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CATALYZING R&D IN MEXICO Needs of the country's oil industry spur catalysis research in universities and national lab MITCH JACOBY, C & E N
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research in Mexico and the picture will be dominated by petroleum. The state-run oil industry looms large in Mexico. It plays a key role in the country's economy and accounts for a substantial fraction of catalyst usage. The petroleum industry doesn't fund research, per se, in Mexico. But its evolving needs for new catalyst technology help shape research programs in the country's universities and national laboratory Mexico's position as a major player in the world petroleum market is based on the operations of its one and only oil company, Petroleos Mexicanos (Pemex).The national company ranked seventh largest in the world in 2 0 0 0 based on production, reserves, sales, and refinery capacity In that year, Pemex produced just over 3 million barrels of crude oil per day and more than 4.5 billion cu ft of natural gas per day According to the company's 2000 annual report, the duties and taxes paid by Pemex to the Mexican government account for onethird of total federal government revenues.
ROUGHLY HALF of the crude oil produced in Mexico is refined in Pemex processing plants. The other half is sold abroad. The company relies on several catalytic processes to convert raw material into gasoline, jet fuel, diesel, and liquefied petroleum gas. Pemex also produces olefins, aromatic compounds, and other petrochemical products byway of catalyzed reactions. Luis Miguel Rodriguez-Otal, a catalytic reforming specialist at Pemex, notes that fluid catalytic cracking (FCC), hydrodesulfurization (HDS), and catalytic reforming are among the company's most important catalytic processes. FCC units in Mexico use thousands of tons of aluminosilicatetype zeolite catalysts each year to crack high-molecular-weight materials into lower molecular weight, higher value products. HDS reactions reduce sulfur levels in transportation fuels through treatment with hydrogen. In the HDS process, sulfur HTTP://WWW.CEN-ONLINE.ORG
is stripped from the feed material and converted to volatile hydrogen sulfide in the presence of cobalt- and nickel-containing molybdenum disulfide catalysts, Rodrfguez-Otal says. H 2 S is then separated and converted to elemental sulfur. Pemex's operations require a few million pounds of HDS catalysts annually Catalytic reforming units convert paraffins and naphthalenes into branched, cyclic, and aromatic compounds. Rodriguez-Otal points out that Pemex's operations include
Dominguez
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two types of reforming processes—one that uses a platinum-rhenium catalyst and another based on a platinum-tin catalyst. The reformed products are valuable, he asserts, because they're used to boost octane ratings in gasoline formulations. Much of the commercial catalyst technology in Mexico—in petroleum processing and other areas—is imported. Pemex's FCC units, for example, use products from W R . Grace, Columbia, Md., and Engelhard, Iselin, N.J. And UOP, Des Plaines, 111., supplies Pemex with reforming catalysts, according to Rodriguez-Otal. In contrast, HDS catalysts and other products used at Pemex were developed locally at the Mexican Petroleum Institute (abbreviated IMP in Spanish). A cross between a national lab and a technology company IMP has long been known as the research and technology arm of Pemex. The state-owned petroleum in-
stitute develops technologies and products and licenses them to Pemex and other companies—including several outside of Mexico. Catalysis research at IMP is carried out by 150 or so scientists and technicians who make up the Catalysis Competency group, which is headed by Jose-Manuel Dominguez. "IMP generates proprietary technology to support the petroleum industry but it must compete with other catalyst companies for Pemex's business," Dominguez explains. Pemex is IMP's best customer— IMP supplies about 40% of its catalysts, he says. But although the oil company's revenues are controlled by the federal government, IMP's operating expenses are not covered directly by government funds. Another feature that marks IMP as a government-run business is a legal requirement that its would-be profits be reinvested into the institute—in capital equipment purchases, for example. The requirement has its advantages. IMP's labs are outfitted with state-of-the-
Hernandez art equipment that sets them apart from other laboratories in Mexico. For example, the institute recently installed robotic instrumentation for high-throughput synthesis and testing of catalysts (C&EN, July 21, pagel4). IMP's combinatorial catalysis facility is the only one of its kind in Latin America, Dominguez notes. In the short time the facility has been up and running, IMP scientists have identified a few candidate catalysts for further investigation. "The robotic equipment offers some real advantages," Dominguez says. "It lets research scientists devote more time planning experiments and interpreting data than performing laboratory operations." I M P also recently acquired highthroughput X-ray diffraction instrumentation. And the institute features an advanced nuclear magnetic resonance spectroscopy facility In the near future, IMP plans to install an X-ray photoelecC&EN
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SCIENCE & TECHNOLOGY tron spectrometer and other ultrahigh-vacuum equipment for analyzing catalyst surfaces. But of all of IMP's assets, perhaps the most valuable to catalysis research— and unique in Mexico—Dominguez says, is IMP's pilot-plant facility which provides a means for kilogram-scale catalyst testing under near-industrial reaction conditions. Turning an IMP catalyst design into a commercial product requires developing strong partnerships abroad because there are no catalyst manufacturers within Mexico's borders. Oscar Bermudez, an I M P manager and liaison to Pemex, explains that IMP conducts applied research to develop catalyst technology and then licenses it to catalyst companies in the U.S. and Europe, for example. "They manufacture the catalysts according to our specifications, and we sell the product to Pemex and provide technical support to run their refineries," he says. IMP also sells its catalysts to companies in the U.S., Venezuela, Romania, and other countries. AS WITH ANY catalyst manufacturer, IMP doesn't support a one-size-fits-all approach. "We tailor-make catalysts according to the customer's needs," Bermudez stresses. That means that IMP studies the properties of its customers' feedstocks and the specifics of their refining units in order to develop durable products that maximize a customer's productivity For Pemex and other refineries that process Mayan crude, "tailor made" means developing catalysts that tolerate the high concentrations of sulfur, vanadium, and nickel typically found in the raw material. Sulfur poisons platinum reforming cata-
Sergio Fuentes
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lysts, and the metals destroy the crystal structure of zeolites used in FCC processes, Bermudez explains. The metals can also deactivate hydrotreating catalysts by blocking their pores and preventing diffusion of reactants and products to and from catalytic sites. 52
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Technical support is an important piece of the catalysis "package" provided by IMP Product manager FranciscoJavier Hernandez points out that IMP specialists are on hand full time at all six Pemex refinery complexes to monitor plant operations and to provide trouble-shooting assistance. Hernandez notes that I M P engineers use process simulators to probe hydrotreating, catalytic cracking, and other refinery processes and to understand catalyst performance. The simulators are also used to predict optimal operating conditions and to assist in problem solving. To keep pace with the growing needs of Mexican industry catalysis education in Mexico is undergoing change. Twenty years ago, very few research groups outside of IMP were active in catalysis investigations. But the number has grown. Nowadays, catalysis groups can be found at several universities. For example, at Metropolitan Autonomous University (known by its Spanish abbreviation, UAM), catalysis research is conducted on campuses in Iztapalapa and Azcapotzalco, both in Mexico City Catalysis research is also carried out at National Autonomous University of Mexico (UNAM) on its campuses in Mexico City and Ensenada. The same is true of National Polytechnic Institute, Mexico
Fuentes, a senior researcher and catalysis group leader at the Center for Condensed Matter Science at UNAM, Ensenada, was deciding about a graduate education in catalysis, there wasn't much choice in Mexico. There were some chemical engineering groups that studied catalysis problems at U N A M , he says, but no full-fledged catalysis research groups. So out of necessity, Fuentes left Mexico and went to graduate school in France. France was a common choice for Mexican scientists at that time, because the Catalysis Research Institute (IRC in French) at Claude Bernard University Lyon, was well known internationally Earlier generations of Mexican scientists who studied at IRC and other institutions in France had already established catalysis contacts there and often advised their younger associates to follow suit. IMP's Dominguez and Hernandez earned Ph.D. degrees in France, as did Gabriela Dfaz, a professor at UNAM's Institute ofPhysics, Mexico City Some of today's middle-aged Mexican scientists went to Russia orJapan to study Others, such as Jorge Ramirez, a research group leader in UNAM's faculty of chemistry, Mexico City, studied in Edinburgh, Scotland. A small number of students came to the U.S. for Ph.D. research in the 1970s. For example, Gustavo A. Fuentes, a chemical engineering professor at UAM Iztapalapa completed his degree at the University of Delaware. It's a different story today With the increase in the number and size of catalysis research groups in Mexico, many of today's Mexican students stay at home. Indeed, Sergio Fuentes estimates that, in his day more than 90% of catalysis students left the country to continue their education, but today the number may be smaller than 50%. The change is good for Mexico because it indicates the growing prominence of catalysis research here, he says. Still, Sergio Fuentes thinks it's a good idea for students to broaden their education outside of Mexico—for example, through a postdoctoral research appointment. That view is echoed by several scientists. Ramirez says that studying abroad is important "because it exposes students to new ideas and different ways of solving
In Mexico, university research programs in catalysis cover a range of topics, but most projects focus on petroleum chemistry or environmental catalysis.
Gustavo Fuentes City, and various smaller state universities located throughout the country Take a poll of senior-level Mexican scientists, and the numbers will show that nearly all catalysis researchers older than, say 50 completed their Ph.D. degrees outside of Mexico. In the mid 1970s, when Sergio
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SCIENCE & TECHNOLOGY project at IMP and had an opportunity to problems." Gustavo Fuentes remarks that collaborate with Japanese scientists. The without some research experience outside experience gave her "a great feeling about of Mexico, researchers may choose not to research—especially for collaborating pursue far-reaching ideas and maybe afraid abroad," she says. to take risks in scientific research. He adds that despite the growing number of opGarcia-Sanchez's enthusiasm for studyportunities for Ph.D. study in catalysis in Mexico, it is still valuable for some Ph.D. students to go abroad and bring back new concepts in catalysis research. One model for studying abroad involves conducting a portion of a Ph.D. program outside the "home" laboratory HugoJ. Tiznado, a Ph.D. student working with Sergio Fuentes, spent some months at the University of California, Riverside, conducting experiments in the lab of chemistry professor Francisco Zaera. Ramirez Viniegra In contrast, Mayela Garciaing outside of Mexico was matched by Sanchez left Mexico after completing a Tomas Viveros, her master's thesis adviser master's degree to study for a Ph.D. degree at UAM Iztapalapa who had studied in Euin the Netherlands with professor Rutger rope. Working in Holland has been a good A. van Santen at Eindhoven University's experience, she says, and everyone—inSchuit Institute of Catalysis. As an undercluding her family—has been supportive. graduate student, she worked on a research
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Garcia-Sanchez adds that studying in a European university has provided her with more than a formal science education. "It's also a cultural experience that teaches you how to work with people from all over the world." Back in Mexico, university reS search programs in catalysis cover a x range of topics, but most projects i focus on petroleum chemistry or n environmental catalysis. For exam| pie, Ramirez's group at U N A M * studies properties of hydrotreating catalysts used for sulfur and nitrogen removal, hydrogenation reactions, conversions of complex mixtures, and other processes. Ramirez's research team, which includes six staff members and roughly 25 students, blends expertise in synthesis, characterization, and other facets of catalysis research. Ramirez notes that his research projects have been funded mainly through Pemex and IMP, but his group has also conducted some contract-type research—for example, catalyst evaluation for the Venezuelan Petroleum Institute. In contrast, many other scientists in Mexico obtain research grants through federal organizations, such as Mexico's National Science & Technology Council, which is roughly equivalent to the U.S. National Science Foundation. At UAM Iztapalapa, chemistry professor Margarita Viniegra and coworkers investigate methods for preparing effective hydrotreating catalysts. Specifically, the group is studying the HDS effects of various preparation procedures on mixedoxide catalyst supports made of zirconia and titania (C&EN, July 7, page 18). The UAM researcher also studies coke deposition on zeolitic reforming catalysts. In the area of automotive catalysis, Viniegra and coworkers are investigating techniques used to synthesize alumina-supported palladium catalysts that feature lanthana additives. The materials are used in NO-reduction studies. Although concentrations of sulfur compounds in Mexican fuels are dropping, residual sulfur levels can affect automobile catalytic converters adversely The problem is especially important in Mexico, where more than one type of fuel and catalytic converter are available. Gustavo Fuentes explains that in Mexico, where automobiles are driven longer on average than they are, for example, in the U.S., there is a market for replacement catalytic converters. "Catalytic activity drops off as the converters age— not entirely but enough so the cars fail emisHTTP://WWW.CEN-ONLINE.ORG
sions-control tests," he says. The aging cars are fitted with replacement units, but the units are not designed with the same specifications as new-car converters. Gustavo Fuentes' group is studying the sensitivity of replacement converters to sulfur content in fuels. But the problem is complex because fuels with differing sulfur levels can be found across Mexico. In urban centers, fuels are required to have low sulfur levels. But higher sulfur-content fuels are sold in rural areas. The group is focusing on the effect of sulfur-concentration swings on catalytic converters. MIXED-OXIDE SUPPORTS are also used in investigations of reforming reactions. UNAM's Diaz uses zirconia modified with lanthana, ceria, and titania to support platinum in studies in which methane is reacted with carbon dioxide to produce hydrogen and CO. Diaz and coworkers are also investigating metallic and bimetallic systems to control nitrogen oxides. Despite the growth of catalysis R&D in Mexico, it's taking time to spread the word. IMP scientists say that the country's expertise in industrial petroleum chemistry has been recognized for years by Latin American countries. And international collaborations between Mexican universities and universities in Europe and elsewhere put Mexico on the catalysis map years ago. The news seems to be traveling more quickly nowadays, thanks in part to the Mexican Academy of Catalysis (ACAT). ACAT is a catalysis "club" that serves—among other roles—to facilitate broader participation ofMexico's catalysis researchers in international conferences. ACAT is involved in organizing the Iberoamerica catalysis conferences, which draw scientists mainly from Spain, Portugal, and Latin America. Mexico will host the next Iberoamerica conference in 2004. And just last month, for the first time, the North American Catalysis Society's international meeting was held in Cancun (C&EN, July 7, page 18). Mexican scientists agree that the international exposure that comes from hosting large meetings benefits catalysis research in their country They say it boosts students' self-confidence by giving them an opportunity to see that their work compares favorably with research going on in better known catalysis labs. The meetings also provide a setting for academic research directors to develop new contacts and build foreign collaborations. And it provides Mexico's petroleum institute with the chance to showcase its work and capabilities. The news has been traveling slowly, but it is traveling. • HTTP://WWW.CEN-ONLINE.ORG
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