Chinese Journal of Chemical Engineering, 20(3) 461468 (2012)

Adsorption onto Activated Carbon Fiber Cloth and Electrothermal Desorption of Volatile Organic Compound (VOCs): A Specific Review
Pierre Le Cloirec*
Ecole Nationale Suprieure de Chimie de Rennes (ENSCR), UMR CNRS 6226 Institut des Sciences Chimiques de Rennes, Campus de Beaulieu, Avenue du Gnral Leclerc, CS 50837, 35708 Rennes cedex 07, France Abstract A general research program, focusing on activated carbon fiber cloths (ACFC) and felt for environmental protection was performed. The objectives were multiple: (i) a better understanding of the adsorption mechanisms of these kinds of materials; (ii) the specification and optimization of new processes using these adsorbents; (iii) the modeling of the adsorption of organic pollutants using both the usual and original approaches; (iv) applications of ACFC in industrial processes. The general question was: how can activated carbon fiber cloths and felts be used in air treatment processes for the protection of environment. In order to provide an answer, different approaches were adopted. The materials (ACFC) were characterized in terms of macro structure and internal porosity. Specific studies were performed to get the air flow pattern through the fabrics. Head loss data were generated and modeled as a function of air velocity. The performances of ACF to remove volatile organic compounds (VOCs) were approached with the adsorption isotherms and breakthrough curves in various operating conditions. Regeneration by Joule effect shows a homogenous heating of adsorber modules with rolled or pleated layers. Examples of industrial developments were presented showing an interesting technology for the removal of VOCs, such as dichloromethane, benzene, isopropyl alcohol and toluene, alone or in a complex mixture. Keywords activated carbon fiber cloth, adsorption, volatile organic compounds, electrothermal desorption, regeneration

INTRODUCTION

The removal of organic compounds in aqueous or gas phase with granular activated carbon (GAC) is commonly performed for the removal of micropollutants in water or volatile organic compounds (VOC) present in air [1-3]. GAC adsorbers have proven to be effective in removing a large number of organic molecules [4-7]. A recent formulation of activated carbon has been developed: activated carbon fiber textile (ACFT) as cloth (ACFC) or felt (ACFF). These carboneous porous materials have received increasing attention in recent years as an adsorbent for purifying water and air [8, 9]. The ACFC for VOC removal seems to be a promising material particularly to remove VOCs in waste gas compared to granular activated carbon (GAC) fixed-beds. Indeed, the compactness of ACFC adsorbers and the simplicity of possible direct electrical regeneration, facilitate the implementation of these filters in terms of engineering and process operations. The desorption procedure offers several advantages such as a great flexibility in the regeneration operating conditions, a reduced maintenance and low operating costs [10]. A research and development program has been performed specifically on ACFC. The general question was: how activated carbon fiber cloths and felts, can be used in air treatments. Focusing on activated carbon fiber cloth for environmental protection had four objectives: (i) a better understanding of the adsorption mechanisms of these kinds of materials; (ii) the specification and optimization of new

processes using these adsorbents; (iii) the modeling of the adsorption of organic pollutants using both the usual and original approaches; (iv) some applications of ACFC in industrial processes for VOC control. In order to provide an answer to the previous question, a general multi-scale approach was adopted as shown in Figs. 1 and 2. This program has included (i) characterization of materials (ii) laboratory studies in terms of performances against pollutants and electrothermal regeneration of saturated materials (iii) pilot studies to get operating conditions and the design of adsorbent modules (iv) industrial applications for VOC or odorous molecule removal from gas streams. 2 2.1 POROUS MATERIAL CHARACTERIZATION Production

ACF cloth or felt is produced from synthetic raw material (asfran, pitch, PAN), and in this case, especially from rayon (viscose) [11-13]. The precursor has an impact on the surface functional groups and pore size distribution [14]. The raw material is carbonized at a temperature ranging from 800 to 1000C in order to remove the volatile components and to develop a graphitic structure [15, 16]. This carbonaceous solid is then reacted with steam or carbon dioxide between 800 and 1200 C so as to increase its specific surface area and pore volume. The production is performed in a batch or continuous feed oven with a yield from 25% to 50%. The mechanical structure of the activated medium has to be strong enough for utilization

Received 2012-02-17, accepted 2012-04-26. * To whom correspondence should be addressed. E-mail: Pierre.le-Cloirec@ensc-rennes.fr

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Figure 1

An integrated research programAn integrated partnership

Figure 2

Sequences of the global research programFrom the material to the process

in adsorbing modules. These oxidative and thermal treatments result in a carbonaceous porous material with original properties in terms of texture, specific weight, chemical composition and porosity. Some characteristics of commercial carboneous porous products are given in Table 1. Some materials have been chemically treated to remove preferentially water vapor or specific organics present in air [17-20]. 2.2 Structural parameters

A large number of ACF weaves are made industrially: twill, sateen, mat or gros tours. Felts or knitteds are also available (Fig. 3). Depending on the residence time in the production oven, the structural parameters of fabrics and felts cover a large range. The fiber shape was found to be multi-lobes separated by longitudinal stripes or ridges [21]. Its equivalent

diameter is between 6 and 25 m. The specific mass range from 120 gm2 to 240 gm2. The thickness is between 0.5 and 1.3 mm and the global porosity (external and internal yarn) ranges from 0.50 to 0.92. The pore openings in the cloth structure vary from 13 to 50 m. These structural parameters have a strong influence on the head loss in the adsorber modules and on the external mass transfer rate. Because of this macrotexture, the material will be chosen according to its properties and these applications: flat, rolled or pleated filter modules, for air treatments and in situ regeneration of the media. 2.3 Chemical features

Activated carbon fibers have a microcrystalline structure with an orientation of graphitic layers less ordered than in graphite [22]. The elemental analysis

Chin. J. Chem. Eng., Vol. 20, No. 3, June 2012 Some characteristics of commercial activated carbon textilesComparisons between grains and cloth
CS 1501 structure armure original material activation size/mm grammage/gm2 density/kgm3 resistance electrique/ surface (BET)/m2g1 surface mesopore/m2g1 microporous volume/cm3g1 mesoporous volume/cm3g1 percentage of microporous volume/% adsorption CCl4/% adsorption butane/% C H N O tissu satin 8 viscose CO2 1200 C 0.41 139 340 ch : 1.6 tr : 1.7 1689 211 0.665 0.025 96.4 >73 >30 >99.00 0.80 ch : 4.9 tr : 6.3 2311 339 0.862 0.057 93.8 100 >41 100.00 ch : 12.5 tr : 23.1 1461 333 0.506 0.237 68.1 >63 >26 92.00 8.00 93.89 0.60 0.50 5.02 969 237 0.327 0.019 94.5 60-75 CS 1901 tissu satin 8 viscose CO2 1200 C 0.58 130 RS 1301 tissu serg 3 viscose H2O 700-1000 C 0.60 >200 noix coco H2O 900 C 1.00-1.50 NC 60 grains

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Table 1

Figure 3 Visualization of activated carbon textiles from macro to microscalefibers-macro-mesoporosity

of the adsorbent shows an almost pure carbonaceous solid with more than 99% carbon and hydrogen (Table 1). Only traces of oxygen and nitrogen are found [21]. Thus, the concentrations of acidic or basic surface

functional groups on the adsorbent surface are very low. The purity of this kind of material in terms of its chemical constitutive elements is a key factor and is promising for applications such as drinking water

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treatment, purification of aqueous solutions or pre-concentration of pollutants, in water or air, before desorption and analysis. 2.4 Porosity, pore volume and specific surface area

The internal porosity of ACFC was investigated using a multi-criteria system. The micropore distribution is very low with a median diameter of about 0.7 nm. Some experimental data on adsorption selectivity show that these micropores are directly connected to the external surface of the material. The microporous volume is close to that of activated carbon grain values, i.e. 0.40 to 0.90 cm3g1. The mesoporous volume is low, representing 6% to 15% of the total porous volume. The specific surface area (BET surface) is of the same order as other carbonaceous porous solids, ranging from 900 to 2300 m2g1 [21]. It should be noted that the porosity data are very similar to those for activated carbon powders or grains, apart from the direct connection of micropores to the external surface of ACFC. 2.5 Electrical and thermal properties

Experimental data have been published previously [23, 24]. Because of the Joule effect, it is possible to heat the cloth at a relatively high temperature, between 20 and 250 C, as a function of the electrical power applied to the module. The heating is homogenous and depends on the specific surface area (SBET) of the adsorbent. Cycles (heating-cooling) are short (from some minutes to 1 h) due to the very weak thermal inertia of the cloths. These characteristics are interesting in terms of the regeneration of the cloth. An original process of adsorption onto ACFC and electrothermal regeneration has been studied, designed and carried out for the control of VOCs in industrial emissions [25].
3 STUDIES ON AIR FLOW PATTERNS

Due to their crystalline structure (graphene), the porous carbonaceous fibers show a resistance when an electrical current is applied. The resistance of ACFC has been measured and found to be dependent on temperature and capacity as shown Fig. 4. From the experimental data, an equation was generated given the resistance as a function of temperature:

R 1 1 = exp R0 T T0 R and R0 are resistances at temperature T and T0 respectively, and is a constant depending on the macrostructure and porosity of ACFC.

The available textures of ACFC give different flow patterns due to the macro-structure and porosity of the cloths. Experimental data for air pressure drops in a flat system have been generated using a large number of fabrics [26-28]. The head loss is relatively low in flat or pleated filters. Classical curves [P/H = f(U)] are found (Fig. 5) [29]. However, it is difficult to apply common equations, such as Carman-Kozeny-Ergun relations, because of the lack of a geometrical parameter. Thus, more recent models are used with two structural parameters: the tortuosity and the solid surface actually in contact with the fluid. Neural network models have also been applied with a good correlation between the experimental data and modeled values [30]. In order to minimize the pressure drop in the adsorber modules, rolled or pleated ACFC were produced and integrated in a reactor. Using experimental values with 2D and 3-D numerical simulations, the flow distribution was visualized in a pleated filter and in a complete system [31]. These approaches are required not only for a better understanding of flow patterns in a specific porous medium but also to optimize the filter design and the absorber system.
4 ADSORPTION OF POLLUTANTS IN GAS STREAM

These studies focused especially on the removal of volatile organic compounds (VOC) and odorous molecules in polluted gaseous emissions.
4.1 Interactions ACFC-pollutant

Figure 4 Evolution of the resistance of an activated carbon cloth loaded with dichloromethane (qe in mmolkg1) as a function of temperature qe/mmolkg1: 0; 0.98; + 1.24; 2.29; 3.24

ACFCs adsorb a large majority of volatile organic compounds well. Mass transfer is very fast due to the significant external surface compared to activated carbon grains. Adsorption capacities were found to be similar to those of other carbonaceous porous materials with very small adsorption fronts [32]. In odor control, mechanisms for the removal of hydrogen

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Figure 5 Pressure drop as a function of velocity for different activated carbon fiber cloths 2/2 twill; 4/4 twill; 4 twill; 8 twill; + 4 sateen; 8 sateen; 2 mat; 4 mat ; square;

gros

tours

sulfide, ammonia or fatty acids were proposed depending on operating conditions [33-35]. In particular, the influence of humidity on the adsorption capacities and mass transfer rate was studied [36]. Some studies were performed to control indoor air pollution [37]. Some models to correlate molecular structure and adsorption parameters were proposed using classical statistical methods or neural networks [38]. An example of adsorption isotherm curve is given in Fig. 6 for Toluene adsorption. Classical curve is found modeled with usual models such as Langmuir or Freundlich equations [39, 40].

capacities were determined. Breakthrough curves of toluene adsorption for different numbers of ACFC layers (1N3) are given in Fig. 7. Classical shape is found. Regeneration by Joule effect shows a homogenous heating of the adsorber module with rolled or pleated layers. Adsorption-desorption cycles were performed for a long time showing the ability of this original process to be industrially developed [44, 45].

Figure 7 Breakthrough curves Adsorption of toluene (307 mgm3) onto activated carbon fiber (velocity 0.5 ms1) N: 1; 2; 3

An example of dichloromethane adsorption and electrothermal desorption is given in Fig. 8. We have

Figure 6 Isotherm of toluene adsorption onto different activated carbon grains (NC 60 and Picabiol) and cloth (FM 30 K) Picabiol; NC 60; FM 30 K

4.2

Adsorption-electrothermal desorption

The interest in ACFC for VOC removal is not only due to its good adsorption capacity but also due to the ability to heat the cloth by electricity [41-43] The breakthrough curves were drawn for the majority of volatile solvents and the dynamic adsorption

Figure 8 Electrothermal desorption (T = 150 C) of ethyl acetate from activated carbon cloth at two velocities (2.4 and 4.8 mh1)

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Figure 9

Presentations of different activated carbon fiber cloth modules (visualization by infra-red camera)

to note that there is good adsorption and regeneration is easy with the application of small amount of electrical power to the material [21, 23]. From lab studies, modules for adsorption-desorption were designed. Several approaches were performed as presented in Fig. 9. About 2 kg of ACFC are wound or pleated depending of the mass load to be treated, the gas velocity and the time of a cycle (time integrating adsorption and desorption phases). These cylindrical modules have 17 cm diameter and 50 cm length. A typical power cost for electrothermal desorption is about 200 W for a module as presented above to increase the temperature to 150 C.
5 INDUSTRIAL DEVELOPMENTS

In a chemical plant, a treatment process was carried

out to control a gaseous emission (flow close to 100 m3h1) loaded with methylene chloride at concentrations ranging between 3 and 30 gm3. A final mass flow of less than 100 gh1 was required in the outlet emission. Two identical cylindrical ACFC modules worked alternately in an adsorption-desorption cycle. The cycle time was close to 1 hour [23]. The outlet pollutant mass flux was found to be less than 4 gh1. After saturation of the adsorbent, the module was electrothermally regenerated. Desorbed methylene chloride was recovered in a cryogenic trap and re-used in the chemical processes of the plant. This system worked continuously for more than 36 months (24 h a day) with no operating problems and giving good performances in terms of VOC outlet emission concentrations. In 2011, several industrial processes were working for the removal of VOC, such as benzene, isopropyl alcohol and toluene, alone or in a complex

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mixture. An industrial example of treatment with two modules (Fig. 9) in series and two absorbers in parallel is shown in Fig. 10.

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Figure 10 Example of an industrial installation of VOC removal by adsorption onto ACFC modules and electrothermal regeneration

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CONCLUSIONS
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These different studies have revealed the possibilities for the utilization of activated carbon fiber cloths in air treatments. This promising material has shown good capacities of adsorption. Original processes can be designed for specific applications in VOC or odor removal in gaseous emissions. Several lines of research using impregnated materials or processes for the combined elimination of multi-pollutants (dust, VOC, bacteria) are being investigated and industrially developed.
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