Energy Fuels 2011, 25, 159161 Published on Web 12/07/2010

: DOI:10.1021/ef1012006

Absorption and Oxidation of H2S in Caprolactam Tetrabutyl Ammonium Bromide Ionic Liquid
Bin Guo, Erhong Duan,*, Yongfei Zhong, Liang Gao, Xuesong Zhang, and Dishun Zhao

School of Environmental Science and Engineering, Hebei University of Science and Technology, Shijiazhuang Hebei 050018, Peoples Republic of China, and College of Chemical and Pharmaceutical Engineering, Hebei University of Science and Technology, Shijiazhuang Hebei 050018, Peoples Republic of China Received September 5, 2010. Revised Manuscript Received November 21, 2010

To explore environmentally benign solvents for absorbing and using H2S, a series of caprolactam tetrabutyl ammonium bromide ionic liquids were synthesized, the solubilities of H2S in which were measured at 303.2-363.2 K and atmospheric pressure. The solubility of H2S in the ionic liquid (1:1 mole ratio) was 5.40% at 303.2 K and ambient pressure, decreased sharply as temperature increased, and increased with the increasing mole ratio of caprolactam. The absorption and desorption of H2S were practically reversible in the ionic liquids, which was characterized by nuclear magnetic resonance. Using air, hydrogen sulfide could be oxidized to elemental S in the ionic liquids, which makes it easier to recycle hydrogen sulfide. Caprolactam tetrabutyl ammonium bromide ionic liquids would be useful for removing and reusing H2S in pollution control and could be regarded as the most potential absorbent and recoverer of H2S.

Introduction H2S is produced along with methane and other hydrocarbons in many gas fields as well as in hydrodesulfurization processes of crude oils containing sulfur compounds. Industrial natural gas treating plants use aqueous solutions mainly consisting of alkanolamines, especially monoethanolamine, diethanolamine, and methyldiethanolamine.1,2 There are some disadvantages associated with the commercial use of these alkanolamine solutions, including transfer of water into the gas stream during the desorption stage and degradation of alkanolamines to form corrosive byproducts, which make the process economically expensive.3 Ionic liquids (ILs) are low-melting salts with extremely low vapor pressures, high thermal and chemical stability, and tunable solvent power for many organic and inorganic compounds. So they can be used as environmentally benign solvents for a number of applications including gas solubility and separations, cellulose processing, catalysis, extraction,
*To whom correspondence should be addressed. E-mail: deh@tju.edu.cn. Fax: 86-311-88632361. (1) Kohl, A. L.; Nielsen, R. B. Gas Purification, 5th ed.; Gulf Publishing Company: TX, 1997. (2) Huang, C. C.; Chen, C. H.; Chu, S. M. Effect of moisture on H2S adsorption by copper impregnated activated carbon. J. Hazard. Mater. B 2006, 136, 866873. (3) Galan Sanchez, L. M.; Meindersma, G. W.; de Haan, A. B. Solvent properties of functionalized ionic liquids for CO2 absorption. Chem. Eng. Res. Des. 2007, 85, 3139. (4) Liu, F. S.; Li, Z.; Yu, S. T.; Cui, X.; Ge, X. P. Environmentally benign methanolysis of polycarbonate to recover bisphenol A and dimethyl carbonate in ionic liquids. J. Hazard. Mater. 2010, 174, 872875. (5) Anderson, J. L.; Dixon, J. K.; Brennecke, J. F. Solubility of CO2, CH4, C2H6, C2H4, O2, and N2 in 1-hexyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide: comparison to other ionic liquids. Acc. Chem. Res. 2007, 40, 12081216. (6) Cole, A. C.; Jensen, J. L. I.; Ntai, K. L.; Tran, T.; Weaver, K. J.; Forbes, D. C.; Davis, J. H., Jr. Novel brnsted acidic ionic liquids and their use as dual solvent-catalysts. J. Am. Chem. Soc. 2002, 124, 5962 5963.
r 2010 American Chemical Society

and high-temperature pyrochemical processing, etc.4,5 For example, acidic ILs have been proven to be efficient catalysts for many acid-catalyzed organic reactions.6 Basic ILs with amino groups were synthesized and used to capture CO2 and H2S7,8 and to promote hydrogenation of CO2.9 ILs can potentially be used as liquid absorbents for permanent gases and as solvents for gas separations. Nowadays, one of the areas of active research is to explore the possibility of replacing taskspecific ionic liquids for conventional alkanolamine solutions in removal of acid gases (CO2 and H2S) in gas sweetening processes.10 One of the properties which is important in the evaluation of ionic liquids as potential substitutes for alkanolamines in industrial natural gas treating processes is the knowledge of gas solubility in ionic liquids at various temperature and pressure conditions. In the past few years, a growing number of measurements reporting CO2 solubility in various ILs have become available.11 However, experimental data for the solubility of hydrogen sulfide in ionic liquids are scarce. Jou has reported the solubility of H2S in [Bmim][PF6] at temperatures from 298.15 to 403.15 K and pressures up to 9.6 MPa.12 At 9 MPa, the mole fraction of H2S in the liquid is about 0.7. At 2 MPa, the solubility (mole fraction of H2S) decreases from
(7) Bates, E. D.; Mayton, R. D.; Ntai, I.; Davis, J. H., Jr. CO2 capture by a task-specific ionic liquid. J. Am. Chem. Soc. 2002, 124, 926927. (8) Li, W. J.; Zhang, Z. F.; Han, B. X.; Hu, S. Q.; Song, J. L.; Xie, Y.; Zhou, X. S. Switching the basicity of ionic liquids by CO2. Green Chem. 2008, 10, 11421145. (9) Zhang, Z. F.; Xie, Y.; Li, W. J.; Hu, S. Q.; Song, J. L.; Jiang, T.; Han, B. X. Hydrogenation of carbon dioxide is promoted by a taskspecific ionic liquid. Angew. Chem., Int. Ed. 2008, 47, 11271129. (10) Crowhurst, L.; Lancaster, N. L.; Arlandis, J. M. P.; Welton, T. Manipulating solute nucleophilicity with room temperature ionic liquids J. Am. Chem. Soc. 2004, 126, 1154911555. (11) Shariati, A.; Peters, C. J. High-pressure phase equilibria of systems with ionic liquids. J. Supercrit. Fluids 2005, 34, 171176. (12) Jou, F. Y.; Mather, A. E. Solubility of hydrogen hulfide in [bmim][PF6]. Int. J. Thermophys. 2007, 28, 490495.

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about 0.84 at 298 K to about 0.2 at 403 K. The solubility of H2S in 1-butyl-3-methylimidazolium-based ILs containing different anions and in a series of bis(trifluoromethyl) sulfonylimide ILs with different cations at 298.15 K and 1.4 MPa is reported by Pomelli.13 Jalili has reported the solubility of H2S in [Bmim][PF6], [Bmim][BF4], and [Bmim][Tf2N] at temperatures ranging from 303.15 to 343.15 K and pressure increases to 1 MPa.14 The solubility of H2S in the studied ILs is in the order [Bmim][Tf2N] > [Bmim][BF4] > [Bmim][PF6].15 A better understanding of the solubility of H2S in ILs is necessary. ILs based on different mole ratios of caprolactam (CPL) and tetrabutyl ammonium bromide (TBAB) were prepared, and the solubilities of H2S in them were determined. The effects of different mole ratios of CPL and TBAB on their capacity for absorption of H2S were systematically investigated, and the recovery of H2S and recycle of the ILs were also conducted by increasing temperature and decreasing pressure. Bubbling air into the ionic liquids absorbed H2S, and H2S was oxidized to elemental S. Experimental Methods
Materials. White crystalline caprolactam powder (CAS No. 105-60-2, C6H11NO) was obtained from Shijiazhuang Refinery, China, the purity of which was >99%. Tetrabutyl ammonium bromide (CAS No. 1643-19-2, C16H36NBr) was bought from Jintan Huadong Chemical Research Institute, China, the purity of which was >99.5%.16 Water was deionized before use. The water contamination of ILs was determined using the Karl Fischer technique. Absorption Measurements. The ILs used here were dried under vacuum for at least 24 h under vacuum at 323.15 K prior to use, and the water content determined by Karl Fischer titration was less than 100 ppm. H2S with a purity of 99.9% was supplied by Beijing Analytical Instrument Factory. The apparatus of absorption of H2S in these ILs was prepared following procedures reported elsewhere.17 H2S gas was bubbled with a flow rate of 10 mL/min through predetermined amounts of the ILs (about 5 g) loaded in a glass vessel, respectively. After 2 h, the weight of the vessel and H2S was not changed, and the equilibrium was considered to be reached. The off H2S was treated by sodium hydroxide. These valves were closed, and the glass vessel was weighed using a balance with an uncertainty of (0.0001 g to get the mass of H2S absorbed, through which the solubility of H2S in the ILs could be calculated. Recycle of CPL-TBAB ILs. The absorption and desorption cycles were conducted to study the recovery of H2S and recycle of these synthesized ILs. Experiments showed that the solubility of H2S in these synthesized ILs is almost zero at the atmospheric pressure when the temperature rises to 373.2 K at 10.1 kPa vacuum. Consecutive absorption (308.2 K, 101.3 kPa) and desorption (383.2 K, 10.1 kPa vacuum) of H2S gas in recycled ILs were studied against times. Standard deviations of the ratios are (0.03.
(13) Pomelli, C. S.; Chiappe, C.; Vidis, A.; Laurenczy, G.; Dyson, P. J. Influence of the interaction between hydrogen sulfide and ionic liquids on solubility: experimental and theoretical investigation. J. Phys. Chem. B 2007, 111, 1301413019. (14) Jalili, A. H.; Rahmati-Rostami, M.; Ghotbi, C.; Hosseini-Jenab, M.; Ahmadi, A. N. Solubility of H2S in ionic liquids [bmim][PF6], [bmim][BF4], and [bmim][Tf2N]. J. Chem. Eng. Data 2009, 54, 18441849. (15) Rahmati-Rahmati, M.; Ghotbi, C.; Hosseini-Jenab, M.; Ahmadi, A. N.; Jalili, A. H. Solubility of H2S in ionic liquids [hmim][PF6], [hmim][BF4], and [hmim][Tf2N]. J. Chem. Thermodyn. 2009, 41, 1052 1055. (16) Guo, B.; Duan, E. H.; Ren, A. L.; Wang, Y.; Liu, H. Y. Solubility of SO2 in caprolactam tetrabutyl ammonium bromide ionic liquids J. Chem. Eng. Data 2010, 55, 13981401. (17) Yuan, X. L.; Zhang, S. J.; Lu, X. M. Hydroxyl ammonium ionic liquids: synthesis, properties, and solubility of SO2. J. Chem. Eng. Data 2007, 52, 596599.

Figure 1. Weight percent of H2S as a function of temperature in different mole ratios of CPL and TBAB: 9, 1:1; b, 2:1; 2, 3:1; 1, 4:1; [, 5:1; O, 6:1; 0, 7:1.

Figure 2. Color changes of H2S in caprolactam tetrabutyl ammonium bromides ionic liquids. (a) Caprolactam tetrabutyl ammonium bromides ionic liquids, (b) after bubbling H2S for 20 min, and (c) after bubbling air for 20 min at 303.2 K.

Characterization of CPL-TBAB ILs. 1H NMR spectra were measured on a Bruker AM 400 MHz spectrometer, using DMSO as a solvent with TMS as the internal standard. Seven different mole ratios of caprolactam and tetrabutyl ammonium bromide ILs were synthesized and characterized. 1H NMR spectra of caprolactam and tetrabutyl ammonium bromide (2:1) are presented. 1 H NMR (400 MHz, DMSO, ): 7.4 ppm (s, 1H, H-N); 3.33-3.17 ppm (t, 8H, N(CH2)4); 3.06-3.03 ppm (t, 2H, HNCH2); 2.29-2.27 ppm (t, 2H, OCCH2); 1.67-1.65 ppm (t, 2H, OCCH2-CH2); 1.59-1.56 ppm (m, 8H, N(CH2CH2)4); 1.54-1.48 ppm (t, 4H, OCCH2CH2CH2CH2); 1.34-1.29 ppm (m, 8H, N(CH2CH2CH2)4); 0.94-0.92 ppm (t, 12H, N(CH2 CH2 CH2CH3)4).

Results and Discussion Effect of Temperature on the Solubility of H2S in CPLTBAB ILs. The absorption concentration of H2S in different mole ratios from 1:1 to 7:1 CPL-TBAB ILs versus temperature from 303.15 to 363.15 K was determined at 101.3 kPa (Figure 1). The solubility of H2S in these ILs decreases when the temperature increases. With the concentration of CPL in ILs increasing, the solubility of H2S decreases slowly. As an overall result of the different mole ratios of CPL and TBAB, CPL-TBAB ILs (1:1, mole ratio) show the highest capacity for absorption of H2S, the weight percent of H2S in which is 5.40% at 303.15 K and 3.45% at 363.15 K. Oxidation of H2S in CPL-TBAB ILs. Clearly, the CPLTBAB IL is colorless and high viscosity (Figure 2 a). The color of the IL-absorbed H2S changed to bluish-green (Figure 2 b).
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Figure 3. XRD spectra of the yellow powder (top) and S standard (bottom).

Figure 5. 1H NMR spectra ((CD3)2SO, 500 Hz) of CPL-TBAB ILs (top) and CPL-TBAB ILs with H2S gas (bottom).

(10 mL 3 min-1) and complete gas desorption in 50 min at 303.2 K and 10.1 kPa. In Figure 4, six consecutive absorption cycles with the ILs were shown. Using ILs multiple times had little influence on the solubility of H2S. Moreover, the ILs could be reused six times without any loss of absorption capability. Therefore, the ionic liquids have excellent reusable performance in H2S. Because ionic liquid CPL-TBAB itself is of a good thermal stability, it is reasonable that CPL-TBAB has good reusable performance in absorption and desorption of H2S gas. Characterization of CPL-TBAB ILs. The chemical shift of the CPL-TBAB IL and CPL-TBAB IL saturated with H2S gas in the 1H NMR spectra (Figure 5) shows that the hydrogen bond influence is small and insufficient to demonstrate in the 1H NMR. From these results, it is evident that the H2S gas must be physically absorbed in the IL, providing no chemical bond between the IL and H2S.
Figure 4. H2S desorption by heating shown as weight percent of H2S to different mole ratios of CPL and TBAB: 9, 1:1; b, 3:1; 2, 5:1.

Conclusions In summary, the CPL-TBAB (1:1, mole ratio) IL could physically absorb large amounts of H2S gas, 5.40% (weight percent) at 303.15 K and 3.45% (weight percent) at 363.15 K. After H2S was absorbed, the color of the IL was changed. When H2S was oxidized, the color of the IL was yellowish green. H2S was oxidized into S by O2. The H2S absorbed in IL remained in the molecular state without any chemical reaction, allowing the IL to be reused six times without loss of capability. It is believed that the CPL-TBAB IL may be useful for H2S removal regarding pollution control. This approach will be studied in future work.
Acknowledgment. This research is supported by the National High Technology Research and Development Program of China (863 Program, the Project No. 2007AA061702).

After bubbled air in the IL absorbed H2S, the color of the IL (Figure 2 b) changed to yellowish-green (Figure 2 c). Then, the IL was filtered and vacuum-dried. We get an amount of yellow powder. The XRD patterns of the yellow powder and S were shown in Figure 3. The conventional XRD pattern from the yellow powder sample is consistent with S. Powder was observed with significant S (23) peak reflection. According to the expanded (23) XRD reflections, powder was S major. This proved that H2S was oxidized into S by O2 in the CPLTBAB ILs. Reusability of CPL-TBAB ILs. Both absorption and desorption of H2S gas in the three examined ILs (the mole ratio of CPL and TBAB = 1:1, 3:1, and 5:1) were relatively fast, providing complete absorption in 1 h with pure H2S gas

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