Supercritical fluid extraction of bitumens from Utah oil sands

The supercritical fluid extraction (SFE) of bitumens from four major Uinta Basin (Utah) oil sand deposits was studied with propane solvent. The deposits studied included Whiterocks, Asphalt Ridge, PR Spring and Sunnyside. The bitumens from these deposits differed widely in physical and chemical properties. The volatilities (components with boiling point <811 K) were 46.6, 53.5, 45.4 and 40.9 wt.%; the molecular weights were 653, 426, 670 and 593 kg/kg mol; and the asphaltene contents (n-pentane insolubles) were 2.9, 6.8, 19.3 and 23.6 wt.% for the Whiterocks, Asphalt Ridge, PR Spring and Sunnyside bitumens, respectively. The SFE experiments were carried out at five conditions, combinations of three different pressures (5.6 MPa, 10.4 MPa, and 17.3 MPa) and three temperatures (339 K, 380 K and 422 K). The cumulative extraction yield increased with increase in solvent density at all operating conditions for the four bitumens. A maximum yield of 45 wt.% was obtained at the highest solvent density with the Whiterocks bitumen. The extraction products were significantly upgraded liquids relative to the bitumens. Comparatively lighter fractions were extracted in the earlier stages of extraction for all the four bitumens, whereas heavier extracts were obtained at higher extraction-solvent densities. The asphaltene contents of the residual fractions were significantly higher than the asphaltene contents predicted on a prorated basis for all four bitumens. This trend was due to the extraction of cosolubilizing components that kept the asphaltenes in suspension in the bitumen. It was concluded that solute polarity played a significant role in the extraction yields of the four bitumens. The Whiterocks bitumen, which was the least polar bitumen based on asphaltenes content, gave higher extraction yields compared to the bitumens from the other three deposits at all five operating conditions. The Sunnyside bitumen with the highest asphaltene content gave the lowest extraction yield at all five conditions. The Asphalt Ridge and PR Spring bitumens with intermediate polarity (based on asphaltene content) gave intermediate extraction yields with the Asphalt Ridge bitumen extraction yields higher than the PR Spring bitumen. Preliminary modeling of the extraction process using the Peng–Robinson cubic equation of state and a pseudocomponent lumping scheme provided a reasonable match with the experimental data for Whiterocks and PR Spring bitumens.     

Supercritical Carbon Dioxide Extraction of <Emphasis Type="Italic">Microula sikkimensis</Emphasis> Seed Oil

The seed oil of Microula sikkimensis had been intensively studied due to its pharmacological actions. In the present study, seed oil of Microula sikkimensis was extracted using supercritical fluid extraction (SFE). Determinations of the extracts composition were performed by gas chromatography (GC). An orthogonal array design (OAD), OA₉ (3⁴), was employed for optimization of the supercritical fluid extraction of the compound with regard to the various parameters. Four factors, namely pressure (21.0–27.0 MPa), the dynamic extraction time, temperature, and CO₂ flow rate of the supercritical fluid, were studied and optimized by a three-level OAD. The effects of the parameters on the yield of seed oil were studied using analysis of variance (ANOVA). The results revealed that the pressure had a significant effect on the yield of seed oil (p < 0.05), while the other three factors, i.e., CO₂ flow rate, dynamic extraction time and temperature, were not identified as significant factors under the selected conditions based on ANOVA. The results show that the best values for the extraction condition of seed oil was pressure 24.0 MPa, extraction time 3 h, temperature 45 °C and a CO₂ flow rate 20 L/h in the 20-L vessel.     

Furfural production by acid hydrolysis and supercritical carbon dioxide extraction from rice husk

The aim of this research was to study the effect of furfural production from rice husk by hydrolysis accompanying supercritical CO₂ (SC-CO₂) extraction. The two-level fractional factorial design method was used to investigate the production process carried out with respect to furfural yield. The process variables are temperature range of 373–453 K, pressure 9.1–18.2 MPa, CO₂ flow rate 8.3 × 10⁻⁵–1.7 × 10⁻⁴ kg/s (5–10 g/min), sulfuric acid concentration 1 to 7 (%wt) and ratio of liquid to solid (L/S) 5 : 1 to 15 : 1 (vol/wt). The results obtained from the experimental design showed that increasing temperature, pressure, CO₂ flow rate and sulfuric acid concentration but decreasing ratio of liquid to solid would improve furfural yield. Moreover, furfural production by two-stage process (pre-hydrolysis and dehydration) can improve furfural yield further to be around 90% of theoretical maximum.     

Effect of temperature on bitumen conversion in a supercritical water flow

This article deals with a study of bitumen conversion (the gross-formula CH_1.47N_0.01S_0.007) in a supercritical water (SCW) flow continuously supplied at the bottom of the vertically located tubular reactor. At the first stage, bitumen was continuously supplied from the top of the reactor into a counter-current SCW flow (400 °C, 30 MPa) for 60 min. At the second stage (after ceasing the supply of bitumen into the reactor), SCW was pumped through the layer of bitumen residue at uniform (2.5 °C/min) temperature increase from 400 to 700 °C at 30 MPa. The amount and composition of the liquid and volatile conversion products were measured. It is revealed that during bitumen supply into the reactor and subsequent pumping of SCW through the layer of bitumen residue in the temperature increasing mode from 400 to 500 °C, the yields of liquid conversion products are equal to 26.9 and 45.4%, respectively, relative to the weight of bitumen supplied into the reactor. Oils are the major components of these liquid products. Participation of H₂O molecules in redox reactions became evident due to the formation of CO and CO₂ even at 400 °C. A significant increase in the yields of H₂, CH₄, and CO₂ are detected at T > 600 °C. Based on the sulfur balance, it can be stated that the degree of bitumen desulfurization at 400–700 °C due to sulphur removal in form of H₂S accounts for 21.6 wt.% A solid carbonaceous bitumen residue, obtained after SCW conversion, is characterized by high specific surface (224 m²/g).     

Oxidation of a coal particle in flow of a supercritical aqueous fluid

A study was made of the conversion of single spherical coal particles of diameter 1–5 mm in a supercritical H₂O/O₂ fluid with an oxygen mass fraction of 0–6.6% in a semibatch reactor at a pressure of 30 MPa and a temperature of 673–1023 K. A decrease in the particle mass was observed in two parallel processes: gasification of coal with water and oxidation of coal with oxygen. An activation energy 19 ± 7 kJ/mole and a pre-exponential factor 10^−2±0.4 sec⁻¹ were obtained under the assumption of zero order for the concentration H₂O and an Arrhenius dependence for the rate of gasification with water. The oxidation with oxygen at a temperature above 780 K was found to be limited by the rate of O₂ diffusion to the coal organic matter. Below 780 K, the rate of heterogeneous oxidation with oxygen is described by a first-order reaction for the concentration of O₂ and a zero-order reaction for the concentration of H₂O with an activation energy of 150 ± 27 kJ/mole and a pre-exponential factor of 10^7.6±1.9 cm³/(g · sec). __________ Translated from Fizika Goreniya i Vzryva, Vol. 44, No. 2, pp. 23–31, March–April, 2008.     

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.     

Response Surface Analysis and Modeling of Flaxseed Oil Yield in Supercritical Carbon Dioxide

Supercritical fluid extraction of flaxseed oil with carbon dioxide was performed. Effects of particle size, pressure, temperature and the flow rate of supercritical carbon dioxide (SC-CO₂) were investigated. Response surface methodology was used to determine the effects of pressure (30–50 MPa), temperature (50–70 °C) and SC-CO₂ flow rate (2–4 g/min) on flaxseed oil yield in SC-CO₂. The oil yield was represented by a second order response surface equation (R ² = 0.993) using the Box-Behnken design of experiments. The oil yield increased significantly with increasing pressure (p < 0.01), temperature (p < 0.05) and SC-CO₂ flow rate (p < 0.01). The maximum oil yield from the response surface equation was predicted as 0.267 g/g flaxseed for 15 min extraction of 5 g flaxseed particles (particle diameter <0.850 mm) at 50 MPa pressure and 70 °C temperature, with 4 g/min solvent flow rate. Total extraction time at these conditions was predicted as 22 min.     

Supercritical Carbon Dioxide Extraction and Characterization of Argentinean Chia Seed Oil

Extraction of chia seed oil was performed with supercritical carbon dioxide (SC-CO₂). To investigate the effects of pressure and temperature on the oil solubility and yield, two isobaric (250 and 450 bar) and two isothermal (40 and 60 °C) extraction conditions were selected. The global extraction yield of chia oil increased with pressure enhancement, but temperature had a little influence on it. The maximum oil recovery using SC-CO₂ at a mass flow rate of 8 kg/h was 97%, which was obtained at 60 °C, 450 bar for a 138-min extraction. The results showed that solubility changed from 4.8 g oil/kg CO₂ at 60 °C–250 bar to 28.8 g oil/kg CO₂ at 60 °C–450 bar. The final extract obtained by SC-CO₂ under different conditions and Soxhlet extraction contained mainly α-linolenic (64.9–65.6%) and linoleic (19.8–20.3%) acids. SC-CO₂ extraction is an interesting alternative methodology because it is possible to achieve a chia oil yield close to that obtained by conventional extraction with a similar fatty acid composition using an environmentally friendly process.     

Supercritical carbon dioxide extraction of fatty and waxy material from rice bran

Waxy and fatty materials were removed from rice bran by supercritical carbon dioxide at pressures up to 28 MPa and temperatures between 40 and 70°C. The yields of the supercritical extraction were only 16–60% of those obtained by Soxhlet extraction with hexane. The highest yield was reached at the highest pressure and temperature used (28 MPa and 70°C), indicating that supercritical extraction of this lipid-bearing material could probably be improved at more severe extraction conditions. The supercritical extract obtained at operational conditions giving high yield was chromatographically characterized. Compared to the hexane extract, the supercritical extract was lighter in color and richer in wax content and long-chain fatty acids C₂₀−C₃₄. Triacontanol was the most abundant alcohol in both extracts. Tocopherol contents were similar.     

Comparison of supercritical fluid and solvent extraction methods in extracting γ-oryzanol from rice bran

Organic solvents were compared with supercritical CO₂ relative to efficiency for extracting lipid and γ-oryzanol from rice bran. A solvent mixture with 50% hexane and 50% isopropanol (vol/vol) at a temperature of 60°C for 45–60 min produced the highest yield (1.68 mg/g of rice bran) of γ-oryzanol among organic solvents tested. The yield of γ-oryzanol without saponification was approximately two times higher (P<0.05) than that with saponification during solvent extraction. However, the yield (5.39 mg/g of rice bran) of γ-oryzanol in supercritical fluid extraction under a temperature of 50°C, pressure of 68,901 kPa (680 atm), and time of 25 min was approximately four times higher than the highest yield of solvent extraction. Also, a high concentration of γ-oryzanol in extract (50–80%) was obtained by collecting the extract after 15–20 min of extraction under optimized conditions.     

Extraction of lignite with water in sub- and supercritical states

On a semi-continuous apparatus, Dayan lignite was extracted with water in sub- and supercritical states. The experiments were carried out to investigate the effect of temperature on extract formation rate, extract yields and product components at different pressures and end temperatures. The results indicated that the extract formation rate has a maximum with the variation of temperature. The temperature corresponding to the maximum extract formation rate, changing with the pressure, is between 400 and 450°C. The extraction yields vary with the conditions. With the increase of pressure, the conversion and extract yield increase. With the increase of end temperature, the conversion also increases, but the increment is mainly gas and light oil. The main fraction in extract is preasphaltene and the main gas component is CO₂.     

Influence of operating variables on yield and quality parameters of olive husk oil extracted with supercritical carbon dioxide

Supercritical fluid extraction is a viable alternative process for extracting oil from olive husk, a residue obtained in the olive oil production. We analyzed the effects of pressure (P) (100–300 bar), temperature (T) (40–60°C), solvent flow (1–1.5 L/min), and particle size (D) (0.30–0.55 mm) on extraction yield, and three oil-quality parameters: acidity (OA), PV, and phosphorus content (PC). A response surface methodology based on the statistical analysis of the experimental data permitted us to obtain mathematical expressions relating the operational variables and parameters studied. At the best extraction condition of the experimental range analyzed (P=300 bar, T=60°C, D=0.30 mm, and solvent flow=1.25 L/min at standard conditions), the oil yield was 80% (w/w) with respect to hexane extraction, whereas the quality parameters OA, PV, and PC were 14% (w/w), 8 meq/kg, and 2.3·10⁻³% (w/w), respectively. These results were compared to those obtained by hexane Soxhlet extraction. The quality of the supercritical extract was superior, requiring only simple refining. This advantage may result in improved economics of the supercritical process in relation to the conventional extraction with hexane.     

Fractionation of peat-derived bitumen into oil and asphaltenes

As a continuation of our previous work on the conversion of peat, we have studied the composition of the bitumens obtained through primary hydrogenation with carbon monoxide in the presence of water as the liquid medium. The proportion of oils in the bitumen varies considerably, between 30 and 60%, as a function of the experimental conditions chosen. CO is preferred over H₂ as the hydrogenating gas. Temperature is the most important single variable, with 350–375 ° C as a suitable range for the conversion. Li₂CO₃ favours significantly the conversion to oils even if K₂CO₃ results in a higher bitumen yield. High CO pressures, surprisingly, lower the oil fraction in the bitumen.     

Effect of Zr/Si molar ratio and sulfation on structural and catalytic properties of ZrO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript> mixed oxides

ZrO₂–SiO₂ mixed xerogel and aerogel samples with varied molar ratios were prepared by sol–gel method followed by oven drying and supercritical drying using n-propanol as a solvent, respectively. Sulfation was carried out to further enhance the acidic properties of the mixed oxides. Effect of drying, Zr/Si molar ratio and sulfation have been studied and correlated with the structural, textural and catalytic properties of ZrO₂–SiO₂ mixed oxides. Both xerogel and aerogel mixed oxides have different structural and textural features, however, the total number of acid sites per unit surface area (0.0021–0.0029 mmol NH₃ m⁻²) and thus the catalytic activity for cyclohexanol conversion (31–41%) was found in the similar range. Sulfated mixed oxide aerogel and xerogel samples showed significant enhancement of cyclohexanol conversion (91–99%).     

Gasification of an Indonesian subbituminous coal in a pilot-scale coal gasification system

Indonesian Roto Middle subbituminous coal was gasified in a pilot-scale dry-feeding gasification system and the produced syngas was purified with hot gas filtering and by low temperature desulfurization to the quality that can be utilized as a feedstock for chemical conversion. Roto middle coal produced syngas that has a typical composition of 36–38% CO, 14–16% H₂, and 5–8% CO₂. Particulates in syngas were 99.8% removed by metal filters at the operating temperature condition of 200–250°C. Sulfur containing compounds of H₂S and COS in syngas were also desulfurized in the Fe chelate system to yield less than 0.5 ppm level. The full stream gasification and syngas purifying system has been successfully operated and thus can provide clean syngas for the research on the conversion of syngas to chemicals like DME and on the future IGFC using fuel cells. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Lipase-catalyzed hydrolysis of canola oil in supercritical carbon dioxide

The effect of pressure, temperature, and CO₂ flow rale on the extent of conversion and the product composition in the enzyme-catalyzed hydrolysis of canola oil in supercritical carbon dioxide (SCCO₂) was investigated using lipase from Mucor miehei immobilized on macroporous anionic resin (Lipozyme IM). Reactions were carried out in a continuous flow reactor at 10, 24, and 38 MPa and 35 and 55°C. Supercritical fluid chromatography was used to analyze the reaction products. A conversion of 63–67% (triglyceride disappearance) was obtained at 24–38 MPa. Mono-and diglyceride production was minimum at 10 MPa and 35°C. Monoglyceride production was favored at 24 MPa. The amount of product obtained was higher at 24–38 MPa due to enhanced solubility in SCCO₂. Complete hydrolysis of oil should be possible by increasing the enzyme load and/or decreasing the quantity of the oil substrate. There was a drop in triglyceride conversion over a 24-h reaction time at 38 MPa and 55°C, which may be an indication of loss of enzyme activity. Pressure, temperature, and CO₂ flow rate are important parameters to be optimized in the enzyme-catalyzed hydrolysis of canola oil in SCCO₂ to maximize its conversion to high-value products.     

Conversion of oils to monoglycerides by glycerolysis in supercritical carbon dioxide media

Glycerolysis of soybean oil was conducted in a supercritical carbon dioxide (SC-CO₂) atmosphere to produce monoglycerides (MG) in a stirred autoclave at 150–250°C, over a pressure range of 20.7–62.1 MPa, at glycerol/oil molar ratios between 15–25, and water concentrations of 0–8% (wt% of glycerol). MG, di-, triglyceride, and free fatty acid (FFA) composition of the reaction mixture as a function of time was analyzed by supercritical fluid chromatography. Glycerolysis did not occur at 150°C but proceeded to a limited extent at 200°C within 4 h reaction time; however, it did proceed rapidly at 250°C. At 250°C, MG formation decreased significantly (P<0.05) with pressure and increased with glycerol/oil ratio and water concentration. A maximum MG content of 49.2% was achieved at 250°C, 20.7 MPa, a glycerol/oil ratio of 25 and 4% water after 4 h. These conditions also resulted in the formation of 14% FFA. Conversions of other oils (peanut, corn, canola, and cottonseed) were also attempted. Soybean and cottonseed oil yielded the highest and lowest conversion to MG, respectively. Conducting this industrially important reaction in SC-CO₂ atmosphere offered numerous advantages, compared to conventional alkalicatalyzed glycerolysis, including elimination of the alkali catalyst, production of a lighter color and less odor, and ease of separation of the CO₂ from the reaction products.     

Effect of mineral matter on product yield in supercritical water extraction of lignite at different temperatures

The effect of demineralization on conversion of Soma Lignite in supercritical water extraction was studied using a batch autoclave operated at 400, 450 and 500 °C under nitrogen atmosphere. The experiments were carried out to investigate the effect of mineral matter and temperature on gaseous, liquid, residue yield and composition of gaseous products. According to the results, main product in gaseous state is CO₂. Temperature is key factor affecting product distribution when compared the effect of minerals in lignite. As temperature was increased, yield of gas and solid residue increased, while yields of liquid decreased for raw and demineralized lignite samples. The removal of mineral matter caused to decrease the conversion for all lignite samples and to increase the carbon content of solid residue in supercritical water extraction.     

Filamentous carbon templated SiO2–NiO aerogel: structure and catalytic properties for direct oxidation of hydrogen sulfide into sulfur

Silica aerogels comprising nickel oxide nanoparticles were synthesized with no use of supercritical drying. A high specific surface area (more than 1000 m²/g), mesoporous structure and considerable stability to sintering up to 900 °C are characteristic of these aerogels. The aerogels were synthesized using the sol–gel method. Filamentous carbon was templated by silica, tetraethoxysilane being used for supplying silica. Carbon was burnt later. Analysis of the aerogel structure revealed the presence of silica nanotubes and nanofibers. Aerogel testing for direct oxidation of H₂S into S⁰ demonstrated as high as 60% conversion of hydrogen sulfide at almost 100% selectivity under stoichiometric conditions at the temperature range of 300–350 °C and 73% conversion at 100% selectivity at a considerable excess of oxygen at 160 °C. This revised version was published online in July 2006 with corrections to the Cover Date.     

Characterization of oil including astaxanthin extracted from krill (Euphausia superba) using supercritical carbon dioxide and organic solvent as comparative method

Krill oil including astaxanthin was extracted using supercritical CO₂ and hexane. The effects of different parameters such as pressure (15 to 25MPa), temperature (35 to 45 °C), and extraction time, were investigated. The flow rate of CO₂ (22 gmin⁻¹) was constant for the entire extraction period of 2.5 h. The maximum oil yield was found at higher extraction temperature and pressure. The oil obtained by SC-CO₂ extraction contained a high percentage of polyunsaturated fatty acids, especially EPA and DHA. The acidity and peroxide value of krill oil obtained by SC-CO₂ extraction were lower than that of the oil obtained by hexane. The SC-CO₂ extracted oil showed more stability than the oil obtained by hexane extraction. The amount of astaxanthin in krill oil was determined by HPLC and compared at different extraction conditions. The maximum yield of astaxanthin was found in krill oil extracted at 25 MPa and 45 °C.