Adsorption With Activated Carbon
Adsorption With Activated Carbon
Adsorption With Activated Carbon
TECHNICAL SHEETS
FOR EFFLUENT TREATMENT PLANTS
IN TEXTILE INDUSTRY
1.- INTRODUCTION
2.- FUNDAMENTALS OF ADSORPTION ONTO ACTIVATED CARBON
2.1.- Factors influencing adsorption
2.2.- Kinetics of adsorption
2.3.- Transport mechanisms
2.4.- Adsorption equilibrium
3.- DESIGN AND OPERATION
3.1.- Description
3.2.- Operation
3.3.- Design variables
3.4.- Typical design values
4.- PARAMETERS AND CONTROL STRATEGIES
4.1.- Breakthrough curve
4.2.- Activated carbon regeneration and activation
5.- PERFORMANCE
6.- PARTICULAR TECHNICAL CONDITIONS
7.- SPECIFICATIONS FOR THE TREATMENT OF WASTEWATER OF TEXTILE INDUSTRY
8.- OPERATION TROUBLESHOOTING
BIBLIOGRAPHY
ANNEX 1 MILLS EXAMPLES WITH AC ADSORPTION ON ITS EFFLUENT TREATMENT PLANTS PROCESS
ANNEX 2 GRAPHICAL DES CRIPTION OF UNIT PROCESSES
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1.- INTRODUCTION
Granular activated carbon (GAC) adsorption is a process used as tertiary treatment of municipal and industrial
wastewater (physical-chemical treatment, followed by secondary treatment) or as a step in the physical-chemical
treatment (coagulation, sedimentation, filtration, GAC adsorption) instead of the secondary treatment. In case of
being applied as a tertiary treatment, GAC is fundamentally used for organic molecules adsorption incorporated to
effluent from the biological treatment. It normally requires a pretreatment, such as lime precipitation followed by
rapid filtration.
In industrial water treatment, the GAC adsorption can be used to meet pretreatment discharge standards to
municipal wastewater treatment plants or to meet discharge standards to environment.
This document is based on the text Activated Carbon for Water and Wastewater Treatment of Ferhan Çeçen and
Ozgür Aktas (2012), with contributions and specific documents for water treatment in the textile industry.
The rate of adsorption is usually limited by various mass transport mechanisms and depends both on the properties
of the adsorbent and the adsorbate. Figure 1 shows the main transport mechanisms of an adsorbate to a carbon
surface and the adsorption phenomena.
Bulk solution transport (advection): Adsorbates must first be transported from the bulk solution to the boundary
layer of water (liquid film) surrounding the activated carbon particle.
External diffusion: Transport of adsorbate from the bulk of solution across the stationary layer of water, called the
hydrodynamic boundary layer, liquid film or external film that surrounds the adsorbent particles. It occurs by
molecular diffusion.
Intraparticle (Internal) diffusion Intraparticle diffusion involves the transfer of adsorbate from the activated
carbon surface to sites within the particle. In modeling of the adsorption of pollutants from water or wastewater,
the surface diffusion is usually assumed to be the dominant intraparticle transport mechanism.
Adsorption. After the transport of the adsorbate to an available site, an adsorption bond is formed. In the case of
physical adsorption, the actual physical attachment of adsorbate onto adsorbent is regarded as taking place very
rapidly. Therefore, the slowest step among the preceding diffusion steps (advection, external diffusion or internal
diffusion), called the rate-limiting step, will control the overall rate at which the adsorbate is removed from solution.
However, if adsorption is accompanied by a chemical reaction that changes the nature of the molecule, the
chemical reaction may be slower than the diffusion step and may thereby control the rate of removal.
ACTIVATED CARBON ADSORPTION FS-TER-002 Page 5 of 18
Adsorption equilibrium is often studied through those called adsorption isotherms, which represent the main
source of information on the adsorption process.
Figure 2 Representation of the general types of adsorption isotherms of solutes in porous media (Martin,
1997).
The amount of adsorbed material per unit mass of adsorbent increases with increasing concentration, but not in
direct proportion. Generally, an isotherm is favorable if its form is convex, and unfavorable if concave. Any point of
an isotherm curve describes an amount of pollutant adsorbed per unit weight of active carbon, or alternatively, the
adsorption capacity at a particular concentration.
As practical issues, the isotherms can be used to select the correct type of active carbon, to estimate the lifetime of
the adsorbent and to study the remaining adsorption capacity of an adsorption unit under continuous operation.
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Continuous flow GAC systems are usually composed of carbon filters, virgin and spent carbon storage, carbon
transport systems and carbon regeneration systems. The carbon filter typically consists of a linear steel column orn
a rectangular steel or concrete tank in which carbon is deposited as "filter bed".
Figure 3 Typical activated-carbon contactor in a pressure vessel (Metcalf & Eddy, 2002)
3.2.- Operation
The main reactor configurations for GAC adsorption systems are the fixed (packed), expanded, and fluidized
beds. A downflow adsorber with low fluid velocities essentially functions as a fixed-bed reactor. Fixed-bed
operation provides filtration as well as adsorption. The fixed-bed configuration is suitable in the case of low-
strength wastewaters containing little or no suspended solids.
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In sizing of GAC columns, the following factors are mainly taken into consideration: the empty-bed contact time
(EBCT), the hydraulic loading rate, the carbon depth, and the number of contactors. GAC filters may be designed as
up or downflow systems consisting of one or more vessels in series or in parallel. The main parameters
characterizing the GAC operation are as follows:
The EBCT is calculated as the total volume of the carbon bed divided by the flow rate of water:
Where
Vb=volume of the GAC bed (L3)
Q=flow rate (L3/T)
Where
LB=depth of GAC bed, (L)
A= cross-sectional area of bed, (L2)
Q/A=hydraulic loading rate (HLR), (L3/L2.T)
The EBCT represents the theoretical residence time in the filter in the absence of packing media. Therefore, it is
actually a fictive parameter whose meaningfulness has been discussed in water treatment.
Effective Contact Time: Since the GAC bed has a void fraction, the effective contact time (τ) of the fluid is as follows
in an adsorber:
Where
εB= void fraction in the carbon bed
Filter Velocities
In water and wastewater treatment the superficial velocity shows the velocity of liquid in an empty bed with a cross-
sectional area A and corresponds to the hydraulic loading rate (HLR). It is also termed the surface loading rate.
On the other hand, the interstitial velocity in an adsorber is a more meaningful parameter, and is defined as follows:
Bed Volume
The bed volume (BV) shows the normalization of throughput volume to the carbon bed volume VB. As such, it allows
a comparison of removal efficiencies of different adsorbers.
Table 1 Typical values for design and operation in GAC filters (Çeçen, 2012)
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As the wastewater flows naturally through GAC adsorbent, contaminants are eliminated by adsorption. The
adsorption of contaminants takes place in zone A, called the mass transfer zone (MTZ) (Figure 5). While in operation,
the transfer zone moves in the direction of flow. In this zone moves downwards, generating the saturation zone
(Zone-Sat) which is saturated with pollutants and is in equilibrium with the influent concentration.
Inside an AC filter pollutant concentration changes along the adsorption column, the area of rapid change of length
is known as concentrations wave front. Inside an adsorber, the concentrations of contaminants change with respect
to both time and reactor length. The region of rapid change in concentration with the length z is termed the wave
front.
The plot of effluent concentration divided by influent concentration (S/S0) as a function of elapsed time, processed
volume, or bed volume generates the “breakthrough curve”. The point at which a predetermined concentration
(SB) appears is defined as the “Breakthrough point”. This point is rather arbitrary and is selected according to purity
requirements.
The carbon adsorption capacity gradually deteriorates with use. When the quality of the effluent reaches the
minimum level set in quality standards, the spent carbon should be regenerated, reactivated or removed.
Activated carbon is a high capital investment and operating cost to operate in both batch and continuous, mainly
due to system regeneration need. The regeneration of the spent adsorbent is the most difficult and expensive part
of the adsorption technology. It carries about 75% of the cost of operation and maintenance of a filtration unit in
fixed bed GAC.
If regeneration of spent carbon is not feasible or it is irreversibly contaminated by the adsorbed substance, used
carbon used will be removed.
The most used techniques for regeneration are thermal, chemical and electrochemical regeneration.
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5.- PERFORMANCE
Table 3 shows qualitative active carbon filtration performance values in comparison with a conventional activated
sludge treatment and improved integrated adsorption and biological treatment process. According to this
reference, the use of both biological treatment and GAC, whether combined or in different steps of the process
line, allow to improve wastewater effluents.
Table 2 Reduction in pollutant groups parameters obtained by adsorption,
biodegradation or both processes integrated.
Figure 5 Activated carbon dispositives. A) Downflow in series. B) Downflow in parallel. C) Moving bed. D)
Upflow expanded bed. (Metcalf, 2002)
The design must also provide:
The specific characteristics of the Activated carbon adsorption process, turn it into a flexible process that can be
located in different places within the plant configuration (Figure 7) with different effluent quality targets. For
various applications in the textile industry it can be found as:
- Process water pre-treatment
- Tertiary treatment with discharge quality objectives
- Tertiary treatment prior to reuse.
Textile wastewaters are generally strongly colored with a high organic content. They are difficult to treat by
conventional biological treatment processes because of the presence of refractory dyes and complex ingredients.
The high color of these wastewaters results from a number of dyestuffs. The BOD5/COD ratio in these wastewaters
is generally too low (<0.2) to support biological treatment. In many cases, activated sludge can be effectively
combined with PAC to decolorize textile effluents since PAC serves as a deposit for dye molecules. For example, it
was shown that in the treatment of a wool-dyeing wastewater the decolorization yield reached 86% upon the
addition of PAC to a batch activated sludge reactor (Chen, 2000).
In addition, BAC filters can be used for dye removal. Simulated aqueous discharge from a carpet printing plant
comprising a mixture of acid dyes was treated for color removal in an aerobic batch BAC reactor dominated by the
bacteria Pseudomonas putida. This BAC system outperformed the combined application of conventional GAC
adsorption and biological treatment. Enhanced color removal was achieved in the BAC system due to the high
utilization of biodegradable anthraquinone dyes. The main factor underlying the enhanced utilization was the
accumulation of dye at the carbon surface. For non-biodegradable azo dyes, biosorption was an important removal
mechanism. In any case, in BAC systems biosorption was higher than the one in conventional immobilized systems.
An upflow biological aerated filter packed with two different layers consisting of GAC and ceramsite (artificial
foundry sand) was employed for tertiary treatment of a secondary textile effluent (Lin, 2008). The reactor performed
well under steady-state conditions. The average COD, NH4+-N, and total nitrogen (TN) in the effluent were, 31, 2 and
8 mg/L respectively, satisfying the standards for domestic reuse in China. At a constant dissolved oxygen (DO)
concentration, the increase in hydraulic loading rate (HLR) from 0.13 to 0.78 m3/m2/h decreased COD NH4+-N, and
TN removal efficiencies from 52% to 38%, 90% to 68%, and 45% to 33%, respectively. When the DO concentration
was raised from 2.4 to 6.1 mg/L, the efficiency of COD and NH4+-N removal increased from 39% to 53% and 64% to
88%, respectively.
ACTIVATED CARBON ADSORPTION FS-TER-002 Page 12 of 18
1: Alto Lura WWTP managed by CIDA Srl in Como area (Italy) treating 22.000 m3/d in a mixture consisting in 17% domestic WW,
32% stormwater, 51% homogenized textile finishing factories effluent (cellulosic, wool, silk and synthetic fibers). 2: Levi’s Strauss
WWTP, Wervik (Belgium).
Figure 6 Compilation of possible technological, commercial and experimental processes for the treatment and
reuse of textile effluents with GAC (modified from Vandevivere, 1998).
Anaerobic processes combined with activated carbon were also considered from the treatment of textile effluents.
For example, the wastewater of a carpet dyeing factory with COD and BOD5 concentrations up to 9000 and 1500
mg/L, respectively, was anaerobically treated in a GAC-UASB (upflow anaerobic sludge blanket) reactor with about
80% efficiency (Kuai, 1998).
In the review work to the effluent treatment plants of INDITEX’s supply chain, it is observed that factories use
activated carbon filters as a tertiary treatment prior to discharge into the natural environment. In all cases rapid
sand filtration precedes GAC filters (Annex I).
In the moving bed system, spent carbon is continuously replaced so that no head loss builds up. Another option in
water and wastewater treatment is to use fluidized bed reactors (FBRs), in which the upflowing liquid suspends the
fine solid particles, which remain in the reactor. Fluidized beds minimize clogging and unintentional filtration. The
carbon can be continuously removed from the reactor while fresh carbon can be added to the top at the same rate.
In contrast to fixed-bed operation, this process will eliminate the need to shut down the contactor after exhaustion
occurs.
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Regeneration, revitalization and replacement of activated carbon costs are the main expense in O&M of
AC filters.
5-10% of the carbon to be replaced is due to losses in the transport processes of activated carbon.
The adsorption capacity of regenerated carbon is slightly lower than that of virgin carbon.
BIBLIOGRAPHY
Çeçen, F. y Aktas, Ö (2012). Activated Carbon for Water and Wastewater Treatment. Germany: Wiley-VCH.
Chen, M., Wang, J., and Wang, Y. (2000) The combination of carbon adsorption with activated sludge for the
decolorization of wool-dyeing wastewater. J. Environ. Sci. Health, A35 (10), 1789-1795.
O. Cooney, David (1999) Adsorption design for wastewater treatment. Boca Ratón, Florida: CRC Press
Metcalf and Eddy, Inc. (2003) Wastewater Engineering: Treatment and Reuse. New York, NY: McGraw-Hill. 4th Ed.
Hendricks, d. (2006) Water Treatment Unit Processes: Phrysical and Chemical. USA: CRC Press
Vandevivere, P. C., Bianchi, R and Verstraete, W. (1998) Treatment and Reuse of Wastewater from the textile Wet-
Processing Industry: Review of Emerging Technologies. J. Chem. Technol. Biotechnol. 1998, 72, 289-302
Walker, G.M. and Weatherley, L.R. (1999) Biological activated carbon treatment of industrial wastewater in stirred
tank reactors. Chem En. J., 75
Liu, F., Zhao, C., Zhao, D., and Liu, G. (2008) Tertiary treatment of textile wastewater with combined media biological
aerated filter (CMBAF) at different hydraulic loadings and dissolved oxygen concentrations. J. Hazardous Mater.,
160, 161-167.
Kuai, L., De Vreeze, I., Vandevivere, P., and Verstraete, W. (1998) GAC ammended UASB reactor for the stable
treatment of toxic textile wastewater. Environ. Technol, 19, 1111-1117.
Martin, M. y Marzal, P. (1997) Modelación de la calidad del agua. Universidad Politécnica de Valencia.
ACTIVATED CARBON ADSORPTION FS-TER-002 Page 14 of 18
ANNEX 1
MILLS EXAMPLES WITH AC ADSORPTION ON ITS
EFFLUENT TREATMENT PLANTS PROCESS
BEXIMCO CONTINUOUS DYEING UNIT Code BAN01
STAGES OF THE
Chemicals added Additional notes
EFFLUENT TREATMENT PLANT
Equalization tank
Ferrous sulphate
Dissolved Air Flotation Clarifier Lime
Polyelectrolite
Sedimentation tanks
Discharge to river
Equalization tank
Ferrous sulphate
Chemical coagulation Lime powder
Flocculation Polyelectrolyte
Discharge to river
ACTIVATED CARBON ADSORPTION FS-TER-002 Page 15 of 18
STAGES OF THE
Chemicals added Additional notes
EFFLUENT TREATMENT PLANT
Screening
Equalization tank
Demulsifier
Flocculation Polymer
Sand filter
Discharge pipe
ACTIVATED CARBON ADSORPTION FS-TER-002 Page 16 of 18
WATER CONSUMPTION: 471600 m3/year (approx.. 1580 m3/day) – 45% public supply, 55% groundwater.
ETP CAPACITY: 30 m3/h (24h/day)
Only 260.000 m3/year go to discharge. Human consumption, heat production and cooling water go directly to
discharge (no WWTP downstream). Insufficient ETP capacity even to give treatment to 55% of water (process water).
Clarifier
Carbon filter
Sand filter
Post-aeration
Discharge pipe
ACTIVATED CARBON ADSORPTION FS-TER-002 Page 17 of 18
ANNEX 2
GRAPHICAL DESCRIPTION OF UNIT PROCESSES
Figure 1. GAC adsorption for taste and odor removal in water purification system (ETAP-Lugo).