Formation of organic acids during the hydrolysis and oxidation of several wastes in sub- and supercritical water

被引:73
作者
Calvo, L [1 ]
Vallejo, D [1 ]
机构
[1] Univ Texas, Environm & Water Resource Engn Program, Supercrit Water Oxidiat Projects, Austin, TX 78758 USA
关键词
D O I
10.1021/ie020441m
中图分类号
TQ [化学工业];
学科分类号
0817 ;
摘要
The objective of this work was to evaluate the transformation characteristics of four organic substances in supercritical water, The purpose was to demonstrate the yield and stability of the acetic acid produced under hydrolytic and oxidative conditions. Other organic acids, such as formic, glycolic, and lactic acids, were monitored. Cellulose and coconut oil solutions, as well as brewery and dairy effluents, were used as feedstocks. Batch tests were performed at fixed conditions of 400 degreesC, 27.6 MPa, and 5 min of reaction time. Hydrogen peroxide was the oxidant. Under hydrolytic conditions, 70% of the initial carbon remained as the liquid product. On the contrary, in the presence of excess oxygen, there was a 95% conversion to the gaseous product. Typically, less than 15% of the initial total organic carbon was converted to the acids. The use of catalysts (i.e., TiO2) and additives (i.e., H2SO4) did not enhanced the organic acid yield. However, catalysts addition facilitated feedstock breakdown at lower oxygen levels. To evaluate the effect of alkali addition and the use of lower temperatures, continuous flow tests were conducted using glucose as the substrate. Under alkaline conditions, organic acid production increased. For example, at 250 degreesC and 27.6 MPa with the addition of NaOH (55.6 wt% glucose) and providing 25% stoichiometric oxygen, about 77% glucose was converted to acetic acid (17%), glycolic acid (22%), and formic acid (38%). These preliminary results indicate that valuable compounds could be obtained during the degradation of organic wastes in sub- and supercritical water instead of complete oxidation to CO2 and water.
引用
收藏
页码:6503 / 6509
页数:7
相关论文
共 20 条
[1]  
CHESLEY KG, 1956, Patent No. 2750414
[2]   Supercritical water oxidation process under energetically self-sufficient operation [J].
Cocero, MJ ;
Alonso, E ;
Sanz, MT ;
Fdz-Polanco, F .
JOURNAL OF SUPERCRITICAL FLUIDS, 2002, 24 (01) :37-46
[3]   Catalytic oxidation in supercritical water [J].
Ding, ZY ;
Frisch, MA ;
Li, LX ;
Gloyna, EF .
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, 1996, 35 (10) :3257-3279
[4]  
FOUSSARD JN, 1983, THESIS NATL I APPL S
[5]   GLUCOSE HYDROLYSIS AND OXIDATION IN SUPERCRITICAL WATER [J].
HOLGATE, HR ;
MEYER, JC ;
TESTER, JW .
AICHE JOURNAL, 1995, 41 (03) :637-648
[6]   Glucose and fructose decomposition in subcritical and supercritical water: Detailed reaction pathway, mechanisms, and kinetics [J].
Kabyemela, BM ;
Adschiri, T ;
Malaluan, RM ;
Arai, K .
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, 1999, 38 (08) :2888-2895
[7]  
KRIETEMAYER S, 1982, EPA504S92006
[8]   DEGRADATION OF POLYSACCHARIDES IN ALKALINE-SOLUTION TO ORGANIC-ACIDS - PRODUCT CHARACTERIZATION AND IDENTIFICATION [J].
KROCHTA, JM ;
TILLIN, SJ ;
HUDSON, JS .
JOURNAL OF APPLIED POLYMER SCIENCE, 1987, 33 (04) :1413-1425
[9]   Gasification of pyrocatechol in supercritical water in the presence of potassium hydroxide [J].
Kruse, A ;
Meier, D ;
Rimbrecht, P ;
Schacht, M .
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, 2000, 39 (12) :4842-4848
[10]   GENERALIZED KINETIC-MODEL FOR WET OXIDATION OF ORGANIC-COMPOUNDS [J].
LI, LX ;
CHEN, PS ;
GLOYNA, EF .
AICHE JOURNAL, 1991, 37 (11) :1687-1697