Showing papers in "Preprints-American Chemical Society Division of Petroleum Chemistry in 1983"

Infrared studies of Ni held at low concentrations on γ-alumina supports

Abstract: On a realise des etudes infrarouge, en utilisant le CO et NO adsorbe comme etalon, sur du Nickel a des concentrations inferieures a 1% sur des supports de grande surface d'alumine γ. Apres reduction de l'alumine pure le Ni donne lieu a des interactions fortes avec le support, donnant des bandes CO dans le domaine 2090-2115 cm −1

Basic research and industrial innovation

Abstract: Criteria for the selection of basic research projects in industry are discussed. Reference will be made to historic and current examples.

Effect of the pore size distribution on the activities of alumina supported Co-Mo catalysts in the hydrotreatment of boscan crude

Abstract: The effects of pore size and distribution on the activity of Co-Mo/Al/sub 2/O/sub 3/ catalysts in the hydrotreatment of asphaltenes have been studied using testing methodology designed to provide initial activities for the catalysis of the critical reactions in the process, hydrodesulfurization (HDS), hydrodemineralization (HDM) (V,NI) and asphaltene conversion to resins and oils (HDA) suitable for subsequent use as refining feedstocks Nine monomodal (micropores) and seven bimodal (micro- and macropores) were tested Maximum HDS occurs with mono- and bimodal catalysts having an average pore diameter of 100 A/sup 0/ Maximum HDA and HDM activity appears at a pore diameter between 150 and 200 A/sup 0/ and increases with increasing macroporosity, macropores allowing more efficient access of the large asphaltene molecular units to active sites Overall catalytic efficiency is dependent upon but HDS and asphaltene hydrogenation rates Variation of pore structures allowed reaction selectivities to be varied and provided control a asphaltene product (resins, oils) composition

Bacterial systems for selective plugging in secondary oil production

Abstract: Etude au laboratoire de la capacite de differentes souches de Leuconostoc mesenteroides a former selectivement des bouchons dans les canaux d'eau dans des conditions similaires a celles des reservoirs a sables non consolides de l'Alberta en vue d'ameliorer la recuperation secondaire par injection d'eau

Techniques for evaluating heavy oil cracking catalysts

Abstract: Commercial performance of heavy oil cracking catalysts is influenced by diffusivity of heavy oil components through the catalyst matrix, catalyst activity and selectivity for cracking heavier portion of the feed, presence of feed contaminant metals and Conradson carbon. Effects of contaminant metals and Conradson carbon have been previously investigated. This study examines effects of reactant diffusivity and feed crackability. Portions of heavy oil cracking feeds have boiling points far in excess of reaction temperatures while the average boiling point is typically less than reactor temperature. Some of the feeds contain large (10-100A diameter) resid molecules. Order of magnitude estimation procedures for diffusivity of vapor and liquid phase hydrocarbon reactants through the matrix of commercial equilibrium catalysts are described. These procedures utilize catalyst pore size distribution determined by nitrogen adsorption and mercury intrusion. Application of the Weisz-Prater criterion using observed cracking reaction rates of commercial heavy oil feeds and estimated diffusivities suggest that cracking of vapor phase reactants in heavy oil feeds is not matrix diffusion limited in commercial catalysts. Matrix diffusion may be a rate determining step for conversion of liquid reactants. Diffusivity of large liquid molecules through the catalyst matrix is strongly influenced by average pore diameter and weaklymore » influenced by pore volume of the catalyst matrix. Higher average pore diameter and pore volume enhance reactant diffusivity.« less

Pressure-temperature microscopy of petroleum-derived hydrocarbons

Abstract: An apparatus allowing microscopy of petroleum derived hydrocarbons at pressures and temperatures comparable to those encountered in the hydroprocessing of coal and oil, and its use in the study of pressure and temperature effects on the crystallization behavior of a decant oil-derived air blown-pitch (DODAB) is described in this paper. Crystallization of the mesophase from aromatic rich precursors can be used as a tracking vehicle whose anisotropy allows easy detection under the polarizing microscope. Mesophase formation pressure dependence using N/sub 2/ and H/sub 2/ reveals that there is a chemical effect associated with H/sub 2/ since N/sub 2/ pressure to 1900 psig had no effect on mesophase formation. In both cases a fine grained anisotropic phase forms initially at the crystallization temperature and 25 psig. In pyrolyzed material mesophase formation under N/sub 2/ is a pressure dependent transformation.

Measurement dependent variations in asphaltene thermal cracking kinetics

Abstract: The kinetics and Arrhenius activation energy of the thermal cracking (coking reactions) of asphaltenes has been found to be measurement method dependent. Thermo gravimetric analysis in the isothermal and non-isothermal modes yield different activation energies for this process. Possible explanations of this discrepancy are discussed.

Hydrothermal screening of reduced crude conversion catalysts

Abstract: Ashland Petroleum Research, in the course of seeking catalysts best suited for Reduced Crude Conversion, has developed a series of tests which can describe a catalyst's anticipated behavior in the 200B/D demonstration unit. These tests not only provide information on how catalysts will maintain activity when contaminated with metals and subjected to the high severity conditions of regeneration, but they also show how they are able to cope with high levels of metal with regard to selectivity. For activity maintenance, the effect of nickel, iron and (to a degree) sodium is less severe than that of vanadium. The degree of destruction with vanadium is dependent on temperature, steam partial pressure and the presence of inhibitors and oxidative or reductive gases. In addition, these temperature differences of metal interaction dictate the need for at least two types of catalyst deactivation screening test series to define better catalyst performance and stability as related to specific regenerator conditions. The presence of coke can alter the ease with which vanadium can destroy the zeolite because of possible changes in the oxidation state of the metal. To properly simulate the commercial RCC process, any steaming test should include oxygen. (JMT)

Development of the PAREX process for separation of p-Xylene from C8-hydrocarbon mixtures

Abstract: En commun avec la plupart des developpements techniques le succes du procede PAREX dependait de contributions coordonnees mais individuelles. Les etapes importantes comprenaient le developpement et l'utilisation de modeles mathematiques, des methodes d'essais de laboratoire et d'equipement, des unites pilotes et des modeles prototypes de composants non conventionnels. Concurremment avec les etudes de developpement, on a concu une unite a l'echelle commerciale

Characterization of a biosurfactant effective in heavy oil viscosity reduction

Abstract: Reduction in the viscosity of heavy oil is a method to improve oil recovery and the processing or transportation of heavy crude oils. In this paper the isolation from soil bacteria of 20 strains which convert alkanes to glycolipids with surfactant properties is reported. A mixed culture (H13) grown on hexadecane medium reduced the surface tension of spent hexadecane growth medium from 71.0 to 30.0 dynes/cm and the interfacial tension from 49.0 to 11.8 dynes/cm. The source microorganism (H13A) was isolated. The surfactant glycolipid, formed in concentrations up to 295 mg/l was isolated and characterized. Hydrocarbon (C/sub 12/-C/sub 20/) growth media comparisons showed tridecane to be the optimum source of glycolipid which contains glucose and a complex mixture of fatty acid derivatives. Growth of H13A on heavy crude oils results in glycolipid production and the formation a stable oil-water emulsion which reduced oil viscosity. Treatment of the oil with cell-free spent medium from hexacecane-grown H13A resulted in a 50% reduction in oil viscosity.

Selected aspects of catalytic refining of middle distillates from Athabasca syncrudes

Abstract: Etude experimentale de l'hydrotraitement d'un distillat moyen d'huile de sable asphaltique ayant subi une cokefaction fluide. Analyse des combustibles produits par spectrometrie de masse a faible pouvoir de resolution

An integrated testing facility for bench scale catalyst research

Abstract: Discovering new catalysts and designing new catalytic processes has long been hindered by equipment that is either designed for hand operation with the data acquisition functions in some stage of automation or is patterned after refinery installations to smaller, pilot plant like facilities. The latter approach has required large vessels (and hence large amounts of experimental catalyst and feedstocks) to be used or the use of improperly fitted control equipment with constant attention to the operation of a small reactor system. Constant attention partially negates the intent of the automation effort. Results from some of these systems are often unsatisfactory because of poor material balances and control. The data from some schemes must then be manually transferred into other databases for use in reports, correlations, etc. An earlier paper from this laboratory (1) described an initial attempt to provide a reliable, reproducible method for more productive catalyst screening, but that system still lacked an automatic data management system and was not flexible with regards to wide range changes of pressure and flow. Also, several different types of experiments could not be run concurrently. Recently, several schemes have appeared (2-6) which deal with distributed systems as they apply to various laboratorymore » and pilot plant operations. This paper describes an automated system that allows for up to 21 reactors to be in operation concurrently with a staff of five people. All units are independently run without normal operator intervention and the system is designed fail safe for unattended operation. It has been used extensively for screening exploratory catalysts, catalytic process optimization, kinetic modeling and increasingly in refinery process optimization.« less

An experimental investigation on the role of bacterial growth and bacterial transport in MEOR processes

Abstract: In order to define the dynamics of Microbial Enhanced Oil Recovery (MEOR) process bench-scale MEOR using Bacillus subtilis was undertaken. The relationship between bacterial transport in the oil containing porous media, growth rate and the efficiency of oil recovery was investigated. Work using Pseudomonas fluorescens and clostridium acetobutylicum is in progress (no data). Heavy crude (API gravity 17/sup 0/) was used in these studies in which Continuous Flooding Process and the combination Huff-and-Puff and Nutrient Flooding Processes were compared. B. subtilis provided greater than 40% oil recovery after secondary flooding. Growth is satisfactory provided adequate nutrient and oxygen supply. Liquid phase metabolites (polysaccharides, lipids) and gaseous phase metabolites (CO/sub 2/, etc.) improve recovery. The Huff-and-Puff, etc. combination process is the most efficient based on nutrient consumption.

The origin and control of SO /SUB x/ emissions from FCC unit regenerators

Abstract: We have presented here an overview of catalytic methods for reducing SO /SUB x/ emissions from FCC regenerators. This important technology has produced commercial catalysts capable of reducing SO /SUB x/ emissions by up to 90% under favorable conditions. The mechanisms, guiding principles, and process variables influencing SO /SUB x/ gettering have been outlined in this paper. What remains to be achieved is to improve these catalysts to increase stability and extend their operating ranges.

Methane-forming bacteria of oil-fields

Abstract: Pure cultures of the methanogenic bacteria, Methanobacterium bryantii and M. formicicum have been isolated, for the first time from oil deposits and their morphological, physiological and biochemical properties studied. All strains grow of H/sub 2//CO/sub 2/ and two of the three M. formicicum also utilize formate as a role source of carbon and energy. In no case could methanol, acetate, methylamine or glucose serve as an energy source for these autotrophs. All strains were resistant to penicillin and streptomycin and neither sulfate or sulfide inhibited their growth. Medium salinity inhibited the growth of M. bryantii but not that of M. formicicum.

Cracking of residual oils with simultaneous generation of hydrogen

Abstract: The catalytic cracking of residual oils and tar sand bitumens with simultaneous generation of hydrogen has been investigated in the laboratory and at the pilot plant level. These catalysts having different proportions of Fe/sub 2/O/sub 3/, NiO, MgO and Al/sub 2/O/sub 3/ were studied. In this process Fe/sub 2/O/sub 3/ is reduced to a mixture of Fe, Fe/sub 3/O/sub 4/ and FeO by coke formed in situ which is then reoxidized by steam to yield hydrogen. No by product coke is produced that deposited being oxidized to produce heat used in the process during catalyst regeneration. Catalyst is cycled between the cracking unit (525 to 545/sup 0/C), regenerator (780 to 830/sup 0/C) and roaster (750 to 810/sup 0/C). Typical Pilot Plant yields of gas (H/sub 2/, Co, Co/sub 2/, H/sub 2/S, C/sub 1/-C/sub 5/), product oil (boiling range, 180 to 560/sup 0/C) and coke are 8, 79 and 13%, respectively.

Hydrodeoxygenation of phenolic components of wood-derived oil

Abstract: Hydrotreatment of wood-derived oil to remove phenolic oxygen is a potential upgrading step by which such materials can be rendered compatible with current petroleum refining technology and converted to a diesel equivalent. Accordingly, the hydrodeoxygenation of model phenols and wood derived oil was studied in a batch reactor. Using phenol, a number of commercial catalysts were evaluated for performance and stability at reaction temperatures from 300 to 425/sup 0/C and hydrogen pressures from 900 to 2050 psig. Product yields and analysis indicate the most efficient catalysts to be Ni (Ni 1404, Harshaw) and presulfided Co-Mo (CoMo 0402, Harshaw), based on yields of benzene and cyclohexane. Due to complications caused by the introduction of sulfur into the system, the Ni catalyst may be preferred. Alkyl phenols, napthol and guiacol were hydrotreated at 400/sup 0/C and 2000 psig using an unsulfided Co-Mo catalyst. In addition to the corresponding alkylated aromatic and saturated cycloalkanes, significant yields of scrambled aromatic product, formed by dealkylation and methyl migration were observed. Guiacol hydrotreatment is complex, there being significant polymerization and dimerization: pyrolysis, not catalystic hydrodeoxygenation is the major reaction path. Wood-derived oils were partially deoxygenated and somewhat upgraded by hydrotreatment using Ni and sulfided Co-Mo catalysts.

Overview of microbial enhancement of oil recovery

Abstract: Resume d'une communication consacree a la synthese des communications presentees au Congres sur la recuperation assistee par microorganismes tenu en 1982 a Afton et aux nouveaux developpements de cette technique effectuees dans 4 Universites des Etats-Unis

Abstracts/symposium on shape selective catalysis of American chemical society. Seattle meeting, march 20-march 25, 1983

Abstract: Catalyse selective de forme dans les zeolites. Proprietes catalytiques physiques et acides des zeolites pentasiles, la conversion bifonctionnelle du cyclooctane

Stimulating innovation. The role of the mentor in the research laboratory

Abstract: A Chinese proverb says, ''A journey of a thousand miles must begin with a step''. The first step in the innovation process may literally be the first step of an infant who realizes that swinging his leg in a new way results in unprecedented mobility. The process of stimulus-response-feedback continues with maturity. As we have seen in previous papers in this symposium, young people are exposed to the fascinating possibilities for technical innovation during high school and college. I now want to focus on what may be the most important period in the technical innovation process, viz., the first assignment of a young scientist or engineer in the laboratory. The first steps of young researchers are critical in determining if their journey into innovation will be a thousand miles or will result in a dead end. In a recent address to Dow Chemical scientists, David Sheetz, Vice President and Director of R and D for the company, provided a definition of innovation which will be used in this paper. He said, ''Successful innovation is a useful new product, process, service or use that is so distinct from and superior to what's out there that it is uniquely valued by themore » market'' (1). A similar definition was used by consultants David Laverty and Erwin Frand who reflected the thoughts of many R and D Directors that innovation is on the decline in the U.S. (2). If we are indeed lagging in the number of unique products brought to the marketplace and in the development of improved processes which can generate these products, then we need to spend more energy determining ways to stimulate innovation. What we will be examining in this paper is the stimulation of innovation among young researchers. What I hope to show is that the first person to guide the career of the young researcher has a profound influence on the attitude of that person toward innovative activity.« less

Partial oxidation of methane over supported molybdenum

Abstract: Steady-state activity (percent conversion) and selectivity for the Mo/silica gel catalyzed oxidation of methane to CH/sub 3/OH and CH/sub 2/O by N/sub 2/O in the presence of steam at 600/sup 0/C have been measured in order to define reaction kinetics and the mechanism of molybdenum catalysis. Both selective and non-selective oxidation occur in this system, the latter yielding carbon monoxide and carbon dioxide. Conversion yields of CH/sub 2/O are independent of H/sub 2/O partial pressure but selectivity for CH/sub 3/OH formation increases with increasing H/sub 2/O partial pressure. The rate law for CH/sub 4/ consumption is complex, being determined by non-selective oxidation and reduction reactions. Spectroscopic evidence indicates that the catalytic role of molybdenum involves a cyclic oxidation state change from the +5 state and back vial the +6 state. Tritiation occurs by the N/sub 2/O oxidation of Mo/sup V/ to yield (Mo/sup VI/O/sup -/) which either reacts with CH/sub 4/ to yield (Mo/sup V/(OCH/sub 3/)/sup -/) or is further reduced to (Mo/sup VI/O/sup -2/). The latter complex requires CH/sub 4/ for reduction to Mo/sup V/ in a non-selective process yielding CO/sub 2/ and H/sub 2/O.

The dynamics of development of aerobic and anaerobic bacteria during aeration of an oil-bearing stratum to enhance oil recovery

Abstract: The distribution and activity of microorganisms in ground formations has been studied in order to assess their use and regulation during oil field exploitation. Experiments were performed on water-flooded oil fields of the Tatar ASSR and revealed some regularity in the distribution of aerobic and anaerobic microflora. Wells were opened after 3, 28 and 68 days after flooding with aerated water supplemented with nitrogen and phosphate salts. Activation of aerobes results in oxidation of residual oil (not released over 3 years of exploitation). The products (CO/sub 2/ fatty acids) of oxidation promote oil recovery. In the longer experiments anaerobic processes, especially methanogenesis from CO/sub 2/ were enhanced.

Nickel and vanadium in chromatographic fractions of petroleum asphaltenes

Abstract: In this paper the distribution of V and Ni in oil-sand and crude-oil asphaltenes in relation to heteroatom (O, N, S) contents of the asphaltene fractions obtained by sequential elution solvent chromatography, is discussed. The distributions of Ni and V do not correlate with heteroatom distributions in the ten asphaltene fractions collected by this method and their concentrations are small compared to heteroatom content. This may be due to the metals being present in less accessible porphyrin-type sites, whereas heteroatom distributions reflect functional group distributions (OH, etc.).

The effects of feed properties on resid cracking yields

Abstract: The general trends of HOC determined by one-parameter analysis of the yield data show basic nitrogen in the feed to have the strongest influence on the catalytic activity whereas carbon residue in the feed and feed density are the feed properties showing the strongest influence on selectivity for the equilibrium and added metals catalysts. The level of metals-on-catalyst determines the second-most influential feed property to the gasoline yield: feed density for the equilibrium catalyst and ppm Ni in the feed for the added metals catalyst. Multiple linear regressions of the same data show the interactions of the feed properties as they influence the yields. The feed property variables of major influence over the equilibrium catalyst activity are feed density, wt % carbon residue, ppm nitrogen and V; wt % aromatics, C/sub 5/ insolubles and ppm Ni are of minor influence upon the activity. As the metals-on-catalysts is increased to 12,900 ppm (effective), the major variables of influence upon activity are basic nitrogen and Nicontaining molecules in the feed. The selectivity problem is influenced most by wt % carbon residue, feed density and ppm Ni for both the equilibrium and added metals catalysts. These results may be used to define themore » strategy of HOC; catalysts activity/selectivity may be increased by a reduction in the levels of feed basic nitrogen and wt % carbon residue. Hydrotreating the feed, with an emphasis on denitrification, may be used.« less

Model for the deactivation of residue hydrodesulfurization catalysts

Abstract: A model for the deactivation of hydrodesulfurization catalysts in petroleum residue processing is discussed. Catalyst deactivation occurs early and is due primarily to the clogging of pores by metal (V, Ni) sulfide deposition. Pore size affects activity metal penetration and capacity for metals or active life. Small pore catalysts show high activity after initial deactivation but exhibit short active life (low metal capacity). Metal capacity increases but activity decreases with increasing pore size. The model allows quantitative prediction of optimum catalyst pore size giving a combination of maximum possible activity and active life.

Petrochemicals. Impoverishment or improvement

Abstract: Modernisation d'unites perimees. Integration d'equipements. Appel a des charges et des combustibles diversifies

Recent work on the fundamentals of catalytic cracking

Abstract: A large effort has been directed over many years toward the development of more active, stable and poison-resistant catalysts, and to the development of kinetic models which describe the cracking of complex feed stocks. Although most of this effort has been directed to the solution of practical problems, considerable basic research has also been carried out in this field. For example, a series of test reactions involving pure reactants which undergo typical cracking reactions while yielding very few products has been studied. Such test reactions can be very useful for comparing the activity of different catalysts in a fast and ''clean'' way avoiding problems of definition connected with using industrial gas-oil feeds. Furthermore, because of the relatively small number of products obtained by cracking pure compounds, it is possible to study in detail the various reactions taking place during catalytic cracking. Finally it was hoped that the test reactions would allow us to relate catalytic activity to the nature and number of the active sites and, hence, assist in guiding catalyst development (1-5). We here present a methodology which allows us on the one hand to compare the activity and decay of various catalysts by using the values of ratemore » constants and activation energies of identified primary reactions in the ''cracking'' of pure hydrocarbons and, on the other hand, to compare conclusions from such experiments to cases where the reactant is a gas-oil.« less

Materials and processing problems associated with sulfate-reducing bacteria in petroleum recovery

Abstract: The corrosion of iron and steel equipment used in petroleum recovery is caused in part by H/sub 2/S formed by the anaerobic bacterial reduction of sulfate. The proposed mechanisms of iron corrosion under anaerobic and neutral conditions are inadequate. Accordingly, the production of volatile organosulfur compounds by sulfate reducing bacteria (desulfovibrio desulfuricans, API mid-continent A strain and a marine strain) under anaerobic conditions has been investigated. When grown on TSY agar raged sea water both strains produced primarily H/sub 2/S and methylmercaptan in smaller amounts. TSY agar/deionized water yielded primarily methylmercaptan (and traces of dimethyldesulfide) in the case of the API A strain: the marine strain of D deslfuricans did not grow in this system. Under anaerobic conditions methylmercaptan produced only neglibiable iron corrosion after several weeks exposure.

Hydroconversion of vacuum gas oil and atmospheric residua

Abstract: Catalyst (CoO/MoO/sub 3/ and NiO/MoO/sub 3/ on Al/sub 2/O/sub 3/) performance and stability and process studies on the mild hydrocracking (MHC) of vacuum gas oil (VGO) and petroleum residues (PR) have been carried out in bench scale trickle bed reactors. Comparison of MHC conditions with 90% hydrodesulfurization (HDS) conditions reveals that the former give superior conversion (24.5% and 5%, respectively) to products in the mid distillate range. Desulfurization (HDS), nitrogen removal (HDN) and demetallization (HDM) also occur. Comparison of the activity of the catalysts used show little difference in MHC activity and stability. HDS and HDN activity differs, however. Very little thermal cracking occurs and the MHC process is temperature and H/sub 2/ pressure dependent. The data are compared with available pilot plant data.