prandtl number is constant for al1 reactor temperatures: the results of . Also.

3 and illustrated in Appendix N. However.1 Conclusions A helicai coi1 reactor system was designed to meet the critena gas and liquid phase thermal cracking of widely varying hydrocarbon feedstock characteristics.calculated temperature rise per unit length was on the order of 1400 Wm (see Appendix B). Although the mode1 closely matched the .The large change in the Prandtl number for the upper section is indicative of the significant change in the number of moles produced as the reactor temperature increases. as described in Section 3.1. Appendix N illustrates the progression towards better temperature control with each experimental run. residence time.5 in the upper section of the reactor for increasing reactor temperature. the controlled variable was heat stationed in the outlet gas Stream instead of measuring the reactor bar stock temperature. and temperatures coupled with the generation of large volumes of liquid product.94 to 0. The heating rate assured a relativeiy instantaneous temperature rise of the feed to reaction conditions. CHAPTER FIVE: CONCLUSIONS A N D RECOMMENDATIONS 5.73 the calculations in Appendix B show that this assumption is invalid. to achieve reactor operation that closely approximated isothermal operation. for the Prandtl number varies fiom 0. The thermal cracking of a hydrotreated middle distillate was completed at a temperature range of 435-700°C and the data compared with the predicted values from the mode1 developed previously by Dong [104]. In addition.53 to 2.90 in the lower section and 0. Its two section design with a smaller tube diarneter for the inlet section was intended to achieve high heating rates for the incoming feed . the calculated product gas outlet temperature from the primary product condenser from Appendix G proves that the heat exchanger is cornpletely ineffective with regards to quenching the reacting gas. although due to the cool walls a measureable quantity of coke did deposit. thereby allowing for a more accurate definition of the residence time.

Secondly. the installation of a mass flowmetet on the nitrogedair line to the inlet of the fûrnace would benefit the system greatly. Simplifjbg assurnptions made during the development of the kinetic model (Dong 11041) have been proven to be incorrect based on the calculations detailed in Appendices B. the nitrogen flowrate does not remain constant. 5. the prirnary condenser. Due to pressure fluctuations in the reactor during operation. although coke buming between runs was completed. hence more accurate coke yields can be determined. Thus. A recomrnended solution would be to d i s c o ~ e cthe t collection train downstream of the primary condenser and connect the coke burn tubing to that downstream connection. This deviation confirms the conclusion of Depeyre et al. Fourthly. Finally. a better experimental design that focuses on varying the residence time while maintaining a constant reactor temperature should be considered for the investigation of heavy oil pyrolysis. . a thennocouple could be bonded to the outside tube wall. and 1. there are. software filtering on ail temperature measurement. the coke could not be accurately quantified. a number of recommendations that were not considered during initial design and construction. the deviations becarne significant for reactor temperatures >550°C. should be completed to assist the operator with maintaining a constant temperature during an experirnental run. [95] and Geniesse and Reuter [136] that the mechanism of thermal cracking of hydrocarbons changes significantiy at temperatures >650°C. for. Firstly. of course. With this access.74 experirnental values for temperatures <50O0C. the method for detennining the quantity of coke produced during the reaction requires improvement. G. This would allow for a more accurate model development and data cornparison.2 Recommendations With a reactor system of this size that was designed to meet a number of dificult criteria. becomes part of the coke removal process. therefore providing a means of directly determining the tube skin temperature profile of the reactor. Thirdly. particularly on the reactor. with the cooling water tumed off. a recommendation that the reactor outer cylinder be drilled such that direct access to the tube wall is available.

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pushed light gas oil feed to the reactor. Both pumps operated in parallel to achieve-the desired flowrate of 480 mWh. The followhg plot illustrates the calibration curves for each pump. 920 15003. .3 007 128 and 006940) were used for supplying hydraulic oil to the transfer cylinder.APPENDIX A : Milton Roy P u m p Calibration Cumes Two Milton Roy metering pumps (Mode1 No. The maximum flowrate one pump can supply is 460 mWh and has a minimum of 4 mL/h. Calibmtion was accomplished by measuring the time to achieve a predetermined volume at the discharge of the pump in a 25 mL graduated cylinder. which. in turn. Serial No.

83 Pump Setting Figure A.1 I I -Pump #2 Curve 1 Pump #2: Flow = 0.30 Pump #3: Flow = 0. 1 Milton Roy Metering Pump Calibration Curves .075 * (setting) + 1.084 * (setting) + 1.

for the "g7* unit is attributed to the gravitational force (9. pressure drop. .135 APPENDIX B : Reactor Reynold's Number. and heat hansfer coefficient for the range of volume flowrates studied. Please note that due to program-specific issues with MathCad. and Heat Transfer Coefficient Calculation The following pages provide the calcuiation details for the determination of reactor Reynold's number. Pressure Drop.81 m/s2). the units designation for grams is ''gn~~~.

2-t2 D . 103 Length of 3/16" tube: L 1 := R .679.947 m Assuming the pressure in the reactor remained constant: kPa := 1000 Pa P atm . := 3. NitrogenFeed gas entering reactor is hydrodynamically fully developed. . and Heat Transfer Coefficient fb36 the Helical Coil Reactor Assumptions: 1. 2.l-= *1 L 1 = 8. The helical coi1 parameters are defmed by the following: 3/16" tube wall thickness: t 1 := 0.400 in d 1 := d 1. Pressure Drop. Feed is completely vapourised prior to entering reactor according to results fiom Appendix 1.000 in H 2 := H 1 L1 = 3. 6. Temperature and pressure are constant.D.925 in Dc2:=Dco-d20 Dcl:=Dco-dlo Section height: H 1 := 12.2-t 1 d 2 := d 2 0 .--9 1.035 in Outside diameters: 3 d lo := Tii in 5 d z0 := T6 in Thus the tube diameters are: Helix outside diameter: Coi1 radius: Pitch := 0.45 kPa . 4. Volume occupied by inlet and outlet thennocouples is negiligible.Cakulation Reynold's Number. The conversion of feed in the lower reactor is negligible 7. The physical properties in the upper reactor section are based on the average of the outlet and inlet hydrocarbon vapou.028 in 5/16" tube wall thickness: t 2 := 0.

MW nit := 28. and the nitrogen mass flowrate defined for each run wax gm m nit := 0.013 .067 s .Critical Reynold's Number: (to determine point at which the flow changes fiom laminar to turbulent) (Gaielinski 11441) / 1 1 Re c.1 + 8 .P niti -- P i MW nit ri Viscosity calcuation is f i o m the correlation of Yaws [566] @ := 1 0 ' ~ poise The density of the inlet feed is calculated assuming an ideal gas since the compressibility of the gas oil vapours is close to 1 : MW f : = 219 gm mo PiMWf p 6 := ri . nitrogen density is. The reactor temperature is based on the calculation for average temperature for the expriment provided in Appendix N. For nitrogen: i := 1 . 6 D x / \ \ Reactor temperature and total run time for each experiment is := 2300. 7 for the number of experiments. 50 37 97 106 min 76 65 107 Universal Gas Constant: The physical properties are determined next..gfî from Yaws 15661 thus.

Now. P r l i := P fi P ravgi ..frac nit frac f .the mass flowrate of the feed LGO and nitrogen is: and the mass fractions for the nitrogen and LGO feed is: frac nit := nit + f fiac f : = L nit + f The average density of the reacting mixture based on the inlet and outlet densities is calculated then the total density of the nitrogen plus the reacting mixture is detennined. and a swnmasy is provided in the viscosity is calculated f i o m the correlation by Gomez [146]: where A and B are detennined fiom a table based on the molecuIar weight of the hydrocarbon vapour. the molecular weight of the product gas is detemined fiom the gas analysis provided in Appendix M.And for the hydrocarbon vapours.2 -- q+pgasi r2i 1 --.

The volumetric flow of the product gas in the upper section is detemined by taking an average of the flows of the exit product gas and the inlet feed gas since it is assumed that there is negligible reaction in the lower section of the reactor based on the work by Hirato et al.s a S i-- mf gmi -Y niQi -- " nit g a ~ 2 ~ nit + Y g a ~ -2~ -- v g a ~ 2 ~ nit Viscosity of the gas in the lower y nitl-P niti section of the reactor based on the assumption that the feed does not p 1. + y gasi'p fi Y gasl + Y nitl. 11901. Molar flowrates of nitrogen and reacting fluid: "t:' r nit * nit f:= "f W f v .'b1 21i and the velocity and Reynold's nurnbers for al1 reactor temperatures in the lower reactor .The method of Wilke (Reid et al 14421) is used to determine the nitrogedproduct gas combined viscosity then the gas velocity in the two sections of the helical coi1 reactor is determined. := ' Y nit1 + Y gast.'bl lzi react sufficiently in this section to change the rnolar flowrate.

.and the flow is turbulent in the lower reactor section for al1 temperatures studied. The Reynold's number for the upper section is now determined using the averages of the physical properties of the feed and product gas for the sarne reason as described for the volurnetric flow.

and reacted gas at the wall is calculated from the correlations described previously. Next. Based on experimental data measured at the surface of the reactor outer shell. For the pressure drop calculation. the typical temperature difference between the tube wall temperature and the bulk flow is inferred below: therefore the viscosity of the feed. . nitrogen.and the fiow is laminar in the upper reactor section for al1 temperatures studied. a check that the mean diameter of curvature is not significantly different from the diameter of curvature (checking severity of coil pitch): therefore the diameter of curvature is suficient for al1 calculations. the method of Mishra and Gupta described in the review paper by Gnielinski (1441 will be used. and the coil pitch is not significant enough to invalidate the correlations used for pressure drop and heat transfer.

7 7 I - 'MW gaszi . - ' ip gaswZi 1 MW nit . I $1 21. 1 . a Pga~w2~ MW nit 1+.P nitwi . I initwi IC. I := 01 1zi.ITKgas2i .

the pressure drop is detemined from the equations defined in Gnielinski [144]. Now.O4 for al1 temperatures and the effect of wall temperature is assumed negligible. 1 j~ J .and the ratio of viscosities is: p rli . rti/ and the pressure &op for the upper helical coi1 is based on the Dean number for that section: .- *- li Therefore the viscosity correction factor is less than 1 .

' F . given that the total pressure &op across the reactor is small.202 13. the assurnption o f a constant pressure operation is valid.145 13. For the calculation of the heat transfer coefficient.442 12.998 11. the correlation presented by Xin and Ebadian (556) will be used. - - Dean Nurnber: De 1 :=Re l' IT Fi De 2 := Re 2 - Helical number: / Pitch \ 2 InDclj check on the bounds.AP total = (10.21 15.264 17-37 ) T M a Therefore.

and the hydrocarbon gas leaving the reactor is sirnilar to n-decane based on an average molecular weight for al1 temperatures. assuming that the hydrocarbon gas in the lower section is sirnilar to n-hexadecane. then the thermal conductivity for both sections is. the specific heat capacity for the components for al1 temperatures based on the correlations provided by Yaws [566] is calculated and summarized in the fol10wing: . feed and reacted gas will be calculat8h5 t'rom the correlations of Yaws 15661. Using the same assumptions on component representation.Now the thermai conductivities of the nitrogen.

Now the thermal conductivity and heat capacity for the fluid will be detemined for 146 each section. The mixing d e s for calculating the thermal conductivity are taken f i o m Reid et al [399]. MW nit .

therefore the assumption that the Prandtl nurnber is constant at 0. and the heat transfer coefficient calculated by Dong 11041 will be in error.74 is not valid (Dong [: SI]). . Based on the viscosity ratios calculated earlier for the pressure equation.Now the bulk specific heat capacity for the nitrogen + feed and nitrogen + product gaW7 in the lower and upper sections of the reactor are detennined fiom the following: Thus the Prandtl number for each reactor temperature is. therefore the average Nusselt numbea for the lower and upper sections of the reactor are detemined fiom the correlations provided by Xin and Ebadian [556]. the assumption that the difference between bulk and wall fluid physical properties is negligible is valid.

the linear average temperature rise per unit len& of reactor is determined from the energy balance. For each section of the reactor. the reactor operates in basically an isothennal mode. . Thus when the difference between the wall and bulk fluid temperature is 50°C or less.and the linear average heat transfer coefficient for each section of the rector and al1 148 experiments is. Based on the temperature data for the reactor. one can assume that the inlet vapouriser completely vapourises the feed and brings the fluid to reactor temperature ptior to entering the reactorForced Convection Heat Transfer Dimensionless Numbers thetefore. the heat transfer at the surface is minimal compared to that transported by the fluid (Stanton number) and conductive heat transfer is minimal compared to convective heat transfer (Peclet number) for each section of the reactor. then.

Pa differential pressure across the wet test meter (mm Hg) barornetric pressure (mm Hg) water vapour pressure at Twand Pa water temperature (OC) P . The Matheson 763IT-604 flowmeter was used in deteminhg the mass ratio and setting the nitrogen flow. + Pw)/760]+(288.APPENDIX C: Nitrogen to Liguid Feed Mass Ratio Cakulation The following page details the calculation procedure for determining the nitrogen to liquid feed mass ratio.l 5+Tw)) Where. + AP.for the "g" unit is attributed to the gravitational force (9. Tw Thus the actual volume measured at standard conditions is: Actual volume = Measured volume * WTMCF Please note that due to program-specific issues with MathCad. the units designation for grams is "gm". AP.lY(273. For determining compensated flowrates using the Zeal wet test meter. the following equation should be used: WTMCF = [ ( P .8 1 m/s2). .

572 This ratio was constant for al1 experiments as shown in Table 4. rmn thus the mass flowrate of air is: m.1 16 S * LGO Ratio = 0. The flowmeter f o r al1 mns completed was set at 45mm. and given that the gauge pressure at the flowmeter is 41 kPa. P . then the mass flowrate is adjusted for the reduced molecular weight and increased pressure.325 kPa at for a i r at standard conditions.therefore the mass ratio is. The temperature is assumed to be equal to the given standard..1. (defined standard conditions in table) Reading := 51 mm V L kPa := I O00 Pa T std := 294 K P std := 101. . and with the mass flowrate of the LGO set at Ratio := nit gm m LGO := 0.81 .Calcuhtion of the Nitrogen to LGO Feed Mass Ratio 150 From the Matheson flow table for the Model No. A. := 2. := V . 763IT-604.

although awkward to disassemble and clean. except for the reactor temperature control: the controlled variable was moved to the outlet gas Stream to achieve more stable operation. confirmed the design principles.APPENDIX D: Electrical and Process Instrumentation Drawings The detailed CAD drawings for the major process equipment are provided on the following pages. The drawings are the 'As-Built' revision. Initial problems with the hydraulic oil system were traced back to air pockets and the lack of pump discharge backpressure valves. The hot and cold glycol systems were commissioned. Instrumentation and control for the system hctioned as designed. and provided the necessary heating and coolhg duties to successfÙlly complete heavy hydrocarbon pyrolysis studies. the highpressure condenser was commissioned. Although liquid phase thermal cracking experiments were not completed. . and.









except for the reactor temperature control: the controlled variable was moved to the outlet gas stream to achieve more stable operation. the highpressure condenser was commissioned. although awkward to disassemble and clean. confimed the design principles. The hot and cold glycol systems were commissioned.APPENDIX E: Reactor and Process Equipment Drawings The detailed CAD drawings for the major process equipment are provided on the following pages. . Initial problems with the hydraulic oil system were traced back to air pockets and the lack of pump discharge backpressure valves. and provided the necessary heating and cooling duties to successfully complete heavy hydrocarbon pyrolysis studies. Although liquid phase thermal cracking experiments were not completed. Instrumentation and control for the system fùnctioned as designed. The drawings are the 'As-Built' revision. and.

























APPENDIX F: Pressure Vesse1 Mechanical Calculations Due to the unique design of the pressure vessels constructed for thïs reactor system. the units designation for grams is "gm".8 1 m/s2). Stress analysis on the vessel walls was not completed. For the quench plate located in the high pressure condenser. Please note that due to program-speci fic issues with MathCad. vessel mechanicd calculations were necessary to ensure the d e t y of the people working in the lab and the offices on the next f l o o r above. The vessel mechanical calculations are based on the t e a by Mahajan [307] and the data for the bolting dimensions and steel yield stresses fiom the text by Megyesy [323]. for the "g" unit is attributed to the gravitational force (9. . for the flanges are the limiting factor compared to the schedule 40 carbon steel pipes used for construction. the heat tmnsfer caiculations were based on the papers by Graham and Rarnadhyani [150] and Pawlowski and Suszek 137 11.

063 Flange Dimensions (note: all dimensions in inches) A := 14. 5 in Appcrrdix E) (see Figure F. No.75 G := 12. Cuthbert Date: April8.110 in . dia y := O N := 0.375 in Corrosion Allowance (in. 70 o f Mahajan [33 71) N bolts := 16 A ab := 0.0 Pipe od := 10. 1998 Design Conditions: Design Pressure (psig) Design Temperature (F) P := 30 T := 275 Flange Material: SA-5 1 6 grade 55 Bolting Material: SA-193 grade 87 Bolt Diameter d bolt := 0.0 C := 13.mange Designfor Independent Ring Type Flange Heat Erckanger Shell Flangefor bitume^ AccumuIator (see Dwg.125 in.0 Gap := 0. 1 for dimension references) Drawing and Calculations: Sean V.) CA := O AIZowable Stress in Materials of Consiruction @om Megyesy [323]) Bolting at design temperature at atmosphenc temperature at design temperature at atmospheric temperature Flange S b := 25000 S a := 25000 S fo := 13800 S fa := 13800 psi psi psi psi G a s k Details: Buna-N O-ring 0.063 B := Pipe 0d + Gap Facing Details: Machine face to smooth finish Bolting Defail (see p.125 m := O b:== N b = 0.

Operafing Lever Arm Fhnge Moment .Gasket Seating Shape Constants .Flange Load .Gasket Seating HGG:=W Lever Arm h =os Fhnge Moment .h ~ M 0 : = M D + M ~ + M ~ FIange Load .Operating M G := H G .h G M D := H D .

Boit Spacing CaIcuIation Correction Factor for Bolt Spucing Thus the desigr. tkickness o f the/longe should be t = 1-019 inches .

b := 0.C(~lcuIatimt o f Maximum Allowabie W d i n g (Operating) Pressure ( i WP)for the 'As-BuW Fia~ges 65 As-built flange thickness t .50 in M a x i m u m pressure based on bolting pattern Maximum pressure based on fiange dimensions and material .


50 g ~0. b = 0.=0.50 b := .193 grade B7 Corrosion Allowance (in.2 for dimension references) Drawing and Calculations: Sean V.063 g . 1998 Design Conditions: Design Pressure (psig) Design Temperature (F) P := 150 T d := 275 Flange Material: Bolting Material: SA-516 grade 55 SA.703 .5625 C ~9. Cuthbert Date: April8.0.625 Gap10.421 B:=Pipeod+Gap R:=C-B-gl h.375 in AIIowable Stress in Materials of Conshwcfionfiom Megyesy f323j") Bolting at design temperature S b := 25000 psi at atmosphenc temperature S a := 25000 psi Flange at design temperature S fo := 12700 psi at atmosphenc temperature S fa := 12700 psi Fiange Dimensions (note: all dimensions in inches) A.11.421 Gaskei Details: y := 2900 "Garlok" High Temperature Graphite-Based clw Fabnc Insertion C-B m := 2.) CA := O Bolt Diameter d bit := 0. No. I in Appendk E) (see Figure F.Flange Design for S C @On Type FIPngefor Raiked Face Gaskefs Product Cas Condenser FIange (see Dwg.0 Pipeod-6.

335 Boft Spacing Calculution .94 U~ 6 . 2 0 g 1 ratio := gO ratio h := r.o ratio = 1 ratio h = 0.64 T E1.Operating M D := H D-h D Shape Constants M T := HT-hT Mo:=MD+MT K:zg A K = 1.74 h 2 =2.Lever Arm FZunge Moment .645 ho:=d& Y s 5.

l02*1o4 S = 1.09640'~ =2. = 1.5s fo = l.945-103 S f.905*lo4 S H =4. 688 i nches .298-104 Radial Beiding Stress ut Boit CenterIine Thus tlae design thickness o f the/range should be 3 t a =0 .27-104 S R = 5.Correction Factorfor Bob Spacing Other Stress Factors Stress Calculutions Maximum Allo wable Stress 1.

.l32 psi . := 0.6875 in M a x i m u m pressure based on bolting pattern Maximum pressure based on flange dimensions and material Therefore the maximum alluwable working pressure of thefïange is. =3l.Calculution of Maximum Aflowable Working (Operatin& Plessure (MM WP)fur tdao 'As-Bur'lt' Flunges As-built flange thickness tb . P .

2 Flange Design Drawing for the Product Gas Condenser Flanges .centre lof Figure F.

20 Flange Material: S A 4 16 grade 55 Bolting Material: SA.75 in Corrosion Ailowance (in.75 Gap:=0. 2 in AppendUr E) (see Figure F.200 in.mange Designfor Independent Ring Type FIange Giycof Tankfor Condenser (see Dwg. Flunge Dimensions (note: all dimensions in inches) A := 15.302 in .193 grade B7 Bolt Diarneter d bolt := 0. 1998 Design Conditions: Design Pressure (psig) Design Temperature (F) P := 30 T := .5 Pipe od := 12. No.063 B:=Pipeod+Gap Facing Details: Machine face to smooth finish Boking De fail (Mahajan [3071) N bolts := 16 A rsb := 0.) CA := O Allo wable Sîress in Materials o f Comtmction fiom Megyesy [323l) Bolting Flange at design temperature at atmospheric temperature at design temperature at atmospheric temperature S b := 25000 S a := 25000 S fo := 13800 S fa := 13800 psi psi psi psi Gasker Details: Buna-N O-ring 0. dia. Cuthbert Date: A p d 8.3 for dimension references) Drawing and Calculations: Sean V.

Operating MD:=HD-~D M G : = H ~ .Operdng H D := 0 .~ ~ .65 Flange Moment . 7 8 5 4 .S W := al Flange Load .~ G M T := H Teh T MO:=MD+M~+MT FZange Load .Gasket Seafing S a p e Constants K A :zg Y z 10.[(A .Gasket Seating H G~ := W Lever Arm h G = 0.56 .~ H G : = H ~ Lever Arm HT:=H-HD Flange Moment .+A b).

Bolt Spacing CaIçuIation bsp := (=C) Correction Factor for Bo& Spacing T/tmthe design tkickness of tlteflange sltould be t = 1-555 inches .

P .P rnax2) Therefore the maximum allowabfe working pressure of theJIange iS. b := 0. 3 8 3 psi .75 in Maximum pressure based on bolting pattern Maximum pressure based on flange dimensions and material P m a := i f ( P rnaxl <P rnax2 .P maxi . = 1 2 5 .Calculafionof Mizrirnum Allowable Working(Opera) 'As-Buüt'Flanges (iCL4 WP)Pressure for tdJ5 As-built flange thickness t .

3 Flange Design Drawing for the Glycol Tank for the Condenser . h I Figure F.I 1 J Centre of Ves I .

1 93 grade B7 Bolt Diameter d h l t := 0-375in Megyesy [ 3 2 3 ] ) Corrosion Allowance (in.302 in .4 for dimension references) Drawing and Calculations: Sean V.Cuthbert Date: April 8. Flange Dimensions (note: afidimensions in inches) A := 6.d + Gap Facing Defails: Machine face to smooth finish Bolring Detaif (Mahajan [307]) N bolts := 16 A rsb := 0.200 in. No. 1998 Design Conditions: Design Pressure (psig) Design Temperature (F) P := 150 T := 359 Flange Material: S A 4 16 grade 55 Bolting Material: SA.50 Pipe := 4.mange Designfor Independent Ring Type Fiangefor Full Face Gaske~s 177 Hear Bchanger SheiI Flangefor Steam Generafor (see Dwg.50 Gap := 0. 6 in Appendk E) (see Figure F.063 B := Pipe .) CA := O Alïowable Stress in Materials of Construction @rn Bolting Flange at design temperature S b := 25000 psi at atmospheric temperature S a := 25000 psi at design temperature S fo := 13800 psi at atmospheric temperature S â := 13800 psi Gasket Defaifs: Buna-N O-ring 0. dia.

h ~ Mo:=MD+MG+MT Fiange Load .Gasket Seating Shape Constunts - .Operating MG:=H G * ~ ~ MT:=HT.6 Flange Moment .Operating Lever Arm Fiange Moment .Gusket Seating HGG:=W Lever Arm h =0.Flange Load .hT M D := H D .

Bolt Spacing CaZcuIation Correction Factorf o r Bolt Spacing Thus the design thickness o f theflange should be t = 2.487 inches .

.b := 0.= 50 1-885 psi .75 in Maximum pressure based on bolting pattern Maximum pressure based on flange dimensions and material Tkerefure the maximum allowable working pressure o f thefrange ir. P.CaIculation o / M ( ~ ~ i m uAlIo r n wable Working (Operatin& 'As-Builf ' Flanges 180 ( B U WP)Pressucefor the As-built flange thickness t .

entre of ves+l I Figure F.4 Flange Design Drawing for the Heat Exchanger Shell Flange .

8 1 m/s2). Please note that due to program-specific issues with MathCad. Qualitative observations indicate that a significant amount of coke and heavy hydrocarbon products condense at the inlet to the exchanger. The purpose of this appendice is to confhn via temperature profile for the tube that the majority of coke would condense at the inlet.182 APPENDIX G: Product Cas Primary Condenser Heat Transfer Calculations The gaseous product exiting the reactor was directed through a double pipe heat exchanger that was originally installed as part of the modifications completed by Dong [104].for the "g" unit is attributed to the gravitational force (9. the duty and exit temperature of the product gas will be calculated. while the product gas flowed inside the tube. Cooling water flowed through the shell side of the exchanger. . In addition. the units designation for grams is bbgrn". the condenser unit was constructed of a stainless steel tube mounted concentncaily with a copper pipe sealed at both ends. Originally intended to provide the necessary heat duty to completely quench the reactor outlet gas.

5 in := 0. Dimensions for the double-pipe condenser are as follows: Shell length: Shell outside diameter: Shell wall thickness: Shell inside diameter: Tube outside diameter: Tube wall thickness: d to := 0.035 in tshe~ Temperature at inlet and outlet shellside: Temperature at inlet tubeside: T := 277 K T := 277.35 K (calculated) T hi := 973 K (no heat losses assumed from reactor outlet to condenser inlet since it was well insulated) (absolute pressure determined from Appendix B) (atmospheric pressure) W Pressure on tubeside: P tube := 122 kPa Pressure on shellside: Thermal conductivity of 3 16 stainless steel (Perry et al.43 Ïïx .035 in L := 15.5 kPa =0.130-T + 11.375 in t tube := 0. := 1.75 in d. Observations nom the cleaning of the condenser have indicated that the majority of coke formed at the inlet of the condenser.Temperature Profile for Primary Condenser Downstream of Reactor Outlet 183 The purpose of this cdculation sheet is to illustrate the temperature profile for the double-pipe heat exchanger constnicted for the cooling/condensing of the prduct gas exiting the reactor. This temperature profile will give an indication of the temperature at which the condensationkoke deposition occurs. [ 3 7 7 ] ) : P shell I := 9 1.

~Pa-s *a+Tci A T := . Temperature difference: Thermal conductivity: Viscosity: Specific heat capacity : Ci air .L + 2- Next.' --0.1000K (Perry et al. The heat gain will be significant due to the heat exchanger king uninsulated.175. The amount of heat gain. and the temperature difference. then. The ambient temperature is required for the correlations used to calculate the natural convection heat transfer coeficient described by Rohsenow et al. [4 161.1006 kg.h i pair --. therefore. T a := 294 K mL min The thermal conductivity of the copper and the arnbient temperature will be used to caiculate the heat gain fiom the environment..0637-T + 420. the temperature of the shell will be 277 K. the temperature difference between the copper shell and the bulk water will be asswned negligible. Since the water is much more conductive than the air.1 0 . the heat transfer resistance of the copper wall will be assumed negligible. F cw := 250.. Since the themal conductivity of the copper wall is much greater than the stainless steel. will be the product of the natural convection heat transfer coefficient.K Density : . the outside surface area of the shell. the physical properties of the ambient air is determined fiom the tables provided by Peny et al. Outside surface area of shell: A := n-d .6 F K . [377] at the average temperature (based on the wall and ambient temperature). The main heat transfer mechanism for the heat gain is natural convection to the outer shell wall and forced convection on the imer shell wall. [3 7 7 1 ) : Cooling water flowrate: Ambient temperature: W A copperm-0..Thermal conductivity of copper for 200.

Q wait := so . NUAT-h .~ ~ .503-10.713 A air The correlations used for calculating the natural convection Nusselt number are (Rohsenow et al. [416]): Nu = 7. the dimensionless Rayleigh nurnber is fmt determined.p .3 K 1 Before calculating the natural convection heat transfer coefficient.046 and the heat flux is. Pr air := P airoCpair Pr . avg 1 185 p air = 3.r = 0.b v-a and the Prandtl number for the air is.Coefficient of thermal expansion (assurning ideal gas): fl air := T .i. Ra- g .

347 10 + D p w . and the temperature increase due to natural convection heat transfer fiom the surrounding air is determined fiom the following: Tn:= 285 K (guess) ..28571 The mass flowrate of the cooling water is. := 0. E n := 0.1 103.1 0 ' ~ mol-K D pw := 5. B pw := 0.9953-10' J * molK' J ' mollS4 C pw := -2.27400 g m l := 18.3469.015 . Now the assumption that the cooling water temperature will not change significantly due to the heat gain f i o m the surrounding air is checked using the correlation for specific heat and liquid density of water by Yaws [566]: Liquid specific heat: A pw := 92.Therefore the heat loss fiom the heat exchanger shell is.3..053 J mo J PW := .10' T C pw-A pw + B pw-T+ C Pw '' Liquid density: A .~ 3 MW.

the overall heat transfer coefficient will be first calculated using the simplifj6ng assumption that the tube watl surface does not become fouled. The physicai properties of the product gas are calculated fiom the correlations for n-hexadecane described by Yaws 15661. = 97. First." / = 277 K Therefore the cooling water temperature is not afliected as a result of not insulating the heat exchanger. however.01 poise Cooling water Reynold's nurnber: Re . the Reynold's number for the cooling water will be determined. specific heat capacity and Prandtl nurnber of the cooling water must now be detemined pnor to calculating the tube outside film heat transfer coefficient (from Yaws 15661). := P 1wsucw..T \ \ / . eq Re .. Liquid thermal conductivity: . Flow area: Cooling water velocity: cw u CW := Equivdent diameter: Liquid viscosity: cP := 0.1 The thermal conductivity.root f'T n) . The assumption that the temperature of the cooling water does not increase significantly as a result of the uninsulated shell is valid. To calculate the temperature profile for the reactor product gas passing on the tubeside of the double pipe heat exchanger.

T ciJ m w Specific heat capacity: C plw := and the Prandtl number for the cooling water is. the total heat transferred to the cooling water is. Finally. [4 16 ] ) .A pw t B pw. := P 1w-cplw Prcw = 11. := 400 K (guess) Check to ensure that the assumption of negiigible wall effects is correct: . therefore the temperature of the outside tube wall skin is.539 Thus the heat transfer coefficient at the cooling water (outer) side of the tube is (neglecting wall effects) (Rohsenow et al. T . Pr. .T ci + C pw-TciL+ D pw.

the thermal conductivity of the stainless steel is. and the outside area of the tube is.L therefore the temperature difference across the steel based on Fourier's equation is. A to := n-d to.316 lww which is significant and the heat transfer coefficient must be recalculated using the viscosity correction factor until the outside wall temperature converges to a constant value. a check of the temperature difference across the tube wall will be completed to determine if the thermal resistance of the metal wall c m be neglected. .1. AT steel '= cw' tube steel-A to The thermal resistance of the steel can therefore be neglected and the inside wall temperature is 287 K. Defined previously. Now. * wo := 400 K (guess) Thus the converged outside w d temperature rS 287 K. Iw .finally the ratio of viscosities is.

The total heat transferred fur a clean tube is detennined fiom the following: cli:' hg-in-d i \ ti *. / q i = 6. := 0. The coefficient will be determined for the entrance initially (assuming the flow is hydrodynamically fully developed). .78 W so that.0. the heat transfer coefficient at the entrance (neglecting boundary layer effects) is: From Appendix B the thermal conductivity of the gas is. then a vector will be created for illustrating the temperature profile for a clean heat exchanger. Ig . [416].LS) T . -.\.952 i 4 ' cw and the heat balance is complete.Finally the heat tninsfer coefficient for the entering product gas will be determined 190 using the average Reynolds and Prandtl numbers for the upper section of the reactor calculated in Appendix B.04 Using the correlation developed by Gnielinski and presented by Rohsenow et al.067 W and the average inside heat transfer coeficient for the total exchanger length is. Reynold's number for product gas: Prandtl number for product gas: Re 2 := 2453 Pr := 1.

and the solution for the outlet temperature found.3458-10g .t := 0.013 gm mol n-Decane gas specific heat capacity: A := 31.2. K J D := .0665 S and the mass flowrate of the product gas is: g := 142.10- J ' molK C := .1. t := 28.The product gas outlet temperature can now be estimated using the clean exchanger 191 condition and assuming the heat capacity is adequately described by the correlations for n-decane presented in the text by Yaws 1. .1161. c i=' Molecular weight: M W g.780 J Eax I O ' J B := 7.0945-10-~ mol. MW .4489.~+ 3E g .26680 mol-K~ E := 9. The mass flowrates for the nitrogen and n-decane have also been previously described in Appendix B. Nitogen mass flowrate (set via Matheson flowmeter): gm m . noDecane is used as a mode1 compound based on the assumptions fiom Appendix B. ~ 4 J '' a C pgasmA g + B g*T+ C g Nitrogen heat capacity: * ~+ 2D The objective function to be minimized can now be described.285 .

and the residence time calculation should account for the length of tubing to the first condenser pot fiom the reactor outlet. However. Since this exchanger serves primarily as a surface upon which coke deposits (based on qualitative observations). the residence time cannot be accurately determined for this reactor given the collection train construction used for the experiments described in this thesis. . To account for the unknown time to quench at the exit of the reactor. and the calculations in Appendk I show that the inlet feed is not at reactor temperature for the fint 3% of the lower section length.5 K i\ 1 O/ Thus the double-pipe exchanger is capable of removing very little of the heat carried by the product gadnitrogen mixture. the unit should be removed and either replaced with a more effective design or a straight tube. T h \ = 972.nit rT ho root lf(T ho\ . Since the buk gas temperature does not change significandy for even the best case of a clean wall. the primary condenser has been shown to provide very little benefit for removing heat fkom the product gss. even though the work by Hirato et al. with an error that could only be determined by the addition of temperature measurement to the collection train. due to the very cool wall temperature. However. the point at which the product gas is quenched in the collection train is unknown: there w a s not temperature measurement along the collection train path. Thus. Thus. the residence time was calculated assurning that reaction occurs at the same rate for the whole length of the reactor. this heat exchanger does not quench the gas. From the above calculations. the residence time calculated using the whole reactor length will consistently overpredict the tnie residence time. [190] shows that the major portion of the products are formed in the second half of the reactor. the gas that does contact the surface will cool suficiently to force the coke and heavier products to deposit locally.

the units designation for grams is "gm'. During construction. a heat transfer enhancement feature was added to the nitrogen tube in the fom of a stainless steel twisted tape. lOOOW fumace describeci in Section 3. Please note that due to program-specific issues with MathCad.APPENDIX H: Nitrogen Preheater Heater Transfer Calculatioas The nitrogen preheater consists of a stainless steel tube passing through the Applied Test Systems Inc. for the "g" unit is attributed to the gravitational force (9. .8 1 m/s2). The tape was inserted the full length of the tube that resided inside the hace. The purpose of this appendice is to detail the calculation method used to determine the maximum mass flowrate of nitrogen that the fumace is capable of heating such that the outlet temperature is a constant 350°C.

3 14 J i i a x Tape thickness: 6 := 0. := (350 + 273) K . Next.0 mm Tube inside diameter: Temperature at inlet tubeside: T i := 294 K Temperature at outlet tubeside: T . the system dimensions and operating conditions will be described: R := 8.125 in Tube length: Tube outside diameter: Tube wall thickness: Twist pitch Iength: H := 45.Nitrogen Preheater Heat Transfer Calculation An illustration of the twisted tape insert geometry is provided below.

t := 0.10.130-T + 11.1000 W Al1 physical properties for the nitrogen were determined from the correlations described in the tex.31 16.1 4 ' mol-' K J J Eïz D nit := -4.t := -3.1 0 ‘ ~ J C kt := 1.Pressure on tubeside: P tube := 132 kPa (absolute pressure determined from 195 Appendix B) (atmospheric pressure) Pressure on shellside: P shell := 91-5 kPa Thermal conductivity of 3 16 staidess steel (Perry et al.43 W m-K q m x .5395.0665 gm S - MW nit := 28.i l mol-K~ mol-' K Nitrogen thermal conductivity: .--.013 IF" moT J mo B . by Yaws 15661: Nitogen mass flowrate (set via Matheson flowmeter): Molecular weight: Nitrogen heat capacity: A ~ i := t 29.5935. 13771): Maximumpoweroutput of h a c e : )i steel -0.0076. los9 J E nit := 2.342 m .

d ti2 .~poise 196 Now. viscosity. the Reynold's number for empty tube flow is necessary dong with the Prandti number. the maximum flowrate of nitrogen through one tube in the fumace.606 )LP lip := 1 0 . and the density.30-MW nit The heat transfer coefficient for the tube complete with a twisted tape insert will now be calculated using the method of Manglik and Bergles [309] [3 IO]. with a flowing veiocity in a straight tube of: nitmax u StC := x P .it$. As part of the calculation. is as calculated fiom the following: max' 0. and thermal conductivity values are.Nitrogen viscosity: A p i t := 42. assuming 30% of the maximum power deliverable is transferred to the nitrogen. Both numbers will be evaluated using the average temperature between the inlet and outlet.

The wall temperature is assurned equal to that rneasured in the bulk air space inside the furnace. Pr dt := C ni& pnit " nit Pr dt = 0. T w i s t ratio: y := q H y = 2.735 Now. First the Nusselt number for a tube with a straight tape insert is calculated. Wall temperature: T := 1273 K The Nusselt number for the straight tape insert is calculated using the following: . the twist ratio and the Swirl parameter is calculated according the relationships defined in the work by Manglik and Bergles 13091. nit and the Prandtl nurnber is. then a second Nusselt number is calculated based on the twist ratio. the correlation developed by Manglik and Bergles [310] will be used to calculate the heat transfer coefficient.605 Swirl parameter: Swirl flow length: Since the flow is in transition to the turbulent regime.Thus the straight tube Reynold's number is.

then.~ nit If the Msted tape was not used.d.4 W is the maximum heat transferred to the nitrogen. :=. Nu SW.. The heat transferred to the nitrogen. Therefore the twisted tape provides an 10% improvement over having just a straight tape in the tube.and the new Nusselt number that accounts for the twist ratio is calculated next: Therefore the heat transfer coefficient is. then the maximum flow of nitrogen is detemined from the following: . ~ t + 2 . t i * ~ s ~ .~ ~ ia~ vz g2 jW 9. / ~ ~ w l. h.4 8 Since the calculated number of 29. is defined by the following: q n i t : = h s w . ' ~ + d t i . the heat transfer coefficient would be.

provided the desired outlet temperature is 350°C.067 g/s nitrogen flow. . This calculation corresponds well with the operating data. for the controller output operated within the 2530% range during expenmental runs with 0. 0 81 g/s.4 nitsMW nit Therefore the maximum mass flowrate for the nitrogen entering the reactor inlet vapouriser is 0 .

the units designation for gram is "gm".81 m/s2). the outiet temperature of the heat exchanger will aiso be determined. In addition. Please note that due to program-specific issues with MathCad.APPENDXX 1 : Reactor Inlet Feed Vapouriser Calculations Prior to entering the reactor. . for the "g" unit is attributed to the gravitational force (9. the gas oil f d was mixed with the hot nitrogen and directed through an enhanced (cormgated) tube heat exchanger. The heat exchanger was coiled around the outside of the reactor such that a constant heat flux existed at the exchanger wall. The purpose of this appendice is to detail the calculations for determinhg if the gas oil feed was completely vapourised pior to entering the reactor.

the final temperature d e r mixing will then be determined prior to entering the vapouriser. Thus the temperature rise of the nitrogen is from 20°C to 350°C. the sensible heat available at the point of the nitrogen mixing with the feed will be calculated.Heat Balance for Reactor Inlet Vapouriser 20 1 First. The temperature of the entering feedhitrogen mixture will also be detennined. Assurning adiabatic mixing. a constant heat flux at the wall will be the assuming boundacy condition for determining if the feed is completely vapourised prior to entering the reactor. and the sensible heat is: . Upon entering the vapouriser at the calculated temperature. The feed i s assumed to be pure n-hexadecane.0665 S The sensible heat carried by the nitrogen is the heat added by the nitrogen preheater (fumace). and the pressure is assumed constant at 141 kPa Ail the physical properties are calculated using the correlations developed by Yaws [566]. Molecular weight: Nitrogen heat capacity (Yaws 15661): Nitogen rnass flowrate (set via Matheson flowmeter): gm m nit := 0.

it' J *623 K (A nit 202 293 K + B nit*T+ C nit.1 16 S Since the mixing of the nitrogen and n-hexadecane is adiabatic.~4'.1478*10-~ mol-IC3 J D f := 5. dT i 7 Assuming the n-hexadecane feed enters the mixing zone at 20°C.T + D .7520.101 J iiïm'c B f:= 2.~ molX4 and the mass flowrate of the liquid feed is set at: gm m f := 0. the sensible heat is constant.~ 3 + E nit. the final temperature of the adiabatic mixing is detertnined as follows: Liquid n-hexadecane heat capacity (Yaws [S661): A f : = 89. t . *Tmix C pfdT + nit ' 293 K J -T mix 623 C pitdT .1 0 .q := * nit MW. Therefore.7062 J mol*K ' J C f : = -6.

From Yaws 1 5 6 6 1 . the total heat required to completely vapourise the feed and raise the nitrogedfeed mixture temperature fiom 157OC to a reactor temperature of 700°C is determined from the following heat balance equation: Each heat term is calculated €rom the mass flowrates and physical property relationships defined earlier and in the text by Yaws (5661.the heat of vapourkation of the feed at 580.01 K (fiom Yaws [566]) T bfp := 600 K Thus the boiling point of the n-hexadecane feed at 1 4 1 kPa reactor pressure is.T mix := 473 K (guess value) and the finai temperature of mixing is. root (f(T ) \ . := 433.the boiling point of n-hexadecane adjusted for the pressure of the reactor is calculated from the Sydney and Young equation described in the text by Syncnide [4763.7 K is. . 3 2 5 wa P := 141 kPa mmHg := P = 1.2 K T .058lo3mmHg 760 T bf := 560.2 K Now. .T = 433. kl := 1000 J Thus. 101 .

J B fg := 6-7397.750K z.~ mol' K E fg := 3.7770. [350]. vreqd := q sfl + vapf + 9 sfg + snit q vreqd = 270-9 Now the heat transfer coefficients for the conugated tube will be calculated using the temperature range of 157°C to 700°C. A fg := 13 1. [4 161.1 0 . then the Reynold's and Prandtl numbers for the assumed single phase gas mixture will be determined.10. The boiling heat transfer coeffkient will be calculated using the correlation by Negishi et al. ' . The total surface area of the comgated tube will first be calculated.10- J ' molKi J C fg := 8. The single phase coefficient will be calculated using the correlation developed by Ravigunirajan and Bergles described in the text by Rohsenow et al.2430.'O Therefore the total heat required to completely vapourise the feed and mise the mixture temperature to 700°C is.1 0 .9785.( A ~ + B f T + C f ~ 2 + D f ~ 3 ) d ~ mix 9 vapf : ' w f mf vapf and the vapour heat capacity is calculated fiom the correlation by Yaws [566].~ mol-K ' J molKS J D fg := .1.

the surface area of the tube wall for one fold will be: diarneter of fold: d fold := 1.Calculation of Heat Trnosfer Coefficients for Inlet Feed Vapouriser 205 A cross-section of the vapouriser wall with dimensions in rnillimeters is shown below.76 mm surface area o f one fold: .55 mm length of fold: L fold := 2. From the drawing above.50 m m inside diameter of tube: d i := 4.35 mm linear height of fold: 1 fold := 2.

given the total length of the vapouriser and that there is one fold per 2. For calculating the heat traasfer coefficient for the enhanced tube.206 Now. A total = 3. fold : ' 2 1 Compared to a straight tube. the increase in surface area with this vapouriser is. then the total surface area is calculated. although the gas oil will be assumed to have the same properties as n-hexadecane for simplicity. the correlation for single phase heat transfer developed by Ravigururajan and Bergles and descnbed in the text by Rohsenow et al.5mm.134 thus the corrugated tube wall increases the tube surface area by a factor of -3. Some parameters used in the correlation are defined as follows: and the Reynold's and Prandtl numbers are defined as follows: These dimensionless quantities are calculated at the average temperature of the vapounser using the relationship. . This correlation requires the physical properties of the feed gas oil plus nitrogen. [416] was used.

An- The physical properties for the feed and nitrogen at the average temperature is calcul%.7500. MW f Vapour density (compressibility factor assumed negligible): p fg := p nit := p r e m.10' K 1 @ s pnit := -9.~ pise B pnit := 4. pnit : ' A nit + nitsTvavg + C nit0Tvavg 2 + D nit0Tvavg 3 + Eni~T vavg 4 P r.d from the correlations by Yaws [566].t R*Tvavg TG l vavg Component themal conductivity: nit := A h i t + lnit'* vavg + C AnitSTvavg 2 Component viscosity: Cip := 1 0 .8800.1 O- d K- .

R . u := nit + Pm&? f m u = 7. Thus. the mixture mass fractions for nitrogen and feed and the total density must be calculated first: x f:= mg a.d iZ The method of Wilke (Reid et al [442]) is used to determine the nitrogedfeed combined viscosity and thermal conductivity. In nit Molar flowrates of nitrogen and feed: Inf v n i t :nit = ~ nit fg + f fg := W Y fg := fg Mole fractions of nitrogen and feed: y nit := " nit " fg + nit 9 1 21 := +1 12- P fg . .The fluid velocity is now calculated based on the assumption that the bulk flow will208 occur through the cross-sectional area defined by the inside diameter of the comigated tube.t x. mf+m.t:= l -Xf 1 -P mix -X f Xnit -+- P fg P nit and the bulk velocity through the tube is.429 S .MW nit -V nit .

995 mix The Reynold's number for the operat ing conditions described lies outside the range defined by Rohsenow et al.1161 (Re>5000).O1 12 Y fg + Y nit-41 21 Finally. [4 163. then the Nusselt number for an equivalent straight tube is determined. 2 8 ~ ~ . the heat capacity of the m i m r e is.' A pmix Pr = 0.3 .- + Y nit + Y fg.$1 21 := $1 12*-* Q-- MW. Finally. For the straight tube: f str := ( i . First the friction factor for the straight tube is calculated. the Nusselt number of the comgated tube is calculated from the correlation in Rohsenow et al.t A nit -NIWT A mix -- . however.ln( Re) .58. Therefore the Reynold's and Prandtl nurnbers are: Pr := P mix. 1. the correlation will be assumed vaiid to the calculated Reynold's number.

[3SO]is based on boiling water at various angles of inclination. .O7 T-Re-Pr f . the comgated tube Nusselt number is: thus the heat transfer coficient for the enhanced tube is found fiom the following: Therefore the maximum theoretical heat that can be transferred by the corrugated tube vapouriser to the single phase fluid fiom the boiling point temperature of 58 1 K to the reactor temperature of 700 K is calculated by assuming that 80% of the vapouriser is used for heating the gaseous mixture (the first 20% is used for boiling).and the straight tube Nusselt number is: Nu str := 1. Al1 correlations presented are described in the text by Yaws [566]. M l y .the correlation by Negishi et al. Thus. The angle of inclination for this calculation will be set at zero. Now. + 12. A nurnber of physical properties for the liquid n-hexadecane is required prior to calculating the boiling heat transfer coefficient.7. and the heat required by the first 20% of the heat exchanger is.

1 . 0 1 5 2 7 ~ .l+ 1 - bfp n O G- 1 = 57.1 K C p l : = 0 .Liquid viscosity: Apl:=-8.1894 cP := 0.i~ ~ : = .092 - dyne cm .~ Liquid thermal conductivity: Liquid surface tension: q:=A.~ ~ .0 1 poise B g : = 1557. 1 0 .092 O fl := 57. 2 3 7 1 .

703.1.if:= R-Tbfp -p mix -- -+- Xf Xnit P nit P fg p mix .847 kg mS Two additional parameters required by the correlation by Negishi et al. 103 W m- O .Liquid density: 212 Liquid heat capacity: A fl := 89. The 330W power assumption is based on the bottom reactor heater supplying one third of its total power to the total length of the enhanced tube. [350] is the heat flux and the fluid to tube volume ratio. Thus the heat flux to the wall of the vapouriser is: power := 330 W Q waii := power total Q waii = 7.7062 J mol-K p . The heat flwr to the wall of the vapouriser will be assumed to be 330W divided by the total surface area of the enhanced tube. .101 J iïax B := 2.

is required before calculating the heat transfer coefficient.[.[ 2 + thusthechargeratiois: ï:= L v*o-2@ ï = 13. the fluid charge ratio on a per second b a i s can be calculated fiom the following: and the volume of the vapouriser is: 1 v := T.. For a constant mass flowrate of 0.jd i + fold + -)] fold + (d i + fold l fold) i folciml folclon. 13501.213 Finally the fluid charge ratio.5". The correlation will be assumed valid for this extrapolation. and the correlation will be assumed valid in this case. then. . Next. the psi value which accounts for the inclination angle will be calculated. T.777 which is outside the valid range for X as described by Negishi et al. The inclination angle for this vapouriser was 22.595 percent which is less than the lower bounds of correlation developed by Negishi et al.1 16 gmk. Thus the heat transfer coeffrcient for the first half of the vapouriser is: AH vap := 213. Dryout is the end result for this vapouriser. The fluid charge ratio is defïned as the volume of liquid to haif the volume of the vapouriser.d fold2. [350] that was set based on the phenornena of dryout occurring in the apparatus described by the authors.

Sensible heat required by feed and nitrogen (gas): 9 sfg + 9 snit = 198. The total theoretical heat that could be transferred in the first section of the heat exchanger is. the feedhitrogen gas mixture is not heated to the reactor temperature before exiting the vapouriser based on the heat required and the heat delivered.TV MW- . which is much greater than the required 213 W.Therefore the average heat transfer coefficient for the first (boiling) section of the vapouriser is. Therefore the assumption that the feed is completely vapourised pnor to entering the reactor is valid.2 W Therefore the fluid temperature at the exit of the vapourïser is: + nit .1 W Heat transferred to fluid: q vg = 58. However.

6 K (( The exit temperature is 324"C. and the length of reactor required for heating the fluid to a temperature of 700°C is calculated nom the temperature rise per unit length calculated in Appendix B. T v j = 597.root f T v j . .267 m or a total of L I100 = 3 reqd percent of the total length of the reactor.T V L reqd := 1 L reqd = 0. Reactor Iength required: Tr.

for the "g" unit i .8 1 rn/s2).216 APPENDIX J: Reactor Residence Time and Axial Dispersion Calculations The following pages provide the detail for the determination of the reactor residence time for the flowrates studied. grams is "gm". the units designation for s attributed to the gravitational force (9. An estimate o f the axial dispersion number as defined by Koutsky and Adler [274] is also provided. Please note that due to program-specific issues with MathCad.

400 in H 1 := 1 2 . 11 6S rn nit := 0.~ m3 .K Now the molar flowrates for the feed gas oil and nitrogen are calculated: gm m f:=0 .013 gm mol . := 3 in 5 d20:=xh Helk outside diameter: Length of 3/16" tube: D := 3 .3611 0 . \ n V = 3. 0 2 8i n S / l 6"tube wall thickness: t 2 := 0 .d . 31 4 mol. 4 5 kPa P rg:= 6 psi P . 0 1m Section height: H 2 := H 1 Reactor Volume (the exit straight tube volume is not included based on the discussion of residence time located at the end of Appendix G): ln V := b . 0 3 5i n Outside diameters: d1 . 9 2 5i n Section height: Pitch := 0.:= P a m + P rg J P r = 1330kPa Universal Gas Constant: R := 8 . 0 0 0 in Length of 5/16"tube: Pitch = 0 . Assuming the pressure in the reactor remained constant: kPa := 1 0 0 0 Pa Patm := 9 1 .ReacLor Volume and Residence Time Calculation 3/16"tube wall thickness: t 1 := 0 .0665 gm S MW f:= 219 ~"'-' mol MW nit := 28.

The reaction temperature is calculated using the procedure in Appendix N.. 9 0 7 0 < ~ mol nit :' nit nit n nit = 8.546 mol 218 Then the molar flowrates of the products are calculated fiom the gas and liquid analyses provided in mass balance tables in Appendix M. The total reaction time is aiso provided in the mass balance tables. 7 for the seven successfiil expenments completed in thi study. g q . min Mass gas := i := 1 .mf nf:=-f nf = 1 .

v r Residence T h e : Bi := and the results are summarized in Table 4. The pressure drop. and density for each reactor temperature were calculated in Appendix B and will not be re-calculated here: For nitmgen: MW nit := 28. Based on the reactor construction. velocity. it is assumed accurate for a first approximation. the tubes can be assumed circular in cross-section.1. Aithough this method does not accurately detemine the residence time (see Appendix G) due to the unknown quench time.067 S Viscosity calcuation is fiom the correlation of Yaws [566] pi' := 1 û 6 poise . Now.013 Bm from Yaws [566] mol gm m nit := 0. the axial dispersion calculation is based on the method presented by Koutsky and Adler [2W].Thus the residence time for each reactor temperature is calculated according to the 219 equation described by Hirato et ai [190]. therefore the ratio of diamters is 1 (parametet required for graphical interpretation).

cf := 0. the mass flowrate of the feed LGO and nitmgen is: m nit = The density of the inlet feed: MW f := 219= PiMWf Pfi:= And for the hydrocarbon vapours: MW gas := the viscosity is calculated fiom the correlation descnbed in Appendix B.067 gm O - s and the mass fractions for the frac nit := nitrogen and LGO feed is: LlLL frac f := f nit + mf *nit + f The average density of the reacting mixture based on the inlet and outlet densities is calculated then the total density of the nitrogen plus the reacting mixture is determined.01 poise NOW. .

-fJ mnit niti mf P ~2~ L :.therefore the velocity of the total gas through each section of the reactor (sections #1 and #2) is defined by the equations to the right. and the Reynold's nurnber for each successful run was determined in Appendix B.d 12 g . . the pressure drop for each section is defined below (see Appendix B for calculation dehils): 22 1 + 1i +- nit - f . and the fiction factor for an equivalent straight tube is given by .d 22 thus the fiction factor for turbulent flow in a helical coi1 is determined from the correlation developed by Ito [201]. P niti p fi -+-U 2.

the axial dispersion number for an equivalent straight tubes is.10- 4 ~ ~ ~ ~ . Now. NDI NDlstr = 0. The axial diffusion number for the upper section of the reactor could not be calculated for the correlation was not valid for laminar flows.222 finally.7 + 1 . Thus from the correlation presented by Koutsky and Adler [246]. el R - I ~ t N D lstr ~ = 2. thus the ratio of dispersion numbers for the helical coil and an equivalent straight tube is. and based on the Reynold's number calculations fiom Appendix B.792. the average axial dispersion number for al1 experimental nuis is calculated. the dimensionless quantity required for the correlation by Koutsky and Adler r2491 is: fiom table 1 in the work by Koutsky and Adler 12491. the linear average Reynold's number for the lower section of the reactor is first calculated. Dlstr --- 1 :3000 60. for comparison to straight tubes.929 therefore the helical coil reactor more closely approximates an ideal plug flow reactor. finally fiom equation (7) of Koutsky and Adler [249]. .

An inlet/outlet temperature difference must be maintained to properly achieve the desired end run temperature. For exarnple. the inlet temperature must be 520°C and the outlet temperature must be 480°C. until reactor attains 90% o f setpoint temperature. place the main reactor heater controller in automatic and slowly increase the setpoint until the desired reactor temperature is satisfied (based on Labview temperature plot). Leave bag under vacuum until ready to take a gas sample. Ensure the regulator at the gas cylinder is set at 44 psig and the flowrate is set for the desired flow using the Matheson Mode1 763 1T-604flowmeter.APPENDIX K : Operating Manual The following procedure was used for ail experimental runs: 1.0 Pre-Experirnent S t a r t Labview data acquisition system on lab PC (d:\Cuthbert\Mike\s4. Power up the nitrogen pre-heater (Applied Test Systems Inc. to operate the experiment at 500°C. Set at 25% and 30%. Open the nitrogen cylinder valve m 0 ) to begin flow to the reactor. Fi11 the Wet Test Meter (WTM) with tap water and zero the meter. Open valve P6 to vent the nitrogen purge. Ensure the air valve. respectively. Tum on pumps and recirculate oil until ready for experimental run. Attach gas sample bag to vacuum line and open sample bag valve to begin vacuuming the bag.Series 3 110) and set the h a c e controller in automatic with a 350°C setpoint. Ensure pumps #2 and #3 are set correctly and the recirculation and feed valves are open. F 1 1. . Record the water temperature from the thermometer attached to the WTM.~i). Once the 90% temperature is met. is closed. Power up main reactor heaters and reactor bottom heater and their respective switches (main reactor heater switches are knife-gate type).

Typically. Monitor system visually and via Labview to ensure proper operation. O Erperimental Run Initiate data acquisition on the computer by clicking on the "Log Reactor" toggle switch on the screen. 1. close the bag valve and reopen the WTM discharge valve that goes to vent (P6). 2. the outlet connection on the distillation unit mut be plugged to force al1 the water to flow to the reactor collection system.8 Ensure the hydraulic oil transfer cylinder is filled to an approxirnate volume of 2 0 0 mL via the transfer pump (vane-type).a manual setpoint of 5% o n the main heatea and 50% on the reactor bottom heater is adequate for a least a two hour runtime.224 1. Purge the sarnple line with product gas for one minute. . Typically. Open the sample bag valve. and fil1 the bag. then attach the sample bag while the line is purging. To achieve adequate flow through the condensers. Once full.and allow the oïl pressure to Close the hydraulic oil recirculation valve. Open valve F6 to begin flowing to the reactor and start the timer. Obtain gas sarnple fiom the outlet of the WTM once the inlet and outlet reactor temperatures have stabilized and attained a minimum difference. Adjust the power output to the heaters on the Yokogawa controllen as necessary to maintain the desired reactor temperature. a temperature difference of 5°C is realized at approximately 203Ominutes into the run. The valve is located at the fume hood. H build up to 10 psig. Obtain another sample if cornpleting a long (>75min) m n to ensure repeatability.9 Pack ice around both condenser pots and ensure the cooling water is cracked open. There will be a slight disturbance in the temperature due to the intermittent stoppage of gas flow while sampling occurred. Close P6 and open P7 to start the WTM. 5 .

Attach the burn stage condenser. Replace filter media in fibre filter unit. Clean condensers and tubing using dichloromethane. . Record the WIM reading. Transcribe reading to mass balance spreadsheet. Close FI 0 and open P6.Stop the feed flow to the reactor by closing F6.10 Clean condenser pots and distillation pot with solvent provided.1 1 Stop recording data by clicking the "Log Reactor" toggle switch on the computer screen. Re-assemble condenser train in preparation for next experimental run. Power down the pumps. Disassemble the condenser train and ensure each condenser pot is corked immediately after disassembly. open F 11 and close FI 0 to begin purge. Open valve F 10 to begin pwging the reactor. [fan analysis of the quantity of coke and extra-heavy hydrocarbons produced during the experimental run is required. 3. Record the masses in the m a s s balance spreadsheet. Obtain the mass of the condenser pots. Open hydraulic oïl recircdation valve H 5 . and distillation pot. Increase the power on the main reactor heaters to 30% to begin the burnlpurge stage. Place the collected fluid/solvent mixture in the distillation unit and switch on Variac to begin heating the mixture. Set the air flowrate at 45mm on the Matheson flowmeter (glass ball). Stop the data acquisition system by clicking on the toggle switch located on the Labview "s4. fibre filter media. refer to the procedure described by Dong [104]. 3. Boil until al1 solvent is distilled" screen. Afier five minutes.

The following tables confimi the manufacturer's general specification for measurement error.APPENDIX L : Thermocoupk Calibrations and Locations Al1 thermocouples used for temperature measurement on the reactor and inside the reactor tube were type K with an Inconel 600 sheath. . The inlet and outlet thermocouples had -90% of the total length inserted into the reactor tube to reduce errors due to heat conduction through the sheath.


0 1 0 . DevL Thennocouple Meastuernent Measured Measured Tc No* Voltage Temp value (C ) (mV) (C Percent Error Calc. 3 0 0 . 4 0 0 .O6 1. 0 2 -1 .99 17. 4 0 1 . 8 1 0 . 2 0 0 .36 1 3 . O 3 1 . 2 8 0-34 0 . 4 2 14.02 0. 0 2 0 . O 4 -1 . 0 5 0 .22 0 . 0 1 0 . 0 2 0 . 1 . 0 4 -0. 5 0 0 . 38 0 . Voltage (mV) (mV) (temp. 4 0 0 . O 6 1 1. 0 4 -1-04 1 . 0 1 Mean S m Sq.~2 ~3 ~4 ~6 SS 0 .04 -0.22 3 . 0 1 0 .05 -0.O6 1-05 1 .O3 1 . 0 2 -0. O 5 13 . 3 5 0 . 3 0 I Dev Std. 4 4 0 .) .

Voltage (mV) Percent Ermr (mV) (temp. Std.26 1 TC No.54 0. Test Value (C Thermocouple Measurement Measured Measured Temp Voltage 1 Calc. 0.S I S m Sq.) (C ) (mV) . Dev.

.Sum Sq. Std. Dev.

2 Thermocouple Locations and Channel Numbers External Multiplexer Board - Misc.Table L. at accumulator vesse1 inlet Fumace gas inlet NIA Cold Outlet ieactor Quenck NIA NIA III Exchanger Outlet Bitumen Temp. TIC I Furnace water inlet Reactor Bulk Steel Accum. Channel Unit TIC Function No. - Description - High Limit Low Limit Chart Number (C (C ) - Chart Label O r TIC TIC TIC I m TIC TIC TIC TIC TIC Cold glycol outlet to tank cooling coils Glycol temperature at reactor quench Glycollsteam heat exchanger outlet ~i tumen temperature in holding tank Outlet from Pre-iieater # 1 Product gas temp. at impingement plate Reactor bulk steel temperaturc Glycol temp. Temp. Array No. Preheat 1 Product Gas 120 III User User User User IV User III NIA NIA m. Glycol 1n Furnace Gas Inlet Fumace Water Inlet .

ai~ds amds aieds iasn III 1 VIN VIN amds 1 VIN VIN .

3 National Instruments Data Acquisition System Board Channel O 1 2 3 4 5 6 L 7 8 9 10 11 12 13 14 15 16 Unit TIC High Limit Low Limit Chart Function Description Chart Label No.Table L. (Oc) (OC) Number CJC Cold Jwiction Compensation CJC Il T/C Tube 1 Reactor skin temperature 600 O 1 12 Tube 2 T/C Reactor skin temperature 600 O 1 Tube 3 13 Reactor skin temperature 600 O 1 TIC 14 Tube 4 TIC Reactor skin temperature 600 O 1 15 Tube 5 TIC Reactor skin temperature 600 O 1 16 Tube 6 Reactoï skin temperature 600 O 1 TIC 17 Tic Reactor skin temperature 600 O 1 Tube 7 18 TIC Reactor skin temperature 600 O 1 Tube 8 19 T/C Reactor Inlet Reactor inlet temperature 600 O 1 20 TIC Reactor Outlet Reactor outlet temperature 600 O 1 T/C MUX Multiplexer input A TIC MUX Multiplexer input .B spare spare - spare 17 18 19 20 21 - spare spare spare spare spare spare - .

.. Raise oven temperature at 20°C/min until 220°C reached 4.Light Gas Oil Tb > 343OC ... Inc..Heavy Gas Oil .... Please refer to Appendk P and Q for a summary of the successfül and rejected experimental runs.... Gas samples were collected in 1... Hold for five minutes at 50°C 2..... Rejected experimental runs are not included in this appendix. Elizabeth Zalewski of the Oil Sands Research Group.. Hold for five minutes at 220°C Al1 molecular weight values are referenced in the text by Yaws [613]... The gas analyses were performed by Dr. Al1 anaiyses were performed by Ms.... Raise oven temperature at 10°C/min until 130°C reached 3.... The liquid components are divided into the following groups based on boiling point: Tb< 196OC .. Liquid sample mass was measured using the calibrated Metzler scale located in the undergraduate unit operations laboratory.. The GC was programmed for the following temperature ramping rates: 1. ~ 0. Nancy Okazawa of the Oils Sands Research Group at the University of Calgary using a Hewlett-Packard 6890GC with Porpak Q and Molecular Sieve packed columns with 28mLlmin helium carrier flow and a TCD detector..53mm bonded phase column (SM 289216) using the ASTM D2887 Extended Megabore method (ASTM [25])... 9 I..... 10m x 0 ..............234 APPENDIX M: Mass Balances The following tables detail the mass balance and gas and liquid molecular weight calculations. Naphtha 196OC 5 Tb5 343OC ..2L plastic gas sample bags complete with an integral sampling valve fiom Fisher Scientific.D. The liquid analysis was determined using GC simulated distillation using a Hewlett- Packard 6890 GC with a Separation Systems... Al1 glassware was cleaned with dichloromethane and allowed to dry prior to re-use..

G. Table M. and axial dispersion number (Appendix J) are based on the data provided in the following tables. Mass Gas Mass Calculation Total Nitrogen Mass Gas Vol @ STP Condenser Pot # 1 Condenser Pot #2 Distill Pot Fibre Mat Box Standard Conditions Temperature Pressure Reactor Pressure Nitrogen Volume (@ STP) . 02-2 1-0 1-0 1 Mass Balance Surnrnary Middle Distillate Thermal Cracking Experiments Mass Balance Sheet Reactor Temperature Total Mass Input Experiment Total Mass Ouput Date Liquid Flowrate Mass Balance Error N2 Scale Reading Recovery N2 Mass Flowrate Duration of Exp't 436 O C Condenser Pot # 1 Condenser Pot #2 Distill Pot Fibre Mat Box Liquid Mass Condenser Pot #1 Condenser Pot #2 Distill Pot Fibre Mat Box Total Liq. residence time (Appendix J). and 1).The cdculations for pressure drop (Appendix B and 1). heat transfer coefficient (Appendix B. 1 Experiment No.

002 wt% 0.000 W t Y o 0.00 5.9 1 743 1 GC Data Molecula. Weight ovgen Nitrogen Carbon Dioxide Methane Ethylene Ethane Propylene Propane n-Butane n-Pentane Total Comp. Bai.20 2783 -73 8.000 W t Y o 1.o0owtO/o 0.00 2805.001 wtYo 0.Gas fiom Cracking Mass of Gas Mass of HC Gas WTM Calculation Initial Reading Final Reading Differential Press Water Temperature Barometric Press Vapour Press.00 0.000 wtY0 0. Equivalent mass fiom total moles defined by Total Component Balance 3.000 wtY0 0.48896 mmHg (correlation fiom Yaws [566]) 0.003 wt% 0.O00 .19 0. H20 WTM Corr.12 0.28 4.992 wtYo 0.00 1 MY0 0.00 0.86 0. Factor Gas Anaiysis 16.00 0.

10 0.00 0.00 0.1 1 MW Frac.Component Density @ STP (fiom Ided Gas Law) ox~gen Nitrogen Carbon Dioxide Methane Ethylene Ethane 1.407 k / m 3 2.00 0.05 0.05 o.00 0.325 kg/& 1.08 0.07 0.14 20.04 0.00 0.00 0.245 kg/m3 Propylene propane n-Butane n-Pentane Total Gas Density 1-743kdm3 1-826k / m 3 2. 4 5 6 7 8 9 10 11 12 13 14 15 mol mol % 0.988 k g i d 1.140 Carbon Dioxide Methane Ethylene Ethane Propylene Propane n-Butane iso-Pentane Liquid Product Analysis Carbon No.05 0.0 1 0.321 14. 0.54 23.162kdm3 1.00 0.32 13-58 19. 160 5-108 Nitrogen 99. 100~01% O.162 kg/& Molecular Weight of Produced Gas Calculation Norrnalize wrt N2 MW Contribution Oxygen O.00 0.05 0.20 1 VOI'YO 0.49 8.00 0.05 0.00 0.1 1 1.00 0.160kdm3 1-823kdm3 0.76 .02 0.00 0.41 4.03 0.373 vol% 0.00 0.664 kdm3 1. 10 0.0 1 0.

Molecular Weight of Sample: Mass Fraction of Naphtha: Mass Fraction of LGO: Mass Fraction o f HGO: .

2 Experiment No. Mass Gas Mass Calculation Total Nitrogen Mass Gas Vol @ STP Gas fiom Cracking Mass of Gas Mass of HC Gas Condenser Pot # 1 Condenser Pot #2 Distill Pot Fibre Mat Box Standard Conditions Temperature Pressure Reactor Pressure Nitrogen Volume (@ STP) WTM Calculation Initial Reading Final Reading .239 Table M. 02-2 1-01-02 Mass Balance Summary Middle Distillate Thermal Cracking Experiments Mass Balance Sheet Reactor Temperature Total Mass Input Experiment Total Mass Ouput Date Liquid Flowrate Mass Balance Error N2 Scale Reading Recovery N2 Mass Flowrate Duration of Exp't Condenser Pot # 1 Condenser Pot #2 Distill Pot Fibre Mat Box Liquid Mass Condenser Pot #1 Condenser Pot #2 Distill Pot Fibre Mat Box Total Liq.

Differential Press Water Temperature Barometric Press Vapour Press. H20 WTM Corr. Factor
Gas Analysis

16.48896mmHg (correlation fiom Yaws 15661) 0.9 17431

GC Data

Molecular Weight

Owgen Nitrogen Carbon Dioxide Methane Ethylene Ethane Propylene Propane n-Butane n-Pentane Total Comp. Bal. Equivalent mass from total moles defmed by Total Component Balance 5.35 0.002W t Y o 2794.42 0.997wt% 3.43 0.001w o 0.000 0.000wt% 0.000 0.000W t Y o 0.000 0.000wt% 0.000 0 . 0 0 0w t Y 0 0.000 0.000W t Y o 0.000 0 . 0 0 0wt% 0.000 0.000Wt%

Component Density @ STP (from ideal Gas Law) Oxygen Ni trogen Carbon Dioxide Methane
1.325 kdm3 1.1 60kdm3 1.823 kg/m3 0.664 kg/m3

propyiene Propane *-Butane n-Pentane

24 1

Ethylene Ethane

1.162 k g i d 1.245kg&

Total Gas Density

1.16 1kg/m3

Molecular Weight of Produced Gas Calculation Nonnalize wrt N2 MW Contribution OWFn 0.17 vol% 0.682 21.821 Nitrogen 99.75 vo1Y0 Carbon Dioxide 0.08 vol% 0.3 18 13.998 Methane Ethylene Ethane Propylene Propane n-Butane iso-Pentane

Liquid Product Analysis Carbon No. 4 5 6 7 8 9 10 Il 12 13 14 15 16
17 18

19 20 21 22

mol mol % 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.0 1 0.0 1 0.0 1 0.03 0.02 0.06 0.04 0.08 0.05 0.1 1 0.05 0.1 1 0.05 0.1 I 0.04 O. 10 0.04 0.09 0.03 0.08 0.03 0.06 0.02 0.04 0.02 0.03 0.0 1 0.02

MW Frac. 0.00 0.00 0.07 0.1 1 O. 16 1.55 4.77 8.73 14.10 19.74

24.02 2 1-97 2 1.90 19.6 1 15.85 12-48 10.30 7.44

Molecular Weight of Sample: Mass Fraction of Naphtha: Mass Fraction of LGO: Mass Fraction of HGO:

224.93 glmol
6.84 wt % 75.89 wt % 17.29 wt %


Table M.3 Experiment No. 02-2 1-0 1-03 M a s s Balance Summary

Middle Distillate Thermal Cracking Experiments Mass Balance Sheet Reactor Temperature Total Mass Input Experiment Total Mass Ouput Date Liquid Flowrate 0.1 i6gIs N2 Scale Reading 45 mm Mass Balance Error N2 Mass Flowrate 0.0665 g/s Recovery Duration of Exp't m i n

503 O C

0.388 % 99.6%

Condenser Pot #1 Condenser Pot #2 Distill Pot Fibre Mat Box

g g g g

Condenser Pot # 1 Condenser Pot #2 Distill Pot Fibre Mat Box Standard Conditions Temperature Pressure

g g g g

Liquid Mas
Condenser Pot #1 Condenser Pot #2 Distill Pot Fibre Mat Box Total Liq. Mass 570.4 g



20.4 g 668.7 g

Gas M a s s Calculation Total Nitrogen Mass Gas Vol @ STP Gas from Cracking Mass of Gas Mass of HC Gas WTM Calculation

387.0 g 336.7 L 3.121 L 390.8 g 3300 g

Nitrogen Volume

333.6 L


Differential Press Water Temperature Barometric Press Vapour Press. H20 WTM Corr. Factor
Gas Analysis

16.48896mmHg (correlation h m Yaws [566])
0.91743 1

GC Data

Molecular Weight

Oxygen Nitrogen Carbn Dioxide Methane Ethylene Ethane Propylene Propane n-Butane n-Pentane Total Comp. Bal. Equivalent mass from total moles defined by Total Component Balance

2767.67 5 . 0 2
5.79 5.07


7 . 8 4
0.000 0.000 0.000

O.O02wt% 0.988 wt% O.O02wt% 0.002wt% O.O02wt% O.O02wt% O.O03wt?40 0.000 wt% 0.000 wt% 0.000 wt%

Component Density @ STP (from Ideal Gas Law) Oxygen Ni trogen Carbon Dioxide Methane 1.325kdm3 1.160kdm3 1.823 kg/m3 0.664 kdm3 Propylene Propane n-Butane n-Pentane


EthyIene Ethane

1.16 2 k / m 3 1.245 kdm3

Total Gas Density

1.161 kg/rn3

Molecular Weight of Produced Gas Calculation Nonnalize wrt N2 MW Contribution 0.177 5.66 1 Oxygen Nitrogen Carbon Dioxide Methane Ethylene Ethane Propylene Propane n-Butane iso-Pentane

Carbon No.
4 5 6

MW 58.123 72.15 86.177

Liquid Product Analysis Tb (K) Tb (OC) wt % mol mol %
272.65 309.22 341.88 -0.5 36.07 68.73
O O 0.04

MW Frac.
0.00 0.00 0.09

0.00 0.00 0.00

0.00 0.00 0.00

Molecular Weight of Sample: Mass Fraction of Naphtha: M a s s Fraction of LGO: M a s s Fraction of HGO:

225.07 g/mol 7.03 wt % 74.86 wt % 1 7 . 9% ~

47 g .4 Experiment No.84L 332.2 g 280.2 L Ni trogen Volume (@ STP) 18. 02-22-01-02 Mass Balance Summary Middle Distillate Thermal Cracking Experiments Mass Balance Sheet Reactor Temperature Total Mass Input ExpeNnent Total Mass Ouput Date Liquid Flowrate Mass Balance Error N2 Scale Reading Recovery N2 Mass Flowrate Duration of Exp't Post-expriment Condenser Pot #1 Condenser Pot #2 Distill Pot Fibre Mat Box Liquid Mass Condenser Pot # 1 Condenser Pot #2 DistilI Pot Fibre Mat Box Total Liq. Mass Gas Mass Calculation Total Nitrogen Mass Gas Vol @ STP Gas fiom Cracking Mass of Gas Mass of HC Gas WTM Calculation Initial Reading Final Reading Condenser Pot #1 Condenser Pot #2 Distill Pot Fibre Mat Box Standard Conditions Temperature Pressure Reactor Pressure 557 O C 303.7 g 29.247 Table M.

000 wtY0 0.97 55.9 15671 GC Data Molecular Weight Oxygen Nitrogen Carbon Dioxide Methane Ethylene Ethane Propylene Propane iso-Butane iso-Pentane Totd Comp.029 w t Y o 0.001 wt% 0.025 w t Y o 0.160kdm3 1.025 w t Y o 0. Factor Gas Analysis 17.664kdm3 Propylene Propane n-Butane n-Pentane .33 47.65 9.3 25 kdm3 1.839 w t Y o 0.30 0. Bal.000 70. Equivalent m a s fiom total moles defined by Total Component Balance 4. H 2 0 WTM Corr.48 1 18.20 0.54766mmHg (correlation h m Yaws [566]) 0.0 19 w t Y o Component Density @ STP (fiom Ideal Gas Law) Oxygen Nitrogen Carbon Dioxide Methane 1.0 17 w t Y o 0.17 2398.Differential Press Water Temperature Barometnc Press Vapow Press.823kglm3 0.5 1 84.32 7 1.003 w t Y o 0.041 wt% 0.

97 150.187kglm3 Molecular Weight of Produced Gas Calculation Normalize wrt N2 Ox~gen Nitrogen Carbon Dioxide Methane Ethylene Ethane Propylene Propane n-B utane iso-Pentane 0.62 469.01 0.07 309.05 329.04 0.93 343.05 0.32 508.02 0.02 0.5 398.3 174.42 5.6 1O vo1Y0 0.10 0.06 0.01 0.05 0.71 7.17 0.08 36.47 9.78 4.15 3.65 356.15 8.02 0.88 0.43 371.68 10.294 0.47 216.03 0.01 286.58 1.09 575.009 0.10 0.5 0.04 0.40 12.9 616.01 0.03 0.8 1 7.03 0.00 0.96 15.86 316.32 20.22 0.08 195.79 9.03 0.04 0.09 0.32 447.73 341.6 489.28 7.16 9. 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 Liquid Product Analysis Tb(K) Tb("C) wt % O 272.1 1 0.02 MW Frac.28 68.86 603.05 0.68 423.000 vol% 0.97 15.87 17.28 21.83 125.1 62 kdm3 1.04 0.74 3.73 253.00 0.5 1 10.00 0.1 1 4.05 0.245 kdm3 Total Gas Density 1.83 270.84 98.6 368.77 526.08 0.03 0. 0.77 20.93 5. 130volYo 85.3 8 7.01 0.52 18.07 0.3 302.58 543.66 589.65 -0.000 Carbon No.82 2.03 0.6 mol mol % 0.0 1 0.86 9.52 3.00 0.02 0.37 560.5 2.249 Ethylene Ethane 1.07 0.62 235.00 0.58 1.00 0.05 0.58 5-40 .000 MW Contribution 0.

96wt % .Molecular Weight of Sample: M a s s Fraction of Naphtha: M a s s Fraction of LGO: Mass Fraction of HGO: 207.45 g/mol 1 3 . 9 2% ~ 73.08 wt % 12.

25 1 Table M. Mass Gas Mass Calculation Condenser Pot #1 Condenser Pot #2 Distill Pot Fibre Mat Box Standard Conditions Temperature Pressure Reactor Pressure Total Nitrogen Mass Gas Vol @ STP Gas from Cracking Mass o f Gas Mass o f HC Gas Nitrogen Volume (@ STP) WTM Calculation Initial Reading Final Reading . 02-22-0 1-03 Mass Balance Summary Middle Distillate Thermal Cracking Expenments Mass Balance Sheet Reactor Temperature Total Mass Input Experiment Total Mass Ouput Date Liquid Flowrate Mass Balance Error N2 Scale Reading Recovery N2 Mass Flowrate Dwation of Exp't Condenser Pot #1 Condenser Pot #2 Distill Pot Fibre Mat Box Liquid Mass Condenser Pot # 1 Condenser Pot #2 Distill Pot Fibre Mat Box Total Liq.5 Experiment No.

000 W t Y o 2 12.160 kdm3 1.325 kg/m3 1.Differential Press Water Temperature Barometric Press Vapour Press. Molecular Weight Equivalent mass from total moles defmed by Total Component Balance 4.664 kdm" Propylene Propane n-Butane n-Pentane .88 0.823 kg/m3 0.43 0.05 0.111wtYo 19.8 1 0.00 1 wtYo 1784.45 0. Factor 18.23 0.000 0.66532mmHg (correlation fiom Yaws [56q) 0. H 2 0 WTM Corr.037 wtYo 316.02 0.007 wtYo 36.11 0.074 wtYo 259.9 13999 GC Data Gas Analysis Oxygen Nitrogen Carbon Dioxide Methane Ethylene Ethane Propylene Propane n-Butane n-Pentane Total Comp. Bal.88 0.041 wtYo Component Density @ STP (from Ideal Gas Law) Oxygen Nitrogen Carbon Dioxide Methane 1.091 wt% 104.625 wtYo 0.013wtYo 1 17.

0 1 0. 2 0 1 1 S8 1 3 .93 343.15 6 . 7 3 398.312 Liquid Product Analysis Tb (K) Tb (OC) wt% 272.177 100.83 125. 0 3 0 .04 0 .49 11 .9 3 . 0 5 0. 0 1 0 . 8 6 8.52 2 . 11 0 .73 253.15 6.22 36.285 1 5 6 . 4 8 616. 7 1 4 .88 68. 8 6 1 8 .78 2 .73 0. 2 31 128. 61 . 7 1 489.00 0 . 0 3 0 .68 5 . 0 8 0 .3 174. 0 5 0. 01 0 . 1 2 3 7 2 .5 O 309. 91 9. 9 6 368. 0 2 0 . 01 0 .Ethylene Ethane Molecular Weight of Produced Gas Calculation Norrnalize wrt N2 OVgen Nitrogen Carbon Dioxide Methane Ethylene Ethane Propylene Propane n-Butane iso-Pentane M W Contribution 0 . 1 12 0. 4 5 mol 0. 0 2 526.47 216. 0 2 0 . 11 0 . 0 8 0 . 01 1 3 . 0 5 0 . 4 5 6 7 8 9 10 11 1 2 1 3 14 1 5 1 6 17 18 1 9 20 2 1 22 MW 5 8 .93 7 .05 0 . 0 8 0 . 0 0 0 .14 341.5 1 .365 198. 4 9 589. 6 1 356. 0 6 0 . 0 1 1 8 . 0 0 0 .473 254. 0 5 0 .527 282.65 -0.97 150. 0 2 0 . 2 5 0. 0 4 6 .32 10.338 184. 1 5 86. 0 .392 212. 0 3 0 . 2 8 423. 3 3 575.00 mol % MW Frac. 0 1 0 .204 1 1 4 .58 98.62 235. 0 9 0 .58 1 543. 9 1 5 6 0 . 0 6 0 . 0 6 0 .44 469.77 4 .298 310. 0 5 0.05 0 .69 0 .82 6 .86 7 .83 270.25 4. 0 3 0 .701v o l % 0. 5 0 2 1 .69 3.3 302.00 0. 0 9 0 .05 329. 2 3 447.419 226.68 8 .07 6.446 240. 01 0 .29 508.43 371.000 0.258 142.000vol% 0 . 31 2 170.86 3 1 603.6 1 . 0 9 0 .553 296. 0 0 3 0-000 Carbon No.00 0.43 2 .08 195. 0 1 1 6 . 1 7 1 0 .47 11. 0 1 286.07 0.5 268. 0 0 0 .127vol% 63.

09 wt % .96 wt % 64.86 wt % 6.Molecular Weight of Sample: Mass Fraction of Naphtha: Mass Fraction of LGO: Mass Fraction of HGO: 179.58 g/mol 28.

2 g 419.2g Nitrogen Volume (@ STP) WTM Calculation Initial Reading Final Reading .255 Table M .2 L 846. Mass Gas Mass Calculation Condenser Pot #1 Condenser Pot #2 Distill Pot Fibre Mat Box Standard Conditions Temperature Pressure Reactor Pressure Total Nitrogen Mass Gas Vol @ STP Gas from Cracking Mass of Gas Mass of HC Gas 426.2 L 406. 6 Expriment No. 02-22-0 1-04 Mass Balance Swnmary Middle Distillate Thermal Cracking Experiments Mass Balance Sheet Reactor Temperature Total Mass Input Expriment Total Mass Ouput Date Liquid Flowrate Mass Balance Error N2 Scale Reading Recovery N2 Mass Flowrate Duration of Exp't 70 1 O C Condenser Pot #1 Condenser Pot #2 Distill Pot Fibre Mat Box Liquid Mass Condenser Pot # 1 Condenser Pot #2 Distill Pot Fibre Mat Box Total Liq.9 g 774.

02 0. Factor Gas Analysis 18. Equivalent mass from total moles defined by Totai Component Balance 3. Bal.160 k / m 3 Propane 1.525 w t Y o Component Density @ STP (from Ideal Gas Law) Oxygen Ni trogen Carbon Dioxide Met hane 1-325kg/m3 Propylene 1.91 3999 GC Data Molecular Weight Oxygen Nitrogen Carbon Dioxide Methane Ethylene Ethane Propylene Propane n-Butane iso-Pentane Total Comp.00 1 WYo 1385.823 k / m 3 n-Butane 0.664 kg/m3 n-Pentane .40 0.Differential Press Water Temperature Barometric Press Vapour Press.66532 mmHg (correlation fiom Yaws [566]) 0. H20 WTM Corr.

63 Carbon No.01 0.08 489.32 12.06 0. 106vo1Y0 0.3 1 1 1.009 2.52 603.067 Ni trogen 49.47 10.39 7.62 235.82 447.49 11-14 23.0 1 0.1 1 0.02 0.07 0.57 423.6 2.04 0.07 0.442 vol% Carbon Dioxide 0.245 kg/m3 Total Gas Density 1.01 0.1 1 0.07 0.93 6.416 0.5 1 6.86 6 302.05 0.04 0.5 O 0.02 MW Frac.78 356.65 -0.97 150.03 0.25 4.32 368.01 0.54 13.55 543.00 0.93 343.07 0.24 526.61 616.00 0.05 0.137 Ethane Propylene 5.15 5.14 341.290 Propane n-Butane O.15 3.83 125.002 0.05 2.71 329.05 0.162ktw3 1.02 0.3 4.27 19.802 g/mol Liquid Product Analysis Tb(K) Tb(OC) wt% 272.9 3.99 371.5 2.14 0.000 Methane 7.06 0.257 Eîhylene Ethane 1.26 7.03 0.7 508.03 0.86 3 16. 155 iso-Pentane 0.43 6.68 7.45 4.10 0.73 3.02 0.47 216. 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 mol mol % 0.00 0.68 560.88 68.79 6.04 0.03 309.3 398.890 Eîhylene 8.839 24.000 0.08 195.00 0.000 vol% 0.58 5.03 0.01 0.06 0.0 1 286.82 .73 253.00 0.99 6.1 589. 0.87 9.83 270.07 0.00 0.00 0.78 4.06 0.77 1 1-43 10-17 10.18 469.01 0.58 98.22 36.49 575.3 174.03 0.O93 kg/m3 Molecular Weight of Produced Gas Calculation Nomalize wrt N2 MW Contribution Oxygen O.

Molecular Weight of Sample: Mass Fraction of Naphtha: Mass Fraction of LGO: Mass Fraction of HGO: 183.29wt % 55wt % 15.69 wt % .O2g/mol 29.

9 g 80.5 g 88.67 g Nitrogen Volume (@ STP) 364.3 L .9 g 9.'2. : ' a .'6 -.9 g 436. Reactor Pressure - _ .1 16g/s Liquid Flowrate N2 Scale Reading 45 mm Mass Balance Error N2 Mass Flowrate 0. pig 4 1-4kPa Total Nitrogen Mass Gas Vol @ STP G a s fiom Cracking Mass of Gas Mass of HC Gas 422.5 g 639. .259 Table M.0665g/s Recovery Dwation o f Exp't min Pre-experiment Post-experiment 541 O C 0.6g 92.717% Liquid Mass Condenser Pot #1 Condenser Pot #2 Distill Pot Fibre Mat Box Total Liq.5 L WTM Calculation . 03-27-01-01 Mass Balance Summary Middle Distillate Thermal Cracking Experiments Mass Balance Sheet Reactor Temperature Total Mass Input Experiment Total Mass Ouput Date 0. Mass Gas Mass Calculation 460.: .7 Experiment No.8 g Standard Conditions Temperature Pressure - OC kPa c.0 L 71-43 L 515.

Differential Press Water Temperature Barometric Press Vapour Press.01 dm01 16.27 0.006wtYo 54. 28.124 dm01 72.043 dm01 28.037 wtYo 57.03 1wtYo 106.020 wtYo 146.35 0.823 k d m 3 n-Butane .0 13glmol 44.Factor Gas Analysis 23.2 1 0.08 0.46 0. H20 WTM Corr.094 g/mo1 58.999 dm01 Oxygen Nitrogen Carbon Dioxide Methane Ethylene Ethane Propylene Propane n-Butane iso-Pentane 2-Methylpentane Total Cornp.0 19wt% 23.15 1 dm01 86.07 g/mol 42.87 0.178 gimol 100mol Equivalent mass fiom total moles defined by Total Component Balance 29.26 16.0 10WYo 23 19-58 0.52 0.78202 mmHg (correlation fiom Yaws [566]) 0.908243 GC Data Molecular Weight 3 1.054 g/mol 30.08 1 g/mol 44.008 wtYo Component Density @ STP (from ldeal Gas Law) Oxygen 1.051wtYo 0.004 wtYo 11.325Wm3 Propylene Nitrogen 1.68 0.24 0.00 1wtYo 87. Bal.1 60 k d m 3 Propane Carbon Dioxide 1.8 12wtYo 3.

0 7 0 . 6 9 9 Nitrogen 82.73 253. 0 3 0 .255 vol% 0. 0 3 0 .22 36. 0. 91 3vo1Y0 0. 6 589. 6 5 0 .090 Ethylene 3. 1 6 2 kdm3 2-Methylpentane 1.O0 1 0 . 1 9 1 9. 0 0 0 1 0 .89 . 5 O 0 .97 1 . 1 6 309. 0 5 0 . 0 6 .15 4 9 5 . 0 4 0 0 . 0 8 11 .58 9. 0 3 0 . 0 0 0 .15 7 .804vol% Carbon Dioxide 0. 1 7 5 .86 3 16-71 6 5-17 603. 4 5 6 7 8 9 IO 11 1 2 13 1 4 1s 1 6 1 7 1 8 1 9 Liquid Product Analysis Tb (K) Tb (OC) wt% 2 7 2 .43 2 5 . 0 2 0 . 0 5 0 .015 0.47 216. 6 8 2 . 9 3 6. 2 8 1 vol% 0.366 Propylenc 3.1 1 .275vol% 0. 179 Ethane 1 . 6 341. 0 0 0 .3 302.480vol% 0.664kdm3 n-Pentane 1 . 8 1 15-62 1 3.053 1 .62 235.074vol% 0. 0 4 0 . 190 Methane 5. 0 8 0 .58 98. 8 8 1 6 .86 8 .08 1 .455vol% 0 . 1 6 489.377 Carbon No.787vol% 0. 9 2 5vol% 0 .01 6 1. 1 8 3 . 0 2 0 . 6 1 371. 5 3 5 6 0 . 0 9 0 .00 0.90 9 . 0 0 0 .3 174.044 3. 6 1 447. 0 5 0 .47 10. 11 2 3.88 68.988 kg/m3 3-569 kg/m3 1 -183 kg/m3 Molecular Weight of Produced Gas Calculation Normalize wrt N2 MW Contribution Oxygen 0 . 0 9 0 . 1 0 0 . 0 8 19-84 1 9 .245 kg/m3 Total Gas Density 2.07 526.83 270.202 8. 0 2 0 MW Frac. 1 6 6.49 1 6 . 6 2 398. 0 5 0 . 1 9 .32 1 .145 2-Methylpentane 0. 5 423. 0 1 286. 31 7 5.03 469.32 8 508.750vol% 0.220 6 .68 9.73 1 . 9 51 iso-Pentane 0. 8 2 3 . 0 6 . 0 5 0 . 9 3 575.83 1 5 0 . 0 1 0-0 . 0 3 0 0 .518 Propane 0. 0 5 0 .655 n-Butane 0 . 0 4 0 0 .9 mol mol % . 0 5 0. 0 3 0 .74 543.016 0 .05 329.07 0 .004 O.261 Methane Ethylene Ethane 0.

Molecular Weight of Sample: Mass Fraction of Naphtha: Mass Fraction of LGO: Mass Fraction of HGO: 196.75 wt % .86 glmol 19.13 wt % 7 0 . 0 3 wt % 10.

The start and end of the mn corresponds to the sudden temperature changes at the extreme lefi and right of the plot. The difference range defined for each experimentai run is based on the temperature difference that occurs for at least 80% of the experimental nui time. The experimental runs that were rejected are included to illustrate the improvement in reactor control over the two initial runs. Data filtering was accomplished using the following relationship: Where. and the conditions for temperature difference determination were relaxed to accommodate the majority of temperature data for the run. 1 through N. Figures N. as it is necessary to illustrate the problems the lack of filtering within the Labview program presented. the controlled variable was heat stationed in . i k i" temperature of data set filtering constant (0-15 for this study) T reactor temperature 6) On occasion there exists a sharp spike in temperatures during a run: this is explained by gas sampling process. Included are the plots unfiltered and filtered temperature data for each run. For some of the runs.APPENDIX N : Reactor Temperature Plots Plots of the inlet and outlet fluid temperatures vs. time for each experimental run is provided on the following pages. Described previously in Chapter 4. this was not possible. Reactor temperatures used in the kinetic mode1 are calculated based on the linear average of the inlet and outlet temperatures afier rejecting al1 those temperatures that faIl outside a defined difference range. 1O illustrate the progression towards improved reactor temperature control. 1. A summary of the temperature differences used for the determination of average reactor temperature is provided in Table N. respectivety. which causes a momentary stoppage of gas flow in the process equipment.

whereas when the thermocouple is heat stationed. 1 ) and the new method (Figure N -24). 10 through N-25. the idet temperature would decrease and the outlet temperature would increase such that the two temperatures would overiap and the reactor was assumed isothemal. In the work by Dong [104]. a type K thermocouple was inserted . 4 to N. this method of inferring the temperature profile of the gas in the tube using the profile of the sold steel bar is not recommended. This figure was used as a basis for the minimum deviation of the inlet and outlet temperatures prior to the introduction of the feed: this deviation.was moved to the heat stationed thermocouple at the exit of the an underestimation of the true fluid temperature by approximately 2S°C. 02-13-0 1-01 (Figure N. as described in Section 5. the underestimation is approximately SOC. and the temperature of the gas inside the reactor tube was assurned to deviate slightly fiom the steel temperature.but not heat stationed into the product gas stream just downstream of the reactor exit. The error associated with not heat stationing the thermocouple . then. The controlled variable . and Figure N. l).reactor temperature . Dong [IO41 used a thermocouple located dong the reactor inner bar stock axis for temperature control of the product gas: the temperature of the steel core provided a stable temperature rneasurement that did not require filtering. would ensure that when the feed was introduçed. However. . In addition.264 the reactor outlet flow after Run No.9 illustrate the temperature deviation trials required to finally achieve tight control as illustrated in Figures N. and the improvement in control was signifiant as il lustrated by comparing the method by Dong [104] (Figure N. Figures N . for it introduces a level of complexity to the temperature calculation that is dificult to the reactor temperatures of interest .2 iilustrates the temperature deviation as a result of the feed introduction and removai.

265 Table N.1 Summary of Temperature Difference Defined for Each Expenmental Run Expriment No.mns rejected for reasons provided in Appendix Q. . Caiculated Reactor Defined Temperature Difference Criteria C C ) ( d d d / y y / R u n #) Temperature (OC) t .









- - - . m .

Reactor Outlet Temp

-Reactor Inlet Temp
. .

______ _ ..

___ _







- ._.

O N : 12
Time (hr)

Figure N. 17 - Unfiltered Data Experiment No. 02-22-01-02

Time (hr)
Figure N. 18 Filtered Data Experiment No. 02-22-01-03


Time (hr)
Figure N.20 Filtered Data


Experiment No. 02-22-01-04

Calculated Reactor Temperature =54 1O C



O: 14:24


0:43: 12


1 :12:OO

1 :26:24

1 :40:48

Time (hr) Figure N.22 Filtered Data Experiment No. 03-27-01-0 1





Inc.29 1 APPENDIX O: Simulated Distillation Plots Al1 simulated distillations were pe&onned by Ms. Elizabeth Zaiewski of the Oil Sands Research Group using a Hewlett-Packard 6890 GC with a Separation Systems.D.53m. .9pm I. 0.m bonded phase colurnn (SM 289216) using the ASTM D2887 Extended Megabore method (ASTM [25]). 10m x 0.

O 20 40 60 80 1O0 Weight Percent Off (wt%) Figure 0. 02.16-0 1-02 Simulated Distillation Boiting Point Curve ASTM D2887 Extended Method .1 Experiment No.

O 20 40 60 80 1 O0 Weight Percent O f f (wt%o) Figure 0. 02-20-0 1-0 1 Simulated Distillation Boi ling Point Cuwe ASTM D2887 Extended Method .2 Experiment No.






1O 0

Weight Percent Off (WO)

Figure 0 . 3 Experiment No. 02-2 1-0 1 -0 1 Simulated Distillation Boiling Point Curve ASTM D2887 Extended Method






1O 0

Weight Percent Off (wt%)

Figure 0.4 Expriment No. 02-2 1-01-02 Simulated Distillation Boiling Point Curve ASTM D2887 Extended Method






1O 0

Weight Percent Off (wt%)

Figure 0 . 5 Experiment No. 02-2 1-01-03 Simulated Distillation Boiling Point Curve ASTM D2887 Extended Method






1O 0

f f( ~ W O ) Weight Percent O

Figure 0.6 Experiment No. 02-22-0 1-0 1 Simulated Distillation Boiling Point Curve ASTM D2887 Extended Method






1 O0

Weight Percent O f f (wt%)

Figure 0 . 7 Experirnent No. 02-22-0 I -02 Simulated Distillation Boiling Point Curve ASTM D2887 Extended Method







Weight Percent Off (wt%)

Figure 0 . 8 Experiment No. 02-22-0 1 -03 Simulated Distillation Boiling Point Curve ASTM D2887 Extended Method






1 O0

Weight Percent Off (wt%)

Figure 0.9 Experiment No. 02-22-0 1-04 Simulated Distillation Boiling Point Curve ASTM D2887 Extended Method

03-27-0 1-0 1 Simulated Distillation Boiling Point Curve ASTM D2887 Extended Method .O 20 40 60 80 1O 0 Weight Percent Off (wtY0) Figure 0.10 Experiment No.

03-27-0 1 -02 SimuIated Distillation Boiling Point Curve ASTM D2887 Extended Method .O 20 40 60 80 100 Weight Percent Off ( ~ W O ) Figure O. t 1 Experiment No.

Faculty o f Engineering Tar Sands Research Group ASTM 02887 Extended Method .O 20 40 60 80 100 Weight Percent Off (wt%) Figure 0.12 Light Gas Oil Feed Boiling Point Curve University of Calgary.

41 1.09 2-56 3.2 1 1. Table P. reactor temperahue deviation.3 99.7 266. mass fkaction of each component.4 3 18.0 99.2 340.2 668. Std. Thus.8 495. The sample nurnber format is: Month-Day-Year-Experiment No.17 1. and the closer the approach to isothermality.80 96. Temp.6 99. Temp. The reactor temperature standard deviation is a measure of the isothermality of the reactor for the duration of the experimental run.3 99.5 247.22 1-10 1-42 1.6 427. Dev.21 Component Mass (g) Gas Feed Liquid 348 258 675 738 529 453 745 4. the smaller the standard deviation. The standard deviation is calculated fiom the temperature data set for the respective run that met the critena for temperature difference as outlined in Appendix N.1 Experiment No. (OC) 3.7 29.8 Recovery wtO/O 99. and concentration of each component. Liquid Mass Fractions (%) Liauic Component Mass (g) c . 1 Summary of Successtùl Expenmental Runs Experiment No.5 181. the tighter the control on the reactor.0 97.7 639.APPENDIX P : Summary of Successful Expcrïments The following tables summarize the recovery.0 99. space velocity.

0024 Density is calculated at a constant pressure of 14 1 kPa.3 Gas 34.5 220. Temp./ Experiment No. . (Oc) 1 Gm L w n Mass ~ Fractions Naphtha 0.747 Al1 values fkom this section are calculated using the method described in Appendix M.25 Experiment No.063 1 HG0 O.0.0029 0. The assumption is correct based on the calculation results in Appendix B.O00 LGO 0. (Oc) 436 Feed 0.0326 Molar Flowrate (moI/min) HG0 Naphtha LGO . Experiment No. 1 Temp.003 8 0. Molecular Weight of Components LGO HG0 Naphtha 147.6 327.0233 Gas 0. 178 1 Total 1.

Component Density at T. Outlet Density (kg/m3) Nitrogen Nitrogen In/Out Density at Mass Fluid Fraction of Flowing Density Total Flow Conditions (wt%) Wm3) (kdm3) Average Density in Reactor (kp/m3) .1 Experiment No.P (kg/m3) Naphtha 1 LGO 1 H G 0 1 Gas Experiment No. (Oc) Feed 1 Component Concentration(mo vm3) Naphtha LGO HG0 1 1 1 Gas Average Experiment Temp. r Temp.

Experiment Temp. No.Please note that the space velocity and density are calculated at reactor temperature and an assumed constant pressure of 132 kPa The assumption for constant pressure is valid based on the results of the calculations in Appendk B. (Oc) Space Time Space Velocity Reactor Volume (m3) (hl 01') .

16-0 1-02 03-27-0 1-02 zeroed correctly Air ingress downstream of final condenser 346.trial 33A run with new sense point 429. .5 valve did not hold z 02-20-0 1-0 1 02-22-0 1-0 1 02-16-01-01 Poor temperature ontrol poor .4 fiinctional . The sample nurnber format is: Month-Day-Year-Expriment No. 1 Summary of Unsuccessful Experimental Runs Experiment No.not t itrogen meterhg did not hold flow steady WTM non- 02.3 ue to multiple 1 Iplexiglass cover The values in the following two sections were experimentally detennined. Table Q.APPENDIX Q: Summary of Unsuccessful Experiments The following tables s u m m a e the experïments that were rejected based on the comments provided in the tables. Std. Since experiment 02. the product liquid was not analyzed. (OC) Temp. Dev Corn] Feed Gas 57.16-0 1-0 1 was rejected prior to analytical testing. 02-13-01-01 Temp.3 p w r temperature ontrol i r 434.

25 Liquid Component Mass (g) Naphtha LGO HG0 1 17-38 30-33 116.35 329.Mass Fractions Naphtha LGO 0. Experiment No. Temp.95 Experiment No. Naphtha L W HG0 12-13-0 1-01 12-20-01-0 1 1 1 .046 Lump . 12-13-01-01 Temp.93 17.76 14.183 T o t a i 1 .740 0.Expriment Liquid Mass Fractions (%) No.O5 6.1 1 1 0.000 -0. (OC) Molec dar Weight of Liquid Cornponents LGO 1 HG0 1 Total Sam~ie .149 0.072 0.179 0.O00 1 .785 0.98 73.787 0.036 -0.97 75.075 1 HG0 0. 1 Gas cOci 413 49 1 507 547 0.18 23-48 74.O00 1.O00 The values in the following section were calculated using the method described in Appendix M.

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