Interactions Between n-Butanol/Propionic Acid and Humic Acid Studied by NMR Spectroscopy

doi:10.11938/cjmr20212893

Abstract

Abstract:

The Fischer-Tropsch process produces liquid fuels. However, the process also yields Fischer-Tropsch wastewater, an acidic and corrosive byproduct enriched with various water-soluble oxygen-containing compounds such as alcohols, aldehydes, ketones and carboxylic acids, demanding careful treatment before discharge. Herein, the interactions between n-butanol and propionic acid, two main components in Fischer-Tropsch wastewater, and humic acid (HA) were studied with nuclear magnetic resonance (NMR) techniques. One-dimensional ¹H chemical shift titration and ¹H relaxation time measurements showed that: the peak width of both n-butanol and propionic acid broadened with increasing HA concentration, while the ¹H chemical shift was unaltered for n-butanol, but moved to high field for propionic acid. The ¹H spin-lattice and spin-spin relaxation time of n-butanol and propionic acid decreased and the ¹H correlation time increased with increasing HA concentration. The interactions between HA and n-butanol were enhanced by increasing the HA concentration, but less affected by solution pH. While, the interactions between HA (20 mg/mL) and propionic acid were promoted by increasing the HA concentration and decreasing the solution pH value. It also appeared that the HA concentration plays a decisive role in the interaction. The study demonstrated that using HA for treatment of Fischer-Tropsch wastewater has a great potential in industrial applications owing to its simplicity and low price.

Key words: liquid-state NMR, adsorption, Fischer-Tropsch wastewater, humic acid, n-butanol, propionic acid

CLC Number:

O482.53

Shu-huai ZHANG,Hui MA,Zhao-hui GUO,Min-jun MA,Yan QIAO,Ying-xiong WANG. Interactions Between n-Butanol/Propionic Acid and Humic Acid Studied by NMR Spectroscopy[J]. Chinese Journal of Magnetic Resonance, 2021, 38(3): 301-312.

Figures/Tables 9

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Table 1

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C_HA/(mg/mL)	T₁/s						T₂/s
C_HA/(mg/mL)	H-1	H-2	H-3	H-4	H-5	H-6	H-1	H-2	H-3	H-4	H-5	H-6
0	4.30	4.26	3.92	4.09	5.90	5.71	3.786	3.692	3.620	3.007	5.322	5.003
1	1.48	1.49	1.39	1.25	1.95	1.53	0.279	0.276	0.283	0.231	0.442	0.378
3	0.59	0.58	0.56	0.48	1.09	0.81	0.092	0.090	0.094	0.080	0.212	0.188
5	0.52	0.51	0.39	0.42	1.04	0.77	0.079	0.078	0.081	0.067	0.205	0.171
10	0.30	0.26	0.26	0.23	0.98	0.72	0.042	0.042	0.044	0.036	0.175	0.150
15	0.15	0.08	0.08	0.09	0.85	0.63	0.018	0.021	0.022	0.016	0.127	0.119
20	0.09	0.08	0.08	0.08	0.64	0.46	0.009	0.013	0.012	0.008	0.087	0.075
25	0.09	0.07	0.07	0.07	0.68	0.46	0.009	0.013	0.012	0.007	0.084	0.084
30	0.09	0.07	0.07	0.07	0.68	0.46	0.009	0.012	0.012	0.007	0.083	0.081

C_HA/(mg/mL)	τ_c/ns
C_HA/(mg/mL)	H-1	H-2	H-3	H-4	H-5	H-6
0	0.13	0.13	0.11	0.18	0.12	0.13
1	0.88	0.89	0.83	0.89	0.76	0.70
3	1.00	0.94	0.96	0.96	0.85	0.74
5	1.02	1.00	0.96	0.99	0.85	0.77
10	1.08	1.00	0.96	1.00	0.91	0.81
15	1.19	1.00	0.96	1.00	1.04	0.88
20	1.32	1.00	1.00	1.32	1.10	1.00
25	1.32	1.00	1.00	1.32	1.17	1.00
30	1.32	1.00	1.00	1.32	1.18	1.00

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