Supercritical water oxidation of polyvinyl alcohol and desizing wastewater: influence of NaOH on the organic decomposition.

Polyvinyl alcohol is a refractory compound widely used in industry. Here we report supercritical water oxidation of polyvinyl alcohol solution and desizing wastewater with and without sodium hydroxide addition. However, it is difficult to implement complete degradation of organics even though polyvinyl alcohol can readily crack under supercritical water treatment. Sodium hydroxide had a significant catalytic effect during the supercritical water oxidation of polyvinyl alcohol. It appears that the OH- ion participated in the C-C bond cleavage of polyvinyl alcohol molecules, the CO2-capture reaction and the neutralization of intermediate organic acids, promoting the overall reactions moving in the forward direction. Acetaldehyde was a typical intermediate product during reaction. For supercritical water oxidation of desizing wastewater, a high destruction rate (98.25%) based on total organic carbon was achieved. In addition, cases where initial wastewater was alkaline were favorable for supercritical water oxidation treatment, but salt precipitation and blockage issues arising during the process need to be taken into account seriously.

The Effect of Molten Phosphate on Corrosion of 316 Stainless Steel, Alloy 625, and Titanium TA8 in Supercritical Water Oxidation Conditions.

The early formation of phosphate oxide formed on 316 stainless steel (316 SS), nickel-based Alloy 625, and titanium alloy TA8 exposed in supercritical water (400 °C, 25 MPa) containing phosphate, chloride, and oxygen was investigated. Phosphate corrosion products of austenitic stainless steel displayed the severest spallation. Stable phosphates oxide films were inclined to form on Alloy 625. TiO2 and Ti2O3 are the two main components of oxide films on TA8. There is a strong synergistic effect between phosphates, oxygen, and supercritical water, leading to severe corrosion. The corrosion behavior of the three alloys at the top and bottom of the reaction tube was compared. Both at the top of the reaction tube and at the bottom of the reaction tube, TA8 showed an increase in mass. 316 SS and alloy 625 showed mass gain at the top and mass loss at the bottom. The alloys' detailed molten corrosion mechanism after exposure to supercritical water is discussed.

Coupling Effect of Hydrostatic Pressure and Erosion on Corrosion Behavior of X70 Steel in Simulated Seawater.

The corrosion behavior of X70 steel under the coupling effect of pressure and erosion in simulated seawater was investigated by using corrosion loss, electrochemical tests, SEM, AFM, XPS, and Raman spectroscopy. The coupling effect of pressure and erosion could induce changes in the amounts and compositions of the corrosion products and increase pitting. The rate of the combined corrosion of X70 steel represents a downtrend, which still displays a higher corrosion rate than only immersion at the same pressure. This means that the coupling of pressure and erosion will accelerate corrosion, but the effect of erosion is weakened by pressure. The larger the pressure is, the more erosion is weakened. The pressure reduces the water cutting force by increasing the liquid viscosity and reduces the surface hardness changes under high pressure by generating magnetite, which is closely bound to the substrate.

Oxidation of high iron content electroplating sludge in supercritical water: stabilization of zinc and chromium.

The stabilization of heavy metals (zinc and chromium) and the degradation of organic pollutants during supercritical water (SCW) and supercritical water oxidation (SCWO) treatment of electroplating sludge (EPS) with a high iron content were studied. Experiments were performed in a batch reactor at temperatures in the range from 623.15 to 823.15 K with an oxygen coefficient (OE) from 0 to 2.0, a reaction time of 7 min and pressure of 25 MPa to examine the effect of the operation conditions. Chemical oxygen demand (COD) and total organic carbon (TOC) in raw sludge and liquid products under different reaction conditions were detected. The results indicated that more organic pollutant degradation occurred under supercritical conditions than in subcritical water. Additionally, as the temperature and amount of oxidant increased, the organic pollutant removal rate increased. In addition, the Zn and Cr removal efficiency from sludge was more than 98% under all conditions. Temperatures under 773.15 K had a positive effect, whereas the oxygen ratio was more significant than the other factors above 773.15 K. Furthermore, leaching toxicity tests of the heavy metals in solid products were conducted based on the toxicity characteristic leaching procedure (TCLP). All heavy metals showed greatly reduced leaching toxicity due to their stabilization. The Zn in the EPS is more easily converted into a solid product after SCWO treatment; however, Cr is more difficult to leach from the solid product. Oxides of iron, zinc, and chromium were detected by X-ray diffraction and an electron probe microanalyzer, and the yield of the oxides increased with increasing temperature and oxidant amount. Using the obtained data and analysis results, the effect of Fe on the stabilization of Zn and Cr was studied.

Treatment of municipal sewage sludge in supercritical water: A review.

With increasing construction of wastewater treatment plants and stricter policies, municipal sewage sludge (MSS) disposal has become a serious problem. Treatment of MSS in supercritical water (SCW) can avoid the pre-drying procedure and secondary pollution of conventional methods. SCW treatment methods can be divided into supercritical water gasification (SCWG), supercritical water partial oxidation (SCWPO) and supercritical water oxidation (SCWO) technologies with increasing amounts of oxidants. Hydrogen-rich gases can be generated from MSS by SCWG or SCWPO technology using oxidants less than stoichiometric ratio while organic compounds can be completely degraded by SCWO technology with using an oxidant excess. For SCWG and SCWPO technologies, this paper reviews the influences of different process variables (MSS properties, moisture content, temperature, oxidant amount and catalysts) on the production of gases. For SCWO technology, this paper reviews research regarding the removal of organics with or without hydrothermal flames and the changes in heavy metal speciation and risk. Finally, typical systems for handling MSS are summarized and research needs and challenges are proposed.

Construction of 1D SnO2-coated ZnO nanowire heterojunction for their improved n-butylamine sensing performances.

One-dimensional (1D) SnO2-coated ZnO nanowire (SnO2/ZnO NW) N-N heterojunctions were successfully constructed by an effective solvothermal treatment followed with calcination at 400 °C. The obtained samples were characterized by means of XRD, SEM, TEM, Scanning TEM coupled with EDS and XPS analysis, which confirmed that the outer layers of N-type SnO2 nanoparticles (avg. 4 nm) were uniformly distributed onto our pre-synthesized n-type ZnO nanowire supports (diameter 80~100 nm, length 12~16 µm). Comparisons of the gas sensing performances among pure SnO2, pure ZnO NW and the as-fabricated SnO2/ZnO NW heterojunctions revealed that after modification, SnO2/ZnO NW based sensor exhibited remarkably improved response, fast response and recovery speeds, good selectivity and excellent reproducibility to n-butylamine gas, indicating it can be used as promising candidates for high-performance organic amine sensors. The enhanced gas-sensing behavior should be attributed to the unique 1D wire-like morphology of ZnO support, the small size effect of SnO2 nanoparticles, and the semiconductor depletion layer model induced by the strong interfacial interaction between SnO2 and ZnO of the heterojunctions. The as-prepared SnO2/ZnO NW heterojunctions may also supply other novel applications in the fields like photocatalysis, lithium-ion batteries, waste water purification, and so on.

Partial oxidation of landfill leachate in supercritical water: Optimization by response surface methodology.

To achieve the maximum H2 yield (GYH2), TOC removal rate (TRE) and carbon recovery rate (CR), response surface methodology was applied to optimize the process parameters for supercritical water partial oxidation (SWPO) of landfill leachate in a batch reactor. Quadratic polynomial models for GYH2, CR and TRE were established with Box-Behnken design. GYH2, CR and TRE reached up to 14.32mmol·gTOC(-1), 82.54% and 94.56% under optimum conditions, respectively. TRE was invariably above 91.87%. In contrast, TC removal rate (TR) only changed from 8.76% to 32.98%. Furthermore, carbonate and bicarbonate were the most abundant carbonaceous substances in product, whereas CO2 and H2 were the most abundant gaseous products. As a product of nitrogen-containing organics, NH3 has an important effect on gas composition. The carbon balance cannot be reached duo to the formation of tar and char. CR increased with the increase of temperature and oxidation coefficient.

Treatment of sewage sludge in supercritical water and evaluation of the combined process of supercritical water gasification and oxidation.

Influences of temperature and oxidation coefficient (n) on sewage sludge treatment in supercritical water and its corresponding reaction mechanism were studied. Moreover, the combined process of supercritical water gasification (SCWG) and supercritical water oxidation (SCWO) was also investigated. The results show that ammonia nitrogen, phenols and pyridines are main refractory intermediates. The weight of solid products at 873K and n=4 is only 3.5wt.% of the initial weight, which is lower than that after combustion. Volatile organics in solid phase have almost released at 723K and n=0. Highest yield of combustible gases was obtained at n=0, and H2 yield can reach 11.81mol/kg at 873K. Furthermore, the combination of SCWG at 723K and SCWO at 873K with a total n=1 is feasible for its good effluent quality and low operation costs.

Partial oxidation of municipal sludge with activited carbon catalyst in supercritical water.

The partial oxidation (POX) characteristics of municipal sludge in supercritical water (SCW) were investigated by using batch reactor. Effects of reaction parameters such as oxidant equivalent ratio (OER), reaction time and temperature were investigated. Activated carbon (AC) could effectively improve the mole fraction of H(2) in gas product at low OER. However, high OER (greater than 0.3) not only led to the combustion reaction of CO and H(2), but also caused corrosion of reactor inner wall. Hydrogenation and polymerization of the intermediate products are possible reasons for the relative low COD removal rate in our tests. Metal oxide leached from the reactor inner wall and the main components of the granular sludge were deposited in the AC catalyst. Reaction time had more significant effect on BET surface area of AC than OER had. Long reaction time led to the methanation reaction following hydrolysis and oxidation reaction of AC in SCW in the presence of oxygen. Correspondingly, the possible reaction mechanisms were proposed.