Preparation and CO2 adsorption of diamine modified montmorillonite via exfoliation grafting route

doi:10.1016/j.cej.2012.11.058

Chemical Engineering Journal

Volumes 215–216, 15 January 2013, Pages 699-708

https://doi.org/10.1016/j.cej.2012.11.058 Get rights and content

Abstract

In this paper, diamine modified montmorillonite was prepared by water aided exfoliation/grafting method. The materials were characterized by elemental analysis (EA), X-ray diffraction (XRD), diffuse reflectance infrared Fourier transform spectrometer (DRIFTS), automated surface area and porosity analyser (ASAP 2420) and thermogravimetric analysis (TGA). Adsorption of carbon dioxide on modified montmorillonite was investigated by isothermal CO₂ adsorption, temperature ramp CO₂ adsorption, regeneration screening test with adsorption/desorption cycles, and multiple cyclic test. The maximum adsorption capacity for modified montmorillonite is 2.4 mmol g⁻¹ at 100 °C. In a 15% CO₂ in N₂ mixture, the material achieves a maximum adsorption capacity of 1.8 mmol g⁻¹, which is 75% of its maximum capacity in pure CO₂. The optimum adsorption and desorption temperature are found to be 80 and 160 °C, respectively, by regeneration testing. The long term performance was also studied in pure CO₂, 15% CO₂ in N₂ and 15% CO₂ in N₂ with 1000 ppm SO₂. The material is stable in pure CO₂ and 15% CO₂ in N₂, while the adsorption capacity drops dramatically with the presence of SO₂. In order to understand the kinetics of CO₂ adsorption, four kinetics models were evaluated, with the Avrami equation providing the best experimental-simulation fit.

Highlights

• We propose a novel adsorbent for post-combustion CO₂ capture. • Diamine modified montmorillonite via water aided exfoliation/grafting method. • Maximum adsorption in 15% CO₂ balanced by N₂ is in the flue gas temperature range. • Long term performance cycling indicates good stability when in pure and 15% CO₂.

Introduction

In the last decade, carbon dioxide (CO₂) emissions have become a serious concern in relation to global climate change [1]. To mitigate the impact of CO₂ on world climate, efficient capture and sequestration of CO₂ from fossil fuel burning power plants is required. Although many technologies exist for CO₂ capture, absorption using alkanolamine solutions is still the most practical technology on a large scale operation. However the method suffers a number of disadvantages such as toxicity, degradability, high regeneration energy requirements and corrosive behaviour [2]. Therefore, solid adsorbents with high adsorption capacity, fast adsorption rate and good stability are highly desirable [3]. When the CO₂ adsorption capacity of solid adsorbents reaches 3 mmol g⁻¹, the energy reduction can be 30–50% or more compared to the optimum aqueous monoethanolamine (MEA) based process [4].

Among various types of solid adsorbents, supported amines have attracted considerable attention. A wide variety of supports have been studied in recent years, including mesoporous silicas [5], [6], [7], [8], [9], carbon nanotubes [10], nanofibre [11] and zeolites [12], [13], layered double hydroxides [14], [15]. N-2-aminoethyl-3-aminopropyl trimethoxysilane (AEAPTS, diamine) is one of the most common surface modification agents in the literature [3].

There are two main operating modes for CO₂ adsorption processes: pressure swing adsorption (PSA) and temperature swing adsorption (TSA). The selection of appropriate regeneration methods is strongly dependent upon the adsorbent properties, such as the nature of the gas-adsorbent interactions. In a PSA process, gases are desorbed by depressurization, whereas desorption takes place by increasing temperature in a TSA process. Because the CO₂ molecules are mainly chemically adsorbed on amine modified materials, TSA is more likely to be the most appropriate method [16].

Montmorillonite (MMT) is a natural inorganic material with a general chemical structure of (OH)₄Si₈(Al₄₋_xMg_x)O₂₀. The crystal structure of MMT consists of two-dimensional layers formed by an octahedral sheet sandwiched between two opposing tetrahedral sheets (Scheme 1). As a low cost and readily available mineral with high swelling ability and high surface area, it has been widely studied as an adsorbent and catalyst support [17]. It is interesting to note that the material cost for mesoporous silicas can be more than 50 times higher than the one for MMT [18]. Aminosilane modified montmorillonite has been reported by a few research groups [19], [20], [21]. However the research was solely focused on the effects on polymer/clay composites. There is no reported investigation of CO₂ adsorption on amine modified montmorillonite.

The aims of this work were to prepare, characterize and for the first time evaluate the CO₂ adsorption capacity of amine modified montmorillonite. In this work, amine modified montmorillonite prepared via an water aided exfoliation method were characterized by elemental analysis (EA), X-ray diffraction (XRD), diffuse reflectance infrared fourier transform spectrometer (DRIFTS), automated surface area and porosity analyser (ASAP 2420) and thermogravimetric analysis (TGA). Detailed CO₂ adsorption studies were carried out by isothermal CO₂ adsorption, temperature ramp CO₂ adsorption, and regeneration screening test with adsorption/desorption cycles, and multiple cycle testing for long term performance. Mathematical modelling has also been applied to isothermal CO₂ adsorption data to study the kinetics of CO₂ adsorption on the materials.

Section snippets

CTAB intercalated MMT

The K10 montmorillonite (MMT) was purchased from Sigma Aldrich and used as received. Roughly 3 g MMT was added in 150 ml 0.1 M hexadecyltrimethylammonium bromide (CTAB) aqueous solution. The mixture was continuously stirred for 4 h at room temperature. The resultant material was filtered, washed with distilled water and then dried overnight at 80 °C. The sample was labelled as MMT CTAB.

Amine surface modification

A water aided exfoliation method was used to introduce amine groups on the surface of montmorillonite or CTAB

Material characterization

Elemental analysis results (Table 1) shows that unmodified MMT contained traces of nitrogen and carbon as impurities. After 4 h mixing MMT powders in CTAB aqueous solution, 0.460 mmol g⁻¹ CTAB cations were intercalated in the interlayer space of MMT. Both amine modified samples, MMT N2 and MMT CTAB N2, had approximate 7.6–7.7 mmol g⁻¹ amine groups. CTAB intercalation had little effect on the amount of amine groups grafted. The maximum amine loadings reported for solid adsorbents modified by

Conclusions

In the present work, diamine modified montmorillonite have been synthesized via water aided exfoliation and grafting route and studied as CO₂ adsorbents. The materials were characterized by EA, XRD, DRIFTS, SEM, N₂ isotherms, and TGA. It is the first time that CO₂ adsorption data has been reported for amine modified montmorillonite. Here the best amine modified montmorillonite is MMT CTAB N2. The material can achieve highest CO₂ adsorption capacity of 2.4 mmol g⁻¹ at 100 °C in pure CO₂ which is

Acknowledgment

The authors acknowledge EPSRC and E.ON for financial support (E.ON-EPSRC strategic call on CCS Project EP/G061785/1).

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Preparation and CO2 adsorption of diamine modified montmorillonite via exfoliation grafting route

Abstract

Highlights

Introduction

Section snippets

CTAB intercalated MMT

Amine surface modification

Material characterization

Conclusions

Acknowledgment

Int. J. Greenhouse Gas Control

J. Colloid Interface Sci.

Chem. Eng. Sci.

Appl. Surf. Sci.

Sep. Purif. Technol.

Chem. Eng. J. (Lausanne)

Chem. Eng. Sci.

J. Colloid Interface Sci.

J. Colloid Interface Sci.

J. Colloid Interface Sci.

J. Colloid Interface Sci.

J. Hazard. Mater.

Adv. Colloid Interface Sci.

Microporous Mesoporous Mater.

Microporous Mesoporous Mater.

Thermochim. Acta

J. Colloid Interface Sci.

Appl. Clay Sci.

Spectrochim. Acta Part A Mol. Biomol. Spectrosc.

Mater. Lett.

Thermochim. Acta

Int. J. Greenhouse Gas Control

Chem. Eng. J.

Energy Procedia

Microporous Mesoporous Mater.

Microporous Mesoporous Mater.

Carbon dioxide capture: Prospects for new materials

Angew. Chem. Int. Ed.

Adsorbent materials for carbon dioxide capture from large anthropogenic point sources

ChemSusChem

Preparation and CO₂ adsorption of diamine modified montmorillonite via exfoliation grafting route