Kinetics of solid acid catalyzed 1-octene reactions with TiO2 in sub- and supercritical water

Acid catalyzed reactions of 1-octene on TiO₂ in sub- and supercritical water were investigated (T = 250-450 °C, P = 11-33 MPa). The main products were 2-octene and 2-octanol. Additionally, other liner C₈ alkenes and liner secondary C₈ alcohols were produced as by-products. Through kinetic analysis, acid catalyzed reactions can divide into the reaction catalyzed by Lewis acidic sites on TiO₂ and the reaction catalyzed by protons produced by the dissociation of water molecules. Each type of the reaction is affected by water density or ionic product of water, respectively, therefore, reaction mechanism changes with temperature and pressure. From the contribution of each reaction type, the temperature dependence of cis/trans ratio of produced 2-octene could also be explained.     

Water density effects on methanol oxidation in supercritical water at high pressure up to 100 MPa

Reaction kinetics of methanol oxidation in supercritical water at high pressure condition (420 °C; 34-100 MPa; ρ = 300-660 kg/m³) was investigated. Pseudo-first order rate constant for methanol decomposition increased with increasing water density. Effects of supercritical water on the reaction kinetics were investigated using a detailed chemical kinetics model. Incorporating the effect of diffusion in a reduced model revealed that overall kinetics for SCWO of methanol is not diffusion-limited. Roles of water as a reactant were also investigated. The dependence of sensitivity coefficient for methanol concentration and rate of production of OH radical on water density indicated that a reaction, HO₂ + H₂O = OH + H₂O₂, enhanced the OH radical production and thereby facilitated the decomposition of methanol. It is presumed that concentration of key radicals could be controlled by varying pressure intensively.     

Phenol oxidation over CuO/Al2O3 in supercritical water

Phenol was oxidized in supercritical water at 380–450°C and 219–300 atm, using CuO/Al₂O₃ as a catalyst in a packed-bed flow reactor. The CuO catalyst has the desired effects of accelerating the phenol disappearance and CO₂ formation rates relative to non-catalytic supercritical water oxidation (SCWO). It also simultaneously reduced the yield of undesired phenol dimers at a given phenol conversion. The rates of phenol disappearance and CO₂ formation are sensitive to the phenol and O₂ concentrations, but insensitive to the water density. A dual-site Langmuir–Hinshelwood–Hougen–Watson rate law used previously for catalytic SCWO of phenol over other transition metal oxides and the Mars–van Krevelen rate law can correlate the catalytic kinetics for phenol disappearance over CuO. The supported CuO catalyst exhibited a higher activity, on a mass of catalyst basis, for phenol disappearance and CO₂ formation than did bulk MnO₂ or bulk TiO₂. The CuO catalyst had the lowest activity, however, when expressed on the basis of fresh catalyst surface area. The CuO catalyst exhibited some initial deactivation, but otherwise maintained its activity throughout 100 h of continuous use. Both Cu and Al were detected in the reactor effluent, however, which indicates the dissolution or erosion of the catalyst at reaction conditions.     

Fast catalytic oxidation of phenol in supercritical water

The catalytic oxidation of phenol in water over a commercial oxidation catalyst, CARULITE 150, was investigated in a fixed bed flow reactor at 250 atm and temperatures from 380°C to 430°C. The phenol and oxygen concentrations at the reactor entrance varied between 0.070 and 1.24 mmol/l, and 9.60 and 39.6 mmol/l, respectively. The reaction conditions produced phenol conversions and selectivities to CO₂ much higher than those produced by non-catalytic oxidation. The kinetics of phenol disappearance and of CO₂ formation were both roughly first-order, and the activation energies were 31 and 47 kcal/mol, respectively. The catalyst did not undergo continuous deactivation during the catalytic oxidation, but rather maintained a high activity even after several days of continuous operation.     

Reforming of methanol and glycerol in supercritical water

Reforming of pure glycerol, crude glycerin, and methanol (pure and in the presence of Na₂CO₃) in supercritical water was investigated. Continuous experiments were carried out at temperatures between 450 and 650 °C, residence times between 6 and 173 s, and feed concentrations of 3-20 wt%. For methanol the gas products are mainly H₂, CO₂, and CO. The carbon-to-gas efficiency and the observed activation energy for pure methanol are higher than for methanol with Na₂CO₃. This can be explained by assuming different decomposition mechanisms for pure methanol and methanol with Na₂CO₃. For glycerol, H₂, CO, CO₂, CH₄, and higher hydrocarbons are produced. The carbon-to-gas efficiencies of crude glycerin and pure glycerol are comparable. Overall, 2 of the 3 carbon atoms present in glycerol end up in carbon oxides, while 1 carbon atom becomes C_xH_y. The overall mechanism of glycerol decomposition involves the dehydration of 1 mole of H₂O/mole glycerol. For both, methanol and glycerol at carbon-to-gas efficiencies below 70%, the gas yields (mole/mole feed) and carbon-to-gas efficiency correlate well.     

Classical simulation of acid and base dissociation constants in supercritical water at constant density

Molecular dynamics simulations were performed to investigate the dissociations of water, NaOH and HCl in water at constant density of 0.9 g cm⁻³ at near-critical and supercritical temperatures. Results were in good qualitative agreement with available data, showing increased temperature favouring all dissociations. The dissociation of water was favoured by more negative values of U/T and an increasing entropy tem, whereas the dissociation of HCl showed both decreasing U/T and entropy. NaOH showed an increasing value of U/T which was dominated by an increasing entropy term. Differences in the energy contributions were attributed to the change in solute charges upon dissociation.     

Supercritical water gasification of glycerol: Intermediates and kinetics

In this paper, the liquid products from supercritical water gasification (SCWG) of glycerol were analyzed and some intermediates were identified. A simplified reaction pathway for gases production from SCWG of glycerol was proposed. The first quantitative kinetics model for describing the gaseous products (H₂, CO, CH₄ and CO₂) of SCWG of glycerol was developed. The model comprises seven reactions to describe the typical reactions in SCWG, and the reaction rate constant of each reaction was obtained by using the nonlinear least-square fitting method. The reaction rate analysis showed that the main sources of hydrogen yield were glycerol pyrolysis and steam reforming of intermediates, while the hydrogen yield from water–gas shift reaction (WGSR) was very small. The temperature estimated by the kinetics model for completely SCWG of glycerol solution was given. In addition, the sensitivity analysis of rate constant of WGSR was done based on the model.     

Upgrading of bitumen with formic acid in supercritical water

Upgrading of bitumen was examined with formic acid in supercritical water (SCW) from 673 to 753 K and at a water/oil ratio from 0 to 3. Decomposition of bitumen in SCW + HCOOH gave higher conversions of asphaltene and lower coke yields than those of pyrolysis or with only SCW. Decomposition of bitumen was also conducted in SCW + H₂, SCW + CO, toluene and tetralin, which revealed that decomposition of asphaltene was promoted and coke formation was suppressed when using SCW + HCOOH. In SCW + HCOOH, an increase in the water/oil ratio promoted both decomposition of asphaltene and suppression of coke formation. Formic acid in SCW seemed to enhance the conversion of bitumen to lower molecular weight compounds because formic acid seems to produce active species in SCW. The low temperature region (ca. 723 K) was suitable for upgrading bitumen with formic acid in SCW since coke formation was strongly promoted at high temperature (>753 K). A reaction model was proposed and the model predicted that hydrogenation of the asphaltene core was important for the suppression of coke formation.     

A rapid transformation of titanate nanotubes into single-crystalline anatase TiO2 nanocrystals in supercritical water

The present study was aimed to investigate the morphological and phase transformations of hydrothermally prepared titanate nanotubes (TNTs) in supercritical water (SCW). We found that single-crystalline anatase nanocrystals including rhombic nanoparticles with the ends faceted with (1 0 1) facets and spindle-shaped nanorods mainly exposing (0 1 0) facets were rapidly generated in 10 min, of which the thicknesses were less than 5 nm. The morphologies and crystal forms of products treated for 6 and 8 min were investigated, showing that the outside nanotube walls were gradually decomposed meanwhile the inside tubular structures underwent a local shrinkage, followed by spontaneous phase transformations. We proposed that TNTs were transformed into anatase nanocrystals by two simultaneous processes. One is a dissolution-nucleation and crystal growth while the other is an in situ nucleation and crystal growth, resulting in the formation of rhombic and spindle-shaped morphologies, respectively.     

Non-isothermal liquefaction of liptobiolith coal in supercritical water flow and effect of zinc additives

The liquefaction of liptobiolith coal in water vapor and supercritical water (SCW) flow at uniform increase in temperature from 300 up to 470 °C and in SCW flow at 400 °C (30 MPa) with addition of zinc shavings to coal has been investigated. Temperature dependences of the yield of liquid and volatile products and kinetic parameters of the process have been obtained. The yields of oil, resin, asphaltene and volatile products in relation to the coal organic matter (COM) are 23.2, 16.1, 5.1 and 14.1%, respectively. CO₂, CO, H₂S and C₁–C₄ alkanes prevail in the composition of volatile products. The generation of oil, resin and asphaltene are found to have occurred in terms of the simultaneous chemical reactions of cleavage of the COM aliphatic CC bonds, while the volatile products result from the consecutive transformations of the COM components in the bulk and SCW solution. Participation of H₂O molecules in thermochemical transformations of COM leads to increase in the oxygen amount in the conversion products and residue by 13.2%. Hydrogen and heat evolution during zinc oxidation by SCW provides for the hydrogenation of COM in situ. Addition of zinc to coal results in increase in the volatile products yield up to 48.6% and decrease in the conversion residue yield up to 20.8%. Under these conditions the yield of resin does not change, while the yields of oil and asphaltene decrease up to 21.2 and 2.5%, respectively. Based on the sulfur balance it is revealed that ≈40% of sulfur atoms pass into ZnS owing to the reactions of H₂S with Zn and ZnO resulting in the removal of H₂S from the volatile conversion products.     

Solubility of Na2SO4, Na2CO3 and their mixture in supercritical water

The solubility of many salts in water decreases dramatically with temperature in the vicinity of the critical point of pure water. Examples of these salts are sulfates of sodium, potassium, lithium and sodium carbonate. These salts are usually produced during supercritical water oxidation (SCWO) and contribute to fouling. The solubility of Na₂CO₃ and Na₂SO₄ has been determined in pure form and in the presence of each other, for the temperature range relevant to SCWO. The experimental procedure was to pass the salt solution through a tube at constant temperature. After a brief initiation period during which no salt sticks to the tube, the salt above the solubility limit deposited on the tube surface. The solution leaving the section was thus at the solubility limit. A rapid decrease in the salt solubility was observed just above the pseudo-critical temperature. For supercritical conditions, the solubility of each salt in the form of a mixture was quite close to the solubility of pure salt. At the highest fluid density considered (480 kg/m³) the presence of Na₂CO₃ reduces the solubility of Na₂SO₄, as might be expected from the “common-ion effect”.     

Destruction of CFC113 in supercritical and subcritical water

Destruction of 1,1,2-trichlorotrifluoroethane (CFC113) in supercritical and subcritical water was performed over a wide range of pressure at 673 K. The hydrolysis reaction of CFC113 in the supercritical water could lead to complete destruction of CFC113, while the CFC113 destruction below the critical pressure of water was quite low. The Cl destruction yields were higher than those of F over the whole pressure range including both supercritical and subcritical regions, which implies that the bonding energy of F on the backbone of CFC113 is stronger than that of Cl . The destruction yields represented by two ions were found to have the linear dependency on the reduced water density.     

Corrosion control methods in supercritical water oxidation and gasification processes

Use of supercritical water (SCW) as a medium for oxidation reactions, conversion of organic materials to gaseous or liquid products, and for organic and inorganic synthesis processes, has been the subject of extensive research, development, and some commercial activity for over 25 years. A key aspect of the technology concerns the identification of materials, component designs, and operating techniques suitable for handling the moderately high temperatures and pressures and aggressive environments present in many SCW processes. Depending upon the particular application, or upon the particular location within a single process, the SCW process environment may be oxidizing, reducing, acidic, basic, nonionic, or highly ionic. Thus, it is difficult to find any one material or design that can withstand the effects of all feed types under all conditions. Nevertheless, several approaches have been developed to allow successful continuous processing with sufficient corrosion resistance for an acceptable period of time. The present paper reviews the experience to date for methods of corrosion control in the two most prevalent SCW processing applications: supercritical water oxidation (SCWO) and supercritical water gasification (SCWG).     

Partial oxidation of n-hexadecane and polyethylene in supercritical water

In this study, we show the results of partial oxidation experiments of n-hexadecane (n-C₁₆) and polyethylene (PE) in supercritical water (SCW). The experiments were carried out at 673 or 693 K of reaction temperature and 5 or 30 min of reaction time using a 6 cm³ of a batch type reactor. Water density ranged from 0.1 to 0.52 g/cm³ (water pressure: 20–40 MPa). The loaded amount of oxygen was set to 0.3 of the ratio of oxygen atom to carbon atom. Some experiments were made using CO instead of oxygen for the partial oxidation of n-C₁₆ and PE to explore the effect of water gas shift reaction. In the results of partial oxidation of n-C₁₆, the yield of CO and some compounds containing oxygen atoms, such as aldehydes and ketones increased with increasing water density. Moreover, 1-alkene/ n-alkane ratio in the products decreased with increasing water density. The 1-alkene/n-alkane ratio was lower than that of pyrolysis in SCW. Also for the case of PE experiments, in dense SCW (0.42 g/cm³), the 1-alkene/n-alkane ratio in partial oxidation was lower than that in SCW pyrolysis. In the case of CO experiments for n-C₁₆ and PE, 1-alkene/n-alkane ratio was a little lower than that of pyrolysis in SCW. These results show that the yield of n-alkane, which is a hydrogenated compound, was higher through water gas shift reaction in SCW and also through partial oxidation in SCW. Therefore, these results suggest the possibility of hydrogenation of hydrocarbon through partial oxidation followed by the water gas shift reaction.     

Effect of cations and anions on properties of zinc oxide particles synthesized in supercritical water

Hydrothermal synthesis of zinc oxide fine particles from zinc salt (Zn(CH₃COO)₂, ZnSO₄, Zn(NO₃)₂) and alkali metal hydroxide (LiOH, KOH) aqueous solution was carried out with a Ti alloy batch reactor in supercritical water. Particle size synthesized in LiOH solution was relatively smaller than that in KOH. Emission spectra of the particle produced from ZnSO₄ and LiOH aqueous solution shows the highest intensity among these systems. Hydrothermal synthesis of zinc oxide fine particles from Zn(NO₃)₂ and LiOH solution was also carried out with a flow-through apparatus for continuous production and rapid heating of the starting solution to supercritical states. Nanoparticles having an average particle diameter of 16 nm was produced at 659 K and 30 MPa.     

固体酸WO3／ZrO2制备生物柴油的研究

采用共沉淀法制备了固体强酸WO_3/ZrO_2,研究了WO_3负载量和焙烧温度对催化剂晶相和比表面积的影响,并且研究了WO_3/ZrO_2催化剂对葵花籽油酯交换反应制备生物柴油(BDF)的催化性能,结果表明,WO_3/ZrO_2催化剂的催化性能与WO_3负载量及晶相结构密切相关,在负载量为0.1 g WO_3/ZrO_2时,经700～800℃高温焙烧,WO_3在ZrO_2表面上达到单层分散,且大部分ZrO_2以四方晶相存在,而四方相的存在对于形成WO_3/ZrO_2的强酸性是很重要的。所制备的催化剂具有较好的催化活性,在反应温度150℃、醇油物质的量比12:1及催化剂用量为葵花籽油质量分数的3%的条件下,反应8 h后葵花籽油的转化率可以达到60%以上。     

Non-catalytic recovery of phenol through decomposition of 2-isopropylphenol in supercritical water

The decomposition of 2-isopropylphenol (IPP) was studied in supercritical water at 723- with a water density of 0- in the absence of catalyst. The main products were phenol, 2-propylphenol (PP), 2-cresol and 2-ethylphenol. The reaction was determined to proceed as follows. At first, the dealkylation and rearrangement of IPP yielded phenol and PP, respectively. Next, the dealkylation of PP lead to the formation of 2-cresol and 2-ethylphenol. The conversion of IPP and the selectivity of phenol increased with the increasing water density, which led to an increase in the yield of phenol. The recoveries of phenol as high as 43% can be obtained in the high water density region at . The rate constant for decomposition of IPP was correlated with a global reaction model for a range of temperatures from 613 to .     

超临界水降解聚丙烯的工艺研究

采用间歇式管式反应器进行了超临界水降解聚丙烯实验,研究了影响聚丙烯降解的因素。实验结果表明,在温度400－450℃、压力23－35MPa及反应时间60－120min的条件下,超临界水能有效地降解聚丙烯。反应温度和反应时间是影响聚丙烯降解的主要因素,温度越高、时间越长,聚丙烯降解越彻底;聚丙烯颗粒度越小降解速率越快,粉末原料在温度400℃、反应时间60min时,以油相产物为主;在温度450℃、反应时间120min时,有利于得到气相产物。     

Preparation of a thick NiAl/Al2O3 coating by embedding method and its corrosion resistance under supercritical water environment

One of the critical issues in the application of supercritical water oxidation technology is to improve the corrosion resistance of reactor materials. Use of Al₂O₃ coating is one of the most promising methods to address this issue. In this study, thick NiAl/Al₂O₃ coatings on Inconel 625 substrates were prepared by a consecutive pack embedding and in-situ thermal oxidation process. The effect of aluminizing and oxidation temperature on phase structure and coating thickness is studied. Results show the diffusion of Al from the exterior to the interior of the alloy matrix to form intermetallic compounds between Al and metal elements in the matrix (Ni, Cr, Mo, etc.). Moreover, the coating thickness can reach above 300 μm at the aluminizing temperature of 950 °C. Increasing the aluminizing temperature above 950 °C will not increase the coating thickness further. After high temperature oxidation subsequently, only phases of NiAl and Al₂O₃ were detected. The formation of Al₂O₃ layer can be ascribed to the surface oxidization of Al. And the NiAl between the alloy substrate and Al₂O₃ coating provides an interfacial layer that can alleviate the crack or exfoliation of ceramic coating due to the mismatching of thermal expand coefficient. The thick NiAl/Al₂O₃ coatings prepared by aluminizing 950 °C and oxidizing at 1100 °C exhibit satisfied corrosion resistance after supercritical water test. This work would provide a significant method to develop advanced ceramics coating for the corrosion resistance of alloys.     

Decomposition of 2-chlorophenol by supercritical water oxidation with zirconium corrosion

The 2-chlorophenol (2-CP) was oxidized in a continuous anti-corrosive supercritical water system. The variation of decomposition efficiency by the corrosion of zirconium 702 was also studied at the variation of feed concentration and reaction time. According to AES depth profile, the oxygen penetration depth to zirconium was not proportional to the exposure time. It might stem from the formation of zirconium oxide layer on the surface delaying the corrosion. However, the increase in feed concentration accelerated the corrosion of zirconium. The corrosion of zirconium at low feed concentration led to the improvement of decomposition efficiency due to the catalytic effect of formed zirconium oxides, while that at high feed concentration deteriorated the decomposition efficiency owing to large consumption of oxidant in corrosion.