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In all cases we have filmed the best available copy. 9001. 2268 ROAD, ANN ARBOR, Mi £0106 TB BEDFORD ROW, LONDON WIR 61, ENGLAND3127004 \VANKLEECK, DAVID ALLEN OXIDATIVE DEHYDROGENATION OF BUTENES OVER MANGANESE FERRITE Rice University PHD. 81 University Microfilms International sow zee Ross, aan Arbo 4106RICE UNIVERSITY OXIDATIVE DEHYDROGENATION OF BUTENES OVER MANGANESE FERRITE By DAVID A, VAN KLEECK ‘A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE DOCTOR OF PHILOSOPHY pf Chemical Engineering ‘irman jeIntire Professor in the Department of Chemical Engineering ~ A. Sostnsky Assistant Professor in| the Department of Chemistry HOUSTON, TEXAS MARCH’ 1981ABSTRACT OXIDATIVE DEHYDROGENATION OF BUTENES OVER MANGANESE FERRITE by David A, Van Kleeck _ Butene oxidative detydrogenation (OX) on a manganese iron oxide catalyst was studied in batch recirculation and microcatalytic pulse reactors at temperatures between 300C and 400C. Mechanistic features of the reaction were examined using C-labeled butadiene (Neiman method), deuterium labeled butene (isotopic tracer technique), and 280- labeled carbon dioxide (oxygen isotope exchange) experiments. Tempera~ ture programmed desorption (TPD) experiments were used to evaluate de~ sorption kinetics. Sovid state changes in the catalyst were examined through x-ray diffraction, magnetization, magnetic susceptibility, thermogravinetric analysis, and electrical conductivity measurements. Reaction products consist of 1,3-butadiene, carbon dioxide, water, and butene isomers. Chromatographic analyses of the reaction products indicated negligible production of carbon monoxide during reaction, In addition, the TPD experiments demonstrated that carbon monoxide is readily oxidized over the catalyst. Initial rates of formation of buta~ diene and carbon dioxide are zero order in both oxygen and butene. The reactions are inhibited by product butadiene, where the low conversion data is modeled adequately by a Langnuir-Hinshelwood type rate expression. ‘The activation energy for butadiene formation is 35.2 Kcal/nole, and that for carbon dioxide production is 37.5 Kcal/mole. Microcatalytic pulse experiments carried out in the absence of gas phase oxygen indi-cated that the reactions may proceed by consuming lattice oxygen. Per- deuterated butene is Jess reactive than non-deuterated butene. Conpari- son of the rates of formation and analysis of isotopic composition of the products revealed significant kinetic isotope effects for both OXD and isomerization (Isotope effect for OX0 = 2.1, Isotope effect for cis- 2-butene to I-butene isomerization = 1.7, botit at 412C). Therefore, carbon-hydrogen bond cleavage is considered rate limiting. Experimental data are consistent with an oxidation-reduction cycle ‘involving either Fe or n+, Butene and oxygen molecules may adsorb ‘into surface anion vacancies associated with either cation. The absence of intermolecular hydrogen-deuterium exchange during isotopic tracer ex- Periments indicates that OXD and isonerization reaction rates are much greater than surface diffusion rates, A deactivation mechanism consistent with solid measurements is pro~ posed. Major crystallographic transitions occur during reaction and Pretreatment operations in agreement with the thermodynamic phase rela~ tions for the tron-manganese-oxygen system. X-ray diffraction measure- ments confirmed that the catalyst aging process parallels the shift from a spinel to-a hexagonal crystal structure. This change corresponds to the irreversible oxidation of Mn2* in the virgin catalyst to Mao in the aged catalyst.ACKNOWLEDGMENTS Few research, projects are individual efforts. The combined efforts of many people are required to produce significant results, and the pres- ent work is no exception. I wish to acknowledge the following partici pants and extend my appreciation to them: Dr, Joe W. Hightower, my advisor, who directed this project and provided the guidance and insights necessary to accomplish the research objectives. Dr, Larry V. McIntire and Dr. Barrie Sosinsky who served as menbers of the thesis committee and who also contributed constructive criticism during the course of this research. Dr. Donald 8. Halcom, Dr. Donald H. Chickering and Dr. Andrei Sklyarov my laboratory associates, who contributed substantially to the design and execution of several experiments and created a stimulating working environment. My family, especially my wife, Marilyn, who provided encouragement and spiritual support throughout my graduate studies. I am joined by Dr. Hightower and the Chemical Engineering Department ‘in expressing gratitude to the Amoco and Melch Foundations for the finan- cial support of my work at Rice University.TABLE OF CONTENTS TITLE PAGE ACKNOWLEDGEMENTS ‘TABLE OF CONTENTS LIST OF FIGURES LIST OF TABLES 1 m. INTRODUCTION General History Incentives for Development Comercial Butene OXD Catalysts ‘Structure and Properties of the Mn-Fe-0 System Objectives EXPERINENTAL Catalyst Gases Apparatus Recirculation System Wicrocatalytic System Mass Spectroneter and TPD System Microbalance and Magnetic Susceptibility System X-ray Diffraction Equipment Atomic Adsorption Spectrometer Radioactivity Measurement Equipment Experimental Procedures Kinetic Experiments Recirculation Experiments with Deuterium Labeled Buteneqr. Radioactive Tracer Experiments Microcatalytic Experiments Electrical Conductivity Experiments Experiments in the Microbalance System Experiments in the TPD System Treatment of Data Kinetic Experiments Deuterium Label Experiments Microcatalytic Pulse Experiments ‘Temperature Programmed Desorption Experiments RESULTS Ki ¢ Experiments General Initial Rate Date Kinetic Mode? Deuterium Label Experiments Radiotracer Experiments C0, Pulse Experiments Butene Pulse Experiments Electrical Conductivity Temperature Progranmed Desorption Experiments General Carbon Dioxide Desorption 1,3-Butadiene Desorption Thermogravinetric Analysis Magnetic Susceptibility Magnetization Measurenents X-ray Diffraction DISCUSSION Catalyst Aging iv 1 a 95 95Kinetic Orders 96 Mechanism 7 V. SUNMARY 193 APPENDIX 1 104 TD 104 APPENDIX 2 105 Deuterfum Exchange in Butenes 105 APPENDIX 3 107 Radiotracer Analysis 107 REFERENCES noFigure ane wn N 10 un 1% B 4 5 16 7 8 19 20 2 LIST OF FIGURES Title Proposed Mechanism for OXD of Butenes over Ferrite Catalysts Batch Recirculation Apparatus Gas Chromatographic System Nicrocatalytic Systen Electrical Conductivity ce11 Temperature Prograrmed Desorption and Mass Spectrometer System Microbalance Furnace Magnet Calibration Typical Kinetic Experiment Butadiene Initial Rates Carbon Dioxide Initial Rates Butadiene Oxidation Butadiene Oxidation Rates Radiotracer Experiments C290, Exchange Experiments Butene Pulse Experiment Butene Pulse Experiment Butene Pulse Experiment Butene Pulse Experiment Electrical Conductivity Experiment Electrical Conductivity Experiment 0, Desorption vi 10 20 24 26 30, 33 35 50 52 53 55 56 66 69 72 73 74 5 7 78 ErFigure 24 25 26 28 29 30 31 Title (02/60) a TPD CO,/(butene + oxygen) Butadiene Desorption Butene Desorption Products Thermogravimetric Analysis Magnetic Susceptibility Relative Magnetization (Virgin Catalyst) Relative Magnetization (Aged Catalyst) Reaction Mechanism Page 83 85 88 90 92 93 99Table we eaVannwn 10 u LIST OF TABLES Title Butene Oxidative Dehydrogenation Patents Crystal and Mineral Types Key to Initial Compositions Initial Rate Parameters Isotopic Composition Data at 412C Deuterium Label Experiments at 412¢ Deuterium Label Experiments at 363C Specific Activity (counts /torr-min) 120, Exchange Experiment (300C) X-ray Diffraction Patterns Comparison of Kinetic and Desorption Rates viti 101T, INTRODUCTION GENERAL Oxidative dehydrogenation (OXD) is a selective partial oxidation technique commonly applied to short chain hydrocarbons. It is used Primarily to produce olefins from paraffins, conjugated diolefins from mono-olefins, and vinyl aromatics from alkyl aronatics. Typical reac- tions include the formation of acrolein from propylene, styrene from ethyl-benzene, and 1,3-butadiene from n-butane or any of the n-butene ‘isomers (1). The butadiene reaction has received considerable attention during the last tio decades, and its comercial application is iTlus- ‘trated by the Petro-Tex Oxo-D and Phillips 0-X-0 processes (2). In comercial processes, oxidative dehydrogenation is carried out using the hydrocarbon feed mixed with an appropriate oxidant (I,, 0,5 S0,) and steam, Use of the oxidant shifts the equilibrium of the dehy- drogenation reaction towards complete conversion through formation of compounds containing the abstracted hydrogen (e.g. H,0, HI, H,S). ‘Steam, on the other hand, may be used to activate the catalyst, remove coke from the catalyst via a water-gas shift reaction, or serve as a diluent for temperature control. In the present investigation, the oxidative dehydrogenation tech nique was applied to butadiene formation from butenes over a mixed iron manganese oxide catalyst. The kinetics of the oxidative dehydrogenation and complete oxidation reactions were evaluated, and solid-state char- acterization of the catalyst were conducted in order to compare and confirm possible reaction mechanisms.HISTORY The loss of natural rubber sources during World War II spurred the development and production of synthetic rubbers in order to meet the high product demand. In the search for a suitable substitute, Styrene~ Butadiene Rubber (SBR) becane the principle synthetic alternative. Since the 1,3-butadiene used in SBR production is not a naturally occur- ing substance, it was necessary to identify and explore a variety of butadiene sources. At the time, the Lebedev and Ostromisslenski proc- esses utilized ethanol derived from fermentation methods (2). However, shortly after the war, U.S. producers abandoned then in favor of proc esses which used more readily available petroleum resources. Historically, the major fraction of butadiene production has been from steam cracking ethylene plants where butadiene is a coproduct rep- resenting 20% to 40% of the C,cut (3). With the dramatic growth in the automobile and tire industries following World War II, coproduct buta- diene could not satisfy the demand for rubber raw materiais. In order to meet this need, dehydrogenation processes using butane and butylenes were developed. The Phillips and Houdry comercial catalytic dehydrogen- ation processes originated during the war and energed as the primary additional sources of butadiene. They remained in use until the mid~ 1970's when uneconomical operation forced the shut down of existing plants (3). During the early 1960's, research on the oxidation of propylene over molybdate catalysts Ted to the discovery that butenes could be dehydrogenated selectively using an oxidative technique over the same catalysts (1, 4). Since this discovery, the oxidative dehydrogenation3 reaction has been studied extensively, with the result that a wide vari- ety of catalysts have been identified as effective for this reaction. Commercial applications of the OX method are found in the Phillips 0-X-D and Petro-Tex Oxo-D processes (2), which offer significant ad- vantages over non-oxidative processes. However, these processes remain highly susceptible to fluctuations in the butadiene market. Over the last two years, most of the OXD plants in the United States have been shut down because of @ decline in the butadiene market during the cur- rent recession. Recently, Petro-Tex has licensed its Oxo-D process to PEMEX (5), suggesting that OXD processes may return to use as butadiene demand recovers. The major derivatives of butadiene are SBR (50%), poly-butadiene (20%), hexamethyTene diamine (10%), and other rubbers (102) (3). Most of the SBR and polybutadiene produced is used in the manufacture of auto- mobile and truck tires. The hexanethylene diamine is used in nylon and the remaining butadiene is used in neoprene and nitrile rubbers. Annual production of butadiene in the United States is approximately 3.0 bil- Tion pounds (3) with a present market price being about 27¢ per pound. INCENTIVES FOR DEVELOPHENT With the formation of stable hydrogen compounds in the OXD reaction, ‘the reaction equilibrium shifts towards complete dehydrogenation. Addi- tionally, the reactions forming hydrogen compounds are highly exothermic with enthalpies of reaction usually larger than the endothermic heat of dehydrogenation. The overall result is an exothermic process. In the present case where oxygen is the oxidant and water is formed, the equilibrium constant for the OXD of I-butene at 480C is 1.6 x 10!2,This is a dramatic shift from the 9.0 x 16°? value found for normal dehydrogenation, and is the primary incentive for comercial application of the technique. In addition to the favorable equilibrium change, ‘the exothermicity of the process yields eneray savings in the form of decreased steam requirements. The steam in OXD processes is used pri marily for temperature control; steam in non-OXD systems serves as an energy carrier for providing the required heat of reaction. A fortuitous result of the research conducted on OXD systems is ‘that the suitable catalysts typically function in the 400¢ to 500C ‘temperature ranges conventional dehydrogenation is carried out above 608C to overcome thermodynamic limits on product yield, The catalysts used for OXD are usually unsupported metal oxides whose syntheses are possible through simple laboratory techniques. These metal oxides are considerably Tess expensive than the supported metal catalysts commonly found in the petroleum industry, and usually they can be tailored to be non-toxic. In spite of their advantages, the OXD reactions do have significant drawbacks. The formation of stable hydrogen compounds (e.9. H20) ine stead of molecular hydrogen results in the loss of this valuable co- product, and in the case of other oxidants such as Ip, recovery of the oxidant becomes an expensive procedure. The use of these alternate oxidants also presents. serious corrosion problems requiring special handling equipment. Thirdly, process streams containing a hydrocarbon/ oxidant mixture are inherently hazardous. Careful handling of the mix- ‘tures and special operational procedures are required to prevent ex- plosions. Lastly, their exothermic nature makes control of thesereactions critical for safe operation; steam is always used to dissipate the heat released and thereby moderate the temperature rise. In fact, the energy debit associated with steam generation for this purpose is a primary factor making these reactions economically unattractive. COMMERCIAL BUTENE OXD CATALYSTS The use of mixed oxide catalysts for oxidative dehydrogenation of mono-olefins has spread rapidly since the early U.S. patents for bismuth molybdates (4). Even though the list of potentially useful catalysts is substantial (see Table 1), all the catalysts contain at Teast one ‘transition metal and can be divided into the four general classes: molybdates, tin phosphates, spinels (ferrites, cobalites, chromites), and non-spinels. Phillips Petroleum has been particularly active in the investigation and production of the phosphate group while Petro-Tex Chemical Company has developed most of the ferrite catalysts (Table 1). Since the molybdate group is the oldest, it appears to be the most exhaustively studied. Early works by Adams, et al. (6) and Tailingol'd, et al. (7) on bismuth molybdates established that a Langmuir-Hinshelwood model could account for the kinetics observed in the formation of buta~ diene, They concluded that the reaction was zero order with respect to oxygen and was not inhibited by product butadiene. Batist, et al. (8) proposed a mechanism which incorporates an oxidation-reduction cycle ‘involving Mo** and MoS* cations. Cote +O + OR ZCQHZ + OHM MoSt + CyHy” > Mo = Cyst Wo = CyHSt + 02 > Mot +0 + OH" + Gye 20H" 7 O2- + O+ HOx@]-04924 xaj-0492q x@L-0430q xal-0uqaq royosnad wnaloazag sdtttts wnaloaqeg sdi wna }043.2q sdvttiud unajouyad Sdt LLtud ‘@4LL ae@fpoog “Duy ooexaL LO LL2us. SaNDISSY Suyuuey, 4061 ACH Le (sn) 026'920'p SPLYIM fuuewysiayy 26 Lady gz Sy O2L* o20'y SPLIEW fuueuastayy — LBL ISNEMY Z to9* 61" L aooug *sytLge ‘suvreg 961 3snBny L (sn) 2gL*vecte aooug ‘suefeg L961 Avenaged £ (sn) vez*eoete snytag 9/6 asnOny € (Sn) yS6°Zc6"E yeziid — $261 taquedsd 6 (Sn) Gob*szo'e auog 4Oz4d ‘UeGOH *URLON —LZ6L AuenueE ZL (sf 4eZi4d OL6L voquanon OL (SN, eyaey SueGoH ‘ueLoN — OLGL YOURH ZL (SN; web} ‘eueog ‘ueLoN —ugL_YoueH ZL {SN ypoysddoy 2261 Aaenuer UL (Sn, a4seh Sd6t aune € (sn lweuuny @ euteaH I96L Aune » (Sn) YOANIANI auva UaAWNN LNBIVE SINALVd NOLLYNDOUOAHIO 3NIL¥OIKO 3NaLNA ee 2} tay ~AQ “Uh 2} fasta -UZ-B4f 124-0 H4to4-09 2414495-P) 24 Ldataj-29 3 fadas-eg O-d-1N O-d-us-H1 O-oH-ta ASAWLVD0, + 20+ 2Mo¥* > 202- + 2Most © = anion vacancy The primary strengths of this mechanism are that it accounts for the zero order oxygen dependence and is consistent with the isotopic cata~ lyst labeling experiments conducted by Keulks (9) indicating that lat- tice oxygen participates in the hydrocarbon oxidation step. Variations of the molybdate catalyst are abundant. Numerous authors report enhanced selectivities through incorporation of one or . more metal oxides into the molybdate. For example, the following oxides have been evaluated: cobalt- boron molybdate (10), zinc molybdate (11), thallium-nickel-iron-bismuth molybdate (12), cobalt molybdate (13), tellurium-cadmium molybdate (14) and titanium molybdate (15). Both Vanhove, et al. (15) and Petrov (12) Suggested that changes in catalyst activity and selectivity are due to alterations in surface acidity induced by the additional metal oxide. Whereas the molybdates have received the most attention in the academic community, the phosphate group has greater commercial applica- tion, Since publication of a phosphorous-tin-oxide catalyst patent by G. J. Nolan in 1967 (16), most of the development and application of Phosphate catalysts has been carried out by Phillips Petroleum Company. Outside the patent literature, very little has been published about the catalysts, their characterization, ot their performance in kinetic studies. Happel, et al. (17) suggested that these catalysts are primari- ly amorphous metal oxide solutions. Most of the catalysts in this family contain tin or nickel and are prepared by treating coprecipitated metal oxides with phosphoric acid to yield phosphorous contents between 0.1and 17.0 mole percent. Marak, et al. (18) used x-ray photoelectron spectroscopy experiments to show that lattice oxygen participates in hydrocarbon oxidation on a Phillips nickel-tin-phosphorous-potassiun- oxide paraffin oxidative dehydrogenation catalyst. Recent work on this catalyst (19) confirms the anorphous crystal structure and indicates that a Nars-Van krevien type model may be applied to the kinetic data. This model implies that a redox cycle is established for one or nore of the metal species. Unlike the molybdate and phosphate groups, the spinel and non- spinel groups have well-defined crystal structures. The spinel lattice is a face-centered cubic oxygen matrix with metal cations distributed in the tetrahedral (A-site) or octahedral (B-site) interstices. The chemical formula for the spinels 1s A820, where typically B may be iron (ferrites), chromium (chromites), or cobalt (cobaltites). Spinels are classified as “normal” when 211 the A cations occupy tetrahedral sites, and "inverse" when they occupy octahedral sites. Excellent reviews of preparation procedures for ferrites are found in Happel, et al. (17) and Standley (20). Petro-Tex Chemical Company has commercialized the ferrites in the Same manner that Phillips Petroleum Company has with the tin-phosphorous- oxide catalysts. Since the patent disclosure by Bajars, et al. (21) in 1965, the Petro-Tex group has continued extensive development of fer- rite catalysts as reflected by mumerous patent claims. It has been re- ported that the Oxo-D catalyst may be manganese ferrite (22). Unlike the Phillips catalysts, the ferrites have been studied extensively by several research groups. In particular, Rennard and Keh1 (23), andMassoth and Scarpiello (24) have published detailed characterization and kinetic studies of the oxidative dehydrogenation of butenes over magnesium-chromium-ferrite and zinc-chromium-ferrite, respectively. Several studies of the same reaction over cobalt, copper and mag- nesium ferrites have been conducted at Rice University (25, 26, 27). All of these groups concluded that the butene oxidation was near-zero order in oxygen and that butadiene inhibited the reaction. Cares and Hightower (25) and Gibson and Hightower (27) used isotopic tracer studies to show that C-H bond cleavage was involved in the rate deter- mining step in both the OXD and isomerization reactions. Massoth and Scarpiello (24) proposed a mechanism consistent with the above findings (Figure 1). This mechanism bears great resemblance to that of Batist, et al. (8) for oxidation over molybdate catalysts via an allylic inter- mediate. However, in the present mechanism, the first hydrogen abstrac- tion occurs through reaction with an adsorbed (0-) oxygen rather than with a lattice oxygen (02-). This may account for the lack of formation of oxygenated coproducts over ferrite catalysts. Within the non-spinel class of catalysts there are several poten- tially useful crystal types. In particular, metal oxides with ilmenite, garnet, hexagonal, or perovskite type lattices are active for catalytic oxydations. a-Fe0, is perhaps the most widely known and used catalyst ‘in this group. It has a hexagonal lattice structure and has been ap- Plied as a catalyst in a variety of chemical processes including Fischer-Tropsch and water-gas shift reactions. The Shel] 105 catalyst used in the Phillips butadiene process has been reported to consist of 90% Fe.03, 4% Cr and 6% K2CO; (22). Happel, et al. (17) reviewed the8384232) 9314494 4aAO SauayNG Jo QXO 04 wistueYay pasodog *| aunBpy 0%, ed wed \ Jv J 4 re ol] (OF nel ) s SS ONY SCY’ DF ry" /- Oo au a u \ aed ed au application of non-spine? oxide catalysts to oxidation reactions and indicated that greater attention would be given to these catalysts in the future. STRUCTURE AND PROPERTIES OF THE Mn-Fe-O SYSTEM As outlined in Happel, et al. (17) and Standley (20), the two Primary techniques for synthesis of stoichionetric oxides are flux melting and coprecipitation. The flux melting or fusion method requires extremely high temperatures (1400C to 1600C) and careful control of the atmosphere above the melt. Single crystals are usually made in this manner, Coprecipitation of the oxides is normally done in basic solu- tions (NaOH or NH,OH) with the metals precipitated as hydroxides or oxa- lates. Subsequently, the catalyst is dried and calcined to yield the final catalyst. As with the melt technique, the atmosphere used during calcination directly affects the final crystal structure of the catalyst. Thermodynamic phase equilibrium diagrams for the Mn-Fe-O system iTlus- trate the effect of oxygen partial pressure on the equilibrium composi- tion and structure of the oxide (28). In the Mn-Fe-0 system, it is necessary to consider the presence of a variety of chemical species with different crystal structures. Be~ cause of the range of miscibility of some of the oxides, chemical for- mulae of the various species are misleading therefore, the mineral names will be used in the descriptions of phase behavior. A summary of the minerals and their chemical formulae, crystal structure and mag- netic behavior is shovn in Table 2. X-ray diffraction measurements on the oxides will yield information only about the crystal type and not necessarily about chemical composition. Thus 11 oxides with the spinel12 TABLE 2 CRYSTAL AND MINERAL TYPES Chemical Mineral Crystal Composé tion Name Structure Nn, Fes_0, -0x.5 Magnetite Spine] (ferrimagnetic) t5exe1.6 Jacobsite Spinel (ferrimagnetic) 1,62%¢2.7 Vredenburgite Cubic (paramagnetic) 2:7e%<3.0 Hausmani te Tetragonal (paramagnetic) Wn Fes_ 205 wOcx 2 Hematite Hexagonal (anti- ferrimagnetic) -2x2.0 Bixbyite Cubic (paramagnetic) Fe203 Maghemi te Spinel (ferrimagnetic) Feo Wistite Cubic (paramagnetic) no Manganosite Cubic (paramagnetic)13 structure give the same x-ray diffraction patterns. In the Mn-Fe~0 system it is possible to identify four crystal types: simple cubic (Naci type), hexagonal (sometimes called rhombohedral), tetragonal {distorted cubic), and spinel (cubic), The wistite and manganosite species having the simple cubic structure are not stable under catalyst preparation or reaction conditions, where they form higher order oxides. Although oxides with spinel and tetragonal structures are miscible over wide ranges of composition, the miscibility of spinel and hexago- nal structures is very small. In the absence of reducing atmospheres, ‘the most stable manganese and iron oxides at calcination and reaction conditions are the sesquioxides (a-Fe20s, Mnz03). The simplified reaca tions below summarize the solid state reactions in the Mn-Fe-0 system (29, 30). reducing atm. Hexagonal (Fe,0;) —————— Spinel (Fe30,) a. oxidizing atm. reducing atm, Cubic (Nn,0,) ———————_ Tetragonal (¥n30,) (2) oxidizing atm. reducing atm, Cubic (Bixbyite) —————"_ Spinel (Jacobsite) (3) oxidizing atm, The extent to which reaction (3) is reversible depends on the limits of miscibility of Fe,0 and Mn0;. In an iron rich system both bixbyite and hematite phases could be formed. Both iron and manganese are magnetic materials, and as should be expected, their oxides possess some very interesting magnetic properties. Néel (31) proposed a theory to explain the behavior of magnetic oxides, and applied the term ferrimagnetism to distinguish their properties from4 those of classically ferromagnetic materials, Magnetism is attri- buted to alignment of the magnetic monents of the metal ions in differ- ent sub-lattices, The sub-lattices in some oxides may be unit cells, groups of unit cells, or different coordination sites within the unit cell, as in the case of the spinels. Néel proposed that magnetism in the spinels is produced by anti-parallel alignment of the magnetic moments of the ions in tetrahedral and octahedral lattice sites, with Parallel alignment among sites of the same type. A detailed description of the Néel theory will not be presented heres however, a brief review is useful in understanding the magnetic behavior of the spinel ferrites. Using the A (tetrahedral) and 8 (oct ahedral) site nomenclature, we must consider interactions of the types AcA, ACB, and B-8 between sub-lattice sites, The basic premise of the theory is that A-A and 8-B interactions are small compared to A-B ‘interactions, and that A-B interactions result in anti-parallel align- ments of the magnetic monents of the ions on A sites versus B sites. From molecular field theory and following the presentation and nomen- clature of Standley (20), B= fo +H, and a) Fin = vi (3) where H is the magnetic field acting on an atom, fy is the externally applied field, Hq is the molecular field arising from ionic interactions, Y is the molecular field coefficient, and fi is the magnetic monent per unit volume of the material. Thus, for A and B ions respectively, Ha = Han + Fas = aaliy + Yall (6)15 and Ay = Fas * Fea ata ert ee aera o where Ay and Hy are the molecular field components of the total field acting on each site, If y is defined to be the fraction of magnetic sites of the B types and 1 = I-u as the fraction of A sites, then it is possible to define the total field acting on each site. Hi, = Hy + Yaga - Yate (8) lo * Yaatls - Yana (3) ‘These definitions tacitly assume antiparallel interactions (minus signs fi, = are used instead of assuming Y_gc0). Neel then postulated a Curie Law dependence for the magnetic moments of each site. 2 Bea, qa) ¥ ay By substituting equations (10) and (11) into equations (8) and (9). solving for iy and Hi, and calculating the magnetization, H= iy + Hi the following expression is obtained: C fF - ul (rpg t 2¥pQ)] TE Gig # Pigg ht + Ean gg Ra) fe a2) The magnetic susceptibility is defined in terms of the magnetization and the external applied field such that x = [MI/[Hj|. Combining this16 definition with equation (12) and performing extensive algebraic mani- pulations, the expression below for the susceptibility may be produced: lie ibs ose bbb 13) where ye 2A Tyg = Tay = Hog (4) es au (2Ypg + Ypq + Ygg) as) 2 salary + Yyyd HU + | ae) In discussions of the magnetic properties of ferromagnetic mat~ erials, the Curie point refers to the tenperature at which the shift from ferromagnetism to paramagnetism occurs. In ferrimagnetic materials a similar transition occurs at the Néel temperature (Ty). An expres- sion for Ty may be obtained by solving equation (13) for its zeros, as x +=. The two ferrimagnetic oxides encountered in the present study are jacobsite (WnFe.0,) and magnetite (Fe,0,) which have Néel tempera- tures of 300¢ and 585C respectively (20).wv OBJECTIVES The objectives of this research were the following: a.) bt e.) Determine the kinetic parameters of the oxidative dehydrogenation and complete oxidation reactions ‘in order to develop rate expressions. Examine reaction pathways using deuterium labeling and 2*C-tracer techniques, and evaluate proposed reaction mechanisms. Correlate catalyst activity and selectivity for oxidative dehydrogenation with changes in solid state properties.18 TL, EXPERINENTAL CATALYST The manganese iron oxide catalyst used in the present study was prepared using a coprecipitation technique. Stoichiometric quantities of Fe(NOs}3 and MnCl2 were dissolved in water, and (NHy)2C20, was added to form the oxalate solution. This solution was added to a strong NH,0H solution in order to precipitate the oxalate salts of Mm and Fe, Following filtration and drying in air for 24 hours at JOC, the catalyst was calcined in air using a temperature progranmed Procedure. The temperature was raised linearly at SC/minute from roon ‘temperature to 700C and held there for one hour before quenching to room temperature. The resulting powder was pressed into pellets and sieved to obtain 20 to 40 mesh particles for use in the catalytic reactors, The specific surface area of the catalyst, as determined by a gravimetric nitrogen BET method, was 2.4 m@/gn. Atomic absorption analysis of the final catalyst showed that the iron to manganese ratio . Xeray diffraction studies demonstrated that the virgin cata- lyst was a ferrite solid solution with the remaining excess iron oxide present as a a-Fe203 phase. GASES The chromatographic carrier gas used in all experiments was Liquid Carbonic zero helium (99.998 percent); it was used without fur= ther purification. Before use in flow experiments, the helium was. passed through a liquid nitrogen trap to remove hydrocarbon and water ‘impurities, The heliun-oxygen mixture used in the magnetic suscepti- bility experiments was prepared by Liquid Carbonic and contained 10.21g Percent oxygen with the balance zero helium, The n-butene isomers and 1,3-butadiene were a11 Phillips research grade (butenes - 99.94 percent, 1,3-butadiene - 99.84 percent) and were each purified before use by vacuum distillation from -78 to -195C and outgassing at the lower temp- erature. Liquid Carbonic high purity grade oxygen (99.99 percent} was used after being passed through a trap at -78C. Following purification, all reactant gases were placed in storage bulbs (Figure 2) for ready access prior to use. The deuterium labeled butene (98 atom percent deuterium) was a mixture of the trans (20%) and cis (80%) isomers provided by Merck, Sharp, and Oohne Ltd. The isomers were separated prior to use by frac- ‘tionation in a propylene carbonate gas chromatographic colunn at 0.0C. The composition of the resulting cis-2-butene-d8 was 84 percent C03 and 16 percent CyD7H. The 180 labeled carbon dioxide was obtained from Alfa Products and contained 99.85 atom percent 380, The }C Jabeled butadiene used in the radio-tracer experiments was provided by Petro-Tex Chemical Company and had an approximate specific activity of 32 micro curies per mole.20 snqeueddy uoy3einouyoay yoeg *z adnbydaa APPARATUS Recirculation System A batch recirculation system was used for the kinetics, isotopic tracer, and radiotracer experiments (see Figure 2), It is a vacuum/ Tow pressure apparatus constructed of pyrex glass utilizing a Welch Duo~ Seal fore pump (FP) and a mercury diffusion pump (D) to maintain a Pressure below 10°§ torr. The pressure is measured by a McLeod gauge. Al] of the valves are high vacuum glass stopcocks sealed with Dow Corning vacuum silicone grease. The recirculation Toop may be traced in Figure 2 in the direction of flow from the reactor bed (R) through stopcocks S24 and S22 to the ice-water trap (T4), and to the recircu- lation pump (PUMP). The loop continues to a mixing volume (not shown) and then through stopcocks $13, S14, S21, and S24 to return to the catalyst bed, The total volume of the Toop is about 480 cm?, The recirculation pump is 2 double action positive displacement Pump containing a glass piston with an iron core. The piston is moved by alternate switching of power to two externally mounted solenoids. The frequency of the switching determines the pumping rate, which can be varied from approximately 508 to 1500 cn?/min using an electronic pump controler. There are two bypass sections in. the recirculation loop. The first is part of a doser formed by stopcocks S12, $13, and S14, The second, formed by stopcocks S21 and S22. permits recirculation of gas mixtures without flow over the catalyst bed.. Pressure in the recircula- ‘tion Toop is measured by a Texas Instruments Model 141 pressure gauge which employs a quartz bourdon tube and is capable of measuring pressure within 0.1 torr.22 The reactor, including S24, may be inserted into or removed from the recirculation Toop through the use of two 10/30 standard taper fittings. The reactor bed has a volune of approximately 2 on? and the catalyst is suspended between two’ glass wool plugs. A glass well ‘is mounted inside the reactor to permit placement of a thermocouple within the catalyst bed. The temperature in the bed is measured by an iron-constantan thermocouple attached to a Leeds and Northrup Nodel 8686 millivolt potentioneter referenced to a 0.0C ice water bath, Temperature control (+1.0¢) is provided by @ Leeds and Northrup Elec- tromax P-I-D temperature controller and a nichrome element tubular fur nace. The control thermocouple is mounted outside the reactor. Gas mixtures can be introduced into the recirculation system via either of two routes. The first is through standard taper 4 (F 4) and $23. The second is through $1, $9, S14, and S15. lihen the second route is used, pressure can also be measured using’a mercury manoneter (MG). Gases to be purified and stored in the system were introduced through $ 2 and S11 to 2 trap (12) thermostatted at -78C. Oxygen was passed via S10 and SI directly into 2 five liter storage bulb equipped with @ mercury manometer (M1). Hydrocarbons were distilled from 72 to Tl, thermostatted at -195C, before being placed into storage bulbs (82, I-butenes A3, cis-2-butenes B4, trans-2-butenes 85, 1,3-butadiene). During kinetic runs, samples of the reactant mixture were expanded ‘into the Toop between S19 and S20. Helium was used to sweep the sample from the Toop into a gas chronatogrash for analysis. When S13 and S14 are closed, continuous helium flow through the detector is maintained by flow through @ capillary bypass. The gas chromatograph (seeFigure 3) consists of a fractionation colum, a thermal conductivity detector, a digital integrator, and a strip chart recorder. The colunn is a 1/4 inch x 35 foot copper tube packed with propylene carbonate (25 wt. percent) supported on 60 - 8 mesh Chromosorb W (AW). During use, the colum is maintained at 0.0C in an ice-water bath. The detec- tor is a four-filament Gow-Mac thermal conductivity cell with a 15 volt direct current power supply. Current in the detector is maintained at 180 millianps; its output is monitored by a Perkin-Elmer Model 1 digital integrator, The detector was kept in an insulated oven at 720C using a Variac power supply and a nichrone resistance heating element. Chromatographic peaks can also be monitored visually on a Leeds and Northrup Speedonax @ strip chart recorder. Individual components can be collected in a sample tube attached to 35 as they emerge from ‘the detector. When radioactive gases are used in the system, an addi- tional copper oxide colum, fitted with a fritted glass dispersion tube and a scintillation vial reservoir, is connected to $5. As radio- active hydrocarbons emerge fron the detector, they are burned to CO, 4m the copper oxide colunn and collected in a basic liquid scintillation cocktail for further analysis. The components of interest have the following response factors and retention times: oxygen, 189.0, 410 seconds; carbon dioxide, 167.0, 530 seconds; I-butene, 99.0, 800 seconds; trans-2-butene, 94.0, 920 seconds; cis-2-butene, 92.0, 1040 seconds; and 1,3-butadiene, 100.0, 1430 seconds. The helium carrier gas flow rates were 60 cm?/min for the sample stream and 6 cm3/ min for the reference stream. These flow rates may be adjusted using Nupro metering valves V2 and V3 shown in Figure 3.24 a1dnvs SON 3d 343u waqSAs opydeuBoxeworyg sep *¢ aunB1y sg ozs BIS WoLoVad Wodd LIS daquoosd LdVHO didls WANDVA OL NWN100 WOLVYOSLNI YOLOaLad doLv1n9sd25 Microcatalytic’ System A mercury-free vacuun/low pressure apparatus similar to the batch recirculation system was used for the microcatalytic pulse, C02 exchange, and electrical conductivity experiments (see Figure 4). It may be operated as either a flow or recirculation system, and it also contains @ vacuum microbalance (MB) for use in gravimetric BET surface area, magnetization, magnetic susceptibility, and thermogravimetric analysis (TGA) experiments. The microbalance system is described in a later Portion of this chapter. Vacuum in the system is maintained ty a Welch Duo Seal fore pump and an of] diffusion pump equipped with a liquid nitrogen cold trap hen the system is not in use, the manifold may be isolated from the diffusion pump by closing V6 and opening VS to an 8 liter per second Varian Vac Ion pump. Pressures below 10°S torr are easily maintained with this pumping arrangement. A Vacuum Electronics ionization gauge (62) 4s used to measure pressure between 107% and 10720 torr. VS, V6, and V7 are Vs inch diameter varian stainless steel bellows valves. and V1, V2, V3, and V4 are Granville-Phillips ultra-high vacuum glass stopcocks. The recirculation loop contains a recirculation pump identi- cal to that in the batch system (Figure 2). The microcatalytic recirculation loop may be traced in the direc- tion of flow from the reactor (R) through S16 and the ice water trap (72) to the pump. After leaving the recirculation pump, gases enter a 300 cn? mixing volume (not shown) before returning to the reactor through stopcocks S18 and S19. As in the batch system, the reactor is connected to the Toop through two 10/30 standard tapers. During26 waqu0oau AuvHo diuis SONVIVva $310d L3NOSVW an Microcatalytic System Figure 4.a electrical conductivity experiments, the reactor is replaced by the glass cell shown in Figure §, The temperature is controlled exactly as it is in the batch system, using the nichrome element furnace and Leeds and Northrup Electromax temperature controller. The gas chromatograph and Sampling loop are also identical to those in the batch system except that a Spectra-Physics Minigrater is used in place of the Perkin~ Elmer Model 1 integrator. Pressure in the recirculation loop is also measured with a Texas Instruments Model 141 Fused Quartz pressure gauge (a1). This system may also be operated as a flow reactor for use in pulse experiments. In this mode, stopcocks $12 through. S20 are turned to permit entry of the gas mixture (or helium carrier gas) into $4 and exit from $1. When samples from a flow experiment are taken, TI is operated as a GC sample Toop with the gas flow through the reactor divert- ed through S15 and $2 while the GC analysis is completed. During pulse experiments, the pulse is collected by thermstatting TI at -195C. The carrier gas is then diverted through 5 2, the sample thawed, and GC analysis conducted on the vaporized pulse. Following the analysis $13, $14, and S15 are turned to direct the gas flow through $1. In order to inject a gas pulse into the helium carrier, the doser loop (2.34 cm volume) between $19 and S20 is filled through J 3 to the de- sired pressure, measured by the TI gauge (GI), and $19 and S20 rotated to permit the carrier gas to sweep the pulse out of the loop and into the reactor (R). When the doser is being filled or evacuated, a capillary bypass allows the carrier gas to flow continuously through the system. The remainder of the apparatus is used for gas handling and storage.ZA LA\— § 10730 Platinum Wires $ 29/42 Fritted Glass Tube Figure 8. Electrical Conductivity Cell2 B1 through B4 are five liter storage bulbs each equipped with a cold finger trap used during purification of the stored gases. Since the system is also used for BET surface area measurements, 81 and 82 are normally filled with nitrogen. Mass. Spectrometer and IPD System The Consolidated Electronics Corporation Model 21-104 mass spec- trometer shown in Figure 6 was used for gas analysis in the isotopic tracer, CO, exchange, and temperature programmed desorption (TPD) ex- periments. The inlet system contains a 3313 cn? sample volume (V) and is equipped with an MKS Baratron electronic manometer. Vacuum in the inlet system is maintained by an oi] diffusion pump with a mechanical fore pump. There are additional diffusion and fore pumps used to evac~ uate the mass spectrometer during start-up operations. Under normal use, the vacuum is maintained by an eighty liter per second Varion Vac Ton pump. Gas samples are fed into the spectrometer from the inlet system through a gold foil leak (C). During all experiments, an anode current of 10 microamps and a nominal ionization voltage of 10 volts were employed. An additional sample handling system was constructed to permit ‘temperature programmed desorption experiments to be performed utilizing the mass spectrometer as the detector. A catalyst sample was placed in ‘the vycor glass sample tube. Any desired gas could be adsorbed onto ‘the catalyst by opening valves V1 and V2 (V10 and V3 are closed) and admitting the adsorbate through J 1. A bourdon tube gauge (G) measured approximate gas pressures over the catalyst sample (+ 10 torr). The catalyst sample was heated by an externally mounted nichrome element30 wa3SXs dezewoJgoads ssey pue uoLzdtoseq owes6o4g aunqesodso *9 aunby4 [ 26] Waquoosd Le VHO} didts: 2g in ane dwnd sj LNOISNadIG 3dod ou LNOO dW3l — HOVNUN FIdNWS_LSATVLYO | 1g Yfurnace controlled by a locally constructed electronic temperature Programmer. Linear programming rates of 5, 10, and 20¢ per minute were possible over the range 25C to 600C, The sample tube and catalyst are normally evacuated through V3 and V5 prior to the beginning of an experiment. A thermal desorption run is conducted by opening VI and V2 (211 other valves are closed) and initiating the temperature pro- gram on the temperature controller. Mass spectra of the desorbed species are displayed on a Hewlett-Packard Model 7100-B strip chart re- corder. The second channel of the recorder may be used to record the ‘temperature using an iron-constantan thermocouple placed near the cata- lyst sample. Microbalance and Magnetic Susceptibility System A Perkin Elmer T6S-2 vacuum microbalance system was used in per- forming BET surface area measurements, thermogravimetric analysis (TGA) and magnetic susceptibility experiments. The system contains a balance control, heater control, temperature programmer, and firgt derivative computer. It is connected to the microcatalytic reactor system (Fig- ure 3) in order to use the gas handling and mercury free vacuum system. With this arrangenent, it is possible to achieve an ultimate vacuum in the balance of 10° torr. The balance is capable of weighing small sam- ples within £1.0 x 10°? grams. The vacuum connections between the bal- ance ‘and the hangéown tubes on both the sample and tare sides of the balance are high vacuum o-ring sealed glass ball joints which facilitate the use of a variety of hangdown tubes. By using the temperature con- troller and temperature programmer, the sample temperature can be main- tained in an isothermal or linear programmed mode in the temperature32 range 25¢ to 1000C. Linear programming rates between 0.31C and 40.0¢ Per minute are possible with an accuracy of + 2C over the entire range. The furnace (Figure 7) uses a platinum resistance element as both a heater and temperature measuring device. The temperature programmer uses the platinum resistance thermo- meter as a control thermocouple; the sample temperature is measured by @ separate thermocouple mounted near the sample pan. The sample tenp- erature is displayed on either a digital volt meter (DVM) or a strip chart recorder, The output from thé: balance is displayed on one channel of a Hewlett-Packard Model 71008 strip chart recorder, and the output from the first derivative computer is displayed on the second channel. Platinun sample pans are used in all but magnetic susceptibility experi- ments where quartz pans are used. Since the furnace is mounted inside the hangdown tube, it did not ‘interfere with the positioning of the hangdown tube between the magnet poles during magnetic susceptibility experiments. The Alpha Scientific Model 7500 electromagnet was equipped with Faraday pole pieces and could be operated between zero and ten amps current using a locally constructed power supply. In order to avoid changes in the magnetic field resulting from heating of the magnet coils by the energizing cur- rent, periodic operation of the magnet was employed. When the Faraday pole pieces are used, the quantity H," a remains constant over a small region near the center of the poles. H, is the magnetic field strength, and z is the vertical coordinate. Secause the autobalance weighs a sample without displacement of the pan, the system is ideally suited for magnetic susceptibility measurements, where the susceptibi-Figure 7. Microbalance Furnace Furnace Hangdown Tube |__ Furnace Support Furnace Adjustment Knob 3334 lity x is defined by ay, Fax ay a7) assuming zero field gradients in the horizontal plans near the sample. F, is the difference between magnetized and non-magnetized sample weight. The calibration of the magnet shown in Figure 8 was performed using manganese oxide (¥n30,) whose room temperature susceptibility is 1.24 x 102 cgs units/gn mole. During magnetic susceptibility experiments, a long hangdown tube is used to insure that the magnetic field does not affect the balance mechanism, The balance system is constructed to allow gases to flow over the catalyst sample during an experiment. A purge gas (normally helium) is admitted to the balance head through S1 (see Figure 4) while the reactant gases are introduced through S21. The entire gas mixture exits through S10 and is vented outside the laboratory. Flow rates of all gases are controlled by Nupro metering valves. Acray Diffraction Equipment A Philips Model 1010 x-ray machine was used to make powder photo graphs. Catalyst samples were prepared by grinding to at least 325 mesh particle size and packing into 0.5 mm quartz capillary tubes. The sample tubes are mounted into a 57 mm radius Debye-Scherrer camera loaded with a strip of x-ray photographic film. Once the camera is aligned on the x-ray machine, the sample is illuminated by a 1500 watt molybdenum source operated at 38 kilovolts and 18 miiTiamps. The Mo K, (A= Q.7107 A) radiation is filtered by a zirconium foil, and the sample is exposed for 36 hours, The exposed film is developed and theH-dH/dz (10° gauss*/cm) 2 3 4 5 Current (Amps) Figure 8. Magnet Calibration36 diffraction pattern analyzed using Bragg's Law to compute crystal d-spacings. d-spacings are identified and indexed through reference to a powder diffraction file. Atomic Absorption Spectrometer The bulk concentrations of metal species in the catalyst were measured using a Perkin-Elmer Model 303 Atomic Absorption spectrometer equipped with an Intensitron (Fe-Cu-Co-Mn-Ho) lamp operated at 30 mil- ‘Tiamps current. Standard solutions were prepared using salts of the metal ions of interest (Fe(NO,), > 9H,0 and MnCl, * 44,0). The catalyst sample was dissolved in aqua regia prior to dilution and analysis. Radioactivity Measurement Equipment A Nuclear-Chicago Unilux scintillation counter was used to analyze radioactive components obtained during radiotracer experiments. Indivi- dual radioactive species were extracted into a liquid scintillation cocktail as they energed from the copper oxide and gas chromatographic colunms in the batch recirculation system (Figure 2). The scintillation fluid used was a mixture of eleven parts Bray's (Baker Chemical) solu- tion to one part ammonium hydroxide (58 percent). Each sample was counted for forty minutes, and then recycled for further counting per~ jods until the specific activity reached a constant level. A correc tion for background activity was applied to all sample analyses. EXPERIMENTAL PROCEDURES Kinetic Runs in Recirculation System Before each experiment, the catalyst was pretreated in 100 torr of oxygen recirculating at 500C. Any water or oxidized hydrocarbons were removed from the flowing stream by thermostatting T4 at -195C. Thisoxygen treatment was continued for one hours then the temperature was lowered to 400¢ prior to evacuation to less than 10-° torr. During evacuation through $19 and S20, TI was thermostatted at -195C to pre- vent mercury vaper from entering the recirculation Toop. When vacuum was achieved (usually less than one hour), S20 and $24 were closed and the reactant gas mixture prepared in the recirculation Toop. With S21 and $22 in the bypass position, the hydrocarbon reactant was in- ‘troduced through S12 and S14 from the gas handling system. The pres- sure was measured on G1. When the desired pressure was reached, S14 was closed and the hydrocarbon condensed in T4 at -195C. Oxygen was then admitted through S12 and S14 to the desired partial pressure. S14 was closed and the hydrocarbon allowed to vaporize while the gases were recirculated through the loop (with S21 and S22 stil] in the bypass position). The gases were pre-mixed in this manner for thirty minutes prior to each kinetic run. Due to the explosive hazards of ‘the hydrocarbon/oxygen mixture, extreme care must be exercised in the Preparation of the reactant mixture to insure that the gas compositions ‘remain outside the explosive region (approximately 5 to 33 percent butene at room temperature). During this mixing period, the desired reactor temperature was set on the temperature controller, and the reactor was allowed to reach a steady isothermal state. After pre- mixing was complete, stopcocks S21, $22, and $24 were turned to the appropriate position to flow the mixture over the catalyst and begin the kinetic run, At desired time intervals, the temperature and pres- sure were recorded and samples were removed from the system for GC analysis as described earlier.38 Recirculation Experiments with Deuterium Labeled Butene The catalyst pretreatnent, reactant mixture preparation, and con- duct of the runs were identical to the procedures used in the kinetic experiments, except that the hydrocarbon fraction was a mixture of 80 torr undeuterated cis-2-butene and 50 torr perdeuterated cis-2- butene. Two runs were performed at temperatures of 363¢ and 412C. ‘As each hydrocarbon component of a GC sample emerged from the detector, ‘it was collected in a u-tube at -195C. Following evacuation of helium in each tube, the tube was warmed to room temperature and its contents expanded into the mass spectrometer for analysis of the isotopic con centrations. Radioactive Tracer Experiments A mixture of approximately 10 percent radioactive 1,3-butadiene ‘in 1-butene was prepared in the recirculation system for each of the three experiments. To this mixture was added oxygen to make the final composition 110 torr hydrocarbon (butene plus butadiene) and 50 torr oxygen. During all three experiments, a reactor temperature of 365C was used. The conduct of the runs was the same as in the recirculation kinetic experiments. As GC samples emerged from the detector, they were burned to CO, ina heated copper oxide colum and collected in the liquid scintillation fluid described earlier. All of the butene isomers were trapped in a single sample, but the carbon dioxide and 1,3- butadiene were trapped separately. The samples were then placed into the scintillation counter for analysis. The counting sequence used was background, carbon dioxide, butenes, butadiene, background. At the conclusion of each experiment, the remaining material in the recircula-tion system was collected and treated for disposal as radioactive waste. Microcatalytic Experiments The butene pulse and C180, exchange experinents were carried out in the microcatalytic system. In both series of experiments, the doser between S19 and S20 (Figure 4) was filled to 185 torr or 1.42 x 108 molecules of the desired reactant. The helium carrier gas Flow rate in all experiments was 60 cm3/min. Depending upon the experiment, various pretreatments of the catalyst were used. In all cases, the recirculation loop was filled with the desired treatment gas (oxygen or butene), and the pretreatment was performed in the batch recircu lation mode. In addition, in the C180, exchange experiments, C160, was allowed to flow over the catalyst at 400C to remove 280 left by previous runs. During butene pulse experiments, the reaction products were col- lected in Tl at - 195C. The helium flow was diverted through S15 and ‘32 while the sample was thawed and swept into the GC for analysis. ‘The carrier flow wes then redirected through TI and 31 for the suc- ceeding pulse. During C180, exchange experiments, a separate u-tube ‘trap was connected to 32 which was maintained at - 195C. With the carrier gas flowing through $2, a C1®0, pulse was passed over the cat~ alyst and collected in the u-tube. The helium was then removed from ‘the sample tube, and the carbon dioxide pulse was expanded into the mass spectrometer for isotopic composition determination.Electrical Conductivity Experinents Tae microcatalytic apparatus was also used in the batch recircu- lation mode during electrical conductivity experiments, The catalyst pellet was prepared by packing a fritted glass cylinder with a cata- lyst slurry, inserting platinum electrodes into each end, and packing the ends with glass wool. The pellet produced was approximately 9 mm in Tength by 5 mm in diameter, The desired gases were prepared in the recirculation loop and pumped over the catalyst during experimental runs. In particular, pure oxygen. pure cis-2-butene, and cis-2- butene/oxygen mixtures were employed. A11 runs were conducted under isothermal conditions except for a few experiments in which tempera~ ture was varied with either an oxygen atmosphere or a vacuum present. Pretreatment between runs consisted of recirculating 100 torr of oxygen at 500C for one hour, with T2 maintained at -195C to remove decoking products from the oxygen atmosphere. The catalyst was then outgassed at 400C for at least one hour prior to initiation of a run, The elec- ‘trodes from the catalyst pellet were connected to a Keithley Model 197 digital multimeter which displayed resistances up to 20 megaohms. The multimeter uses a direct current voltage for resistance measurement. Experiments in the Microbalance System ‘The experiments performed in the microbalance system included therm ogravimetric analysis (TGA), magnetization, and magnetic susceptibility experiments, and they were designed to provide information on catalyst solid behavior, In addition, with slight modifications, the system was used to determine nitrogen BET surface areas. During all experi- ments, approximately 50 milligrams of the catalyst were placed in the4a sample pan and tared both electronically and mechanically to null out the weight of the sample pans and hangdown wires, In the magnetic susceptibility experiments, a quartz sample pan was used to reduce susceptibility contributions from the pan, The magnet current was pre~ set to 4 amps and the magnet switched on and off during experiments to avoid heating the magnet coils. During operation, the magnet pro- duced a steady-state field within a few seconds of being energized. The sample weight was noted when the magnet was on and when it was off. The difference between the two measurenents yielded the magnetic force F, where Fz = gz AW. The effects of thermal convection and bouancy were examined by conducting runs with inert samples (quartz chips). Corrections for these effects were then applied to the results of experiments on cata- lyst samples. In the case of the magnetic studies, these corrections were negligible conpared to the magnetic responses. Pretreatments of the catalyst were conducted in flowing atmospheres of either helium or a helium/oxygen mixture (10.2 percent Op). The pretreatment gases were admitted to the system from the GC sample Toop (M1). They passed through stopcocks S11, S13, and $1 and the balance head to the catalyst and exited through S19. The reactant, 1-butene, was introduced through Nupro metering valve (V8) with helium flowing through the balance head as a purge gas. No attempt was made to flow a butene-oxygen mixture over the catalyst because of the potential ex- plosive hazards, In the TA and magnetization experiments, flowing helium was used as the atmosphere above the catalyst, and temperature was raised lin-2 early at 20C/min from room temperature to 700C. The magnetic suscep- tibility runs were conducted isothermally at 400¢. Because the entire gas Flow could not be directed through the catalyst bed, meaningful analyses of the exit gas composition could not be made, Experiments. in the Temperature Progranmed’ Desorption (TPO) System Approximately 50 milligrams of the catalyst were placed in the sample tube (see Figure 6) for TPD runs. Prior to each run, the cat- alyst was treated in 100 torr of oxygen at 500C, cooled to 100¢ and then evacuated to less than 10-7 torr pressure. Evacuation was not conducted above 400¢ in order to avoid decomposition of the catalyst. Response factors for the system were determined using known samples and calculated using the procedure outlined in Appendix 1. In order to reduce readsorption of desorbed species during experi- mental runs, the maximum pressure attained during desorption was limi~ ted to 10-S torr. Under this limitation, the time lag due to diffusion through the system was negligible. The tenperature programming rate was restricted to 10C/min to minimize the thermal Tag between the con trol thermocouple and the catalyst sample. The mass spectra of desorbed species were obtained by scanning the mass ranges of interest approxi- mately twice per minute. In this manner, simultaneous records of de- sorption behavior of several species were produced, A variety of adsorbates were used in the TPD experiments. However, the principal compounds of interest were carbon monoxide, carbon dioxide, oxygen, the three normal butene isomers, and 1,3-butadiene. Normally, the catalyst (at a preset tenperature) was exposed to an adsorbate at~ mosphere between 100 torr and 700 torr for at least fifteen minutes.The sample was cooled to room temperature and then evacuated through valves V1, V3, and V5 to less-than 10-7 torr prior to initiation of a desorption run, One series of experiments was conducted with butene ‘in which the exposure of the catalyst to the adsorbate (Exposure = Pressure of adsorbate x time of exposure) was varied in an attempt to measure rates of adsorption. ‘TREATHENT OF DATA Kinetic Experiments Data collected in the kinetics experiments in the recirculation system included the gas phase compositions, pressure, and tenperature as a function of time. The information obtained was first analyzed for ‘initial rate data, In most of the experiments, a sample of the reaction mixture was taken thirty minutes after initiation of the run. The par- ‘tial pressure of each component was determined, and the initial rate of formation of each was calculated as the change in composition of that component divided by thirty minutes. In order to evaluate kinetic models, additional rate information was necessary. Specifically, instantaneous rates as a function of time were required, and these were calculated by numerical differen- tiation of the partial pressure versus tine data. The differentiation procedure utilized second order polynomial fits of three successive data points to determine the slope at the intermediate point. The rate ‘information generated in this manner was suitable for use in testing different kinetic models. abel Experiments ‘The isotopic composition of each of the hydrocarbon components in Deuteriisamples taken from the recirculation system were determined in the deuteriun-label experiments. Using the methods of Hall and Hightower (32) and Cares and Hightoner (25) it is possible to define isotope ef- fects for both isonerization and butadiene formation. The method is based on the following assumptions: a. Product butene molecules containing less than four deuterium atoms originate from dy species; molecules con- taining more than four deuterium atoms originate from dy species. Product d, molecules originate from both direc- ‘tions equally. b. Product butadiene molecules containing less than three deuterium atoms originate from light starting materials, and those containing more than three deuterium atoms origi- nate from heavy starting materials. The d, species is prod- uced equally from both directions. ¢. The concentration of the trans and I-butene isoners is always smal, such that the reverse isomerization reactions are negligible compared to the cis— trans and cis—1-butene reactions. d, An average isotope effect is considered rather than specific effects for each dj species. An isotope effect for isonerization is then defined 3 8 le Nip + “1A [3 Nip + ta] L.E-isom #73 55 8 2 Nip + Nye YS 2 Nin t 3 Nop io iS (8)and an isotope effect for oxidative dehydrogenation is defined as 2 é E Nip + 5 Nap £ ip + Ry] LE-oxp [: , Vi (19) ENG + EN, DONG, + 5M where p now refers to butadiene species. Details of the derivations for average nunber of molecules exchanged and isotopic composition cor- rections are shown in Appendix 2. Microcatalytic Pulse Exoeriments There were two different types of experiments perforned using the pulse system. The first was an isotope exchange experiment in which C2®Q,was pulsed over the catalyst and the 160 and 280 distribution in the product carbon dioxide analyzed. In the second type of experiment, pure cis-2-butene pulses were used and chromatographic analysis was performed on the reaction products. These experiments were designed to provide information about the mobility and reactivity of the catalyst lattice oxygen. In the exchange experiments, it is assumed that exchange equili- brium is achieved between the catalyst and the reactant pulse, and that the isotope effect in carbon-oxygen bond breaking is negligible. Under these conditions, the oxygen isotopic distribution in the exchange products will follow a binomial distribution. From knowledge of the pulse size and the isotopic composition of its product, the nunber of ‘oxygen atoms exchanged can be calculated. The data may be linearized by a relationship of the form Sf pee, (20)where Z is the cumulative oxygen exchange, P is the pulse number, and ze is the total exchangable oxygen (10). Aside from illustrating the effect of surface oxygen on the prod- uct composition in the cis-2-butene pulse experiments, the data ob- tained were used to determine the magnitude of removeable oxygen. This was done through mass balances on the total carbon and oxygenated prod ucts. The final results are expressed in terms of monolayers of oxygen removed. Temperature Programmed Desorption Experiments Experimental data collected in TPD runs were in the form of de~ sorption rate versus temperature. Since linear programming rates were used, temperature and time are interchangeable in the equations des- cribing the thermal desorption process. In order to produce data suit- able for use in the desorption equations, the raw experimental data were converted to fractional coverage through numerical integration and the following function: (21) where T, and T,bracket the desorption peak of species i, dN/dt is the desorption rate (dN/dt = adN/dT, where ais the heating rate) which is Proportional to the peak heights measured by the mass spectrometer, and 94 is the fractional coverage of species i. Since do Beak (22) ar47 where, 1, is ra (23) hh the information needed for testing suitable rate expressions is known, The well-known Polanyi-Wigner equation forms the basis for the deter- mination of al] desorption kinetic parameters in the present study. «) (s).n exp (-Eq/RT) (24) de qr a> Since the functional dependence of e and 42 are known, k and Ey may be determined for assuned values of n using the following method: a, Assume an arbitrarily low value of Eq. b, Vary k to obtain the best Fit to the experimental data. Goodness of fit is determined by the correlation coefficient of the linear regression performed on the parity plot of actual versus predicted de/dT. c, Assume successively higher values of Eq, repeating step (b) for each Eg, until a maximum value of the correlation coefficient 4s found. 4, Repeat (a) through (c) for a different value of n. In this work, only integral values for n of 1 and 2 were used.IIT. RESULTS KINETIC EXPERIMENTS General A series of experiments was conducted in the batch recirculation system in which the initial ratio of butene to oxygen in the reactant mixture was varied. The data obtained were used to determine reaction orders and to develop a kinetic model. The experiments were conducted over 0.20 gm of catalyst, aged by performing OXD runs until the cata- lyst activity remained constant between runs. A decline from the initial activity of about 50 percent was observed. Since the reaction is highly exothermic, low reactor temperatures were used in order to prevent large temperature excursions in the reactor bed. However, the use of low temperatures restricts the con- version of hydrocarbon to relatively low values (Tess than 10% in the present study). Because of the expense of research grade reactants, high conversion experinents in a flow system were not conducted. The time interval between samples was progressivdy increased during each experiment, This procedure minimizes the effect of reac- ‘tant loss (approximately 1 percent) on the outcome of the experiment. The use of the propylene carbonate GC column does not permit resolution of carbon monoxide from oxygen peaks. However, previous work on ferrite catalysts indicates that the CO/CO, ratio is always small (8, 23, 24, 32). As will be shown in detail in a later section, temperature pro- gramed desorption experiments on the present catalyst indicate that carbon monoxide is readily oxidized to carbon dioxide at reactionconditions. Thus, the CO0/0, GC peak is assumed to be only oxygen. Between kinetic runs, the catalyst was pretreated in 100 torr of oxygen at 500C. Because of the sensitivity of the Mn-Fe-0 system phase behavior to oxygen pressure at temperatures above S00C, no attempt was made to correlate different pretreatments with catalyst activity. In order to insure reproducible results throughout the series of experi- ments, only the above pretreatment was used. Initial selectivity, defined as a0 * * Peo, i was approximately 80 percent in all kinetic experiments. Data from a typical experiment are displayed in Figure 9. The most important feature illustrated is that butene isomers, 1,3-butadiene, and carbon dioxide product formation rates all decrease with time. This is a clear indication that product inhibition may be an important fac- tor in the development of a kinetic model. Initial Rate Data Data obtained in the recirculation experiments were analyzed first to determine a power-law type kinetic expression for the initial rates of reaction. This technique leads to the determination of rate constants used in later evaluation of kinetic models. In most experiments, the first sample was taken thirty minutes after initiation of the run; this was the data point used in all initial rate calculations. Conver- sion at this sampling time was usually less than one percent. The ini- tial compositions and temperatures used in the kinetic experiments are listed in Table 3. An attempt was made to fit the data obtained to rate(torr) Pressure 41000> kgoPdy yielding: BoB a co, * pee 2 PSR D FB R (32) Second, for the same conditions, inversion of equation (32) provides,% So. "Bo =14 BR: (33) Reo, % OE Since Fg does not change much during’ the run, a plot of 109 (kg/Rup,-1) versus log (Pao/P,) should be a straight Tine with slope d/f. Values Of Rep, are determined by numerical differentiation of the composition W.tine data. Fitting the expression to various initial compositions and temperatures shows that both d and f equal to 1.0. Since ky is known from initial vate data, ky = 52.07 exp (-18870/T), K'gp/K'y may also be calculated end has the value 4.77 exp (1430/T). Conbining this information with the initial rate data shown in Table 3, the fol- Towing expression is obtained for carbon dioxide formation: 52.07 exp(-18870/T) -P,+1.32 exp(-14840/T) «Ppp Ron = (34) Ce Py * 4.77 exp(1430/7) Pap With the rate parameters for combustion knom, it 1s now possible to linearize equation (30) in order to calculate the OXD parameters. It 1s noted that the second term in equation (30) is the rate of complete oxidation of butadiene (R',,) which is already known. Thus with some algebraic manipulation, equation (30) becomes oe oy 2 (35) Fao "gp BFE fs with the carbon dioxide expression, a plot of Tog (kgp/Rgy -1) versus og (Pyp/P,) should yield a straight Tine with sTope c/a. Using the values of A calculated fron the differentiation of the composition data, c/a is equal to 1.0 and K,)/K, is 5.02 x 10722 exp (16960/T). Thus, ‘the final form of the rate expression for butadiene formation is60 6.26 exp (-17720/T) +P, Rgp = By F S.02 x 10 exp (T6960/TI- Pep +33 exp (-14840/7)-Pgp Py + 077 expUI4S07T) “Pp (36) Tne rate expressions developed here fit the data within experimental error over the range of conversions and temperatures investigated. DEUTERIUM LABEL EXPERIMENTS Summaries of the results from the deuterium label experiments are presented in Tables 5, 6, and 7. Experiments were conducted at 363C and 472C using initial reactant mixtures of 50. torr undeuterated cis-2-butene, 50 torr perdeuterated cis-2-butene, and 50 torr of oxy- gen. Catalyst pretreatment between experiments was the same as in the kinetic runs. Isotope effects for isomerization and oxidative dehy- drogenation were computed using equations (18) and (19). The denomi~ nator of these equations is the ratio of light to heavy material in the reactant and is, therefore, a function of time. In the present study, the initial value of the denominator was used as the normaliza~ tion factor for all calculations to yield an average isotope effect over the time intervals of interest, Details for calculating the atoms exchanged per molecule are outlined in Appendix 2. H/D scrambling could be expected to occur in the hydrocarbon molecules in the gas reactant mixture. If rapid exchange occurs, a binomial distribution of deuterated molecules is produced where the maximum dj concentration occurs for the dg (butenes) of dg (butadiene) species. However, as shown in Tables 6 and 7, very little exchange occurs over the entire period of the experiment. This small interaction4 tape out" ees" 9b" €60° sez" zLe* TopeAT eToy gto" 60° sez* e60* ott’ 2te* LLo* 920° “= eho" = 050) 200" e00* > OD T= CH Ty WORNGHaSTG LeyuOUTE seg" e9b* gest 66° 960° . ‘auarpeang-e* | souaqng au 2 auoypeang-e | au be ‘auaang-2-suea) au 92 aulaang=L au pe. auaqng-2-519 0 euaang-2-S19 ST woSey | TuaiomIED ‘Sete LV Viva NOILISOdNOD I1d0L0ST 9 a1a¥L660° ore ozL* 96 092; 8o"L abeuany Lore ‘pso° vO" 862" ‘ au 92 +02 e00° 8 Laz ay 2b eve val €8 6zz 449 v2 ezt* 80'L e2z lore ue PRES. PT PRE Dy Pi TT sy ‘swogy adoqos} ‘swory 10308] ‘StH 3Y adojos] SUDTPEANE-E*L ‘Buoqng=g-sueIT Sia O’Lb AY SANBNTYSdX3 “T3eV7 WOTYRLNIG 9 37a.63 - is'z LL" we os ev'z 960° 802 oo 068" = s9°z aBeuany 192" ous" 95° BLL ay 2 90" +18" 46" are aug gol" 906° or ~ Hy POR Pye ‘swOqy ‘adojos} ‘suBIpeIng-E° PHU Poy paowpxy Fay BML wryoesy sway _adoxosq_suoqy —_adogosy, auag=2=SUeIT SUaTTEL ‘SESE LY SINSHTNAdKa T3SV7 WnTYaLNaG £7.64 between Tight and heavy molecules is strong eyidence that both isomer ization and OXD proceed via intramolecular pathways, The isotope effects shown in Tables 6 and 7 are significant for ‘isomerization to 1-butene and OXD, Double bond rotation displays: the Teast effect, and butadiene the greatest, The presence of isotope effects indicates that C-H bond cleavage is involved in the rate determining steps. RADIOTRACER EXPERIMENTS Summaries of two experinents conducted using identical initial conditions and 1*c-labeled butadiene as a tracer are presented in Table 8 and Figure 14, The same 0.20 gm catalyst sample and pretreat~ ments used in the kinetic and deuterium label experiments were employed in the radiotracer experiments. The starting mixtures were 100 torr of I-butene, 50 torr of oxygen, and 10 torr of }C-labeled 1,3-butadiene, and the reactor temperature was 365C. As indicated previously, the reaction products were collected in a scintillation fluid as they emerged from the GC and copper oxide colums, Activities were deter mined by averaging the counting rates for each sample over several counting periods and deducting background readings. Two features in the plot of the data shown in Figure 14 are im portant. First, there is a maximum in the carbon dioxide peak, indi- cating that the carbon dioxide is produced from both 1-butene and 1,3- butadiene. Second, the specific activity of the butadiene decreases monotonically with time. The butene isoners were collected during each experiment and analyzed for radioactivity. In none of the runs was any activity detected in the butenes; therefore, the OXD reaction65 e2e at 80E le uy OBL eve 9 vee 95 uy 06 oe ve 26 te uy 09 966 lz ay a uw og 285 = vey = 0 SISTPRMEET_SPHOTG WoGeD SUNPENEE L_Boia Wome) SUL Wop Oeay @ ung Tung Viv YS0VEL 3ALLOVOIOVY 8 31MLSpecific Activity (counts/torr: min) p ° ° ol ° ° Nn ° oO ° oO = Run 1, 1,3-butadiene = un 2, 1,3-butediene = Run 1, carbon dioxide = Pun 2, carbon dioxide I 2 3 Time (hr) Figure 14, Radiotracer Experiments 66or ‘is considered to be irreversible, and the reactions of importance are 1 a, Cy #40, —e oH, + #0 v2 t Ge + Lo, 400, + a 2 ¥3 C. Cully + 60, ——e 400, + 44,0 Since this system is a reaction network, the Neiman tracer tech- nique for data analysis is used (33, 34), Details of the mathematical treatment of the system are presented in Appendix 3. The result of the mathematical analysis is that the rates of the carbon dioxide formation reactions b and ¢ are related by the following algebraic function: neo, wee et (37) ae “eH The constants apy and ag 4 are the specific activities of carbon dioxide and 1,3-butadiene at the maximum of the carbon dioxide specific activity curve, From equation (37) the relative rate of formation of carbon dioxide from butadiene and butene (r,/r,) is 1.1. This value is subject to two primary sources of error; uncertainty of maximum Toca- tion, and activity counting error due to low specific activity of the starting 1,3-butadiene. However, the yalue obtained indicates that the ‘two rates of formation of carbon dioxide are approximately equal. This result is consistent with the observed kinetic behavior.68 180, PULSE EXPERINENTS A series of experiments was conducted in the microcatalytic sys ‘tem in which C190, gas pulses (1.42 x 1020 molecules) were passed over 0,98 grams of catalyst, The primary objective of these experiments was to demonstrate that oxygen is highly. mobile inthe catalyst surface, This technique assumes that carbon dioxide adsorbs on the catalyst surface and exchanges its oxygen atoms in a statistical manner with ‘the oxygen species on the surface. However, statistical exchange can occur only when the pulses each attain an exchange equilibrium with the catalyst. In such a case, the isotopic composition of 160 and 4180 in the carbon dioxide product should be described by a binomial distribution. The mathematical treatment of this process is described by Chickering (19), and will not be repeated here. However, the final result is given by equation (20) which permits an evaluation of the ‘total exchangeable surface oxygen where i is the pulse number, and 2 (C360,); + (C260220)5 * 38) i (ct80,); + (cH60280); + (C180,); = and, i 3 = (Pulse Size) 265 (38) 4; in equation (38) is the average number of oxygen atoms exchanged per carbon dioxide molecule in pulse i, and 24 in equation (39) is the total number of oxygen atoms exchanged through pulse i. Figure 15 shows the results of the exchange experiments conducted at 308C, 350C, and 400¢ plotted using the linearized equation (20),cS o © (,_swoiD-o o¢g ° ° oO t+ \ oO A a Aw Vo oO + nu _O1) &/1 6 8 1.0 4 |/Pulse Number Figure 18, C180, Exchange Experiments 2Detailed nunerical results are presented in Table 9. Tt is clear from examination of Table 9 that oxygen mobility is high under reaction conditions. This is an indication that bulk and surface diffusion of oxygen may play an important role in the OXD mechanism, BUTENE PULSE EXPERIMENTS Following completion of the C180, exchange experiments, a series of butene pulse experiments was conducted on the same catalyst sample (0,98gn). In this series, cis-2-butene pulses (1.42 X 102 molecules) were passed over the catalyst in a helium carrier gas with the reaction bed maintained at 350C. The purpose of these experiments was to evalu- ate the participation of lattice oxygen in the OXD reaction. A variety Of pretreatments were used prior to the experiments; however, other than a slight decrease in activity, there were no qualitative differences between the first and last pulse experiments. Figures 16 through 19 show the results of the pulse experiments. The pretreatment prior to ‘the final run consisted of evacuation for 18 hours at S00C. These conditions are sufficient to reduce the catalyst partially; yet, as is clearly illustrated in Figure 19, both 1,3-butadiene and carbon dioxide continue to be produced throughout the experiment. The first pulse alone removes approximately five monolayers of oxygen from the catalyst, and the total oxygen removed during the experiment is about sixteen monolayers. It is significant that carbon dioxide formation drops most rapidly as surface oxygen is depleted. Also, the continued formation of butadiene and carbon dioxide indicates that lattice oxygen“4p0=10/suoye-9, ‘om pue ouaz uaamag A1eA Aew pabueyoxs uo}goeuy aU) 0) pabueydxy aAyye {nungFraction Mole 004 Po = Carbon dioxide I-butene Virgin catalyst pretreated in 100 torr oxygen for T hr. at S00C evacuated for Thr. at 400¢ 2 Trans-2-butene Cis-2-butene (reactant) 1,3-butadiene 3 4 Pulse Number Figure 16. Butene Pulse Experiment 72Fraction Mole OD = carbon dioxide A - 1-butene V - Trans-2-butene © - cis-2-butene (reactant) © - 1,3-butadiene on © =O x Pretreated 1 hr. in 100 torr 0,at 500¢ Evacuated overnight, at 400c | 23 45 67 8 Pulse Number Figure 17. Butene Pulse ExperimentMole Fraction O0dPH Carbon dioxide 4 I-butene Trans-2-butene Cis-2-butene (reactant) 1,3-butadiene QO Pretreated overnight in 100 torr 02 at 500C Evacuated for 2 hrs. at 4506 2 2 4 5 Pulse Number Figure 18, Butene Pulse ExperimentMole Fraction OOdPE ~ Carbon dioxide 7 + I-butene ~ Trans-2-butene ~ Cis~2-butene (reactant) = 1,3-butadiene No oxygen pretreatment Evacuated 18 hrs. at 500C 2 3 4 5 Pulse Number Figure 19. Butene Pulse Experiment76 not only participates in both reactions but also migrates rapidly from the bulk to replace ost surface oxygen. ELECTRICAL CONDUCTIVITY EXPERIMENTS Absolute values of resistance were measured using the apparatus described, and several experiments were performed under different con ditions, As a check on the catalyst aging process, resistance meas urements as a function of temperature were made between runs in which the catalyst was exposed to butene. The data were fitted to the equation = 9 exp (E/2kT) (40) where E may be considered to be the electron band gap for material (35). The band gaps determined in this manner are 1.21 eV for virgin catalyst, and 1.06 eV for aged catalyst. Results of two recirculation runs are Presented in Figures 20 and 21. In these experiments, the resistance ‘is measured as a function of time at a constant temperature of 300C. Figure 20 shows the electrical behavior when a recirculating mixture of cis-2-butene (49.6 torr) and oxygen (16.9 torr) are passed over the catalyst. The resistance maximum corresponds to depletion of gas phase oxygen and marks the beginning of catalyst reduction. Figure 21 illus- trates the electrical behavior when pure cis-2-butene (97.4 torr) is recirculated over the catalyst. The monotonic decline in resistance with time results in an overall order of magnitude decrease. Assumption Of a linear dependence of resistance on percent reduction of the catalyst Permits estimation of its oxidation state under reaction conditions. The completely oxidized resistance was 2.34 Kohm and the completely reduced resistance was 0.26 Kolm. From Figure 20, an operating condition7 quaw}4edea Ay}AygonpUo) [e}499213 "OZ adnbIy (UJ) aw OSZ O02 OSGI OO! OG ‘ peyaidap % ‘@unyx | UabAxo/auazNg paye[NosLoay “AY L 40s 200b 3@ pazenseng “4t| [40g ua6AXo 4403 ODL UL paeEdaadg ot ° a oe) nN (WYOy) eoUDISISay78 quoupsodeg AypAysonption [eo4.ty9913 +12 e4n6}4 (uw) ewid oo€ oOS2 002 Os! oO os ‘2angxju auaang pageino. joy “ay L 403 900 9 payenseng “ay L dog uaBAxo wo} DDL UL pazeadzadd (wYyoy) eouDysisay79 resistance is approximately 1.50 ohm. The linear interpolation of these resistances yields a 40 percent reduction estimate for the cata- lyst under reaction conditions. The increase in resistance when the catalyst is oxidized is due to removal of electrons from the conduc- tion band by adsorbed oxygen, and is typical of the behavior of n-type semi-conductors (38, 36, 37, 38, 39). ‘TEMPERATURE PROGRAMMED DESORPTION EXPERIMENTS General The objective of the TPD experinents was to obtain quantitative ‘information about the desorption behavior of carbon dioxide and 1,3- butadiene. AI1 of the chemical species encountered in the OXD system were used as adsorbates in this investigation. Following adsorption of any of the hydrocarbons, both water and carbon dioxide were observed as desorption products. Butene desorption was not observed following adsorption of any of the butene isomers, and TPD spectra were independent of the butene isomer chosen as the adsorbate. Butadiene desorption was observed following adsorption of efther butadiene or butene. Carton monoxide was never found in the desorption spectra, even after adsorption ‘of carbon monoxide. Because water adsorbed on the walls of the TPO systen, it was not possible to obtain meaningful desorption spectra for water. Also, some residual hydrocarbon contamination, most probably from the of1 dif- fusion pump, contributed to a high temperature carbon dioxide peak. However, the size of this peak was always small compared to other peaks ‘in the spectrum,80 In order to simplify further discussions, a shorthand notation will be adopted for identifying desorption species corresponding to the adsorbate used, The notation has the form A/B(T) where A is the desorbed species, B is the adsorbate, and T is the temperature at which adsorption was conducted, Thus, CO,/butadiene (100C) refers to ‘the desorption of carbon dioxide after adsorption of butadiene at 180C. Use of this notation is convenient; however, it must be recog- nized that when the desorption product and the adsorbate are not the same, the observed process is not simple desorption but rather 2 com bination of reaction and desorption. Carbon Dioxide Desorption A series of experinents using carbon dioxide as the adsorbate was performed utilizing different adsorption tenperatures. For C0,/C0, (Te100¢), a11 experiments produced a single peak with a temperature at ‘the maximum (Ty) of about @5C, For CO,/C0, (100< T< 450C), a single peak was again observed, but with a Ty of 120C. These results are shown graphically in Figure 22. Integration of the two peaks indicates that the site density (assuming one molecule per site) for both are ‘the same order of magnitude. Thus, the differences in the two peaks nay be attributed to the presence of water on the surface at tempera~ ‘tures below 100C. Evaluation of the desorption kinetic parameters for curve (b) provides a first order expression with @ pre-exponential of 5.1 x 108 sec™ and activation energy of 14.6 Keal/mole. Results of a C0,/CO (200C) experiment are shown in Figure 23. There are at least three peaks present in this spectrum, The low temp-81 erature peak is attributed to readsorption of carbon monoxide. This peak corresponds closely to curve (b).in Figure 22, The mid-temperature peak represents a combined reaction and desorption process and is highly dependent on the surface coverage of oxygen. The high temperature peak appears to originate fron oxidation of hydrocarbon contamination, since blank runs also display this peak. The carbon dioxide desorption spectra obtained when butadiene was the adsorbate are very similar to those for butene adsorbates (Figure 250¢ 24). In these spectra, there are at least two peaks with Ty for the lower temperature peak and Ty = 350C for the higher temperature peak. Since there are no C0,/CO, (T > 200C) peaks, the C0,/butadiene and CO, /butene peaks occur from reactions of the adsorbates. The com- plexity of the spectra does not permit evaluation of the kinetic para- meters for CO2/butadiene and CO2/butene processes. 1,3-Butadiene Desorption Aside from the carbon dioxide and water spectra already discussed, butadiene was also desorbed when butadiene was the adsorbate. The de- sorption of butadiene occurs as a single Tow temperature peak (Ty = 80C) regardless of the temperature of adsorption. A typical desorption experiment is shown in Figure 25. The desorption kinetic parameters for this peak are ky = 1.1 X 109 sec"? and Ey = 18.0 Keal/nole for a first order desorption. Butadiene desorption was a7so observed when any of the butene isoners were the adsorbates. Simultaneous desorption spectra for 1,3- butadiene/butene (25C) and carbon dioxide/butene (25C) are displayed in Figure 26, The irregular shape of the butadiene peak indicatesa) -14 moles/s-cm Ropes (10 a-CO5/C0g (25 C) b-CO,/ CO, (200 C) 100 200 Temperature (C) Figure 22. C02 Desorption83 OOv oo¢e (09/709) *e2 eunbiy (9) e4nyoaodwey 002 ool m o o n 0 : saa (2ue-s/sejow . ol) ¥84 00g (uaBAvo + 8uaqnq)/%09 dL “ye a4nb Lg (0) eAangosedwe) 00v oo€ 002 orountrtrnmnon— saa 1-00) uy wo-sysejow (S /88|: 2 moles/s-cm (io7!5 Roes ou nN 5.0 75 Temperature 100 (c) Figure 25. Butadiene Desorption 8586 sem?) moles/s -13 Roes (10 oo¢e stonpoud uo}ydioseg ausqng *92 aunBL (0) e4nposedway 002 ool © : sad (gwo-sssejow g1-0)) a87 the presence of a second low temperature peak that corresponds to re- adsorption of butadiene from the gas phase. As with other reaction processes encountered in the TPD experiments, kinetic parameters were not evaluated for butadiene/butene spectra. ‘THERMOGRAVINETRIC ANALYSIS (TGA) EXPERIMENTS TGA experiments were performed in the microbalance system in order to evaluate oxygen desorption from the catalyst. Blank TPD experiments indicated that oxygen was readily desorbed in vacuum above S00C. However, the magnitude of the desorption indicated that a de~ composition of catalyst was occurring and made kinetic evaluation im Possible. The T6A performed on the catalyst confirmed that deconposi- tion was occurring. The results are presented in Figure 27, where 51.613 mg of catalyst and a temperature programming rate of 20C/min were used. When the temperature reached 908C, it was held constant for one hour before cooling. Detectable weight loss occurs at about 600C, and the ultimate weight loss corresponds to about four monolayers of oxygen removed, MAGNETIC SUSCEPTIBILITY MEASUREMENTS These experinents were designed to provide information about solid state changes in the catalyst under reaction conditions. The excess ‘ron present in the catalyst makes the probability of forming magnetite (Fes0,,) high in these experiments. Since the Néel temperature for magnetite is 585C, it was not possible to operate in a temperature range where only paramagnetic behavior is observed. Therefore, magnetic force responses normalized to the sample weight were used instead of absolute