Lucas - SIMULATION OF THE PHYSICAL PROPERTIES OF BRAZILIAN PRE-SALT BRINES PDF

SIMULATION OF THE PHYSICOCHEMICAL PROPERTIES
OF BRAZILIAN PRE-SALT BRINES
Lucas Cruz
Projeto de Graduação apresentado ao Curso de
Engenharia de Petróleo da Escola Politécnica,
Universidade Federal do Rio de Janeiro, como
parte dos requisitos necessários à obtenção do
título de Engenheiro.
Orientadores: Santiago Gabriel Drexler e Paulo
Couto.
Rio de Janeiro
Junho de 2019
Lucas Cruz
PROJETO DE GRADUAÇÃO SUBMETIDO AO CORPO DOCENTE DO CURSO DE
ENGENHARIA DE PETRÓLEO DA ESCOLA POLITÉCNICA DA UNIVERSIDADE
FEDERAL DO RIO DE JANEIRO COMO PARTE DOS REQUISITOS
NECESSÁRIOS PARA A OBTENÇÃO DO GRAU DE ENGENHEIRO DE
PETRÓLEO.
Examinado por:
_________________________________________
Prof. Santiago Gabriel Drexler, D.Sc.
_________________________________________
Prof. Paulo Couto, D.Eng.
_________________________________________
Prof. Rafael Mengotti Charin , Ph.D.
_________________________________________
Prof. Paulo Goldfeld, Ph.D.
RIO DE JANEIRO, RJ - BRASIL
JUNHO DE 2019
Cruz, Lucas
Simulation of the Physicochemical Properties
of Brazilian Pre-Salt Brines / Lucas Cruz. – Rio de
Janeiro: UFRJ/ Escola Politécnica, 2019.
XVI, 55 p.: il.; 29,7 cm.
Orientadores: Santiago Gabriel Drexler e Paulo
Couto.
Projeto de Graduação – UFRJ/ Escola
Politécnica/ Curso de Engenharia de Petróleo, 2019.
Referências Bibliográficas: p. 36-38.
1. Introduction. 2. Literature Review. 3.
Research Methodology. 4. Results. 5. Conclusion. I.
Drexler, Santiago Gabriel e Couto, Paulo. II.
Universidade Federal do Rio de Janeiro, Escola
Politécnica, Curso de Engenharia de Petróleo. III.
SIMULATION OF THE PHYSICOCHEMICAL
PROPERTIES OF BRAZILIAN PRE-SALT
BRINES.
iii
Dedico este trabalho a toda minha
família, em especial, meus amados pais,
Sidney Cruz e Célia Pereira Cruz, e aos
meus queridíssimos irmãos, Alexandre
Cruz e Matheus Cruz. Sem vocês, este
trabalho e outros sonhos nunca se
concretizariam.
iv
AGRADECIMENTOS
Primeiramente, gostaria de agradecer a minha amada família. Meus queridos pais
que moveram montanhas e não mediram esforços para que eu chegasse onde estou, e me
deram a mais incrível evidência em todo esse tempo de seu doce amor. Meus avós, que
me deram apoio e suporte ao longo de todo esse tempo apesar da distância e sempre me
fizeram sentir especial aos seus olhos. Meus irmãos Alexandre, meu modelo a seguir por
toda minha infância, que inúmeras vezes veio ao meu socorro em momentos de
necessidade, permitindo que as experiências mais incríveis da minha vida, que
contribuíram grandemente na formação de meu caráter, se concretizassem, a isso serei
eternamente grato; e Matheus (Duduba), que me motiva como ninguém uma pessoa
melhor ao buscar em mim, muitas vezes o caminho a seguir, o carinho e afeição que tenho
por você são inexplicáveis.
Meus professores Paulo Goldfeld e Flávio Dickstein, e amigo Renan Pinto que
num momento tão frágil me deram um voto de confiança, me acolheram e deram uma
oportunidade enriquecedora no Laboratório de Matemática Aplicada ao Petróleo
(LabMAPetro) a despeito de minha inexperiência, sendo sempre muito pacientes comigo,
tirando minhas dúvidas por mais simples que fossem (o Renan especialmente) e
permitindo que eu priorizasse meus estudos, serei sempre grato pelo que fizeram por mim,
vocês são pessoas incríveis.
Meu professor orientador Paulo Couto, que teve papel fundamental na minha
formação profissional sendo um verdadeiro orientador em todos os sentidos da palavra,
estando a frente de muitas de minhas lutas, apesar de todas as muitíssimas ocupações que
o cercavam. Nunca poderei retribuir tudo o que o senhor fez por mim, nesses anos como
v
professor, coordenador e orientador, fico inteiramente grato pela confiança e mentoria a
mim dados.
Meu orientador Santiago Gabriel Drexler, que me orientou em cada etapa na
produção deste trabalho, e tomou tempo para me mostrar o caminho a seguir e o que
refazer apesar de tantas outras atividades que o rodeavam, fico agradecido por tudo que
fez. Também toda a equipe do LRAP, e seus patrocinadores, por permitirem esse trabalho.
Meus professores Rosemarie Bröker Bone, Rafael Charin que prontamente me
ajudaram no momento de maior necessidade de minha vida acadêmica, a despeito das
possíveis consequências envolvidas. Essa conquista não seria possível sem vocês.
Meus colegas de trabalho da Norwegian Research Centre AS (NORCE AS), Ying
Guo, que foi uma verdadeira mãe para mim durante meu intercâmbio acadêmico, fazendo
questão de cuidar de mim em tudo que lhe era possível, me dando o de vestir, comer, se
preocupando com os menores detalhes, e garantindo que minhas experiências pessoal,
acadêmica e profissional também fossem as melhores possíveis; Ingebret Fjord, que fora
um excelente professor e colega de trabalho, Widuramina Sameendraneth que com muito
carinho organizou uma festa de despedida para mim, e proporcionou diversas aventuras
nos laboratórios da NORCE AS, muito do que lá aprendi, devo a você e Erzuah Samuel
que fez esses dias de trabalho muito mais divertidos com seu espírito alegre e inabalável.
Agradeço também aos meus queridos amigos que fizeram essa longa caminhada
mais alegre, Mariana Carranza, Rodrigo Alves Rangel, Milos Herceg Tilb Akes Tående
Blitzkrieg (meus irmãos de outra mãe), Gustavo Medeiros, Thayna Gonçálves, Matheus
Gonzaga, Marco Túlio, Adilson Vieira, John Anderson, amigo mais estranho que já tive
e por isso um dos meus favoritos, Mussa Banjai, Aleksej Fjodorov, Hassan Altmimi,
Halvor Berntsen Fabian Garbog, Raoul Nilsen, Ragib Nilsen, Gustavo Maia, Gilberto
Cervantes e todos os demais que fizeram parte dessa jornada.
vi
Resumo do Projeto de Graduação apresentado à Escola Politécnica/ UFRJ como parte dos
requisitos necessários para a obtenção do grau de Engenheiro de Petróleo.
SIMULAÇÃO DE PROPRIEDADES FÍSICO-QUÍMICAS DE
SALMOURAS DO PRÉ-SAL BRASILEIRO
Lucas Cruz
Junho, 2019
Orientadores: Santiago Gabriel Drexler e Paulo Couto.
Curso: Engenharia de Petróleo
Este trabalho apresenta um método computacional, baseado no software OLI Studio, para
obtenção de propriedades físico-químicas de salmouras saturadas de CO2, sendo essas
propriedades a saturação de CO2, sua densidade e seu pH, e os resultados de sua aplicação
em salmouras do Pré-sal brasileiro saturadas de CO2. A validação do método é feita por
meio da reprodução de resultados da literatura considerando sistemas similares, porém
mais simples do que as salmouras complexas estudadas. Os resultados obtidos no estudo
destas salmouras foram consistentes, qualitativamente, com os dados da literatura.
Palavras-chave: salmouras do Pré-sal brasileiro, propriedades físico-químicas de
salmouras saturadas com CO2, solubilidade de CO2, pH e densidade de salmouras.
vii
Abstract of Undergraduate Project presented to POLI/UFRJ as a partial fulfillment of
the requirements for the degree of Engineer.
Lucas Cruz
June, 2019
Advisors: Santiago Gabriel Drexler and Paulo Couto.
Course: Petroleum Engineering.
This study presents a computational-based method, using OLI Studio, to obtain
physicochemical properties of CO2 saturated brines, namely, CO2 solubility, density and
pH. It also presents the results obtained when applying this method in CO2-saturated
Brazilian Pre-Salt brines. The validation of the method is made by reproducing results
from the literature considering similar, but simpler systems then the complex brines under
study. The results thus obtained were found to be qualitatively consistent with literature
data.
Keywords: Brazilian Pre-Salt brines, physicochemical properties of CO2 saturated brines,
CO2 solubility in brines, pH and density of CO2 saturated brines.
viii
CONTENTS
CHAPTER I: INTRODUCTION……………………………………………………….1
1.1 Motivation …………………………………….…………..…………………1
1.2 Objective of this study ………………….………..…………………………..2
1.3 Structure of the text……………………………………..…………………….3
CHAPTER II: LITERATURE REVIEW………………………………………………...4
2.1 CO2 solubility in brine…………………………………..……………………4
2.2 Brine pH……………………………………..……………………………….8
2.3 Brine density……………………………………..…………………………10
CHAPTER III: RESEARCH METHODOLOGY………………………………………11
3.1 Modelling aqueous electrolyte thermodynamics with OLI Studio………..…11
3.2 Reliability validation of OLI Studio…………………………………….…..21
3.3 Determining CO2 solubility of Pre-Salt brines with OLI Studio………...…..13
CHAPTER IV: RESULTS……………………………………………………………...26
4.1 CO2 solubilities in brines B, D and DSW …………………………………...27
4.2 Brines B, D and DSW densities. …………………………………………….28
4.3 Brines B, D and DSW pHs…………………………………………………..32
4.4 Summary of Remarks……………………………………………………….34
CHAPTER VI: CONCLUSIONS………………………………………………………35
BIBLIOGRAPHY……………………………………………………………………...36
APPENDIX A: TABLES OF PHYSICOCHEMICAL PROPERTIES OF BRINES USED
FOR VALIDATION………………………………………………………………...….39
ix
APPENDIX B: AQUEOUS AND MSE THERMODYNAMICAL FRAMEWORK
COMPARISON TABLES……………………………………………………………...44
APPENDIX C: TABLES OF PHYSYCOCHEMICAL PROPERTIES OF BRAZILIAN
PRE-SALT BRINES………………….………………………………………….……..47
x
CHAPTER I: INTRODUCTION
1.1 Motivation
The data generated in this study has application in many areas of study. Some of
its applications are: input data for multiphase flow simulations and for the calculation of
interfacial tension of the oil-brine-CO2 system; prediction of carbonate minerals
dissolution as a function of pH; quantitative data that indicates the effect of CO2 both in
the sweep properties of water and in the wettability of a given reservoir (since the latter
strongly depends on its pH) and, last but certainly not least, carbon dioxide capture and
sequestration (CCS), to mention a few of them.
In order to obtain a better understanding of the fate and transport of CO2 in saline
aquifers, high resolution simulations of multiphase flow of CO2 and brine are a valuable
tool, not just for that, but also to elucidate the influence of small-scale heterogeneity on
brine displacement efficiency and CO2 saturation distributions (Benson, 2008), for
instance.
Also, the interfacial tension of the oil-brine-CO2 system is of major importance
in Reservoir Engineering and Enhanced Oil Recovery, once it is the parameter that
determines the magnitude of the capillary forces into the pores, and consequently, the
necessary pressure the driving fluid must overcome to displace the fluid that is trapped
(Drexler, 2018).
The prediction of carbonate mineral dissolution becomes of ultimate importance
in the very context of CCS, that is, the disposal and sequestration of captured
anthropogenic CO2 into the oceans, basically consisting in the geologic storage of the
transported captured CO2 (Folger, 2013). Thus, when considering CCS in carbonate
formations (which are ideal candidate for geological storage because of its storage
1
capacity), one has to worry about CO2 leakage problems once the dissolved CO2 can
form a weak acid in brine that can dissolve carbonate rocks by various geochemical
reactions potentially enhancing the existing natural fracture system and thus forming
highly conductive pathways for possible CO2 leakage (Yuan, 2017).
Given that it is not always the case that one is able to obtain this data
experimentally, it is possible to grasp, from the examples given above, the relevance of
this simulated data and see how the alternative of simulating these properties may come
in quite handy when obstacles in obtaining experimental data come up.
The brines themselves may present several restrictions, once they are usually
found under high pressures, requiring considerably powerful pumps to experimentally
reproduce reservoir conditions. Also, their high corrosiveness and CO2 concentration may
present limitations for experimental measurements of physicochemical properties, since
these features require methods that measures conductivity under these conditions which
may be considerably expensive.
1.2 Objective of this study
This study aims to provide simulated data of paramount importance to the Oil &
Gas Industry, particularly for the companies working on the Pre-Salt fields in Brazil,
where the injection of CO2 in the reservoirs comes up as an important enhanced oil
recovery method (Lake, 1989) and to describe the simulation method used to obtain them.
This data corresponds to physicochemical properties of CO2 saturated Brazilian
Pre-Salt brines, such as its density, pH and CO2 solubility at relevant temperatures and
pressures for the context mentioned above. The characterization of physicochemical
properties of these fluids after their mixture with CO2 helps to provide a better
2
understanding of the influence of CO2 solubility, pressure and temperature in these
properties.
1.3 Structure of the text
This study is divided in six chapters, having the following structure:
• CHAPTER I: INTRODUCTION – This chapter establishes the context,
motivation and objective of this study, and also briefly describes some
important applications for the data presented in Chapter IV.
• CHAPTER II: LITERATURE REVIEW – This chapter presents an
overview of the results found in the scientific literature, reporting different
data points for systems similar to those considered in this study.
• CHAPTER III: METHODOLOGY – This chapter lays down in a detailed
manner the methodology used in this study, covering the computational
procedures and data analysis methods used.
• CHAPTER IV: RESULTS – This chapter presents the results obtained
using the methodology described in the previous chapter, that is, the
physicochemical properties of different Brazilian Pre-Salt brines in the
range of 0-10000 psi and 0-100 ºC. It also aims to discuss the obtained
results presented.
• CHAPTER VI: CONCLUSIONS – This chapter presents a summary of
the problem at hand and a review of the methodology used and next steps
to be followed from this study.
• BIBLIOGRAPHY – This chapter contains the references used in the
elaboration of this study.
3
CHAPTER II: LITERATURE REVIEW
This section contains an overview of the results found in the scientific literature
in what relates to physicochemical properties of CO2 saturated brines, reporting different
data points for systems similar to the ones considered in this study, for the sake of a future
comparison, and also summarizing the conclusions drawn from them.
2.1 CO2 solubility in brine
Considering the purpose of this study and the fact that solubility data is scarce for
CO2 + H2O + Salt systems, it should be enough to mention the results obtained from
Messabeb et al, 2016; Koschel et al, 2006 and Rumpf et al, 1996, in order to illustrate
how CO2 solubility is affected by pressure, temperature and salinity.
2.1.1 Messabeb et al, 2016
Messabeb et al. obtained solubility measurements by potentiometric titration after
sample trapping in sodium hydroxide solution. Its results, which are shown in Table 2.1,
were compared to literature data and found to be consistent.
From this study, it can be concluded that the rise in pressure leads to a significant
increase in CO2 solubility, although this significance is decreased as pressure increases.
Similarly, the rise in temperature leads to a decrease in CO2 solubility, even though the
temperature dependence diminishes at higher temperatures. It can also be concluded that
the increase in salt molality clearly reduces the CO2 solubility.
4
Table 2.1 NaCl brine CO2 solubility data from Messabeb et al, 2016
mNaCl T (K) P (MPa) CO2 solubility

(mol-kg) (mol/kg) - Exp
0 323,15 5,01 0,791
323,15 10,03 1,164
323,15 15,04 1,234
323,15 20 1,308
1 323,15 5,03 0,650
323,15 10,02 0,965
323,18 15,06 1,042
323,15 20,01 1,081
3 323,15 4,99 0,452
323,15 10,06 0,676
323,15 14,97 0,713
323,15 19,96 0,779
6 323,15 5,05 0,291
323,15 10,09 0,438
323,15 14,99 0,484
323,15 20,04 0,509
1 373,15 50,01 0,376
373,15 10,08 0,668
373,15 15,02 0,850
373,15 19,96 0,942,
3 373,15 5,08 0,289
373,15 10,07 0,492,
373,15 15,01 0,609
373,15 20,16 0,727
6 373,15 5,08 0,196
373,15 10,07 0,331
373,15 15,01 0,408
373,15 20,16 0,471
1 423,15 5,03 0,305
423,15 10,04 0,877
423,15 15,05 0,804
423,15 20,01 0,960
3 423,15 5,06 0,245
423,15 10,1 0,425
423,15 14,96 0,570
423,15 20,23 0,717
6 423,15 5,04 0,162
423,15 10,1 0,285
423,15 14,96 0,379
423,15 20,21 0,463
5
2.1.2 Koschel et al, 2006
Koschel et al. determined the solubility of CO2 in NaCl solution by a calorimetric
technique through the measurement of mixture enthalpy. Their results match with the
literature values they used for comparison within an uncertainty of 7% and, in agreement
with Messab et al., they conclude that CO2 solubility decreases with an increase in
salinity. The results obtained by them is found in Table 2.2.
Table 2.2 NaCl brine CO2 solubility data from Koschel et al, 2006 (δ: uncertainty in CO2
solubility, m: NaCl molality)
Molality T P δp CO2 solubility δx (mol

(K) (MPa) (mol percent) percent)
323,15,10 0,02 0,0111 0,0007
10,03 0,02 0,0164 0,0008
14,38 0,02 0,0177 0,0010
1,0 m 20,24 0,02 0,0181 0,0009
373,1 5,07 0,03 0,006 0,0004
10,40 0,07 0,0112 0,0007
19,14 0,03 0,0161 0,0013
323,15,00 0,02 0,0083 0,0007
10,04 0,02 0,0114 0,0007
14,41 0,02 0,0124 0,0008
20,24 0,02 0,0137 0,0009
3,0 m
373,1 5,04 0,01 0,0043 0,0003
10,29 0,05 0,0080 0,0005
19,02 0,06 0,0112 0,0007
2.1.3 Rumpf et al, 1994
Rumpf et al. obtained solubility data from CO2-H2O-NaCl systems, shown in
Table 2.3, through a bubble point method from the exact amount of component injected
into the system and also concluded that CO2 is salted out by NaCl.
6
Table 2.3 NaCl brine CO2 solubility data from Rumpf et al, 1994
mCO2 mNaCl P mCO2 mNaCl P

T (K) (mol/kg) (mol/kg) (MPa) T (K) (mol/kg) (mol/kg) (MPa)
313,16 0,0497 3,997 0,467 432,97 0,000 4,003 0,515
313,14 0,0995 3,997 0,911 432,86 0,0506 4,003 1,662
313,14 0,1996 3,997 1,900 432,96 0,1013 4,003 2,858
313,19 0,3098 3,997 3,147 432,95 0,2188 4,003 5,912
313,19 0,4529 3,997 5,123 432,98 0,3254 4,003 9,048
313,19 0,5497 3,997 6,917 313,31 0,0517 5,999 0,602
333,13 0,0509 3,997 0,625 313,22 0,1035 5,999 1,232
333,16 0,0909 3,997 1,141 313,28 0,2074 5,999 2,640
333,16 0,1073 3,997 1,328 313,27 0,3133 5,999 4,430
333,15 0,1922 3,997 2,514 313,31 0,4177 5,999 6,799
333,16 0,2184 3,997 2,871 313,19 0,4693 5,999 8,427
333,14 0,257 3,997 3,521 333,12 0,0526 5,999 0,820
333,17 0,3305 3,997 4,737 333,12 0,1047 5,999 1,678
333,15 0,4472 3,997 7,303 333,10 0,2106 5,999 3,657
333,16 0,5272 3,997 9,642 333,00 0,3388 5,999 6,844
353,12 0,0505 4,001 0,817 333,05 0,3965 5,999 8,670
353,12 0,1014 4,001 1,642 353,12 0,0509 5,999 0,997
353,10 0,2032 4,001 3,387 353,11 0,1021 5,999 2,032
353,10 0,3084 4,001 5,592 353,08 0,2043 5,999 4,394
353,12 0,3594 4,001 6,940 353,10 0,3085 5,999 7,610
353,11 0,4116 4,001 8,337 353,08 0,3553 5,999 9,044
353,11 0,4613 4,001 9,637 393,09 0,000 5,999 0,151
393,06 0,000 4,003 0,169 393,17 0,0518 5,999 1,421
393,07 0,0518 4,001 1,204 393,14 0,1031 5,999 2,778
393,19 0,1035 4,003 2,331 393,13 0,2067 5,999 5,937
393,10 0,2084 4,001 4,742 393,12 0,3049 5,999 9,135
393,19 0,3135 4,003 7,650 413,10 0,000 5,999 0,275
393,12 0,3657 4,003 9,328 413,09 0,0511 5,999 1,661
413,06 0,000 4,003 0,301 413,09 0,1024 5,999 3,195
413,07 0,0505 4,003 1,393 413,09 0,2051 5,999 6,291
413,08 0,1011 4,003 2,550 413,12 0,2878 5,999 9,201
413,09 0,2027 4,003 5,042 433,12 0,000 5,999 0,471
413,07 0,3272 4,003 8,671 433,07 0,0512 5,999 1,898
433,05 0,1025 5,999 3,406
431,08 0,2052 5,999 6,578
433,05 0,2743 5,999 8,981
7
2.2 Brine pH
Similarly, it should be enough to mention the results from Haghi et al, 2017 and
Meyssami et al, 1992 to provide information about the behavior of pH in brine as a
function of pressure, temperature and salinity.
2.2.1 Haghi et al, 2017
Haghi et al. uses a spectroscopic technique to measure the pH of CO2 saturated
NaCl brines and its results are shown in Table 2.4. From their study, it can be concluded
that the pH value decreases sharply with increasing pressures for several isotherms, with
this reduction being less for higher pressures due to changes in CO2 solubility. It can
also be concluded that there is a decrease in the pH value as salinity increases and an
increase in it as temperature increases.
2.2.2 Meyssami et al, 1992
Meyassami et al obtained experimental pH values for different CO2 + H2O
systems, which are shown in Table 2.5, by using high pressure probes for measurements:
Markson probe (Phoenix, AZ) and InterOcean probe (San Diego, CA). From their study,
it can be concluded that pH values increased with an increase in temperature due to the
decrease of CO2 solubility, which is in agreement with the conclusions from Haghi et al.
8
Table 2.4 CO2 saturated water pH data from Haghi et al, 2017 (mNaCl: molality of
component NaCl)
T (K) P (MPa) mNaCl (mol/kg) pH (Experimental)

293,5 0,70 1 3,49
1,51 1 3,31
2,89 1 3,15
4,26 1 3,09
5,58 1 3,04
323,15 1,18 1 3,40
2,65 1 3,29
3,79 1 3,22
5,08 1 3,17
5,90 1 3,12
293,15 0,89 2 3,40
2,05 2 3,17
3,52 2 3,09
4,19 2 3,04
5,11 2 3,02
5,55 2 3,00
323,15 0,85 2 3,55
1,57 2 3,37
2,99 2 3,27
4,45 2 3,18
5,63 2 3,12
293,15 1,17 3 3,28
1,79 3 3,15
2,85 3 3,09
4,19 3 2,99
5,55 3 2,95
323,15 1,23 3 3,39
1,70 3 3,33
2,66 3 3,24
3,86 3 3,15
5,60 3 3,08
Table 2.5 CO2 saturated water pH data from Meyssami et al, 1992
pH
P (MPa) T = 32 °C T = 37 °C T = 42 °C
0 5,68 5,70 5,80
0,690 3,55 3,57 3,66
1,379 3,42 3,44 3,51
2,758 3,30 3,29 3,33
4,137 3,23 3,23 3,26
5,516 3,19 3,20 3,24
9
2.3 Brine density
The results reported for the density of CO2-brine systems were taken from Teng
et al, 1997. Density measurements of CO2-brine system are quite scarce in the scientific
literature so only the results of the previously mentioned study are reported.
Teng et al. reports density data of CO2 + H2O, which is shown in Table 2.6, that
suggests an increase of density with the increase of pressure and a decrease of density
with the increase of temperature, but they don’t compare their results with literature data
based on the fact that no literature data was found to be suitable for comparison.
Table 2.6 CO2 saturated water density data from Teng et al, 1997
Termperature (K) Pressure (MPa) Density (kg/m3)

6,44 1016,97
14,77 1019,4
283
19,68 1020,75
29,49 1023,98
6,44 1013,68
14,77 1015,97
293
19,68 1017,72
29,49 1019,79
10
CHAPTER III: RESEARCH METHODOLOGY
This chapter presents a summary of the methods used in the development of this
study. It presents the processes used to collect and analyze the data of interest for this
project, that is, the solubility of CO2, density and pH of different brines from the Pre-Salt
fields at different pressures (14,696 psia – 10.000 psia) and temperatures (0 ºC – 100 ºC).
The physicochemical properties mentioned above, were modelled using the
software OLI Studio (OLI Systems Inc.), by using the brine composition, CO2
concentration, pressure and temperature as input parameters.
In order to check the software’s reliability, simulations were performed
reproducing the conditions reported on several articles from the scientific literature and
the simulated physicochemical properties were compared to the reported experimental
data.
In what follows, a description of the methods used by OLI Studio to model
aqueous electrolyte thermodynamics and also of the method used to determine the CO2
solubility of a particular brine and its physicochemical properties when CO2 saturated is
made.
3.1 Modelling aqueous electrolyte thermodynamics with OLI Studio
Different thermodynamic frameworks can be used to perform simulations in OLI
Studio. Here the MSE-SRK (Mixed Solvent Electrolyte with Soave-Redlich-Kwong
Equation of State) thermodynamic framework (Jberthold, 2018), which is the
recommended one when working with water-organic-salt systems presenting high
pressure levels, (OLI SYSTEMS, INC., 2018), is used to perform the simulations with the
11
Brazilian Pre-Salt brines, and the choice of this thermodynamic framework will be
justified in the following section.
3.1.1 Mixed-Solvent-Electrolyte + Soave-Redlich-Kwong thermodynamic
framework
In the MSE-SRK model, the electrolyte-containing liquid phase is represented by
a combination of the Helgeson-Kirkham-Flowers-Tanger equation of state (the detailed
equations of state are given in Helgeson et al, 1974), for standard-state properties and the
MSE activity coefficient model for solution nonideality, from the MSE theory of Wang
et al, 2002.
Here, the chemical potential of a species i in a liquid electrolyte phase is calculated
as:
𝜇𝑖𝐿 = 𝜇𝑖𝐿,0,𝑥 (𝑇, 𝑃) + 𝑅𝑇 ln 𝑥𝑖 𝛾𝑖𝑥,∗ (𝑇, 𝑃, 𝑥)
where 𝜇𝑖𝐿,0,𝑥 (𝑇, 𝑃) is the standard-state chemical potential from HFK, 𝑥𝑖 is the mole
fraction, and 𝑥𝑖 𝛾𝑖𝑥,∗ (𝑇, 𝑃, 𝑥) is the activity coefficients from the MSE theory of Wang et
al, 2002.
On the other hand, the organic phase is modeled using SRK-EOS, so its potential
is calculated as:
𝑃𝑦𝑖 𝜙𝑖 (𝑇, 𝑃, 𝑦)
𝜇𝑖𝐺 = 𝜇𝑖𝐺,0 (𝑇) + 𝑅𝑇 ln
𝑃0
where 𝜇𝑖𝐺,0 (𝑇) is the chemical potential of pure component i in the ideal gas state, 𝑦𝑖 is
the mole fraction, 𝜙𝑖 (𝑇, 𝑃, 𝑦) is the fugacity coefficient from the SRK-EOS, P is the total
pressure, and 𝑃0 = 1 atm.
12
3.2. Reliability validation of OLI Studio
In order to verify the reliability of the method used here, all three properties, CO2
solubility, brine density and pH, were simulated reproducing the conditions of
experimental studies from the scientific literature for the sake of comparison.
Figure 3.5 Density values (kg/m3) comparison from Teng el al, 1997 at 283 K
Figure 3.6 Density values (kg/m3) comparison from Teng el al, 1997 at 293 K
13
Figure 3.7 CO2 solubility values comparison from Teng el al, 1997 at 283 K
Figure 3.8 CO2 solubility values comparison from Teng el al, 1997 at 293 K
In what follows, the physicochemical properties experimentally obtained from
Teng et al, 1997 and Peng et al, 2013 are presented and compared with the data obtained
from the simulations using OLI Studio.
The detailed data given in the figures listed in this subsection and its associated
relative errors can be found in appendix B of this study.
14
3.2.1 Physicochemical properties from Teng et al, 1997
In their study, Teng el al, 1997 experimentally obtain the solubility of CO2 in
distilled water and its density once saturated with CO2. for pressures between 6 and 30
MPa and for temperatures of 283 and 293 K. The results are found in Figure 3.4 to Figure
3.7, and the average relative error for density and CO2 solubility obtained were 0,66%
and 5,81%, respectively, and are therefore found to be consistent.
Figure 3.9 pH values comparison from Peng et al, 2013 at 308,3 K
3.2.2 Chemical properties from Peng et al, 2013
In their study, the authors experimentally obtain the pH of distilled CO2 saturated
water for up to 15 MPa and for temperatures between 308 and 423 K. The results are
found in Figure 3.9 to Figure 3.14 and the average relative error obtained was 1,4%.
15
Figure 3.10 pH values comparison from Peng et al, 2013 at 323 K
Figure 3.11 pH values comparison from Peng et al, 2013 at 343 K
3.2.3 Observations regarding thermodynamic frameworks in OLI Studio
It is very important to mention at this point the importance of the thermodynamic
framework used in the simulations. In this particular case, where a CO2 rich phase is
16
considered, the MSE-SRK thermodynamic framework is the one indicated by OLI Studio
to perform the desired simulations.
3.2.3 Observations regarding thermodynamic frameworks in OLI Studio
It is very important to mention at this point the importance of the thermodynamic
framework used in the simulations. In this particular case, where a CO2 rich phase is
17
Figure 3.15 CO2 solubility values comparison from Ahmadi, 2013 at 303,16 K using the
aqueous and MSE-SRK thermodynamic frameworks
considered, the MSE-SRK thermodynamic framework is the one indicated by OLI Studio
to perform the desired simulations.
18
In what follows, the discrepancies in results one may obtain by using an inappropriate
thermodynamic framework are illustrated. More precisely, two different thermodynamic
frameworks are compared (Figure 3.15 to Figure 3.18) and their performance are
19
evaluated by using experimental data from Ahamdi, 2018 as a reference. The results from
Drexler, 2018 are also compared for the same effect. It is worth noting that using different
frameworks won’t necessarily imply in major difference in results, as can be seen from
Figure 3.15, for instance. On the other hand, it is certainly the case that in some cases the
discrepancy can be extremely large as it is the case of Figure 3.17, for instance.
In the study of Drexler, 2018, the aqueous thermodynamic framework is used. As
one can see from Figure 3.19 to Figure 3.21, shown below, the results can be either quite
similar or considerably different depending on which thermodynamic framework is being
used, pointing out the fact that one must consider the system composition and physical
conditions under consideration in its choice of a thermodynamic framework.
20
Figure 3.19 CO2 solubility values for brine B comparison from Drexler, 2018 at 60 ºC
using the aqueous (reference) and MSE-SRK thermodynamic frameworks
Figure 3.20 CO2 solubility values for brine D comparison from Drexler, 2018 at 60 ºC
using the aqueous (reference) and MSE-SRK thermodynamic frameworks
3.3 Determining CO2 solubility and physicochemical properties of Pre-Salt brines
with OLI Studio
In what follows, the CO2 solubility of a particular brine at a given pressure and
temperature will be obtained in order to illustrate the method used to obtain the CO2
21
solubility of the brines studied in this study. Once the composition of a brine is given, one
Figure 3.21 CO2 solubility values for brine DSW comparison from Drexler, 2018 at 60
ºC using the aqueous (reference) and MSE-SRK thermodynamic frameworks
can analyze the behavior of the amount of CO2 in the aqueous phase as a function of the
total amount of CO2 in the system to determine its solubility at a given pressure and
temperature. In this example, the brine mass composition, and the pressure and
temperature of the system are given in Figure 3.1.
22
Figure 3.1. Defining brine composition in OLI Studio
The maximum amount of CO2 that can be dissolved in the system will be given
by the total amount of CO2 injected when the amount of CO2 in the aqueous phase
becomes constant as the former increases. In this example, as illustrated in Figure 3.2,
this value is approximately 2,3 mols.
23
Figure 3.2. Plot of CO2 in the aqueous phase as a function of total amount of CO2 in the
system
With that information one can calculate the ratio between the maximum amount
of CO2 that can be dissolved in the system and the total amount of substance in the system
and obtain the solubility of that system at that given temperature and pressure.
In this particular case, one can see that at 303,160 K and 35,3860 MPa, those
values are 2,31 mol of CO2 and 104,926 amounts of substance, respectively. The ratio
between those values are given by 0,002201, that is, the CO2 solubility of that brine at the
given pressure and temperature conditions is 2,201%.
Once the CO2 amount necessary to saturate the brine is known, one can check out
the “Survey Parameters” section and the simulated data corresponding to that particular
composition, as illustrated in Figure 3.4.
24
Figure 3.3. Report of total and phase amounts of a system
Figure 3.4. Report of survey parameters of the system

25
CHAPTER IV: RESULTS
This chapter presents the results obtained using the methodology described in the
previous chapter, that is, the physicochemical properties of different Brazilian Pre-Salt
brines in the range of 0-10000 psi and 0-100 ºC.
In Table 4.1, one can find the composition of two formation brines from producing
wells in two Pre-Salt fields (Field B and Field D) and of a third brine, corresponding to
the desulfated injection water commonly used in Pre-Salt fields to avoid calcium, barium
and strontium sulfate scaling problems.
Table 4.1 Composition of brines under consideration in this study
BRINE B BRINE D DSW

Compound g/L Compound g/L Compound g/L
NaCl 146,3114 NaCl 166,7014 NaCl 30,3689
CaCl2.6H2O 132,5587 CaCl2.6H2O 6,906 CaCl2.6H2O 2,733
MgCl2.6H2O 17,7361 MgCl2.6H2O 2,5254 MgCl2.6H2O 14,2156
KCl 2,2898 KCl 3,3079 KCl 0,9533
BaCl2.2H2O 0,0391 BaCl2.2H2O 0,4019 SrCl2.6H2O 0,0274
SrCl2.6H2O 3,8327 SrCl2.6H2O 2,1779 Na2CO3 0,0548
Na2SO4 0,0798 NaBr 0,7559 NaHCO3 0,1391
CaCl2.2H2O 88,8143 CaCl2.2H2O 4,627 CaCl2.2H2O 1,8311
The following section presents the results from the simulations using the method
describ ed in the previous section.
26
4.1 CO2 solubilities in brines B, D and DSW
Figure 4.1 to Figure 4.3 contain the simulated CO2 solubilities for the different
brines under consideration when submitted to pressures varying from 14,696 psia to
10.000,00 psia and temperatures varying from 0 ºC to 100 ºC.
Figure 4.1: Brine B CO2 solubilities
Figure 4.2: Brine D CO2 solubilities
27
Figure 4.3: Brine DSW CO2 solubilities
Comparing the results from Figure 4.1 to Figure 4.3 one can observe that,
regardless of the composition of the brine, the CO2 solubility tends to increase with the
increase of pressure, to decrease with an increase of temperature. One can also observe a
decrease in the CO2 solubility with increasing salinity and a loss of temperature
significance as it increases. These reported results are in agreement with results
previously reported in the scientific literature (Messabeb et al, 2016).
4.2 Brine B, D and DSW densities
Figure 4.4 to Figure 4.6 contain the simulated densities for the different brines
under consideration when submitted to pressures varying from 14,696 psia to 10.000,00
psia and temperatures varying from 0 ºC to 100 ºC.
28
Figure 4.4: CO2 saturated Brine B - Densities
Figure 4.5: CO2 saturated Brine D - Densities
29
Figure 4.6: CO2 saturated Brine DSW – Densities
Comparing the results from Figure 4.4 to Figure 4.6 one can observe that,
regardless of the composition of the brine, the brine density tends to increase with the
increase of pressure, to decrease with an increase of temperature. These reported results
are in agreement with results previously reported in the scientific literature (Yan et al,
2011).
For the sake of comparison, it is also shown in Figure 4.7 to Figure 4.9 plots
comparing the densities of the different brines with and without CO2 at 60 ºC, where it
can be seen that the dissolution of CO2 in brine results in an increase of its density.
30
Figure 4.7: Brine B density comparison with and without CO2 dissolution
Figure 4.8: Brine D density comparison with and without CO2 dissolution
31
Figure 4.9: Brine DSW density comparison with and without CO2 dissolution
4.3 Brine B, D and DSW pHs
Figure 4.10 to Figure 4.12 contain the simulated pHs for the different brines under
consideration when submitted to pressures varying from 14,696 psia to 10.000,00 psia
and temperatures varying from 0 ºC to 100 ºC.
Figure 4.10: CO2 saturated Brine B - pHs
32
Figure 4.11: CO2 saturated Brine D – pHs
Figure 4.12: CO2 saturated Brine DSW – pHs
Comparing the results from Figure 4.10 to Figure 4.12 one can also observe that,
regardless of the composition of the brines, the pH of the brine tends to decrease with
increasing pressure (sharply decrease at lower pressures), to increase with increasing
temperature and to increase with decreasing salinity, in accordance with results
previously reported in the scientific literature (Haghi et al, 2017).

33
It is also worth mentioning that in carbonate rocks, mineral dissolution by brine
acidification (described by CaCO3(s) + H2O(l) + CO2 ⟶ Ca2+(aq) + 2 HCO3-(aq)) occurs
(Santiago et al, 2019) and with the CO2 dissolution that comes along with, a pH shift
occurs, increasing the brine pH.
4.4 Summary of Remarks
A brief summary of what was done in this section is presented below:
• The composition of three different Pre-Salt brines were given.
• Their physicochemical properties CO2 solubility, density and pH were simulated
over the pressure range of 14,69 to 10.000 psia and the temperature range of 0 to
100 ºC and the resulting plots were given in section 4.2, 4.3 and 4.4, whereas the
actual values that were plotted were given in Appendix B.
• Comparing the obtained results with literature data, the agreement between them
is remarked.
34
CHAPTER VI: CONCLUSIONS
In this study a solution to the problem of obtaining representative data on the
physicochemical properties of CO2 saturated brines by means of using the software OLI
Studio to simulate it is presented. A considerable amount of data on physicochemical
properties of brines from the Brazilian Pre-Salt fields, namely, their CO2 solubility,
density and pH under the pressure range of 14,696 to 10.000 psi and temperature range
of 0 to 100 ºC is also given.
Upon further analysis of the presented data, it can be concluded that it presented
the trend observed in the scientific literature in what regards the behavior of the
physicochemical properties considered as a function of pressure, temperature and salinity.
The method used, despite not being as precise as the experimental method, came
out as a significant alternative tool in the cases where the latter approach may not be an
option.
The use of OLI Studio ’s MSE-SRK thermodynamic framework for the simulation
was shown to be considerably satisfactory, considering that in the examples reproduced
from the scientific literature, the relative error presented a mean value of 3,0% and
standard deviation value of 3,1%.
A natural recommendation of future study for this project is to experimentally
obtain the value of the physicochemical properties here presented for the different brines
under consideration for a better evaluation of the method here used.
Another suggestion would be to use a different software, or even other
thermodynamic frameworks from OLI Studio itself to reproduce the results here
presented for the sake of comparison.
35
BIBLIOGRAPHY
AHMADI, P., CHAPOY, A., 2018, CO2 solubility in formation water under
sequestration conditions, Fluid Phase Equilibria · February 2018
BENSON, S., 2008, Multiphase Flow of CO2 And Brine In Saline Aquifers,
Society of Exploration Geophysicists
DREXLER, S., 2018, Study of the Fluid-Fluid and Rock-Fluid Interactions:
Impact of Dissolved CO2 on Interfacial Tension and Wettability for the Brazilian
Pre-Salt Scenario, Tese (doutorado) – UFRJ/ COPPE/ Programa de Engenharia Civil,
2018.
DREXLER, S., SILVEIRA, T., DE BELLI, G., COUTO, P., 2019, Experimental
study of the effect of carbonated brine on wettability and oil displacement for EOR
application in the Brazilian Pre-Salt reservoirs. Energy Sources, Part A: Recovery,
Utilization, and Environmental Effects, DOI: 10.1080/15567036.2019.1604877
FOLGER, P., 2013, Carbon Capture: A Technology Assessment,
Congressional Research Service
HAGHI, R.K., CHAPOY, A., PEIRERA, L.M.C., YANG, J., TOHIDI, B., 2017
pH of CO2 saturated water and CO2 saturated brines: Experimental measurements
and modelling, International Journal of Greenhouse Gas Control 66 (2017) 190–203
HAMIDI, H. ATIB, N.F.A.M., AZDARPOUR, A., MOHAMMADIAN, E., 2015,
Study of CO2 Solubility in Brine under Different Temperatures and Pressures,
Advanced Materials Research Submitted: 2014-09-19 ISSN: 1662-8985, Vol. 1113, pp
440-445
HELGESON, H.C., KIRKHAM, D.H., FLOWERS, G.C. 1974, 1976, 1981,
Theoretical Prediction of the Thermodynamic Behavior of Aqueous Electrolytes at
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High Pressures and Temperatures - Parts I through IV, American Journal of Science
1974, 1976, 1981.
JBERTHOLD, 2018, MSE-SRK Thermodynamic Model in the OLI Software.
Disponível em: <http://wiki.olisystems.com/wiki/MSE-SRK#How_does_MSE-
SRK_work.3F>. Acesso em: 20 de abril de 2019.
KOSCHEL, D., COXAM, J.Y., RODIER, L., MAJER, V., 2006. Enthalpy and
solubility data of CO2 in water and NaCl(aq) at conditions of interest for geological
sequestration. Fluid Phase Equilibria 247, 107–120
LAKE, W.L., 1989, Enhanced Oil Recovery, Prentice Hall – Technology and
Engineering
MESSABEB, H., CONTAMINE, F., CÉZAC, P., SERIN, J.P., GAUCHER, E.C.,
2016, Experimental Measurement of CO2 Solubility in Aqueous NaCl Solution at
Temperature from 323.15 to 423.15 K and Pressure of up to 20 MPa, J. Chem. Eng.
Data, 2016, 61 (10), pp 3573–3584 DOI: 10.1021/acs.jced.6b00505
OLI SYSTEMS, INC., 2018, A Guide to Using OLI Studio Version 9.6. 1a ed.
New Jersey, OLI Systems, Inc.
PENG, C., CRAWSHAW, J.P., MAITLAND, G.C., TRUSLER, J.P.M., VEGA-
MAZA, D., 2013, The pH of CO2-saturated water at temperatures between 308 K
and 423 K at pressures up to 15 MPa, J. of Supercritical Fluids 82 (2013) 129– 137
OLI SYSTEMS, INC., 2019, MSE-SRK: Mixed Solvent Electrolyte + Soave-
Redlich-Kwong A thermodynamic model for HPHT upstream oil and gas Disponível
em: < http://downloads.aqsim.com/2019-OLITechnology-MSE-SRK.pdf>. Acesso em:
17 de Maio de 2019.
37
RUMPF, B., NICOLAISEN, H., OCAL, C., MAURER, G., 1994. Solubility of
carbon dioxide in aqueous solutions of sodium chloride: experimental results and
correlation, Journal of Solution Chemistry 23, 431–448
TENG, H., YAMASAKI, A., CHUN, M., LEE, H., 1997, Solubility of liquid
CO2 in water at temperatures from 278K to 293K and pressures from 6.44 MPa to
29.49 MPa and densities of the corresponding aqueous solutions, National Institute of
Materials and Chemical Research and Department of Chemical Engineering, Korea
Advanced Institute of Science and Technology
WANG, P., ANDERKO, A., YOUNG, R.D., 2002, A speciation-based model
for mixed-solvent electrolyte systems, Fluid Phase Equilibria vol. 203, pp.141-176
YAN, W., HUANG, S., STENBY, E.H. 2011, Measurement and modeling of
CO2 solubility in NaCl brine and CO2–saturated NaCl brine density, International
Journal of Greenhouse Gas Control 5 (2011) 1460–1477
YUAN, T., NING, Y., QIN, G., 2017, Bulk phase CO2 injection can provide
substantive reduction in CO2 emissions, SPE-185845-MS
38
APPENDIX A: TABLES OF PHYSICOCHEMICAL PROPERTIES OF BRINES
USED FOR VALIDATION
A.1 Teng et al, 1997
Table A.1 Comparison between density simulated on OLI Studio and experimentally
obtained density at T = 283 K from Teng et al, 1997
T =283K
Density (kg/m3) Density (kg/m3)
Pressure (MPa) Experimental OLI Studio
6,44 1016,97 1019,25
14,77 1019,4 1023,87
19,68 1020,75 1027,77
29,49 1023,98 1038,31
Table A.2 Comparison between CO2 solubility simulated on OLI Studio and
experimentally obtained CO2 solubility at T = 283 K from Teng et al, 1997
T = 283K
CO2 Solubility (mol percent) CO2 Solubility (mol percent)
6,44 2,79% 2,64%
14,77 3,05% 2,81%
19,68 3,26% 2,92%
29,49 3,34% 3,17%
Table A.3 Relative errors from Table A.1 and Table A.2
T = 283K
Pressure (MPa) Relative Error - Density Relative Error - CO2 Solubility
6,44 0,22% 5,38%
14,77 0,44% 7,87%
19,68 0,69% 10,43%
29,49 1,40% 5,09%
39
Table A.4 Comparison between density simulated on OLI Studio and experimentally
obtained density at T = 293 K from Teng et al, 1997
T =293K
Density (kg/m3) Density (kg/m3)
6,44 1013,68 1015,61
14,77 1015,97 1020,49
19,68 1017,72 1024,01
29,49 1019,79 1032,71
Table A.5 Comparison between CO2 solubility simulated on OLI Studio and
experimentally obtained CO2 solubility at T = 293 K from Teng et al, 1997
T = 293K
CO2 Solubility (mol percent) CO2 Solubility (mol percent)
6,44 2,50% 2,43%
14,77 2,75% 2,64%
19,68 2,93% 2,75%
29,49 3,12% 2,97%
Table A.6 Relative errors from Table A.4 and Table A.5
T = 293K
Pressure (MPa) Relative Error - Density Relative Error – CO2 Solubility
6,44 0,19% 2,80%
14,77 0,44% 4,00%
19,68 0,62% 6,14%
29,49 1,27% 4,81%
40
A.2 Peng et al, 2013
Table A.7 Comparison between pH simulated on OLI Studio and experimentally
obtained pH at T = 308,3 K from Peng et al, 2013
T = 308,3 K
p (MPa) pH - Exp pH - Sim Relative Error
0,38 3,71 3,67 1,1%
0,61 3,58 3,56 0,6%
0,97 3,46 3,46 0,0%
2,43 3,22 3,27 1,6%
6,23 3,05 3,1 1,6%
9,28 3,01 3,06 1,7%
15,38 2,97 3,03 2,0%
obtained pH at T = 323 K from Peng et al, 2013
T = 323 K
0,38 3,76 3,73 0,8%
0,61 3,63 3,61 0,6%
0,98 3,52 3,51 0,3%
2,43 3,36 3,32 1,2%
6,23 3,14 3,14 0,0%
9,28 3,07 3,09 0,7%
15,36 3,04 3,04 0,0%
41
obtained pH at T = 343 K from Peng et al, 2013
T = 343 K
0,38 3,89 3,8 2,3%
0,61 3,72 3,69 0,8%
0,99 3,59 3,58 0,3%
2,43 3,42 3,39 0,9%
6,22 3,25 3,21 1,2%
9,28 3,18 3,14 1,3%
15,39 3,12 3,08 1,3%
T = 368,1 K
0,6 3,97 3,81 4,0%
1 3,77 3,69 2,1%
2,42 3,56 3,49 2,0%
6,36 3,35 3,29 1,8%
9,3 3,28 3,22 1,8%
15,41 3,23 3,15 2,5%
T = 398,3 K
1 3,97 3,86 2,8%
2,44 3,63 3,63 0,0%
6,29 3,47 3,42 1,4%
9,36 3,34 3,34 0,0%
15,36 3,32 3,25 2,1%
42
T = 423,2 K
p (MPa) pH - Exp pH - Sim Error (%)
1 4,11 4,05 1,5%
2,44 3,78 3,76 0,5%
6,29 3,59 3,53 1,7%
9,36 3,54 3,44 2,8%
15,37 3,49 3,34 4,3%
43
APPENDIX B: AQUEOUS AND MSE THERMODYNAMICAL FRAMEWORKS
COMPARISON TABLES
B.1 Ahmadi et al, 2018
Table B.1 Comparison between CO2 solubility at T = 303,16 K simulated on OLI
Studio using the aqueous and MSE frameworks
T = 303,16K
Pressure Relative
(MPa) Reference AQ MSE Relative Error AQ Error MSE
1,625 0,527% 0,552% 0,543% 4,74% 3,04%
6,612 1,649% 1,582% 1,601% 4,06% 2,91%
8,675 1,804% 1,686% 1,714% 6,54% 4,99%
20,519 1,913% 1,902% 1,949% 0,58% 1,88%
35,39 2,096% 2,1% 2,183% 1,5% 4,151%
T = 323,20K
Pressure Relative
1,763 0,443% 0,417% 0,388% 5,87% 12,4%
6,257 1,192% 1,194% 1,099% 0,17% 7,8%
10,719 1,540% 1,564% 1,431% 1,56% 7,1%
18,172 1,708% 1,771% 1,620% 3,69% 5,2%
38,86 1,975% 2,1% 1,931% 6,7% 2,2%
44
T = 373,19K
Pressure Relative
1,929 0,232% 0,253% 0,224% 9,05% 3,45%
8,172 0,860% 1,003% 0,822% 16,63% 4,42%
22,895 1,561% 1,959% 1,469% 25,50% 5,89%
38,81 1,877% 2,6% 1,799% 36,1% 4,156%
Relative
Pressure Error
(MPa) Reference AQ MSE Relative Error AQ MSE
2,415 0,244% 0,224% 0,204% 8,20% 16,39%
5,434 0,498% 0,562% 0,493% 12,85% 1,00%
9,253 0,879% 0,984% 0,799% 11,95% 9,10%
24,335 1,720% 2,367% 1,586% 37,62% 7,79%
36,949 1,999% 3,0% 1,984% 51,3% 0,750%
B.2 Drexler, 2018
Table B.5 Comparison between CO2 solubility simulated on OLI Studio and simulated
CO2 solubility for Brine B at T = 60 ºC from Drexler, 2018
Brine B - T = 60ºC
Pressure (psia) CO2 (mol percent) - AQ CO2 (mol percent) - MSE Relative Error
1000 0,56% 0,47% 16,41%
2000 0,67% 0,65% 3,36%
3000 0,74% 0,72% 3,09%
4000 0,80% 0,78% 2,09%
5000 0,85% 0,83% 2,01%
45
CO2 solubility for Brine D at T = 60 ºC from Drexler, 2018
Brine D - T = 60ºC
1000 0,83% 1,41% 69,6%
2000 1,15% 1,95% 69,5%
3000 1,28% 2,19% 71,2%
4000 1,38% 2,33% 68,8%
5000 1,47% 2,50% 70,2%
CO2 solubility for Brine DSW at T = 60 ºC from Drexler, 2018
Brine DSW - T = 60ºC

1000 1,34% 1,20% 10,6%
2000 1,87% 1,65% 11,8%
3000 2,09% 1,82% 12,9%
4000 2,26% 1,99% 11,8%
5000 2,40% 2,11% 12,0%
46
APPENDIX C: TABLES OF PHYSICOCHEMICAL PROPERTIES OF
BRAZILIAN PRE-SALT BRINES
C.1 Brine B
Table C.1: Physicochemical properties of brine B at 0 ºC
Brine B - T = 0ºC
CO2 Solubility
Pressure (psi) (mol percent) Density (g/cm3) pH
14,696 0,0470% 1,227 3,15
1000 1,2932% 1,238 2,42
2000 1,3717% 1,241 2,39
3000 1,4599% 1,243 2,35
4000 1,5380% 1,246 2,32
5000 1,6031% 1,248 2,29
6000 1,6844% 1,250 2,26
7000 1,7493% 1,253 2,23
8000 1,8141% 1,255 2,20
9000 1,8951% 1,257 2,17
10000 1,9597% 1,259 2,14
Brine B - T = 20ºC
CO2 Solubility
14,696 0,0218% 1,211 3,26
1000 0,8890% 1,217 2,44
2000 0,9616% 1,220 2,41
3000 1,0274% 1,223 2,37
4000 1,0801% 1,225 2,34
5000 1,1293% 1,227 2,32
6000 1,1785% 1,229 2,29
7000 1,2278% 1,231 2,26
8000 1,2605% 1,234 2,24
9000 1,3096% 1,236 2,21
10000 1,3587% 1,238 2,19
47
Brine B - T = 40ºC
CO2 Solubility
14,696 0,0131% 1,201 3,35
1000 0,6309% 1,205 2,49
2000 0,7635% 1,207 2,43
3000 0,8164% 1,209 2,40
4000 0,8659% 1,211 2,37
5000 0,9154% 1,213 2,34
6000 0,9649% 1,214 2,32
7000 0,9978% 1,217 2,29
8000 1,0472% 1,219 2,27
9000 1,0801% 1,221 2,24
10000 1,1129% 1,223 2,22
Brine B - T = 60ºC
CO2 Solubility
14,696 0,0081% 1,192 3,45
1000 0,4681% 1,194 2,56
2000 0,6475% 1,196 2,47
3000 0,7171% 1,198 2,43
4000 0,7833% 1,200 2,40
5000 0,8329% 1,201 2,37
6000 0,8659% 1,203 2,34
7000 0,9154% 1,205 2,32
8000 0,9484% 1,207 2,30
9000 0,9813% 1,209 2,27
10000 1,0143% 1,211 2,25
48
Brine B - T = 80ºC
CO2 Solubility
14,696 0,0047% 1,182 3,59
1000 0,3749% 1,183 2,62
2000 0,5746% 1,185 2,52
3000 0,6675% 1,187 2,47
4000 0,7337% 1,188 2,43
5000 0,7834% 1,190 2,40
6000 0,8329% 1,192 2,37
7000 0,8825% 1,194 2,35
8000 0,9155% 1,195 2,32
9000 0,9649% 1,197 2,30
10000 0,9979% 1,199 2,28
Brine B - T = 100ºC
CO2 Solubility
14,696 0,0014% 1,170 3,88
1000 0,3282% 1,172 2,68
2000 0,5148% 1,174 2,57
3000 0,6344% 1,175 2,51
4000 0,7172% 1,177 2,47
5000 0,7834% 1,179 2,43
6000 0,8330% 1,180 2,40
7000 0,8825% 1,182 2,38
8000 0,9320% 1,183 2,35
9000 0,9650% 1,185 2,33
10000 1,0144% 1,187 2,30
49
C.2 Brine D
Table C.7: Physicochemical properties of brine D at 0 ºC
Brine D - T = 0ºC
CO2 Solubility
14,696 0,1263% 1,001 3,87
1000 3,6555% 1,032 3,09
2000 3,9898% 1,038 3,05
3000 4,1560% 1,043 3,03
4000 4,4868% 1,049 2,99
5000 4,6514% 1,053 2,97
6000 4,8153% 1,057 2,94
7000 5,0765% 1,062 2,91
8000 5,2391% 1,067 2,89
9000 5,4980% 1,072 2,86
10000 5,6590% 1,076 2,84
Brine D - T = 20ºC
CO2 Solubility
14,696 0,0686% 0,999 3,90
1000 2,5701% 1,018 3,08
2000 2,8437% 1,023 3,04
3000 3,0480% 1,028 3,01
4000 3,1158% 1,031 2,99
5000 3,2851% 1,035 2,96
6000 3,4538% 1,039 2,93
7000 3,6220% 1,044 2,90
8000 3,6891% 1,047 2,89
9000 3,8564% 1,051 2,86
10000 3,9231% 1,054 2,84
50
Brine D - T = 40ºC
CO2 Solubility
14,696 0,0379% 0,993 3,98
1000 1,8966% 1,007 3,10
2000 2,2949% 1,012 3,04
3000 2,4671% 1,016 3,01
4000 2,6215% 1,02 2,98
5000 2,7584% 1,024 2,96
6000 2,8778% 1,027 2,93
7000 2,9970% 1,031 2,91
8000 3,1159% 1,034 2,89
9000 3,2175% 1,038 2,87
10000 3,3358% 1,041 2,84
Brine D - T = 60ºC
CO2 Solubility
14,696 0,0217% 0,983 4,10
1000 1,4073% 0,994 3,16
2000 1,9487% 1,000 3,07
3000 2,1913% 1,005 3,03
4000 2,3294% 1,009 3,01
5000 2,5014% 1,012 2,97
6000 2,6215% 1,016 2,95
7000 2,7413% 1,020 2,93
8000 2,8437% 1,023 2,90
9000 2,9630% 1,026 2,88
10000 3,0650% 1,030 2,86
51
Brine D - T = 80ºC
CO2 Solubility
14,696 0,0119% 0,972 4,24
1000 1,1643% 0,981 3,23
2000 1,7398% 0,988 3,12
3000 2,0181% 0,992 3,07
4000 2,2258% 0,996 3,04
5000 2,3983% 1,000 3,01
6000 2,5358% 1,004 2,98
7000 2,6729% 1,008 2,95
8000 2,7754% 1,011 2,93
9000 2,9119% 1,015 2,91
10000 3,0140% 1,018 2,89
Brine D - T = 100ºC
CO2 Solubility
14,696 0,0001% 0,959 5,40
1000 1,0194% 0,967 3,30
2000 1,6000% 0,974 3,18
3000 1,9487% 0,979 3,12
4000 2,1913% 0,983 3,08
5000 2,3638% 0,987 3,05
6000 2,5358% 0,991 3,02
7000 2,7071% 0,995 2,99
8000 2,8437% 0,999 2,97
9000 2,9800% 1,003 2,94
10000 3,0819% 1,006 2,92
52
C.3 Brine DSW
Table C.13: Physicochemical properties of brine DSW at 0 ºC

CO2 Solubility
14,696 0,1202% 1,033 4,91
1000 3,2270% 1,059 3,50
2000 3,4436% 1,064 3,44
3000 3,6427% 1,069 3,39
4000 3,8245% 1,073 3,34
5000 4,0056% 1,077 3,29
6000 4,1696% 1,082 3,24
7000 4,3495% 1,086 3,20
8000 4,5123% 1,09 3,16
9000 4,6746% 1,094 3,12
10000 4,8364% 1,098 3,08

CO2 Solubility
14,696 0,0583% 1,029 5,03
1000 2,2316% 1,045 3,46
2000 2,4017% 1,049 3,41
3000 2,5713% 1,053 3,35
4000 2,7065% 1,057 3,31
5000 2,8414% 1,060 3,26
6000 2,9591% 1,064 3,22
7000 3,0765% 1,068 3,18
8000 3,1769% 1,071 3,14
9000 3,2938% 1,074 3,10
10000 3,3937% 1,078 3,07
53

CO2 Solubility
14,696 0,0337% 1,022 5,18
1000 1,5795% 1,033 3,52
2000 1,9238% 1,038 3,41
3000 2,0950% 1,042 3,35
4000 2,1975% 1,045 3,31
5000 2,3338% 1,049 3,26
6000 2,4357% 1,052 3,22
7000 2,5974% 1,055 3,18
8000 2,6390% 1,059 3,15
9000 2,7403% 1,062 3,11
10000 2,8246% 1,065 3,08

CO2 Solubility
14,696 0,0207% 1,012 5,38
1000 1,1981% 1,021 3,61
2000 1,6486% 1,027 3,46
3000 1,8208% 1,030 3,39
4000 1,9924% 1,034 3,33
5000 2,1121% 1,038 3,29
6000 2,2145% 1,041 3,25
7000 2,3167% 1,044 3,21
8000 2,4187% 1,048 3,17
9000 2,5205% 1,051 3,13
10000 2,6052% 1,054 3,10
54

CO2 Solubility
14,696 0,0112% 1,001 5,68
1000 0,9538% 1,009 3,73
2000 1,4758% 1,014 3,53
3000 1,7175% 1,019 3,44
4000 1,8551% 1,022 3,39
5000 2,0266% 1,026 3,33
6000 2,1292% 1,029 3,29
7000 2,2316% 1,033 3,25
8000 2,3678% 1,036 3,21
9000 2,4697% 1,039 3,17
10000 2,5375% 1,042 3,14

CO2 Solubility
14,696 0,0089% 0,988 6,57
1000 0,8557% 0,995 3,84
2000 1,3649% 1,001 3,62
3000 1,6486% 1,005 3,52
4000 1,8551% 1,009 3,45
5000 2,0095% 1,013 3,40
6000 2,1463% 1,017 3,35
7000 2,2827% 1,020 3,31
8000 2,3848% 1,024 3,27
9000 2,5205% 1,027 3,23
10000 2,6221% 1,031 3,19
55

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SIMULATION OF THE PHYSICOCHEMICAL PROPERTIES

OF BRAZILIAN PRE-SALT BRINES

Projeto de Graduação apresentado ao Curso de

Engenharia de Petróleo da Escola Politécnica,

Universidade Federal do Rio de Janeiro, como

parte dos requisitos necessários à obtenção do

Orientadores: Santiago Gabriel Drexler e Paulo

OF BRAZILIAN PRE-SALT BRINES

PROJETO DE GRADUAÇÃO SUBMETIDO AO CORPO DOCENTE DO CURSO DE

ENGENHARIA DE PETRÓLEO DA ESCOLA POLITÉCNICA DA UNIVERSIDADE

FEDERAL DO RIO DE JANEIRO COMO PARTE DOS REQUISITOS

NECESSÁRIOS PARA A OBTENÇÃO DO GRAU DE ENGENHEIRO DE

Prof. Santiago Gabriel Drexler, D.Sc.

Prof. Paulo Couto, D.Eng.

Prof. Rafael Mengotti Charin , Ph.D.

Prof. Paulo Goldfeld, Ph.D.

RIO DE JANEIRO, RJ - BRASIL

Simulation of the Physicochemical Properties

of Brazilian Pre-Salt Brines / Lucas Cruz. – Rio de

Janeiro: UFRJ/ Escola Politécnica, 2019.

XVI, 55 p.: il.; 29,7 cm.

Orientadores: Santiago Gabriel Drexler e Paulo

Projeto de Graduação – UFRJ/ Escola

Politécnica/ Curso de Engenharia de Petróleo, 2019.

Referências Bibliográficas: p. 36-38.

1. Introduction. 2. Literature Review. 3.

Research Methodology. 4. Results. 5. Conclusion. I.

Drexler, Santiago Gabriel e Couto, Paulo. II.

Universidade Federal do Rio de Janeiro, Escola

Politécnica, Curso de Engenharia de Petróleo. III.

SIMULATION OF THE PHYSICOCHEMICAL

PROPERTIES OF BRAZILIAN PRE-SALT

Primeiramente, gostaria de agradecer a minha amada família. Meus queridos pais

necessidade, permitindo que as experiências mais incríveis da minha vida, que

contribuíram grandemente na formação de meu caráter, se concretizassem, a isso serei

por você são inexplicáveis.

oportunidade enriquecedora no Laboratório de Matemática Aplicada ao Petróleo

(LabMAPetro) a despeito de minha inexperiência, sendo sempre muito pacientes comigo,

vocês são pessoas incríveis.

formação profissional sendo um verdadeiro orientador em todos os sentidos da palavra,

Meu orientador Santiago Gabriel Drexler, que me orientou em cada etapa na

Meus professores Rosemarie Bröker Bone, Rafael Charin que prontamente me

ajudaram no momento de maior necessidade de minha vida acadêmica, a despeito das

Meus colegas de trabalho da Norwegian Research Centre AS (NORCE AS), Ying

preocupando com os menores detalhes, e garantindo que minhas experiências pessoal,

um excelente professor e colega de trabalho, Widuramina Sameendraneth que com muito

Cervantes e todos os demais que fizeram parte dessa jornada.

requisitos necessários para a obtenção do grau de Engenheiro de Petróleo.

SIMULAÇÃO DE PROPRIEDADES FÍSICO-QUÍMICAS DE

SALMOURAS DO PRÉ-SAL BRASILEIRO

Orientadores: Santiago Gabriel Drexler e Paulo Couto.

Curso: Engenharia de Petróleo

obtenção de propriedades físico-químicas de salmouras saturadas de CO2, sendo essas

em salmouras do Pré-sal brasileiro saturadas de CO2. A validação do método é feita por

meio da reprodução de resultados da literatura considerando sistemas similares, porém

mais simples do que as salmouras complexas estudadas. Os resultados obtidos no estudo

destas salmouras foram consistentes, qualitativamente, com os dados da literatura.

Palavras-chave: salmouras do Pré-sal brasileiro, propriedades físico-químicas de

salmouras saturadas com CO2, solubilidade de CO2, pH e densidade de salmouras.

the requirements for the degree of Engineer.

SIMULATION OF THE PHYSICOCHEMICAL PROPERTIES

OF BRAZILIAN PRE-SALT BRINES

Advisors: Santiago Gabriel Drexler and Paulo Couto.