Résumés
Résumé
L'élimination de la matière organique et la réduction de volume des boues peuvent être obtenues par incinération, par oxydation sous pression en milieu humide ("wet air oxidation") ou par combustion en eau supercritique ("supercritical water oxidation"). Une étude en autoclave agité a permis de comparer sur une même boue d'épuration les performances des deux techniques d'oxydation voie humide et d'oxydation supercritique, en mettant l'accent sur les sous-produits résiduels en phase liquide et la composition de la phase gaz.
Les résultats obtenus montrent que l'élimination de la DCO dépend fortement de la température: l'abattement de la DCO passe de 70 % à 235 °C à 94 % à 430 °C. L'azote organique de la boue est transformé en NH4+ mais seule une élimination limitée de l'azote totale est obtenue à 430 °C. Les sous-produits résiduels dans la phase liquide sont constitués en majorité d'acides gras, d'aldéhydes et de cétones, l'acide acétique étant prédominant.
Hormis le CO2, les sous-produits gazeux majeurs formés par des réactions complexes comme la pyrolyse, le réformage et la méthanation sont CO, H2 et CH4. Dans les conditions supercritiques, tous les sous-produits gazeux sont fortement oxydés. L'augmentation de la température de traitement permet d'obtenir un résidu solide de plus en plus inerte, les cendres obtenues en conditions supercritiques contenant moins de 1 % de matière organique.
Les performances des deux procédés étudiés laissent envisager leur développement à moyen terme comme voies alternatives d'élimination des boues.
Mots-clés:
- Oxydation supercritique,
- oxydation humide,
- traitement des boues,
- DCO,
- COT,
- sous-produits,
- acides gras volatils,
- azote ammoniacal,
- cendres
Abstract
Context
As the number of wastewater treatment plants increases, and the efficiency of treatment improves, the problem of how to dispose of the ever increasing amounts of generated sludge has intensified. For the beginning of the next century 1 million tons of sludge will be produced annually in France; disposal in landfills will be impossible and agricultural use could be limited by tight quality standards. Therefore, the development of effective and acceptable sludge processes is urgently needed.
Destruction of organic matter in sludge and large reductions in sludge volume are achieved either by incineration or by wet air oxidation (WAO), which needs no fuel and generates no smoke, fly ash or emissions of NOx and SO2. Supercritical water oxidation (SCWO) offers an attractive alternative. Water, above its vapor-liquid critical point of 374°C and 221 bar, is an excellent solvent for organic compounds and becomes completely miscible with oxygen. Reported results of sewage sludge SCWO demonstrate rapid and effective treatment. The objective of this study was to compare sub- and supercritical water oxidation of sludge in terms of organic matter destruction and formation of by-products in both gas and liquid phases.
Methodology
Oxidation of sludge was studied in a 0.5 L batch reactor rated for 450°C-300 bar. The raw material was a biological sludge containing 4% solids with a chemical oxygen demand (COD) value of 52 g/L. In the standard experimental procedure, 100 mL sludge were heated up to reaction temperature and oxygen was then introduced in 50% excess with respect to COD. Heating was maintained during 1 hour before slow cooling to room temperature. The overall organic destruction was quantified in terms of total organic carbon (TOC) and COD. Gas and liquid phases sampled at room temperature after reaction were analyzed by gas chromatography (GC). Sulfur and nitrogen species were also analyzed.
Results
When the temperature increased from 210 to 383°C, COD destruction increased significantly (Table 1). At 383°C, a COD destruction efficiency of 94.3% was obtained. However, at 430°C, organic matter oxidation was only marginally improved. In WAO tests, considerable acetic acid was produced and remained in the substrate. The produced acetic acid was oxidized rapidly under SCWO conditions. Surprisingly, the concentrations of the other volatile fatty acids (VFA) remained approximately constant between 310 and 430°C (Table 2). In addition to VFA, which represent ca. 50% of the residual COD, oxygenated organic compounds such as aldehydes, ketones and alcohols were produced (Table 3).
The data in Table 4 show that decomposition of organic nitrogen compounds into ammonia was completed at 383°C, while nitrates were reduced to N2 by reaction with organic matter and ammonia. NOx were not detected in the gas phase. The low reactivity of ammonia in supercritical water had been previously demonstrated. At 430°C, ammonia removal from sludge was limited to 15%. On the other hand, even in WAO conditions all sulfur species were totally converted to sulfate.
Under subcritical conditions, the gas phase contained significant concentrations of hydrogen and carbon monoxide in addition to water, residual oxygen and carbon dioxide. Traces of methane and C2-C3 hydrocarbons were also detected (Figs. 1 and 2). These gases result from a complex chemistry including pyrolysis, steam reforming and water-gas shift. Under supercritical conditions, all these compounds were extensively eliminated by oxidation. Under supercritical conditions the residual solids contained less than 1% organic matter. By X-ray diffraction hydroxyapatite, quartz and kaliophilite were identified in the residual solids.
These results confirm that supercritical water oxidation is a new sludge treatment concept of great interest. The degree of conversion of organic carbon is high, while liquid and especially gaseous by- products are produced in minor amounts compared to subcritical conditions. Temperatures higher than 430°C would be needed for substantial nitrogen removal.
Keywords:
- Supercritical water oxidation,
- wet air oxidation,
- sludge,
- chemical oxygen demand,
- by-products,
- volatile fatty acids,
- ammonia,
- solids
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