Solubility of Carbon Dioxide, Methane, and Nitrogen in Liquid

Article Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX

pubs.acs.org/jced

Solubility of Carbon Dioxide, Methane, and Nitrogen in Liquid Dibenzyl Toluene Anatol Leinweber† and Karsten Müller*,† †

Institute of Separation Science and Technology, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Egerlandstraße 3, Erlangen, 91058, Germany

Downloaded via KAOHSIUNG MEDICAL UNIV on August 25, 2018 at 09:20:10 (UTC). See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

S Supporting Information *

ABSTRACT: Dibenzyl toluene is a promising liquid organic hydrogen carrier (LOHC), which can be applied in chemical energy storage through reversible hydrogenation. As nowadays hydrogen is primarily produced through methane steam reforming, coproducts such as carbon dioxide, nitrogen, and methane can be present in significant amounts in the gas stream. Taking this mixed gas stream to hydrogenate the LOHC material is one possible scenario. Besides that of hydrogen the physical solubility of these coproduct gases is of high relevance for process development. In this work the solubility of CO2, N2, and CH4 is measured in both hydrogenated and dehydrogenated form of the LOHC material using the static isochoric saturation method. All measurements were performed at pressures up to 8 bar and within the temperature range of 310 to 390 K. In both solvents, dibenzyl toluene and its hydrogenated derivative, carbon dioxide gas has the highest solubility followed by methane and nitrogen, which has by far the lowest gas solubility.

■

INTRODUCTION Liquid organic hydrogen carriers (LOHC) have drawn rising attention in recent years as a means of storing hydrogen under ambient conditions with a high storage density. In this approach an aromatic compound takes up hydrogen via a reversible hydrogenation reaction forming the corresponding saturated compound. To release the hydrogen again, a dehydrogenation is performed at elevated temperatures (about 250−310 °C).1−3 A very interesting material for application as an LOHC is dibenzyl toluene.4,5 One molecule of dibenzyl toluene (H0-DBT) can take up nine hydrogen molecules forming perhydro-dibenzyltoluene (H18-DBT). For designing LOHC processes knowledge about the properties of the materials is essential. An important step in the chemical reaction is the physical solving of hydrogen gas into the carrier material. Hydrogen solubility is important for the kinetics of the hydrogenation reaction. Aslam et al.6 measured the solubility of hydrogen in different potential LOHC materials including H0-DBT and H18-DBT. However, hydrogen is often not provided in a pure form, but can be accompanied by other substances. Hydrogen from electrolysis might for example contain traces of water. To deal with issues related to that fact the solubility of water in these LOHC materials have been measured by Aslam et al.7 as well. Another important hydrogen production technology, which is currently the dominant technology in this field, is reforming of natural gas or other hydrocarbons. Hydrogen derived from this approach is always accompanied by coproduced gases such © XXXX American Chemical Society

as carbon monoxide, carbon dioxide, and low amounts of residual methane as well as residual air nitrogen. The only strict requirement concerning purity is the amount of carbon monoxide. It has been demonstrated that the catalysts used for the hydrogenation of unsaturated hydrocarbons are poisoned by carbon monoxide.8 However, if the carbon monoxide concentration is kept low enough, the hydrogenation reaction does not require further purification to remove other gases. Consequently, it can be interesting to operate the hydrogenation reaction with a gas mixture to reduce the effort for purification. For such an operation of the hydrogenation process it is helpful to know the solubility of the accompanying gases. In this work the solubilities for methane, carbon dioxide, and nitrogen in dibenzyl toluene (H0-DBT) and its hydrogenated form (H18-DBT) have been measured in an isochoric gas solubility cell. The measurements have been done at different temperatures, and correlations for temperature dependency of the Henry coefficients are presented.

■

EXPERIMENTAL SECTION Material. Nitrogen, methane, and carbon dioxide were purchased from Linde Gas, Germany. Dibenzyl toluene (H0DBT) was obtained from Sasol as an isomeric mixture, also Received: May 16, 2018 Accepted: August 10, 2018

A

DOI: 10.1021/acs.jced.8b00407 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 1. Supplier and Purity Data for the Chemicals Used in This Study chemicals

CASRN

formula

supplier

purity (mole %)

nitrogen methane carbon dioxide dibenzyl toluene perhydro-dibenzyltoluene

7727-37-9 74-82-8 124-38-9 26898-17-9 1802472-83-8

N2 CH4 CO2 H0-DBT H18-DBT

Linde Gas Linde Gas Linde Gas Sasol hydrogenation

>99.999 >99.95 >99.995 >98 (GC) >97 (GC)

known as Marlotherm SH. Perhydrodibenzyltoluene (H18DBT) as a fully hydrogenated form of H0-DBT was prepared via hydrogenation at the Institute of Chemical Reaction Engineering, FAU, Germany. Supplier information and details on purity were given in Table 1. Setup. The solubility of the gases was measured using the isochoric saturation method. A schematic drawing of the experimental setup can be found in Figure 1.

data were recorded by PIR 001 and TIR 001 to calculate the amount of hydrogen gas within the gas reservoir. After the system has reached stationary pressure and temperature conditions, V3 was opened and the pressure in the system decreased until the liquid in the cell was saturated with the gas. Gas liquid equilibrium was assumed after 5 h of constant pressure and temperature. After a stationary state was reached, temperature in the cell was varied again up to 413 K. TIR 002 recorded the temperature of the liquid. The procedure for one gas solubility experiment is shown exemplarily in Figure 2. For each experiment the cell (3) was

Figure 1. Experimental setup: (1) pressurized gas bottle; (2) gas reservoir (volume incl. pipes between V1, V2 and V3); (3) cell with magnet stirrer as liquid reservoir (volume incl. pipes up to V3); (4) quick coupling between gas and liquid reservoir.

Figure 2. Experimental procedure of one experimental run at initial gas load of 6.018 bar CH4 gas in contact with liquid H0-DBT.

For gas solubility measurements, the volume of both reservoirs needs to be known precisely. The volumes of the liquid reservoir (3) and gas reservoir (2) have been determined using water and nitrogen gas, respectively. The detailed procedure is reported elsewhere.9 The resulting volumes of the liquid (2) and gas reservoir (3) are 50.6 ± 0.4 mL and 171.6 ± 0.2 mL, respectively. The two reservoirs are divided by lock valve V3 and can be set to a specific temperature level with an oil thermostat and an air circulation oven. An external LAUDA ECO RE 415 Thermostat that pumps a heat transfer oil through the heating jacket of the cell (3) controls the temperature in the liquid reservoir (3). A tangential fan is circulating the air in an oven that covers the complete gas reservoir (2) in an acrylic housing. The thermoregulation of the reservoir (2) is realized with a heating wire along the tangential fan inside the housing. The solution of gas in liquids is driven by the contact of both liquid and gaseous phase and takes place in the cell (3) which is equipped with a magnetic stirrer to intensify mass transfer. For each measurement the cell has been filled with a defined amount of liquid sample, which has been degasified under vacuum conditions in a supersonic bath for at least 3 h. Furthermore, the liquid sample was purged in situ by evacuating the whole system through valve V1 to ensure the removal of residual gas within the liquid phase. Subsequently, V3 was closed to fill the gas reservoir with the respective gas via valve V2 up to a specific pressure. Pressure and temperature

filled with degassed liquid (here: H0-DBT) and evacuated before the gas reservoir (2) was filled up to an initial gas pressure (here: 6.018 bar of CH4). Only after opening valve V3 did the pressure drop due to the evacuated gas volume above the liquid phase in cell (3), and the gas starts diffusing into the stirred liquid phase. Gas and cell temperature were kept constant during the measurement. Equilibrium was assumed after at least 2 h of stationary state conditions (p, V, and T = const.). Then the cell temperature was increased stepwise to reach respective saturation conditions while the gas temperature was kept constant during the whole experiment. Using the stationary state pVT-data, the amount of gas can be calculated directly using an equation of state. In this work, the virial equation is used, terminated after the second virial coefficient: G ngas (P , V , T , Bgas ) =

PV RT + Bgas P

(1)

nGgas

where is the amount of gas in the gas phase. Bgas is the second virial coefficient, R is the universal gas constant, and P, V, and T represent the pressure, volume, and temperature in the gas phase. Temperature-dependent values for the second virial coefficient of CO2, N2, and CH4 were taken from the DIPPR database.10 The amount of gas dissolved in liquid DBT can be calculated by applying material balance given in eq 2. B


Journal of Chemical & Engineering Data L ngas

=

G ngas,i

−

G ngas,f

Article

L ij Vcell − (mDBT + Mgasngas )/ρDBT yzz zz − jjjj zz G j vcell { k

ΔnLgas as a function of nGgas,i, nGgas,f, vGcell, Vcell, ρDBT and mDBT. The uncertainties of nGgas,i, nGgas,f and vGcell are functions of temperature, pressure, volume, and the parameters of the equation of state used (here: second virial coefficient) according to the Virial eq 1 and eq 3, respectively. Therefore, the Gaussian error propagation method was applied repeatedly on eq 1 and eq 3. A detailed description of the procedure is given in the Supporting Information. Further uncertainties for the temperature (Conatex Pt100) and pressure (WIKA) measuring devices were assumed as given by the manufacturer. The uncertainty is less than 0.01 K for ΔT and less than 1.0% of the maximum working pressure for ΔP. For ΔV the volumes of the liquid (2) and gas reservoir (3) are given with a standard deviation of 0.4 and 0.2 mL, respectively. The uncertainty in the second virial coefficient was taken from DIPPR database.10 The uncertainty in density was calculated as a derivative of density (eq 4) with respect to temperature.

(2)

nLgas

The term is the amount of gas dissolved in the liquid phase, nGgas,i is the initial number of moles of gas in the reservoir (before opening V3) and nGgas,f is the final number of moles of gas after reaching phase equilibrium. The last term enclosed in brackets takes the additional gas volume in the liquid reservoir (3) into account as the cell is charged with liquid DBT only to a certain level considering expansion of the liquid due to temperature variation and increasing content of dissolved gas. Here Vcell is the volume of the equilibrium cell, mDBT/g is the mass of DBT charged into the cell, Mgas/(g mol−1) is the molecular weight of the respective gas, ρDBT is the density of DBT and has a strong dependency on temperature. The density of dissolved gas is assumed to be equal to the one of DBT. vGcell is the molar volume of gas in the cell and can be calculated using eq 3. G vcell (P ,

4PBgas zyz zz 1+ RT zz {

RT jijj T , Bgas ) = j1 + 2P jj k

■

RESULTS The solubility of carbon dioxide, nitrogen, and methane was measured in both dibenzyltoluene (H0-DBT) and its hydrogenated compound (H18-DBT), respectively. The suitability of the experimental setup has been evaluated before and is reported elsewhere.6 The experimental data in this work have been obtained with the same routine. Experimental data for the solubility of CO2, N2, and CH4 in both H0-DBT and H18-DBT are shown in Table 3 and Table 4, respectively. Experiments were performed at different pressure levels (2, 4, 6, and 8 bar; these pressure levels represent the starting point of each experiment). The temperature-dependent solubilities of CO2, N2, and CH4 in dibenzyltoluene (H0-DBT) are plotted in Figure 3, Figure 4, and Figure 5. The solubilities of the gases in hydrogenated H18-DBT are presented in Figure 6, Figure 7, and Figure 8. The solubility of CH4 in both H0-DBT and H18-DBT is almost independent of temperature with a weak tendency to decrease with increasing temperature in H18-DBT. However, the solubility of CO2 is decreasing significantly with rising temperature, while the solubility of N2 increases slightly with temperature. The temperature dependency of CH4 and N2 is remarkably higher in H18-DBT compared to H0-DBT, while CO2 shows a stronger dependency in H0-DBT. The weaker temperature dependency in the case of N2 and CH4 compared to CO2 is consistent with what can be expected from thermodynamics. According to Prausnitz and Shair12 the solubility of gases decreases with increasing temperature until it reaches a minimum at a reduced temperature of about 2. At higher reduced temperatures solubility starts to increase slowly again with increasing temperature. In the case of CO2, the reduced temperature (i.e., temperature divided by critical temperature of the gas) is only in the order of magnitude of 1, while it is about 3 in the case of N2 and 2 in case of CH4. As a result the trend of solubility is in accordance to the expectations in the given temperature range. Basically, the relative uncertainty in the solubility measurement was higher for experiments at lower pressures. The relative uncertainty in solubility of CO2 in DBT is less than 31%. In the case of CH4 and N2 the value is less than 38% and 78%, respectively. The increasing relative uncertainty can be explained by the decreasing solubility in the following order:

(3)

where B is the second virial coefficient and P, T, and R are pressure, temperature, and universal gas constant, respectively. Densities of both hydrogenated and dehydrogenated MBT (which are denoted with H18 and H0, respectively) were measured by Müller et al.11 using high precision vibrating tube density meter Anton Paar DMA 5000 in a temperature range from 293 to 353 K. The temperature dependent density was described by eq 4. Respective correlation parameters for the density calculation are listed in Table 2. Density values at higher temperatures have been extrapolated, respectively. ρ(T )/(g cm−3) = AT /K + B

(4)

Table 2. Correlation Parameters for eq 4.11 H0-DBT H18-DBT

A

B

−0.0007150 −0.0006384

1.2537113 1.1005251

With the use of the iteration method the quantity of dissolved hydrogen was calculated using eq 2. Subsequently, the Henry coefficients were determined using eq 5. Hgas/MPa = lim

x→0

G f gas (T , P )

xgas

(5)

fGgas

where is the fugacity of the respective gas and xgas is its molar fraction in the liquid phase. To calculate the total uncertainty in the molar fraction the Gaussian error propagation method (eq 6) was used: 2 ij ∂x y ij ∂x yz jj z L z ΔmDBTzzz jj L Δngaszzz + jjjj z j ∂ngas z k ∂mDBT { k { 2

Δx =

(6)

The mass of liquid solvent in the cell was measured using a Mettler Toledo electronic balance with standard uncertainty of 0.01 g (Δm). To calculate the uncertainty of ΔnLH2 the Gaussian error propagation method was applied on eq 2 using C



Article

Table 3. Experimental Data of Gas Solubility in Dibenzyltoluene (H0-DBT) Regarding CO2, N2, and CH4 CO2 in H0-DBT (x ± Δx)/mol % T/K

(x ± Δx)/mol % T/K

2.003 bar

314 336 357 399 437 472

± 0.14 ± 0.14 ±0.14 ± 0.15 ± 0.15 ± 0.15

1.27 1.07 0.92 0.70 0.58 0.48

314 336 358 399 437 473

T/K

± ± ± ± ±

0.18 0.19 0.19 0.20 0.20

± ± ± ± ± ±

0.27 314 0.27 336 0.28 357 0.28 397 0.29 436 0.29 471 N2 in H0-DBT

3.86 3.29 2.88 2.29 1.94 1.73

T/K 0.12 0.12 0.12 0.12 0.12

311 329 348 367 386

T/K

± ± ± ± ±

0.24 311 0.24 329 0.24 347 0.24 366 0.24 384 CH4 in H0-DBT .

2.02 bar

T/K

311 330 348 366 385 404

± ± ± ± ± ±

0.42 0.41 0.41 0.40 0.40 0.39

314 336 357 398 435 470

0.14 0.14 0.14 0.15 0.15 0.15

311 329 347 366 385 403

± ± ± ± ±

7.997 bar

0.36 0.36 0.36 0.36 0.36

± ± ± ± ± ±

5.08 4.36 3.82 3.09 2.71 2.48

0.52 0.54 0.55 0.57 0.58 0.59


6.013 bar 0.48 0.50 0.52 0.53 0.54


0.39 0.40 0.41 0.43 0.43 0.44

(x ± Δx)/mol %

4.016 bar 0.33 0.35 0.36 0.36 0.36

± ± ± ± ± ±


6.010 bar

(x ± Δx)/mol %

2.003 bar

311 328 347 366 384

T/K

2.57 2.19 1.90 1.56 1.38 1.23

(x ± Δx)/mol %

(x ± Δx)/mol %

4.001 bar

311 329 347 366 384

8.05 bar ± ± ± ± ±

0.65 0.66 0.69 0.71 0.71

0.48 0.49 0.48 0.49 0.49

(x ± Δx)/mol % 6.018 bar 1.22 1.22 1.21 1.20 1.20 1.20

± ± ± ± ± ±

0.39 0.40 0.41 0.43 0.43 0.44

Table 4. Experimental Data of Gas Solubility in Perhydrodibenzyltoluene (H18-DBT) Regarding CO2, N2, and CH4 CO2 in H18-DBT

T/K 333 354 374 394

(x ± Δx)/

(x ± Δx)/

mol %

mol %

2.005 bar

T/K

± ± ± ±

0.13 334 0.13 356 0.14 375 0.14 395 N2 in H18-DBT

1.25 1.11 1.00 0.90 (x ± Δx)/ mol %

T/K 331 350 369 387

2.041 bar 0.15 0.16 0.16 0.17

± ± ± ±

0.07 0.07 0.07 0.07

(x ± Δx)/ mol % T/K

328 348 367 386

1.958 bar 0.58 0.56 0.53 0.50

± ± ± ±

0.04 0.04 0.04 0.04

5.078 bar

330 0.36 ± 0.09 349 0.43 ± 0.08 368 0.46 ± 0.08 387 0.49 ± 0.08 CH4 in H18-DBT


8.095 bar

330 349 368 388

5.281 bar 1.74 1.67 1.61 1.57

± ± ± ±

0.08 0.08 0.08 0.08

0.20 0.22 0.24 0.26

(x ± Δx)/ mol % T/K 330 349 368 387


± ± ± ±

5.02 4.54 4.16 3.85

7.970 bar 0.61 0.70 0.74 0.79

± ± ± ±

0.13 0.13 0.13 0.13

Figure 3. Solubility of carbon dioxide (CO2) in dibenzyltoluene (H0DBT).

(x ± Δx)/ mol % T/K 330 349 368 387

by the uncertainty of pressure and gas phase temperature measurement. Detailed itemization of uncertainties and their contributions are given in the Supporting Information. The Henry coefficient was calculated as a mean value of at least two measurements at different initial gas load pressures. The standard deviation for the reproducibility of the Henry Coefficient is below 10% in the case of all three gases. Resulting Henry coefficients are listed in Table 5. As it is demonstrated in Figure 9 the experimental solubility data for the Henry coefficient of CO2 in H0-DBT shows a relative deviation of a maximum 11% compared to data

8.022 bar 2.64 2.59 2.51 2.43

± ± ± ±

0.12 0.12 0.12 0.12

xCO2 > xCH4 > x N2

The main contribution to the overall uncertainty of x is the uncertainty of volume within the experimental setup, followed D



Article

Figure 4. Solubility of nitrogen (N2) in dibenzyltoluene (H0-DBT).

Figure 7. Solubility of nitrogen (N2) in perhydro-dibenzyltoluene (H18-DBT).

Figure 5. Solubility of methane (CH4) in dibenzyltoluene (H0-DBT). Figure 8. Solubility of methane (CH4) in perhydro-dibenzyltoluene (H18-DBT).

Table 5. Henry Coefficients of CO2, N2, and CH4 in Dibenzyltoluene (H0-DBT) and Its Hydrogenated Compound (H18-DBT) (H ± σ)/MPa T/K

Figure 6. Solubility of carbon dioxide (CO2) in perhydrodibenzyltoluene (H18-DBT).

reported by Götz et al.13 In average the relative deviation is around 8% lower.

CO2

314 336 357 398 436 472

11.4 14.0 16.7 22.1 26.5 30.9

334 354 374 396

12.6 14.4 16.3 18.4

(H ± σ)/MPa T/K

N2

(H ± σ)/MPa T/K

In Dibenzyltoluene (H0-DBT) ± 0.1 311 104.3 ± 5.4 311 ± 0.2 329 102.0 ± 4.9 329 ± 0.3 348 99.6 ± 4.3 348 ± 1.0 366 98.5 ± 3.9 366 ± 1.8 385 98.4 ± 4.2 385 ± 3.2 404 In Perhydrodibenzyltoluene (H18-DBT) ± 0.1 330 126.3 ± 4.1 329 ± 0.2 349 112.3 ± 6.7 349 ± 0.4 368 108.2 ± 8.8 368 ± 0.5 387 104.1 ± 11.1 387

CH4 39.7 40.7 41.5 42.3 42.9 43.6

± ± ± ± ± ±

0.4 0.2 0.02 0.09 0.1 0.5

26.1 27.3 28.9 30.4

± ± ± ±

1.4 1.5 1.9 2.3

Benson and Krause14−17 suggested a temperature-dependent correlation for calculation of Henry coefficients using eq 7: E



Article

Figure 9. Comparison of measured CO2 solubility in H0-DBT with the literature.13 n

ln(HG,S/MPa) =

∑ i=0

ai (T /K)i

Figure 10. Temperature dependency of the Henry coefficient CO2, N2, and CH4 in H0-DBT. Symbols represent the experimental data. Lines represent the modeled data using eq 7.

(7)

where HG,S is the Henry coefficient of a certain gas G in the solvent S in MPa and T is the temperature in K. Equation 7 is used with three regression parameters a0, a1, and a2. The regression parameters were determined by fitting eq 7 to experimental data through minimizing the sum of squared errors (SSE). The SSE is given by eq 8: N

SSE =

exp calc 2 − HG,S ) ∑ (HG,S

(8)

i=1

Hexp G,S

Hcalc G,S

where are the experimental data and is the calculated value of the Henry coefficient using eq 8. Resulting regression parameters are presented in Table 6. Furthermore, the quality of this fit is expressed by statistical parameters (coefficient of determination R2 and sum of squared error SSE). In Figure 10, experimental and calculated data of the Henry coefficient is compared for H0-DBT as the solvent. The comparison of the Henry coefficients in H18-DBT is shown in Figure 11. The error bars for the Henry data representing the experimental standard deviation are shown in Table 5. For N2 the relative deviation in terms of reproducibility is within 5% in the case of H0-DBT and within 10% in the case of H18-DBT. For CH4 the relative deviation is within 1% in the case of H0DBT and within 8% in the case of H18-DBT. For CO2 the relative deviation is within 10% in the case of H0-DBT and within 4% in the case of H18-DBT.

Figure 11. Temperature dependency of the Henry coefficient CO2, N2, and CH4 in H18-DBT. Symbols represent the experimental data. Lines represent the modeled data using eq 7.

dibenzyltoluene within the temperature range of 320 and 390 K and pressures up to 8 bar. Furthermore, resulting Henry coefficient dependencies have been correlated as a function of temperature for all gases using the Benson and Krause approach. With increasing temperature carbon dioxide was found to show a strong decreasing gas solubility, while the solubility of nitrogen becomes higher as temperature rises. Methane solubility is almost constant in both solvents within the temperature range studied.

■

CONCLUSION In this contribution physical solubility of steam reforming coproduct gases such as carbon dioxide, nitrogen, and methane have been measured in both dibenzyltoluene and perhydro-

Table 6. Regression Parameter for eq 7 Including Parameter Regarding the Quality of Fit in H0-DBT a0 a1 a2 R2 SSE

in H18-DBT

CO2

N2

CH4

CO2

N2

CH4

4.766 −424.4 −9.703 × 1004 0.9999 0.0344

5.457 −686.2 1.353 × 1005 0.9913 0.226

3.901 7.315 −2.360 × 1004 0.9995 0.005

5.921 −1515 1.282 × 1005 1.0000 0.0000

9.836 −4082 8.030 × 1005 0.9889 3.1237

5.560 −1243 1.599 × 1005 0.9983 0.0182

F



■

Article

(12) Prausnitz, J. M.; Shair, F. H. A thermodynamic correlation of gas solubilities. AIChE J. 1961, 7, 682−687. (13) Götz, M.; Ortloff, F.; Reimert, R.; Basha, O.; Morsi, B. I.; Kolb, T. Evaluation of Organic and Ionic Liquids for Three-Phase Methanation and Biogas Purification Processes. Energy Fuels 2013, 27, 4705−4716. (14) Benson, B. B.; Krause, D. The concentration and isotopic fractionation of gases dissolved in freshwater in equilibrium with the atmosphere. 1. Limnol. Oceanogr. 1980, 25, 662−671. (15) Benson, B. B.; Krause, D. A thermodynamic treatment of dilute solutions of gases in liquids. J. Solution Chem. 1989, 18, 803−821. (16) Husson-Borg, P.; Majer, V.; Costa Gomes, M. F. Solubilities of Oxygen and Carbon Dioxide in Butyl Methyl Imidazolium Tetrafluoroborate as a Function of Temperature and at Pressures Close to Atmospheric Pressure. J. Chem. Eng. Data 2003, 48, 480− 485. (17) Hefter, G. T.; Tomkins, R. P. T.; The Experimental Determination of Solubilities; John Wiley & Sons: New York, 2003.

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.8b00407. 'Detailed information on used materials; detailed procedure for calculating the uncertainty of molar fraction of dissolved CO2, N2, and CH4 in H0- and H18-DBT via Gaussian error propagation method; intermediate results of uncertainty calculation with relative contribution of influencing factors. (PDF)

■

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Tel.: +49 9131 8527455. ORCID

Karsten Müller: 0000-0002-7205-1953 Notes

The authors declare no competing financial interest.

■ ■

ACKNOWLEDGMENTS The authors wish to thank Prof. Wolfgang Arlt for his support of this work. REFERENCES

(1) Teichmann, D.; Arlt, W.; Wasserscheid, P.; Freymann, R. A future energy supply based on Liquid Organic Hydrogen Carriers (LOHC). Energy Environ. Sci. 2011, 4, 2767−2773. (2) Amende, M.; Schernich, S.; Sobota, M.; Nikiforidis, I.; Hieringer, W.; Assenbaum, D.; Gleichweit, C.; Drescher, H.-J.; Papp, C.; Steinrück, H.-P.; et al. Dehydrogenation Mechanism of Liquid Organic Hydrogen Carriers: Dodecahydro-N-ethylcarbazole on Pd(111). Chem. - Eur. J. 2013, 19, 10854−10865. (3) He, T.; Pei, Q.; Chen, P. Liquid organic hydrogen carriers. J. Energy Chem. 2015, 24, 587−594. (4) Brückner, N.; Obesser, K.; Bösmann, A.; Teichmann, D.; Arlt, W.; Dungs, J.; Wasserscheid, P. Evaluation of Industrially Applied Heat-Transfer Fluids as Liquid Organic Hydrogen Carrier Systems. ChemSusChem 2014, 7, 229−235. (5) Markiewicz, M.; Zhang, Y. Q.; Bosmann, A.; Bruckner, N.; Thoming, J.; Wasserscheid, P.; Stolte, S. Environmental and health impact assessment of Liquid Organic Hydrogen Carrier (LOHC) systems - challenges and preliminary results. Energy Environ. Sci. 2015, 8, 1035−1045. (6) Aslam, R.; Müller, K.; Müller, M.; Koch, M.; Wasserscheid, P.; Arlt, W. Measurement of Hydrogen Solubility in Potential Liquid Organic Hydrogen Carriers. J. Chem. Eng. Data 2016, 61, 643−649. (7) Aslam, R.; Müller, K.; Arlt, W. Experimental Study of Solubility of Water in Liquid Organic Hydrogen Carriers. J. Chem. Eng. Data 2015, 60, 1997−2002. (8) Grunes, J.; Zhu, J.; Yang, M.; Somorjai, G. A. CO Poisoning of Ethylene Hydrogenation over Pt Catalysts: A Comparison of Pt(111) Single Crystal and Pt Nanoparticle Activities. Catal. Lett. 2003, 86, 157−161. (9) Buchele, A.; Modeling of the supported ionic liquid phase catalysis: Modellierung katalysierter Reaktionen in geträgerten Ionischen Flüssigkeiten. Ph.D. Thesis, Friedrich-Alexander-Universität Erlangen-Nürnberg, 2013. (10) DIPPR Database, Thermophysical Properties, https://dippr. aiche.org/SampleDb (accessed Mar 13, 2018). (11) Müller, K.; Stark, K.; Emel’yanenko, V. N.; Varfolomeev, M. A.; Zaitsau, D. H.; Shoifet, E.; Schick, C.; Verevkin, S. P.; Arlt, W. Liquid Organic Hydrogen Carriers: Thermophysical and Thermochemical Studies of Benzyl- and Dibenzyl-toluene Derivatives. Ind. Eng. Chem. Res. 2015, 54, 7967−7976. G


Solubility of Carbon Dioxide, Methane, and Nitrogen in Liquid

Recommend Documents