An Industrial Chemistry Course in Applied Catalysis at Illinois State University Michael J. Baird' Illinois State University, Normal, IL 61761 As a continuing effort by Illinois State University (ISU) t o prepare their chemistry students for industry, the chemistry department established a Visiting Chemist's position, which is occupied bv a scientist from industrv who spends a semesteaching a course in h i s o r her-specialty plus ter a t ~ S U assists with undergraduate laboratories. During the Fall Semester of 1987, I w& the third Industrial chemist to participate in the program, and I presented a course in applied catalysis to seniors and first-year graduate students. In addition to introducing students to applied chemical applications via the Visiting Industrial Chemist, ISU has a very strong undergraduate industrial co-op program. Manv chemistrv students who beein their careers in a cbemich or petroieum industry are k u a l l y involved with catalvsts and often find their first formal trainine in the area to b e one of the many one-week short c ~ u r s e ~ o f f e r eby d several universities or the American Chemical Society. These courses usually cover a lot of material, and, unless the new emplovee has received some trainine in catalysis, these coursesma~ybe difficult to comprehend:~herefo~e,the obiectiveof thiscourse was to study in detail the major areas of catalysis that are offered by theshort courses. The course outline is given in Table 1.Approximately twothirds of the course focused on applied .. catalvsis. while the remainder described various commercial cat&icprocesses. Satterfield's book Heterogeneous Catalysis in Practice ( I ) , which gives an excellent overview of industrial catalysis, was used as the text. T o supplement the text several additional references were used (2-6). Transparencies and slides were used to present the material. and a detailed outline of each lecture was given out before each class. T o add variety to the lectures, three guest speakers from industry (Amoco Research Center) presented seminars on their areas of expertise. Grading was based on three one-hour exams (60%),homework problems (15%),anda two-hour final (25%).The homework ~ r o h l e m swere desiened to introduce the students to typicA calculations that are performed in industry-many of the oroblems and examples presented durine the lectures were derived from the autior'ipast experienclin the petroleum industry and a t the Pittsburgh Energy Technology Center. In place of working homework problems, the students were given the option of writing a short term paper. Suggested topics are listed in Table 2. For future courses, i t is sueeested that both homework and a term . paper . be require-d; each is good mechanism for teaching. In the introduction section the students weredvena list of 26 dates emphasizing different milestones and important events in catalytic research, which proved to be a good way to present the history and background of catalysis. Next, a physical model of a metal-supported catalyst was described,
and several examples of different types of commercial catalvsts were shown. Three common earlv theories (geometric, ekctronic, and transition-state) were ;resented t; illustrate how earlv researchers explained catalytic reactions. T o familiarize-the students w%h catalytic tkrminology, 15 terms were defined. Examples of these were relative activity, turnover number, selectivity, poisons, etc.--each being explained by an example problem or a catalytic reaction. Homework oroblems were derived from these terms. The instructor's l'hl) research on the "lsomerization of 1-Hutene over MeO" (7)was presented to illustrate a typical problem kinetic in cat&sis.'~he seminar stressed the correlt%on data to various measurable surface sites in order to characterize the reaction site. The presentation also introduced the students to BET surface area measurements, ESR techniques, and flow reactors. For catalyst preparation section, the common techniques of precipitation of a support (A1203) and the impregnation of active metals on the support were discussed. Slides of various types of pilot plant equipment, suchas blenders, conveyor belt filters, mullers, extruders, and pellet machines were shown. The common tests (crush strength, bulk density, and abrasion loss) used in industry to measure the physical properties of catalysts were described. A more detailed description of catalyst preparation was presented in a seminar on the "Preparation of Ranev Nickel for Catalytic Methanation" (8): The first m e s t lecturer, Jim Kaduk, presented a very enthusiastic lecture on zeolites. The use of several plastic models was beneficial in illustrating the complex structure of these important class of catalysts. Commercial applirntions of zeolites for xylene isomerizntion and the conversiun of methanol to gasoline were discussed. The students were fortunate in being introduced to one of the newest areas in catalvsis-com~uterized molecular modeling. Chris Marshall, t i e secondguest lecturer, described how Amoco Oil uses comnuterized techniaues to studv molecular interactions. he my stem providesinformation that can increase one's understanding of how zeolites are formed and how their structures control product selectivity in hydrocarbon upgrading. The colorful computer-drawn slides were helpful in illustrating complex zeolite structures and their interaction with other molecules. Three lectures were devoted to chemical and physical adsorption. Use of the Langmuir model to describe surface
' Resent address: U.S. Department of Energy. Morgantown Energy Technology Center. Morgantown. WV 26507.
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Table 1.
Course Outline
I. lntrcduction A. B. C. D. E.
Background of Catalysis Description of a Catalyst Early Theaies Definltion~and Statemena Seminar-"isomeriration of l-Butene Over M g O
11. Catalyst Preparation A. lmrcdUCtl0" B. General Propwiles ot Metals, Oxides, and Catalyst Suppwts C. Common Manutacturing Techniques D. Slides of Equipment E. Tests-Bulk Density. C w h Strenglh, and Abrasion Loss F. Seminar-"Preparation of Raney Nickel f w Catalytic Methanallon" Ill. zeoliies
A. B. C. D.
Plaslic Madels heparations Reactions Current Research
IV. Computarlzed Molecular Madeling of Zeolites V. Chemical Adsorption A. B. C. D. E.
m e Adswption Pmcess Characteristics of Chemical Adsorption Thermcdynamics Langmuir Isotherms Frendlich and Temkin Isotherms
VI. Physical Adsorption A. ChsraCteristics of Physical Adsorption B. Physical Adsorption lsolbnns C. b a t s of Adsorption D. Surface Area Measurements--BET E. Mcdei of Physical Adsorption F. Calculation of Pwe Volume. Pore Radius, and Pore-Size Dlsbibutlon Vil. SpectrwcaplclAnalytical lnsbumena A. ESCA. AES, ISS. SIMS. MID. TGA-DTA VIiI. Kinetics A. B. C. D. E.
HOmoge~~)us v e m s HeterogeneousReanions Langmuir-Hinshelwood Kinetics Empirical Rate Expressions External and Internal Dlfiusian EfieCtiVeneSSFactors
X. Ted Reactors XI. Petroleum Processes A. Overall Refinery B. Reforming C. Hydrocracking XII. OMBr Processes A. Fischer-Tropsch B. Catalytic Converters
coveraee was eiven in detail to prepare the students for eassolid G e t i c ;eactionr. ater rial frmn Gregg and ~ i n ~ ' s i e x t (3) was used to describe the model for phvsical adsorption. Calculations using the BET equation and adsorption isotherms for determining pore-size distribution were -presented in class and assignedas homework prohlems. Two lectures covered spectroscopic and analytical instruments that are commonly used to characterize fresh, used, and regenerated catalysts. The approach taken was to describe the theory and experimental procedure first, and then to discuss the type of information that can be obtained from the technique. When applicable, examples of spectra were shown and/or recent results from the literature were presented to illustrate the usefulness of the particular instrument. 568
Journal of Chemical Education
Table 2.
Suggested Topics fw Term Papers
A. Catalyst Preparation 1. Preparation of Zeolites 2. Preparation of HydroheatingCatabts B. Adswption-Kinetics 3. Physical Adsorption-BET Equation 4. Adswption Isotherms 5. DeterminingPwe-Sire Dlsblbution C. Spechmwpic lnstrumena f a Catalysis 6. ESCA (Electron Specboscopy for Chemical Analysis) 7. AES lAuoer . " Electron Soecbwwov\ 8. ISS (Ion Scattering Spectroscopy) 9. SlMS (Secondary Ion Mass Spectroscopy) ~F~
D. PebOleum Processes 10. Catalytic Cracking 11. Reforming 12. Hydrotreating 13. lsamerization E. Other Prom589 14. Fischer-Tropsch 15. Methanol-tc-Gasoline 16. Catalytic Gasification of Coal
When discussing kinetics, the differences between homogeneous and heterogeneous reactions were explained. Special emphasis was focused on the additional resistances, such as external mass transfer and internal pore diffusion, that are usuallv encountered in eas-solid reactions. Exoerimental technihues used to milimize these diffusional effects were discussed. The wwer-rate law and Lanemuir-Hinshelwood models for de&ribing the overall rate oTcatalytic reactions were demonstrated usine *pilot plant data and also presented in homework problems. Two lectures were devoted to the verv important topics of catalyst deactivation and regeneration.~he-commondeactivation processes of poisoning, fouling, and sintering were described. An industrial project involving catalyst regeneration was presented in order to introduce the students to a typical problem faced by many industries that utilize catalysts. Laboratory experiments and the follow-up commercial tests to determine the ootimum orocess for reeeneratine hydrotreating catalysts were presented. Next, the students were introduced to various types of laboratory test reactors that are used to screen catalysts for initial activity and to obtain process data, such as deactivation rates and product yields. The difference between differential and integral systems was emphasized, and the advantages and d i s a b n i a g e s of severai types of reactors, as reported by Weekman (9).were discussed. - The final three weeks of the course were devoted to describing various commercial catalytic processes. First, an overall description of a petroleum refinery was presented where common units, such as crude distillation, alkylation, catalytic cracking, reforming, bydrotreating, hydrocracking, and coking were discussed. For this introduction, many slides of flow diagrams and pictures of process units were shown. Then, two lectures were devoted to a more detailed description of hydrocracking and hydroprocessing. The third guest, Chris Nikolaides, presented the seminar on hydroprocessing that stressed the importance of process models for guiding refinery personnel in unit operations and in predicting economics. His presentation gave the students an idea of wKat a chemical engineer does in petroleum R&D. To illustrate CO Hp catalysis, the Fischer-Tropsch process was described. Following a brief introduction o f the history of the process, research and development that was conducted a t the Pittsburgh Energy Technology Center of the U.S. Department of Energy during the '70's was present-
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+
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ed. Special emphasis was given to the use of iron catalysts flame-soraved . " onto a tube-wall reactor for uroducine easoline boiling range products (10). The final industrial application of catalysis focused on the automobile catalytic converter. The reactions tor removing CO. NO,, and hvdrorarhona, the available commercial catalysts, and the tipes of react'or configurations used by automobile comoanies were discussed. There was good feedback from the students concerning the usefulness of the course. Since the text ( I ) did not contain "in depth" material and reference hooks were limited, the handouts were very helpful. Also, by having a detailed outline of the lectures, the students only had to take a few notes to clarify certain points that allowed them more time to listen to the lectures. The use of euest soeakers from industry was very beneficial. In addit;& to &senting the material from a different oersoecti\.e, thev also illustrated the type of research that chemists and chemicalengineers do in the field.
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A course in industrial chemistry, such a s heterogeneous catalvsis. is verv beneficial to a chemistrv curriculum. In addiiion'to intr"oducing the students to practical applications of chemistrv. it also conveys to them what chemists actually do in pa&cular industries. Literature Clled 1. Satterfieid, C. N. Hefomgemoua Catalysis in Pmelieo; MeGraw-Hill: Nea Yark.
York.1967.
0. Chemical ReoctionEngineoring; Wiley: NcaYork, 1972. 5. Gate8.B. C.:ffitzer. J. R.:Sehuit,G.C . A. Chemisfryo/CotolyficPmcess~s;McGraaHill: N e w York, 1979. 6. Gary. J. H.; Hsndwerk.G.E.PetroloumRe/ifining TeehnologyondEconom'cs,2nd ed.: Dekker: NeaYork, 1984. 7 . Bsird, M . J.; Lunsford.J.H. J. Cololyala 1971,16,MC450. 8. Baird, M . J.; Sfeffgen,F. W. I&ECPmduel R&D 1317,16,142-147. 9. Weekmsn. V. W . AIChEJ 1374.20.833-843 . J.I&EC &duct R&D 1989.19.175-191. 10. Baird, M 4. Levenspiel,
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