Applied Catalysis A: General 197 (2000) 39

Catalysis research in Latin America

M.M. Ramirez-Corredores
PDVSA-Intevep, Renacin y Petroqumica, Apdo.76343, Caracas 1070A, Venezuela

Abstract Catalysis research is very strong in well industrialized countries, but rather poor in those underdeveloped. Although, catalysis history is as old as more than a century, its activities in Latin America have been growing only for the last three decades. Research areas concern petroleum, petrochemical and ne chemicals catalysts, environmental and theoretical catalysis. The whole community might be of about 1200 people, from whom only around 200 might be occupying scientic leadership positions. Participation in the international forum has been growing through the years. This work tries to summarize the status of the eld in the Latin American countries, mainly in those with representative research groups, namely Argentina, Brazil, Colombia, Chile, Mexico and Venezuela. 2000 Elsevier Science B.V. All rights reserved.
Keywords: Catalysis; Latin America; Petrochemical industry; Environmental catalysis; Petroleum rening catalysts; HDT; HDS; FCC

1. Introduction Catalysis is the core of numerous chemical processes that transform inexpensive raw materials into valuable products relevant to human needs in energy, transportation, health and comfort. Its dynamism is evidenced by the short obsolescence period of its technologies. Development (and so research) is oriented towards two alternatives, one dealing with improvements on existing catalysts, and the other towards the search for applications on new materials. The evolution of industrial catalysis has moved from a sort of art into building the basis of a science. Nevertheless, most of the current operating industrial processes are rather based on empirical issues than on scientic proven knowledge.

Tel.: +58-9086055; fax: +58-9087230. E-mail address: ramirezmt@pdvsa.com (M.M. Ramirez-Corredores)

The future of the catalysts business (about 7000 million $ per year) is determined by the needs of their main clients, namely petroleum and chemical industry, as well as the requirements of environmental regulations. Research activities can not escape from this reality, and so are strongly inuenced by the industrial development achieved by each particular country. So, research is very strong in well industrialized countries, but rather poor in those underdeveloped. Although, the catalysis history is as old as more than a century, its activities in Latin America have been growing only for the last three decades at most. Initial activities were concentrated in human resources formation, together with the implementation of the technical infrastructure. That, one might say, is still in progress. However, for the last twenty years, research and development activities have collected several achievements. Within the Latin America region at its beginnings, the catalytic research was highly oriented towards the petroleum and petrochemical applications. Mostly,

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the petroleum industry in the region is controlled by each country government, i.e. state-owned companies, with the exception of Argentina which has been privatized recently. However, foreign oil interests are growing again even in countries, such as Venezuela, where Petroleos de Venezuela (a state-owned company also) had established opening policies in order to attract private investments. Incidentally, countries whose economics is highly dependant on oil business are those with the oldest catalytic tradition (Argentina, Mexico and Venezuela). Then, scientic governmental policies would favor petroleum related subjects, and more particularly in areas such as Catalysis. However, recently environmental catalysis and theoretical catalysis are increasingly considered. Fine chemicals is another area of study, specially in groups collaborating with European researchers. As mentioned, the oldest tradition in catalysis research in Latin America began in Argentina, Mexico and Venezuela. Newer efforts have been pursued by Brazil, Colombia and Chile. Emerging areas are Peru, Bolivia and Uruguay. Applied Catalysis already collected a global overview of various aspects of the catalytic research in some of these countries [13]. We will summarize here some historical events and relevant facts related to the catalytic upcoming of those six countries where catalysis is occupying an important place within the overall scientic research.

2. Background history and status Catalysis research in Argentina started in 1961 when a small group, led by Dr. J.M. Parera and belonging to the Santa Fe University, began to work mainly on solid acid catalysts. This group evolved to become INCAPE, an institute devoted to catalysis and petrochemical research. CINDECA and PLAPIQUI constitute two other important organizations devoted to catalytic research, the rst one located in La Plata and the other in Bahia Blanca. Smaller centers are INTEQUI in San Luis, INIQUI in Salta, CITeQ in Cordoba and INTEMA en Mar del Plata. Nearly 170 people (100 researchers), from the gures of CONACA (National Committee on catalysis) are currently involved in these activities. Most of Argentinean researchers work in heterogeneous catalysis, originally in subjects connected to petroleum ren-

ing and petrochemistry. New areas of research relate to pollution abatement, clean fuels and ne chemistry are now emerging. Nevertheless, such important subjects as alkane activation and classical areas as supported metal and acid catalysts continue to be studied in view of the continued production of oil and gas within Argentina. Catalysis is relatively a new comer to the scene of science in Brazil. Pioneering efforts of Dr. Remolo Ciola at the University of Rio de Janeiro (UFRJ) and Dr. Leonardo Nogueira at PETROBRAS (the Brazilian state petroleum company) R&D center, in the 1970s are acknowledged. During the 1980s a boom in catalysis research in this country took place leading to the appearance of a fair number of catalysis research groups both at the universities and within the petrochemical industry, which later founded the Brazilian Catalysis Society in 1997. Brazil is the only Latin American country with manufacturing installations represented by two large-scale catalyst factories, one for the production of FCC catalysts (FCC S.A., a joint venture of Akzo, PETROBRAS and OXITENO) and another for the manufacture of automobile exhaust catalysts, (Newtechnos, a Degussa subsidiary company). The main center for catalysis research (NUCAT) is located at the Federal University of Rio de Janeiro. A large economic recession stroke negatively on research activities. A notable exception was PETROBRAS center which, due to its association with FCC S.A. and the special problems associated with Brazilian crudes kept its catalyst division (DICAT) active in all aspects of FCC and hydroprocessing catalyst research. The Newtechnos-Degussa research center only evaluates the performance of their own catalysts. The catalytic community has about 200 individual members and six associated industries. Foremost among the interests of Brazilian catalysis scientists are zeolites, no doubt stimulated by the interest of FCC S.A. and PETROBRAS in this area. Closely following zeolites, catalysis on metals is the second developed area. Bimetallic catalysts, support effects (especially SMSI), preparation, regeneration and application of metal catalysts to parafn dehydrogenation, watergas shift reaction, environmental catalysis, oxide catalysts (selective oxidation of propane, ethanol dehydration, oxidation, dehydrogenation and condensation, methane oxidative coupling) coordination catalysis, (including homoge-

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neous transition metal catalysis, heterogenized homogeneous catalysts and ZieglerNatta catalysis), olen oligomerization, metathesis, hydroformylation and polymerization are some other areas of Brazilian interests. Hydroprocessing catalysis has not aroused much attention in Brazilian academic circles and remains largely a eld of proprietary research at PETROBRAS. Indeed, catalysts development is a prominent activity at Dicat, patent databases report 10 US, one Japanese and another European patents protecting polymerization, FCC and hydrotreating catalysts (some of theses patents have equivalents in other countries). Since Brazil holds 90% of the world reserves of niobium, the study of catalytic applications of this element as an active component, catalyst support or catalysts promoter involve a great effort among Brazilian researchers. As mentioned above, catalysis is of recent appearance in Colombia. The leaders population is of about 25 people, located at the largest universities: Nacional, Antioquia, Industrial de Santander, Valle, Atlntico, and the Colombian Petroleum Institute (ICP). The most relevant interests concern isomerization, reforming and cracking of hydrocarbons, hydrotreatment (particularly hydrodesulfuration), catalyst poisoning, selective oxidation, synthesis and characterization of strong solid acid catalysts, design of novel micro and mesoporous materials for the conversion of hydrocarbons, lean NOx reduction catalysts, catalytic destruction of polychlorinated aromatics, heterogeneous catalytic routes for the synthesis of ne chemicals, photocatalysis and computational catalysis. In such a short period of growth, some patents can be counted on their achievements, examples such as vanadium traps for FCC catalysts, new molecular sieves, and novel carbon supports can be cited. The number of scientists involved in research on catalysis and adsorption in Chile is rather small, about 25 researchers (data taken from the catalysis division of the Chilean Chemistry Society). The rst work in catalysis carried out in this country were performed at the Universidad de Chile under the supervision of Dr. Sergio Droguett at the beginning of the 1970s. A group at the Universidad de Concepcin, which nowadays is the largest of the country, having eight researchers, was created in 1975. Two additional groups placed at the Universidad del Bio-Bo and Universidad de Talca were derived later from the Universidad de Concepcin groups. Another large group works at the

Universidad de Santiago de Chile, in the Department of Chemistry. The Universidad de Chile also has a small group at the Department of Chemical Engineering. Chilean research interests concern hydrodesulfurization (hydrotreatment) catalysts, environmental catalysis, adsorption (clays, activated carbon, etc.), photocatalysis, ZieglerNatta type catalysts for polymerization reactions, catalytic cracking, Monte Carlo simulations for surface reactions, electrophoretic migration, watergas shift reaction, epoxidations, hydrogen peroxide decomposition, stereoregular polymerization, blocks polymerization and colloidal systems. The records of the Catalysis Academia (created in 1987) in Mexico shows nearly 140 members working at 14 institutions. However, only about 40% of these members can be considered research leaders. This number did not take into account the Mexican Petroleum Institute (IMP, another 20), where a direct link with Pemex (Petroleos Mexicanos) exists and their activities are consequently oriented towards petroleum applications. Although, by a patent search in the current databases no more than six US patents have been assigned to IMP in the catalysis and catalytic processes area, the world catalyst reports [4] cited several IMP catalysts for the petroleum industry. In fact, the IMP catalysts commercial portfolio contains more than 50 catalysts, which as informed by IMP on its leaets, have been used in the Pemex reneries and petrochemical complex. Their sales during the last 10 years exceeded 35,000 t. Research activities in Mexico, involve preparation and characterization of catalysts and supports, oxides, clays, suldes, supported metals, zeolites (natural and synthetic), pillared clays, mesoporous materials, surface science, photocatalysis, calorimetry, hydrotreatment, FCC, reforming, dehydrogenation, theoretical and environmental catalysis. Environmental protection is a main eld of application of catalytic technology and research in Mexico. Atmospheric pollution in urban areas such as Mexico City, Guadalajara and Monterey is a main health concern because of harmful emissions from cars and industry. The laws of Environmental Protection which was passed in 1988 demanded the use of better fuels (low leaded gasoline, low sulfur diesel and gasoline) and periodic revision of emissions. Since 1993, all new cars must have a catalytic converter installed. Very recently (1995) one plant dedicated to the pro-

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duction of catalytic converters has been installed in Mexico. In the future, the use of catalytic technology to control emissions in industry is expected to be reinforced. Several groups are located at Universities throughout the country (Ensenada, San Luis Potos, Puebla, Ciudad Madero, Universidad Nacional Autnoma de Mxico, Instituto Politcnico Nacional and Universidad Autnoma Metropolitana) and at the IMP. The beginnings of catalysis research in Venezuela dated back to 1964 when H. Noller invited his student P. Andru to establish a group in that country. Since then, the growing of the area never stopped. The science faculty of the Universidad Central de Venezuela began a pioneer work, which gave rise to all the existing groups. R&D activities are carried out by both, academia and industry. Within the academia various groups at universities (Universidad Central de Venezuela, Universidad de Oriente, Universidad de Los Andes and Universidad del Zulia), polytechnic schools (Instituto Universitario de Tecnologa: Region Capital and Cuman) and research centers (IVIC) are devoted to the study of C1 chemistry, electronic and crystalline properties of transition metal suldes, environmental monolith catalysts, ne chemical catalysts, polymerization process simulation, homogeneous catalysis, pillared clays, upgrading of heavy oil fractions, hydrotreatment reactions, characterization of metal and oxide catalysts, activated carbon, zeolite and molecular sieves catalysts, light alkane transformations (aromatization, hydrocracking, hydroisomerization, dehydroisomerization, etc.) and bifunctional catalysis (kinetics, mechanisms, deactivation, etc.). The Venezuelan Catalysis Society holds more than 200 members, from which about 50 are research leaders. Catalyst development activities are mainly concentrated at PDVSA-Intevep, where work is focused to rening catalysts (hydrotreatment, FCC, reforming, alkylation, hydrocracking, hydroisomerization, etc.) and in a lesser proportion to polymerization catalysts. Intevep holds 75 US patents (with equivalents to sum up a total of 152) for catalysts applied in the areas already mentioned. Participation in the international forum (Fig. 1) has been growing through the years, but where the Latin American catalysis community participates more actively is in the Iberoamerican Symposium on Catalysis (Fig. 2), which constitutes the most important

Fig. 1. International participation of the Latin American catalysis community.

scientic space for technical discussions. The meeting takes place on even years, by now 16 have been convoked since 1968 and next one will be held in Porto (Portugal) in July 2000. This symposium has grown to hold more than 1000 attendees, presenting around 400 oral and poster presentations. The contribution of the considered countries (percentage of the total number of works) in this symposium (Fig. 2) has always been quite signicant, the growing trend is stopping now when it is reaching a steady level of about 75%, as mentioned above new comers are appearing, so further increase is then almost impossible. The scientic interaction and cooperation among the Iberoamerican countries is strong and highly promoted by multilateral organizations such as CYTED (Ciencia y Tecnologa para el Desarrollo) through a program on Catalysis and Adsorption (Subprogram V) coordinated by Dr. Paulino Andru. The Cyted leaets states the objectives of the Program as to promote the cooperation in the eld of applied research and technological development for obtaining results which might be incorporated directly into the productive sector and so improve the life quality within the region.

Fig. 2. Participation of the Latin American catalysis community in the Iberoamerican Symposium.

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The activities are categorized as subject networks (discussion groups around a subject and human resources formation workshops), research projects and innovation projects. Regarding, the Subprogram V, subject networks deals with computational catalysis, homogeneous catalysis and environmental catalysis, while research projects are concerned with adsorbents for gas separations, NOx abatement and ne chemicals.

acidic site (A0 /H+ ), as a function of EFGS/H+ relation, shows that aromatization is kinetically limited by initial dehydrogenation step produced on EFGS. Also, EFGS inactivate the acid sites of the structure.

3.2. Rening (HDS and FCC) catalysts Some other petroleum rening reactions are included, such as catalytic cracking and hydrodesulfurization (HDS). The inuence of different rare earth ions on hydrogen transfer over Y zeolite was considered by de la Puente et al. (Argentina; Brazil). Nowadays, the search for new catalytic systems for enhancing the octane/barrel ratio in FCC operations involves the control and knowledge of the hydrogen transfer reactions. Interestingly, the authors evaluated the catalytic activity in a uidized bed reactor. An index was dened using the corresponding kinetic constants of a simple lumped model to show that the relative importance of the hydrogen transfer reactions increased linearly as a function of both Brnsted acidity of the catalysts and ionic radius of the rare earth element considered. The differences observed in the effect of the various rare earth elements on hydrogen transfer were moderate, but a certain degree of catalytic control can be exerted on these reactions through the selection of the rare earth elements to be loaded into commercial catalysts. Regarding HDS reactions, two different set of works are included, those dealing with non-conventional catalytic systems and those dealing with new preparation routes to conventional formulations. The effect of the preparation method and metal loading on the hydrodesulfurization (HDS) of thiophene, and on the dispersion and location of Ni and/or W species in Ni, W and NiW suldes supported on USY zeolite, was investigated by Bendez et al. (Chile; Spain). Their catalysts displayed signicant differences in dispersion, location and suldation of the Ni and W phases dependent on the preparation method. However, none of these factors alone accounted for the activity trend. In general, it was found that a combination of high acidity and metal dispersion led to catalysts with high initial HDS activity. The use of noble metals within conventional Mo formulations was considered by Merio et al. (Colombia). Pt was found to be the best in improv-

3. Current activities Preparation, characterization and evaluation activities, carried out within Latin American groups, have been fully covered (in this issue) on a wide range of catalytic materials, which are of interest for the chemical and petroleum industries. Support materials and catalysts, both have been considered. Regarding reactions, hydrogenation, hydrodesulfurization, cracking, reforming, hydrogenolysis, aromatization and dehydrogenation have been included. In brief, some comments on the issue content is given below. 3.1. Metal catalysis Borgna et al. (Argentina) studied the simultaneous deactivation by coke and sulfur in reforming and found that the PtRe/Al2 O3 activity was signicantly decreased by both deactivation processes. The changes in catalyst selectivity can be interpreted in terms of selective deactivation by coke and sulfur of individual reaction pathways involved in the n-hexane reforming mechanism. The motivation of such study is the understanding of the deactivation causes, in order to develop new catalytic formulations. A related system was considered by Scott et al. (Venezuela), namely, RuMo/Al2 O3 , for which they found that Mo is more easily reduced in the presence of Ru, increasing electron transfer from partially reduced Mo species to the Ru centers. They use these ndings to explain the increase on hydrogenolysis catalytic activity of the system. Another reforming reaction, aromatization, was evaluated on MeNH3 -[Ga, Al]-ZSM-5 zeolites by Montes et al. (Venezuela), who compared the role of extraframework gallium species (EFGS) with that of the acid sites (H+ ). A linear dependence of initial activity (A0 ) in propane aromatization per protonic

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ing HDS, while the one for hydrogenation was Ru. The nature of the noble metal and sulding agent have a noticeable inuence on the reducibility of the molybdenum sulde phase. The characterization and catalytic activity of CoMo HDS catalysts supported on alumina-MCM-41 were presented by Ramrez et al. (Mexico). The so-called, accessibility problem on deep HDS has led to the inclusion of open structured materials as catalytic supports, MCM-41 is one of the most studied. Although, in such a material an interaction between Co and Mo exists, not all the Co present in the catalysts is completely sulded and therefore may not contribute to the formation of the catalytic active CoMoS mixed phase. A new preparation method of CoMo/ -Al2 O3 HDS catalyst has been developed by Cabello et al. (Argentina), using the (NH4 )3 [CoMo6 O24 H6 ]7H2 O Anderson type heteropolyoxomolybdate supported on -Al2 O3 . As discussed by the authors, in comparison with the traditional HDS catalysts, this new system shows the following relevant aspects: (a) although the Co content is lower, the activity for the HDS of thiophene is similar in both cases; (b) the phase adsorbs well onto the support; (c) the activity of molybdenum seems to be promoted by the presence of cobalt in the ordered distribution of the heteropolyanion on the surface of -Al2 O3 ; (d) the conventional catalysts can be prepared through a series of steps (two impregnation operations, one for drying and another for the calcination at 550 C), the proposed method only requires one impregnation step and a drying step at 80 C. Alonso et al. (Mexico) suggest the use of tungsten tetraalkylammonium thiosalts as precursors for the in situ formation of WS2 HDS catalysts. The improved catalytic properties of WS2 catalysts derived from alkylammonium thiosalts in the HDS of DBT are attributed to the formation of carbon-containing tungsten sulde phases on the catalysts surface.

3.3. Preparation and characterization of catalytic materials New synthesis routes and the catalytic potential of the so obtained materials are also part of this issue. Two preparation methods were tested and compared for niobia on silica production, by Pereira et al. (Ar-

gentina; Brazil). The interaction of these materials with nickel was also included in this work. The nickel compounds interacts preferentially with niobia rather than with silica. These nickel species favored lower dehydrogenation activity, suggesting the choice of niobia as a nickel trap. Lopez et al. (Mexico) infer on the effect of sulfation on the acidity of TiO2 SiO2 , prepared by a solgel method. One step sulfated in situ TiO2 SiO2 solgel preparations resulted in catalysts with homogeneous and strong acidity. The solgel preparation of ZrO2 Al2 O3 solid solutions was carried out by Dominguez et al. (Mexico). A synergetic effect was found between zirconia and alumina, for the propanol dehydration reaction. The surface acidbasic character of the Al2 O3 ZrO2 materials led to a higher yield of propylene over acetone, indicating a stronger acidic character compared to the single oxides. Acidity was also considered by Lopez et al. (Venezuela) on AFI-like molecular sieves (silicoaluminophosphates). The effect of Si content was examined focusing the catalytic activity for ne chemicals production. They found that, as the silicon content increases the total acidity per gram of solid, as determined by NH3-TPD, also increases. Camphene and limonene were the main products of the -pinene transformation on these catalysts, amounting up to 80% of the -pinene converted, with a camphene/(camphene+limonene) ratio of 0.50, at conversion levels between 48 and 55%. Undesirable heavy compounds were less than 1%. Other materials and their synthetic routes together with their use for ne chemicals, where also examined in two other works. Santori et al. (Argentina) pursued Surface Organometallic Chemistry on Metals techniques to promote Pt/SiO2 catalysts with tin. The obtained organobimetallic catalysts exhibit very high selectivities to crotyl alcohol (80% at 5% conversion), during crotonaldehyde hydrogenation. The stability of a cobalt modied LTL-type zeolite for the epoxidation of R-(+)-limonene was related to the incorporation of Co in the framework of the zeolite, by Montes et al. (Colombia; Venezuela). The method employed for the isomorphic substitution of Co in the structure was also described. EPR characterization of the changes in the structure of Cu2+ in ZSM-5 after short and long TOS isother-

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mal reaction in the presence of 10% H2 O is discussed by Gomez et al. The environmental interest on this type of catalyst lies on the fact that Cu-ZSM-5 is one of the best catalysts for selective catalytic reduction of NO with hydrocarbons (SCR-HC) in the absence of H2 O in the feed. The results showed that only changes in the distribution of Cun + sites and neither structural changes nor dealumination of the zeolite are responsible for deactivation. 3.4. Kinetic studies The group of Musante et al. proposed a two-phase model for describing the catalyzed reaction of formation of piracetic acid, using a sulphonated ion-exchange resin acting as both, a sorbent and a heterogeneous catalyst. Relevant aspects with regards to the different afnities of the reactive species toward the liquid and resin phases has been incorporated in the model. The selective partitioning of each component between the two phases and the resin swelling ratio with varying composition were quantied and taken into account in the kinetics. They have conrmed the convenience of using a microreticular ion-exchange resins as heterogeneous catalysts for epoxidizing unsaturated triglycerides due to the fact that protons can be conned inside the polymer phase and prevents

the formation of higher oxirane indexes than those achievable in homogeneous catalytic processes.

4. Conclusions Research activities in catalysis have been growing in Latin America for the last three decades only. The areas of interest concern petroleum, petrochemical and ne chemicals catalysts, environmental and theoretical catalysis. The scientic interaction and cooperation among the countries (including Spain and Portugal) is strong and highly promoted by multilateral organizations. Although, participation in the international forum has been growing through the years, it is the Iberoamerican Symposium on Catalysis the natural space for results discussion. This issue (of applied catalysis) shows a sample of the diversity and quality of the Latin American work on catalysis. References
[1] S. Fuentes, Appl. Catal. 142 (1996) 179. [2] M.M. Ramirez de Agudelo, P. Reyes, Appl. Catal. 140 (1996) 118. [3] M.M. Ramirez de Agudelo, Appl. Catal. 140 (1996) 113. [4] A.K. Rhodes, Oil Gas J. 95 (1997) 41.