Hydrous pyrolysis of New Albany and Phosphoria Shales: production kinetics of carboxylic acids and light hydrocarbons and interactions between the inorganic and organic chemical systems

被引:36
作者
Knauss, KG [1 ]
Copenhaver, SA [1 ]
Braun, RL [1 ]
Burnham, AK [1 ]
机构
[1] Lawrence Livermore Natl Lab, Geosci & Environm Technol Div, Livermore, CA 94550 USA
关键词
hydrous pyrolysis; carboxylic acids; kinetics; speciation modeling; solubility; light hydrocarbons; New Albany Shale; Phosphoria Shale;
D O I
10.1016/S0146-6380(97)00081-8
中图分类号
P3 [地球物理学]; P59 [地球化学];
学科分类号
0708 ; 070902 ;
摘要
Hydrous pyrolysis in flexible gold-bag autoclaves was used to study the production of carboxylic acids and light hydrocarbons from two marine type IIb source rocks (New Albany and Phosphoria Shales). Kerogen pyrolysis produced significant amounts of the monocarboxylic acids (acetic>propionic>butyric). The gases were dominated by CO2 and methane, in that order, and progressively smaller amounts of the alkanes (ethane>propane>butane>pentane). Kinetic analyses of production rates for the New Albany Shale suggest mean activation energies (E) of 51-54 kcal/mol for both the light hydrocarbons and acids. Pressure had little effect on measured production rates for either shale over the pressure range investigated. Chemical thermodynamic speciation modeling suggests that in these experiments metal-organic acid anion complexation had little impact on aluminum speciation/solubility, but was important with respect to the alkaline earths. (C) 1997 Published by Elsevier Science Ltd. All rights reserved.
引用
收藏
页码:477 / 496
页数:20
相关论文
共 61 条
[1]   YIELDS AND CARBON ISOTOPIC COMPOSITION OF PYROLYSIS PRODUCTS FROM ARTIFICIAL MATURATION PROCESSES [J].
ANDRESEN, B ;
BARTH, T ;
IRWIN, H .
CHEMICAL GEOLOGY, 1993, 106 (1-2) :103-119
[2]   THERMAL GENERATION OF CARBON-DIOXIDE AND ORGANIC-ACIDS FROM DIFFERENT SOURCE ROCKS [J].
ANDRESEN, B ;
THRONDSEN, T ;
BARTH, T ;
BOLSTAD, J .
ORGANIC GEOCHEMISTRY, 1994, 21 (12) :1229-1242
[3]   ORGANIC-ACIDS FROM SOURCE-ROCK MATURATION - GENERATION POTENTIALS, TRANSPORT MECHANISMS AND RELEVANCE FOR MINERAL DIAGENESIS [J].
BARTH, T ;
BJORLYKKE, K .
APPLIED GEOCHEMISTRY, 1993, 8 (04) :325-337
[4]   ORGANIC-ACIDS IN RESERVOIR WATERS - RELATIONSHIP WITH INORGANIC-ION COMPOSITION AND INTERACTIONS WITH OIL AND ROCK [J].
BARTH, T ;
BORGUND, AE ;
RIIS, M .
ORGANIC GEOCHEMISTRY, 1990, 16 (1-3) :489-496
[5]   ESTIMATING KINETIC-PARAMETERS FOR GENERATION OF PETROLEUM AND SINGLE COMPOUNDS FROM HYDROUS PYROLYSIS OF SOURCE ROCKS [J].
BARTH, T ;
NIELSEN, SB .
ENERGY & FUELS, 1993, 7 (01) :100-110
[6]   GENERATION OF ORGANIC-COMPOUNDS BY HYDROUS PYROLYSIS OF KIMMERIDGE OIL-SHALE - BULK RESULTS AND ACTIVATION-ENERGY CALCULATIONS [J].
BARTH, T ;
BORGUND, AE ;
HOPLAND, AL .
ORGANIC GEOCHEMISTRY, 1989, 14 (01) :69-76
[7]   INTERACTIONS BETWEEN ORGANIC-ACID ANIONS IN FORMATION WATERS AND RESERVOIR MINERAL PHASES [J].
BARTH, T ;
RIIS, M .
ORGANIC GEOCHEMISTRY, 1992, 19 (4-6) :455-482
[8]   THERMAL-DECOMPOSITION OF ACETATE .3. CATALYSIS BY MINERAL SURFACES [J].
BELL, JLS ;
PALMER, DA ;
BARNES, HL ;
DRUMMOND, SE .
GEOCHIMICA ET COSMOCHIMICA ACTA, 1994, 58 (19) :4155-4177
[9]  
Bethke C., 1992, The Geochemist's Workbench: A Users Guide to Rxn, Act2, Tact, React, and Gtplot
[10]   GENERATION OF SHORT-CHAIN ORGANIC-ACIDS FROM CRUDE-OIL BY HYDROUS PYROLYSIS [J].
BORGUND, AE ;
BARTH, T .
ORGANIC GEOCHEMISTRY, 1994, 21 (8-9) :943-952