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.     

Inference of reaction kinetics for supercritical water heavy oil upgrading with a two-phase stirred reactor model

We present the development and application of a two-phase stirred reactor model for heavy oil upgrading in the presence of supercritical water (SCW), with coupled phase-specific thermolysis reaction kinetics and multicomponent hydrocarbon–water phase equilibrium. We demonstrate the inference of oil and water phase kinetics parameters for a compact lumped reaction kinetics scheme through the application of this model to two different sets of batch reactor experiments reported in the literature. We infer that, although SCW can suppress the formation of newer polynuclear aromatics (PNA) from distillate range species, it is broadly ineffective in deterring the combination of pre-existing PNA fragments in the oil feed. Quantification of the conversion to distillate liquids before the onset of coke formation helps arrive at a clear conclusion on whether the use of SCW in the batch reactor leads to better product outcomes for different oil feeds and operating conditions.     

An experimental and modeling study of vacuum residue upgrading in supercritical water

Arabian Heavy crude oil was fractionated into distillate and vacuum residue fractions. The vacuum residue fraction was treated with supercritical water (SCW) at 450°C in a batch reactor for 15–90 min. The main products were gas, coke, and upgraded vacuum residue; the upgraded residue consisted of gasoline, diesel, and vacuum gas oil range components. The molecular composition of gas and upgraded vacuum residue was analyzed using gas chromatography (GC, GC × GC). SCW treatment converted higher carbon number aliphatics (≥C₂₁) and long‐chain (≥C₅) alkyl aromatic compounds into C₁?C₂₀ aliphatics, C₁?C₁₀ alkylaromatics, and multiringed species. The concentrations of gasoline and diesel range compounds were greater in the upgraded product, compared to the feed. A first‐order, five lump reaction network was developed to fit the yields of gas, coke, diesel, and gasoline range components obtained from SCW upgrading of vacuum residue. Distillation of crude oil followed by SCW treatment of the heavy fraction approximately doubled the yield of chemicals, gasoline, and diesel, while forming significantly less coke than conventional upgrading methods. © 2018 American Institute of Chemical Engineers AIChE J, 64: 1732–1743, 2018     

Lumped reaction kinetic models for pyrolysis of heavy oil in the presence of supercritical water

The reaction kinetics of the pyrolysis of heavy oil in the presence of supercritical water (SCW) and high pressure N₂ were measured. At any reaction temperature applied, the pyrolysis under SCW environments is faster than that under N₂ environments. Meanwhile, at lower temperatures the pyrolysis under both environments is accelerated by the introduction of coke into the feedstock. On the basis of a first‐order four‐lump reaction network consisting of the sequential condensation of maltenes and asphaltenes, the pyrolysis in whichever medium can be preferably described either by the lumped reaction kinetic model modified with autocatalysis and pseudoequilibrium or by the model modified solely with pseudoequilibrium. Benefited from the reduced limitation of diffusion to reaction kinetics, the pyrolysis in the SCW phase is more sensitive to the increase in reaction temperature than that in the oil phase, disengaging readily from the dependence on autocatalysis at a lower temperature. © 2015 American Institute of Chemical Engineers AIChE J, 62: 207–216, 2016     

Effect of supercritical water on upgrading reaction of oil sand bitumen

The advantages of supercritical water (SCW) as a reaction medium for upgrading oil sand bitumen were investigated through a comprehensive analysis of the output product, which includes gaseous products, middle distillate, distillation residue, and coke. Canadian oil sand bitumen mined by the steam assisted gravity drainage method was treated in an autoclave at 420-450 °C and 20-30 MPa for up to 120 min with three kinds of reaction media: SCW, high-pressure nitrogen, and supercritical toluene. The yields of gaseous products indicated that a very small amount of water was involved in the upgrading reaction. The analytical results of the middle distillate fractions were almost the same using water and nitrogen at 450 °C. The distillation residues produced in SCW had lower molecular weight distributions, lower H/C atomic ratios, higher aromaticities, and consequently more condensed structures compared to those produced in nitrogen. The coke produced using SCW also had lower H/C values and higher aromaticities. Judging from all the analytical results, the upgrading of bitumen by SCW reaction was primarily considered to be physical in nature. As a result, it is possible to highly disperse the heavy fractions by SCW. This dispersion effect of SCW led to intramolecular dehydrogenation of the heavier component and prevention of recombination reactions, and consequently gave the highest conversion.     

Colloidal monolayer titania quantum dots prepared by hydrothermal synthesis in supercritical water

Two-dimensional monolayer titania quantum dots (MTQDs) with ∼0.4 nm thickness and ∼2 nm lateral size are synthesized by supercritical water (SCW) treatment of titania nanotubes (TNTs). The morphology, chemical characteristics and the structure of MTQDs are studied. The formation mechanism of the MTQDs and the differences between SCW and low-temperature hydrothermal treatment are discussed. During the reaction, the high temperature, high pressure and high H⁺/OH⁻ concentration of SCW dissolved TNTs into MTQDs, and the intercalation property of the “active” water clusters formed from the broken hydrogen bonding network facilitated the detachment of the MTQDs from the TNTs. The above two reasons lead to the capture of the dissolved tiny particles, which could hardly preserved in low-temperature hydrothermal treatment. The MTQDs may be the minimum constituent unit existing in the reality of the anatase TiO₂. As a new member of the monolayer family, this new kind of 2D material may shed new light on the study of the monolayer materials.     

Formation of coke in thermal cracking of jet fuel under supercritical conditions

Continuous-flow reactor experiments were carried out to study coke formation from thermal cracking of home-made jet fuel RP-3 under supercritical conditions. The mechanism and precursor of coke forming were analyzed. The starting cracking temperature of RP-3 fuel was determined to be 471.8°C by differential scanning calorimetry (DSC). Temperature-programmed oxidation and scanning electron microscopy (SEM) characterizations of the stressed tubes showed that there are three different coke species including chemisorbed carbon, amorphous carbon and filamentous coke in the solid deposits. More than 90% of coke deposits are carried away by the supercritical fluid, which has strong capabilities of extraction for coke deposits and their precursors. There were 17.1 wt-% of iron and 11.1 wt-% of chromium found on the coke surface detected by energy dispersive spectroscopy (EDS) which suggests carburetion on alloy. RP-3 fuel and its cracking liquids were analyzed by GC-MS,which showed that the content of alkyl benzene and alkyl naphthalene increased evidently in cracking liquids.     

The pyrolysis of propane. I. Production of gases,liquids and carbon

Studies have been carried out on the formation of gases, tars and carbon from the pyrolysis of propane under conditions pertinent to steam cracking. Careful analysis has been carried out to relate the production of gases, liquids and solids in the presence and absence of hydrogen and helium diluents. The experimental observations agree with predictions of gas production from a mathematical model. The reactor surface is shown to influence the production of carbon and possibly the production of gases and tars. Minimisation of coke formation in steam cracking is shown to depend, at least in part, on the correct choice of material for reactor construction.     

玉米芯与羧甲基纤维素钠的超临界水气化制氢

采用Gibbs自由能最小原理,建立了生物质超临界水气化制氢的化学平衡模型。将该模型应用于玉米芯/羧甲基纤维素钠(CMC)的超临界水气化制氢,分析模拟和实验结果,得到反应温度对化学平衡产物的作用如下:在300—374℃的亚临界区,气体产物的摩尔分数排序为x(CO2)>x(CH4)>x(H2),在375—420℃的低温超临界区,气体产物排序为x(CO2)>x(H2)>x(CH4),在420℃以上的高温超临界区,H2摩尔分数跃居最高,可达65%以上。较高的反应温度有利于提高H2的摩尔分数和气化率,但降低了气体的高热值。获得玉米芯/CMC制氢的最佳温度范围为420—600℃。表明农业废弃物的超临界水气化制氢是一种极具发展前景的能源转化新技术。     

Comparison of YAG: Eu phosphor synthesized by supercritical water and solid-state methods in a batch reactor

Phosphor yttrium aluminum garnet (Y₃Al₅O₁₂, YAG) doped with Eu (10 at%) was synthesized by supercritical water (SCW) and solid-state methods in a batch reactor. The crystals, morphologies and luminescent properties of the phosphors obtained from different pH conditions in the SCW were studied. Pure YAG phase was successfully synthesized at the alkaline condition in the SCW without formation of intermediate phases, while the size and luminescent property of YAG: Eu were strongly affected by pH condition. The luminescent intensity of YAG: Eu by the SCW method without further thermal treatment is stronger than that by the solid-state method with thermal treatment.     

Pyrolysis of heavy oil in the presence of supercritical water: The reaction kinetics in different phases

In the presence of supercritical water (SCW) and N₂, the pyrolysis of heavy oil was investigated to distinguish the difference in the reaction kinetics between the upgrading in the SCW and oil phases. The pyrolysis in the SCW phase is faster than that in the oil phase, but the reaction in whichever phase is retarded by vigorous stirring. The pyrolysis can be preferably described by a four‐lump kinetic model consisting of the condensation of maltenes and asphaltenes in series. In the SCW phase, highly dispersed asphaltenes are isolated by water clusters from maltenes dissolved in SCW surroundings, by which the condensation of asphaltenes is drastically accelerated. Benefited from excellent mass transfer environments in SCW, the condensation of maltenes is promoted simultaneously. The introduction of SCW into the pyrolysis of heavy oil results in an effectively increased upgrading efficiency, but its influence on the properties of equilibrium liquid products is minor. © 2014 American Institute of Chemical Engineers AIChE J, 61: 857–866, 2015     

Corrosion of ceramics for vinasse gasification in supercritical water

Supercritical water gasification (SCWG) is a very efficient process to convert wet biomass into energetic gases. Unfortunately, SCWG reactor may strongly corrode due to the addition of temperature, pressure and the presence of corrosive species. In the present paper, the corrosion of various ceramic materials in subcritical and supercritical water (SCW) gasification process was studied in a batch reactor. We compare the corrosion in distillated water and the corrosion in sugar beet slurry that will be gasified under supercritical conditions. The experimental temperatures were 350 °C and 550 °C and the pressure was 25 MPa. Technical ceramics (SiC, alumina, Y stabilized zirconia, Si₃N₄, BN, aluminosilicate, cordierite-mullite) show poor capability to sustain corrosion whereas graphite and glassy carbon are the highest performance materials in our working conditions.     

Combustion of carbonized coal residue in a mixture of ammonium nitrate and supercritical water

The possibility of low-temperature oxidation of a solid carbonized coal residue in a mixture of NH₄NO₃ and supercritical water (723 K and 30 MPa) is shown for the first time and its mechanism is described. Conjugate processes of oxidation of the carbonized residue and formation of combustible gases H₂ and CH₄ caused by the participation of H₂O in redox reactions was found. It was established that the ash residue has a high porosity and consists of agglomerated nanoparticles of silicon and metal oxides.     

Experimental investigation of high-temperature coal tar upgrading in supercritical water

The upgrading of high-temperature coal tar in supercritical water (SCW) was investigated using an autoclave reactor. The effects of temperature (673–753 K), pressure (24–38 MPa) and residence time (1–80 min) on product distribution were studied. The yields and characteristics of products in SCW were compared with those obtained in N₂. In order to study the reaction mechanism of coal tar upgrading, the experiments of model compounds were carried out in SCW at 673 K and 34 MPa for 20 min. The results indicate that the asphaltene conversion and the maltene yield are significantly higher in SCW. The H/C atom ratios of oil obtained in SCW are higher than those obtained in N₂. More valuable aromatic compounds such as naphthalene, fluorene and anthracene are obtained in SCW. The results of model compounds suggest that water in SCW could participate in coal tar upgrading and promote the formation of light products.     

Formation of coke in thermal cracking of jet fuel under supercritical conditions

Continuous-flow reactor experiments were carried out to study coke formation from thermal cracking of home-made jet fuel RP-3 under supercritical conditions. The mechanism and precursor of coke forming were analyzed. The starting cracking temperature of RP-3 fuel was determined to be 471.8°C by differential scanning calorimetry (DSC). Temperature-programmed oxidation and scanning electron microscopy (SEM) characterizations of the stressed tubes showed that there are three different coke species including chemisorbed carbon, amorphous carbon and filamentous coke in the solid deposits. More than 90% of coke deposits are carried away by the supercritical fluid, which has strong capabilities of extraction for coke deposits and their precursors. There were 17.1 wt-% of iron and 11.1 wt-% of chromium found on the coke surface detected by energy dispersive spectroscopy (EDS) which suggests carburetionon alloy. RP-3 fuel and its cracking liquids were analyzed by GC-MS,which showed that the content of alkyl benzene and alkyl naphthalene increased evidently in cracking liquids. __________ Translated from Petrochemical Technology, 2006, 35(12): 1151–1155 [译自:石油化工]     

Catalytic cracking of n-dodecane over HZSM-5 zeolite under supercritical conditions: Experiments and kinetics

The catalytic cracking of n-dodecane over HZSM-5 zeolite catalyst was investigated at 400–450 °C under supercritical and subcritical pressures (0.1–4.0 MPa). The results show that both the activity of the catalyst and its stabilization towards deactivation decrease with increasing pressure, and the catalyst maintains substantially higher activity when feed rate exceeds 4.00 ml/min under supercritical conditions. A first-order Langmuir kinetic model with a novel decay function is developed for the supercritical catalytic cracking of hydrocarbon incorporating supercritical extraction effect on catalyst stability, which is satisfactory to describe the kinetic behaviors of catalytic cracking of supercritical n-dodecane. According to the estimated reaction rate and adsorption constant of n-dodecane on HZSM-5 at different temperature, the activation energy of 125.4 kJ/mol and adsorption heat 109.5 kJ/mol were calculated. An index of CRSE is proposed to define contribution ratio of supercritical extraction to the activity of the HZSM-5 catalyst in the developed kinetics model, and it is found that the CRSE increases with increasing hydrocarbon feed rates and decreasing catalytic activities, and reaches maximum value when the coke formation rate equals to the coke removal rate by supercritical hydrocarbon.     

醋酸钾对轻石脑油裂解结焦的影响

为考察碱金属元素对裂解结焦的影响,以醋酸钾为结焦抑制剂,在850℃下对退役25Cr35Ni炉管试样内表面进行了结焦实验。利用扫描电子显微镜(SEM)、场发射扫描电镜(FE-SEM)、能量色散谱仪(EDS）、X射线衍射(XRD)和Raman光谱对退役25Cr35Ni炉管试样内表面和焦层进行了表征。结果表明,退役25Cr35Ni炉管内表面主要由Cr_1.3Fe_0.7O₃相似文献   

Reductive atmosphere of supercritical water with RuO2 resulting in TcO2 colloid: Spectroscopic, morphological and crystallographic study on solutions and precipitates in Hastelloy C-22

In order to study the complicated behavior of technetium observed under various conditions of supercritical water (SCW), i.e. quantitative transfer to solid phase, strong adsorption onto the metal surface, or efficient dissolution from the metal surface, solutions and precipitates prepared in reactors made of Hastelloy C-22 in contact with the SCW containing technetium solutions were studied by absorption spectroscopy, TEM, EDX and electron diffraction. Under SCW with or without H₂O₂, NiCr₂O₄ and NiMoO₄ was produced as the scales (corrosion products) of Hastelloy C-22. Under SCW with RuO₂ the formation of colloidal structure comprised of ruthenium metal and TcO₂, which may be named as “Tc-Ru-Colloid”, were observed. It is worthy of note that the formation of TcO₄²⁻ from pertechnatate TcO₄⁻ (+0.596 V) and the disproportionation of TcO₄²⁻ is plausible at present in spite of the moderate reductive atmosphere (−0.533 to +0.114 V) estimated from the observation (the existence of TcO₂ and the absence of NiMoO₄) by TEM and electron diffraction.     

Comparison of YAG: Eu phosphors synthesized by supercritical water in batch and continuous reactors

Luminescent yttrium aluminum garnet (YAG, Y₃Al₅O₁₂) nanoparticles doped with Eu (10 at%) were synthesized in batch-type and continuous-type supercritical water (SCW) reactors. In the case of the continuous-type SCW method, the particles of YAG: Eu phosphors were much smaller and demonstrated a uniform spherical-like shape. Inversely, in the case of the batch-type SCW method, a needle-like or elliptical-like shape was formed because a finite amount of time was required to reach SCW conditions from ambient conditions. However, the emission intensity of YAG: Eu phosphors synthesized by using the batch-type SCW method was stronger. Therefore, it is concluded that the continuous-type SCW method is superior to the batch-type SCW method from the viewpoint of the particle size and shape, but the luminescence property of phosphors in the continuous-type SCW method needs to be improved. In addition, a calcination process slightly improved the luminescence intensities of YAG: Eu phosphors generated by using either the batch-type or continuous-type SCW methods.