VALORIZATION OF BIOGAS THROUGH SIMULTANEOUS CO<sub>2</sub> AND H<sub>2</sub>S REMOVAL BY RENEWABLE AQUEOUS AMMONIA SOLUTION IN MEMBRANE CONTACTOR

doi:10.15302/J-FASE-2022473

Front. Agr. Sci. Eng.

2023, Vol. 10

Issue (3) : 468-478 https://doi.org/10.15302/J-FASE-2022473

RESEARCH ARTICLE

VALORIZATION OF BIOGAS THROUGH SIMULTANEOUS CO₂ AND H₂S REMOVAL BY RENEWABLE AQUEOUS AMMONIA SOLUTION IN MEMBRANE CONTACTOR

Tao SUN^1,^2,³, Wenlong LI^1,^2,³, Jiandong WEI^1,^2,³, Long JI^1,^2,³, Qingyao HE^1,^2,³(

), Shuiping YAN^1,^2,³(

)

¹. College of Engineering, Huazhong Agricultural University, Wuhan 430070, China
². Technology & Equipment Center for Carbon Neutrality in Agriculture, Huazhong Agricultural University, Wuhan 430070, China
³. Key Laboratory of Agricultural Equipment in Mid-lower Yangtze River, Ministry of Agriculture and Rural Affairs, Wuhan 430070, China

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Abstract

● Simultaneous H₂S and CO₂ removal from biogas is studied.

● Renewable absorbent from biogas slurry is used in membrane contactor.

● More than 98% of H₂S can be removed by membrane absorption.

● The impurities have less influence on H₂S removal efficiency.

Upgrading biogas into biomethane not only improves the biogas utilization as vehicle fuel or natural gas substitute, but also reduces the greenhouse gases emissions. Considering the principle of engineering green energy process, the renewable aqueous ammonia (RAA) solution obtained from biogas slurry was used to remove H₂S and CO₂ simultaneously in the hollow fiber membrane contactor. RAA was mimicked in this study using the ammonia aqueous solution mixed with some typical impurities including ethanol, acetic acid, propionic acid, butyric acid and NH₄HCO₃. Compared with the typical physical absorption (i.e., pure water) removing 48% of H₂S from biogas, RAA with 0.1 mol·L⁻¹ NH₃ could remove 97% of H₂S. Increasing the NH₃ concentration from 0.1 to 0.5 mol·L⁻¹ could elevate the CO₂ absorption flux from 0.97 to 1.72 mol·m⁻²·h⁻¹ by 77.3%. Among the impurities contained in RAA, ethanol has a less impact on CO₂ absorption, while other impurities like CO₂ and acetic acid have significant negative impacts on CO₂ absorption. Fortunately, the impurities have a less influence on H₂S removal efficiency, with more than 98% of H₂S could be removed by RAA. Also, the influences of operating parameters on acid gases removal were investigated to provide some engineering suggestions.

Keywords biomethane biogas purification CO₂ removal H₂S removal membrane absorption

Corresponding Author(s): Qingyao HE,Shuiping YAN

Just Accepted Date: 02 December 2022 Online First Date: 09 February 2023 Issue Date: 20 September 2023

Cite this article:

Tao SUN,Wenlong LI,Jiandong WEI, et al. VALORIZATION OF BIOGAS THROUGH SIMULTANEOUS CO₂ AND H₂S REMOVAL BY RENEWABLE AQUEOUS AMMONIA SOLUTION IN MEMBRANE CONTACTOR[J]. Front. Agr. Sci. Eng. , 2023, 10(3): 468-478.

URL:

https://academic.hep.com.cn/fase/EN/10.15302/J-FASE-2022473
https://academic.hep.com.cn/fase/EN/Y2023/V10/I3/468

Fig.1 Experimental setup for biogas upgrading using a hollow fiber membrane contactor.

Fig.2 CO₂ and H₂S absorption flux profile using pure water, 0.1 mol·L⁻¹ RAA solution and 0.1 mol·L⁻¹ KOH solution in hollow fiber membrane contactor. Experimental conditions: absorbent feed temperature and flow rate were 20 °C and 50 mL·min⁻¹, feed gas flow rate was 400 mL·min⁻¹.

Tab.1 Henry constants of CO₂ and H₂S in the different solutions

CO₂-NH₃· H₂O reaction	H₂S-NH₃· H₂O reaction
$N H 3 (aq) + H 2 O ? N H 4 + + O H −$	$N H 3 (aq) + H 2 O ? N H 4 + + O H −$
$C O 2 (g) ? C O 2 (aq)$	$H 2 S(g) ? H 2 S(aq)$
$C O 2 (aq) + H 2 O ? H 2 C O 3$	$H 2 S(aq) ? H S − + H +$
$H 2 C O 3 ? H + + HC O 3 −$	$H S − ? H + + S 2 −$
$C O 2 (aq) + O H − ? HC O 3 −$	$H 2 S(aq) + O H − ? H S − + H 2 O$
$HC O 3 − ? H + + C O 3 2 −$	$H S − + O H − ? S 2 − + H 2 O$
$N H 3 (aq) + HC O 3 − ? N H 2 CO O − + H 2 O$	$N H 3 (aq) + H S − ? N H 4 + + S 2 −$

Tab.2 Reactions of CO₂ and H₂S absorption with aqueous ammonia solution

Fig.3 CO₂ and H₂S absorption performance using RAA solution as the absorbent with TAN concentration varied from 0.1 to 0.5 mol·L⁻¹. (a) CO₂ absorption flux and CO₂ concentration in outlet. (b) Acid gas removal efficiency. Experimental conditions: absorbent feed temperature and flow rate were 20 °C and 50 mL·min⁻¹, feed gas flow rate was 400 mL·min⁻¹.

Fig.4 Effect of impurities in RAA solution on the CO₂ and H₂S absorption performance. Effect of impurity types and their concentration (0.01, 0.03 and 0.05 mol·L⁻¹) on CO₂ absorption flux (a), CO₂ removal efficiency (b), H₂S removal flux (c), and H₂S removal efficiency (d). Experimental conditions: 0.1 mol·L⁻¹ RAA, absorbent feed temperature and flow rate were 20 °C and 50 mL·min⁻¹, feed gas flow rate was 400 mL·min⁻¹.

Fig.5 Effect of CO₂ loading on CO₂ and H₂S absorption performance. (a) Effect of CO₂ loading on CO₂ and H₂S absorption flux. (b) Effect of CO₂ loading on acid gas removal efficiency. (c) Effect of CO₂ and H₂S loading on H₂S absorption flux using 0.1 mol·L⁻¹ RAA solution. Experimental conditions: absorbent feed temperature and flow rate were 20 °C and 50 mL·min⁻¹, feed gas flow rate was 400 mL·min⁻¹.

Fig.6 Effect of absorbent temperature (25, 45, 55 and 65 °C) on CO₂ (a) and H₂S (b) removal performance using 0.1 mol·L⁻¹ RAA solution cycling in the tube side of hollow fiber membrane contactor. Experimental conditions: absorbent feed flow rate was 50 mL·min⁻¹, feed gas flow rate was 400 mL·min⁻¹.

Fig.7 Effect of biogas feed flow rate on CO₂ (a) and H₂S (b) removal performance using RAA solution with TAN concentration of 0.2, 0.3 and 0.5 mol·L⁻¹. Experimental conditions: absorbent feed temperature and flow rate were 20 °C and 50 mL·min⁻¹, without cycling. Effect of absorbent feed flow rate on CO₂ (c) and H₂S (d) removal performance using RAA solution with TAN concentration of 0.1 mol·L⁻¹ without absorbent cycling. Experimental conditions: absorbent feed temperature was 20 °C, feed biogas flow rate was 400 mL·min⁻¹.

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