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Calculation and analysis of sub/supercritical methanol preheating tube for continuous production of biodieselvia supercritical methanol transesterification

Wen CHEN, Weiyong YING, Cunwen WANG, Weiguo WANG, Yuanxin WU, Junfeng ZHANG,

《能源前沿（英文）》 2009年 第3卷 第4期   页码 423-431 doi: 10.1007/s11708-009-0075-0

摘要： Biodiesel is an important renewable energy. Supercritical methanol transesterification for biodiesel has recently been concerned because of its obvious advantages. The tubular reactor is an ideal reactor for continuous preparation of biodiesel via supercritical methanol transesterification. A methanol preheating tube is necessary for the tubular reaction system because the reaction temperature for supercritical methanol transesterification is usually 520―600K. Therefore, in the range of 298―600K, changes of the density, isobaric capacity, viscosity and thermal conductivity of sub/supercritical methanol with temperature are first discussed. Then on the basis of these thermophysical properties, an integration method is adopted for the design of sub/supercritical methanol preheating tube when methanol is preheated from 298K to 600K at 16MPa and the influencing factors on the length of the preheating tube are also studied. The computational results show that the Reynolds number and the local convection heat-transfer coefficient of sub/supercritical methanol flowing in ф6mm×1.5mm preheating tube change drastically with temperature. For the local overall heat transfer coefficient and the average overall heat transfer coefficient , temperature also has an important influence on them when the inlet velocity of methanol is lower than 0.5m/s. But when the inlet velocity of methanol is higher than 0.5m/s, and almost keep invariable with temperature. Additionally, both the outlet temperature and the inlet velocity of methanol are the key affecting factors for the length of the preheating tube, especially when the outlet temperature is over the critical temperature of methanol. At the same time, the increase of tin bath’s temperature can shorten the required length of the preheating tube. At the inlet flow rate of 0.5m/s, the required length of the preheating tube is 2.0m when methanol is preheated from 298K to 590K at 16MPa with keeping the tin bath’s temperature 620K, which is in good agreement with the experimental results.

关键词： sub/supercritical methanol     preheating tube     integration method     biodiesel    

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Simulation analysis of methanol flash distillation circulation process in biodiesel production with supercritical

Zhengjiao TANG, Cunwen WANG, Weiguo WANG, Jia GUO, Yuanxin WU, Jinfang CHEN, Yigang DING

《能源前沿（英文）》 2011年 第5卷 第1期   页码 93-97 doi: 10.1007/s11708-010-0028-7

摘要： High methanol-to-oil ratio is required to obtain a high conversion of oil for the production of biodiesel with supercritical methanol. Recovering the methanol of a stream issuing from a transesterification supercritical reactor by flash distillation instead of evaporation was analyzed. The one-stage and two-stage flash distillation processes were presented and compared. The difference of the recovery percentage of methanol of the above two flash processes is less than 0.5% and the methanol concentration in the vapor for the one-stage process decreases rapidly when feed temperature increases. The process in which the product of transesterification of soybean oil with supercritical methanol is cooled to an appropriate temperature (about 240°C) first and then flashed was put forward. The effect of cooling temperature, feed pressure and flash pressure on methanol concentration and recovery percentage was investigated. According to this study, when the feed pressure range is 15–30 MPa, the flash pressure equals 0.4 MPa, and cooling temperature range is 240°C–250°C, the recovery percentage of methanol is not less than 85%, and the concentration of the vapor in mass fraction of methanol is approximately 99%. Thus, the vapor leaving the flash tank can be directly circulated to the transesterification reactor.

关键词： supercritical methanol     biodiesel     recovery     flash distillation    

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Biodiesel production from waste frying oil in sub- and supercritical methanol on a zeolite Y solid acid

Jorge MEDINA-VALTIERRA, Jorge RAMIREZ-ORTIZ

《化学科学与工程前沿（英文）》 2013年 第7卷 第4期   页码 401-407 doi: 10.1007/s11705-013-1354-1

摘要： Waste frying oil (WFO) is a very important feedstock for obtaining biodiesel at low cost and using WFO in transesterification reactions to produce biodiesel helps eliminate local environmental problems. In this study biodiesel was produced from WFO in sub- and super-critical methanol on a zeolite Y solid acid catalyst. The procedure was optimized using a design of experiments by varying the methanol to WFO molar ratio, the reaction temperature, and the amount of catalyst. Typical biodiesel yields varied from 83 to nearly 100% with methyl esters content ranging from 1.41–1.66 mol·L and typical dynamic viscosities of 22.1-8.2 cP. Gas chromatography was used to determine the molecular composition of the biodiesel. The reaction products contained over 82 wt-% methyl esters, 4.2 wt-% free acids, 13.5 wt-% monoglycerides, and 0.3 wt-% diglycerides. The transesterification of WFO with methanol around its critical temperature combined with a zeolite Y as an acid catalyst is an efficient approach for the production of biodiesel with acceptable yields.

关键词： biodiesel     methanol     critical temperature     waste frying oil     zeolite Y    

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Impacts of methanol fuel on vehicular emissions: A review

《环境科学与工程前沿（英文）》 2022年 第16卷 第9期 doi: 10.1007/s11783-022-1553-4

摘要：

● Methanol effectively reduces CO, HC, CO2, PM, and PN emissions of gasoline vehicles.

关键词： Methanol fuel     Vehicular emission     Emission reduction     Cleaner fuel     Gasoline substitute    

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Confinement effects in methanol to olefins catalysed by zeolites: A computational review

German Sastre

《化学科学与工程前沿（英文）》 2016年 第10卷 第1期   页码 76-89 doi: 10.1007/s11705-016-1557-3

摘要： Small pore zeolites, containing 8-rings as the largest, are widely employed as catalysts in the process of methanol-to-olefins (MTO). Reactants and products diffuse with constraints through 8-rings and this is one of the reaction bottlenecks related to zeolite micropore topology. Small pore zeolites and silicon-aluminophosphates(SAPOs) containing cavities, where olefins are mainly formed through the hydrocarbon pool (HP) mechanism, are frequently tested for MTO. Shape selectivity of transition states within the side-chain methylation will be reviewed as this is one of the controlling steps of the MTO process, with particular attention to the role of hexamethylbenzene (HMB) and heptamethylbenzenium cation (HeptaMB ), which are the most tipically detected reaction intermediates, common to the paring and side-chain routes within the HP mechanism. The relative stability of these and other species will be reviewed in terms of confinement effects in different cage-based zeolites. The role of the different alkylating agents, methanol, dimethyl ether (DME), and surface methoxy species (SMS) will also be reviewed from the computational viewpoint.

关键词： small pore zeolites     SAPOs     methanol-to-olefins     hydrocarbon pool mechanism     alkylation of polymethylbenzenes    

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Hydrogen production from methanol through dielectric barrier discharge

Baowei WANG, Xu ZHANG, Haiying BAI, Yijun Lü, Shuanghui HU

《化学科学与工程前沿（英文）》 2011年 第5卷 第2期   页码 209-214 doi: 10.1007/s11705-010-1018-3

摘要： The hydrogen fuel cell is a promising option as a future energy resource and the production of hydrogen is mainly depended on fossil fuels now. In this paper, methanol reforming to produce H through dielectric-barrier discharge (DBD) plasma reaction was studied. Effects of the power supply parameters, reactor parameters and process conditions on conversion of methanol and distribution of products were investigated. The best reaction conditions were following: input power (45 W), material of inner electrode (stainless steel), discharge gap (3.40 mm), length of reaction zone (90.00 mm), dielectric thickness (1.25 mm), and methanol content (37.65%). The highest conversion of methanol and the yield of H were 82.38% and 27.43%, respectively.

关键词： methanol     dielectric-barrier discharge     hydrogen     plasma    

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Experimental study on premixed combustion of spherically propagating methanol-air-nitrogen flames

Xiangang WANG, Zhiyuan ZHANG, Zuohua HUANG, Xibin WANG, Haiyan MIAO,

《能源前沿（英文）》 2010年 第4卷 第2期   页码 223-233 doi: 10.1007/s11708-010-0016-y

摘要： The outward propagation and development of surface instability of the spark-ignited spherical premixed flames for methanol-air-nitrogen mixtures were experimentally studied by using a constant volume combustion chamber and a high-speed schlieren photography system. The laminar burning velocities, the mass burning fluxes, and the Markstein lengths were obtained at different equivalence ratios, dilution ratios, initial temperatures, and pressures. The laminar burning velocities and the mass burning fluxes give a similar curve versus the equivalence ratios. They increase with the increase of initial temperature and decrease with the increase of dilution ratio. The laminar burning velocity decreases with elevating the initial pressure, while the mass burning flux increases with the increase of the initial pressure. Markstein length decreases slightly with the increase of initial temperature for the rich mixtures. High initial pressure corresponds to low Markstein length. Markstein length increases with the increase of dilution ratio, which is more obvious when the mixture becomes leaner. Equivalence ratio has a slight impact on the development of the diffusive-thermal cellular structure at elevated initial pressures. The initial pressure has a significant influence on the occurrence of the flame front cellular structure. At the elevated pressures, the cracks on the flame surface branch and develop into the cell structure. These cells are bounded by cracks emitting a bright light, which may indicate soot formation. For very lean mixture combustion, the buoyancy effect and cooling effect from the spark electrodes have a significant impact on the flame propagation. The hydrodynamic instability, inhibited with the increase of initial temperature around the stoichiometric equivalence ratio, is enhanced with the increase of initial pressure and suppressed by mixture dilution.

关键词： methanol     spherical flame     propagation characteristics     flame instabilities    

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Mechanism of methanol decomposition on the Pd/WC(0001) surface unveiled by first-principles calculations

Jinhua Zhang, Yuanbin She

《化学科学与工程前沿（英文）》 2020年 第14卷 第6期   页码 1052-1064 doi: 10.1007/s11705-019-1908-y

摘要： In this study, the decomposition of methanol into the CO and H species on the Pd/tungsten carbide (WC)(0001) surface is systematically investigated using periodic density functional theory (DFT) calculations. The possible reaction pathways and intermediates are determined. The results reveal that saturated molecules, i.e., methanol and formaldehyde, adsorb weakly on the Pd/WC(0001) surface. Both CO and H prefer three-fold sites, with adsorption energies of ‒1.51 and ‒2.67 eV, respectively. On the other hand, CH O stably binds at three-fold and bridge sites, with an adsorption energy of ‒2.58 eV. However, most of the other intermediates tend to adsorb to the surface with the carbon and oxygen atoms in their sp and hydroxyl-like configurations, respectively. Hence, the C atom of CH OH preferentially attaches to the top sites, CHOH and CH O adsorb at the bridge sites, while COH and CHO occupy the three-fold sites. The DFT calculations indicate that the rupture of the initial C–H bond promotes the decomposition of CH OH and CH OH, whereas in the case of CHOH, O–H bond scission is favored over the C–H bond rupture. Thus, the most probable methanol decomposition pathway on the Pd/WC(0001) surface is CH OH → CH OH → -CHOH → CHO → CO. The present study demonstrates that the synergistic effect of WC (as carrier) and Pd (as catalyst) alters the CH OH decomposition pathway and reduces the noble metal utilization.

关键词： density functional theory     methanol     direct methanol fuel cells     WC(0001)-supported Pd monolayer     decomposition mechanism    

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A review on catalytic & non-catalytic bio-oil upgrading in supercritical fluids

Sainab Omar, Yang Yang, Jiawei Wang

《化学科学与工程前沿（英文）》 2021年 第15卷 第1期   页码 4-17 doi: 10.1007/s11705-020-1933-x

摘要： This review article summarizes the key published research on the topic of bio-oil upgrading using catalytic and non-catalytic supercritical fluid (SCF) conditions. The precious metal catalysts Pd, Ru and Pt on various supports are frequently chosen for catalytic bio-oil upgrading in SCFs. This is reportedly due to their favourable catalytic activity during the process including hydrotreating, hydrocracking, and esterification, which leads to improvements in liquid yield, heating value, and pH of the upgraded bio-oil. Due to the costs associated with precious metal catalysts, some researchers have opted for non-precious metal catalysts such as acidic HZSM-5 which can promote esterification in supercritical ethanol. On the other hand, SCFs have been effectively used to upgrade crude bio-oil without a catalyst. Supercritical methanol, ethanol, and water are most commonly used and demonstrate catalyst like activities such as facilitating esterification reactions and reducing solid yield by alcoholysis and hydrolysis, respectively.

关键词： bio-oil     upgrading     supercritical     review    

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Polydimethylsiloxane assisted supercritical CO

Weixia Wang, Shuai Zhou, Zhong Xin, Yaoqi Shi, Shicheng Zhao

《化学科学与工程前沿（英文）》 2016年 第10卷 第3期   页码 396-404 doi: 10.1007/s11705-016-1577-z

摘要： Foamable high melt strength polypropylene (HMSPP) was prepared by grafting styrene (St) onto polypropylene (PP) and simultaneously introducing polydimethylsiloxane (PDMS) through?a?one-step?melt extrusion process. The effect of PDMS viscosity on the foaming behavior of HMSPP was systematically investigated using supercritical CO as the foaming agent. The results show that the addition of PDMS has little effect on the grafting reaction of St and HMSPP exhibits enhanced elastic response and obvious strain hardening effect. Though the CO solubility of HMSPP with PDMS (PDMS-HMSPP) is lower than that of HMSPP without PDMS, especially for PDMS with low viscosity, the PDMS-HMSPP foams exhibit narrow cell size distribution and high cell density. The fracture morphology of PDMS-HMSPP shows that PDMS with low viscosity disperses more easily and uniformly in HMSPP matrix, leading to form small domains during the extrusion process. These small domains act as bubble nucleation sites and thus may be responsible for the improved foaming performance of HMSPP.

关键词： high melt strength polypropylene (HMSPP)     polydimethylsiloxane (PDMS)     supercritical CO2     foaming behavior    

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Kinetic study of the methanol to olefin process on a SAPO-34 catalyst

Mehdi SEDIGHI,Kamyar KEYVANLOO

《化学科学与工程前沿（英文）》 2014年 第8卷 第3期   页码 306-311 doi: 10.1007/s11705-014-1440-z

摘要： In this paper, a new kinetic model for methanol to olefin process over SAPO-34 catalyst was developed using elementary step level. The kinetic model fits well to the experimental data obtained in a fixed bed reactor. Using this kinetic model, the effect of the most important operating conditions such as temperature, pressure and methanol space-time on the product distribution has been examined. It is shown that the temperature ranges between 400 °C and 450 °C is appropriate for propene production while the medium temperature (450 °C) is favorable for total olefin yield which is equal to 33%. Increasing the reactor pressure decreases the ethylene yield, while medium pressure is favorable for the propylene yield. The result shows that the ethylene and propylene and consequently the yield of total olefins increase to approximately 35% with decreasing the molar ratio of inlet water to methanol.

关键词： methanol to olefin     SAPO-34     kinetic modeling     elementary step    

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Corrosion mechanisms of candidate structural materials for supercritical water-cooled reactor

Lefu ZHANG, Fawen ZHU, Rui TANG

《能源前沿（英文）》 2009年 第3卷 第2期   页码 233-240 doi: 10.1007/s11708-009-0024-y

摘要： Nickel-based alloys, austenitic stainless steel, ferritic/martensitic heat-resistant steels, and oxide dispersion strengthened steel are presently considered to be the candidate structural or fuel-cladding materials for supercritical water-cooled reactor (SCWR), one of the promising generation IV reactor for large-scale electric power production. However, corrosion and stress corrosion cracking of these candidate alloys still remain to be a major problem in the selection of nuclear fuel cladding and other structural materials, such as water rod. Survey of literature and experimental results reveal that the general corrosion mechanism of those candidate materials exhibits quite complicated mechanism in high-temperature and high-pressure supercritical water. Formation of a stable protective oxide film is the key to the best corrosion-resistant alloys. This paper focuses on the mechanism of corrosion oxide film breakdown for SCWR candidate materials.

关键词： supercritical water-cooled reactor     general corrosion     oxide film     corrosion mechanism    

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Development of a supercritical and an ultra-supercritical circulating fluidized bed boiler

Junfu LYU, Hairui YANG, Wen LING, Li NIE, Guangxi YUE, Ruixin LI, Ying CHEN, Shilong WANG

《能源前沿（英文）》 2019年 第13卷 第1期   页码 114-119 doi: 10.1007/s11708-017-0512-4

摘要： The supercritical circulating fluidized bed (CFB) boiler, which combines the advantages of CFB combustion with low cost emission control and supercritical steam cycle with high efficiency of coal energy, is believed to be the future of CFB combustion technology. It is also of greatest importance for low rank coal utilization in China. Different from the supercritical pulverized coal boiler that has been developed more than 50 years, the supercritical CFB boiler is still a new one which requires further investigation. Without any precedentor engineering reference, Chinese researchers have conducted fundamental research, development, design of the supercritical CFB boilers independently. The design theory and key technology for supercritical CFB boiler were proposed. Key components and novel structures were invented. The first 600 MWe supercritical CFB boiler and its auxiliaries were successfully developed and demonstrated in Baima Power Plant, Shenhua Group as well as the simulator, control technology, installation technology, commissioning technology, system integration and operation technology. Compared with the 460 MWe supercritical CFB in Poland, developed in the same period and the only other supercritical one of commercial running in the word beside Baima, the 600 MWe one in Baima has a better performance. Besides, supercritical CFB boilers of 350 MWe have been developed and widely commercialized in China. In this paper, the updated progress of 660 MWe ultra-supercritical CFB boilers under development is introduced.

关键词： supercritical     circulating fluidized bed boiler     development     demonstration    

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Thermo-economic analysis of a direct supercritical CO electric power generation system using geothermal

《能源前沿（英文）》 2022年 第16卷 第2期   页码 246-262 doi: 10.1007/s11708-021-0749-9

摘要： A comprehensive thermo-economic model combining a geothermal heat mining system and a direct supercritical CO2 turbine expansion electric power generation system was proposed in this paper. Assisted by this integrated model, thermo-economic and optimization analyses for the key design parameters of the whole system including the geothermal well pattern and operational conditions were performed to obtain a minimal levelized cost of electricity (LCOE). Specifically, in geothermal heat extraction simulation, an integrated wellbore-reservoir system model (T2Well/ECO2N) was used to generate a database for creating a fast, predictive, and compatible geothermal heat mining model by employing a response surface methodology. A parametric study was conducted to demonstrate the impact of turbine discharge pressure, injection and production well distance, CO2 injection flowrate, CO2 injection temperature, and monitored production well bottom pressure on LCOE, system thermal efficiency, and capital cost. It was found that for a 100 MWe power plant, a minimal LCOE of $0.177/kWh was achieved for a 20-year steady operation without considering CO2 sequestration credit. In addition, when CO2 sequestration credit is $1.00/t, an LCOE breakeven point compared to a conventional geothermal power plant is achieved and a breakpoint for generating electric power generation at no cost was achieved for a sequestration credit of $2.05/t.

关键词： geothermal heat mining     supercritical CO2     power generation     thermo-economic analysis     optimization    

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Production of renewable fuels by blending bio-oil with alcohols and upgrading under supercritical conditions

Sainab Omar, Suzanne Alsamaq, Yang Yang, Jiawei Wang

《化学科学与工程前沿（英文）》 2019年 第13卷 第4期   页码 702-717 doi: 10.1007/s11705-019-1861-9

摘要： The work studied a non-catalytic upgrading of fast pyrolysis bio-oil by blending under supercritical conditions using methanol, ethanol and isopropanol as solvent and hydrogen donor. Characterisation of the bio-oil and the upgraded bio-oils was carried out including moisture content, elemental content, pH, heating value, gas chromatography-mass spectrometry (GCMS), Fourier transform infrared radiation, C nuclear magnetic resonance spectroscopy, and thermogravimetric analysis to evaluate the effects of blending and supercritical reactions. The GCMS analysis indicated that the supercritical methanol reaction removed the acids in the bio-oil consequently the pH increased from 2.39 in the crude bio-oil to 4.04 after the supercritical methanol reaction. The ester contents increased by 87.49% after the supercritical methanol reaction indicating ester formation could be the major deacidification mechanism for reducing the acidity of the bio-oil and improving its pH value. Simply blending crude bio-oil with isopropanol was effective in increasing the C and H content, reducing the O content and increasing the heating value to 27.55 from 17.51 MJ·kg in the crude bio-oil. After the supercritical isopropanol reaction, the heating value of the liquid product slightly further increased to 28.85 MJ·kg .

关键词： bio-oil     blending     supercritical     upgrading     characterisation    

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标题 作者 时间 类型 操作

Calculation and analysis of sub/supercritical methanol preheating tube for continuous production of biodieselvia supercritical methanol transesterification

Wen CHEN, Weiyong YING, Cunwen WANG, Weiguo WANG, Yuanxin WU, Junfeng ZHANG,

期刊论文

Simulation analysis of methanol flash distillation circulation process in biodiesel production with supercritical

Zhengjiao TANG, Cunwen WANG, Weiguo WANG, Jia GUO, Yuanxin WU, Jinfang CHEN, Yigang DING

期刊论文

Biodiesel production from waste frying oil in sub- and supercritical methanol on a zeolite Y solid acid

Jorge MEDINA-VALTIERRA, Jorge RAMIREZ-ORTIZ

期刊论文

Impacts of methanol fuel on vehicular emissions: A review

期刊论文

Confinement effects in methanol to olefins catalysed by zeolites: A computational review

German Sastre

期刊论文

Hydrogen production from methanol through dielectric barrier discharge

Baowei WANG, Xu ZHANG, Haiying BAI, Yijun Lü, Shuanghui HU

期刊论文

Experimental study on premixed combustion of spherically propagating methanol-air-nitrogen flames

Xiangang WANG, Zhiyuan ZHANG, Zuohua HUANG, Xibin WANG, Haiyan MIAO,

期刊论文

Mechanism of methanol decomposition on the Pd/WC(0001) surface unveiled by first-principles calculations

Jinhua Zhang, Yuanbin She

期刊论文

A review on catalytic & non-catalytic bio-oil upgrading in supercritical fluids

Sainab Omar, Yang Yang, Jiawei Wang

期刊论文

Polydimethylsiloxane assisted supercritical CO

Weixia Wang, Shuai Zhou, Zhong Xin, Yaoqi Shi, Shicheng Zhao

期刊论文

Kinetic study of the methanol to olefin process on a SAPO-34 catalyst

Mehdi SEDIGHI,Kamyar KEYVANLOO

期刊论文

Corrosion mechanisms of candidate structural materials for supercritical water-cooled reactor

Lefu ZHANG, Fawen ZHU, Rui TANG

期刊论文

Development of a supercritical and an ultra-supercritical circulating fluidized bed boiler

Junfu LYU, Hairui YANG, Wen LING, Li NIE, Guangxi YUE, Ruixin LI, Ying CHEN, Shilong WANG

期刊论文

Thermo-economic analysis of a direct supercritical CO electric power generation system using geothermal

期刊论文

Production of renewable fuels by blending bio-oil with alcohols and upgrading under supercritical conditions

Sainab Omar, Suzanne Alsamaq, Yang Yang, Jiawei Wang

期刊论文