Experimental and simulation studies on mineral trapping of CO2 with brine

doi:10.1016/j.enconman.2003.09.029

Energy Conversion and Management

Volume 45, Issues 11–12, July 2004, Pages 1845-1859

https://doi.org/10.1016/j.enconman.2003.09.029 Get rights and content

Abstract

The reaction of carbon dioxide (CO₂) with brine samples collected from the Oriskany Formation in Indiana County, PA, was investigated in an autoclave reactor under various conditions. A geochemical code, PHREEQC, was used as to simulate the reaction in the autoclave reactor. The combined experimental and modeling data suggests that pH (pH > 9) plays a key role in the formation of carbonate minerals. The effects of temperature and CO₂ pressure have a lesser impact on the formation of carbonate minerals.

Introduction

Carbon dioxide (CO₂) is the main contributor to global warming [1]. CO₂ is primarily emitted into the atmosphere from combustion of fossil fuels in power plants. Many techniques to capture and store CO₂ are currently being investigated. It is believed that permanent sequestration of CO₂ can reduce the greenhouse effects generated from fossil fuel combustion. CO₂ injection into saline aquifer formations is one of the most promising geologic CO₂ sequestration options. It offers two major advantages: first, the estimated carbon storage capacity of saline aquifer formations in the United States is large (500 Gt. of CO₂), making them a viable long term solution, and second, most existing large CO₂ point sources are located near saline aquifer formations, making CO₂ transportation costs minimal. Therefore, sequestration of CO₂ into saline aquifer formations is an important strategy to mitigate global warming [1], [2].

Upon injection of CO₂ into saline aquifers, CO₂ may be stored by hydrodynamic, solubility and mineral trapping. In hydrodynamic and solubility trapping, CO₂ is captured in saline aquifers as a fluid (CO_2(l)) or aqueous component (H₂CO₃, HCO₃⁻, CO₃⁼ and CO_2(aq)). The most critical concern of hydrodynamic trapping is the potential for CO₂ leakage through imperfect confinement. The main issue that affects solubility trapping is the limited CO₂ solubility in brine. In mineral trapping, CO₂ is converted into carbonate minerals by a series of reactions with aqueous ions found in the saline aquifer. Various carbonates such as calcite (calcium carbonate), magnesite (magnesium carbonate), dolomite (calcium–magnesium carbonate) and siderite (iron carbonate), can be formed in the brine aquifer by mineral trapping. These carbonate minerals can be stored in saline aquifer formations for millions of years [1], [2], [3], [4]. However, conversion of CO₂ to stable carbonate minerals is expected to be slow. The Alberta Research Council in Canada [4] conducted a computer simulation of the mineral trapping process (kinetic water–rock reaction model, PATHARC.94) under reservoir conditions. These authors calculated times for precipitation of the various carbonates on the order of hundreds of years. These results suggest that mineral trapping conversion of CO₂ to carbonate minerals may contribute significantly to CO₂ sequestration within saline aquifers but only in the very long term.

Some researchers have conducted mineral trapping studies in the laboratory. Sass et al. [5] studied CO₂ and brine reactions with mineral rocks for 7 days at a pressure of 5.44 MPa and 110 °C. They found increased levels of calcium, magnesium and carbonate in solution, which were due to the dissolution of dolomite. They interpreted the decreased aqueous calcium and sulfate concentrations as evidence for anhydrite precipitation. Lebro'n and Suarez [6] reported the precipitation rate of calcite increased as the partial pressure of CO₂ increased (0.035–10 kPa). Their interpretation suggested that by increasing the partial pressure of CO₂, the solution pH decreases and the ionic strength increases. These conditions strongly influence nucleation of new calcite crystals. However, no extensive laboratory studies directed at the sequestration of CO₂ in brine aquifers have been conducted. In this study, the physical and chemical properties of brine from the Oriskany Sandstone aquifer of the Appalachian Basin are examined to assess its potential to sequester CO₂ in the near term via the mineral trapping pathway upon reaction with CO₂. This study attempts to evaluate the ability of such brines alone to serve as a mineral trapping medium. It is prudent to investigate the variables that effect mineral carbonates formation in brines in the absence of interference introduced by the presence of formation rocks. Once these effects are clearly defined, then experiments that include rock will be undertaken. The computer program PHREEQC version 2 also modeled carbonation of Oriskany Formation brine. PHREEQC version 2 is a computer program that is designed to perform a wide variety of low temperature aqueous geochemical calculations. The PHREEQC computer program and manual can be obtained from the USGS web site [7].

In this study, we explored the mineral trapping pathway for the reaction of CO₂ with brine samples. The optimum reaction conditions that favor the formation of mineral carbonates were investigated with autoclave experiments and geochemical modeling with PHREEQC [7]. Specifically, the effects of pH, CO₂ pressure and temperature on the reaction between CO₂ and brine samples to form carbonate minerals were investigated.

Section snippets

Experimental apparatus and procedure

To examine the process of mineral trapping under controlled temperature and pressure conditions in an autoclave reactor, brine samples were collected from the Oriskany Sandstone aquifer in Indiana County, PA. Samples were collected directly from the well after purging at a formation depth of 2800 m. The brine was collected in polyethylene bottles with air tight caps to reduce exposure to the atmosphere. The brine was tested as received without further filtration. Although there are some

Results

Preliminary autoclave experiments were conducted to investigate the effect of pH and reaction time for the reaction of CO₂ with brine samples. The pH experiments were conducted in two ways: the brine was used as received (pH=3.9) before reaction with CO₂ (Rxn 1: 155 °C, 6.19 MPa of CO₂, 400 rpm and 1 h), and the pH of the brine was adjusted with KOH to pH 11.0 before reaction with CO₂ (Rxn 2: 155 °C, 4.6 MPa of CO₂, 400 rpm and 1 h). In general, the ionic concentrations of the aqueous brine

Discussions

Mineral trapping may occur via the simplified reactions , , , , , , , shown below. CO₂ gas dissolves into solution (1). Carbonic acid is formed (2), which then dissociates into bicarbonate (3) and carbonate ions (4). Thus, the pH of an aqueous solution decreases with the addition of CO₂ [10]. Then, ions such as Ca, Mg and Fe react with the carbonate ions to form minerals, such as calcite, dolomite, siderite and magnesite , , , , respectively. $CO_{2} (gas)↔ CO_{2} (aq)$ $CO_{2} (aq)+ H_{2} O ↔ H_{2} CO_{3}$ $H_{2} CO_{3} ↔ H^{+} + HCO_{3}^{−}$ $HCO_{3}^{−} ↔$

Conclusions

The reactions between CO₂ and brine samples collected from the Oriskany Formation in Indiana County, PA, were investigated experimentally using a 1/2 l autoclave under various conditions and theoretically using the geochemical code PHREEQC. The results of the experimental study show that the amount of calcite precipitate depends primarily on the pH of the brine. The CO₂ pressure and temperature have a lesser impact on the formation of carbonates. In addition, the simulation model used in this

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Published by Elsevier Ltd.

Experimental and simulation studies on mineral trapping of CO2 with brine

Abstract

Introduction

Section snippets

Experimental apparatus and procedure

Results

Discussions

Conclusions

Energy Convers. Manage.

Energy Convers. Manage.

Geochim. Cosmochim. Acta

Energy Convers. Manage.

CO2 reduction––prospects for coal

Experimental and simulation studies on mineral trapping of CO₂ with brine

CO₂ reduction––prospects for coal