Chemistry Journals

Adsorption isotherm of dibenzyltoluene and its partially hydrogenated forms over
phenylhexyl silica
--Manuscript Draft--

Manuscript Number: Chemistry Journals-17-221

Full Title: Adsorption isotherm of dibenzyltoluene and its partially hydrogenated forms over
phenylhexyl silica

Short Title:

Article Type: Research Article

Section/Category: Modern Chemistry & Applications

Keywords: adsorption isotherms; LOHC; RP-HPL

Corresponding Author: Rabya Aslam, Ph.D
University of the Punjab, Lahore
Lahore, PAKISTAN

Corresponding Author Secondary
Information:

Corresponding Author's Institution: University of the Punjab, Lahore

Corresponding Author's Secondary
Institution:

First Author: Rabya Aslam, Ph.D

First Author Secondary Information:

Order of Authors: Rabya Aslam, Ph.D

Karsten Müller, PhD

Order of Authors Secondary Information:

Manuscript Region of Origin: GERMANY

Abstract: Liquid organic hydrogen carriers (LOHC) are an interesting option for chemical energy
storage and hydrogen transportation. Dibenzyltoluene (H0-DBT), heat transfer oil, is
capable of reversibly storing hydrogen emerged as a feasible LOHC system. However,
it is not available as a pure compound but consists of an isomeric mixture of 6 to 8
compounds. During the hydrogen storage process a high number of stable
intermediate species is formed. These compounds can be categorized into four main
classes according to their degree of hydrogenation. To implement H0-DBT as a LOHC
system, thermophysical data of these intermediate compounds are required. In our
previous work, a reversed phase HPLC method was developed using phenylhexyl
silica stationary phase and acetone/water as eluent to separate these partially
hydrogenated fractions with a purity > 98%. For further designing a batch or continuous
HPLC process, adsorption isotherm data are required. In this work, adsorption
isotherms for dibenzyltoluene and its partial and fully hydrogenated forms namely
hexahydro-dibenzyltoluene, dodecahydro-dibenzyltoluene, and octadecahydro-
dibenzyltoluene are measured over phenylhexyl silica in acetone/water solvent using
the static method. Sip's equation (Combined Langmuir-Freundlich isotherm) fits the
data better as compared to simple Freundlich, Langmuir or competitive Langmuir
adsorption isotherms.

Suggested Reviewers: Sofia Chaudry, PhD
Murdoch University
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Experienced in the field

Chung Sung-Tan
National Tsing Hua University
cstan@che.nthy.edu.tw

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Technische Universitat Munchen
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Manuscript Click here to download Manuscript manuscript-OMIC.docx

Adsorption isotherm of dibenzyltoluene and its

partially hydrogenated forms over phenylhexyl silica

Rabya Aslam1,2, Karsten Müller,*1

1
Institute of Separation Science and Technology, Friedrich-Alexander-Universität Erlangen-Nürnberg.
2
Institute of Chemical Engineering & Technology, University of the Punjab, Lahore, Pakistan.
* (Tel.: +92 42 9230462; Fax. +92 42 9231159; e-mail: rabya.icet@pu.edu.pk )

LOHC. To implement H0- DBT as a LOHC system. adsorption isotherm data are required. it is not available as a pure compound but consists of an isomeric mixture of 6 to 8 compounds. However. In this work. adsorption isotherms for dibenzyltoluene and its partial and fully hydrogenated forms namely hexahydro-dibenzyltoluene. a reversed phase HPLC method was developed using phenylhexyl silica stationary phase and acetone/water as eluent to separate these partially hydrogenated fractions with a purity > 98%. During the hydrogen storage process a high number of stable intermediate species is formed. Dibenzyltoluene (H0-DBT). dodecahydro-dibenzyltoluene. heat transfer oil. For further designing a batch or continuous HPLC process. Key words: adsorption isotherms. thermophysical data of these intermediate compounds are required.Abstract Liquid organic hydrogen carriers (LOHC) are an interesting option for chemical energy storage and hydrogen transportation. In our previous work. Sip’s equation (Combined Langmuir-Freundlich isotherm) fits the data better as compared to simple Freundlich. These compounds can be categorized into four main classes according to their degree of hydrogenation. and octadecahydro-dibenzyltoluene are measured over phenylhexyl silica in acetone/water solvent using the static method. RP-HPLC . is capable of reversibly storing hydrogen emerged as a feasible LOHC system. Langmuir or competitive Langmuir adsorption isotherms.

a reversed phase high pressure liquid chromatography method was developed and successfully scaled up to semi preparative scale for the separation of these partially hydrogenated derivatives of dibenzyltoluene with phenylhexyl silica as stationary phase and a acetone water mixture as mobile phase (96/4. Recent studies shows the potential of dibenzyltoluene (H0-DBT) as a competitive LOHC system due to its reasonable hydrogen storage capacity and thermal stability [5. and octadecahydro-dibenzyltoluene (H18-DBT). Adsorption isotherms can experimentally be determined using static (shake-flask and adsorption-desorption methods) or dynamic methods (frontal analysis method. hexahydro-dibenzyltoluene (H6-DBT). respectively. to implement it as LOHC system. In order to simulate and design a linear or non-linear chromatographic processes. More than 24 compounds are observed in a partially hydrogenated reaction mixture which can be classified into four main fractions on the basis of their degree of hydrogenation namely dibenzyltoluene (H0-DBT). its thermophysical data are required. Due to the chemical bonding of the hydrogen in the hydrogenated LOHC compound. However.1 Introduction Liquid organic hydrogen carriers (LOHC) are a promising approach for hydrogen storage and transportation. adsorption isotherm data over mobile and stationary phase are required which describe the distribution behavior of the DBT fractions in the chromatographic system[8-10]. elution curve methods and minor perturbation . 6]. Since it is not available as pure compound and partial hydrogenation further produces a number of stable intermediate species. v/v %)[7]. This concept is based on the reversible cycle of hydrogenation and dehydrogenation for uptake and release of hydrogen[1-5]. In our previous work. dodecahydro-dibenzyltoluene (H12-DBT). The LOHC system consists of a pair of dehydrogenated and hydrogenated compounds representing the hydrogen lean and rich forms. Each H0-DBT molecule can store 9 molecules of hydrogen in the form of octadecahydro-dibenzyltoluene (H18-DBT). the latter can store H2 at ambient conditions over longer periods.

v/v%) within a concentration range of 0-25 mg/ml at 22 ± 1 °C. hexahydro-dibenzyltoluene. for a mixture. 12].2. The details of the chemicals used are given in Table 2. The HPLC grade acetone was purchased from VWR Germany and 18 MΩ water produced by a Milli Q integral-3 system (Merck Millipore) was used in the experimental work.1. Moreover.2 Methods 2. The specifications of the adsorbent provided by the supplier are summarized in Table 1. Germany. ------------------------Table 1------------------------- ---------------------Table 2----------------------------- 2. 100 °A) was purchased from Phenomenex. competitive isotherms can be predicted using single solute adsorption isotherm but it often comes with limited applicability range and accuracy[8]. 2 Materials and methods 2.1 Materials The stationary phase phenylhexyl silica (Luna 15 μm. hexahydro-dibenzyltoluene.1 Separation of dibenzyltoluene derivatives . dodecahydro-dibenzyltoluene and octadecahydro-dibenzyltoluene were separated and purified via vacuum distillation and reversed phase high pressure liquid chromatography with > 99 % purity. In this work. 11. The single isomers of dibenzyltoluene. and octadecahydro- dibenzyltoluene are determined using static method over phenylhexyl silica from a acetone/water solution (96/4.2.methods)[8. adsorption isotherm data of single isomers of dibenzyltoluene derivatives such as dibenzyltoluene. dodecahydro-dibenzyltoluene. The details of the separation process are described in section 2.

Then in the second step.)) using reversed phase liquid chromatography. The same procedure was repeated for the determination of the isotherms of . 2. Solutions in acetone/water (96/4 %.2. The uncertainty of the initial concentration was ± 0. Firstly. i. The GC analysis and NMR analysis of each isomer used in this work is given in the supporting information. Germany) equipped with Sulzer structured packing (L = 2m.01 mg/ml.003 g) of phenylhexyl silica was added to each bottle and the tightly closed bottles were kept for 24 hours under stirring. pure compounds were not obtained via distillation but fractions consisting of compounds with similar boiling points were obtained.D. Preliminary experimental studies indicate that the adsorption equilibrium was reached after 18 hours for all components.1-25 mg/ml . hexahydro-dibenzyltoluene (H6-DBT). Due to the overlapping range of boiling points. The upper threshold of concentration was determined on the basis of the least soluble compound. using those fractions as feed. and octadecahydro-dibenzyltoluene (H18-DBT) were prepared in 10 ml bottles for the concentration range of 0. DXP. v/v) containing equal concentration of dibenzyltoluene (H0-DBT).Single isomers of dibenzyltoluene derivatives representing each fraction of dibenzyltoluene were separated in two steps. The batch plot for vacuum distillation experiment and boiling point range of DBT-fractions is provided in the supporting information..5 ±0. The distillation was performed in packed distillation column (Normag GmbH. SS 1. dodecahydro-dibenzyltoluene (H12-DBT).1 Measurement of adsorption isotherm The adsorption isotherms were measured using a static method (shake-flask method)[13]. single isomers representing each fraction of dibenzyltoluene were separated on semi-preparative scale column (250 mm (L) x 50 mm (I. The detailed procedure can be found somewhere else[7]. vacuum distillation was used to separate a partially hydrogenated reaction mixture.e. Then a fixed amount (0.4404). H18-DBT in acetone/water solvent.

-----------------Table 3----------------- ------------------Table 4------------------- . hexahydro- dibenzyltoluene. v/v %) at 22 ± 1 °C are presented in Table 3 and 4. Each measurement was repeated three times and the standard deviation was found to be less than 5 %. respectively. (𝐶𝑖 − 𝐶𝑒 ) ∙ 𝑣 𝑞𝑒 = (1) 𝑚 where Ci and Ce are initial and equilibrium concentrations of solutes.e. dodecahydro-dibenzyltoluene. 3 Results The experimental data for the adsorption isotherm for fraction of dibenzyltoluene and octadecahydro-dibenzyltoluene and single components of dibenzyltoluene. and octadecahydro-dibenzyltoluene over phenylhexyl silica in acetone/water solvent (96/4. It was observed that adsorption to stationary phase increased with degree of hydrogenation of compounds i. It should be noted that fraction represents the isomeric mixture of components with same degree of hydrogenation.dibenzyltoluene and octadecahydro-dibenzyltoluene fractions. The amount of solutes adsorbed on phenylhexyl silica were determined with initial and equilibrium concentrations using eq. m is the mass of the phenylhexyl silica phase in gram and v is the volume of solution. phenylhexyl silica has three times more adsorption capacity for fully hydrogenated octadecahydro-dibenzyltoluene in comparison to fully dehydrogenated dibenzyltoluene at the same concentration. The initial and final concentrations were measured using Gas Chromatography (Agilent technology 7890 A system). (1).

Moreover. The Freundlich correlation did not fit the experimental data satisfactorily (with 13 data . Langmuir and combined Langmuir-Freundlich (also known as Sip’s equation) were evaluated for the correlation of the experimental data. 15]. the results show that within the studied concentration range (0 to 25 mg/ml). and Sip’s equation are presented in Table 4. 𝑏 ∙ 𝑐𝑖 𝑞𝑒 = qsat ∙ (3) 1 + 𝑏 ∙ 𝑐𝑖 Where qsat is the saturation capacity of monolayer and b is second Langmuir parameter which quantifies the adsorption energy Hads using eq (4)[14]. ------------------------------------Figure 1----------------------- 3. 𝐻𝑎𝑑𝑠 𝑏= (4) qsat The parameters for the Freundlich equation. The Freundlich isotherm with two parameters is given by eq (2). Langmuir equation. the adsorption isotherm for H0-DBT and H18-DBT were not influenced by other species as single component data were comparable with the competitive adsorption isotherms within deviation of only 1 % as shown in Figure 1.[14. Several equations for correlating single component adsorption data such as Freundlich. 15] 𝑞𝑒 = 𝑘 ∙ 𝑐𝑖 𝑛 (2) Where qe is the amount of solute adsorbed on the stationary phase. k and n are Freundlich parameters. The Langmuir adsorption isotherm with two parameters is described by eq (3) [14. it was assumed that components do not influence each other during adsorption within concentration range studied.1 Correlation of experimental data Due to the negligible difference between the single and competitive adsorption isotherms (Figure 1).

For the Langmuir model.. The average relative error for the Freundlich model was 11. (𝑏. the fitting results were better in comparison to the Freundlich correlations. However. 15].4 % observed at low concentrations.2 % with a maximum error of 13 %.points for each compound). The relative error was high at low concentrations while the fit was observed to be better at high concentrations.5 % with a maximum value of 0. the bi-Langmuir adsorption isotherm (eq (6)) was used to correlate the experimental data by assuming the maximum loadability equal for all components in the system [14. ------------------Figure 2------------- The Sip’s equation with three parameters (eq (5)) correlates the experimental data within the working concentration range better compared to the other correlations. -----------------------Figure 3: -------------------- Additionally. A comparison of the Langmuir and Freundlich isotherms with experimental data is presented in Figure 2. higher values of adj. . The comparison of the Sip’s equation data with the experimental data is presented in Figure 3. the calculated average relative deviation was only 0. 𝐶𝑖 )𝑛 𝑞𝑒 = 𝑞𝑠𝑎𝑡 (5) 1 + (𝑏. 𝐶𝑖 )𝑛 Although the number of parameters (three instead of two) increases. R2 (adjusted determination coefficient) and Q2 (cross validated determination coefficient) show the better fit quality (compare Table 5). especially at low concentrations. The average relative error for the Langmuir isotherm was 6.6 % with a maximum deviation of 18.6 %. Additionally. the Langmuir model fits the H0-DBT and H6-DBT data satisfactorily but gives poor fitting for H12-DBT and H18-DBT data.

hexahydro- dibenzyltoluene. v/v) liquid phase and a phenylhexyl silica (stationary phase) at 22 ± 1°C within the concentration range from 0 to 25 mg/ml. Thus. adsorption isotherms data for single components of dibenzyltoluene and octadecahydro- dibenzyltoluene were comparable with their competitive adsorption isotherms. Moreover. 8 parameters would be needed to fit eq (6) to 13 experimental data points. If maximum loadability is considered to be different for all compounds. Good agreement with experimental data was found for Sip’s equation as compared to the other models. Thus. The distribution of these components has been investigated between a acetone/water (96/4. within the studied concentration range. Sip’s equation was found to be the best suited correlation for the adsorption isotherms of all partially hydrogenated derivatives of dibenzyltoluene. Such a high number of parameters do not seem to be reasonable. the model based on this assumption did not fit the data well because the loadability for various hydrogenated fractions is fairly different for the different compounds.𝑒 = 𝑞𝑖. dodecahydro-dibenzyltoluene and octadecahydro-dibenzyltoluene are presented. 𝑏𝑗 ∙ 𝑐𝑖 𝑞𝑖. Langmuir and Freundlich isotherms with 2 parameters and Sip’s equation (combined Langmuir-Freundlich equation) with 3 parameters and multicomponent isotherm based on the Langmuir model (with 8 parameters) were used to correlate the experimental data.𝑠𝑡𝑎 ∙ 6 1 + ∑𝑛𝑗=1 𝑏𝑗 ∙ 𝑐𝑗 As expected. influence of the individual components on each other were found to be negligible within the studied concentration range. 4 Conclusions In this work. . adsorption isotherm data for single isomers of dibenzyltoluene.

List of Tables Table 1: Specifications of phenylhexyl Silica provided by manufacturer Table 2: Purity information of chemicals used Table 3: Experimental competitive adsorption isotherm data for dibenzyltoluene derivatives from acetone/water (96/4.Acknowledgments This work has been done within the framework of the Bavarian Hydrogen Center and has been funded by the state of Bavaria. and Michael Müller for the provision of partially hydrogenated dibenzyltoluene mixture and Prof. Wolfgang Arlt as well as Prof. Malte Kaspereit for valuable discussion. Dr. v/v) solution over phenylhexyl silica Table 5: Model parameters for adsorption isotherms with statistical parameters List of Figures Figure 1: Comparison of single component isotherm with competitive isotherm for H0-DBT and H18-DBT Figure 2: Comparison of experimental and modelled data using Langmuir and Freundlich isotherms. Peter Wasserscheid. v/v) solution over phenylhexyl silica Table 4: Single component adsorption isotherm data for dibenzyltoluene and octadecahydro- dibenzyltoluene from acetone/water (96/4. Andreas Bösmann. Figure 3: Comparison of experimental and modelled data using Sip’s equation. . The authors wish to thank Prof.

Ruthven. 2012. Multicomponent adsorption of whey proteins by ion exchanger. 7(1): p.. et al. Production. 2005: Wiley. 275-281. P. Markiewicz. K.. 2012. AIChE Journal. et al. Arlt. Environmental and health impact assessment of Liquid Organic Hydrogen Carrier (LOHC) systems . O. 3. 8(3): p. Prausnitz.. Amine Borane Based Hydrogen Carriers: An Evaluation. 18118-18132. 501-511. Innovative Food Processing Technologies: Advances in Multiphysics Simulation. 908(1–2): p. 1035-1045. Journal of Chromatography A. W.. 33(24): p. and Utilization. 2001.challenges and preliminary results. 2013. 2014. Wasserscheid. 8. Seidel-Morgenstern. International Journal of Hydrogen Energy. The Catalytic Dehydrogenation of Methylcyclohexane over Monometallic Catalysts for On-board Hydrogen Storage. Arlt. . Part A: Recovery.. 121-127. et al. 2. and A. Müller. Status and Development in Hydrogen Transport and Storage for Energy Applications... 2015. and J. Usman. 9. Utilization. 13. Energy & Fuels. Myers. D. and Environmental Effects. K. 1(9): p. H. Preparative Chromatography: Of Fine Chemicals and Pharmaceutical Agents. A. Energy Technology. 11. Aslam. 1965. R. C. 3691-3696. Liquid Organic Hydrogen Carriers as an efficient vector for the transport and storage of renewable energy. 2011: Wiley. and W.M. M.. 11(1): p.. Bonomo.M.L. 4. 2016. Knoerzer. 5.R. 7. Müller. 1990.. Energy & Environmental Science... K. Lisec. ChemSusChem. 229-235. and P. R.References: 1... A study of multicomponent adsorption equilibria by liquid chromatography.. Schmidt-Traub. N. AIChE Journal. et al. K. Evaluation of Industrially Applied Heat-Transfer Fluids as Liquid Organic Hydrogen Carrier Systems. Frontal analysis method to determine competitive adsorption isotherms. M. 36(2): p. Brückner. 2011. Chu. 37(23): p. Hugo. and D.H. Teichmann.B. 12. et al. Development of a liquid chromatographic method for the separation of a liquid organic hydrogen carrier mixture Separation and Purification Technology. 6.. Ching. 10. 26(6): p. Thermodynamics of mixed-gas adsorption. Energy Sources. 2231-2238. 19- 34.

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Sincerely yours. The manuscript has not been submitted simultaneously for publication elsewhere and has not been published before.icet@pu.pk .edu. Looking forward to hearing from you. Please find enclosed the manuscript “Adsorption isotherm of dibenzyltoluene and its partially hydrogenated forms over phenylhexyl silica” by the authors Rabya Aslam and Karsten Müller to be submitted for publication in OMICS Group .Chemistry Journals. Dr. D-91058 Tel +49 9131 85 27449 Fax +49 9131 85 27441 rabya. Rabya Aslam Researcher Chair of Separation Science & Technology Friedrich-Alexander University Erlangen-Nuremberg Egerlandstrasse 3 Erlangen.Cover Letter Dear Editor.

Figure 1 Click here to download Figure Figure 1.JPG .

Figure 2 Click here to download Figure Figure 2.JPG .

JPG .Figure 3 Click here to download Figure Fig 3.

docx Table 1: Specifications of phenylhexyl Silica provided by manufacturer Parameter Value Particle size 11-15 μm Particle size distribution 1.8 (dp 90/10) Pore diameter 100 °A Surface diameter 390 m2/g Bulk density 0.58 g/cm3 Total carbon 16 % Metal contents 11 ppm .Table 1 Click here to download Table Tables 1.

docx Table 2: Purity information of chemicals used Degree of Purity Analysis Chemicals hydrogenation (mass %) method (%) Dibenzyltoulene > 99 0 GC-MSa (H0-DBT)+ Hexahydro-dibenzyltoluene > 99 33 GC-MSa (H6-DBT)+ dodecahydro-dibenzyltoluene > 99 67 GC-MSa (H12-DBT)+ octadecahydro-dibenzyltoluene > 99 100 GC-MSa (H18-DBT)+ Acetone > 99 .Table 2 Click here to download Table table 2. - .

87 195.04 2749.61 620.84 450.3 1.24 2260.3 14.38 84.docx Table 3: Experimental competitive adsorption isotherm data for dibenzyltoluene derivatives from acetone/water (96/4.24 41.25 36.98 325.0 14.8 .24 47.8 6.6 0.9 0.1 1.2 0.6 2.7 0.5 0.8 2.88 1754.57 143.57 92.81 533.98 283.9 0.8 26.8 11.25 17.92 656.06 4814.2 4.5 7.98 169.8 0.4 9.9 1.9 0.92 1927.38 3564.93 206.52 1760.38 27.08 1856.2 1.89 553.2 14.56 39.0 2.2 0.7 10.4 23.1 5.40 2960.1 0.77 704.8 2.0 4.00 70.4 4.37 69.45 2470.42 4160.73 2721.52 1435.86 1264.7 0.86 1055.64 244.92 357.9 0.Table 3 Click here to download Table table 3.7 9.54 109.4 25.5 10.4 3.0 23.39 59.92 133.8 4.55 1190.9 4.98 6484. v/v) solution over phenylhexyl silica H0-DBT H6-DBT H12-DBT H18-DBT Ce qe Ce qe Ce qe Ce qe mg·ml-1 mg.55 3602.4 7.61 928.g-1 mg·ml-1 mg·g-1 mg·ml-1 mg·g-1 mg·ml-1 mg·g-1 0.58 793.4 8.7 0.5 0.3 14.27 1025.3 1.

v/v) solution over phenylhexyl silica H0-DBT H18-DBT Ce qe Ce qe mg·ml-1 mg.88 133.9 533.5 0.g-1 mg·ml-1 mg.10 2749.2 4.10 4814.6 244.0 1.95 656.58 143.80 1054.4 7.docx Table 4: Single component adsorption isotherm data for dibenzyltoluene and octadecahydro- dibenzyltoluene from acetone/water (96/4.0 3.88 1925.3 2.92 325.1 0.24 48.37 84.8 2.24 17.Table 4 Click here to download Table table 4.8 25.4 8.55 793.0 0.99 283.95 70.58 620.g-1 0.8 .98 1190.3 14.5 9.0 1.05 6487.2 4.0 0.5 0.2 24.7 10.7 0.7 0.85 195.54 39.56 3602.50 1760.3 14.3 4.36 27.

5 6.293 0.942 0.988 0.92 7.999 0.15 1.999 0.0023 0.920 0.996 0. R2 0.docx Table 5: Model parameters for adsorption isotherms with statistical parameters Parameters H18-DBT H12-DBT H6-DBT H0-DBT Langmuir equation qsat 14.023 0.37 0.207 9.999 0.991 b 0.042 6.2 1.55 0.01 Adj.068 b 0.996 Q2 0.961 0.8 Sip’s equation qsat 9.025 n 1.999 0.0001 .8 5.058 0.32 1.995 0.4 9.999 Q2 0.752 Adj.995 0.999 0.79 0. R2 0.999 ARD / % 13.024 Adj.89 1.999 ARD / % 0.0003 0.915 2.042 0.0078 0.01 Freundlich equation k 0.215 10.945 0.78 0.029 0.999 Q2 0.979 0.991 ARD / % 14.21 3.977 0.999 0.779 0.068 0.5 16. R2 0.Table 5 Click here to download Table table 5.999 0.883 3.998 0.034 0.099 n 0.

University of the Punjab. +49 9131 8527441.icet@pu. Karsten Müller. Lahore. e-mail: rabya. Pakistan.: +49 9131 8527455. Fax. * (Tel. 2 Institute of Chemical Engineering & Technology.Supplementary files SUPPORTING INFORMATION Adsorption isotherm of dibenzyltoluene and its partially hydrogenated forms over phenylhexyl silica Rabya Aslam1.pk ) . Friedrich-Alexander-Universität Erlangen-Nürnberg.*1 1 Institute of Separation Science and Technology.edu.2.

1: Batch plot for the DBT-reaction mixture Table S1: Boiling point range of DBT-Fractions at 1. Boiling point range of dibenzyltoluene fractions is given in Table S1. Figure Error! No text of specified style in document.0 ± 1 mbar Boiling Degree of DBT-Fraction Chemical Formula point hydrogenation/ % range/ °C dibenzyltoulene C21H20 0 208-227 (H0-DBT) Hexahydro-dibenzyltoluene C21H26 33 198-213 (H6-DBT) Dodecahydro-dibenzyltoluene C21H32 67 184 .193 (H18-DBT) . All the isomers of the same degree of hydrogenation were collected as one fraction and the overall purity of a fraction was determined using GC-MS. Fully hydrogenated and dehydrogenated fractions were separated with a high purity but intermediate fractions were separated with an overall purities of up to 50 % due to the overlapping boiling point range of various fractions.205 (H12-DBT) octadecahydro-dibenzyltoluene C21H38 100 180 .S1: Batch plot of vacuum distillation experiment The batch plot representing the main DBT-fractions as a function of time is presented in Figure S1..

an auto sampler (7683 D and a Restek Rxil7Sil column (30 m x 250 μm x 0.S2 Analysis of dibenzyltoluene derivatives GC-analysis dibenzyltoluene derivatives was performed using an Agilent technology 7890 A system.25 μm). For the analysis. The gas chromatograms for both H0-DBT and H18-DBT are shown in Figure S2 to S5. The retention times for dibenzyltoluene derivatives used in this work are given in Table S2. Figure S2: Gas chromatogram of dibenzyltoluene (isomeric mixture) . The system was equipped with a flame ionization detector. ≈ 10 mg/ml). and then 3 °C/min to 300 °C with the final holding time of 1 min. The injection temperature was 300 °C and the program for oven was as follows: 70 °C for 2 min. the injection sample was prepared in n-hexane (injection conc. then 40°C/min to 160 °C. respectively.

47 11.1 H6-DBT-2 31. Figure S2: Gas chromatogram of perhydro-dibenzyltoluene (isomeric mixture) Table S3: Composition of dibenzyltoluene Isomer Retention time/ min % age in the mixture H0-DBT-1 30.92 17.45 29.91 8. The purity information is provided in table S4.4 H12-DBT-3 32. Figure S3: GC analysis of H0-DBT-single isomer .7 H18-DBT-4 33.6 S3 GC Analysis of single isomers The GC analysis of purified isomers using semi-preparative HPLC are given in Figure S3-S6.

Figure S4: GC analysis of H6-DBT-single isomer .

6 (H12-DBT) octadecahydro-dibenzyltoluene C21H38 98.0 (H6-DBT) Dodecahydro-dibenzyltoluene C21H32 99. Figure S5: GC analysis of H12-DBT-single isomer Figure S6: GC analysis of H18-DBT-single isomer Table S4: purity information of single isomers of Dibenzyltoluene and its derivatives separated using HPLC DBT-Fraction Chemical Formula Purity/ mass-% dibenzyltoulene C21H20 99.9 (H0-DBT) Hexahydro-dibenzyltoluene C21H26 99.6 (H18-DBT) S4 NMR-Analysis .

The NMR of single isomers of dibenzyltoluene derivatives are shown in Figure S9 to S12.Nuclear magnetic Resonance (NMR) analysis was ECX 400 from JEOL. 1 mL of liquid sample was diluted in 1 mL of Dichloromethane-d2. Figure S7: 1H NMR spectrum for dibenzyltoluene Figure S8: 1H NMR spectrum for octadecahydro-dibenzyltoluene . 0. The NMR analysis of full fractions of dibenzyltoluene and octadecahydro-dibenzyltoluene is shown in Figure S7 and S8.

Figure S9: 1H NMR spectrum for dibenzyltoluene (H0-DBT) Figure S10: 1H NMR spectrum for dibenzyltoluene (H6-DBT) .

Figure S11: 1H NMR spectrum for dibenzyltoluene (H12-DBT) Figure S12: 1H NMR spectrum for dibenzyltoluene (H18-DBT) .

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