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Desalination 228 (2008) 263–276

Use of zeolites for treating natural gas co-produced waters
in Wyoming, USA
Hongting Zhaoa, George F. Vancea*, Girisha K. Ganjegunteb,
Michael A. Urynowiczc

Department of Renewable Resources, cDepartment of Civil & Architectural Engineering,
1000 E. University Avenue, University of Wyoming, Laramie, WY 82071, USA
Tel. +1 (307) 766-2297; Fax: +1 (307) 766-6403; email:
Department of Soil and Crop Sciences, Texas Agricultural Experiment Station, Texas A&M University System,
1380 A&M Circle, El Paso, TX 79927, USA
Received 29 May 2007; Accepted 14 August 2007

Fast development of the coalbed natural gas (CBNG) industry in many parts of the western US has resulted in
the co-production of potentially saline-sodic waters, hereafter referred to as CBNG water. Management of CBNG
water is a major environmental challenge because of its quantity and quality. In this study, the potential utilization
of three calcium (Ca2+)-rich zeolites were examined for removal of sodium (Na+) from CBNG waters. The zeolite
samples examined were from the St. Cloud (ST) mine in Winston, NM, the Bear River (BR) mine in Preston, ID,
and a mine in Arizona (AZ). The zeolite materials were used in adsorption and column experiments to evaluate
sorption as a function of water chemistry, particle size and flow rate. Regeneration and potential reuse of the media
were also examined. Surrogate CBNG waters that simulated the water chemistry of CBNG waters were used in the
different studies. Although the AZ-zeolite is a Ca2+-rich chabazite, results from column studies indicate there was
essentially no Na+ exchange, suggesting the Ca2+ is tightly held on chabazite adsorption sites. Results for ST-zeolite
and BR-zeolite, which are clinoptilolite zeolites, indicated that a Langmuir model fit the adsorption data well. The
maximum adsorption capacities from the adsorption curves for ST-zeolite and BR-zeolite were 9.6 and 12.3 (mg/g),
respectively, accounting for approximately 38% and 39% of their measured CEC values. Column studies indicated
that a metric tonne (1,000 kg) of ST-zeolite and BR-zeolite can be used to accumulatively treat 16,000 and 60,000 L
of CBNG water, respectively, in order to lower the sodium adsorption ratio (SAR, mmol1/2L!1/2) of the simulated
CBNG water from 30 to an acceptable level of 10. Based on the results of this study, Na+ removal with clinoptilolite
zeolite appears to be a potential water treatment technology for maximizing the beneficial use of poor-quality CBNG
water. Ongoing studies are evaluating water treatment techniques involving the direct application of zeolite to CBNG
waters and development of a field scale prototype.

Zeolite; Clinoptilolite; Chabazite; Sodic-saline water; Adsorption; Sodium; Calcium; Coalbed
methane co-produced water; Powder River Basin; Sodium adsorption ratio; SAR; Water treatment

*Corresponding author.
0011-9164/08/$– See front matter © 2008 Published by Elsevier B.V.

such as orthoclase and plagioclase feldspars.8 to greater than 8.0. of which the zeolite types A. with the most predominant consisting of analcime. which can render soils unsuitable for plant growth [1–3]. Utah. and phillipsite. clinoptilolite cation selectivity follows the order of: Cs > Rb > K > NH4 > Ba > Sr > Na > Ca > Fe > Al > Mg > Li. heulandite. clinoptilolite. and it is defined as: SAR (mmol1/2 L!1/2) = [Na+]/ [Ca2++ Mg2+]1/2 (1) where Na+. whereas chabazite selectivity is Tl > Cs > K > Ag > Rb > NH4 > Pb > Na = Ba > Sr > Ca > Li [5]. and have cation preferences that result in cation selectivity. For example.9 dS m!1. and phillipsite [5]. erionite. X. and Wyoming. mordenite. it is often not suitable for direct irrigation. One of the most serious concerns of the CBNG development is the coproduction of copious quantities of potentially poor quality groundwater required to recover the natural gas. The objectives of this study were to (1) evaluate the potential of naturally Ca2+-rich zeolites to reduce Na+ concentration in CBNG waters and (2) develop a costeffective treatment technology for utilizing CBNG waters for beneficial purposes. Natural zeolites have been effectively utilized to remove toxic elements from polluted waters [4–6]. Y and ZMS-5 are the most common [7]. Idaho. low mining cost and their capacity to retain cations. and Mg2+ represent millimolar concentrations (mmol L!1) of the respective ions. erionite. Other components. Zhao et al. The primary concern with CBNG co-produced waters is the amount of Na+ and its influence on the environments.4 to 4. ion-exchange. Montana and other western US states during the past 10 years has resulted in the generation of a significant energy resource as well as some serious environmental and regulatory concerns [1–3]. laumontite. Zeolites are hydrated aluminosilicates of alkaline and alkaline-earth metals. smectite. CBNG water is dominated by sodium (Na+) and bicarbonate (HCO3!) ions. Oregon. Introduction Coalbed natural gas (CBNG) development in Wyoming. and are located in Arizona. Ca2+. sodium adsorption ratio (SAR) from a low of 5 to a high of 70 mmol1/2 L!1/2 and total dissolved solid concentrations from 270 to 2720 mg L!1 [1]. / Desalination 228 (2008) 263–276 1. Texas. quartz and volcanic glass are present in the different deposits. Therefore. New Mexico. chabazite. Different zeolites exhibit distinctive cation exchange capacities (CEC) and adsorption pro- perties. mordenite. Zeolites in these deposits are chabazite. with pH ranging from 6. molecular sieve and catalytic properties. The SAR is a measure of the relative preponderance of Na+ to calcium (Ca2+) and magnesium (Mg2+) to water. clinoptilolite. Clinoptilolite and chabazite zeolites have a preference for larger cations. About 40 natural zeolites have been identified during the past 200 years [7]. Although the quality of CBNG water varies within the western US. The slightly higher preference of Na+ over Ca2+ of clinoptilolite zeolites makes them a better choice for removing Na+ from CBNG waters.264 H. Commercial zeolite deposits in the US are associated with the alteration of volcanic tuffs in alkaline lake deposits and open hydrologic systems. California. cost-effective technologies are needed in order to allow the CBNG waters to be used for beneficial purposes. Natural and synthetic zeolites are used commercially because of their unique adsorption. Within the Powder River Basin (PRB) of Wyoming. opal. Long-term irrigation of soils with water of high SAR values can result in deterioration of soil physical and chemical properties such as soil infiltration and permeability. Nevada. electrical conductivity (EC) from 0. Some of the advantages of utilizing natural zeolite as a cation exchanger for CBNG water treatment are the large number of deposits throughout the western US. A reduc- . ferrierite. More than 150 zeolites have been synthesized.

Zeolite exchangeable cation concentrations and cation exchange capacities (CEC) were determined by a modified method of Cerri et al. CBNG water used in this study (Table 2) was developed by compiling published data from various sources [3. and a commercial pre-activated Ca-rich chabazite from Arizona (AZ-Zeolite) [Cabsorb® Chabazite Products (Cabsorb ZS500RW)].com).4 65. The sum of major exchangeable cation concentrations was used to 2. Zhao et al.gsaresources.90 . availability and potential performance. 1. [9]. Materials and chemicals Upon consideration and comparison of the cost. NM) Zeolite-Clinoptilolite (Bear River. Table 2 Water chemistry of synthetic CBNG waters (mg/L) used in the study Parameters Na Ca Mg K Cl SO4 HCO3 SiO2 SAR pH CBNG Water I CBNG Water II CBNG Water III 205 411 822 10 10 10 2.gsaresources.5 45. provided by GSA Resources Inc.0 g of zeolite sample was reacted for 2 h with 33 ml of 1 M ammonium acetate (NH4OAc) at room temperature followed by centrifugation and filtration (Whatman filter #42) of the supernatant.5 2.2.2 8. com) (Table 1). Experimental 2.25 2. / Desalination 228 (2008) 263–276 tion in the amount of Na+ and the release of exchangeable Ca2+ from zeolites facilitates the lowering of SAR levels. (http://www.1. the following natural zeolites were selected: two commercially available natural clinoptilolite samples obtained from the St.8 65.5 2. This process was repeated two more times with the three extracts combined in a 100 ml volumetric flask that was brought to volume using 1 M NH4OAc. The water chemistry of surrogate Table 1 Exchangeable cations (meq/100 g) and effective CEC (meq/100 g) of Ca-rich zeolites used for treatment of CBNG waters Sample Designation Na+ Ca2+ Mg2+ K+ CEC Zeolite-Clinoptilolite (St. Pulverized samples were scanned using Cu Kα radiation at 1.5 1.90 8. 2. NM and the Bear River zeolite (BR-Zeolite) mine in Preston. ID.5 30. A bench scale study was conducted to evaluate the applicability of natural zeolites in order to develop a cost-effective treatment system for removing Na+ from CBNG waters.1 60.54 Å.265 H.8] and prepared using appropriate amounts of inorganic chemicals and tetraethyl orthosilicate as the silicon (Si) source. resulting in CBNG waters that can be beneficially used by industry. Samples were first dried at approximately 80°C for several hours with water loss ranging from <1% to 6%. Material characterization X-ray analysis was conducted on the different zeolite samples.5 2. ID) Zeolite-Chabazite (Arizona)a ST-Zeolite BR-Zeolite AZ-Chabazite 4 10 — 77 67 Dominant 18 3 — 13 56 — 112 136 250 a According to the product specification provided by the manufacturer (http://www.20 8. land owners and other downstream users. Cloud.8 5 10 10 505 1010 1010 5 10 10 15. Briefly. Cloud zeolite (STZeolite) mine in Winslow.

5%). The samples were then acidified using a few drops of concentrated nitric acid (HNO3) and stored until analyzed. Batch adsorption kinetic and equilibrium studies Adsorption kinetic studies were carried out using 20. K2O (3. For the Arizona chabazite.0 g zeolite sample was weighed into 50 ml polyethylene bottles containing varying concentrations of NaCl. 15.21%). MnO (0. The solutions were also measured for pH and electrical conductivity (EC) using pH and conductivity meters.49%).44%).99%). Effluent was collected using an automated fraction collector.2%) and loss on ignition values (LOI) (11. Material characterization X-ray diffraction (XRD) analysis (data not shown) indicated a significant occurrence of clinoptilolite in ST-zeolite samples (80% and 85% clinoptilolite. Zhao et al. model P300) with K+ analyzed using atomic absorption (AA) spectroscopy (Perkin Elmer.28%).07%). 2. model 2380). For BR-zeolite.0 g zeolite samples diluted with the surrogate CBNG water to 1. 34.4.44%). 132. Fe2O3 (1. 3. Al2O3 (10. 3.000 ml at ambient temperature.9%).0%).1 M CaCl2 at a flow rate that was half of that used for the CBNG water. A 5. column diameter. Al2O3 (12.57%) and LOI (12. The tubes were shaken on a reciprocal shaker for 48 h. 250 mm (for ST-zeolite) and 260 mm (for BR-zeolite). Results and discussion 3.1%). TiO2 (0. Aliquots of these samples (~5 ml) were collected at various times using a syringe with a GHP Acrodisc 0. 125 cm3. quartz.4%). Ca2+. 2. feldspar and illite. with the balance of materials comprised of chalcedony. / Desalination 228 (2008) 263–276 determine the effective cation exchange capacity (ECEC).06%). column set-up parameters were: weight of zeolite. flow rate. and column media length. flow rates. The measured CECs were 112 and 136 meq/100g for ST-zeolite . Instrumental The concentrations of cations (Na+. which was similar to the manufacturer’s specifications).87%). For ST-zeolite. column media length.0 or 16 ml/min. K2O (4. MgO (0.0 ml/min. 2. TiO2 (0. other minerals identified by XRD analysis included smectite.32%). The initial Na+ concentrations in the tubes ranged from 0 to 5. Fe2O3 (1. and BR-zeolite as SiO2 (66. Column parameters were as follows: weight of zeolite. CaO (2. Na2O (0.266 H.0.1. cristobalite. Mg2+) in solution were analyzed using inductively coupled plasma (ICP) spectroscopy (Thermo Jarrell Ash. and the supernatant solution filtered and acidified as described above.010 mg/L as HCO3!. CaO (2. Packed column and regeneration study A continuous flow-through column apparatus was utilized in order to predict zeolite performance under practical treatment system conditions. centrifuged. Exchangeable cations and effective CEC for the zeolites are listed in Table 1.000 mg/L.5. 6. 5. 25. P2O5 (0.0 mm.0 cm.0 mm. Adsorption studies were conducted using the batch equilibration technique [10]. The tubes were then filled with 45 ml of sodium bicarbonate (NaHCO3) solution with a concentration of 1. Na2O (0. 32.5%).44%).3. MgO (1. The columns were extensively rinsed with 3–4 L of DI water to remove pore residual CaCl2 (checked by AgNO3 solution). respectively. Regeneration studies on the spent media were conducted using 0. and bed volume. XRD analysis also confirmed a dominant presence of clinoptilolite (85–92%) with no apparent impurities.0 g.33%). column diameter.2 g.2 µm filter attached. Total chemical analysis indicated zeolite composition of ST-zeolite as SiO2 (66.

it has been found that the pseudo-second-order kinetic equation agrees well with chemisorption as the ratecontrolling step. Adsorption kinetics is related to many factors including particle size.1. respectively. Fe2O3 (4.47%). and zeolite adsorption capacities for Na+.89%).49%). 1) were analyzed by the pseudo-second-order kinetic model to estimate rate constants. v0 and Qeq values for kinetic studies can be determined. Adsorption data (Fig. It is interesting to note that BR-zeolite contains considerable exchangeable K+ (56 meq/100 g) as compared to that of ST-zeolite (13 meq/100 g) (Table 1). the following linear equation can be obtained: t 1 1 = + t Qt v0 Qeq (3) v0 = k * Qeq2 (4) where v0 (mmol/g*min) is the initial adsorption rate.H. two kinetic models of adsorption have been frequently used: (1) active available site model and (2) chemical reaction rate model. For many adsorption processes occurring on heterogeneous materials. BR-zeolite removed more Na+ and released greater amounts of Ca2+ than ST-zeolite. In addition.e. increased levels in the treated water would be beneficial for agricultural irrigation purposes. pore structure and solute diffusion. Other major exchangeable cations (i.12]: 2 d Qt = k * (Qeq − Qt ) dt (2) where Qeq is the sorption capacity at equilibrium. Qt is the solid-phase loading of Na+ at time t (min) and k (g/mmol*min) is the pseudo-secondorder rate constant. by plotting t versus t/Qt. The Ca-rich Arizona zeolite (Cabsorb ZS500RW) was used as received from the company. High coefficient of determination values (R2 ~0. The upgrading processes ranged from none to partial recrystallization with the exchangeable cations in the final product dominated by Ca2+.2. Since K+ is an important plant nutrient. Al2O3 (16. Adsorption kinetics Fig. The pseudo-second-order kinetic 267 rate equation can be expressed as [11.97–0. K+ and/or Mg2+) were also replaced by Na+ and released into the solution. More Ca2+ and K+ were released by BR-zeolite than from ST-zeolite. The results also suggest that equilibrium may not be obtained in the pilot tests where empty bed contact times (EBCT) are on the order of 3–5 min [13]. Zhao et al. K2O (1.40%). TiO2 (0. 3.33%). Relevant parameters are summarized in Table 3. Considering the boundary conditions of Qt = 0 (at t = 0) and Qt = Qt (at t = t). which is based upon the mass law concept. Generally.32%) and MgO (0. Rate constants and initial adsorption rates decrease in the order of BRZeolite > ST-Zeolite with BR-Zeolite having the . According to the manufacturer this product originated from a natural high Na chabazite that was thermally treated at low to high temperatures.6%). CaO (4. initial sorption rates. Adsorption kinetic and equilibrium studies 3. / Desalination 228 (2008) 263–276 and BR-zeolite. Na2O (2.2.. Approximately 22% to 32% of the initial Na+ in solution (about 411 mg/L) was removed by the end of the 24-h equilibration period. 1 indicates that Na+ adsorption rates are faster for BR-zeolite compared to ST-zeolite. Both ST-zeolite and BR-zeolite samples are naturally enriched with exchangeable Ca2+. and has a composition of SiO2 (69.99) indicated that the adsorption of Na+ on the tested media were well described using the pseudosecond-order kinetic model. Therefore. Adsorption results show that a 24-h equilibration period (1440 min) was sufficient to establish steady state or equilibrium for future sorption experiments using similar particle sizes and initial Na+ concentrations.5%).

Zhao et al. highest equilibrium sorption capacity in the kinetic tests.e. Adsorption kinetic parameters are informative in predicting Na+ removal from CBNG waters. Results of pseudo-second-order model fitting are shown for Na+ adsorption.60 R2 = model-fitting coefficient.999 0. Note scale differences on the y-axis.127 1.36×10!3 1.268 H. v0 = initial adsorption rate (mmol/g*min). pore size.. 1. surface area. compo- sition. / Desalination 228 (2008) 263–276 Fig.05×10!2 0.036 0. surface charge. Qeq = sorption capacity at equilibrium (mmolAs/g) or mg/g. Differences in adsorption by the two zeolites can be attributed to variations in the physical and chemical properties of the media (i.287 4.972 0. sodium affinity). Mg2+ and K+ release kinetics for ST-zeolite (14×40 mesh) and BR-zeolite (14×40 mesh).195 0. K = pseudo-second-order rate constant for the kinetic model (g/mmol*min). Diffusion coefficients are also important parameters for predicting the diffusion .47 6. Table 3 Kinetic parameters for Na+ adsorption by zeolites in CBNG Water II using pseudo-second-order model Media R2 K v0 Qeq (mmol/g) Qeq (mg/g) ST-Zeolite (14×40) BR-Zeolite (14×40) 0. Na+ adsorption and Ca2+.

respectively. qmax is the maximum adsorption capacity of the solid phase. The values for effective diffusivity De (cm2/s) calculated based on data points with Mt /Mmax above 40% and assuming an average particle size of 0. In order to determine the effective diffusivity of Na+ in the macropores of adsorbent media. proposed by Ruthven (1984) [14]. Mmax (µg/L) is the mass gain of adsorbent at infinite time. Dp (cm2/s) is the macropore diffusivity of adsorbate in the adsorbent. . The macropore diffusivity (Dp) is assumed to be independent of concentration in the above equation. De. was used: (1 − ε ) ∂∂qt + ε p p ⎛ ∂ 2 c 2 ∂c ⎞ ∂c = ε p Dp ⎜ 2 + ⎟ (5) ∂t R ∂R ⎠ ⎝ ∂R where εp is adsorbent particle porosity. BR-zeolite has a higher De value than that of ST-zeolite. and an intercept of ⎛ 6 ⎞ ln ⎜ 2 ⎟ ⎝π ⎠ from which the effective diffusivity. 2). Adsorption of Na+ by ST-zeolite (14×40) and BR-zeolite (14×40).01×10!9 (R2 = 0. time should generate a straight line with a slope of ⎛ −π2 De ⎞ ⎜⎜ ⎟⎟ 2 R p ⎝ ⎠ Fig.03×10!9 (R2 = 0.H. and R (cm) is the radial distance from the center of the adsorbent particle. for Na+ diffusion in the macropores of the media can be calculated. q(R. For fractional adsorption uptake (Mt /Mmax).2. the solution for the equation with a 2% error is given by [13]: ⎛ π2 De t ⎞ Mt 6 ≅ 1 − 2 exp ⎜ ⎜ R 2 ⎟⎟ M max π ⎝ p ⎠ (6) where Mt (µg/L) is the mass gain of adsorbent at time t. / Desalination 228 (2008) 263–276 269 rate of adsorbate molecules in porous media [13]. 2. are 2. c (µg/L) is the adsorbate concentration in the supernatant solution. a diffusion equation for a macropore-controlled system on a spherical shell element of the adsorbent particle.t) is the adsorbed phase concentration (µg/L of adsorbate). t (s) is time. Adsorption equilibrium studies The Na+ adsorption curves showed L-type adsorption on ST-zeolite and BR-zeolite (Fig. The L-type adsorption curves are described well using the Langmuir equation [10]: q= qmax KC 1 + KC (8) where q is the amount adsorbed (mg/g).2. and De (cm2/s) is the effective diffusivity defined by: De = ε p Dp ε p + (1 − ε p ) K (7) A plot of ln[1!(Mt /Mmax)] vs. 3.948) for BR-zeolite (14×40).939) for STzeolite (14×40) and 7. Zhao et al.315 mm.

6 and 12. the ease of which Ca2+ exchanged from ST-zeolite is lower than that of the BR-zeolite.e..e. a one-point adsorption study was carried out using BR-zeolite samples with varying particle sizes in different CBNG waters (Fig. Rearranging to a linear form. Effect of water chemistry and particle size The effects of water chemistry and zeolite particle size on the CBNG water quality were also studied. with the BR-zeolite having a higher Na+ adsorption capability than ST-zeolite. Overall. which suggests that the difference is probably due to the release of other cations. Considering charge balance. (7) becomes: C 1 C = + q Kqmax qmax (9) Plotting C/q vs. Mg2+ and K+.270 H. Results indicate the finer particle size materials had a greater reduction in SAR of the three CBNG waters.3. cation valence/hydration degree and pre-existing cations. Eq.42 and 0. ST-zeolite (14×40) has been characterized [15] to have an average pore diameter of 4 Å. C results in a slope of 1/(qmax) and intercept of 1/(Kqmax). 3.6 12. crystallinity. the adsorption results of this study suggest that both zeolites can be used to reduce Na+ level in CBNG waters by releasing Ca2+. Although STzeolite contains slightly higher exchangeable Ca2+ concentrations than that of BR-zeolite. respectively. making the Ca2+ in BR-zeolite Table 4 Langmuir adsorption parameters for the adsorption of Na+ by ST-Zeolite (14×40 mesh) and BR-Zeolite (14× 40 mesh) Sample qmax (mg/g) K R2 ST-Zeolite BR-Zeolite 9. Long-term experiments may provide better evidence for the removal of Na+ from CBNG waters. 2 and Table 4) for STzeolite and BR-zeolite are 9. more easily replaced by Na+ than that in STZeolite.3 872 1053 0. The BR-zeolite had a greater adsorption affinity for Na+ than did the ST-zeolite at the same equilibrium solution Na+ concentrations. media purity. ion concentration and multiple adsorption sites with varying degree of accessibility as well as rate-limiting steps (mass transfer and diffusion) [10].54 (meq/g). / Desalination 228 (2008) 263–276 K is the Langmuir constant and C is the solution Na+ concentration at equilibrium. 14×40 < 40×100 – 100×140 – !140 – !325. The previously reported cation selectivity order indicated Na+ is only slightly preferred over Ca2+ on clinoptilolite. Similar to the previously described adsorption studies. Mg2+ and K+ released accounted for more than 85% of the adsorbed Na+ on both ST-zeolite and BR-zeolite. Cation adsorption behavior (i. The binding strength constant of BR-zeolite is higher than that of ST-zeolite. which accounts for approximately 38% and 39% of their measured effective CEC values.965 0. the majority of reactive sites are on internal surfaces. adsorption capacity and selectivity) by zeolites are related to a variety of factors such as mineral purity. The higher K+ in BR-zeolite suggests the preference for K+ on stronger adsorption sites.3 (mg/g) or 0. suggesting that the Ca2+ in ST-zeolite may occupy stronger adsorption sites. This could result in Ca2+ bound to relatively weak adsorption sites. Zhao et al. while K+ is more strongly adsorbed [5]. For example. The adsorption results are consistent with the findings observed in the kinetic studies. The maximum Na+ adsorption capacities from the adsorption curves (Fig. indicating that Na+ could be more strongly adsorbed by BRzeolite.983 qmax = maximum adsorption capacity. 3). In porous materials such as zeolites. i. K = binding strength constant. an internal CEC of . the amount of Ca2+..

0 ml/min). and contact time as well as water chemistry [13].1 meq/g. water flow rate. smaller particle-sized zeolite materials would generally give rise to higher adsorption rates and capacities due to shorter paths within and between particles. 3. 4. Packed column study and data analysis Column studies are useful for designing scaled-up pilot projects for future applications. 40×100. 4–7.10). adsorption capacity. Results of column breakthrough studies using 14×40 ST-zeolite and BR-zeolite at a flow rate of 3. with some internal surfaces of the larger particles not utilized for adsorption. Column performance depends upon a variety of factors that include adsorbent type. diffusional resistance to mass transport within larger particle-sized zeolites is generally higher than that of smaller particle-sized zeolites.H.30) and for BR-zeolite (pH 8. Column breakthrough curves for ST-zeolite (14×40 mesh) in CBNG water II and corresponding change in effluent SAR values (flow rate = 3.8 meq/g. BR-zeolite was found to remove more Na+ from the synthetic CBNG waters and that there was a longer break-through period for . weight of adsorbent in Fig. particle size. Effect of particle size and water chemistry (Table 2) on SAR values by BR-zeolite (14×40. there was no significant change in pH values of the leachates for ST-zeolite (pH 9. column diameter. as compared to influent solution (pH 8. adsorbent bed depth. As a result. !140 and !325 mesh. 100×140. column. The column performance results are consistent with the trends observed in the batch adsorption kinetic and equilibrium studies.0 and 6. Zhao et al. respectively). Monitoring of the effluent solution pH indicated that. 3.00±0.10). about 0.90±0. and an external CEC of about 0. Therefore. / Desalination 228 (2008) 263–276 271 Fig.4.90±0.0 ml/min are shown in Figs.

6).0 ml/min). which. involves heating and recrystallization. the area between the SAR curve and SAR = 10 cutoff line (lower shaded area in Figs. CBNG waters processed initially would have very low SAR values (n10) with progressive treatment resulting in water with higher SAR values (>10). 6. This would allow for prediction of the amount of CBNG water (SAR = 30 mmol1/2L!1/2) that can be treated per metric ton (1. for BR-zeolite significant K+ was also released. suggesting that the Ca2+ in the pre-activated Ca-rich chabazite is strongly adsorbed. Thus.0 ml/min). Column breakthrough curves for AZ-chabazite (14×40 mesh) in CBNG water II and corresponding change in effluent SAR values (flow rate = 5. respectively.000 L of CBNG water (SAR = 30) could be treated by a ton of ST-zeolite (14×40) and BRzeolite (14×40). 5. 4 and 5) can be used to estimate flow- through treatment system processes that results in effluent SAR of 10 mmol1/2 L!1/2. Column breakthrough curves for BR-zeolite (14×40 mesh) in CBNG water II and corresponding change in effluent SAR values (flow rate = 3. It is interesting to note that. Zhao et al. if treated waters with high SAR (>10) were mixed with the initially treated waters with low SAR (n10). which is an important plant nutrient. though it has Ca2+ as the dominant exchangeable cation and high CEC. Fig. In the Powder River Basin. SAR breakthrough curves (Figs. 4 and 5) was integrated. Therefore.000 kg) of ST-zeolite and BRzeolite. if CBNG water were treated in a column and continuously collected in a large containment reservoir. / Desalination 228 (2008) 263–276 Fig. CBNG water is generally pumped into reservoirs or ponds. Our results indicate about 8.272 H. according to the manufacturer. The total amount of additional CBNG waters that could be treated and combined with the initially processed waters to reach a final SAR value of 10 would therefore be estimated using an equivalent . then the overall SAR would be less. WY.000 and 30. If one considers CBNG water with SAR values equal to or less than 10 to be suitable for land application. the BR-zeolite compared to the ST-zeolite. This may be attributed to the upgrading treatment process of the raw materials. There was almost no removal of Na+ or Ca2+ released in the column study for the AZ-chabazite (Fig. In order to estimate the overall water volume that can be treated to a mean SAR value of 10.

(b) BR. However.0 to . Therefore. Column breakthrough curves (SAR) as a function of water chemistry. CBNG water II.zeolite (14×40 mesh).000 kg) of ST-zeolite (14×40) or BR-zeolite (14×40) can treat approximately 16.H. Zhao et al. respectively. Effect of flow rate. flow rate 6. 4. 7. BRzeolite can treat nearly four times more water than ST-zeolite. suggesting BRzeolite can only treat 1. Extrapolating the results suggests that one metric ton (1. CBNG water II. the maximum adsorption capacities obtained from the adsorption curves were 12.3 times more than that of ST-zeolite. respectively.b) show that when flow rates were increased from 3.000 or 60. 7a. This concept of accumulative treatable water volume is used throughout the following studies. 3. flow rate 3.0 ml/min.1. flow rate 6. CBNG water III.4. / Desalination 228 (2008) 263–276 273 Fig. This large discrepancy could presumably be attributed to the lower effective diffusivity (De) for Na+ diffusion in the macropores of the ST-zeolite than BR-zeolite as observed in the kinetic studies. flow rate 16. to a final SAR around 10. (c) BR-zeolite (14×40 mesh).6 (mg/g) for BR-Zeolite and ST-Zeolite.0 ml/min. which is considered safe for land application for agricultural use. area above SAR 10 (upper shaded area). CBNG water II. (d) BR-zeolite (40×100 mesh).0 ml/min. particle size and water chemistry Column study results (Figs.0 ml/min. flow rate and particle size: (a) ST-zeolite (14×40 mesh).3 and 9. 5.000 L of the synthetic CBNG Water II (SAR = 30).

it is reasonable to assume that more water can be treated if the CBNG water contains less Na+. the treatable water volume by one ton of ST-zeolite (14×40) and BR-zeolite (14×40) was reduced from 16. Reduction in contact time results in less Na+ removed and lower concentrations of Ca2+ and Mg2+ released. 7c. Regeneration of spent BR-zeolite column in 0.2. . 3.000 L/ton compared to 60. 8b) indicated that ~2 L 0.000 L/ton. Fig. In addition. Results of the regeneration effluent solution composition (Fig. 8. for practical CBNG water treatment. Fig. 3.000 mg/L). which is consistent with regeneration results obtained on 14×40 BR-zeolite column study at a flow rate of 6. Regeneration of spent media and recycle A preliminary regeneration study was conducted using BR-zeolite (14×40).000 and 50. however.274 H.000 L to 11. higher flow rates could result in less Na+ adsorption and Ca2+ release due to the limit of diffusion process depending on zeolite particle size. Increasing the concentration of the regeneration CaCl2 solution could result in less CaCl2 solution used as well as a lower volume of spent brine generated. This suggests that the finer zeolite particle size and higher flow rate are capable of producing a similar treatment as that using larger particle size and a lower flow rate. / Desalination 228 (2008) 263–276 6. However. thus reducing treatment cost. 3 suggests that finer particle size zeolites could result in a greater reduction in SAR.000 L/ton for CBNG Water II. the Fig.0 ml/min (Fig. the actual treatable water volume will be dependent upon its composition chemistry and other factors. Zhao et al.1 M CaCl2 solution (Ca2+ = 4. suggesting the spent media can be recycled. The breakthrough curve of CBNG Water III in BR-zeolite (14×40) column) is shown in Fig. which is similar to that observed for 14×40 BR-zeolite at a flow rate of 3. A column study using 40×100 BR-zeolite at a flow rate of 16 ml/min (Fig. which was approximately 21.1 M CaCl2 solution (a) BR-zeolite (14×40 mesh) and (b) BRzeolite (40×100 mesh). This would imply that the reaction is controlled by an external diffusion process. BR-zeolite (40×100) (flow rate = 16 ml/min) columns were also regenerated using a 0. 7d) indicated a volume of treatable water of approximately 60.000 L/ton. Thus an increase in the initial Na+ concentration in the CBNG Water resulted in a lower treatable water volume. SAR and Na+ concentration in CBNG Water III are twice as high as that of CBNG Water II. Based upon results in Fig.000 or 60.0 ml/min.1 M CaCl2 solution should be sufficient to remove a majority of the adsorbed Na+. 8a indicates that a majority (90%) of the adsorbed Na+ can be replaced by Ca2+ after leaching 2 L 0.0 ml/min. 5). respectively.1 M CaCl2 solution.4.

King and G. Wyoming Water Development Commission. Reddy. processing.40 per barrel. Jackson and K. 9).F. more CBNG water was treated upon regeneration (76. Therefore. Soil Poll. not considering other expenses and the potentials 275 of regeneration and reuse of the media. Vance and L. regional and/or nationwide uses. Qual. making the use of zeolite treatment a more feasible. For example. Geochemistry of CBNG produced water in the Powder River Basin: Salinity and sodicity. The prices for industrial or agricultural applications ranged from $30 to $70 per ton for granular products down to 40 mesh and from $50 to $120 per ton for finer (!40 to +325 mesh) ground material. Column breakthrough curves (SAR) for the regenerated BR-zeolite (40×100 mesh) in CBNG water II at a flow rate of 16. Ganjegunte. thus making more Ca2+ available for replacement and greater treatable water volumes. This can be attributed to a higher concentration of Ca2+ (4. J.E. and world markets [16. Economic feasibility Prices for natural zeolite vary with zeolite content. water treatment. Zhao et al. G.K. obtained through a US Geological Survey of domestic zeolite producers.80–1.50 to $4. Therefore. Ganjegunte.0 ml/min. / Desalination 228 (2008) 263–276 Fig. aquaculture.00 per barrel (159 L).20–0. Reflections. or odor control applications with prices ranging from $0. . The bulk of the tonnage sold ranged from $80 and $140 per ton. King. zeolites are used for products such as pet litter. Soil chemical changes resulting from irrigation with water co-produced with coalbed natural gas. As compared to the first treatment using the BR-zeolite (40×100). USDA National Research Initiative grant (GFV) and a US Department of Energy special grant to the State of Wyoming for investigating the treatment of CBNG waters using zeolites. for BR-zeolite approximately $0. The regenerated BR-Zeolite (40×100) column was subjected to further CBNG Water II treatment (Fig.15]. On-line. Air. the cost would be reduced.e.. Coalbed methane co-produced water: Management options. References [1] G. [3] R. Acknowledgement This research was supported by the US Geological Society. fish tank media. 9. We appreciate the X-ray diffraction analysis provided by Robert Gregory of the Wyoming State Geological Survey. the cost of treating CBNG water with ST-zeolite is about $0. 3. Na+. June (2004) 31–34. K+. ranged from $50 to $140 per metric ton.. 34 (2005) 2217–2227. there could be a significant reduction in the treatment cost. household products.17].K. If repeated use of the column is considered.F. Vance.H. Mg2+) upon treatment in CBNG water.50/kg.000 mg/L) in CaCl2 regeneration solutions resulting in further replacement of un-exchanged cations (i. cost-effective technology for CBNG water treatment.5. industry and air/gas treatment [5. 2007. It is well known that zeolites have many applications as adsorbents in agriculture. L.000 L). by exploring applications of the spent zeolite media for other locally. Environ.J. Unit values for the 2005 zeolite market.A. Water..A. [2] G.

Y. Zhao. SME. Clays Clay Miner. Hoboken. D. Vols. 281 (2005) 68–79. Idaho Mining and Exploration. [10] H. USA.S. Siegel. Casper. Langella. US Department of Interior. A. London. Clays Clay Miner. Satinder. J. [8] Bureau of Land Management (BLM). Harsh. Pansini and P. 2002. 2003. Bennett. Academic Press. La roca magica: Uses of natural zeolites in agriculture and industry.R. 39 (2005) 4606– 4613. CO. Inglezakis.. M. Gillerman. Y. A. Boyle. Italy. USA. Y. Water Res.B. Natl. H.M. Gerhardfurrer and R. Metallurgy and Exploration (SME) National Meeting.J.J. Process. The kinetics of sorption of divalent metal ions onto sphagnum moss peat. Ho and G. and Remediation. 2007. J. Analysis. Proc. WY. M. 50 (2002) 127–135. Principles of Adsorption and Adsorption Processes. S. 1–4. Environ.. M.T. M. Sci.S.S. ed. M. Ruthven. [9] G. NJ. Deng. R.J. 2004. Cerri. [7] V. Bowman. Acad. St. McKay. G.L. Wiley-Interscience.G. Flury and J. BLM. New York. Zhao et al.H. Zhao. McKay.A. Sci. Prediction of arsenic removal by adsorptive media: Comparison of field and laboratory studies. Barrer. for Mining. Schulin. Methods of determining cation exchange capacities for clinotilolite-rich rocks of the Logudoro region in Northern Sardinia. . Biochem. Cappelletti. Sci. Virta. Removal of heavy metals from mine waters by natural zeolites.J. / Desalination 228 (2008) 263–276 [4] R. 34 (2000) 735–742. Aragon. Proc. Aragon. Final Environmental Impact Statement and Proposed Plan Amendment for the Powder River Basin Oil and Gas Project.. Wiley. The concept of “capacity” in zeolite ion-exchange systems.. [5] F. in: A. Idaho Geological Survey. V.M. Nocon and M. Arsenic Contamination of Groundwater: Mechanism. Austin and R. C.276 H. 1978. Colloid Interf.S.S. 96 (1999) 3463–3470. US Geological Survey Minerals Yearbook. Technol. 2005. Ho and G. Weaver and E. Littleton. Alternation of kaolinite to cancrinite and sodalite by simulated Hanford Tank Waste and its [11] [12] [13] [14] [15] [16] [17] impact on cesium retention.D. ed. 1984. Mumpton.. Cloud Mining Company’s Stone House Zeolite Mine and new uses for clinoptilolite.. Pseudo-second order model for sorption processes. [6] U.. 52 (2004) 1–13. Deng. Wingenfelder. Zeolites and Clay Minerals as Sorbents and Molecular Sieves.T. Soc. 34 (1999) 451–465..