Citation: DING Qi-zhong, ZHANG Jun, ZHAO Liang, LU Qi-an. Conversion of carbon monoxide in supercritical water and the influence of alkaline potassium salts[J]. Journal of Fuel Chemistry and Technology, ;2019, 47(8): 980-986. shu

Conversion of carbon monoxide in supercritical water and the influence of alkaline potassium salts

1.
Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, Southeast University, Nanjing 210096, China;
2.
School of Materials Science and Engineering, Nanjing Forestry University, Nanjing 210037, China

Corresponding author: ZHANG Jun, junzhang@seu.edu.cn
Received Date: 22 April 2019
Revised Date: 17 June 2019

Fund Project: Open Fund of Key Laboratory of Efficient & Clean Energy Utilization of Hunan Provincial Education Department, China 2017NGQ005Open Fund of Innovation Platform of Hunan Provincial Education Department, China 17K002The project was supported by the National Natural Science Foundation of China(51606103), Open Fund of Key Laboratory of Efficient & Clean Energy Utilization of Hunan Provincial Education Department, China (2017NGQ005), Open Fund of Innovation Platform of Hunan Provincial Education Department, China (17K002)the National Natural Science Foundation of China 51606103

Figures(9)

The conversion of carbon monoxide in supercritical water was investigated in a continuous reaction system which could dissolve carbon monoxide in water at high pressure. Meanwhile, due to the diversity of potassium salts in biomass supercritical water gasification, the influence of various alkaline potassium salts (KHCO₃, K₂CO₃ and KOH) on the water gas shift reaction were investigated at 450-600 ℃, 23-29 MPa and with a residence time of 3-6 s. The results show that under non-catalytic conditions, the increases in reaction temperature and residence time both lead to higher CO conversion. The effect of pressure on CO conversion is distinct at low pressure (23-25 MPa), but rather minor at higher pressure (25-29 MPa). The rate expression for the non-catalytic water gas shift reaction is k=10^3.75×exp(-0.66×10⁵/RT)(s^-1). The potassium salts can promote the CO conversion significantly and the activity of three salts follows the order of KHCO₃ > K₂CO₃ > KOH; the conversion of CO is enhanced at higher temperature and longer reaction time, whereas the effect of pressure on CO conversion is much complicated. The catalytic effect of alkaline potassium salts in the CO conversion may be explained by the formation of oxalate (HC₂O₄^-) and formate (HCOO^-) intermediates.
- alkaline potassium salts,
- water gas shift,
- supercritical water,
- CO conversion
1. [1]
  RATNASAMY C, WAGNER J P. Water gas shift catalysis[J]. Catal Rev, 2009,51(3):325-440.
2. [2]
  MADENOĞLU T G, YILDIRIR E, SAĞLAM M, YÜKSEL M, BALLICE L. Improvement in hydrogen production from hard-shell nut residues by catalytic hydrothermal gasification[J]. J Supercrit Fluids, 2014,95:339-347. doi: 10.1016/j.supflu.2014.09.033
3. [3]
  MELIUS C F, BERGAN N E, SHEPHERD J E. Effect of water on combustion kinetics at high pressure[C]//Proceedings of the Twenty-Third Symposium (International) on Combustion. Pittsburgh: The Combustion Institute, 1990: 217-223.
4. [4]
  RICE S F, STEEPER R R, AIKEN J D. Water density effects on homogeneous water-gas shift reaction kinetics[J]. J Phys Chem A, 1998,102(16):2673-2678. doi: 10.1021/jp972368x
5. [5]
  SATO T, KUROSAWA S, SMITH JR R L, ADSCHIRI T, ARAI K. Water gas shift reaction kinetics under noncatalytic conditions in supercritical water[J]. J Supercrit Fluids, 2004,29(1/2):113-119.
6. [6]
  ARAKI K, FUJIWARA H, SUGIMOTO K, OSHIMA Y, KODA S. Kinetics of water-gas shift reaction in supercritical water[J]. J Chem Eng Jpn, 2004,37(3):443-448. doi: 10.1252/jcej.37.443
7. [7]
  ZHAO Liang. Study on effects of potassium existing in biomass on small molecule intermediates gasification conversion in supercritical water[D]. Nanjing: Southeast University, 2013.
8. [8]
  ELLIOTT D C, SEALOCK JR L J. Aqueous catalyst systems for the water gas shift reaction. 1. Comparative catalyst studies[J]. Ind Eng Chem Prod Res Dev, 1983,22(3):426-431. doi: 10.1021/i300011a008
9. [9]
  ELLIOTT D C, HALLEN R T, SEALOCK JR L J. Aqueous catalyst systems for the water gas shift reaction 2. Mechanism of basic catalysis[J]. Ind Eng Chem Prod Res Dev, 1983,22(3):431-435. doi: 10.1021/i300011a009
10. [10]
  ELLIOTT D C, SEALOCK JR L J, BUTNER R S. Aqueous catalyst systems for the water gas shift reaction 3. Continuous gas processing results[J]. Ind Eng Chem Prod Res Dev, 1986,25(4):541-549. doi: 10.1021/i300024a007
11. [11]
  SCHUCHARDT U, SOUSA M F B. Oxalate as an intermediate in the base catalyzed water-gas shift reaction[J]. Fuel, 1986,65(5):669-672. doi: 10.1016/0016-2361(86)90362-5
12. [12]
  AKGÜL G, KRUSE A. Influence of salts on the subcritical water-gas shift reaction[J]. J Supercrit Fluids, 2012,64:207-214.
13. [13]
  BARBIERB H, VINAUGER M, COLCOMBET J, EPHRITIKHINE G, FRACHISSE J M, MAUREL C. Anion channels in higher plants:functional characterization, molecular structure and physiological role[J]. Biochim Biophys Acta, 2000,1465(1/2):199-218.
14. [14]
  YASAKA Y, YOSHIDA K, WAKAI C, MATUBAYASI N, NAKAHARA M. Kinetic and equilibrium study on formic acid decomposition in relation to the water-gas-shift reaction[J]. J Phys Chem A, 2006,110(38):11082-11090. doi: 10.1021/jp0626768
15. [15]
  XU Yue. Chemical Reaction Kinetics[M]. 1st ed. Beijing:Chemical Industry Press, 2005.
16. [16]
  AKIYA N, SAVAGE P E. Roles of water for chemical reactions in high-temperature water[J]. Chem Rev, 2002,102:2725-2750. doi: 10.1021/cr000668w
17. [17]
  ONSAGER O T, BROWNRIGG M S A, LØDENG R. Hydrogen production from water and CO via alkali metal formate salts[J]. Int J Hydrogen Energy, 1996,21(10):883-885. doi: 10.1016/0360-3199(96)00031-6
18. [18]
  KRUSE A, DINJUS E. Influence of salts during hydrothermal biomass gasification:The role of the catalyzed water-gas shift reaction[J]. Z Phys Chem, 2005,219(3):341-366.
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沈阳化工大学材料科学与工程学院沈阳 110142