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期刊论文 49

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碳酸盐岩 3

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Novel eco-efficient reactive distillation process for dimethyl carbonate production by indirect alcoholysis

Iulian Patraşcu, Costin S. Bîldea, Anton A. Kiss

《化学科学与工程前沿(英文)》 2022年 第16卷 第2期   页码 316-331 doi: 10.1007/s11705-021-2047-9

摘要: Dimethyl carbonate is an eco-friendly essential chemical that can be sustainably produced from CO , which is available from carbon capture activities or can even be captured from the air. The rapid increase in dimethyl carbonate demand is driven by the fast growth of polycarbonates, solvent, pharmaceutical, and lithium-ion battery industries. Dimethyl carbonate can be produced from CO through various chemical pathways, but the most convenient route reported is the indirect alcoholysis of urea. Previous research used techniques such as heat integration and reactive distillation to reduce the energy use and costs, but the use of an excess of methanol in the trans-esterification step led to an energy intensive extractive distillation required to break the dimethyl carbonate-methanol azeotrope. This work shows that the production of dimethyl carbonate by indirect alcoholysis of urea can be improved by using an excess of propylene carbonate (instead of an excess of methanol), a neat feat that we showed it requires only 2.64 kW·h·kg dimethyl carbonate in a reaction-separation-recycle process, and a reactive distillation column that effectively replaces two conventional distillation columns and the reactor for dimethyl carbonate synthesis. Therefore, less equipment is required, the methanol-dimethyl carbonate azeotrope does not need to be recycled, and the overall savings are higher. Moreover, we propose the use of a reactive distillation column in a heat integrated process to obtain high purity dimethyl carbonate (>99.8 wt-%). The energy requirement is reduced by heat integration to just 1.25 kW·h·kg dimethyl carbonate, which is about 52% lower than the reaction-separation-recycle process. To benefit from the energy savings, the dynamics and control of the process are provided for ±10% changes in the nominal rate of 32 ktpy dimethyl carbonate, and for uncertainties in reaction kinetics.

关键词: dimethyl carbonate     reactive distillation     process design     plantwide control    

Influence of crystalline phase of Li-Al-O oxides on the activity of Wacker-type catalysts in dimethylcarbonate synthesis

Yadong GE, Yuanyuan DONG, Shengping WANG, Yujun ZHAO, Jing LV, Xinbin MA

《化学科学与工程前沿(英文)》 2012年 第6卷 第4期   页码 415-422 doi: 10.1007/s11705-012-1214-4

摘要: The catalysts supported on LiAl O (spinel) for vapor phase synthesis of dimethyl carbonate (DMC) from methyl nitrite (MN) have been studied. Their catalytic activities on supports prepared by different methods were evaluated in a continuous reactor. The samples were characterized by powder X-ray diffraction, N adsorption-desorption isotherms, fourier transform infrared spectroscopy and temperature-programmed reduction of H . Li/Al molar ratio and calcination temperature greatly influence the structure of crystalline phase of Li-Al-O oxides. Desirable LiAl O (spinel) was formed at 800°C, while LiAl O (primitive cube) formed at 900°C is undesirable for the reaction. A high Li/Al molar ratio, which was related with LiAlO , also slowed the reaction rate. The electron transfer ability and the interaction with active component are the important properties of the spinel-based supports. The CuCl -PdCl /LiAl O (spinel) with better electron transfer ability and low Pd reduction temperature exhibited a better catalytic ability.

关键词: Wacker-type catalyst     dimethyl carbonate     methyl nitrite     spinel    

Direct synthesis of dimethyl carbonate over rare earth oxide supported catalyst

JIANG Qi, CHENG Jiye, GAO Zhiqin

《化学科学与工程前沿(英文)》 2007年 第1卷 第3期   页码 300-303 doi: 10.1007/s11705-007-0055-z

摘要: Solid base catalysts for the direct synthesis of dimethyl carbonate (DMC) from carbon dioxide, methanol, and propylene oxide were prepared by loading KCl and KCO on the surface of LaO, YO, CeO and NdO. The catalysts were characterized by thermogravimetric analysis (TGA) and X-ray diffraction (XRD) techniques. The catalytic activities were efficiently influenced by the preparation conditions. The optimal loading amount of KCO is 17.6% (mass) for KCl-KCO/YO and 22.2% for other catalysts. Supports affected the activity of catalyst. KCl-KCO/NdO exhibited the highest activity. The activity of KCl-KCO/YO increased with the increase of calcination temperature in the range of 800ºC–900ºC. The formation of KYO, YOCl or YO species probably promoted the catalysts.

关键词: thermogravimetric analysis     increase     KCl-KCO/NdO     catalytic     KCl-KCO/YO    

Ozone kinetics of dimethyl sulfide in the presence of water vapor

Haitao WANG

《环境科学与工程前沿(英文)》 2013年 第7卷 第6期   页码 833-835 doi: 10.1007/s11783-013-0570-8

摘要: The outdoor smog chamber was used to thorough investigate the rate constants of gas-phase reaction between dimethyl sulfide (DMS) and ozone (O ) under conditions of relative humidity 55.0%–67.8% at (296±2)K for the first time. The rate constants were measured, at a total pressure of 1 atm, to be (10.4±0.2) × 10 cm ·molecule ·s at relative humidity of 67.5%±0.3% at 298K, (10.1±0.1) × 10 cm ·molecule ·s at relative humidity of 66.5%±0.5% at 296K, (7.75±0.39) × 10 cm ·molecule ·s at relative humidity of 64.8%±0.1% at 294K and (3.42±0.21) × 10 cm ·molecule ·s at relative humidity of 55.8%±0.8% at 295K. Base on these results, it is possible to see the reaction of O /DMS in the presence of water vapor as an important sink for DMS in the earth atmosphere.

关键词: rate constants     ozone (O3)     dimethyl sulfide (DMS)     water vapor    

Catalytic activity of cerium-doped Ru/AlO during ozonation of dimethyl phthalate

ZHOU Yunrui, ZHU Wanpeng, CHEN Xun

《环境科学与工程前沿(英文)》 2008年 第2卷 第3期   页码 354-357 doi: 10.1007/s11783-008-0059-z

摘要: In this paper, factors influencing the mineralization of dimethyl phthalate (DMP) during catalytic ozonation with a cerium-doped Ru/AlO catalyst were studied. The catalytic contribution was calculated through the results of a comparison experiment. It showed that doping cerium significantly enhanced catalytic activity. The total organic carbon (TOC) removal over the doped catalyst at 100 min reached 75.1%, 61.3% using Ru/AlO catalyst and only 14.0% using ozone alone. Catalytic activity reached the maximum when 0.2% of ruthenium and 1.0% of cerium were simultaneously loaded onto AlO support. Results of experiments on oxidation by ozone alone, adsorption of the catalyst, Ce ion’s and heterogeneous catalytic ozonation confirmed that the contribution of heterogeneous catalytic ozonation was about 50%, which showed the obvious effect of Ru–Ce/AlO on catalytic activity.

关键词: Ru–Ce/AlO     dimethyl phthalate     mineralization     comparison experiment     catalytic ozonation    

Polyethylene glycol-supported ionic liquid as a highly efficient catalyst for the synthesis of propylene carbonate

Rui YAO, Hua WANG, Jinyu HAN

《化学科学与工程前沿(英文)》 2012年 第6卷 第3期   页码 239-245 doi: 10.1007/s11705-012-1297-y

摘要: The coupling reaction of propylene and CO to form propylene carbonate (PC) was promoted by an ionic liquid (IL) covalently bound to polyethylene glycol (PEG). The supported ionic liquid, which has both acidic and basic components, proved to be an active catalyst for PC synthesis under mild conditions. The effects of different cations and anions, reaction temperature, CO pressure, and reaction time were investigated. It was demonstrated that the acid group in the catalyst plays an important role in the reaction. With this system, a high PC yield (95%) was achieved under mild conditions (3.0 MPa, 120°C and 4 h) without a co-solvent. In addition, the catalyst was readily recovered and reused. Based on the experimental results, a plausible mechanism for the catalyst was proposed.

关键词: ionic liquid     PEG-supported ionic liquid     carbon dioxide     propylene carbonate    

Biomass to dimethyl ether by gasification/synthesis technology

Tiejun WANG, Yuping LI, Longlong MA, Chuangzhi WU

《能源前沿(英文)》 2011年 第5卷 第3期   页码 330-339 doi: 10.1007/s11708-010-0121-y

摘要: Technical and economic analysis was done for the biomass to dimethyl ether (DME) technology to promote the gasification/synthesis route for biofuel production and its application as a fossil fuel substitute. The technology of biomass gasification/synthesis has obvious advantages, including production flexibility, environmental friendliness, economic feasibility, and application versatility. Biomass gasification/synthesis technology integrates bio-DME synthesis, fertilizer production, electricity generation, and waste heat utilization to convert waste biomass residues to DME for use as liquid petroleum gas, transportation fuel substitute, and chemical intermediates, which has been proven to be one of the most effective and clean biomass utilization routes. The 1000 t/a-scale demonstration plant has a bio-DME production rate of 6 to 7 / , biomass gasification efficiency of≥82%, once-through CO conversion of ≥70%, DME selectivity (DME/DME+other organic products) of ≥90%, and a total system efficiency of ≥38%. The demonstration plant also has self-sufficient steam and electricity supply. The 10,000tons/a-scale bio-DME production cost with or without feedstock subsidy is estimated to be 1968 Yuan/t and 2868 Yuan/t, respectively in China. Because of the limitation in biomass feedstock collection cost, massive and disperse commercial plants with a capacity of 10000 t/a bio-DME are more suitable for rural areas.

关键词: technical and economic analysis     biomass     dimethyl ether     gasification/synthesis    

Effect of wastewater composition on the calcium carbonate precipitation in upflow anaerobic sludge blanket

Shucheng YANG, Yanling HE, Charles CHOU, Pengxiang ZHANG, Dongqi WANG, Yonghong LIU,

《环境科学与工程前沿(英文)》 2010年 第4卷 第2期   页码 142-149 doi: 10.1007/s11783-010-0026-3

摘要: Calcium carbonate often precipitates in anaerobic reactors treating wastewater with high calcium content. The aim of this paper is to study the effect of wastewater composition on calcium carbonate precipitation in upflow anaerobic sludge blanket (UASB) reactors. Two laboratory-scale UASB reactors were operated with calcium-containing influents using acetate and carbohydrate as substrate, respectively. There was an obvious accumulation of inorganic precipitate observed in the biogranules. Observations via scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS) showed that the acclimated biogranules in the two reactors differed in microstructure. Calcium carbonate was found to have precipitated on the surface of acetate-degrading biogranules, but precipitated at the core of the carbohydrate-degrading biogranules. The results indicated that substrates had significant influence on the location of calcium carbonate precipitation in anaerobic granular sludge, which was expected due to the different methanogens distribution and pH gradient within the granular sludge degrading various substrates. Moreover, the location of calcium carbonate precipitation substantially affected the specific methanogenic activity (SMA) of the granular sludge. The SMA of the acetate-degrading biogranules dropped from 1.96 gCOD·gVSS·d to 0.61 gCOD·gVSS·d after 180-d of operation in the reactor. However, the SMA of the carbohydrate-degrading biogranules was not adversely affected by calcium carbonate precipitation.

关键词: calcium carbonate     precipitation     anaerobic granular sludge     wastewater composition     microstructure     upflow anaerobic sludge blanket (UASB)    

Performance and emission characteristics of QHCCI dimethyl ether engine

WANG Ying, LI Wei, ZHOU Longbao, LIU Shenghua, HU Tiegang

《能源前沿(英文)》 2008年 第2卷 第4期   页码 401-405 doi: 10.1007/s11708-008-0075-5

摘要: Experimental investigation into the effects of different pilot amounts of dimethyl ether (DME) on the performance and emission of a single-cylinder direct-injection DME engine is conducted. The results show that a DME engine can operate at a wider range of speeds and loads at quasi-homogenous charge compression ignition (QHCCI) mode. The brake thermal efficiency increases while the exhaust temperature decreases. NO emission decreases by about 30%–50% although there is a slight increase in HC and CO emissions. NO, HC and CO emissions increase with an increase in the amount of DME pilot. QHCCI is a good way to increase thermal efficiency and decrease NO emission.

关键词: Experimental investigation     single-cylinder direct-injection     exhaust temperature     dimethyl     compression ignition    

A density functional theory study on the mechanism of Dimethyl ether carbonylation over heteropolyacids

Kai Cai, Ying Li, Hongbao Shen, Zaizhe Cheng, Shouying Huang, Yue Wang, Xinbin Ma

《化学科学与工程前沿(英文)》 2021年 第15卷 第2期   页码 319-329 doi: 10.1007/s11705-020-1957-2

摘要: Dimethyl ether (DME) carbonylation is considered as a key step for a promising route to produce ethanol from syngas. Heteropolyacids (HPAs) are proved to be efficient catalysts for DME carbonylation. In this work, the reaction mechanism of DME carbonylation was studied theoretically by using density functional theory calculations on two typical HPA models (HPW, HSiW). The whole process consists of three stages: DME dissociative adsorption, insertion of CO into methoxyl group and formation of product methyl acetate. The activation barriers of all possible elementary steps, especially two possible paths for CO insertion were calculated to obtain the most favorable reaction mechanism and rate-limiting step. Furthermore, the effect of the acid strength of Brønsted acid sites on reactivity was studied by comparing the activation barriers over HPW and HSiW with different acid strength, which was determined by calculating the deprotonation energy, Mulliken population analyses and adsorption energies of pyridine.

关键词: dimethyl ether     carbonylation     mechanism     heteropolyacids     density functional theory    

Exergy losses in premixed flames of dimethyl ether and hydrogen blends

Tongbin ZHAO, Jiabo ZHANG, Dehao JU, Zhen HUANG, Dong HAN

《能源前沿(英文)》 2019年 第13卷 第4期   页码 658-666 doi: 10.1007/s11708-019-0645-8

摘要: A second-law thermodynamic analysis was conducted for stoichiometric premixed dimethyl ether (DME)/hydrogen (H )/air flames at atmospheric pressure. The exergy losses from the irreversibility sources, i.e., chemical reaction, heat conduction and species diffusion, and those from partial combustion products were analyzed in the flames with changed fuel blends. It is observed that, regardless of the fuel blends, chemical reaction contributes most to the exergy losses, followed by incomplete combustion, and heat conduction, while mass diffusion has the least contribution to exergy loss. The results also indicate that increased H substitution decreases the exergy losses from reactions, conduction, and diffusion, primarily because of the flame thickness reduction at elevated H substitution. The decreases in exergy losses by chemical reactions and heat conduction are higher, but the exergy loss reduction by diffusion is slight. However, the exergy losses from incomplete combustion increase with H substitution, because the fractions of the unburned fuels and combustion intermediates, e.g., H and OH radical, increase. The overall exergy losses in the DME/H flames decrease by about 5% with increased H substitution from 0% to 100%.

关键词: second law analysis     flame     dimethyl ether (DME)     hydrogen     binary fuels    

Dimethyl ether as alternative fuel for CI engine and vehicle

Zhen HUANG , Xinqi QIAO , Wugao ZHANG , Junhua WU , Junjun ZHANG ,

《能源前沿(英文)》 2009年 第3卷 第1期   页码 99-108 doi: 10.1007/s11708-009-0013-1

摘要: As a developing and the most populous country in the world, China faces major challenges in energy supply and environmental protection. It is of great importance to develop clean and alternative fuels for internal combustion engines. On the basis of researches on DME engine and vehicle at Shanghai Jiaotong University in the last twelve years, fuel injection, combustion, performance and exhaust emissions of DME engine and DME vehicle are introduced in this paper. The results indicate that DME engines can achieve high thermal efficiency and ultra low emissions, and will play a significant role in meeting the energy demand while minimizing environmental impact in China.

关键词: dimethyl ether (DME)     fuel injection     combustion process     emission control     CI engine     vehicle    

Impact of dimethyl ether on engine seal materials

WU Ning, ZHANG Wugao, HUANG Zhen

《能源前沿(英文)》 2008年 第2卷 第3期   页码 279-284 doi: 10.1007/s11708-008-0042-1

摘要: The resistance of many kinds of rubber materials to dimethyl ether (DME) was studied. Both the mass and volume change of rubber materials, which were put in DME and then exposed to the air for different periods of time were measured. The results show that fluorine rubber (FKM), silicone rubber (SIR), and nitrile rubber (NBR) are unsuitable as seal materials for DME engines. Common polyvinylchloride (PVC) dissolved completely in DME, which has almost no impact on vulcanizing nylon material. The constitution of ethylene propylene terpolymer rubber (EPDM) has a major impact on its resistance to DME. A kind of EPDM with good resistance to DME was found, whose reliability was validated by 100 hours of DME engine operation.

关键词: impact     Common polyvinylchloride     different     constitution     ethylene propylene    

地下水碳酸平衡检查系统

刘建刚,郑克勋,傅伟宁,吴顺华

《中国工程科学》 2003年 第5卷 第9期   页码 61-64

摘要:

文章主要研究地下水在不同温度和CO2分压条件下碳酸三种存在形式与pH值的关系,以便更有效地对地下水水质资料进行可靠性检查。分析认为HCO3-出现峰值的分界pH0值,纯水在CO2分压1~105Pa,温度0~30℃时的变化范围为7.92~8.60,碳酸盐岩地下水的变化范围为8.28~8.57。pH0值随温度的升高而降低。石灰岩和白云岩的pH0十分接近,碳酸盐岩地区的平衡特性将取决于方解石成分。

关键词: 碳酸盐岩     地下水     碳酸平衡     pH值    

Multi-objective optimization of molten carbonate fuel cell system for reducing CO

Ramin ROSHANDEL,Majid ASTANEH,Farzin GOLZAR

《能源前沿(英文)》 2015年 第9卷 第1期   页码 106-114 doi: 10.1007/s11708-014-0341-7

摘要: The aim of this paper is to investigate the implementation of a molten carbonate fuel cell (MCFC) as a CO separator. By applying multi-objective optimization (MOO) using the genetic algorithm, the optimal values of operating load and the corresponding values of objective functions are obtained. Objective functions are minimization of the cost of electricity (COE) and minimization of CO emission rate. CO tax that is accounted as the pollution-related cost, transforming the environmental objective to the cost function. The results show that the MCFC stack which is fed by the syngas and gas turbine exhaust, not only reduces CO emission rate, but also produces electricity and reduces environmental cost of the system.

关键词: molten carbonate fuel cell (MCFC)     multi-objective optimization (MOO)     Pareto curve     genetic algorithm     CO2 separation    

标题 作者 时间 类型 操作

Novel eco-efficient reactive distillation process for dimethyl carbonate production by indirect alcoholysis

Iulian Patraşcu, Costin S. Bîldea, Anton A. Kiss

期刊论文

Influence of crystalline phase of Li-Al-O oxides on the activity of Wacker-type catalysts in dimethylcarbonate synthesis

Yadong GE, Yuanyuan DONG, Shengping WANG, Yujun ZHAO, Jing LV, Xinbin MA

期刊论文

Direct synthesis of dimethyl carbonate over rare earth oxide supported catalyst

JIANG Qi, CHENG Jiye, GAO Zhiqin

期刊论文

Ozone kinetics of dimethyl sulfide in the presence of water vapor

Haitao WANG

期刊论文

Catalytic activity of cerium-doped Ru/AlO during ozonation of dimethyl phthalate

ZHOU Yunrui, ZHU Wanpeng, CHEN Xun

期刊论文

Polyethylene glycol-supported ionic liquid as a highly efficient catalyst for the synthesis of propylene carbonate

Rui YAO, Hua WANG, Jinyu HAN

期刊论文

Biomass to dimethyl ether by gasification/synthesis technology

Tiejun WANG, Yuping LI, Longlong MA, Chuangzhi WU

期刊论文

Effect of wastewater composition on the calcium carbonate precipitation in upflow anaerobic sludge blanket

Shucheng YANG, Yanling HE, Charles CHOU, Pengxiang ZHANG, Dongqi WANG, Yonghong LIU,

期刊论文

Performance and emission characteristics of QHCCI dimethyl ether engine

WANG Ying, LI Wei, ZHOU Longbao, LIU Shenghua, HU Tiegang

期刊论文

A density functional theory study on the mechanism of Dimethyl ether carbonylation over heteropolyacids

Kai Cai, Ying Li, Hongbao Shen, Zaizhe Cheng, Shouying Huang, Yue Wang, Xinbin Ma

期刊论文

Exergy losses in premixed flames of dimethyl ether and hydrogen blends

Tongbin ZHAO, Jiabo ZHANG, Dehao JU, Zhen HUANG, Dong HAN

期刊论文

Dimethyl ether as alternative fuel for CI engine and vehicle

Zhen HUANG , Xinqi QIAO , Wugao ZHANG , Junhua WU , Junjun ZHANG ,

期刊论文

Impact of dimethyl ether on engine seal materials

WU Ning, ZHANG Wugao, HUANG Zhen

期刊论文

地下水碳酸平衡检查系统

刘建刚,郑克勋,傅伟宁,吴顺华

期刊论文

Multi-objective optimization of molten carbonate fuel cell system for reducing CO

Ramin ROSHANDEL,Majid ASTANEH,Farzin GOLZAR

期刊论文