Reactions of HCl and D2O with Molten Alkali Carbonates

被引:8
作者
Krebs, Thomas [1 ]
Nathanson, Gilbert M. [1 ]
机构
[1] Univ Wisconsin, Madison, WI 53706 USA
基金
美国国家科学基金会;
关键词
SUPERCOOLED SULFURIC-ACID; HOT FLUE-GASES; HYDROGEN-CHLORIDE; REACTION-KINETICS; MOLECULAR-BEAM; EUTECTIC MIXTURE; SODIUM-CARBONATE; CALCIUM-OXIDE; MINERAL DUST; LIMESTONE;
D O I
10.1021/jp107182d
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The acidic oxide SO2 and protic acid HCl are among the gases released in the combustion of coal and the incineration of municipal waste. They are typically removed by wet or dry scrubbing involving calcium carbonate or calcium hydroxide. The molten alkali carbonate eutectic provides a liquid-state alternative that readily absorbs SO2 and HCl and does not become covered with a passivating layer. Gas-liquid scattering experiments utilizing the eutectic mixture (44 mol % Li2CO3, 31 mol % Na2CO3, 25 mol % K2CO3) reveal that the reaction probability for HCl(g) + CO32- --> CO2(g) + OH- + Cl- is 0.31 +/- 0.02 at 683 K and rises to 0.39 at 783 K. Gaseous CO2 is formed within 10(-4) s or less, implying that the reaction takes place in a liquid depth of less than 1000 angstrom. When the melt is exposed to D2O, the analogous reaction D2O(g) + CO32- --> CO2 (g) + 2OD(-) occurs too slowly to measure and no water uptake is observed. Together with previous studies of SO2(g) + CO32- --> CO2(g) + SO32- these results demonstrate that molten carbonates efficiently remove both gaseous HCl and SO2 while reacting at most weakly with water vapor. The experiments further highlight the remarkable ability of hot CO32- ions to behave as a base in reactions with protic and Lewis acids.
引用
收藏
页码:482 / 489
页数:8
相关论文
共 48 条
[1]   Water, sulfur dioxide and nitric acid adsorption on calcium carbonate: A transmission and ATR-FTIR study [J].
Al-Hosney, HA ;
Grassian, VH .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2005, 7 (06) :1266-1276
[2]   Ionization cross sections by electron impact on halogen atoms, diatomic halogen and hydrogen halide molecules [J].
Ali, M. A. ;
Kim, Yong-Ki .
JOURNAL OF PHYSICS B-ATOMIC MOLECULAR AND OPTICAL PHYSICS, 2008, 41 (14)
[3]   CALCIUM OXIDE-CARBON DIOXIDE SYSTEM IN PRESSURE RANGE 1-300 ATMOSPHERES [J].
BAKER, EH .
JOURNAL OF THE CHEMICAL SOCIETY, 1962, (FEB) :464-&
[4]  
Claes P, 1999, EUR J INORG CHEM, P583
[5]   A THERMOGRAVIMETRIC STUDY OF THE REACTION OF HYDROGEN-CHLORIDE GAS WITH CALCINED LIMESTONE - DETERMINATION OF KINETIC-PARAMETERS [J].
DAOUDI, M ;
WALTERS, JK .
CHEMICAL ENGINEERING JOURNAL AND THE BIOCHEMICAL ENGINEERING JOURNAL, 1991, 47 (01) :1-9
[6]  
Defay R., 1966, SURFACE TENSION ADSO
[7]   ALTERATION WITH REACTION PROGRESS OF THE RATE-LIMITING STEP FOR SOLID-GAS REACTIONS OF CA-COMPOUNDS WITH HCL [J].
DUO, W ;
KIRKBY, NF ;
SEVILLE, JPK ;
CLIFT, R .
CHEMICAL ENGINEERING SCIENCE, 1995, 50 (13) :2017-2027
[8]   MOLECULAR-BEAM ELECTRIC DEFLECTION STUDIES OF WATER POLYMERS [J].
DYKE, TR ;
MUENTER, JS .
JOURNAL OF CHEMICAL PHYSICS, 1972, 57 (11) :5011-&
[9]   VISCOSITY OF THE EUTECTIC LI2CO3-NA2CO3-K2CO3 MELT [J].
EJIMA, T ;
SATO, Y ;
YAMAMURA, T ;
TAMAI, K ;
HASEBE, M ;
BOHN, MS ;
JANZ, GJ .
JOURNAL OF CHEMICAL AND ENGINEERING DATA, 1987, 32 (02) :180-182
[10]   Kinetic modeling of the reaction of HCl and solid lime at low temperatures [J].
Fonseca, AM ;
Orfao, JJ ;
Salcedo, RL .
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, 1998, 37 (12) :4570-4576