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Elucidating Kinetic, Adsorption and Partitioning Phenomena from a Single Well Tracer Method: Laboratory and Bench Scale Studies

  • M. Otero-López , M. González-Brambila , A. Dutta ORCID logo and C. O. Castillo-Araiza EMAIL logo
Published/Copyright: August 24, 2016
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International Journal of Chemical Reactor Engineering
From the journal International Journal of Chemical Reactor Engineering Volume 14 Issue 6

Abstract

This study is aimed at giving some insights on kinetics, adsorption and partitioning of ethyl acetate during a single well tracer test. Synthetic formation water, an specific crude oil and a silicate-dolomite rock were used during experiments performed in laboratory and bench scale systems. Independent sets of experiments were designed to calculate the partition coefficient of ethyl acetate between the formation water and the oil, to develop a kinetic model for the hydrolysis of ethyl acetate, and to derive isotherm and kinetic models for the adsorption of ethyl acetate on the rock. These tracer experiments were evaluated at a concentration range (100–300 mmol.L−1) similar to that supposed to be used in the single well tracer method. All parameters determined from these experiments were validated describing observations from stirred batch and column systems, in which kinetic, adsorption and partitioning phenomena occurred at the same time. Pseudo-heterogeneous models, accounting for three phases namely the formation water, the rock and the oil, were applied to elucidate the interaction of the different mechanisms involved in these set-ups. Main results are summarized as follows: (i) partition coefficients (KEA) were apparent varying from ca. 5–8 because of thermodynamic constraints; (ii) kinetic models for the hydrolysis of ethyl acetate were developed under acid and basic conditions since at neutral ones there were negligible conversions; (iii) the combined Langmuir-Freundlich isotherm and the Langmuir kinetics were the most suitable models describing equilibrium and adsorption rate observations, respectively; (iv) the studied rock adsorbed significant amounts of ethyl acetate, leading to a maximum adsorption capacity (qEAm) of ca. 7.0 mmol.g−1 at studied operating conditions; (v) the adsorption kinetic model rather than the simplified isotherm model seems necessary to describe this phenomenon from the single well test evaluating ethyl acetate as the tracer; and (vi) partition, hydrolysis and adsorption parameters evaluated from independent experiments allowed us to describe observations from both stirred batch and column systems. These results disclose the importance of accounting for partition, hydrolysis and adsorption mechanisms in a single well method using ethyl acetate as the tracer.

Keywords: single well tracer test; partition; kinetics; adsorption; and modeling

Nomenclature

Roman letters

A′i,k

natural logarithm of the pre-exponential factor for the i-th reaction in the k-th hydrolysis, mmol1−n.L1−n.min−1

ai

interfacial area of the phase i-th per unit volume of the same phase i-th, m2.m−3.

CEAoe

concentration of ethyl acetate in liquid phase at equilibrium, mmol.L−1

CEAwe

Concentration of ethyl acetate in formation water at equilibrium, mmol.L−1

CEAin

initial concentrations of ethyl acetate, mmol.L−1

Cij

concentration of the i-th component in j-th phase, mmol.L−1

Cijin

initial concentration of the i-th component in j-th phase, mmol.L−1

Ck,n

the n-th experimental response for the k-th observation, mmol.L−1

Dax

axial dispersion coefficient, mm2.min−1

DiL

diffusion coefficients of component i-th in liquid phase, mm2.min−1

Dr

radial dispersion coefficient, mm2.min−1

dp

particle diameter, mm

dr

column diameter, mm

EA,k

activation energy factor for the k-th hydrolysis, KJ. mmol−1

ka

adsorption rate constant, g.min−1. mmol−1

kd

desorption rate constant, g.L−1.min

KEA

partition coefficient of ethyl acetate, mmolEAoe. mmolEAwe−1

ki,j,

overall interfacial mass transfer coefficients corresponding to the interface aqueous-solid, mm.min−1

ki

interfacial mass transfer coefficients at the liquid interface, mm.min−1

kj

interfacial mass transfer coefficients at the solid interface, mm.min−1

KL

Langmuir adsorption constant related to adsorption affinity of ethyl acetate on the reservoir rock, L. mmol−1

KF

adsorption affinity constant in Freundlich isotherm, mmol1−n.L1−n.g−1

T

reaction temperature, K

T*

averaged reaction temperature, K

m

mass of the reservoir rock evaluated in the batch adsorber, g

n

adsorption affinity constant, dimensionless

nexp

number of independent experiments

nk

order of the reaction of the k-th hydrolysis, dimensionless

Pe

Peclet number, dimensionless

qEAe

amount of ethyl acetate adsorbed on a unit weight of adsorbent at equilibrium, mmol.g−1

qEAm

maximum amount of ethyl acetate adsorbed per unit weight of adsorbent, mmol.g−1

r

radial position along column radius of the bed, mm

Rg

universal gas constant, KJ. mmol−1.K−1

Rt

Column radius, mm

Rep

particle Reynolds number, dimensionless

V

volume of ethyl acetate solution contained in the stirred batch adsorber, L

vz

interstitial axial velocity of the fluid, mm.min−1

vz0

superficial axial velocity calculated as the ratio of the volumetric flow rate divided by the cross-sectional area of the bed, mm.min−1

z

axial position along the column, mm

Greek letters

ν

kinematic viscosity of the solution, mm2.min−1

νj,k

stoichiometric coefficient of the component j-th in the k-th hydrolysis.

ρL

fluid density, g.L−1

ρp

batch system density, g.L−1

ρij

binary linear correlation coefficients

ρB

column system density, g.L−1

εi

void fraction of the phase i-th,

μL

dynamic viscosities of liquid phase

β

optimal parameter vector

Abbreviations

ACS

American Chemical Society

HPLC

high performance liquid chromatography

pH

potential of hydrogen

EA

ethyl acetate

E

ethanol

AA

acetic acid

SA

sodium acetate

AH

acid hydrolysis

B-HYD

basic hydrolysis

N-HYD

neutral hydrolysis

Highlights

  1. We studied the partition, hydrolysis and adsorption mechanisms at bench scale.

  2. Kinetic models for the hydrolysis of ethyl acetate were developed.

  3. A Langmuir-Freundlich isotherm was developed.

  4. A Langmuir kinetic model was developed.

  5. Two and three phase laboratory systems were adequately described

Acknowledgments

Martha Otero-López acknowledges to Universidad Autónoma Metropolitana for postgraduate fellowship and to Instituto Mexicano del Petróleo (IMP).

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Published Online: 2016-8-24
Published in Print: 2016-12-1

©2016 by De Gruyter

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  3. Preface to the Special Issue dedicated to the First International Energy Conference, IEC 2015
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https://doi.org/10.1515/ijcre-2016-0043
Keywords for this article
single well tracer test; partition; kinetics; adsorption; and modeling

Articles in the same Issue

  1. Frontmatter
  3. Preface to the Special Issue dedicated to the First International Energy Conference, IEC 2015
  4. Derivation of an Upscaled Model for Mass Transfer and Reaction for Non-Food Starch Conversion to Bioethanol
  5. Elucidating Kinetic, Adsorption and Partitioning Phenomena from a Single Well Tracer Method: Laboratory and Bench Scale Studies
  6. Thermodynamic Analysis of Ethanol Synthesis from Glycerol by Two-Step Reactor Sequence
  7. Modeling the Transient VOC (toluene) Oxidation in a Packed-Bed Catalytic Reactor
  8. Substrate Feeding Strategy Integrated with a Biomass Bayesian Estimator for a Biotechnological Process
  9. Comparison Tools for Parametric Identification of Kinetic Model for Ethanol Production using Evolutionary Optimization Approach
  10. Hydrodeoxygenation of Phenol Over Sulfided CoMo Catalysts Supported on a Mixed Al2O3-TiO2 Oxide
  11. Experimental and Computational Analysis of Single Phase Flow Coiled Flow Inverter Focusing on Number of Transfer Units and Effectiveness
  12. Dynamic Effectiveness Factor for Catalytic Particles with Anomalous Diffusion
  13. Experimental and Artificial Neural Network Modeling of a Upflow Anaerobic Contactor (UAC) for Biogas Production from Vinasse
  14. Novel Feedback Control to Improve Biohydrogen Production by Desulfovibrio alaskensis
  15. Influence of an Alkaline Zeolite on the Carbon Flow in Anaerobiosis of Three Strains of Saccharomyces cerevisiae
  16. CCS, A Needed Technology for the Mexican Electrical Sector: Sustainability and Local Industry Participation
  17. Olefins and Ethanol from Polyolefins: Analysis of Potential Chemical Recycling of Poly(ethylene) Mexican Case
  18. CFD Simulations of Copper-Ceria Based Microreactor for COPROX
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