annual activity report - INCT

ANNUAL ACTIVITY REPORT
RIO DE JANEIRO / AGOSTO DE 2010
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INSTITUTO NACIONAL DE ÓLEO E GÁS
(INCT/CNPQ - FAPERJ)
RELATÓRIO ANUAL – MAIO DE 2010
Project Coordinator: René Rodrigues ([email protected])
Exploration: Coordinator Egberto Pereira ([email protected])
Production: Coordinator Abel Carrasquilla (abel @lenep.uenf.br)
Refining: Coordinator Fátima Maria Zanon Zotin ([email protected])
Environment Coordinator: Renato Carreira ([email protected])
Regulation: Coordinator Marilda Rosado de Sá Ribeiro ([email protected])
INTRODUÇÃO
The gradual depletion of reserves of oil and gas in the world causes concern and often it is
blamed as the main responsible for recessions, wars and diplomatic crises. On the other
hand, it can also be understood as the engine that drives many projects in the search for
alternative energy sources, looking for an outlet for the oil and gas industry. In this
direction, the recently created National Institute of Oil and Gas (INOG) are dedicated
mostly to the research of non-conventional deposits.
In almost its entirety, the oil company has been devoted to research and development of
hydrocarbons obtained from conventional deposits. This type of deposit involves the
occurrence of hydrocarbons generated from the normal maturation of sediments rich in
organic matter related to the burial history of sedimentary basins, which is a generation
model well established for the Brazilian marginal basins. However, when we look for the
other Brazilian basins, especially the Paleozoic basins, which cover almost 30% of the
country, the conventional model generation does not always apply. In these basins the
origin of oil involves a process of generation considered unconventional. Thus, the proposal
of INOG is to study, at first, these unconventional deposits, which is a relevant study, since
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the Paleozoic basins as exploration frontiers still remain, requiring deeper knowledge about
the mechanisms that control the formation of its petroleum systems. Petroleum systems are
called atypical or non-conventional generators when the horizons suffer thermal maturity
due to igneous intrusions. However, we can´t forget that there are also other forms of
unconventional oil and gas: gas from shale (gas shale) and generation of oil and gas from
oil shale (oil shale). There are also new forms of energy generation using the biogas, which
also fits into the context of a form of unconventional gas generation. For this whole range
of possibilities, there are no consolidated technologies for exploration and development;
there are also no established protocols for the regulatory aspects and the environmental
control of these new areas of exploration and production of these resources. Thus, in order
to comply with this growing demand for technology services and skilled labor, INOG
wants to be a national reference center for this sector, working in partnership with other
entities, through the development of innovative scientific research. For this, INOG will
have an organizational structure composed of five areas of oil industry: exploration,
production, refining, environment and regulation. Through an interdisciplinary approach of
the issues involved in these five key thematic areas, INOG main goal is to train researchers
and highly qualified professionals to meet the demands of the productive sector and the
academy. The INOG, therefore, has a multidisciplinary character. UERJ is the research
centre of INOG, but other educational and research institutions of Brazil are involved:
UENF, UFF, UFPE, PUC-RIO, EMBRAPA and ON, with financial support from CNPq
and FAPERJ.
EXPLORATION
TEAM: René Rodrigues, Egberto Pereira, Sérgio Bergamaschi, Hernani A.F. Chaves,
Maria Antonieta Rodrigues, Francisco Dourado (DRM-RJ), Mario Lima Filho (UFPE).
Students: Renata Marins Alvin Gama, Darly Erika Silva dos Reis, Felipe Catanzaro
Zarzour, Ivan Soares Loutfi, Fernanda Setta Duarte.
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1- INTRODUCTION
The great Brazilian reserves of oil and gas are laid in the Campos’ and Santos’
basins. This geologic/geographic localization, even before the discovery of the pre-salt
reserves, allowed the set of the tech-scientific infrastructure in Rio de Janeiro, which has
attracted many different companies on the oil and gas field to be settled. So, several
companies from different segments from the productive complex of the oil and gas field
have chosen the State of Rio de Janeiro as the base for their activities in the country and
also in Latin America.
In almost its totality, this productive complex has been devoted to research and
development on hydrocarbons obtained from conventional oil and Gas accumulations. This
type of deposits involves the occurrences of hydrocarbons generated from normal
maturation of organic-rich source rocks due to burying history of the sedimentary basins.
This type of oil and gas generation is well established for the Brazilian marginal basins.
However, when we observed the other Brazilian basins, especially the Paleozoic basins,
which cover almost 30% of the national territory, the model of conventional generation of
Oil and Gas does not always apply. In these basins the generation of oil involves a process
regarded as unconventional. Thus, the proposal of this Institute to study, in a first moment,
these unconventional deposits becomes relevant, since the Paleozoic basins still remain as
exploratory frontiers, requiring more detailed knowledge about the mechanisms that
controlled its petroleum systems.
Petroliferous systems are called atypical (Magoon & Dow, 1994 apud Araújo et al.,
2000) or non conventional (Rodrigues, 1995) when the generating horizons suffer thermal
maturation due to the igneous intrusions. However, we must not forget that there are also
other forms of unconventional oil and gas production from shale-gas and generation of oil
and gas from oil-shale. Please note that the oil shales are commercially exploited by
Petrobras in the city of São Mateus do Sul, Paraná State and there is oil black-shale in other
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interior basins, especially the Taubaté Basin, where the actual knowledge isn´t enough to
economic potential evaluation.
2- PROJECTS RESULTS
The exploration group focuses their activity, in the last year, in the development of
the following two research projects: a) Oil shales; b) Non-conventional oil and gas
generation by thermal effect of igneous intrusions.
a) Oil shales
Introduction:
Bituminous oil shales occur in several countries, from which about 33 have relevant
deposits from the economic point of view. Among these, three countries (U.S., Russia and
Brazil) account for approximately 86% s, in terms of bituminous oil shales resources
(Brentow, 2003)1. In Brazil, these resources are associated to distinct sedimentary basins,
and the following stratigraphic units are considered relevant: Irati Formation (Permian,
Paraná Basin); Tremembé Formation (Oligocene, Taubaté Basin); Codó Formation
(Aptian, Parnaíba Basin); Santa Brígida Formation (Permian, Recôncavo Basin); layers
of bituminous oil shales of Maraú (Cretaceous, Camamu Basin); Barreirinhas Formation
(Devonian, Amazonas Basin); Santana Formation (Cretaceous, Araripe Basin). Of these,
two deposits have received the most interest: (1) the lacustrine oil shale of Tremembé
Formation; and (2) the oil shale of the Permian Iratí Formation, a widespread unit in the
southern part of the country.
Currently, the industrial exploration of such important energy sources in Brazil is
restricted to the industrial plant named SIX / Petrobras, in São Mateus do Sul, PR, where
the extraction of hydrocarbons from the Irati Formation is performed through rock
pyrolysis. The oil shale is mined in an open pit mine. A first study concerning the oil shale
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Brendow, K. 2003. Global oil shale issues and perspectives. Synthesis of the symposium on
Oil Shale held in Tallin (Estonia) on 18 and 19 November 2002. Oil Shale, 2003, 20(1): 81-92.
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evaluation was carried out by the former CNP (National Oil Council) in the 1940’s and the
1950’s. In these studies, the CNP developed a pilot project to extract oil from bituminous
oil shales of the Tremembé Formation in the municipality of Pindamonhangaba, SP.
However, this pilot plant was shut down in the early 50’s, due to the technological and
economical aspects.
The Taubaté Sedimentary Basin is part of an important northeast-trending system of
Cenozoic taphrogenic basins sub parallel to the main structural elements of the southeastern
region of the South American Platform.
Objective, Materials and Methods:
In 2009 we studied in more detail the oil shale deposits contained in the Tremembé
formation, a pelitic unit up to 500m thick of lacustrine origin, Oligocene in age. The focus
of the research was the interval (ca. 50 m thick) of higher concentration of organic matter
of the Tremembé formation.
In order to contribute to the evaluation of the generator potential of bituminous
shale interval of the Tremembé formation, two shallow wells were drilled along the
depocenter of the basin, distant about 4 km from each other. The two wells (TMB-01-SP
and PND-01-SP) were located, respectively in Tremembé and Pindamonhangaba regions,
São Paulo State. In the TMB and PND wells 48 and 46 meters thick shales of Tremembé
formation were recovered, respectively. From the recovered cores of these wells 335
samples of shale were collected, at an average distance of about 20 cm. The following
analysis was carried out: Total Organic Carbon (TOC), Total Sulfur contents (S), RockEval pyrolysis, organic matter C isotopes analysis and major, minor and trace chemical
element contents.
Results:
Based on these data, a high-resolution chemostratigraphic analysis was performed,
which made possible to recognize ten chemostratigraphic units, which were correlated in
the two studied wells. The chemical elements analysis in addition to TOC data shows a
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very good correlation to the definition of chemostratigraphic units in a high resolution
approach (Figures 1 and 2). On the other hand, the application of chemostratigraphy to
sequence stratigraphic analysis also proved to be a very effective tool (four 5th order
sequences were identified). There is an excellent correlation between the TOC data and
hydrocarbon generation potential (S2), showing that for the intervals with TOC > 2.0%,
organic matter contained in the shales already has an excellent potential for generating
hydrocarbons (S2 values> 10 mg HC / g rock). The ratio of TOC and hydrogen index (HI)
also indicates that, for the intervals with TOC > 2.0%, the generation potential would be
for oil and gas (HI values > 300 mg HC / g TOC). For TOC contents < 2.0%, the values of
IH are less than 300 mg HC / g rock, and therefore the generation potential would be
mainly for gas and condensate.
Figure 01 – Chemostratigraphic units and their correlations between wells PND-1-SP and
TMB-1-SP. Datum = top of the shallow layer of smectite.
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Figure 02 – Chemostratigraphic units and correlations between data elements of V, Ce and
Zn and TOC data in the well PND-1-SP.
Conclusions:
The correlation of data obtained for the two wells contributed to the characterization
of the potential for economic exploitation of the oil contained in the bituminous shales of
the
Tremembé
formation.
Metric
cycles
were
also
recognized,
representing
sedimentological and geochemical variations of major importance for paleoenvironmental
interpretation of the unit.
Considering that the analyzed interval presents a low degree of thermal evolution, it
would only be possible to exploit the high potential for generating oil and gas through
industrial processing, as is performed by Petrobras in the bituminous intervals from the Irati
formation (Permian of Paraná Basin) in São Mateus do Sul (Paraná State). Based on
organic geochemistry data, the most attractive intervals for industrial exploitation of oil
shale are the chemostratigraphic units C (average values of the potential generation of oil =
93.6 mg HC / g rock), E (average values of the potential generation of oil = 94, 08 mg HC /
g rock) and G (average values of the potential generation of oil = 84.51 mg HC / g rock),
especially the layers of papyraceous shale in chemostratigraphic units C and E (Figure 02).
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The highest average contents of TOC in the TMB-01-SP area (Tremembé) suggest that this
area is more attractive for industrial exploitation of oil shale than the area of the PND-01SP (Pindamonhangaba).
b) Non-conventional generation of oil and gas by thermal effect of igneous
intrusions.
Introduction:
Brazilian Paleozoic basins show thick Silurian and Devonian shaly sections. These
sections often display interlaminated mudstones/siltstones/very fine sandstones deposited in
offshore conditions. Black shale intervals having relatively high TOC values (> 4.0%) were
detected in these sections. In the Paraná Basin, these shales are restricted to the
stratigraphic record specialty. However, in the Amazon and Solimões basins the black shale
intervals are thicker than those found in the Paraná Basin.
In the first year of the project our attention was driven to the Paraná and Amazon
basins studies. Previous described boreholes from these basins were submitted to a highresolution chemostratigraphy study. It was carried out a major, minor and trace elemental
analysis, as well as organic geochemistry and isotopic studies.
Paraná Basin:
A) Jaguariaíva Section
The trace-element redox proxies (Mo, Cu, Ni,) show a discrete increment in the
direction of the Pragian Maximum Flooding Surface (MFS) (Figure 03). The MFS is well
marked by a TOC peak. The P2O5 excursion follows the same relationship and could
suggest an increment of productivity. Moreover, the Mn, V and Ti excursions show an
inverse relationship to redox proxies and could indicate the progressive decrease of detritus
influx in to the basin. The δ13Corg.(‰) values shows an inverse correlation to TOC
contends, probably related to the increase of organic matter preservation and the type of
organic matter. The more negative isotope values probably represent the interval of better
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preservation of the marine organic matter. Using these proxies, it is possible to subdivide
the Pragian section into four chemostratigraphy units. These units represent parasequence
sets and the parasequence sets are clearly defined by the facies succession.
Figure 03: Jaguariaíva Section, Southern Paraná Basin
B) Tibagi Section
The Efilian/Givetian Tibagi Section (Figure 04) show a well defined progradacional
pattern. The distribution of the trace-elements does not show a good correlation with the
TOC and δ13Corg.(‰) excursions. However, based on the TOC and δ13Corg.(‰) excursions it
is possible to subdivide the stratigraphic record into four chemostratigraphic units. Unit II
corresponds to the less oxic sedimentation conditions. In general the elements associated to
Fe-sulfide (Zn) and siliciclastic (Ni, Ti, Ba) show a discrete increase to the top section,
following the progradational tendency and the respective increase of detritus influx in to
basin.
Figure 04: Tibagi Section, Southern Paraná Basin
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C) Rio Verde Section
In the Late Pragian Rio Verde Section the first Devonian marine transgression that
reached all the Paraná Basin is well marked (Figure 05). The transgression took place in
steps. In step I, the conditions are oxic and the Cruziana ichnofacies is predominant. In
steps II and III the conditions became progressively more dysoxic, and in the maximum
flooding surface the anoxic/dysoxic conditions were established. At this moment the
Zoophycos ichnofacies were dominant. The TOC content and the HI and S2 values show
the same tendency, indicating a better preservation of organic matter to the top section, as
also shown by the inverse tendency of δ13Corg.(‰) values. The increase of the sea-level
permitted the deepening of the basin. The offshore conditions became dominant and
disoxic/anoxic conditions were more constant. In consequence, the bioturbation intensity
dropped. The trace-element redox proxis didn’t work well. There is a slight increase of the
Cu and Ni in direction to the more disoxic/anoxic interval (Figure 05).
Figure 05: Rio Verde Section, Northern Paraná Basin
D) Dom Aquino Section
The Givetian / Frasnian Rio Verde Section show the progressive flooding that took
place during the Devonian time (Fig. 06). In the record, it is possible to observe four well
defined TOC increase cycles. The TOC contentwas growing up progressively, and it
reached 4 (wet %) in the Frasnian interval. The δ13Corg.(‰) values follow an inverse
pattern, becoming more negative to the top section. Probably, these more negative isotopic
signals suggest a better preservation of the marine organic matter. The better relationship
between the TOC contend and the S2 and HI values were observed in cycle III, where the
HI and S2 peaks reached higher values.
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Figure 06: Dom Aquino Section, Northern Paraná Basin
Amazon Basin:
A) Silurian Sequence
The chemostratigraphy relationship observed in the Silurian of the Amazon Basin is
relatively similar to those observed in the Devonian dysoxic intervals of the Paraná Basin.
The studied Silurian section was subdivided into four chemostratigraphy units (Figure
07A). Unit II shows the best preservation conditions which were reflected by an increase of
the TOC content and the decrease of the δ13Corg.(‰) values. The detritus trace-element Ba
and La shows an inverse relationship to TOC, for the same interval. However, more
dysoxic conditions in this interval are not reflected in the V, Ni and Zn data.
B) Devonian Section
Compared to the others Brazilian Basins the Black Devonian shales of the Amazon
Basin represents the best oil generation interval of the Early Paleozoic Brazilian Basins.
During the Devonian time, an unequivocal anoxic sedimentation condition took place in the
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Amazon Basin, which are reflected in its higher TOC content. In figure 07B, this change in
the depositional conditions is marked by an abrupt shift in the different studied proxies.
Figure 07: Amazon Sections.
Conclusions:
The results point out to an anoxic/dysoxic depositional condition for the TOC rich
intervals which corresponds to flooding surfaces. This depositional condition is
characterized by high TOC and HI values, very low bioturbation intensity, low δ13Corg (‰)
values and relative high concentration of organophyle chemical elements.
In the studied basins, the gas accumulations related to the TOC rich intervals
normally display a dry composition which indicates a generation at higher maturation stage
that was not reached by burial in the central area of the basin. Therefore, a non
conventional oil and gas generation process is considered to be the most important
hydrocarbon generation process in the Brazilian Paleozoic Basins. In the Paraná Basin, the
recovered oil and gas samples has shown thermal evolution indexes which are normally
greater than those measured on rock samples collected in areas of maximum burial of the
basin, not affected by dolerite intrusions. A good agreement between oil and rock samples
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thermal maturation values were obtained when was considered the heat effect produced by
dolerite intrusions on the source rock intervals.
The preliminary organic geochemical results for the Solimões and Parnaíba Basins
pointing out to an immature stage of the source rock interval before the igneous intrusions.
The overall immature stage of the potential source rocks was due to its shallow burial,
reaching a maximum of 3,000 m depth in the central part of the basin. Therefore, all oil and
gas shows (Parnaíba Basin) or oil and gas production (Solimões Basin), probably, are
related to thermal effect caused by basic igneous intrusions. On the other hand, in the
Amazonas and Paraná basins the thermal maturation due to burial was reached before the
igneous intrusions, as shown by the vitrinite reflectance data: Ro < 0.60% in the basin
margins to 0.60% < Ro < 1.35% toward the central part of the basin. Therefore, the
noncommercial oil and gas production in these basins could be due to conventional and non
conventional hydrocarbons generation processes.
3- ACTIVITIES FOR THE TO NEXT YEAR (2010)
In the next year it was planed news drillings in the Taubaté Basin and starts the
studies concerning the Parnaiba Basin. The drills in Taubaté Basin will focus the central
part of the basin. The two news shallow drills will be analyzed using a high resolution
approach. For the Paraná and Amazon basins the next step will be to propose a basin
modeling based in an unconventional generation process.
4- INTERNATIONAL MEETINGS
The AAPG International Conference & Exhibition – Rio de janeiro (2009)
AAPG’s 2009 International Conference & Exhibition took place in Rio de Janeiro.
on November 15th to 18th of the last year. The professor René Rodrigues, Egberto
Pereira, Hernani Chaves and Sérgio Bergamaschi and the researchers Cleveland M. Jones
and José Diamantino Dourado participate in the event. All researches presented distinct
expositions linkage to INOG projects.
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Latin Oil Week – Rio de Janeiro (2010)
The 16ª Latin Oil Week took place during the week of March 22 to 24 (2010), at the
Sheraton Rio Hotel. The event was directed to top executives of oil and gas companies
which operate in Latin America, or expect to do so. Latin Oil Week is already an annual
tradition in Rio de Janeiro, ever since ANP held its bid auctions for some rounds at the
same time as the Latin Oil Week event.
Global Pacific & Partners invited, once again, researchers Cleveland M. Jones
(FGEL), Visiting Professor Emeritus (FAPERJ) Hernani A. F. Chaves (FGEL) and José
Diamantino Dourado (CEFET/RJ), from the Research Group PETROUERJ, to participate
in the event. Cleveland represented UERJ and PETROUERJ, presenting an exposition
about biofuels in Brazil. UERJ and USP were the only institutions of higher learning
represented in the event. During his presentation entitled “Brazil´s Push for Biofuels”,
Cleveland described the potential of biofuels and the implications for future biofuel
investments in the region, and suggests that biofuels will become even more significant in
the energy matrix in Brazil, and that they represent a great business opportunity for
companies in the oil and gas business.
The scale and the expected growth of biofuels in Brazil took some executives by
surprise, despite the fact that important companies in the oil and gas industry already
consider themselves energy companies, and not merely oil and gas companies.
GTW – Houston, TX (2010)
The event took place on March 16th and 17th of this year. AAPG invited researchers
Cleveland M. Jones (FGEL), Visiting Professor Emeritus (FAPERJ) Hernani A. F. Chaves
(FGEL) and José Diamantino Dourado (CEFET/RJ), from PETROUERJ Research Group,
to participate in the Geoscience Technology Workshop, held in Houston, Texas.
The GTW event had as its theme “Deepwater and Ultradeepwater Reservoirs in the
Gulf of Mexico”. Cleveland represented UERJ and the PETROUERJ Research Group,
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making a presentation about natural gas hydrates. Cleveland’s presentation theme was a
relevant topic, as the Gulf of Mexico holds the first natural gas hydrate accumulations
considered commercially exploitable, in the Walker Ridge area, a region where Petrobras is
present and has operations. Another favorable result of the participation in the event was
the subsequent invitation for the authors to participate in the organizing steering committee
for the next GTW event, which will take place in Brazil, in early next year.
X Congresso de Geoquímica dos Países de Língua Portuguesa – Porto,
Portugal (2010)
This event took place on March 28th to April 01th of this year. The event is directed
at geochemistry researchers from speak Portuguese countries. Professors Egberto Pereira
and Sérgio Bergamaschi participate in the event. Both professors presented expositions
about the preliminary studies from the INOG projects.
5- STUDENT SUPERVISING
Young Investigator
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Student: Raphaael Motta de Oliveira.
Title: High resolution stratigraphy applied to oil and gas research.
Advisor: Egberto Pereira
Course: Graduation in Geology, Rio de Janeiro State University
•
Student: Rafael Moraes Rodrigues
Title: Chemostratigraphic and isotope analyses of the Devonian interval, east side of
Paraná Basin.
Advisor: Egberto Pereira
Course: Graduation in Geology, Rio de Janeiro State University
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Student: Analice Ramos Pereira Gomes.
Title: Detailed chemostratigraphic analyses of the Tremembé Formation
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Advisor: Sérgio Bergamaschi
Course: Graduation in Geology, Rio de Janeiro State University
Monographs concluded
•
Student: Renata Marins Alvin Gama.
Title: High resolution stratigraphy applied to Eodevonian of the Paraná Basin,
Jaguariaiva area (PR).
Advisor: Egberto Pereira
Course: Graduation in Geology, Rio de Janeiro State University
•
Student: Pedro Monteiro Benac.
Title: High resolution stratigraphy applied to Pitinga Formation sediments: Lower
Silurian of the Amazon Basin.
Advisor: Egberto Pereira
Course: Graduation in Geology, Rio de Janeiro State University
•
Student: Eduardo Felipe Alves Lucas.
Title: Detailed chemical stratigraphy study of the Tremembé Formation in the
Pindamonhangaba area (SP) – Taubaté Basin.
Advisor: Sérgio Bergamaschi
Course: Graduation in Geology, Rio de Janeiro State University
•
Student: Leonardo Simões Pimentel.
Title: Chemostratigraphic analyses of the Tremembé Formation based on COT, S
and RI data in wells drilled in the Taubaté Basin.
Advisor: Sérgio Bergamaschi
Course: Graduation in Geology, Rio de Janeiro State University
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Monographs in Progress
•
Student: Carlos Roberto N. Cardoso
Title: Organic geochemistry of Lower Devonian Jaguariaíva and Tibagi session,
Paraná State, Paraná Basin.
Advisor: René Rodrigues
Course: Graduation in Geology, Rio de Janeiro State University
•
Student:Caroline Marchon Caetano
Title: Chemical stratigraphy of the Palermo Formation, east border of the Paraná
Basin, Paraná State.
Advisor: René Rodrigues
Course: Graduation in Geology, Rio de Janeiro State University
•
Student: Tatiane Moura do Nascimento
Title: Organic geochemistry of drilled wells in Santos Basin.
Advisor: René Rodrigues
Course: Graduation in Geology, Rio de Janeiro State University
Master Theses concluded
•
Student: Leonardo Costa de Oliveira.
Title: Relationships between the stratigraphic setting and the diagenetic alterations
observed in the Devonian session of the Paraná Basin.
Advisor: Egberto Pereira
Course: Graduation in Geology, Rio de Janeiro State University
Master Theses in Progress
•
Student: Darly Erika Silva dos Reis
Title: Geochemical characterization of Codó Formation in the Parnaíba Basin (MA).
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Advisor: René Rodrigues
Course: Master Thesis in Geology, Rio de Janeiro State University
•
Student: Renata Marins Alvim Gama
Title: Organic geochemistry in the Irati Formation: Herval Velho and São Sepé
áreas (RS).
Advisor: René Rodrigues
Course: Master Thesis in Geology, Rio de Janeiro State University
•
Student: Josela Ghisoni Serafim
Title: Oil biodegradation in the Anhembi Area and its relationship with the
sedimentary fácies.
Advisor: René Rodrigues
Course: Master Thesis in Geology, Rio de Janeiro State University
•
Student: Filipe Abreu de Oliveira
Title: Organic geochemistry of Palermo Formation (Paraná Basin): Northeast area
of Paraná State.
Advisor: René Rodrigues
Course: Master Thesis in Geology, Rio de Janeiro State University.
•
Student: Lisa Marie Avelar Ribeiro
Title: Amazon Basin: conventional and nonconventional petroleum systems.
Advisor: René Rodrigues
Course: Master Thesis in Geology, Rio de Janeiro State University.
•
Student: Felipe Catanzaro Zarzour
Title: Major, minor and trace chemical elements in chemical stratigraphy: Irati
Formation, Paraná Basin.
Advisor: René Rodrigues
Course: Master Thesis in Geology, Rio de Janeiro State University.
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•
Student: Ivan Soares Loutfi
Title: Geological characterization of oil occurrence in the Rio Bonito Formation
related to nonconventional generation model.
Advisor: Egberto Pereira
Course: Master Thesis in Geology, Rio de Janeiro State University
•
Student: Fernanda Setta Duarte
Title: Contribution to the evaluation of the generation potential of the bituminous
shales of the Tremenbé Formation (Oligocene of Taubaté Basin), based on well core
analysis.
Advisor: Sergio Bergamaschi
Course: Master Thesis in Geology, Rio de Janeiro State University
•
Student: Patricia Nascimento Maia
Title: Evolution of the production and reserves and the prices of the oil, natural gas
and biocombustíveis. the importance of the biocombustíveis in the world-wide
scene.
Advisor: Hernani A.F. Chaves
Course: Master Thesis in Geology, Rio de Janeiro State University
•
Student: Guilherme Carvalho Dias
Title: Estimate of resources for discovering (yet you - find) in the Basin of SergipeAlagoas, applying the concepts of “play assessment” shaped by modeling tools of
exploration process
Advisor: Hernani A.F. Chaves
Course: Master Thesis in Geology, Rio de Janeiro State University
Doctoral Theses in progress
•
Student: Marco Antônio Ruivo de Castro e Brito
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Title: Caracterização dos intervalos geradores e correlação geoquímica de óleos e
extratos orgânicos das regiões de Alcobaça, Torres Vedras e do Barreiro (Bacia
Lusitânica, Portugal)
Advisor: René Rodrigues
Course: Master Thesis in Geology, Rio de Janeiro State University.
•
Student: Cleveland Maximino Jones.
Title: evaluation of the possible impact of the techniques of meor (microbial
enhanced oil recovery) in the factor of recovery of the reserves of oil and gas in
brazil
Advisor: Hernani A.F. Chaves
Course: Master Thesis in Geology, Rio de Janeiro State University
•
Student: Giovanni Gonella.
Title: “Uncertainty in the distribution of properties of the reservoir using the
Diffuse Logic (Fuzzy)”
Advisor: Hernani A.F. Chaves
Course: Master Thesis in Geology, Rio de Janeiro State University
•
Student: Francisco Dourado Assis Da Silva.
Title: The influence of royalties and the social/economic impacts of the variation of
the oil production and natural gas in the of the state of Rio de Janeiro cities and the
State of Rio De Janeiro - an analysis based on Geotecnology
Advisor: Hernani A.F. Chaves
Course: Master Thesis in Geology, Rio de Janeiro State University
6- FACILITIES
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Carbon and sulphur determinator (Leco SC 632)
Carbon and sulphur determinator (Leco SC 444)
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Transmitted and reflect light microscope
Gas Chromatography (Agilent 7890 GC System)
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GC (Agilent 6890) - Mass Selective Detector (Agilent 5973)
Isotope Ratio Mass Spectrometer (Delta V Advantage) coupled with Flash EA (1112
Series)
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Carbonate Device (Kiel IV) –Isotope Ratio Mass Spectrometer (Delta V Plus)
Isotope Ratio Monitoring/Gas chromatography/Mass Spectrometry (IRM/GCMS)
25
ABSORÇÃO
ATÓMICA
ICP-MS
Atomic Absorption Spectrometer (A Analyst 200) and Inductively Coupled Plasma Mass
Spectrometer (Elan DRC II Axial Field Technology)
26
Sample preparation Laboratory – Microwave 3000 Reaction System
PETROLEUM ENGINEERING AREA (PRODUCTION)
1- INTRODUCTION
Observing the schedule of the project, we can note that the first three steps are very
advanced. Thus, in the first months, we focus on training the team work to perform the
specific research project and acquisition of infrastructure. Moreover, because the original
project scope was detrital and carbonate oil reservoirs, actually we are in a stage to adapt
the focus of our research for the central theme of INOG that are the unconventional
deposits (tight sands and gas shale). To achieve these objectives, we are consulting the
literature related to this topic (see references).
2- ACQUISITION OF INFRASTRUCTURE
27
In this first phase of the project, we focus on assembling the work infrastructure, which
consisted principally of the location of a space inside UENF; purchase of computers for
computational modeling, real data processing and interpretation; and, the acquisition
of operational and interpretive software’s, namely:
a. Physical Space: 2 rooms of 30 m2 were transferred by UENF to develop the
project.
b. Computers: hardware purchased in the project refers to: 1) workstations for heavy
processing and interpretation (02); 2) desktop computers for light work and editing
of texts at office (02); 3) laptops to lighter work and editing of texts at home or in
places outside the University (03); 4) printers to print the papers, articles, reports,
etc. (02); 5) nobreak units to keep the energy in its absence (01); 6) units of backups
to store data and results safely (01); and, 6) data storage unit for storing large
amounts of data (01).
c. Software: relate to: 1) operational system (WINDOWS, acquired along with the
computers); 2) mathematical tools (MATLAB); 3) text editing (MICROSOFT
28
OFFICE, acquired along with computers); 4) image editing (CORELDRAW, is
being acquired); 5) scanning well logs (WINDIG, is being acquired); and, 6)
geosciences interpretative software (PARADIGM and LANDMARK grants, which
are being acquired).
Still, it is necessary to purchase some computers, Nuclear Magnetic Resonance (NMR)
laboratory equipment (see next figure) and consumables.
3. FORMATION OF WORK TEAM
The project will include the collaboration of the following researchers:
•
Dr. Alfredo Carrasco (UNIGRANRIO);
•
Dr. Ailton Silva (UFF-Macae);
•
Dr. Klaus Cozzolino (UFPA);
•
Dr. Pedro Romero (BAKER HUGHES); and,
29
•
Dr. Carlos Torres-Verdin (University of Texas at Austin).
Regarding students, those who participate in the project are:
•
Marilea Ribeiro (PhD level);
•
Jamilson Deleposte (Master level);
•
Carlos da Silva (Master level);
•
Julio Pereira (Master level);
•
Visney de Oliveira (undergraduate);
•
Fernando Santos (undergraduate).
The following officials will also participate, making the administrative support of the
project:
•
Remilson Rosa;
•
Thiago de Souza;
•
Sidna Abreu;
•
Anayansi González.
5. AGREEMENT NEGOCIATIONS
As a result of this project, we are negotiating different agreements for collaboration
with researchers and institutions related to the theme of non-conventional deposits:
PETROBRAS, transfer of cores and well logs data;
a. Dr. Erdal Ozkan, collaboration, Colorado School of Mines – USA.
b. Dr. Brian Evans, collaboration, University of Curtin, Perth - Australia
c. PARADIGM, software grant for academic use.
6- CONCLUSIONS
In almost its entirety, the production complex in the oil has been devoted to research and
development of hydrocarbons obtained from conventional deposits. This type of deposit
involves the occurrence of hydrocarbons generated from the normal maturation of
sediments rich in organic matter related to the burial history of sedimentary basins, which is
a generation model well established for the Brazilian marginal basins. However, when we
30
look the other Brazilian basins, especially the Paleozoic basins, which cover almost 30% of
the country, the conventional model generation does not always apply. In these basins the
origin of oil involves a process of generation considered unconventional. Thus, the proposal
of INOG is to study, at first, these unconventional deposits, which is a relevant study, since
the Paleozoic basins as exploration frontiers still remain, requiring deeper knowledge about
the mechanisms that control the formation of its petroleum systems. Petroleum systems are
called atypical or non-conventional generators when the horizons suffer thermal maturity
due to igneous intrusions. However, we can’t forget that there are also other forms of
unconventional oil and gas: gas from shale (gas shale) and generation of oil and gas from
oil shale (oil shale). There are also new forms of energy generation using the biogas, which
also fits into the context of a form of unconventional gas generation. For this whole range
of possibilities, there are no consolidated technologies for exploration and development;
there are also no established protocols for the regulatory aspects and the environmental
control of these new areas of exploration and production of these resources.
7- REFERENCES
− Carrasco, A. 2004. Modelagem tridimensional da resposta de sondas de indução em
ambientes geológicos complexos, utilizando equações integrais como técnica de
modelagem numérica. Tese de Doutorado, LENEP/UENF, Macaé - RJ, 119 p.
− Coates, G., Gardner, J. & Miller, D. 1994. Applying pulse-echo NMR to shaly sand
formation evaluation, paper B, 35th Annual SPWLA Logging Symposium
Transactions, 22 p.
− Coates, G., Xiao, L. & Prammer, M. 1999. NMR Logging Principles and Applications.
Halliburton Energy Services, Houston, 253 pp.
− Dodge, W. et al. 1998. A case study demonstrating how NMR logging reduces
completion uncertainties in low porosity, tight gas sand reservoirs, 39th Annual
SPWLA Logging Symposium Transactions, 14 p.
− Ellis, D. 1987. Well logging for earth scientist. Elsevier, New York. 532 p.
− Hallenburg, J. 1997. Introduction to Geophysical Formation Evaluation. Lewis
Publishers, Boca Raton, 181 p.
31
− Hallenburg, J. 1997. Standard Methods of Geophysical Formation Evaluation. Lewis
Publishers, Boca Raton, 442 p.
− Petricola, M. & Troussaut, X. 1999. Applications of fast NMR logging in shaly gasbearing sands invaded by oil filtrate, 40th Annual SPWLA Logging Symposium, 10 p.
− SCHLUMBERGER.
1989.
Log
Interpretation
Principles/Applications,
SCHLUMBERGER Educational Services, Houston, 116 p.
− Serra, O. 1984. Fundamentals of well log interpretation. V.1, Amsterdam: Elsevier
Science Publishers B. V., 423 p.
− Tittman, J. 1986. Geophysical Well Logging, Academic Press Inc., 175p.
− Thomas, J. 2001. Fundamentos de Engenharia de Petróleo, Interciência, Rio de Janeiro,
271 p.
8- PUBLICATIONS
− Carrasquilla, A. & Leite, M. 2009. Fuzzy logic in the simulation of sonic log using as
input combinations of gamma ray- resistivity- porosity and density well logs from
Namorado Oilfield. Proceedings, 11th International Congress of the Brazilian
Geophysical Society, Salvador – BA.
− Carrasquilla, A. & Ribeiro, M. 2009. Calculating the mud drilling invasion through
geophysical well logs in theoretical reservoirs models. Proceedings, 11th International
Congress of the Brazilian Geophysical Society, Salvador – BA.
− Carrasquilla, A. & Deleposte, J. 2009. Lithological differentiation through wavelet
transform and zonation process using geophysical well logs of Namorado Oilfield.
Proceedings, 11th International Congress of the Brazilian Geophysical Society, Salvador
– BA.
− Carrasco, A.; Carrasquilla, A. & Pereira, J. 2009. Avaliação do cimento em poços
revestidos com fibra de vidro com a modelagem numérica da resposta do perfil de
indução. Anais (CD) do XII Encontro de Modelagem Computacional, Instituto Militar
de Engenharia, Rio de Janeiro - RJ.
− Carrasquilla, A. & Deleposte, J. 2010. Using wavelet transform and geophysical well
logs to make lithological differentiation along boreholes of Namorado Oilfield, Campos
32
Basin, Southeast Brazil. Accepted in the Inverse Problems, Design and Optimization
Symposium, João Pessoa, Brazil, August 25-27, 2010.
− Carrasquilla, A. & Deleposte, J. 2010. Stratigraphic differentiation using wavelet
transform and well logs of Namorado Oilfield. Accepted Rio Oil and Gas 2010, Expo
and Conference, Rio de Janeiro, 13-16/September/2010.
− Carrasquilla, A. & Fontes, S. 2010. Integrating geophysical methods in a
hydrogeological pilot study in the Northern Coastal Plain of Rio de Janeiro State –
Brazil. Aceito na Revista Águas Subterrâneas.
− Leite, M.V.; Carrasquilla, A., Silva, J.; Lobo, L.; Curtinhas, R. & Batista, S. 2010.
Aplicação de perfis geofísicos em projetos de perfuração de poços de petróleo no Golfo
de México. Aceito na Revista Brasileira de Geociências.
REFINING
1- INTRODUCTION
The research team of the National Institute of Oil and Gas (INOG) which is dedicated to the
Refining thematic field is composed by chemical engineering researchers with different
backgrounds, such as thermodynamic, process optimization, adsorption, catalytic process
and corrosion. The scientific investigations conducted in INOG focused on technological
problems of the refining of nonconventional fossil fuel sources, involving the following
research projects:
-
Physicochemical characterization of streams of different sources of oil from
properties of liquid mixtures
-
Denitrogenation and desulphurization of shale naphtha
-
Biogas
-
Corrosion in the shale oil processing
In this first year, the activities of the group were dedicated to organize the projects and to
develop some actions to achieve the proposed objectives, as:
33
-
Acquisition of the equipment included in the project planning
-
Assembling and commissioning of the equipments
-
Startup of the research activities that have a previous installed infrastructure
-
Supervision of graduate and undergraduate students involved with the research
projects
-
Prepare scientific papers for scientific congress and international journals
Next, a summary of the main activities and productions carried out in each subproject that
compose the refining thematic field in this period is presented.
2- PHYSICOCHEMICAL CHARACTERIZATION OF STREAMS OF DIFFERENT
SOURCES OF OIL FROM PHYSICOCHEMICAL PROPERTIES OF LIQUID
MIXTURES
Energy demand worldwide is constantly increasing. Nowadays, 90% of global
energy demand is provided by fossil fuels. For the transport sector, fossil fuel demand is
clearly more pronounced, once power consumption is 98% dependent on oil. However,
concern about environmental pollution and global warming have been leading to the need
for less pollutive energy sources and more efficient energy uses (ISENBERG, 1999).
The current oil resources seem to be sufficient to meet demand until 2030.
However, there is a real possibility that global oil production reaches a peak or a plateau in
the relatively near future (KJÄRSTAD; JOHNSSON, 2009). This scenario suggests an
increase in the production of unconventional oil, which can be mixed or not with
conventional fuel oil (KJÄRSTAD; JOHNSSON, 2009). Indeed, the need for increased
production of fuel will put pressure on the production of non-conventional oils. This is
confirmed after a recent study stating that the production of unconventional oil should rise
more than 10% per annum in order to effectively mitigate the decline after the peak of
conventional oil production (CASTRO; MIGUEL; MEDIAVILLA, 2009). Furthermore,
the current mixing of unconventional oils with conventional flows will lead to continuous
changes in the chemical nature of fuel in the future.
34
The processing of oil to produce fuels involves the proposal of innovative processes,
the design of new refining units, and operational optimization of existing ones. To do so,
process simulators are widely used. However, even the most modern simulation techniques
within the most modern simulators can not ensure the best design and the optimum
operational conditions of an industrial unit if the chemical and physical properties of the
simulated streams are calculated improperly. When accurate models are available, the
process engineers can save billions of dollars in investments, projects, construction, and
operating costs of a refinery (RIAZI, 2005).
For these reasons, this line of research is concerned with the continuous change of
physical and chemical properties of fuel that must persist more in the coming decades. The
changes mentioned will affect the modeling and simulation of processes for producing fuel.
Due to the increasing content of non-conventional oils, even the properties of fossil fuels
can be significantly altered.
Despite the importance of the availability of accurate properties of process streams,
it is important to bear in mind that refineries usually process mixtures containing different
type of oil. Each blend per se can generate products with different properties. Furthermore,
the more complex the refining scheme, the greater the number of streams that combine to
produce a final product. This variety of systems leads to a huge number of experiments to
determine all the basic properties of each mixture, mainly when keeping in mind that the
properties of derivatives of non-conventional oils can be significantly different from those
of conventional oils.
The challenge then is accurately calculate the properties of oils and their fractions
using minimal experimental data. By doing this, an experimental routine could be viable
enough to provide a basis for predicting all the data necessary for simulation and process
planning. However, due to the huge number of components in a chain of intermediate and
heavy fuel, the molecular composition assessment is feasible only for light fuels such as
gasoline. Even for gasoline the number of components is too high to be used in
conventional process simulation. To solve the problem of molecularly describing a fuel, the
macroscopic properties of oils and oil fractions are usually described by correlations
between macroscopic properties, especially among those routinely measured such as
35
average boiling point, density, viscosity, flash point, analysis types of oil, etc. Different
approaches can be employed for such purpose, such as those following.
Base-component and Second Order Models
Two approaches are traditionally used in the petroleum industry for predicting
properties of crude oil and its fractions: base-component mixture models, and second order
correlations. In the first case, mixture models calculate properties of a oil mixtures or a oil
fraction mixtures ("blend") using, as input, the properties of the "basic components", ie, oils
or oil fractions which give rise to the final "blend". Then, the quantities and properties of
the basic components are needed. In the second case, the physicochemical properties of a
given oil (or fraction) are calculated from knowledge of other physical and chemical
properties of that oil (or fraction). Therefore, the models for this purpose correlate
physicochemical properties.
In both cases it is not necessary to propose pseudo-components to represent the oil
or fraction thereof. At most in case of PNA characterization (paraffinic, naphthenic, and
aromatic), the fractions of each family of molecules are estimated.
Pseudo-component and Compositional Modeling
Two other approaches for predicting properties of crude fractions employ a
description of the mixture through a restricted number of components that are able to
represent well the properties of the whole. One approach is to mix a number of pseudocomponents, characterized by their physicochemical properties but without the proposition
of molecular structures for them. Thus, in the approach of pseudo-components, the mixture
is characterized by a set of pseudo-components, their compositions and properties such as
temperature and critical pressure, density and viscosity, as in the works of Quann and Jaffe
(1992) and Hu and Zhu (2001). This approach is usually used in the calculation of physical
separations, like distillation, in which the actual composition of the mixture need not to be
known in order to allow an adequate modeling.
36
Another approach, especially used when the composition of families is an important
key to the process, molecular structures are proposed for the components chosen to represent
the mixture as a whole. Medeiros et al. (2002) showed this concept trying to demonstrate the
importance of this approach mainly for processes with chemical reactions.
Research Interests of the Present Line of Project
Aiming to meet the demands presented above, this line of research has as main
focuses experimental obtaining of physicochemical properties to representative systems of
conventional and non-conventional petroleum and petroleum fractions, as well as the
modeling of these properties to contribute to the characterization of oils and fractions. All
the above approaches are of interest to the current line, base-component, second order,
pseudo-components or compositional modeling.
A strategy recently developed by this research group was based on the use of
physicochemical modeling for compositional modeling off petroleum fractions using a semitheoretical model for viscosity of mixtures. In this model, the viscosity of mixtures was
calculated from the viscosity of pseudo-components with explicit composition. The output of
this model provides the carbon content in paraffinic, naphthenic and aromatic structures, molar
mass, beyond the fraction by type of compound. All such information is obtained from the
entry of experimental data of properties traditionally measured in laboratory with good
accuracy, even for medium and heavy fractions: viscosity, viscosity variation with temperature,
density and density variation with temperature (ANDRADE et al., 2007).
The group is in the process of consolidating his experimental infrastructure
concurrently with investments in modeling properties of oil fractions.
References
ANDRADE, B, F., MENEZES, B. C., SAKAI, P. N., MARTINI R. F., PAREDES, M. L. L.,
REIS, R. A., Utilização de viscosidade, densidade e o unifac-visco para a
caracterização de frações de petróleo. Anais do 4o PDPETRO, Campinas, 2007.
CASTRO, C.; MIGUEL, L. J.; MEDIAVILLA, M. Energy Policy 2009, 37 1825-1833.
37
HU, S.; ZHU, F.X.X. Applied Thermal Engineering 2001, 21, 1331-1348.
ISENBERG, G. J. Pow. Sourc. 1999, 84 214-217.
KJÄRSTAD, J.; JOHNSSON, F. Energy Policy 2009, 37 441-464.
QUANN, R.J.; JAFFE, S.B. Industrial and Engineering Chemistry Research 1992, 31(11),
2483-2497.
RIAZI, M. R. Characterization and Properties of Petroleum Fractions, first ed., ASTM
international: West Conshohocken, 2005.
MEDEIROS, J.L.; ARAUJO, O.; SILVA, R.M.C.F. A compositional framework for feed
characterization applied in the modeling of diesel hydrotreating processes. In: 17th World
Petroleum Congress, 2002, Rio de Janeiro. Proceedings of the 17th World Petroleum
Congress, Rio de Janeiro: London Institute of Petroleum, 2002. v. 3, p. 419-424.
Team
Professors: Márcio L. L. Paredes; Rodrigo A. Reis; André L. H. Costa
Students: Rejane G. Gama; Luciana L. P. R. Andrade; Amanda A. Silva; Rafael N. G.
Santos; Giselle J. Santos; Carla F. Martins; Hugo Carneiro Neto; Caroline P. M. Morais
Technical-scientific results
∗
Papers in Journals
1. BEZERRA, Elizabeth S.; SANTOS, Joana M.T.; PAREDES, Márcio L.L., A new
predictive model for liquid/air surface tension of mixtures: Hydrocarbon mixtures, Fluid
Phase Equilibria, v. 288, p. 55-62, 2010.
2. SILVA, Amanda A.; REIS, Rodrigo A.; PAREDES, Márcio Luis Lyra, Density and
Viscosity of Decalin, Cyclohexane, and Toluene Binary Mixtures at (283.15, 293.15,
303.15, 313.15, and 323.15) K, Journal of Chemical and Engineering Data, v. 54, p. 20672072, 2009.
3. ANDRADE, Luciana L P R; PAREDES, Márcio Luis Lyra ; RAJAGOPAL,
Krishnaswamy,
High-Pressure
Viscosity
Measurements
for
the
Binary
System
38
Cyclohexane + n-Hexadecane in the temperature range of (318.15 to 413.15) K, Journal of
Chemical and Engineering Data, in press, 2009.
∗
Papers in Congress
1. LOPREATO, L G ; SICCHIERI, T B ; FARAH, Marco. A. ; PAREDES, Márcio Luis
Lyra, Evaluation of Prediction Methods for Critical Properties and Molecular Weight of
Hydrocarbons and Petroleum Fractions, Proceedings of the VIII Iberoamerican Conference
on Phase Equilibria and Fluid Properties for Process Design, Praia da Rocha, 2009.
2. MORAIS, C. P. M.; REIS, Rodrigo Azevedo ; PAREDES, Márcio Luis Lyra, TPT1
approach for estimation of heavy HC critical properties from light solvent + heavy HC
bubble point data, Proceedings of the VIII Iberoamerican Conference on Phase Equilibria
and Fluid Properties for Process Design, Praia da Rocha, 2009.
3. GAMA, R G; DIAS, J; TORRES, A R.; REIS, R A; PLATT, G M; PAREDES, M L ;
XAVIER, G M, Evaluation of Correlations for Fuel Oil and Diesel Properties, Proceedings
of the VIII Iberoamerican Conference on Phase Equilibria and Fluid Properties for Process
Design, Praia da Rocha, 2009.
4. ANDRADE, L L P R ; PAREDES, Márcio Luis Lyra ; RAJAGOPAL, Krishnaswamy,
Estimation of viscosity of blends at high pressure using mixing rules, Proceedings of the
VIII Iberoamerican Conference on Phase Equilibria and Fluid Properties for Process
Design, Praia da Rocha, 2009.
5. AMORIM, J A; CHIAVONE-FILHO, O; PAREDES, M L L; RAJAGOPAL, K.,
Evaluation of Characterization Factors of Petroleum Fractions by a Paraffin-Naphthenic
Synthetic Mixture, Proceedings of the 5th Brazilian Congress on Research and
Development in Petroleum and Gas, Fortaleza, 2009.
39
6. AIMOLI, C G; SCHIAVOLIN, M; PAREDES, Márcio Luis Lyra, Impacts of Terminal
Waste Processing on the Estimation of Production of Diesel Oil by Atmospheric
Distillation, Proceedings of the 5th Brazilian Congress on Research and Development in
Petroleum and Gas, Fortaleza, 2009.
7. CREMONEZI, A O ; SCHIAVOLIN, M ; PAREDES, Márcio Luis Lyra, Evaluation of a
Predictive Method for Acidity of Petroleum and Derivatives, Proceedings of the 5th
Brazilian Congress on Research and Development in Petroleum and Gas, Fortaleza, 2009.
∗
Dissertations in Development
1. Student: Rejane Gomes Gama.
Advisors: Márcio Paredes and Rodrigo Reis.
Title:Evaluation of Correlations for Predicting the Properties of Petroleum Products.
Course: Master in Chemical Engineering - Rio de Janeiro State University.
Probable concluding date: June/2010.
2. Student: Luciana Loureiro de Pinho Rolemberg Andrade.
Advisors: Márcio L.L. Paredes and Krishnaswamy Rajagopal
Title: Experimental Measurement and Modeling of High Pressure Viscosity of
Asymmetric Hydrocarbon Mixtures.
Course: Master in Chemical Engineering - Rio de Janeiro State University.
Probable concluding date: June/2010.
∗
Monograph Concluded
1. Students: Carlos Mendes, Laslo Boros, Luiz Lopreato and Thiago Sicchiero.
Advisor: Márcio Luis Lyra Paredes
Title: Evaluation of Methods for Prediction of Thermodynamic Properties of
Hydrocarbons.
40
Course: Lato sensu post-graduation course - Specialization in Petroleum Processing
Engineer - Rio de Janeiro State University
3- DENITROGENATION AND DESULPHURIZATION OF SHALE NAPHTHA
The removal of nitrogen- and sulfur-containing compounds from light gas oil and
heavy catalytic naphtha in refinery streams has received special attention in last years but
almost nothing is dedicated to non-conventional oil streams.
Therefore, the objective of this project is to use adsorbents to selectively remove the
sulfur and/or nitrogen compounds in liquid hydrocarbon fuels of conventional and nonconventional origin. This is one of the promising approaches for producing ultra clean fuels
able to reach the most stringent fuel specifications. Additionally, it is an important
alternative related to fuel cell applications.
In this context, the research of this topic in INOG has concentrated efforts in the
selection and purchase of the laboratory equipment that will be employed in the planned
experiments.
In parallel, there were contacts with Petrobras aiming to establish a partnership
involving the proposed research. It is important to mention that Brazil has large resources
of shale oil and Petrobras has facilities in São Mateus do Sul (PR) which were dedicated for
processing this raw material.
The team is formed by:
-
Professors: Marco Antonio Gaya de Figueiredo
-
Students: Gisele Vanzan Estrela e Wallace Carvalho de Souza
4- BIOGAS
The transformation of biogas in an alternative raw material for generation of basic
petrochemicals is the aim of the Biogas Project. It is divided in three subprojects:
-
Biogas purification
41
-
Methanol production from biogas
-
Olefins production from methanol
The team is formed by:
-
Professors: André Luiz Hemerly Costa, Cristiane Assumpção Henriques, Fátima
Maria Zanon Zotin
-
Student: Flávia F. Almaraz
The next paragraphs present an overview of the advance of the research activities in
each subproject:
Biogas purification:
This subproject was approached through the development of a mathematical model
able to describe the behavior of an adsorption unit. The unit is composed by two columns that
operate in a cyclic pattern: at each instant, one of the columns is adsorbing biogas impurities
and the other is being regenerated (desorption). The mathematical model is composed of a
system of partial differential equations of mass and energy balances.
In the current stage of the work, the focus is directed to implement a computational
algorithm for simulating the adsorption unit, employing a first proposal for the
mathematical model.
Unfortunately, the postdoctoral position that is planned in the INOG budget to work
in this subproject is still open, because we could not find an adequate candidate. Since this
problem can delay the advance of the research, we are going to intensify the efforts to
identify a good collaborator.
Methanol production from biogas:
The work on this subproject was based on the activities of an engineer that was
hired according to the INOG budget. This professional organized a set of computational
routines for simulation of the methanol synthesis loop. The intention is to integrate the
routines of the synthesis loop with computational codes able to simulate steam reforming
and/or autothermal reforming units. However, this engineer left INOG last month because
42
she was approved in a public selection for a Brazilian university. At this moment, we are
trying to find another professional to continue the work.
Olefins production from methanol
The worldwide demand for basic raw materials for petrochemical industries as
ethylene and propylene has been growing. There are several processes for olefin
production, and Methanol to Olefin (MTO) is one of them. This process can convert
methanol to ethylene and propylene at about 75–80% carbon selectivity. In this subproject,
the focus is to develop new catalysts and optimize the experimental conditions to obtain
higher activity and olefins selectivity.
In this first year, the main activity was focused on the selection and importation of a
high pressure reactor for studying the pressure effect in olefins production from methanol.
In parallel, the olefin production at atmospheric pressure was studied changing some
reactional parameters.
During the period from the start of the INOG activities until the present moment, 3
full papers at conferences were published, 1 lato sensu monograph in a post-graduation
course was concluded and 2 dissertations are in development, all regarding the Biogas
research project.
These results are summarized below.
Technical-scientific results
∗
Papers in Congress
2. SOUSA, Zilacleide S. B., SOUZA, Bianca F., SENA, Fagner C., FERNENDES,
Lindoval D. ZOTIN, HENRIQUES, Cristiane A., Light olefins production from methanol
over SAPO-34 and MeAPSO-34 molecular sieves, accepted for presentation at 16th
International Zeolite Conference, Sorrento, Italy, July 4 -9, 2010.
3. ALMARAZ, Flavia F., SOUSA, Z. S. B., ZOTIN, F.M.Z., HENRIQUES, Cristiane A.,
Conversão do metanol em olefinas catalisada por zeólitas com com diferentes
43
características ácidas e estruturais, accepted for presentation at 18th Brazilian Congress of
Chemical Engineering, Foz do Iguaçu, Brazil, September 19-22, 2010.
∗
Dissertations in Development
1. Student: Flavia de Figueiredo Almaraz.
Advisors: Cristiane Assumpção Henriques e Fátima Maria Zanon Zotin
Title: Conversion of methanol to light olefins catalyzed by zeolites with different
structural properties
Course: Master in Chemical Engineering - Rio de Janeiro State University.
Probable concluding date: July/2010.
2. Student: Tâmara Nascimento
Advisors: Cristiane Assumpção Henriques e Fátima Maria Zanon Zotin
Title: Linear parafins hydromerization: the influence of the textural properties of the
support
Course: Master in Chemical Engineering - Rio de Janeiro State University.
Probable concluding date: July/2010.
5- CORROSION IN THE SHALE OIL PROCESSING
Corrosion problems are always present in the production and processing of shale
derivatives due to the aggressive medium and to the high temperatures used. As a
consequence, expressive values are usually spent on maintenance and shutdowns for
repairs. This project intends to study intends to study the corrosion processes developed in
shale processing medium, based in the following subprojects:
-
Corrosion of stainless steel AISI 304 in simulated shale processing medium;
-
Corrosion of mild steel AISI 1020 in H2S contaminated water;
-
Naphthenic acid corrosion.
The team is formed by:
44
-
Professors: Dalva Cristina Baptista do Lago, Lilian Ferreira de Senna.
-
Technicians: Camilla Pinheiro and Antônio Vitor de Castro
-
Students: Márcio Franklin de Oliveira.
The next paragraphs present an overview of the advance of the research activities in
each subproject:
In this first year, the main activity was to evaluate the effects of the operational
conditions (temperature, sulfur content and kind of sulfur source) in the corrosion process
of steel in both simulated shale processing medium and contaminated water. The initial
results indicated that the temperature and the sulfur source (organic sulfur) had a great
influence on the corrosion processes.
During the period from the start of the INOG activities until the present, 1 full paper
at conference was published and another one is accept for presentation. In addition, 1
dissertation is in development, regarding the present research project.
These results are summarized below.
Technical-scientific results
∗
Papers in congress
1. OLIVEIRA, Márcio F., do LAGO, Dalva C. B., SENNA, Lilian F.. Estudos de corrosão
em sistema simulado de retortagem de xisto. Accept for presentation at the 19th Brazilian
Congress of Material Science and Engineering, Campos do Jordão, Brazil, November 2125, 2010.
∗
Dissertations in Development
1. Student: Márcio Franklin de Oliveira.
Advisors: Dalva Cristina Baptista do Lago e Lílian Ferreira de Senna
Title: Corrosion of stainless steel AISI 304 in simulated shale processing medium.
Course: Master in Chemical Engineering - Rio de Janeiro State University.
45
Probable concluding date: June/2010.
ENVIRONMENT
1- INTRODUCTION:
The environmental impacts associated with the activities of the oil industry are still
relatively poorly known. This stems, in part, by the large number of compounds with
distinct environmental toxicity and persistence, making it difficult to establish relationships
of cause and effect. Moreover, the diversity of the oil industry resulting in multiple sources
of contaminants present in liquid effluents, gaseous emissions and solid waste. Finally, the
systems of exploitation and production are challenges towards the use of cleaner
technology and minimization of environmental impacts. In the particular case of nonconventional deposits, all of these issues have more relevance, because of the lack of
information on the composition of oil and gas produced and the emissions generated by the
production chain.
The projects within the theme of INOG 4 (methodology and environmental assessment)
seek to develop and disseminate scientific and technological research to allow the proposal
of measures for effective assessment and environmental monitoring, remediation of
contaminated areas and effluent treatment and waste with focus on unconventional
resources, such as the bituminous shales and biogas from landfills. The knowledge
generated will be disseminated through the strengthening of existing monitoring networks
and creating a network of technologies for remediation of contaminated sites, as well as the
training of highly qualified human resources for professional work in related areas.
At first, the INOG-Environment will focus on two lines of research, considering the
expertise of the group, but other topics will be discussed along with the development of
other areas of the project (exploration, production and refining).
Line 1: Assessment and Monitoring.
Line 2: Development of technologies for remediation of contaminated areas and effluent
46
treatment and waste.
The two lines of research are focused to provide the common scientific and technology
development for the domestic industry of oil and gas can act with low impact, with
adequate level of safety and to ensure the maintenance of environmental integrity of areas
and regions of operation , aiming to provide solutions to problems that arise with the
exploration / production / refining of non-conventional deposits. Within the broader
concept of technological innovation, it also intends to promote actions disseminate
technologies with cleaner and more efficient removal of regulatory barriers.
The first line aims to characterize the origin and influence of natural factors and human
activities on the distribution of aliphatic and aromatic hydrocarbons in different
compartments (water, sediment, vegetation and biota) through the implementation and
optimization of methods for molecular and isotopic determination of these compounds as
well as the monitoring of greenhouse gases in the atmosphere, allowing reduction of GHG
emissions (Clean Development Mechanism - CDM) with the aim of carbon credits. By
INOG, you can consolidate a group of highly qualified to propose methodologies for
evaluating the environmental impacts that will arise with the exploitation of unconventional
reservoirs, particularly in aquatic environments and atmosphere.
The second line aims to develop and deliver technologies, protocols and procedures based
on chemical processes and systems, physical-chemical and biological remediation of
contaminated areas of supply chain activities for oil and gas, including exploration,
processing, transport and storage of oil from unconventional deposits, as well as
technologies for the treatment of emissions, effluents and waste derived from such
activities. In this sense, the projects developed in this line of research will have direct
relationship with the other themes developed by INOG, especially in the areas of
bituminous shales and biogas.
In the area of Environment, the two lines coalesce research projects:
3-
47
4-LINE 1: Assessment and environmental monitoring related to exploration,
production and consumption of petroleum hydrocarbons.
In this line of research will be worked two themes: the origin and distribution of
hydrocarbons in aquatic systems and monitoring of air emissions.
Projects that will initially be studied in this line are:
Project 1.1. Characterization of sources and fate of hydrocarbons in aquatic systems in
coastal and oceanic areas.
Project 1.2. Optimization methodology for determining the isotopic composition of
aliphatic hydrocarbons in sediments and mangrove leaves.
Project 1.3. Monitoring of hydrocarbons in mussels.
Project 1.4. Composition of biogenic hydrocarbons in leaves of mangrove.
Project 1.5. Evaluation of emissions of greenhouse gases.
Project 1.6. Development of clean development mechanisms (CDM) in landfills, in order
to produce biogas.
5-LINE 2: Technologies for remediation of soil and effluent treatment solids,
liquids and gases generated during the production process of oil and gas from
unconventional deposits with emphasis on heavy oil
Initially, we detailed the following projects:
Project 2.1 New Technologies for the Removal of Heavy Oil Wastewater:
Project 2.2 Design of Chemical Remediation, Bioremediation and Phytoremediation of
Contaminated Soil
The projects are developed in four laboratories UERJ, namely: Laboratory School of
Oceanography; Instrumental Characterization Laboratory of the Institute of Chemistry
(photos 1 and 2); Laboratory & phytotechnologies and Bioremediation and Laboratory of
Environmental Technology.
48
Photo 1: Instrumental Characterization Laboratory of the Institute of Chemistry
Photo 2: Instrumental Characterization Laboratory of the Institute of Chemistry
Production Science Technology of the Period 2009-2010
1. ANDRADE, Alexandre Cerqueira, RUSSO, Carlos Marques, MRC. Application of
technique using current eletrofloculação alternated in treatment of water production from
oil industry. Regular Tchê Chemistry (print). , v.7, p.33 - 45, 2010.
2. PEREIRA, Carolina Acioli, Pérez, Daniel Vidal, Marques, MRC. Evaluation of the
potential of pseudo-fenton processes for remediation of soils contaminated by diesel. New
chemistry (Print). , V.32, p.2200 - 2202, 2009.
49
3. Cerqueira, A., Russo, C., Marques, MRC. Electroflocculation for textile wastewater
treatment. Brazilian Journal of Chemical Engineering (Print). , V.26, p.659 - 668, 2009.
4. CERQUEIRA, Alexandre Andrade, Marques, MRC, RUSSO, Carlos Andrade, TAG the
process of water management of production: historical, environmental policies and
alternative technology. UNIARA magazine. , V.12, p.21 - 36, 2009.
5. Teixeira, MCS, de Aguiar, MRMP, Shin, MC, ZIOLLI, RL, Perez, DV. Study of Pyrene
Adsorption on Brazilian Soils. Revista de Chimie (Bucuresti). , V.60, p.583 - 587, 2009.
6. PÉREZ, DV; MARQUES, M. ; AGUIAR, CRC. Remediation of contaminated areas in
Brazil: Reflections on the challenges of Soil Science. Newsletter (Brazilian Society of
Soil Science), v. 34, p. 16-19, 2009.
7. THUNDER, RH; CAREER, RS. Aliphatic hydrocarbons in surface sediments of the bay
of Flamengo, the Guanabara Bay / RJ. Geochimica Brasiliensis, v. 23, p. 193-202, 2009.
8. CAREER, RS RIBEIRO, Patricia Valley; Silva, CEM; FARIAS, CO. Hydrocarbons and
sterols as indicators of sources and fate of organic matter in sediments from Sepetiba Bay,
Rio de Janeiro. New chemistry (Print), v. 32, p. 1805-1811, 2009.
9. Kalas, Francine A. ; Career, Renato S. ; Macko, Stephen A. ; R. Wagener, Angela L.
Molecular and isotopic characterization of the particulate organic matter from an
eutrophic coastal bay in SE Brazil. Continental Shelf Research, v. 29, p. 2293-2302, 2009
Guidelines Masters completed
1. André de Souza Blond. Remediation of soils and groundwater at gas stations via the
Fenton process: a case study. 2010. Thesis (Chemistry) - Chemistry Institute (UERJ)
2. Carlos Eduardo Soares Canejo Pinheiro da Cunha. Hazardous Waste Management in
50
Petroleum Refineries. 2009. Dissertation (Masters in Environmental Engineering) University of Rio de Janeiro.
3. Andressa Moreira de Souza. Phytoremediation of soils contaminated with used
lubricating oils. 2009. Dissertation (Master in Chemistry) - University of Rio de Janeiro
4. Michelle Araújo Passos. Study on the evolution of natural and anthropogenic inputs of
organic matter for sediments of a tropical lagoon-estuarine system (Mundaú-Manguaba,
Alagoas) using lipids as molecular markers. 2010. Dissertation (Master in Oceanography) State University of Rio de Janeiro.
5. Talitha Lopes Ferreira da Costa. Origin and composition of particulate organic matter in
the estuarine-lagoon complex Mundaú-Manguaba using lipids as molecular markers. 2010.
Dissertation (Master in Oceanography) - State University of Rio de Janeiro.
6. Jorgina Rosete Teixeira. Impact of the Morro do Céu landfill into the atmosphere. 2009.
0 f. Dissertation (Master of Masters in Chemistry) - University of Rio de Janeiro.
Guidelines Masters underway
1. Takubunji Nakamura. Remediation of contaminated soils. 2010. Thesis (Chemistry) Chemistry Institute (UERJ)
2. Rafael de Paula Couto Schirmer. Removal and determination of ammonia in manure
samples. 2009. Thesis (Chemistry) - Chemistry Institute (UERJ)
3. Amanda Araújo de France. Optimization of physical, chemical and biological parameters
operating in ex situ bioremediation of soils contaminated by petroleum hydrocarbons.
Home: 2010. Dissertation (Masters in Environmental Engineering) - University of Rio de
Janeiro
4. Clooer Costa de Oliveira. Evaluation of schist as adsorbent of organic and inorganic
51
pollutants present in wastewaters produced in the petroleum industry. Home: 2010.
Dissertation (Masters in Environmental Engineering) - University of Rio de Janeiro.
5. Graciane Silva. Bioremediation of soils contaminated by lubricating oil used in jet pilot:
abiotic processes, natural attenuation, biostimulation and bioaugmentation. Home: 2009.
Dissertation (MSc in Chemical Engineering) - University of Rio de Janeiro.
6. Roberta Carvalho Ciannelli. Microbiological aspects of bioremediation of soils
contaminated with oil fumes. Home: 2008. Dissertation (Master in Chemistry) - University
of Rio de Janeiro.
7. Maria de Fatima Barbosa Almeida. Bioremediation of polycyclic aromatic compounds in
soil contaminated with oil fumes. Home: 2008. Dissertation (Master in Chemistry) University of Rio de Janeiro.
8. Dulce Raquel P. Oliveira. Origin and composition of organic matter along the continental
shelf in the region of Cabo Frio. Home: 2009. Thesis (M.Sc. Graduate Program in
Oceanography) - State University of Rio de Janeiro,
Doctoral theses in progress
1. Teixeira Silvio César Godinho. Study of adsorption of PAHs in Brazilian soils. 2009.
Thesis (Chemistry) - Chemistry Institute (UERJ)
2. Jackeline Bahé. Recovery of ammonia from manure. 2009. Thesis (Environment) University of Rio de Janeiro
3. Felix Maria Luiza Marques Kede. Use of phosphates in soils associated with
phytoremediation of Santo Amaro (Ba) contaminated by toxic metals. Home: 2010. Thesis
(Ph.D. in Environment) - University of Rio de Janeiro.
4. Jorge Antonio Lopes. Operating Parameters of Biopilhas A System for the Treatment of
52
Soils Contaminated with Petroleum Hydrocarbons. Home: 2008. Thesis (Ph.D. in
Environment) - University of Rio de Janeiro.
5. Christiane Rose Chafim Aguiar. Phytoremediation of soils contaminated with petroleum
and its derivatives: an emphasis on rhizosphere processes and plant metabolism. Home:
2007. Thesis (Ph.D. in Environment) - University of Rio de Janeiro.
6. Pedro Paulo de Oliveira Pinheiro. Assessment of contamination of marine sediments by
oil from the petroleum activities and discarding / accidents for vessels in major port regions
of the southeastern Brazilian coast. Home: 2009. Thesis (Ph.D. in Environment) University of Rio de Janeiro.
7. Livia Gebara Muraro Serrate Lamb. Origin and composition of organic matter on a
regional scale in the Campos Basin using lipid markers as a study tool. Home: 2009. Thesis
(Ph.D. in Environment) - University of Rio de Janeiro.
8. Marcio Goncalves Franco. Impacts on the atmosphere from the soil bioremediation
process. Home: 2009. Thesis (Ph.D. doctoral program on the Environment) - University of
Rio de Janeiro.
REGULATION
1. GROUP MEMBERS
Coordinator: Prof. Marilda Rosado de Sá Ribeiro
Research Team:
− Clarissa Brandão de Carvalho
− Flávia Limmer
53
− Luizella Branco
− Marcos Martins
2. DIFUSION ACTIVITIES: CONGRESS, EVENTS, SEMINARIES
9 10 years Commemorative exposition of ANP/FINEP-MCT (PRH) Human
Resources Program, made by Law and Geology Universities, in past October 14 to
16 of 2009 on UERJ, with exposition of panels about the developed works through
the convention length and the realization of “Challenges to exploration & Oil
production in Pré-Sal areas and others Sedimentary Basins” lecture, made by Prof.
Marilda Rosado.
9 Workshop about E&P contract models, performed in June 21 to 24, on JW Marriott
Hotel with the AIPN members (Association of International Petroleum
Negotiators).
9 Oil Law Seminary, performed in Vitória-ES on November 20 of 2009, with
“Explorations Contracts – inclinations and challenges” lecture, made by Marilda
Rosado.
9 II International Laws Seminary UERJ-UFRJ, performed on June 08 and 09, with
realization of “International Commerce and the Oil Industry” lecture, made by
Clarissa Brandão, in 08-06-2009 and “International Commerce and the Oil
Industry” lecture, made by Marilda Rosado, in 09-06-09, on Law Federal University
- UFRJ.
9 “Environmental aspects of E&P industry of oil & gas offshore” lecture, performed
in 27-04-09, 2a.f, in 10:00AM, with presence of Edimilson Maturana, Oil & Gas
License Coordinator of IBAMA/CGPEG, Prof. Maurício Motta, Professor in PRH33 and PHD Luiz Gustavo Bezerra, Lawyer, specialist in Environmental Law and
ex-exhibitioner at PRH-33.
9 Participation at 5° Brazilian Congress of R&D in Oil and Gas, carried out by
ABPG – Brazilian Association of Oil and Gas, in period of October 18 to 22, 2009,
in Fortaleza – CE, with presentation “Unitization and Challenges”, by Prof. Marilda
Rosado.
54
9 Lecture “Accumulation of pré-sal: facts and risks to foment the juridical debate”,
with presence of André A. Bender, Jorge Pedroso and Clarissa Brandão, carried out
in April 16, 2009, at UERJ Law Academy.
9 Seminar “Challenges of the Exploration and Production of Oil in the areas of PréSal and others Sedimentary Basin”, carried out in October 16, 2009, 09h00 to
12h00, at UERJ Law Academy, carried out in cooperation with LENEP/UENF,
participation of Professors Vitor Hugo and Ana Catarina Medeiros in October 16,
2009, carried out in UERJ Law Academy.
9 Speech of Post-Graduation in International Law, carried out at December 10, 2009,
in UERJ Law Academy.
9 Lecture about the New Regulatory Mark of Pré-Sal, in Macaé, with cooperation of
PRH 20 (LENEP/UENF), at September 1º, 2009.
9 Participation in public audience of Oil Exploration in Pré-Sal. Panel 1: Regime de
Partilha. 2009. (Seminar).
9 Seminar: International Law and Geopolitics of Oil - Escola de Guerra Naval.
Distribution of power, juridic determinants and brazilian perspectives. 2009.
(Seminar).
9 Workshop of Oil of UNICAMPI. Round Table: Regulatory Mark of Oil. 2009.
9 Law Forum in Oil Exploration: Analysis of Legal Aspects and Impacts of
Regulatory Affairs in the New Exploration and Production Oil. Joint venture in oil
and gas industry: legal aspects of business partnerships. 2009. (Another).
9 The new legislation on pre salt - UFRN.A new legislation on the presalt. 2009. (Another).
9 Petroleum and Natural Gas Contracts - IBDE. Contract granting the
NPA. 2009.(Another).
Publications
Books
− ROSADO, Marilda (org). New Directions for the Law of Petroleum. Rio de
Janeiro: Renovar, 2009.
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Chapter Books
− ALVES, Clarissa Brandão. Lex Petrolea: Private international law in the Oil
Industry. In: ROSADO, Marilda (org). New Directions for the Law of
Petroleum. Rio de Janeiro: Renovar, 2009.
− ALVES, Clarissa Brandão. Joint Ventures International Oil Industry. In:
FERREIRA JUNIOR, Lier Pires; WAR, Sidney. (Org.). International environmental
law and oil. Rio de Janeiro: Lumen Juris, 2009, v. 1, p. 139-156.
− ROSADO, Marilda. Environmental Aspects of the Petroleum Industry. In:
FERREIRA JUNIOR, Lier Pires; WAR, Sidney. (Org.). International environmental
law and oil. Rio de Janeiro: Lumen Juris, 2009, v. 1, p. 139-156.
3. PRODUCTS DEVELOPED
Theses concluded
Amalia Del Carmen Casas Corral. The energy integration in South America: legal
and institutional instruments for regional gas field projects. Thesis (Doctorate in
Law) - University of Rio de Janeiro. (Advisor: Marilda Rosado).
Doctoral Theses in progress
Luizella Giardino Barbosa Branco. Biofuels and Mercosur. Prospects for the creation
of an Integrated Energy Policy in the Block. Home: 2007. Thesis (Doctorate in Law)
- University of Rio de Janeiro. (Advisor: Marilda Rosado).
Master degree Dissertation in progress
- Juliana Cardoso de Lima. “International Law of Investments and the oil industry
regulatory risks”. Dissertation (Law master degree) - Rio de Janeiro State University.
(Counselor: Marilda Rosado).
- Marcos José Martins Mendes. The International Investment Law and the area of
Biofuels. (Counselor: Marilda Rosado)