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1.
Two sets of experiments on typical Class G well cement were carried out in the laboratory to understand better the potential processes involved in well leakage in the presence of CO2. In the first set, good-quality cement samples of permeability in the order of 0.1 μD (10?19 m2) were subjected to 90 days of flow through with CO2-saturated brine at conditions of pressure, temperature and water salinity characteristic of a typical geological sequestration zone. Cement permeability dropped rapidly at the beginning of the experiment and remained almost constant thereafter, most likely mainly as a result of CO2 exsolution from the saturated brine due to the pressure drop along the flow path which led to multi-phase flow, relative-permeability effects and the observed reduction in permeability. These processes are identical to those which would occur in the field as well if the cement sheath in the wellbore annulus is of good quality. The second set of experiments, carried out also at in situ conditions and using ethane rather than CO2 to eliminate any possible geochemical effects, assessed the effect of annular spaces between wellbore casing and cement, and of radial cracks in cement on the effective permeability of the casing-cement assemblage. The results show that, if both the cement and the bond are of good quality, the effective permeability of the assemblage is extremely low (in the order of 1 nD, or 10?21 m2). The presence of an annular gap and/or cracks in the order of 0.01–0.3 mm in aperture leads to a significant increase in effective permeability, which reaches values in the range of 0.1–1 mD (10?15 m2). The results of both sets of experiments suggest that good cement and good bonding with casing and the surrounding rock will likely constitute a good and reliable barrier to the upward flow of CO2 and/or CO2-saturated brine. The presence of mechanical defects such as gaps in bonding between the casing or the formation, or cracks in the cement annulus itself, leads to flow paths with significant effective permeability. This indicates that the external and internal interfaces of cements in wells would most probably constitute the main flow pathways for fluids leakage in wellbores, including both gaseous/supercritical phase CO2 and CO2-saturated brine.  相似文献   

2.
Real-time electrochemical measurements of corrosion rate were performed to evaluate the respective corrosion rates of one boiler waterwall material (SA210) and three boiler superheater materials (T22, P91 and 347H) while firing Utah Western bituminous, Illinois high-sulfur bituminous and Powder River Basin (PRB) sub-bituminous coals in a 1.5 MW pulverized coal-fired furnace. The raw average measured corrosion rates were very low, between 0.0003 and 0.016 mm/year (0.012 and 0.63 mils/year) for most materials under air- and oxy-fired conditions. For some high-sulfur conditions measured corrosion rates were as high as 0.72 mm/year (28 mils/year). Waterwall corrosion rates decreased consistently when converting from air- to oxy-firing while superheater corrosion rates generally increased, although they were less than twice the air-fired rate under most conditions. Corrosion rates for the lower alloyed materials (SA210 and T22) increased significantly during transients from reducing to oxidizing conditions. Measured increases in the corrosion rate of 347H material under high sulfur and low temperature conditions, and associated decrease in corrosion rate at higher temperatures on this alloy, were consistent with the formation of trisulphates in the superheater deposits. The increase of corrosion rate with increased metal temperatures was demonstrated, as was the consistently repeatable nature of the observed results.  相似文献   

3.
Wellbore integrity is one of the key performance criteria in the geological storage of CO2. It is significant in any proposed storage site but may be critical to the suitability of depleted oil and gas reservoirs that may have 10’s to 1000’s of abandoned wells. Much previous work has focused on Portland cement which is the primary material used to seal wellbore systems. This work has emphasized the potential dissolution of Portland cement. However, an increasing number of field studies (e.g., Carey et al., 2007), experimental studies (e.g., Kutchko et al., 2006) and theoretical considerations indicate that the most significant leakage mechanism is likely to be flow of CO2 along the casing–cement microannulus, cement–cement fractures, or the cement–caprock interface.In this study, we investigate the casing–cement microannulus through core-flood experiments. The experiments were conducted on a synthetic wellbore system consisting of a 5-cm diameter sample of cement that was cured with an embedded rectangular length of steel casing that had grooves to accommodate fluid flow. The experiments were conducted at 40 ° C and 14 MPa pore pressure for 394 h. During the experiment, 6.2 l of a 50:50 mixture of supercritical CO2 and 30,000 ppm NaCl-rich brine flowed through 10-cm of limestone before flowing through the 6-cm length cement–casing wellbore system. Approximately 59,000 pore volumes of fluid moved through the casing–cement grooves. Scanning electron microscopy revealed that the CO2–brine mixture impacted both the casing and the cement. The Portland cement was carbonated to depths of 50–250 μm by a diffusion-dominated process. There was very little evidence for mass loss or erosion of the Portland cement. By contrast, the steel casing reacted to form abundant precipitates of mixed calcium and iron carbonate that lined the channels and in one case almost completely filled a channel. The depth of steel corroded was estimated at 25– 30μm and was similar in value to results obtained with a simplified corrosion model.The experimental results were applied to field observations of carbonated wellbore cement by Carey et al. (2007) and Crow et al. (2009) to show that carbonation of the field samples was not accompanied by significant CO2–brine flow at the casing–cement interface. The sensitivity of standard-grade steel casing to corrosion suggests that relatively straight-forward wireline logging of external casing corrosion could be used as a useful indicator of flow behind casing. These experiments also reinforce other studies that indicate rates of Portland cement deterioration are slow, even in the high-flux CO2–brine experiments reported here.  相似文献   

4.
A method, based on spatial analysis of the different criteria to be taken into consideration for building scenarios of CO2 capture and storage (CCS), has been developed and applied to real case studies in the Hebei province. Totally 88 point sources (42 from power sector, 9 from iron and steel, 18 from cement, 16 from ammonia, and 3 from oil refinery) are estimated and their total emission amounts to 231.7 MtCO2/year with power, iron and steel, cement, ammonia and oil refinery sharing 59.13%, 25.03%, 11.44%, 3.5%, and 0.91%, respectively. Storage opportunities can be found in Hebei province, characterised by a strong tectonic subsidence during the Tertiary, with several kilometres of accumulated clastic sediments. Carbon storage potential for 25 hydrocarbon fields selected from the Huabei complex is estimated as 215 MtCO2 with optimistic assumption that all recovered hydrocarbon could be replaced by an equivalent volume of CO2 at reservoir conditions. Storage potential for aquifers in the Miocene Guantao formation is estimated as 747 MtCO2 if closed aquifer assumed or 371 MtCO2 if open aquifer and single highly permeable horizon assumed. Due to poor knowledge on deep hydrogeology and to pressure increase in aquifer, injecting very high rates requested by the major CO2 sources (>10 MtCO2/year) is the main challenge, therefore piezometry and discharge must be carefully controlled. A source sink matching model using ArcGIS software is designed to find the least-cost pathway and to estimate transport route and cost accounting for the additional costs of pipeline construction due to landform and land use. Source sink matching results show that only 15–25% of the emissions estimated for the 88 sources can be sequestrated into the hydrocarbon fields and the aquifers if assuming sinks should be able to accommodate at least 15 years of the emissions of a given source.  相似文献   

5.
Norwegian industrial tailings and by-products, as well as naturally occurring minerals and ores have been surveyed with the purpose of identifying candidate oxygen carrier materials for use in a chemical looping combustion process. Nine materials, based on manganese and/or iron oxide, were selected for an initial screening test; six were deemed promising and were hence investigated further. Thermogravimetric experiments were performed to investigate the oxygen capacity, the reaction kinetics and reversibility of the oxygen absorption reaction. A manganese ore with a reversible capacity of 4.9 wt% oxygen at 1000 °C was selected as the most promising for chemical looping combustion applications. This material was modified by addition of calcia to explore the possibility of enhancing the kinetic, catalytic and mechanical properties. The addition of excess calcium relative to manganese resulted in formation of calcium manganite and related phases. The oxygen capacity of the modified material was 4.5 wt% at 1000 °C, but it has potential advantages in terms of kinetics and chemical and mechanical stability relative to the pure ore.  相似文献   

6.
The objective of this work was to assess the effect of agitation rate and impeller type in two mechanically stirred sequencing batch reactors: one containing granulated biomass (denominated ASBR) and the other immobilized biomass on polyurethane foam (denominated AnSBBR). Each configuration, with total volume of 1 m3, treated 0.65 m3 sanitary wastewater at ambient temperature in 8-h cycles. Three impeller types were assessed for each reactor configuration: flat-blade turbine impeller, 45°-inclined-blade turbine impeller and helix impeller, as well as two agitation rates: 40 and 80 rpm, resulting in a combination of six experimental conditions. In addition, the ASBR was also operated at 20 rpm with a flat-blade turbine impeller and the AnSBBR was operated with a draft tube and helix impeller at 80 and 120 rpm. To quantify how impeller type and agitation rate relate to substrate consumption rate, results obtained during monitoring at the end of the cycle, as well as the time profiles during a cycle were analyzed. Increasing agitation rate from 40 rpm to 80 rpm in the AnSBBR improved substrate consumption rate whereas in the ASBR this increase destabilized the system, likely due to granule rupture caused by the higher agitation. The AnSBBR showed highest solids and substrate removal, highest kinetic constant and highest alkalinity production when using a helix impeller, 80 rpm, and no draft tube. The best condition for the ASBR was achieved with a flat-blade turbine impeller at 20 rpm. The presence of the draft tube in the AnSBBR did not show significant improvement in reactor efficiency. Furthermore, power consumption studies in these pilot scale reactors showed that power transfer required to improve mass transfer might be technically and economically feasible.  相似文献   

7.
Post-combustion carbonate looping processes are based on the capture of carbon dioxide from the flue gases of an existing power plant in a circulating fluidized bed reactor (CFB) of calcium oxide (the carbonator) particles. The calcination of calcium carbonate in a new oxy-fired CFBC power plant regenerates the sorbent (calcium oxide particles) and obtains high purity carbon dioxide. This communication presents experimental results from a small test facility (30 kWt) operated in continuous mode using two interconnected CFB reactors as carbonator and calciner. Capture efficiencies between 70 and 97% have been obtained under realistic flue gas conditions in the carbonator reactor (temperatures around 650 °C). The similarity between process conditions and those existing in CFBC power plants should allow a rapid scaling up of this technology. The next steps for this process development are also outlined.  相似文献   

8.
The aim of this work was to study the mineralization of wastewater effluent from an integrated-gasification combined-cycle (IGCC) power station sited in Spain to meet the requirements of future environmental legislation. This study was done in a pilot plant using a homogeneous photo-Fenton oxidation process with continuous addition of H2O2 and air to the system.The mineralization process was found to follow pseudo-first-order kinetics. Experimental kinetic constants were fitted using neural networks (NNs). The NNs model reproduced the experimental data to within a 90% confidence level and allowed the simulation of the process for any values of the parameters within the experimental range studied. At the optimum conditions (H2O2 flow rate = 120 mL/h, [Fe(II)] = 7.6 mg/L, pH = 3.75 and air flow rate = 1 m3/h), a 90% mineralization was achieved in 150 min.Determination of the hydrogen peroxide consumed and remaining in the water revealed that 1.2 mol of H2O2 was consumed per each mol of total organic carbon removed from solution. This result confirmed that an excess of dissolved H2O2 was needed to achieve high mineralization rates, so continuous addition of peroxide is recommended for industrial application of this process.Air flow slightly improved the mineralization rate due to the formation of peroxo-organic radicals which enhanced the oxidation process.  相似文献   

9.
Long-term integrity of existing wells in a CO2-rich environment is essential for ensuring that geological sequestration of CO2 will be an effective technology for mitigating greenhouse gas-induced climate change. The potential for wellbore leakage depends in part on the quality of the original construction as well as geochemical and geomechanical stresses that occur over its life-cycle. Field data are essential for assessing the integrated effect of these factors and their impact on wellbore integrity, defined as the maintenance of isolation between subsurface intervals. In this report, we investigate a 30-year-old well from a natural CO2 production reservoir using a suite of downhole and laboratory tests to characterize isolation performance.These tests included mineralogical and hydrological characterization of 10 core samples of casing/cement/formation, wireline surveys to evaluate well conditions, fluid samples and an in situ permeability test. We find evidence for CO2 migration in the occurrence of carbonated cement and calculate that the effective permeability of an 11′-region of the wellbore barrier system was between 0.5 and 1 milliDarcy. Despite these observations, we find that the amount of fluid migration along the wellbore was probably small because of several factors: the amount of carbonation decreased with distance from the reservoir, cement permeability was low (0.3–30 microDarcy), the cement–casing and cement-formation interfaces were tight, the casing was not corroded, fluid samples lacked CO2, and the pressure gradient between reservoir and caprock was maintained. We conclude that the barrier system has ultimately performed well over the last 3 decades. These results will be used as part of a broader effort to develop a long-term predictive simulation tool to assess wellbore integrity performance in CO2 storage sites.  相似文献   

10.
Concentrated, aqueous piperazine (PZ) is a novel solvent for carbon dioxide (CO2) capture by absorption/stripping. One of the major advantages of PZ is its resistance to thermal degradation and oxidation.At 135 and 150 °C, 8 m PZ is up to two orders of magnitude more resistant to thermal degradation than 7 m monoethanolamine (MEA). After 18 weeks at 150 °C, only 6.3% of the initial PZ was degraded, yielding an apparent first order rate constant for amine loss of 6.1 × 10?9 s?1. PZ was the most resistant amine tested, with the other screened amines shown in order of decreasing resistance: 7 m 2-amino-2-methyl-1-propanol, 7 m Diglycolamine®, 7 m N-(2-hydroxyethyl)piperazine, 7 m MEA, 8 m ethylenediamine, and 7 m diethylenetriamine. Thermal resistance allows the use of higher temperatures and pressures in the stripper, potentially leading to overall energy savings.Concentrated PZ solutions demonstrate resistance to oxidation compared to 7 m MEA solutions. Experiments investigating metal-catalyzed oxidation found that PZ solutions were 3–5 times more resistant to oxidation than MEA. Catalysts tested were 1.0 mM iron (II), 4.0–5.0 mM copper (II), and a combination of stainless steel metals (iron (II), nickel (II), and chromium (III)). Inhibitor A reduced PZ degradation catalyzed by iron (II) and copper (II).  相似文献   

11.
The coal stream ignition process is critical to the performance of modern pulverized coal burners, particularly when operating under novel conditions such as experienced in oxy-fuel combustion. However, experimental studies of coal stream ignition are lacking, and recent modeling efforts have had to rely on comparisons with a single set of experiments in vitiated air. To begin to address this shortfall, we have conducted experiments on the ignition properties of two U.S. and two Chinese coals in a laminar entrained flow reactor. Most of the measurements focused on varying the coal feed rate for furnace temperatures of 1230–1320 K and for 12–20 vol.% O2 in nitrogen. The influence of coal feed rate on ignition with a carbon dioxide diluent was also measured for 20 vol.% O2 at 1280 K. A second set of measurements was performed for ignition of a fixed coal feed rate in N2 and CO2 environments at identical furnace temperatures of 1200 K, 1340 K, and 1670 K. A scientific CCD camera equipped with a 431 nm imaging filter was used to interrogate the ignition process. Under most conditions, the ignition delay decreased with increasing coal feed rate until a minimum was reached at a feed rate corresponding to a particle number density of approximately 4 × 109 m?3 in the coal feed pipe. This ignition minimum corresponds to a cold flow group number, G, of ~0.3. At higher coal feed rates the ignition delay increased. The ignition delay time was shown to be very sensitive to (a) the temperature of the hot coflow into which the coal stream is introduced, and (b) the coal particle size. The three high volatile bituminous coals showed nearly identical ignition delay as a function of coal feed rate, whereas the subbituminous coal showed slightly greater apparent ignition delay. Bath gas CO2 content was found to have a minor impact on ignition delay.  相似文献   

12.
Chemical-Looping Combustion (CLC) is an emerging technology for CO2 capture because separation of this gas from the other flue gas components is inherent to the process and thus no energy is expended for the separation. Natural or refinery gas can be used as gaseous fuels and they may contain different amounts of light hydrocarbons. This paper presents the combustion results obtained with a Cu-based oxygen carrier using mixtures of CH4 and light hydrocarbons (LHC) (C2H6 and C3H8) as fuel. The effect on combustion efficiency of the fuel reactor temperature, solid circulation flow rate and gas composition was studied in a continuous CLC plant (500 Wth). Full combustions were reached at 1073 and 1153 K working at oxygen to fuel ratios, ? higher than 1.5 and 1.2 respectively. Unburnt hydrocarbons were never detected at any experimental conditions at the fuel reactor outlet. Carbon formation can be avoided working at 1153 K or at ? values higher than 1.5 at 1073 K. After 30 h of continuous operation, the oxygen carrier exhibited an adequate behavior regarding attrition and agglomeration. It can be concluded that no special measures should be taken in a CLC process with Cu-based OC with respect to the presence of LHC in the fuel gas.  相似文献   

13.
Grassland vegetation can provide visual cover for terrestrial vertebrates. The most commonly used method to assess visual cover is the Robel pole. We test the use of digital photography as a more accurate and repeatable method. We assessed the digital photography method on four forage grassland species (Pseudoroegneria spicata, Festuca campestris, Poa pratensis, Achnatherum richardsonii). Digital photos of 2-dimensional cutout silhouettes of three bird species sharp-tailed grouse, western meadowlark and savannah sparrow were used to model the impact of clipping (i.e., grazing) on visual cover. In addition, photos of artificial voles were used to model litter on cover available to small mammals. Nine sites were sampled and data were analyzed by the dominant grass species in each study plot. Regression analysis showed that digital photos (r2 = 0.62) were a better predictor than the Robel pole (r2 = 0.26) for assessment of cover. Clipping heights showed that clipping at less than 15 cm left the silhouettes 50% exposed. Digital photo analysis revealed that visual cover was affected by the type of grass species, with F. campestris > P. pratensis > A. richardsonii > P. spicata. Biomass and litter were both positively related to cover for small mammals.  相似文献   

14.
Use of amines is one of the leading technologies for post-combustion carbon dioxide capture from gas and coal-fired power plants. This study assesses the potential environmental impact of emissions to air that result from use of monoethanol amine (MEA) as an absorption solvent for the capture of carbon dioxide (CO2). Depending on operation conditions and installed reduction technology, emissions of MEA to the air due to solvent volatility losses are expected to be in the range of 0.01–0.8 kg/tonne CO2 captured. Literature data for human and environmental toxicity, together with atmospheric dispersion model calculations, were used to derive maximum tolerable emissions of amines from CO2 capture. To reflect operating conditions with typical and with elevated emissions, we defined a scenario MEA-LOW, with emissions of 40 t/year MEA and 5 t/year diethyl amine (DEYA), and a scenario MEA-HIGH, with emissions of 80 t/year MEA and 15 t/year DEYA. Maximum MEA deposition fluxes would exceed toxicity limits for aquatic organisms by about a factor of 3–7 depending on the scenario. Due to the formation of nitrosamines and nitramines, the estimated emissions of DEYA are close to or exceed safety limits for drinking water and aquatic ecosystems. The “worst case” scenario approach to determine maximum tolerable emissions of MEA and other amines is in particular useful when both expected environmental loads and the toxic effects are associated with high uncertainties.  相似文献   

15.
This work presents results from a rate-based model of strippers at normal pressure (160 kPa) and vacuum (30 kPa) in Aspen Custom Modeler® (ACM) for the desorption of CO2 from 5 m K+/2.5 m piperazine (PZ). The model solves the material, equilibrium, summation and enthalpy (MESH) equations, the heat and mass transfer rate equations, and computes the reboiler duty and equivalent work for the stripping process. Simulations were performed with IMTP #40 random packing and a temperature approach on the hot side of the cross-exchanger of 5 °C and 10 °C. A “short and fat” stripper requires 7–15% less total equivalent work than a “tall and skinny” one because of the reduced pressure drop. The vacuum and normal pressure strippers require 230 s and 115 s of liquid retention time to get an equivalent work 4% greater than the minimum work. Stripping at 30 kPa was controlled by mass transfer with reaction in the boundary layer and diffusion of reactants and products (88% resistance at the rich end and 71% resistance at the lean end). Stripping at 160 kPa was controlled by mass transfer with equilibrium reactions (84% resistance at the rich end and 74% resistance at the lean end) at 80% flood. The typical predicted energy requirement for stripping and compression to 10 MPa to achieve 90% CO2 removal was 37 kJ/gmol CO2. This is about 25% of the net output of a 500 MW power plant with 90% CO2 removal.  相似文献   

16.
MEA solutions were subjected to oxidative degradation at both low and high gas rates. Solutions were degraded with 100 mL/min of 98%O2/2%CO2 with mass transfer achieved by vortexing. Solutions were analyzed for degradation products by IC and HPLC. In a parallel apparatus 7.5 L/min of 15%O2/2%CO2 was sparged through solution, with additional mass transfer achieved by vortexing. A Fourier Transform Infrared (FTIR) analyzer collected continuous gas-phase data on volatile products.Hydroxyethyl-formamide (HEF) and hydroxyethylimidazole (HEI) are the major liquid-phase oxidation products. In the presence of Fe2+ and Cu2+, HEF, HEI, and MEA losses increase by a factor of 3 compared to Fe2+ alone. Cr3+ and Ni2+, two metals present in stainless steel alloys, resulted in MEA losses that are 55% greater. In terms of oxidative degradation potential (greatest to lowest): Cu2+ > Cr3+/Ni2+ > Fe2+ > V5+.Inhibitor A reduces the formation of known products by 90% when catalyzed by Fe2+ and Cu2+ and by 99% with Cr3+/Ni2+. Inhibitor B reduces product rates by 97% and MEA losses by 75%, while a 100:1 ratio of EDTA to Fe2+ completely inhibits oxidation.  相似文献   

17.
Fenton oxidation pretreatment was investigated for enhancement of biodegradability of wastewater sludge (WWS) which was subsequently used as substrate for the production of value- added products. The Response surface method with fractional factorial and central composite designs was applied to determine the effects of Fenton parameters on solubilization and biodegradability of sludge and the optimization of the Fenton process. Maximum solubilization and biodegradability were obtained as 70% and 74%, respectively at the optimal conditions: 0.01 ml H2O2/g SS, 150 [H2O2]0/[Fe2+]0, 25 g/L TS, at 25 °C and 60 min duration. Further, these optimal conditions were tested for the production of a value added product, Bacillus thuringiensis (Bt) which is being used as a biopesticide in the agriculture and forestry sector. It was observed that Bt growth using Fenton oxidized sludge as a substrate was improved with a maximum total cell count of 1.63 × 109 CFU ml?1 and 96% sporulation after 48 h of fermentation. The results were also tested against ultrasonication treatment and the total cell count was found to be 4.08 × 108 CFU ml?1 with a sporulation of 90%. Hence, classic Fenton oxidation was demonstrated to be a rather more promising chemical pre-treatment for Bt - based biopesticide production using WWS when compared to ultrasonication as a physical pre-treatment.  相似文献   

18.
Based on the method of material flow analysis (MFA), a static model of Austrian aluminum (Al) flows in 2010 was developed. Extensive data research on Al production, consumption, trade and waste management was conducted and resulted in a detailed model of national Al resources. Data uncertainty was considered in the model based on the application of a rigorous concept for data quality assessment. The model results indicated that the growth of the Austrian “in-use” Al stock amounts to 11 ± 3.1 kg yr−1 cap−1. The total “in-use” Al stock was determined using a bottom-up approach, which produced an estimate of 260 kg Al cap−1. Approximately 7 ± 1 kg of Al yr−1 cap−1 of old scrap was generated in 2010, of which 20% was not recovered because of losses in waste management processes. Quantitatively, approximately 40% of the total scrap input to secondary Al production originated from net imports, highlighting the import dependency of Austrian Al refiners and remelters. Uncertainties in the calculation of recycling indicators for the Austrian Al system with high shares of foreign scrap trade were exemplarily illustrated for the old scrap ratio (OSR) in secondary Al production, resulting in a possible range of OSRs between 0 and 66%. Overall, the detailed MFA in this study provides a basis to identify resource potentials as well as resource losses in the national Al system, and it will serve as a starting point for a dynamic Al model to be developed in the future.  相似文献   

19.
Following the feasibility study of sour compression process as a novel purification method of producing NOx-free, SO2-free oxyfuel-derived CO2 using actual fluegas, in this paper, we present the study of the individual reactions taking place in the process in a controlled environment. We have previously showed that an increase of NO/NO2 concentration in the inlet stream is beneficial for SO2 removal as NO2 promotes SO2 oxidation and the further removal as liquid acid. In this study we show that the reaction SO2 + NO2  SO3 + NO does not take place significantly in the absence of liquid water at a range of conditions relevant to the sour compression process. When liquid water is present, SO2 is oxidised by NO2 regenerating NO with the rate of conversion of SO2 being dependent on the acid concentration in the liquid. The formation of small liquid droplets where very low levels of pH (?0) can be reached is shown to be of great importance to the SO2 + NO2 conversion process.  相似文献   

20.
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