CO2 sorption of Pomeranian gas bearing shales – the effect of clay minerals

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Energy (2017) 000–000 457–466 EnergyProcedia Procedia125 00 (2017) www.elsevier.com/locate/procedia

European Geosciences Union General Assembly 2017, EGU European Geosciences Union General Assembly 2017, Division Energy, Resources & Environment, ERE EGU Division Energy, Resources & Environment, ERE

CO2 sorption of Pomeranian gas bearing shales – the effect of clay The of 15thPomeranian International Symposium on District Heating CO2 sorption gas bearing shales – and theCooling effect of clay minerals minerals Assessing the the heat demand-outdoor a,∗ feasibility of using Marcin Lutyńskia,∗, Patrycja Waszczukaa, Piotr Słomskibb, Jacek Szczepańskibb Marcin Lutyński , Patrycja , Piotr Słomskiheat , Jacek Szczepański temperature function for aWaszczuk long-term district demand forecast Silesian University of Technology, Faculty of Mining and Geology, ul. Akademicka 2, Gliwice 44-100, Poland a a

b Institute of Geological Sciences, University of Wrocław, ul. Maksa Borna 9, 50-204 Wrocław, Poland Silesian University of Technology, Faculty of Mining and Geology, ul. Akademicka 2, Gliwice 44-100, Poland

a,b,c a a b c Institute of Sciences, University of ul. Maksa.,Borna 9, 50-204 Wrocław, Poland I. Andrić *,Geological A. Pina , P. Ferrão , Wrocław, J. Fournier B. Lacarrière , O. Le Correc b

a IN+ Center for Innovation, Technology and Policy Research - Instituto Superior Técnico, Av. Rovisco Pais 1, 1049-001 Lisbon, Portugal Abstract b Veolia Recherche & Innovation, 291 Avenue Dreyfous Daniel, 78520 Limay, France Abstract c Département et Environnement IMTshale Atlantique, Alfred Kastler, 44300 Nantes, The idea behind this studySystèmes was toÉnergétiques assess the sorption capacity- of rocks 4asruepotential CO2 storage sites. France Thinly laminated mudrocks (gas bearing shaleswas from with matrix composed K-mica chlorites andThinly varying amount The idea behind this study to Baltic assess Basin) the sorption capacity of shalemostly rocks of asillite, potential COand sites. laminated 2 storage of organic (gas matter were shales selected for Baltic the study. Results of sorption measurements to the pressure 15 MPaand andvarying at temperature mudrocks bearing from Basin) with matrix composed mostly ofupillite, K-mica andofchlorites amount 50°C and 80°Cwere wereselected compared XRD Results compositional analysis of samplesup and values. of Our of organic matter for with the study. of sorption measurements to TOC the pressure 15experiments MPa and at demonstrate temperature Abstract also occur clay values. minerals. that whenand organic is nearly absent in mudstones CO2 sorption of 50°C 80°C matter were compared with XRD compositional analysismay of samples andinTOC Our experiments demonstrate that when organic matter is nearly absent in mudstones CO2 sorption may also occur in clay minerals. heating networks are commonly in the literature as one of the most effective solutions for decreasing the ©District 2017 The Authors. Published by Elsevier addressed Ltd. ©greenhouse 2017 The The Authors. Published Elsevier Ltd. gas emissions fromby theElsevier building sector. These of systems require high investments which areGeneral returnedAssembly through the heat © 2017 Authors. Published by Ltd. Peer-review under responsibility of the scientific committee the European Geosciences Union (EGU) 2017 Peer-review under of theconditions scientific committee of therenovation European Geosciences (EGU) General Assembly sales. DueEnergy, to theresponsibility changed climate and building heatUnion demand in the future could decrease, under responsibility ofthe theEnvironment scientific committee of the Europeanpolicies, Geosciences Union (EGU) General Assembly 2017 –Peer-review Division Resources and (ERE). 2017 – Division Energy, Resources and the Environment (ERE). the investment return period. –prolonging Division Energy, Resources and the Environment (ERE). The mainCO scope of thisgaspaper is to assess theOrganic feasibility of using the heat demand – outdoor temperature function for heat demand Keywords: bearing shales; Total Carbon; clay minerals; 2 sorption; forecast. CO The district gas of bearing Alvalade, located in Lisbon (Portugal), was used as a case study. The district is consisted of 665 Keywords: shales; Total Organic Carbon; clay minerals; 2 sorption; buildings that vary in both construction period and typology. Three weather scenarios (low, medium, high) and three district scenarios were developed (shallow, intermediate, deep). To estimate the error, obtained heat demand values were 1.renovation Introduction with results from a dynamic heat demand model, previously developed and validated by the authors. 1.compared Introduction TheDepleting results showed that whengas onlyreservoirs weather change considered, and the margin of error be acceptable some applications conventional forcediscompanies operators for could the search of otherforreservoirs where (theDepleting error in annual demand was lower than 20% forcompanies all weather and scenarios considered). However, after introducing renovation conventional gas reservoirs forced operators for the search of other reservoirs where gas can be produced. Exploration of unconventional gas reservoirs such as shale gas and tight gas started the scenarios, the error value increased up to 59.5% (depending on the weather and renovation scenarios combination considered). gas can be produced. Exploration of unconventional gas reservoirs such as shale gas and tight gas started the energetic revolution in the first decade of 21st century in USA and to the lesser extent also in Canada [1,2]. Most The value of slope coefficient increased on average within the range of 3.8% up to 8% per decade, that corresponds to the energetic revolution in the first decade of 21st century in USA and to the lesser extent also in Canada [1,2]. Most intensive gashours and oil in Europe tookthe place in the Lower Paleozoic Basin decrease exploration in the numberofofshale heating of 22-139h during heating season (depending onBaltic-Podlasie-Lublin the combination of weather and intensive of shale in Europe took place in the Lower Paleozoic Baltic-Podlasie-Lublin inrenovation Poland exploration [3,4]. The considered). first shalegas gas exploration wellfunction in Poland was opened infor 2010 and until first (depending quarter ofBasin 2017 scenarios Onand theoil other hand, intercept increased 7.8-12.7% perthe decade on the in Poland [3,4]. TheThe first shale gasdrilled, exploration in inparameters 2010 and for until first quarter of 2017 over 70 exploration wells were including 16toPoland horizontal wells [5]. The prospective shale formations are coupled scenarios). values suggested could bewell used modifywas theopened function thethe scenarios considered, and over 70 exploration wells were drilled, including 16 horizontal wells [5]. The prospective shale formations are improve the accuracy of heat demand estimations.

© 2017 The Authors. Published by Elsevier Ltd. Peer-review under responsibility of the Scientific Committee of The 15th International Symposium on District Heating and ∗ Corresponding author. Tel.: +48-32-2372487 Cooling. ∗ E-mail address:[email protected] Corresponding author. Tel.: +48-32-2372487 E-mail address:[email protected] Keywords: Heat demand; Forecast; Climate change 1876-6102 © 2017 The Authors. Published by Elsevier Ltd. Peer-review underThe responsibility of theby scientific of the European Geosciences Union (EGU) General Assembly 2017 1876-6102 © 2017 Authors. Published Elsevier committee Ltd.

–Peer-review Division Energy, Resources andofthe (ERE). of the European Geosciences Union (EGU) General Assembly 2017 under responsibility theEnvironment scientific committee – Division Energy, Resources and the Environment (ERE). 1876-6102 © 2017 The Authors. Published by Elsevier Ltd. Peer-review under responsibility of the Scientific Committee of The 15th International Symposium on District Heating and Cooling. 1876-6102 © 2017 The Authors. Published by Elsevier Ltd. Peer-review under responsibility of the scientific committee of the European Geosciences Union (EGU) General Assembly 2017 – Division Energy, Resources and the Environment (ERE). 10.1016/j.egypro.2017.08.153

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spread over a large area of 37000 km2 with depths ranging from about 2000 m to 5000 m [6,7]. The Lower Palaeozoic shale succession form ca. 700 km long belt extending from South Sweden, through Poland do Ukraine and resting on crustal basement of SW margin of the East European Craton (EEC) [8]. The European Union energy policy is focused on CO2 emission reduction [9] and there is a strong need for finding alternative CO2 storage places, particularly in countries where fossil fuels are a dominant source of energy. In Poland, where the vast majority of energy is generated from coal [10] the idea of Carbon Capture and Storage (CCS) could be a viable solution to reduce CO2 emissions. Although different trapping mechanisms govern the CO2 storage, the basic idea is to inject CO2 and securely store it permanently underground. The option to inject CO2 into deep underground traps could be extended to shale gas reservoirs [11–13]. In this case, CO2 can be physically adsorbed on organic matter and/or clay minerals in the same way as methane. Recent studies show that not only organic matter contributes to the overall sorption capacity of shales but also clay minerals have a micro-porous structure which adsorbs gases and can enhance sorption [14–16]. This study explores the CO2 sorption potential of shales as a function of their organic and mineral composition. 2. Materials and methods 2.1 Materials For the study 4 samples with similar Total Organic Carbon (TOC) and varying by clay minerals content were chosen. Samples were all acquired from the exploratory borehole located in the Baltic Basin and represented Ordovician and Silurian mudstones from the depth interval of 3620 – 3720 m. The Baltic basin is considered as one of the Polish basins with the highest shale gas potential. The TOC content was measured by means of LECO apparatus at ACME labs. The TOC fall in the range between 0.98 – 4.19%wt. The mineral composition of samples was established with X-ray Powder Diffraction technique (XRD) at the Polish Academy of Sciences and the results of XRD analysis as well as TOC content are shown in Table 1. Three out of the four samples have very similar TOC content (0.98-1.3 %wt) whereas the fourth one has a considerably higher content of 4.19 %wt. The clay mineral content of samples is between 52.7 and 58.3 %. Table 1 XRD analysis and TOC of samples. Sample

1

2

3

4

Quartz. % Kspar. %

26.5 1.3

25.7 1.3

24.5 1.1

28.1 1.5

Plagioclase. % Calcite. % Dolomite. % Ankerite. % Pyrite+Marcasite. %

3.4 6.2 2.2 3.2 4.2

4 3.7 1.6 2.7 2.7

3.7 3.3 1.6 1.8 2.8

4 1.9 0.1 0.5 2.5

Barite. % Gypsum. % Fe (oxy-) hydroxide. % Apatite. % Anatase. % Kaolinite. %

0 0 0.1 0 0.3 0.7

0 0.4 0.4 0.4 0.5 1

0 0.3 0.7 0 0.3 0.5

0 0.2 0.5 0.2 0 0

2:1 Al Clay. %

44.6

48.4

49.3

52.2

Chlorite. %

7.4

6.4

8.5

5.5

Σ Clay. % TOC. wt%

52.7 0.98

55.8 1.3

58.3 1.25

57.7 4.19



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2.2. Sorption measurements For conducting an experiment the manometric method of sorption measurement was used. The main assumption in this method is reduction of pressure while gas molecules transfer from free phase to the surface of sorbent. This means that in constant temperature and volume the pressure change is proportional to the amount of adsorbed gas. The adsorbed amount of gas (nsorbed ) can be calculated as a difference between the total amount of gas which was transferred to the volume of reference cell (ntotal ) and the amount of gas occupying volume of apparatus after sorption equilibrium is reached (nfree ): nsorbed = ntotal - nfree

(1)

The amount of free gas can be calculated if the void volume of the sample cell (Vvoid ) is known. Vvoid is a total volume which can be occupied by gas, a difference between sample cell volume and a space occupied by solid sample. Vvoid also includes a pore space in sample. An amount of free gas can be calculated as a product of void volume and density of the gas (ρP.T ) at particular pressure and temperature (2): nfree = Vvoid · ρP.T

(2)

The sorption isotherm is determined by conducted consecutive steps. During every step a mass of gas (in steady state of temperature and pressure) is transferred from the reference cell to the sample cell. An amount of transferred gas can be calculated with the equation below (3): 2 ntransferred = ∑Ni=1 Vref ·ρi

CO

f.CO2

e.CO2

-ρi



(3)

Where ρi 2 and ρi 2 refer to the density of CO2 in the reference cell before it is connected with the sample cell and after equilibration. and Vref is a known volume of a reference cell. A scheme of one step of a measurement is shown in Fig. 1. f.CO

e.CO

Fig.1. Schematic diagram of the manometric sorption methodology used in the study. The diagram shows procedure for one sorption step.

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It can be seen that every step of experiment has 4 stages. Before the first step in experiment any gas from apparatus volume must be removed. It is done by vacuuming the reference and sample cell during 24 hours. Next, the reference cell is filled with gas (in case of this study with CO2), and the gas stays inside until it reaches thermal equilibrium. At stage 3 the valve between sample cell and reference cell is opened – it leads to connection between gas and a sample cell. The gas stays in sample cell for about 24 hours until the sorption process is finished i.e. until the pressure equilibrium is reached. At the last stage the valve between cells is closed and the next pressure step can be commenced, starting from filling reference cell with additional portion of gas. Due to the fact that shales have a much lower sorption capacity than other organic sorbents such as coal, it is crucial to accurately measure the void volume. In order to measure void volume a helium expansion method was used as the helium is the inert gas and does not interact with the surface of microporous adsorbents. To accurately estimate the density of Helium a McCarthy equation of state [17] was used, whereas for CO2 the Span&Wagner equation of state was used [18]. Additionally, a void volume calculation method proposed by Gasparik et al.[19] was applied where the total amount of helium transferred successively into the sample cell is plotted against helium density. The setup used for experiments consists of a sample cell, reference cell, valves, tubing, pressure transducers and temperature sensors. The system consists of two identical setups allowing two parallel measurements to be performed at the same time. The gas is injected into the setup by the MAXIMATOR DLE 5-30-GG high pressure pump and to evacuate the system a vacuum pump is used. Pressure is monitored using KELLER-DRUCK X33 pressure transducers (0.05% Full Scale accuracy) with temperature compensation, connected to the data acquisition system which records pressure readings every 5 s using CCM software. The temperature is monitored with Pt100 sensors of 1/10B class resistance tolerance. Temperature sensors are connected to the multi-channel temperature data-logger L200-RTD (resolution 0.01°C). Sample cells designed and constructed at the Silesian University of Technology are made from 314L stainless steel. Reference cells have a volume of 150.8 cm3 and 151.1 cm3. Fittings used in the setup are high pressure SWAGELOK fittings made of stainless steel with ¼” tubing and diaphragm valves. Setup is immersed in demi water in custom made thermo bath with electronic temperature stabilization (<0.1°C).

Fig. 2. Scheme of the high-pressure manometric setup.



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3. Results 3.1 Excess sorption Sorption experiments were conducted at the temperature of 50°C and 80°C, in the range of pressure 0 - 15 MPa. The CO2 excess sorption on samples is shown in Fig. 3.

Fig. 3. Excess sorption of CO2 on shale samples at the temperature of 50°C (left) and 80°C (right).

Isotherms of CO2 excess sorption have a slanting shape when reaching supercritical region (above 7.1 MPa) and the isotherms becomes negative at the pressure above 8MPa. This shape does not resembles any of the classic IUPAC isotherms since the classification is mostly focused on condensable vapors and many important gas/solid systems fall outside this classification (eg. carbon dioxide) [20]. Similar phenomena for shales was observed elsewhere [19,21]. It can be explained by various factors i.e.: low adsorbed phase density (sorption energy) of shales [22] or experimental artifacts and behavior of CO2 near critical point (density change). Another reason could be the overestimation of void volume by helium measurements; the helium particle is smaller than CO2 and can penetrate much smaller pores. The new classification of isotherms [23] extends the IUPAC classification of isotherms by sorption of gases at supercritical conditions on microporous adsorbents. At supercritical conditions, the isotherm is not monotonic and the shape in this study falls into the type I isotherm according to the new classification. 3.2 Sorption modelling An excess sorption on samples was modelled with the Langmuir model modified with density rather than pressure as proposed by Sakurovs [24]. The equation of model is shown below (4), where mabs is an absolute sorption of CO2, ma is a monolayer volume, called a Langmuir volume, bv is an equilibrium constant (an inverse of Langmuir pressure), ρg and ρa are gas densities, free phase and adsorbed phase respectively:

mabs =

ma ·ρg bv +ρg

ρg

1- 

(4)

ρa

The absorbed phase density was used as a free parameter. The fitting of model was done by minimizing residual sum of squares to the experimental data with EXCEL solver. In order to calculate the absolute sorption a density of 22.0 mmol/ml (liquid phase density of CO2) of the adsorbed phase was assumed. Next. the conventional Langmuir model (5) was applied.

V=

VL ·P PL +P

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where VL is the Langmuir volume (m3/t) and PL is the Langmuir pressure (MPa). Results of model fitting for the isotherms at 50°C are shown in Fig. 4. a

b

Fig.4. Langmuir model of CO2 excess sorption (a) and absolute sorption (b) at temperature of 50°C.

The Langmuir model parameters were calculated and are shown in Table 2. As it was expected sorption at 80°C was lower than for 50°C. This trend is reflected in maximum sorption capacity of Langmuir model (VL). Table 2. Parameters of Langmuir model of absolute sorption. Sample

1

2

3

4

VL (50°C) , m3/t

10.54 0.85

11.28 1.04

13.92 1.53

18.51 2.60

PL (50°C), MPa VL (80°C), m3/t

3.98

5.52

5.28

13.60

PL (80°C), MPa

2.53

4.17

1.71

5.16

3.3 A correlation between sorption capacity, TOC and clay mineral content The correlation between TOC and Langmuir volume (VL) is shown in Fig. 5. The coefficient of determination is considerably high: 0.86 in case of the temperature 50°C and 0.996 in case of the temperature 80°C. The correlation at 50°C is lower due to a higher variation of VL for the first three points.

Fig.5. Langmuir model of CO2 excess sorption (left) and absolute sorption (right) at temperature of 50°C.



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Positive linear relationship between the TOC and sorption capacity is reported in various publications related to sorption of gases on shales [25–27]. Organic matter in the investigated samples is highly porous [28] and this pore volume is most probably responsible for observed sorption. However, porosity in samples with low TOC values is related to clay mineral aggregates [28]. In Fig. 6b the sum of clay minerals (represented by kaolinite, illite, K-micas and chlorites) is correlated with the calculated VL parameter of absolute sorption. The correlation is rather low (R2 - 0.2-0.5) but the trend is positive toward increasing clay minerals content. The range of clay minerals is rather narrow and the correlation between sum of clay mineral as well as Kaolinite+2:1 Al clay is lower at 80°C. a

b

Fig. 6. Correlation between VL and sum of clay minerals (a) and sum of kaolinitie and 2:1 Al clay minerals group, without chlorite (b).

Since the sorption on clay minerals decreases in the order smectite>illite>kaolinite>chlorite [29] it was assumed that chlorite will have the lowest pore volume and therefore was subtracted from the sum of clay minerals. When comparing the correlation between the sum of kaolinite and 2:1 Al clays the fit is even better, see Fig. 6a. Sorption tests carried out by the authors on pure halloysite samples, a two-layer mineral belonging to the kaolinite subgroup represented by the same chemical formula Al2Si2O5(OH)4•nH2O show that sorption capacity of halloysite is similar to that of shale samples with high clay mineral and kaolinite content i.e. sample 2 and 3, see Fig. 7. Obviously, since halloysite is a pure clay mineral and does not contain quartz and other non-sorptive minerals its overall sorption capacity is higher. Nevertheless, the range of values is comparable to shale samples in the study.

Fig. 7. CO2 excess sorption on sample 1, 2, 3, 4 and pure halloysite mineral.

Additional low pressure CO2 and N2 adsorption tests with the use of Micromeritics ASAP 2020 Surface Area and Porosimetry System (see Table 3) show that SBET specific surface area of pores bigger than 2 nm correlates well

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with the content of clay minerals, Fig. 8a. The micropore volume (VDA) calculated with Dubinin-Astakhov model based on low pressure CO2 adsorption does not show a satisfactory correlation but a positive trend, Fig. 8b. Table 3. Low pressure N2 and CO2 sorption test results VBJH VDA PSBET N2 SDR (m2/g) PSBET CO2 (cm3/g) (nm) (cm3/g) (nm) 1 12.750 0.025 8.473 9.443 0.008 1.296 2 13.769 0.026 8.162 9.737 0.008 1.374 3 14.288 0.026 7.923 10.071 0.007 1.322 4 17.778 0.042 9.955 15.882 0.012 1.351 SBET - specific surface area of pores bigger than 2 nm (based on BET model), N2 adsorption SDR - specific surface area of pores bigger than 2 nm (based on DR model), CO2 adsorption VBJH - mesopores volume (based on Barret-Joyner-Halenda model), N2 adsorption PSBET - mesopores and micropores average pore width (based on BET model) VDA - micropores volume (Dubinin–Astakhov model), CO2 adsorption Sample

SBET (m2/g)

b a

Fig. 8. Correlation between specific surface area (SBET) from N2 low pressure sorption test (a) and micropore volume (VDA) from CO2 low pressure sorption test (b) with sum of kaolinite and 2:1 Al clay content.

4. Conclusions Experimental data of CO2 sorption on shales in a manometric setup show some overview of sorption capacities and sorption behavior of Baltic Basin gas shales. These shales are represented by thinly laminated mudrocks with matrix composed of clay minerals. Results of high pressure sorption tests show that maximum excess sorption capacity is of range 0.4-0.55 mmol/g and isotherms tend to negative value above the pressure of 8 MPa. Good correlation between TOC and calculated VL parameter (maximum sorption capacity) was observed. Low pressure N2 and CO2 adsorption tests show that clay minerals (mostly kaolinite, illite, K-micas and chlorites) significantly contribute to the micropore system in the investigated samples what is also confirmed by SEM study [28]. Therefore, we speculate that clay minerals might be responsible for relatively high sorption capacity of these shales. Consequently, results of our study demonstrate that when organic matter is nearly absent in mudstones CO2 sorption may occur also in clay minerals. Acknowledgements The research leading to these results has received funding from the Polish-Norwegian Research Programme operated by the National Centre for Research and Development under the Norwegian Financial Mechanism 20092014 and Project Contract No. PL12-0109. We would like to thank Maria Mastalerz from Indiana Geological Survey (Bloomington, USA) for enabling the porosimetry measurements and Arkadiusz Derskowski from Polish Academy of Science for enabling XRD analysis.



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