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1993 SCA Conference Paper Number 9302

A D S O R P T I O N M E A S U R E M E N T S IN DEVONIAN SHALES
X. Lu, F.C. Li, and A.T. Watson Department of Chemical Engineering Texas A&M University

Abstract
The Devonian shales in the Appalachian basin are considered a major potential source of future domestic natural gas. In these formations, natural gas is believed to be stored as conventional "free" gas in porous spaces as well as "adsorbed" gas on shale matrix. Studies have suggested that more than half of the total gas storage in the Devonian shales exists as an adsorbed state. Despite the importance of gas adsorption in Devonian shales, measurements of adsorption isotherms are scarce due to the difficulties associated with gas-shale systems. In this study, experimental methodologies have been developed for accurate gas-shale adsorption measurement at different temperatures. To ensure the accuracy of the measurements, emphasis is placed on developing laboratory procedures that ensure accurate cell calibration and precise temperature control. Detailed error analyses have been performed to guide the apparatus design. Methane isotherms on various shale samples have been measured, the gas storage mechanisms of Devonian shales are investigated, and various factors which would affect the gas-shale adsorption are elucidated.

Introduction
Large amounts of natural gas accumulations exist in the Devonian shale formation of the Appalachian, Michigan, and Illinois basins. It is estimated that several thousand trillion cubic feet (Tcf) of gas are contained in this area [1]. These Devonian shales are a major potential source of future domestic natural gas. The gas storage mechanisms in Devonian shales are quite different from those in conventional gas reservoirs. In the Devonian shales, natural gas is believed to be stored as conventional "free" gas in the porous space as well as a condensed phase on the shale matrix and organic materials. Some studies suggest that more than 50% of the total gas storage in the Devonian shales exist as a condensed phase [2-4]. The condensed phase gas storage includes the adsorbed gas on shale surfaces and soluted gas in organic materials. Certain types of clay minerals and the organic kerogen in the Devonian shales are the main components believed to be responsible for condensed phase gas storage. We will use the term "adsorbed gas" to refer the condensed phase gas since the measured adsorption isotherm includes all the condensed phase. The importance of gas adsorption in Devonian shales has been revealed in the studies of Lane et al. [5,6]. They indicated that when adsorbed gas is present in the shales, production forecasts that include the effects of gas adsorption are often far more accurate than when adsorption is not taken into account. Another consideration is that the prediction of the effects of stimulation efforts can be significantly affected by the manner in which gas is stored. For example, raising 1

the gas molar densities at different stages can be calculated with an appropriate equation of state (EOS). the method has hot yet been demonstrated in the field. By measuring the pressures and temperatures before and after gas expansion. the adsorption capacity is considerably less than adsorbents typically of interest in adsorption studies.0 standard cubic centimeter per gram sample (sec/gram) [2-4]. In this paper we report on a laboratory apparatus and experimental methodology for measuring gas adsorption in Devonian shales accurately at high pressures and at various temperatures on Devonian shales. [5. Measurements of adsorption isotherms for Devonian shale samples have not been widely available. a volumetric adsorption apparatus was designed and constructed for gas-shale isotherm measurements. and the gas is expanded into the sample cell. the methane adsorption capacity of activated carbons is about 120 sec/gram [8]. a certain amount of gas is charged into the reference cell. if gas were stored just in the conventional manner. adsorption of methane gas. is the relationship between the 2 . Two types of isotherms. there would be relatively little enhancement [6]. This observation. By increasing the amount of gas charged into the reference cell. the amount of adsorbed gas at another pressure level can be obtained. particular attention is given to the development of laboratory procedures for accurate cell calibration and precise temperature control. then the amount of gas adsorbed at one pressure level can be calculated. Consider. During the isotherm measurement.6] determined that adsorption generally cannot be determined accurately from history matching production data alone. have been measured. If an apparatus can measure adsorption isotherms for zeolite within 5 % error. the same apparatus would give more than 100 % errors for measurements on Devonian shales. Volumetric Adsorption Measurements Isotherm Calculation In this study. At the same conditions. the major component of natural gas. The measurement errors which can be tolerated with other adsorbents would invalidate the results for Devonian shales. There is more than an order of magnitude difference in the methane adsorption capacities between Devonian shales and other conventional adsorbents. Even though the adsorption mechanism is clearly important in the shales. coupled with the fact that relatively small amounts of sample may be available for such tests.5. The isotherm is obtained by repeating these procedures until the measurement at the highest desired gas pressure is achieved. for example. Nsorb(P). The main parts of the apparatus are the reference cell and the sample cell as shown in Figure 1. means that many of the standard laboratory methods are not suitable for work with Devonian shales.000 psi pressure. We also investigate gas storage mechanisms on various Devonian shale samples. the adsorption isotherm and total sorption isotherm. and that for coals is about 25 sec/gram [10].1993 SCA Conference Paper Number 9302 the temperature of the reservoir can greatly enhance the production rate when there is significant storage by adsorption. The testing of actual shale samples from core samples is necessary for characterizing adsorption in Devonian shales. and elucidate various factors which will affect adsorption of gas in shales. Lane et al. the valve between the cells is opened. To ensure the accuracy of the measurement. The total sorption isotherms. that for zeolite is about 100 sec/gram [9]. which clearly would invalidate the measurement results. is the relationship between the amount of adsorbed gas and the gas pressure. While they proposed a specific well-test design to determine adsorption from reservoir data [7]. After equilibrium is reached.5 . and repeating the same procedures. the methane adsorption capacities of Devonian shales are around 0. At room temperature and about 1. The adsorption isotherm. Na(ia(P).

1993 SCA Conference Paper Number 9302 total amount of sorbed gas.Pe(j)] .2. The subscripts c and e stand for charging and equilibrium. 3 . 2 can be written as: i Nad.. First.. In order to measure these two isotherms. helium and methane. 3. 4 can be written as: I NSorb(i) = Vref J ^ M j ) ~ Pe(j)] j=l ~ (Vcell ~ V. <j>. At the t'-th pressure level. which is the sum of the adsorbed gas and the "free" gas stored inside the sample pore volume... Since methane gas is the major component of natural gas. we can assume that no helium gas will be adsorbed on the sample when helium gas is expanded from reference cell to sample cell. Fce//> and bulk sample volume. NTej(P) is the amount of gas remaining inside the reference cell at equilibrium. the isotherm measurement with helium gas is performed.(P) . The void volume is defined as the total "free" volume that helium gas can penetrate when the sample is present inside the sample cell. two gases. and the gas pressure.(i) = Vref Y^lPcU) .arnple)pe(i) t = 1. respectively. p is the gas molar density calculated at measured pressure and temperature. This experimental run serves the purpose of measuring the void volume. 2 . we have for the t'-th pressure level: t VV0id(i)pe(i) = Vref J2iPcU) ~ Pe(j)] t = 1.Nvoid(P) (2) where Ntotai(P) is the total amount of gas charged into the reference cell over the course of the experiment. the isotherm measurement with methane is performed. For the measurement of the adsorption isotherm. With the knowledge of void volume.n (5) Equations 1. Vrej is the reference cell volume.. .. Eq. n for helium 3=1 (1) where t refers to for the t'-th pressure level. n (3) For the measurement of the total sorption isotherm..Nref(P) . are used. it is expected that the isotherms measured with methane gas are representative of those of natural gas. At t'-th pressure level.NceUsampUP) (4) where Nceu-sampie is the amount of "free" gas contained in the volume which is the sample cell volume less the bulk sample volume.. Eq.Vvoidpe(i) j=i i = 1. the amount of adsorbed gas at pressure P is given by: Nada(P) = Ntotal(P) . Assuming that the adsorption isotherm is measured at n pressure levels. Since helium gas is virtually non-adsorbable at room temperature. and 5 are the main equations used to calculate the isotherms in the volumetric isotherm measurement. and Nvoid(P) is the amount of gas filling the void volume. and Vvoa is the void volume. the sample porosity.. and Vaampie is the bulk sample volume. sample cell volume. the amount of gas sorbed by the sample at pressure P is given by NSOrb(P) = Ntota.Nref(P) ..2. can be calculated: i ''void 'sample •cell where Vceiu is the sample cell volume. Vaample. Next.

The other primary errors arise from the cell volume calibrations AVrej and AVce//. The functional forms of EOS. linear isotherms and the ideal gas law for gas density were assumed for simplicity.02 % . This is explored in Figures 2a and 2b. and the apparatus can be designed to achieve accurate isotherm measurements. cell volumes and sample volume used in our apparatus. To our knowledge. 1. Here the total cell volume is the sum of reference cell volume and sample cell volume. or the ratio of sample volume to total cell volume increases. Table 1 lists the primary errors and their magnitudes encountered in our measurements. total sorption isotherm. were used.13]. A/?. which was designed with the guidance of the error analysis. Eq. 3. All three primary errors contribute to the over all measurement error via gas density calculations. There are numerous published studies on equations of state for various gases [11-14]. the accuracy of the estimation of the amount of gas adsorbed becomes a crucial issue. A P and AT. and the relatively small adsorptive capacity. and the error of the empirical equation of state (EOS). and 5. P E O S ( P . and the second and third terms account for errors caused by temperature and pressure measurement errors. we expect that the actual errors encounted during measurement will be smaller than that. so that simulated errors correspond to the maximum possible errors. and the sample bulk volume measurement AVaampie. During the simulation. can be expressed as: A^A^os + ^ A r + ^ A P (6) Here Apsos 1S t f l e error of the EOS. The computer simulations revealed that selection of reference cell and sample cell volumes can strongly affect the measurement errors. For a volumetric adsorption measurement.03 %. 6 can be written as Ap ApEOS = AT + AP + T ~~7~ ~ ~P~ () The first term on the right-hand-side accounts for errors arising from the EOS. the primary errors arise from the errors of the pressure and temperature measurements. Computer simulations of measurement errors were performed based on the equations governing the overall measurement errors (see Appendix). We will apply the simplest EOS —the ideal gas law— to describe the temperature and pressure dependence of the molar densities since any empirical EOS has similar temperature and pressure effects. Details of the mathematical derivations are shown in Appendix. From the literature. The overall measurement errors associated with the adsorption isotherm. it is desirable to 4 . The design was based on a typical sample size of about 18 cc.1993 SCA Conference Paper Number 9302 Error A n a l y s i s Due to the relatively small amount of sample material generally available. no systematic error analysis for a volumetric adsorption apparatus has ever been reported. based on measured pressure P and temperature T. During the simulation. By doing so. The total error in gas density calculations from an EOS. factors which will affect the measurement accuracies can be identified. and that for methane gas is 0. the error for the equation of state of helium gas is 0. respectively. and void volume can be estimated based on the Eqs. T ) . By performing an error analysis. Basically. This necessitates a sample cell size of about 25 cc after allowing for tubing and fittings. The inequality signs in those equations were replaced with equalities. are quite complicated for most of the practical EOS's. It can be seen that the measurement accuracy increases when the ratio of reference cell volume to total cell volume decreases. We chose the most recently published EOS's for our experiments [12.

The combination of various volumes was carefully selected. pressure transducers.083 inch) stainless steel. the simulation results show that.25 inch) with a thick wall 0. The VCR fitting can provide good seals under high pressures even after numerous assembly-disassembly processes. 5. figures 2c and 2d show the dependence of measurement error on the error of reference cell volume calibration. in our apparatus.69 (scf/ft3) or 2. All the valves.005 of set point.01% was used to measure system pressures. this cell must be sufficiently large so that the pressure measurements are within the range of the pressure transducer. In the conventional calibration methods. The design of the apparatus was guided with the results of the error analysis. and temperature control units are interfaced with a personal computer. Of course.635 cm o. (0. It is also desirable that the sample cell be filled to the fullest extent possible during the measurement. The simulations shown that overall measurement errors can be reduced by reducing magnitudes of primary errors.4 (cc/gram) at 1000 psi. A 7 r e / . usually helium [10. The accuracy of this method is limited 5 . as expected. a liquid (distilled water or mercury) is used for the calibration of one of the cell volumes. It can be see that the dependencies are almost linear. All tubings used in the apparatus are 0.d. For example. and on the error of temperature measurement. The sample cell and reference cell are constructed with stainless steel. Apparatus Figure 3 shows the schematic diagram of the volumetric adsorption measurement apparatus. Cell Calibration As revealed by the error analysis. the accuracy of the cell volume calibration will strongly affect the accuracy of the adsorption measurement. In this cell combination. Precise temperature control was designed which can maintain the system temperature within ±0. The reference cell (4. The valve is chosen because of its durability under high pressures (up to 3500 psi) and high temperatures. reducing primary errors. was assumed in this case. can effectively reduce the measurement errors. the percentage errors for both adsorption isotherm and total sorption isotherm measurements are less than 8%. The simulations also show that sufficient accuracy of isotherm measurement on low adsorption capacity adsorbents such as Devonian shale can be achieved with a carefully designed volumetric adsorption apparatus. The connection of the sample cell with the system is provided by a Swagelok VCR Metal Gasket Face Seal Fitting to provide easy assembly-disassembly. Entrainment of adsorbent in the cell during vacuum is prevented by employing a filter gasket between the conjunction of tubing and the VCR fitting.000 psi. the maximum gas pressure encounted during the isotherm measurements is less than 2. The volumes of tubing and fittings associated with the sample cell which are not filled by the samples were kept as small as possible to ensure a relatively large ratio of Vsampie/Vtotai. This will result in the most accurate determination of the amount of gas charged into the system. Therefore. and the remaining volume is calibrated by filling the volume with a known amount of a non-adsorbing gas. A water bath is employed to provide a constant temperature environment for the system.15. such as improving the cell calibration accuracy and increasing the precision of temperature control.16]. AT.86cc) is much smaller than sample cell (25 cc) to ensure smaller measurement errors.21 cm (0. or part of the apparatus volume.1993 SCA Conference Paper Number 9302 use as small a reference cell as is possible. Using the parameters listed in Table 1. The operation of the apparatus is fully automatic. as shown in Table 2. which is within the operating range of our pressure transducer. Swagelok tube fittings and Nupro "HB" series air actuated high pressure valves are used in this apparatus. The typical shale adsorption capacity. A piezoelectric type pressure transducer with nominal accuracy of 0.

~ Vref ^ (8) Here p(Pc) and p(Pe) are the gas molar densities at charging and equilibrium gas pressures.4 %. 8 and 9. we used silicon crystals obtained from the National Institute of Standards and Technology (NIST) as the volume standard.1^. there are errors associated with reading the amount of liquid entering the cell. both cells are empty.) p{p*e) (11) Since we used the NIST volume standard.3289819 ± 0. respectively. in the second gas expansion. 1 % to 2 % calibration error is possible. the system pressure Pe is measured. Finally. First. There is no quantitative method to estimate the total error for this cell volume calibration method. Again. From Table 1. we get the reference cell volume: P(pc)-p(pe) ^ref — 'standard/ P(P:)-P(P:)] P{P. The error in this calibration method can be estimated as follows. In the second gas expansion. the error of AVatandardlVstandard c a n be neglected. 14 is less than 0. Solving these two equations simultaneously. There may also be air bubbles in the liquid. The density of the crystal was accurately measured (2.) AP(P:Y iP(pe) v P(PC) p(Pe) J P(P:) \ P{P. there may exist some spaces which the liquid can not invade. and p(P*) and p(P£) are the gas molar densities at charging and equilibrium pressures.0000014 gram/cc) [17].// and Vrej. respectively. For this reason. The description of the calibration method follows. the following equation can be derived: AV r e / 'ref AVstandard 'standard Vref ' standard •p(pc) (AP(PC) AP(Pe)\ P(P:) (AP(P. we can get the sample cell volume Vce//. As shown in Figure 2b. we have: v 'cell v -v P(pc)-P(p:) 7~p*"^ (^ ^ ' 'standard — 'ref Here Vatandard 1S * fle volume of crystals in the sample cell.1998 SCA Conference Paper Number 9302 for several reasons. From Eq. 13. a volume standard is placed in the sample cell. By a mass balance. by mass balance. due to the complex volume structure caused by fittings and valves. When equilibrium is reached. we used a dual-gas expansion method. There are two unknows in Eqs.) p(pe) (10) Substituting Vref into Eq. In the first gas expansion. In the first expansion. By our experience. we know that the typical error for density calculation is less than 0. So the calibration error estimated by Eq. a certain amount of helium gas inside reference cell at pressure Pc is expanded into the sample cell. we have: p(Pc)-p(Pe) Vca. and the same procedures as the first expansion are followed. It must be noted that all the calibration procedures are carried out at a constant temperature. The calibration consists of two gas expansion processes. The accuracy of this calibration method is highly dependent upon the accuracy of the volume standard. which is much better than the conventional liquid filling method. 6 . large measurement errors will occur with such calibration errors. To achieve high accuracy in the cell volume calibration. the silicon crystal (NIST volume standard) is loaded into the sample cell. 11.044% for helium gas.

AT.Ttet] dt + c. the solution of Eq. as follows: Tp = mcp/UA (14) (15) Kp = 1/UA Eq. representation of the process.6 psi at 1000 psi. a model of the process is required. using the following model of the controller: c (*) = Ke[T(t) . Assuming that the water is perfectly mixed. the variation of temperature during the experiment will cause errors in temperature measurement. variations in temperature of ±0. is the controller's bias signal. Kp. can be selected by the root-locus method [4]. Using the process model. although not entirely accurate.Ttet) + ^ Tj J f[T(t) . It can be seen that the simple model provides a reasonable. TJ and Kc. an energy balance yields the following equation: q-UA(T-Teo) = mep^ (13) where m is the mass of water in the tank. According t o the ideal gas law. r/. r p . this pressure uncertainty will in turn cause additional measurement errors according to Eq. and c. the parameters for the controller model. the true equilibrium system pressure can not be accurately measured. heat transfer to the surrounding air can be represented with a single overall heat transfer coefficient. (12) where T(t) is the measured system temperature.1993 SCA Conference Paper Number 9302 T e m p e r a t u r e Control Precise temperature control is crucial for accurate isotherm measurement. cp is the water heat capacity. and the heat capacity of the tank is negligible. A electric heater with a proportional-integral (PI) controller was used to maintain the temperature at selected levels. First. The root-locus method [18] was used to select the controller gain. q = C0. 7. By defining the time constant of the process. and integral time constant. A is the total heat transfer area. For that analysis.e-^") +^ (17) In order to obtain the process parameters Kp and r p . and Too is the temperature of surrounding air.-(T-T0o) = Tp^ (16) Assuming a constant step input heat rate. Also. 13 can be rewritten as: qK. For such large pressure fluctuations. the temperature response to a series of input heat rates. 17. were measured. Second.1 at 25°C will cause gas pressure fluctuations of 0. The measured data along with the predicted response obtained from the least-squares estimates are shown in Figure 4a. q is the heat rate provided by the electric heater. Tiet is the set point temperature. the variation of the temperature will cause fluctuations of system pressures. U is the overall heat transfer coefficient between water and air. A least squares procedure was used to obtain estimates of Kp and r p using Eq. 7 . Kc. C0. (16) is: T(t) = C0KP(1 . and steady-state gain of the process.

To see the relationship between the adsorption capacities and the total organic carbon (TOC) present in the shales. The system temperature can be stabilized within a couple of hours after a change in set point as shown in Figure 4b.1998 SCA Conference Paper Number 9302 Using this method. this ratio did not change significantly with isotherm temperatures in this temperature range [4]. two kinds of isotherms were measured for each sample. we may ask what factors are responsible for the adsorbed gas storage. The average ratio among these samples is 61%. The differences of repeated results are all within 3%. The isotherm temperatures vary from sample to sample. Most of the Devonian shales have relatively small porosities. Samples The samples used in this study are from Gas Research Institute (GRI) sponsored Devonian shale study wells. It was found that in some Devonian shales with high organic material contents. we checked the reproducibility of the adsorption measurements by running replicate experiments. ranging from 24°C to 37. Because significant organic materials exist in most Devonian shales. which means that adsorbed gas accounts for more than half of the total stored gas. the adsorption isotherm and the total sorption isotherm.005°C of the set point. indicating that organic material is one of the important factors responsible for adsorbed gas storage. Results and Discussion First. The ability of Devonian shale to hold significant amounts of natural gas is the result of condensed phase gas storage. It was found that. for a shale sample. isotherms were measured on twenty-four Devonian shale samples obtained from five different wells. the adsorbed gas may exists as a solution in the organic materials. the ratio is larger than 50%. To see the relative importance of adsorbed gas storage to total gas storage. As indicated before. which includes adsorbed gas on shale surfaces and soluted gas in organic materials. The adsorption isotherm accounts for the condensed gas storage. one of the major mineral components of Devonian shale.78°C. The good reproducibilities show the consistency and accuracy of the measurements. we achieved a temperature control to within ±0. The adsorption isotherm slope is related to the Henry's constant at very low gas pressures. The CSW samples are from wells in West Virginia and Kentucky. and the Antrim samples are from wells in Michigan. Figure 6 is a histogram of the ratios among twenty-four samples. The histogram indicates that for most of the samples. Figure 5 shows the replicated measurement results for two shale samples. Since adsorption plays an important role in natural gas storage in Devonian shales. Fairly good linear correlations between the adsorbed gas amount and TOC are observed in Figure 7. and the organic materials have significant solubilities of natural gas. But. It is shown that reproducibilities of both adsorption isotherms and total sorption isotherms are good. The illite sample. the total sorption isotherm accounts for both condensed gas storage and "free" gas storage in porous spaces. and the ratios of the amount of adsorbed gas to the total storage at 500 psi pressure were calculated. was acquired from Clay Mineral Society. the amount of adsorbed gas versus the total organic carbon [19] at two gas pressures for eight shale samples are plotted in Figure 7. ranging from 1% to 8%. there is a linear correlation between the adsorption isotherm slopes and the total organic carbon (TOC) [3]. shale samples with very 8 . The samples are crushed to 18-25 mesh size particles and degassed at 50-60°C for 24 hours in a vacuum oven prior to isotherm measurement. The samples are regenerated after each measurement by evacuation at 50°C overnight. as one can see from Figure 7.

A detailed error analysis has been performed for the volumetric gas-shale adsorption apparatus. Elite may be responsible for adsorbed gas storage in shale samples with very low organic content. To verify this. The results of adsorption measurements on twenty-four shale samples obtained from five wells have shown that more than half of the total gas storage in the Devonian shales exists in a condensed state. A new cell volume calibration method using dual-gas expansion and NIST volume standard has been developed. It suggests that some other minerals are responsible for the adsorbed gas storage. The adsorption capacity of the shales increase as the temperature decreases. A temperature control system has been designed so that the apparatus can be operated at selected temperatures. Since the main mineral compositions of Devonian shale are clay (mainly illite). With the isotherms measured at multiple temperatures. further studies of gas storage mechanisms and gas-shale thermodynamic properties can be performed. has been observed. With these isotherm data. which indicates that gas solution on organic material is one of major mechanisms of adsorbed gas storage in shales. 7. Conclusions 1. quantities characterizing the gas-shale system. carbonates and quartz [19]. Figure 9 shows measured results for two shale samples.1993 SCA Conference Paper Number 9302 low organic carbon contents (less than 1% TOC) still have significant adsorbed gas storage. We measured isotherms at temperatures ranging from 25°C to 60°C. can be quantified. and since carbonates and quartz are non-adsorbable for natural gas. The high precision temperature control (± 0. We also examined the temperature effect on the gas adsorption of Devonian shales by measuring the isotherms at different temperatures. However. adsorption isotherms were measured on an illite sample. This information is crucial for studies of thermal stimulation of gas reservoirs[6]. and the adsorbed natural gas on illite can contribute significantly to the total gas storage in Devonian shales. maximum adsorption capacity and heterogeneities. and various factors which would affect the accuracy of the measurement were identified. Adsorption isotherms at various temperatures have been measured. illite may be the other factor for the adsorbed gas storage. There are about 10% to 40% weight percent of illite present in Devonian shales [19]. such as isosteric heat. 5. the mechanisms of adsorbed gas storage could be identified using carefully selected models. 9 . The new calibration method resulted in much higher accuracies in the cell volume calibrations than the conventional liquid filling method. Significant gas adsorption capacity on illite. 6. 2. The analyses were used to guide the apparatus design. 4. A fairly linear correlation between adsorption capacities and total organic contents of shale samples has been observed. which is expected since gas adsorption on solids is an exothermic process.005°C) is important for accurate adsorption measurements. 3. no measurements of gas-shale isotherms at multiple temperatures have ever been reported. which is one of the major mineral contents in shales. It can be seen that the adsorption capacity of illite is significant compared with that of Devonian shales. Also. the results are shown in Figure 8. and adsorption isotherms at other temperatures can be predicted.

Nomenclature A cp c(t) c. and Jim Holste in the early stages of this work. Chih-An Hwang. and many helpful discussions with Paul Schettler throughout the work. C0 EOS K m N P Q R T Too t U V Greek = = = = = = = = = = = = = = = = = heat transfer area (m 2 ) heat capacity (Joule/°K/gram) actuating signal (Joule/sec) temperature controller's bias signal (Joule/sec) step input of heat rate (Joule/sec) equation of state steady-state gain (sec°K/Joule) mass of water in tank (kg) amount of gas (mole) adsorbate pressure (psi) heat rate (Joule/sec) gas constant (Joule/°K/mole) absolute temperature (°K) absolute temperature of surrounding air (°K) time (sec) heat transfer coefficient (Joule/m 2 /°K/sec) volume (m 3 ) 4> p T = helium porosity (%) = molar density (mole/m 3 ) = time constant (sec) = = = = = = = = = = = = = = adsorption charge methane gas sample cell equilibrium equation of state helium gas pore volume reference cell shale sample set point total sorption total amount of gas void volume Subscript ads c CH4 cell e EOS He pore ref sample set sorb total void 10 . The authors wish to acknowledge important contributions by Scott Lane.1998 SCA Conference Paper Number 9802 Acknowledgement The authors gratefully acknowledge the financial support of this work by the Gas Research Institute.

A. and de Reuck.T. S. B. Thermodynamic TaThermodynamic 14. "Analysis of High Pressure Adsorption of Gases on Activated Carbon by Potential Theory". Schettler. R. GRI-89/0205.. (1991). R. Kentucky. 1992. S. Li. Z. J.M. Vol. R. Trappeniers.C." paper SPE 23422.. SPE Form.J." Energy Sources.. Methane—International Tables of the Fluid State-5. (1989). J. Armstrong. Oxford (1978). 1722(1991). 10.. D. 11.."Isotherms and Thermodynamic Properties of Methane at Temperatures Between 0° and 150°C and at Densities up to 570 Amagat. "High Pressure Adsorption of Methane in Nax. and Hayhurst. E. C. CaX. Chem. H. Topical Report to the Gas Research Institute. In Geological and Geochemical Studies of the New Albany Shale Group (DevonianMississippian) in Illinois. DOE/METC/12142-0026. H. (1974). Chem. Ill. T. K. P. "Adsorption of Gases on Coals and Heat-treated Coals at Elevated Temperature and Pressure". (1943)..M. H.. 2. No. Second Eastern Gas Shale Symposium Preprints. Ponec.T. and Frost.. N. McCarty. Princeton. Knor. 15. Cleveland. K.C. 923 (1973). J... Brunaur. 1988)... 11 . 4. Watson. Identifying and Estimating Desorption from Devonian Shale Gas Production Data. Thesis.. December. Lane. V. Phys. "Contributions to Total Storage Capacity in Devonian Shales. S. S. Yang. and Cerny. MgX. (1980). 7. Eds. presented at the SPE Eastern Regional Meeting held in Lexington.. T. Watson. Oxford (1977). Lane.T. K. 337 (1991)." J. D. DOE/METC/SP-78/6. B. II 73 (1978). and Schwarz.1993 SCA Conference Paper Number 9302 Reference 1. Helium—International bles of the Fluid State~4. Shimp..4.. A. J.. Jr. Carbon... 13. J." Physica 98A.M. Methane Adsorption on Devonian Shales. 26(6). Bergstrom and N.A. The Adsorption of Gases and Vapors.S. October 22-25.S... F. R. 616(1985). . Armstrong. Vol.. Princeton University Press. Rajiv. SrX. 9. 8.. D. J. 5. 289 (1979). and Parmely. Gatens. 95. and Lancaster. S. 6. Vol. 16. Wassenaar. 3. 64. "Thermodynamic Properties of Helium 4 from 2 to 1500 K at Pressures to 108 Pa. F. "A Practical Approach to Evaluating Shale Hydrocarbon Potential". Fuel... Inc.. Thomas. E. 215 (Mar. Lancaster. Angus. 873(1988). 0 . Adsorption on Solids. 12. Texas A&M University. Saunders. and Watson.T. Pergamon Press.. Smith. Talu. and Abels. S. E. E.A.. CRC Press. Holditch and Associates. 13. Angus. and Lane. D. S.. Vol. Robert D. Eval.. A. S. Pergamon Press.. C. and de Reuck. "Model Selection for Well Test and Production Data Analysis". "Adsorption/Desorption Studies of Gases through Shales". R. Data. and BaX Zeolite". Phys. M. 2.. T. Zhang."Characterizing the Role of Desorption in Gas Production From Devonian Shales.

«/ < AVreJ e /+ . Olszewski..\ • . R..orb(i) < ^AKe/+ ^^Apc0-)+ g|^ AMj .ample)pe(i) Vvoid{i) < 1»W.W. Engineering and Instrumentation. Bowman. the errors associated with the measurements of adsorption isotherm. Shchigolev. No. (1965). Elsevier Publishing.-vi *^ APe(i) /»e(0 Vref EUiPcU)-Pe(J)} These are the equations describing the errors in a volumetric adsorption measurement. Schoonover. Stephanoponlos.. Annual Technical Report to Gas Research Institute.1993 SCA Conference Paper Number 9302 17. GRI-90/0300. Mathematical Analysis of Observations. "Formation Evaluation Technology for Production Enhancement". ANads(i). 3.M. Chemical Process Control-An Introduction to Theory and Practices.K.A...e(^ + ^^Ayw(0 ANads(i) dNa < ^ A K dv. 1. 12 .. H. and Raymer.L. October (1990). "Procedure for High Precision Density Determinations by Hydrostatic Weighing. Appendix Based on the Eqs. F. L." Journal of Research of the National Bureau of Standard-C. AN„orb(i). 20.M. AVvoid(i). New York.) + (VceU Vsample)&Pe(i) dVcM +^ ^ A V ^ + O 'sample J£^AVsarnpU < AVref ^[PcU) ~ Pe(j)] + VreJ Yli&PcU) + Ape(j)] + (AVcell + AV.. New Jersey (1984). D. 71c. A.L. Guidry.PcU)] + VreJ £ [ A M i ) + i=l j=l ^Pe(j)} + AVvoid(i)pe(i) Vvoid{i)Ape(i) AN... Prentice Hall. 19. NY. total sorption isotherm. 18. M.. Luffel. and 5. can be estimated according to the theory of error analysis [20]: ^dNaa dNadt ^ dNads E^AMi) + E^A. Houston.a ( .A V . Restech Inc. G. and void volume.J. B. ) + g MT) A"'W + g 2KB) Ap'U) AVref(i) —' 1^ lVV0id(i) r^A&Pcjj) + Ape(j)] w—*• r / . 3 (August 1967).ti**tf) + fr{ dpeti) dVvoid(i) 5 > c ( j ) . and Jones.

Error analysis for volumetric adsorption apparatus Reference Cell Volume: Sample Cell Volume: Sample Volume: Pressure (psi) 100 200 300 400 500 600 700 800 900 1000 Nsorb 4.0 7.0 and 25.70 4.01 0.0 Table 2.41 3.3 to 4.75 (%) 7.40 0.044 0.50 4.14 1. P (psi) Helium EOS Methane EOS Helium Density.88 1.71 2.61 4.32 7.38 5.26 5.00 7.38 7. pne (mole/It) Methane Density.94 5.0 0.43 5.59 13 .63 3.69 Porosity: 5.28 2.64 7. sorb (%) 7./ (cc) Sample.034 0. (scf/ft3) 0.0 and 19. V^.28% 60.19 7.51 7.0034 0.0 cc 18.25 7. Primary errors and the magnitudes Error Sources Reference Cell.13 (scf/ft3) 0.20 0.3 to 4.75 2. Vref (cc) Sample Cell. T (°K) Pressure.12 5.02 0.58 7.28 % Kamp/e /(Kef + Vcell): \ &N.45 4.29 4.1993 SCA Conference Paper Number 9302 Table 1.84 3.25 6.86 cc 25.03 0.12 4.88 8.78 4.40 0.orb/N &Nada/Nad.ampu (cc) Temperature.10 5. pcHt (mole/It) Typical Value 4.86 13.45 7.57 1.13 7.00% Vref/(Vref + Vcell): 16.98 4.55 5.0 295 to 343 100 to 1200 Magnitude (%) 0.0 cc Nad. V.

5 2.4 0.0 1.8 1.O 0.5 1.86 cc Simple Cell Volume: 25X1 cc Simple Volume: 18X1 cc 15 $ w W o t 10 Total Sorption Isotherm Adsorption Isotherm O.0 O.1993 SCA Conference Figures Pressure and Temperature f j Sensor ^-i-^ Pressure and Temperature f ) Sensor ^r-' Paper Number 9302 Figure 1.2 0. Schematic Diagram of Volumetric Adsorption Measurement Method 12 Pressure: 500 pd Simple Cefl Volume: 2SX> cc Sample Volume: 18X1 cc 30 Pressure: SOOpri Reference Cell Volume: 4 AS cc Simple Cell Volume: 25X1 cc 20 10 # o >^^ 10 Total Sorption Isotherm w Adsorption Isotherm h w • \^T~"-^_ b • • Adsorption Isotherm 20 30 40 50 •—^ 60 0 10 20 30 40 50 60 0 10 Ratio of Reference Cell Volume to Total Volume (%) Ratio of Sample Volume to Total Volume (%) 20 SOOpri Pressure: Reference Cell Volume: 4.0 Error of Temperature Measurement (°C) Error in Reference Cell Calibration (%) Figure 2. Dependence of Measurement Errors on Primary Errors 14 .6 0.O 0.

' " M Co-294. I I I M . Water Tank 8.1(a«fec) * i l l " " nmmmf " l .rftzn^**—**™* Co-6193 (at/xc) Co-55U(»«/»oc) ttf • OBSERVED CALCULATED . D ^ © 1.7 (erg/sec) 20 30 a Time (hour) © c o M P U T E R 53233 £ 5 S3 V4 h© © ® Set Point : 45 *C © OXv © © . Co-423.9 (erg/Mc) >*•'""""'*"* Co-166. Schematic Diagram of the Adsorption Apparatus ^ ^ " »—>"*• • 100 Time. Heater 7.. l l " " " i ' . Temperature Contol of Water Bath . Vacuum Pump 9. mln Figure 4. High Pressure Gauge 3. 6. Sample Cell Set Point : 6S 'C Figure 3. Thermometer JL-XJ- ®Q. Gas Inlet 2. Reference Cell 10.w»»«« . Pressure Transducer 5. Low Pressure Gauge 4.

a S3|duiBS jo jaquin^j .2 <T3 cO 8.u9Juoo SBO « 3 Oil 16 and ss c 8 Ti • ^ • a • ni l> — * >: • 0 Ft 0 H Sorpt % V u 3 c« ^ 2 ss c 1 % § a> u 3 ents mains £3 ^ A •b t D.uo3 SBQ (CvW/PS) .v o " - Sj? lHao «2 00 I3 t-~ 3 "O a o i .1998 SCA Conference Paper Number 9302 Figures o % 2 ^ ••"< D. E fl) 1 D • 0 5 0 H H) </ • a • 0 ft » C O fc % t 8 Cfl • % • D rature: 37 e: CSW2- ' rption Sorption a Temperatu re: 23 Sample: A ntrim a> u. H (ev«/ps) . ••»_• • « • • & osp 8 00 *crt £. 0 < •fi 0 g C/3 0 • c 0 . m • • • • • CH tf CA < = '9 2 fr 0 • Adsotpti O a • D 0 • 0 l« (/J a> 0 • • Total So 1st 2edrun £.a ? g c o O o •3 < "8 o •o rga O Car u c -Q *8 tal o H 3 ^ o o t .ua.< J .f i c s — o u.'»• £«> s • • VI U U •a*o n « > 05 vn D.a a ^5 (€v«/Ps) ^pede3 uoijdjospy 5. 3 o u c o •a •3.

00°C Co Figure 8. Adsorption Isotherms Measured at Various Temperatures I Is 3 8* i -i .00°C 37. °A °A a n o o o VI • * * 5? 200 400 600 *• • o *• 25.W3 Sample: CSW2-3434 A A I A A 12 D z t c o S 2 * A • A A • • 2 • O # ° A 10 W 8 U Ml Sample: Mite Temperature: 37.00°C 60.00°C 800 1000 o ° o •a < c c o U t/i 4> • o 4 - o 10 Pressure (psi) a o • 0 o O et < ° Adsorption D Total Sorption 9 8 7 6 5 • Sample: Antrim-1428 A A A A • A u w • © A a s o 0 200 400 600 800 1000 A • " .< u .78°C 50. Adsorption and Total Sorption Isotherms of Illite 800 1000 3 3 Pressure (psi) Figure 9.008C 60.00°C 37. • O A * * A «o «o «o ° O A A Pressure (psi) E <3 •a 4> x: u o en TJ A 4 3 2 1 0 200 • * A • o A ° A • X 400 600 A • ° A 25.78°C 50.78°C a a a a a • • e A o A * •a < a> Ui I • A .

Adsorption and Total Sorption Isotherms of Ulite Figure 9. Schematic Diagram of Volumetric Adsorption Measurement Method Figure 2. Replicated Measurements of Adsorption Isotherm and Total Sorption Isotherm Figure 6.199S SCA Conference Paper Number 9302 Captions Figure 1. Temperature Control of Water Bath Figure 5. Schematic Diagram of Adsorption Apparatus Figure 4. Adsorption Isotherms Measured at Various Temperatures 18 . Dependence of Measurement Errors on Primary Errors Figure 3. Histogram of Ratio of Adsorbed Gas to Total Stored Gas Figure 7. Relationship Between Adsorption Capacity and Total Organic Carbon Figure 8.