Synthesis of Fe and Co catalysts supported on aluminophosphates for the reaction

of Fischer-Tropsch
Rafael Ricardo Celin Mancera
Masters, Pontifical Catholic University of Rio de Janeiro, Rio de Janeiro, RJ.

ABSTRACT
The Fischer synthesis reaction - Tropsch has received great attention for its technological
and scientific interest. Naturally this interest is largely associated with the problem of oil
shortage, as the Fischer - Tropsch synthesis provides a convenient route for the
transformation of solid in liquid and gaseous fuels and basic materials in the petrochemical
industry. Given the structure of the Brazilian market, this interest is primarily directed to the
replacement of diesel and fuel oil. Experience has shown that, through a suitable selection
of catalyst and operating conditions, it is possible to change, within certain limits, the
distribution of products obtained in the synthesis reaction. This paper presents a new
series of obtaining catalysts containing cobalt and / or iron supported on aluminofosfastos
for application in the catalytic conversion of synthesis gas into liquid hydrocarbons in a
process called Fischer-Tropsch synthesis (FTS). The aluminofosfastos seran crystallized
by hydrothermal method with microwave energy. The aim of this research, identify some
possible avenues for the development of optimized catalysts, more active and more
selective for certain product fractions (gasoline, diesel, olefins).
Keywords: Hydrothermal synthesis, aluminophosphates, cobalt and iron catalysts,
Fischer-Tropsch synthesis.

RESUMO: A reao de sntese de Fischer - Tropsch tem merecido uma grande ateno
pelo seu interesse tecnolgico e cientfico. Naturalmente este interesse est, em grande
parte, associado ao problema da escassez do petrleo, na medida em que a sntese de
Fischer - Tropsch oferece uma rota adequada para a transformao de combustveis
slidos em combustveis lquidos e gasosos e em insumos bsicos da Industria
petroqumica. Dada a estrutura do mercado brasileiro, este interesse est essencialmente
dirigido para a substituio do leo diesel e do leo combustvel. A experincia mostra
que, atravs de uma seleo adequada do catalisador e das condies operatrias,
possvel alterar, dentro de certos limites, a distribuio dos produtos obtidos na reao de
sntese. Neste trabalho apresentada uma nova obteno de sries de catalisadores
contendo cobalto e/ou ferro suportados em aluminofosfastos para aplicao na converso
cataltica de gs de sntese em hidrocarbonetos lquidos, num processo denominado de
sntese de Fischer-Tropsch (SFT). Os aluminofosfastos sero cristalizados pelo mtodo
hidrotrmico com energia de microondas. Pretende-se com esta investigao, identificar
algumas possveis vias para o desenvolvimento de catalisadores otimizados, mais ativos
e mais seletivos, para determinadas fraes de produtos (gasolina, diesel, olefinas, etc).

Palavras-chave: Sntese Hidrotrmica, Aluminofosfastos, Catalisadores de Cobalto e

Ferro, Sntese de Fischer-Tropsch.

INTRODUCTION
The catalytic conversion of natural gas into chemicals of greatest economic value has
been intensively studied in many countries, because of its large commercial interests.
Currently, most of the methanol produced in the world has as raw material gas. Nearly half
of all the H2 produced in the world comes from the catalytic conversion of natural gas with
water vapor. Today's world is dependent on the transport of liquid fuels, so the conversion
of natural gas in remote areas to liquid fuels is a viable alternative to the economic use of
many of these reserves. An example of a possible application of these remote sources, the
current conversion technology could provide about 100,000 bpd of high quality fuels for
about 20 years from a reservation with only 0.17 trillion cubic meters of gas. Among the
most viable technologies for converting natural gas into hydrocarbons can highlight the
Fischer-Tropsch synthesis (FTS), which consists in subjecting natural gas to a reforming
reaction with steam to obtain a mixture of CO and H2, known as synthesis gas. This
mixture, which is much more reactive than methane (main fraction of natural gas) is
converted to hydrocarbons such as gasoline, diesel, lubricating oils, etc. through a
hydrogenation reaction on the base metal catalysts of metals of group VIII of the periodic
table, especially cobalt, iron, nickel and ruthenium. Brazil has natural gas reserves in the
Amazon region that are virtually unexplored because of its great distance from the main
consumer markets. The Brazilian government has implemented recently an energy policy
that aims to increase the share of natural gas in the national energy matrix. Thus, an
alternative to immediate use Amazon natural gas would be to convert them into liquid fuels
by the Fischer-Tropsch synthesis, and therefore the development of more efficient
technologies for obtaining fuel from natural gas is a theme extremely important for the best
economic use of gas from remote areas. In this design will studied the catalytic conversion
of synthesis gas into hydrocarbons using heterogeneous catalysts containing iron and
cobalt supported on aluminofosfastos. These materials are known to have properties of
selective manner, ie molecules which can react or are formed within the pores should
have dimensions compatible with the diameter of aluminofosfastos channels. These
properties of aluminofosfastos can be extremely important in natural gas conversion
reactions of hydrocarbons, since they can direct the formed products of these catalysts
within a narrow range of carbon number maximizing the production of fuels such as
gasoline and diesel, then the synthesis catalysts supported on aluminofosfastos for use in
the SFT is a highly relevant topic for the best economic use of natural gas.

METHODOLOGY
The aluminophosphates are synthesized by hydrothermal method, using microwave,
phosphoric acid (Merck), hexadecahidratado aluminum sulphate - Al2 (SO4) 3.16H2O
(99%, Merck) as the source of Al, tretapropilamnio bromide (TPABr) as a structural
director (99 %, Merck) and distilled water as the solvent followed by calcination to obtain
the material. This calcination procedure aims at removing the organic structure director in
a milder way, avoiding that this be rapidly burned by oxygen. This would result in the
2

release of large amounts of heat within the pores aluminofosfastos causing damage to the
crystal structure. The precursor materials are mixed in stoichiometric proportions in order
to obtain a gel with the following molar composition: 10.6 TPABr. The absorbers are
characterized by X-ray diffraction, thermogravimetric analysis (TGA), fluorescence
scanning electron microscopy x-ray (SEM). The airline specifies, Volumen and diameter
will be determined by the BET method (Brunauer-emmet teller).

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