Partial oxidation of alkanes to oxygenates in supercritical carbon dioxide

The catalytic partial oxidation of propane in supercritical carbon dioxide has been investigated in a stirred batch reactor. Various metals (oxides) have been used as supported catalysts with respect to their activity and selectivity for the formation of oxygenates. The reactions run with a 1:2.3–2.9:68–108 molar ratio of propane:synthetic air:CO₂ at 453–573 K and 80–100 bar. Using a precipitated 2.4 wt.% Co₃O₄–SiO₂ catalyst at 573 K, a total oxygenate (i.e. acetic acid, acetone, acetaldehyde, methanol) selectivity of 59% and a propene selectivity of 21% were obtained at a propane conversion of 12 mol%. The same catalyst has been used to investigate the influence of the supercritical conditions and initial feed composition on the reaction, varying the density of CO₂ and the concentration of synthetic air, respectively.     

Partial oxidation of propane in compressed carbon dioxide using CoOx/SiO2 catalysts

The application of compressed carbon dioxide as an alternative reaction medium was investigated for the heterogeneously catalysed partial oxidation of propane. The catalytic tests were performed in a stirred batch as well as in a continuous flow reactor at 553–623 K, 2.6–11.3 MPa and a CO₂:synthetic air:propane molar ratio of 94–124:4–7:1 using precipitated CoO_x/SiO₂ (2.4–3.7 wt.% Co) catalysts. In addition, the critical temperature and pressure of the reaction mixture were determined by the opalescence method in a high-pressure optical cell. The catalytic experiments revealed a significantly higher cumulative oxygenate selectivity (i.e. acetic acid, methanol, acrolein, acetone) with increasing pressure. It is supposed that the formed oxygenates were removed more easily from the catalyst surface without being totally oxidised due to the higher solvent power of the dense CO₂ in the supercritical phase.     

超临界二氧化碳和醇类体系的相平衡计算

应用Peng-Robinson(P-R)状态方程对超临界CO2系统进行了相平衡模拟。对超临界CO2和醇类二元系统进行了汽液相平衡计算,结果表明,P-R状态方程模拟高压下CO2系统的相平衡具有较高的精度。     

Ring hydrogenation of naphthalene and 1-naphthol over supported metal catalysts in supercritical carbon dioxide solvent

Catalytic ring hydrogenations of naphthalene and 1-naphthol were studied over several supported metal catalysts in supercritical carbon dioxide solvent at low temperature. Higher concentration of hydrogen in supercritical carbon dioxide and lower reaction temperature were responsible for higher catalyst activity and selectivities to the desired partial ring hydrogenated products as compared with those observed in organic solvent for the same catalyst.     

Hydrodeoxygenation of guaiacol on noble metal catalysts

Hydrodeoxygenation (HDO) performed at high temperatures and pressures is one alternative for upgrading of pyrolysis oils from biomass. Studies on zirconia-supported mono- and bimetallic noble metal (Rh, Pd, Pt) catalysts showed these catalysts to be active and selective in the hydrogenation of guaiacol (GUA) at 100 °C and in the HDO of GUA at 300 °C. GUA was used as model compound for wood-based pyrolysis oil. At the temperatures tested, the performance of the noble metal catalysts, especially the Rh-containing catalysts was similar or better than that of the conventional sulfided CoMo/Al₂O₃ catalyst. The carbon deposition on the noble metal catalysts was lower than that on the sulfided CoMo/Al₂O₃ catalyst. The performance of the Rh-containing catalysts in the reactions of GUA at the tested conditions demonstrates their potential in the upgrading of wood-based pyrolysis oils.     

Polymerization of acrylonitrile in supercritical carbon dioxide

A series of fluorinated diblock copolymers, consisting of styrene (St)-acrylonitrile (AN) copolymer [poly(St-co-AN)] and poly-2-[(perfluorononenyl)oxy]ethyl methacrylate, with various compositions as well as with different molecular weights were synthesized by atom transfer radical polymerization and characterized. Dispersion polymerization of acrylonitrile in supercritical carbon dioxide (scCO₂) at 30 MPa and at 65 °C with this kind of amphiphilic block copolymer as a stabilizer and 2,2′-azobisisobutyronitrile as an initiator was investigated. The experimental results indicated that, in the presence of a small amount of poly(St-co-AN) (5 wt% to AN), spherical particles of polyacrylonitrile (PAN) were prepared with small diameter and narrow polydispersity (d_n = 153 nm, d_w/d_n = 1.12), resulting from the high stabilizing efficiency of this fluorinated block copolymer. Furthermore, the polymerization of AN in scCO₂ under different initial pressures especially under low pressure (<14 MPa) was studied. When the polymerization was carried out around the critical pressure of CO₂ (7.7-7.8 MPa), the PANs with high molecular weight (M_ν ≈ 130,000-194,000) were synthesized at high monomer conversion (>90%) no matter whether the stabilizer was added, compared to those synthesized by dispersion polymerization at 30 MPa. It was also found that the crystallinity of PAN synthesized at 7.7-7.8 MPa was somewhat higher than that synthesized at 30 MPa, while its crystallite size did not change.     

Combined CO2 reforming and partial oxidation of n-heptane on noble metal zirconia catalysts

The combined CO₂ reforming and partial oxidation (POX) of n-heptane was studied on various noble metal zirconia catalysts between 700 and 900 °C. The activity order of the metals was Rh > Pd > Ir > Pt. Selectivity to syngas increased with the activity of the catalysts but the H₂ to CO molar ratio decreased. The activity and selectivity of the 0.25 wt% Rh/ZrO₂ catalyst were close to the performance of a commercial 15 wt% NiO/Al₂O₃ catalyst. The conversions and product compositions were compared to the calculated thermodynamic equilibria.     

Acetylation of plant cellulose fiber in supercritical carbon dioxide

Natural cellulosic ramie fiber was acetylated using supercritical carbon dioxide (sc-CO₂) as a reaction medium. The structure and properties of the acetylated fibers were investigated using infrared spectroscopy, scanning electron microscopy, X-ray diffraction (including synchrotron microbeam X-ray diffraction), nano-Raman scattering, and a tensile test. The acetylation reaction proceeded without using an organic solvent, and it reached to the core part of the fiber within a short period while maintaining the fiber morphology. The crystallites of cellulose triacetate II and cellulose coexist in the fiber. The acetylated fiber with an average degree of substitution of 1.9 showed high modulus (34.5 GPa) and high strength (763 MPa), which are the highest values for cellulose diacetate so far reported to date.     

Selective oxidation of cyclohexane in supercritical carbon dioxide

A feasibility study into the novel concept of using molecular oxygen to carry out one-step catalytic oxidation of cyclohexane to adipic acid in supercritical carbon dioxide over two types of catalysts, namely and Ag polyoxometallate, the silver decamolybdodivanadophosphate was carried out. Poor activity and selectivity towards adipic acid were initially noted over the aqueous micellar catalyst for the cyclohexane oxidation in supercritical carbon dioxide while under comparable conditions, the same catalyst gave a high activity for alkylaromatics oxidation to corresponding acids. It was later found that the adipic acid, being the extremely polar oxidised products, was virtually insoluble in the supercritical phase, which was rapidly degraded to carbon oxides after its prolonged contact with catalyst and O₂. Thus, the one-step cyclohexane oxidation to adipic acid with good selectivity can only be achieved by modifying the solvent with acetic acid or methanol, which enabled isolation of the acid from further oxidation. On the other hand, , in methanol modified supercritical carbon dioxide gave an impressive selectivity for cyclohexane conversion to other oxygenates.     

Solubility of chlorpheniramine maleate in supercritical carbon dioxide

Solubility of chlorpheniramine maleate in supercritical carbon dioxide at different temperatures (308–338 K) and pressures (160–400 bar) is measured using static method coupled with gravimetric method. The measured solubility data demonstrated that the solubility of chlorpheniramine maleate was changed between 1.54 × 10⁻⁵ and 4.26 × 10⁻⁴ based on the mole fraction as the temperature and pressure are changed. The general trend of measured solubility data shows a direct effect of pressure and temperature on the solubility of chlorpheniramine maleate. Finally, the obtained solubilities correlated using four semi-empirical density-based correlations including Mendez Santiago–Teja (MST), Kumar and Johnston (KJ), Bartle et al., and Chrastil models. Although the results of modeling showed that the KJ model leads to the average absolute relative deviation percent (AARD %) of 8.1% which is the lowest AARD %, deviation of other utilized correlations are rather the same.     

Catalyst retention in continuous flow with supercritical carbon dioxide

This review discusses the retention of organometallic catalysts in continuous flow processes utilizing supercritical carbon dioxide. Due to its innovative properties, supercritical carbon dioxide offers interesting possibilities for process intensification. As a result of safety and cost considerations, processes that use supercritical carbon dioxide are preferably done in continuous flow, as they require a pressure upwards of 74 bar. Many of the reactions that benefit from the application of supercritical carbon dioxide also involve the use of a homogeneous catalyst however, requiring efforts to recycle the catalyst when these are applied in continuous flow. Alternatively, the catalyst may be retained in the reactor by modifying the process or catalyst, such as by catalyst immobilization, membrane separation, or biphasic processing exploiting the properties of supercritical carbon dioxide. Each of these methods is discussed, including their advantages and drawbacks. Also discussed are milli- and micro-flow processes and their possibilities for integrated catalyst retention and handling supercritical carbon dioxide.     

Cross-linking polymerization of acrylic acid in supercritical carbon dioxide

Cross-linking polymerization of acrylic acid in supercritical carbon dioxide (scCO₂) was studied in a batch reactor at 50 °C and 207 bar with either triallyl pentaerythritol ether or tetraallyl pentaerythritol ether as the cross-linker and with 2,2′-azobis(2,4-dimethyl-valeronitrile) as the free radical initiator. All polymers were white, dry, fine powders. Scanning electron microscopy showed that the morphology of the polymer particles was not affected by cross-linking. As the cross-linker concentration was increased, the polymer glass transition temperature first decreased, then increased. Water-soluble and water-insoluble polymers were synthesized by adjusting the cross-linker concentration. Viscosity measurements showed that the polymer thickening effect strongly depended on the degree of cross-linking. Finally, cross-linking polymerization of acrylic acid in scCO₂ was carried out in a continuous stirred tank reactor. The use of cross-linker decreased the monomer conversion in this system.     

超临界二氧化碳发泡EPDM/LDPE热塑性弹性体微孔泡沫

本文通过熔融共混制得了EPDM/LDPE热塑性弹性体,压制标准试样,然后使用超临界二氧化碳作为发泡剂在高压反应釜中进行物理发泡。通过万能拉力机测试了弹性体力学性能,用扫描电镜观察了拉伸断面和泡孔的微观结构。结果表明：DCP硫化体系的热塑性弹性体的综合力学性能要优于硫黄硫化体系,随着硫化剂用量的增多,拉伸强度和撕裂强度有一个最大值,硬度上升;橡塑比在4:6时,力学性能达到最佳,最大拉伸强度为7.5MPa,最大撕裂强度为27.6MPa。扫描电镜观察其拉伸断面形貌,表明EPDM橡胶相与LDPE塑料相呈现“海-岛”两相微观结构;泡孔大小均匀性较好,成功制备了微米级微孔泡沫且泡孔大小分布均匀。     

SC-CO_2氛围中制备Ni/CNTs催化剂催化性能研究

碳纳米管负载金属镍催化剂可以用于甲醇常压气相羰基化反应,但是甲醇转化率及乙酸收率均不理想。本文在SC-CO2氛围中,利用SC-CO2在碳纳米管中较高的扩散性能,将金属镍粒子带入碳纳米管内腔,以提高金属镍在载体表面的分散度,从而提高催化剂的催化性能。结果显示,此法制备出的催化剂,其甲醇转化率及乙酸收率均比由普通浸渍法制备的催化剂显著提高;制备催化剂时SC-CO2最佳温度为308.15 K,最佳压强为15.0 MPa。     

Noble metal catalysed aerial oxidation of alcohols to aldehydes in supercritical carbon dioxide

Platinum and palladium supported on carbons are shown to be excellent catalysts for selective oxidation of organic alcohols to aldehydes (>99%) at high yields using dioxygen as an oxidant in supercritical CO₂ fluid medium. There is no detectable over-oxidation of the product to acid and no metal leaching that are commonly encountered in the conventional aqueous medium. It is also found that the hydrophobicity/hydrophilicity of the catalyst surface relative to the CO₂ solvent plays a crucial role in the resulting catalytic activity and stability. Adding 1% Teflon onto the noble metal–carbon catalysts dramatically enhances the activity and lifetime of the catalysts during the aerial oxidation of fine chemicals in scCO₂ fluid.     

Solubility and partial molar volume of N,N-dimethylformamide diethyl acetal in supercritical carbon dioxide: Measurement and correlations

The solubilities of N,N-dimethylformamide diethyl acetal were measured at temperatures ranging from 313 to 353 K and pressures from 7.8 to 13.3 MPa in supercritical carbon dioxide. The measured solubility data were correlated using the Chrastil, Sung and Shim (SS), and Jouyban–Chan–Foster (JCF) semiempirical models. Consequently, the calculated results showed satisfactory agreement with experimental data and differed from the measured values by between 4.56 and 6.10%. The correlated results indicated that the JCF model provided the best fitness. Solubility data were also utilized to estimate the partial molar volume for the compound in the supercritical phase using the theory developed by Kumar and Johnston.     

Selective oxidation of cyclohexane in supercritical carbon dioxide over CoAPO-5 molecular sieves

A series of cobalt-incorporated aluminophosphates (CoAPO-5) with different Co contents were hydrothermally synthesized. The tetrahedral Co²⁺ in the lattice framework was evidenced by various spectroscopic characterizations, which could be partially oxidized to Co³⁺ to form redox centers upon calcination. Over CoAPO-5, the selective oxidation of cyclohexane was carried out with CO₂ as an additional solvent under supercritical conditions, where the different phase regions were categorized by the critical properties of the nominal reacting mixture (cyclohexane + nitrogen + carbon dioxide + cyclohexanol + cyclohexanone + water) that varies with the reaction extent. The results indicated that CoAPO-5 is an effective catalyst for the selective oxidation of cyclohexane to cyclohexanol and cyclohexanone; in the compressed CO₂, the total selectivity of objective products increased and the by-products were suppressed considerably. The conversion of cyclohexane decreased, while the selectivity to cyclohexanol and cyclohexanone increased with the increase of the apparent density.     

Effect of supercritical carbon dioxide on polystyrene extrusion

A study on the extrusion of polystyrene was carried out using supercritical carbon dioxide (scCO₂) as foaming agent. scCO₂ modifies the rheological properties of the material in the barrel of the extruder and acts as a blowing agent during the relaxation at the passage through the die. For experiments, a single-screw extruder was modified to be able to inject scCO₂ within the extruded material. The effect of operating parameters on material porosity was studied. Samples were characterized by using water-pycnometry, mercury-porosimetry and scanning electron microscopy. Polystyrene with expansion rate about 15–25% was manufactured. A rapid cooling just downstream the die is important to solidify the structure. The die temperature allows the control of the porosity structure. CO₂ concentration shows no significant influence.     

Ignition in alkane oxidation on noble-metal catalysts

The ignition behavior in the oxidation of four simple alkanes (methane, ethane, propane and isobutane) with air on a platinum-foil catalyst, as well as that of ethane/air mixtures on four noble-metal foil catalysts (Pt, Pd, Rh, and Ir) was studied at atmospheric pressure over the entire range of fuel-to-air ratios. While, Pd showed the widest range of surface flammability, ignition temperatures for ethane/air mixtures were lowest on Pt. Both, Rh and Ir deactivated rapidly under fuel-lean conditions and ignited considerably higher than Pd and Pt. The surface ignition temperatures were found to correlate well with the C–H bond energy of the hydrocarbon and the metal-oxygen bond energy of the noble metal. A very simple analytical model was able to reproduce the dependence of surface ignition temperatures on fuel-to-air ratios, yielding apparent activation energies for the surface reactions and indicating an oxygen-covered surface before catalytic ignition due to strong site competition between the hydrocarbon and oxygen on the catalyst surface.     

Foam processing of poly(ethylene-co-vinyl acetate) rubber using supercritical carbon dioxide

Soft rubber foams like poly(ethylene-co-vinyl acetate) (EVA) are industrially applied in a broad range of products, including sports gear, insulation materials and drug delivery systems. In contrast to glassy polymers, few studies in literature concern the foaming of soft rubbers using supercritical carbon dioxide. In this study, open microporous matrices of EVA have been formed with CO₂. Prior to the foam expansion, sorption and swelling isotherms of CO₂ in EVA have been measured and the obtained isotherms have been correlated using the Sanchez-Lacombe equation of state. Additionally, a pressure-independent diffusion coefficient of CO₂ in EVA has been obtained from these experiments. The microporous foams have been formed by a pressure quench of the CO₂-swollen polymer matrix. Sorption pressure as well as temperature and decompression times appear to determine the pore size and bulk density of the foam. These parameters allow for a control of the foam structure of EVA rubbers.