硫化物生物氧化脱硫技术研究现状

介绍了近年来国内外硫化物生物氧化为单质硫的各种脱硫技术.分析总结了硫化物生物氧化为单质硫工艺的各种影响因素,包括氧硫比、溶解氧浓度、硫化物浓度、化学氧化、微生物菌种、pH值、温度等因素.提出了生物氧化脱硫技术的发展前景.该技术将脱硫和单质硫的回收和为一体,是一种安全、低成本将含硫废液变废为宝的工艺技术.     

Verdant vehicles via viscoelasticity

The combustion of hydrocarbon (HC) fuels in internal combustion (IC) engines is modified by the presence of a few parts per million of megadalton molecular weight elastomers. The viscoelasticity imparted provides: reduced fuel vaporization, lesser back pressure, larger average droplet sizes, and lower combustion chamber temperatures. These effects result in: a reduction of emissions of HC, CO and NO_x of more than 70%, a substantial decrease in the number of particulates from diesel engines, a drop in combustion temperatures of more than 30vv°C, increases in engine power of more than 10%, an improved fuel octane rating, and economies of fuel consumption of more than 20%. The results are magnified during transitions, especially in the lower gears, used more often in urban traffic, where normal fuels emit more pollutants. These effects have a positive public health impact due to reductions in ozone, acid rain, particulates and partially oxidized HC.     

Characteristics of stable biodiesel emulsion fuel with the aid of lipophilic surfactant,polyglycerol polyricinoleate (PGPR)

ABSTRACT

Biodiesel emulsion fuel is reported as one of the most feasible options capable of generating lower NOx emission than that from fossil fuels. However, oil and water in the emulsion fuel are easily separated and unstable. The aim of the present study is to consider the production and stability of biodiesel emulsion fuel by using tetraglycerin ester (CR-310), i.e., one of lipophilic surfactant, polyglycerol polyricinoleate (PGPR) and biodiesel, i.e., Waste cooking Oil Methyl Ester (WOME) produced based on waste cooking oil. The corresponding heat rate, water content, and viscosity are measured. Emphasis is placed on the effects of water content and surfactant on biodiesel emulsions. It is found that: (i) stable emulsion fuel is obtained by adding at least 2.0% of CR-310 and is maintained over 1 month, (ii) there is no effect of water content on stable emulsion fuel if CR-310 is used over 2.0%, and (iii) the viscosity of emulsion fuels is higher than that of the biodiesel fuel and is gradually increased with an increase in the water content.     

Effect of gas composition in Chemical-Looping Combustion with copper-based oxygen carriers: Fate of sulphur

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 sulphur compounds, such as H₂S and COS. This paper presents the combustion results obtained with a Cu-based oxygen carrier using mixtures of CH₄ and H₂S as fuel. The influence of H₂S concentration on the gas product distribution and combustion efficiency, sulphur splitting between the fuel reactor (FR) and the air reactor (AR), oxygen carrier deactivation and material agglomeration was investigated in a continuous CLC plant (500 W_th). The oxygen carrier to fuel ratio, ?, was the main operating parameter affecting the CLC system. Complete fuel combustion were reached at 1073 K working at ? values ≥1.5. The presence of H₂S did not produce a decrease in the combustion efficiency even when working with a fuel containing 1300 vppm H₂S. At these conditions, the great majority of the sulphur fed into the system was released in the gas outlet of the FR as SO₂, affecting to the quality of the CO₂ produced. Formation of copper sulphide, Cu₂S, and the subsequent reactivity loss was only detected working at low values of ? ≤ 1.5, although this fact did not produce any agglomeration problem in the fluidized beds. In addition, the oxygen carrier was fully regenerated in a H₂S-free environment. It can be concluded that Cu-based oxygen carriers are adequate materials to be used in a CLC process using fuels containing H₂S although quality of the CO₂ produced is affected.     

Chemical-looping with oxygen uncoupling for combustion of solid fuels

Chemical-looping with oxygen uncoupling (CLOU) is a novel method to burn solid fuels in gas-phase oxygen without the need for an energy intensive air separation unit. The carbon dioxide from the combustion is inherently separated from the rest of the flue gases. CLOU is based on chemical-looping combustion (CLC) and involves three steps in two reactors, one air reactor where a metal oxide captures oxygen from the combustion air (step 1), and a fuel reactor where the metal oxide releases oxygen in the gas-phase (step 2) and where this gas-phase oxygen reacts with a fuel (step 3). In other proposed schemes for using chemical-looping combustion of solid fuels there is a need for an intermediate gasification step of the char with steam or carbon dioxide to form reactive gaseous compounds which then react with the oxygen carrier particles. The gasification of char with H₂O and CO₂ is inherently slow, resulting in slow overall rates of reaction. This slow gasification is avoided in the proposed process, since there is no intermediate gasification step needed and the char reacts directly with gas-phase oxygen. The process demands an oxygen carrier which has the ability to react with the oxygen in the combustion air in the air reactor but which decomposes to a reduced metal oxide and gas-phase oxygen in the fuel reactor. Three metal oxide systems with suitable thermodynamic properties have been identified, and a thermal analysis has shown that Mn₂O₃/Mn₃O₄ and CuO/Cu₂O have suitable thermodynamic properties, although Co₃O₄/CoO may also be a possibility. However, the latter system has the disadvantage of an overall endothermic reaction in the fuel reactor. Results from batch laboratory fluidized bed tests with CuO and a gaseous and solid fuel are presented. The reaction rate of petroleum coke is approximately a factor 50 higher using CLOU in comparison to the reaction rate of the same fuel with an iron-based oxygen carrier in normal CLC.     

Bacterial desulfurization of Turkish lignites

The applicability of bacterial coal desulfurization to Turkish lignites and Nalligan-Cayirhan lignites was investigated in shake-flask culture systems. Effect of various parameters such as pulp density, particle size, type of inoculum, media and temperature on the efficiency of desulfurization by Thiobacillus ferrooxidans were tested. A Thiobacillus related moderately thermophilic mixotroph was found to remove some of the organic sulfur as well.     

Auto-adaptive Air Distribution and Structure Optimization of Ejector Burner for Biomass Alcohol Fuels

A plenty of studies on the utilization of biomass alcohol fuels have been conducted, but combustion efficiency and stability of this fuels still need to be improved. Based on biomass alcohol fuels (bio-methanol and bio-ethanol), this paper studied auto-adaptive air distribution characteristics and optimum structure parameters of an ejector burner by numerical simulation method. Also, an experiment was conducted to verify the numerical results. The results show that the mole air entrainment ratio (MAER) keeps almost constant when the ejector fuel nozzle exit locates at the segment between the ejector throat and the suction chamber entrance, but a bigger ratio α would lead to a higher MAER till the α is bigger than 8.5 for bio-methanol and 11.5 for bio-ethanol. The bio-ethanol fuel is more beneficial for air carrying role because of its big molecular weight. Operation pressure (P_w) has a little impact on MAER of the two fuels, but the rise of back pressure (P_b) would lead to rapid decrease of MAER for the two fuels. For the optimum structure burners, the MAER can be maintained at the value of theoretical complete combustion. Its changing rate is less than 2.3% for bio-methanol and 2.5% for bio-ethanol when the burner load changes from 30% to 120%, which is highly consistent with the experimental results. The optimum burner can distribute air supply automatically with the changing of burner load.     

Simulation Study of a PEM Fuel Cell System with Steam Reforming

Abstract

This article summarizes the results of a study for a 100 kWe DC electrical power PEM fuel cell system. The system consists of a pre-steam reformer, a steam reformer, high and low temperature shift reactors, a preferential oxidation reactor, a PEM fuel cell, a combustor, and an expander. Acceptable net electrical efficiency levels can be achieved via intensive heat integration within the PEM fuel cell system. The calculations take into account the auxiliary equipment such as pumps, com pressors, heaters, coolers, heat exchangers and pipes. The process simulation package “Aspen-HYSYS 3.1’’ has been used. The operation parameters of the reactors have been determined considering all the technical limitations involved. A gasoline type hydrocarbon fuel has been studied as hydrogen rich gas source. Thermal efficiencies have been calculated for all of the major system components for selected operation conditions. The fuel cell stack efficiency has been calculated as a function of cell numbers (500, 750, 1000, and 1250 cells). Efficiencies of all of the major system components along with auxiliary unit efficiencies determine the net electrical efficiency of the PEM fuel cell system. The obtained net electrical efficiency levels are between 34 (500 cells) to 41% (1250 cells).     

Characterization of a limestone in a batch fluidized bed reactor for sulfur retention under oxy-fuel operating conditions

CO₂ and SO₂ are some of the main polluting gases emitted into atmosphere in combustion processes using fossil fuel for energy production. The former is one of the major contributors to build-up the greenhouse effect implicated in global climate change and the latter produces acid rain. Oxy-fuel combustion is a technology, which consists in burning the fuel with a mix of pure O₂ and recirculated CO₂. With this technology the CO₂ concentration in the flue gas may be enriched up to 95%, becoming possible an easy CO₂ recovery. In addition, oxy-fuel combustion in fluidized beds allows in situ desulfurization of combustion gases by supplying calcium based sorbent.In this work, the effect of the principal operation variables affecting the sulfation reaction rate in fluidized bed reactors (temperature, CO₂ partial pressure, SO₂ concentration and particle size) under typical oxy-fuel combustion conditions have been analyzed in a batch fluidized bed reactor using a limestone as sorbent. It has been observed that sulfur retention can be carried out by direct sulfation of the CaCO₃ or by sulfation of the CaO (indirect sulfation) formed by CaCO₃ calcination. Direct sulfation and indirect sulfation operating conditions depended on the temperature and CO₂ partial pressure. The rate of direct sulfation rose with temperature and the rate of indirect sulfation for long reaction times decreased with temperature. An increase in the CO₂ partial pressure had a negative influence on the sulfation conversion reached by the limestone due to a higher temperature was needed to work in conditions of indirect sulfation. Thus, it is expected that the optimum temperature for sulfur retention in oxy-fuel combustion in fluidized bed reactors be about 925–950 °C. Sulfation reaction rate rose with decreasing sorbent particle size and increasing SO₂ concentration.     

Effect of gas composition in Chemical-Looping Combustion with copper-based oxygen carriers: Fate of light hydrocarbons

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 W_th). 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.     

Usability of food industry waste oils as fuel for diesel engines

Two cogeneration units were each fitted with a prechamber (IDI) diesel engine in order to test the feasibility of using waste oils from the food industry as a fuel source, and additionally to test emissions generated by the combustion of these fuels. Esterified waste oils and animal fats as well as mustard oil were tested and compared to the more or less "common" fuels: diesel, rapeseed oil and rapeseed methyl ester. The results show that, in principle, each of these fuels is suitable for use in a prechamber diesel engine. Engine performance can be maintained at a constant level. Without catalytic conversion, the nitrogen oxides emissions were comparable. A significant reduction in NO(x) was achieved through the injection of urea. Combining a urea injection with the SCR catalytic converter reduced NO(x) emissions between 53% and 67%. The carbon monoxide emissions from waste oils are not significantly different from those of "common" fuels and can be reduced the same way as of hydrocarbon emissions, through utilization of a catalytic converter. The rate of carbon monoxide reduction by catalytic conversion was 84-86%. A lower hydrocarbon concentration was associated with fuels of agricultural origin. With the catalytic converter a reduction of 29-42% achieved. Each prechamber diesel engine exhibited its own characteristic exhaust, which was independent of fuel type. The selective catalytic reduction of the exhaust emissions can be realized without restriction using fuels of agricultural origin.     

Development of Customized Fire Behavior Fuel Models for Boreal Forests of Northeastern China

Knowledge of forest fuels and their potential fire behavior across a landscape is essential in fire management. Four customized fire behavior fuel models that differed significantly in fuels characteristics and environmental conditions were identified using hierarchical cluster analysis based on fuels data collected across a boreal forest landscape in northeastern China. Fuel model I represented the dense and heavily branched Pinus pumila shrubland which has significant fine live woody fuels. These forests occur mainly at higher mountain elevations. Fuel model II is applicable to forests dominated by Betula platyphylla and Populus davidiana occurring in native forests on hill slopes or at low mountain elevations. This fuel model was differentiated from other fuel models by higher herbaceous cover and lower fine live woody loading. The primary coniferous forests dominated by Larix gmelini and Pinus sylvestris L. var. mongolica were classified as fuel model III and fuel model IV. Those fuel models differed from one another in average cover and height of understory shrub and herbaceous layers as well as in aspect. The potential fire behavior for each fuel model was simulated with the BehavePlus5.0 fire behavior prediction system. The simulation results indicated that the Pinus pumila shrubland fuels had the most severe fire behavior for the 97th percentile weather condition, and had the least severe fire behavior under 90th percentile weather condition. Fuel model II presented the least severe fire potential across weather conditions. Fuel model IV resulted in greater fire severity than Fuel model III across the two weather scenarios that were examined.     

汽车排放标准与改进燃料品质降低排放污染

本文综述了美国、日本、欧洲经济委员会（ＥＣＥ）及中国的汽车（主要是汽油车）排放标准；汽车排放与燃料品质有直接关系，通过改进燃料品质如使用无铅汽油，含氧燃料和替代燃料以及降低汽油中芳烃及硫含量等都能改善汽车排放污染。     

Numerical simulation of chemical looping combustion process with CaSO4 oxygen carrier

Chemical-looping combustion (CLC) is a promising technology for the combustion of gas or solid fuel with efficient use of energy and inherent separation of CO₂. The technique involves the use of an oxygen carrier which transfers oxygen from combustion air to the fuel, and hence a direct contact between air and fuel is avoided. A chemical-looping combustion system consists of a fuel reactor and an air reactor. A metal oxide is used as oxygen carrier that circulates between the two reactors. The air reactor is a high velocity fluidized bed where the oxygen carrier particles are transported together with the air stream to the top of the air reactor, where they are then transferred to the fuel reactor using a cyclone. The fuel reactor is a bubbling fluidized bed reactor where oxygen carrier particles react with hydrocarbon fuel and get reduced. The reduced oxygen carrier particles are transported back to the air reactor where they react with oxygen in the air and are oxidized back to metal oxide. The exhaust from the fuel reactor mainly consists of CO₂ and water vapor. After condensation of the water in the exit gas from the fuel reactor, the remaining CO₂ gas is compressed and cooled to yield liquid CO₂, which can be disposed of in various ways.With the improvement of numerical methods and more advanced hardware technology, the time needed to run CFD (Computational fluid dynamics) codes is decreasing. Hence multiphase CFD-based models for dealing with complex gas-solid hydrodynamics and chemical reactions are becoming more accessible. Until now there were a few literatures about mathematical modeling of chemical-looping combustion using CFD approach. In this work, the reaction kinetics model of the fuel reactor (CaSO₄ + H₂) was developed by means of the commercial code FLUENT. The bubble formation and the relation between bubble formation and molar fraction of products in gas phase were well captured by CFD simulation. Computational results from the simulation also showed low fuel conversion rate. The conversion of H₂ was about 34% partially due to fast, large bubbles rising through the reactor, low bed temperature and large particles diameter.     

CO2 emissions from Polish cement industry

The cement industry is one of the most significant sources of anthropogenic emissions of CO₂. It is connected with the specific character of the production processes, during which great quantities of CO₂ are produced. Basic actions to reduce CO₂ emissions recommended by the European Union's, Reference Document on Best Available Techniques in the Cement and Lime Manufacturing Industries, include: reduction of fuel consumption, selection of raw materials with low content of organic compounds and fuels with low coal contribution to heating value. All actions connected with the improvement of energy conversion efficiency of the cement production process cause CO₂ emissions reduction. The use of at most acceptable by the valid standards amounts of waste as raw materials and additives for cement production, also brings about the reduction of significant part of CO₂ emissions. These measures have been and continue to be pursued by the cement factories in Poland. This article describes the evolution of the cement industry in Poland over the period 1998–2008 and the resulting changes in CO₂ emissions and explores the drivers for these changes. The sources of CO₂ emissions in cement industry have been presented in this article as well as a discussion of potential ways to reduce Polish cement industry emissions even further.     

Fuel substitution in sub-Saharan Africa

Deforestation and decline in agricultural productivity are major concerns over large parts of sub-Saharan Africa. One of the principal causes for both these phenomena is the export of woodfuels from rural agroecosystems to urban markets. This process is noteworthy because of the size of the trade. Wood fuels (fuelwood, charcoal, and agricultural residues) constitute the most important source of energy in these countries, varying from 60% to 95% of total energy consumption. In terms of the environmental impact of the fuelwood trade, solutions typically considered are the introduction of improved cookstoves, fuelwood plantations, and fuel substitution by conventional fuels. This article examines the structure of the fuelwood problem, reviews the successes and failures of past experiences, and focuses on the potential for fuel substitution as an option to reduce the urban demand for fuelwood.     

Estimation of annual CH4 and N2O emissions from fluidised bed combustion: An advanced measurement-based method and its application to Finland

The aim of this study was to develop and apply an advanced, measurement based method for the estimation of annual CH₄ and N₂O emissions and thus gain improved understanding on the actual greenhouse gas (GHG) balances of combustion of fossil fuels, peat, biofuels and REF. CH₄ and N₂O emissions depend strongly on combustion conditions, and therefore the emission factors used in the calculation of annual emissions contain significant uncertainties. Fluidised bed combustion (FBC) has many good properties for combustion of different types of fuels and fuels of varying quality, e.g., biofuels and wastes. Therefore, it is currently increasing its market share. In this study, long term measurements (up to 50 days) were carried out at seven FBC boilers representing different size classes, loadings and fuel mixes. Both decreasing load and increasing share of coal in fuel mix increased N₂O emissions. Measurement results from different loading levels were combined with the common loading curves of similar plants in Finland to estimate annual emissions. Based on the results, recommendations for emission factors for the Finnish GHG emission inventory are given. The role of FBC as a potential technology for the utilisation of biofuels and wastes with future GHG reduction requirements is discussed.     

Investigation effect of hydrogen addition on the performance and exhaust emissions of Pongamia pinnata biodiesel fueled compression ignition engine

In the recent decades, the energy demand for transport and industrial sector has increased considerably. Fossil fuels which were the major fuel source for decades are no more sustainable. Biodiesel is an efficient alternative compared to depleting fossil fuels. The prospect of biodiesel as the best alternative fuel is a reliable source compared to depleting fossil fuels. Hydrogen is also considered as an attractive alternative fuel producing low emission with improved engine performance. This paper investigates the performance and emission characteristics of a single cylinder compression ignition engine using hydrogen as an inducted fuel and biodiesel, aka Pongamia pinnata as injected fuel. The experiments are conducted for different quantities of hydrogen induction through the intake manifold in order to improve the performance of the engine. The performance parameters such as brake thermal efficiency, brake specific fuel consumption, exhaust temperature and emission quantities like HC, NO_X, CO, CO₂ of biodiesel fueled CI engine with variable mass flow rate of hydrogen are investigated. The performances of biodiesel combined with hydrogen at varying mass flow rates are also compared. The 10 LPM hydrogen induction with biodiesel provided 0.33% increase of brake thermal efficiency compared with diesel and increase of 3.24% to biodiesel at 80% loading conditions. The emission of HC decreased by 13 ppm, CO decreased by 0.02% by volume and CO₂ decreased by 3.8% by volume for biodiesel with induction of hydrogen at 10 LPM to that of neat biodiesel for 80% load conditions.     

The potential for increased atmospheric CO2 emissions and accelerated consumption of deep geologic CO2 storage resources resulting from the large-scale deployment of a CCS-enabled unconventional fossil fuels industry in the U.S.

Desires to enhance the energy security of the United States have spurred renewed interest in the development of abundant domestic heavy hydrocarbon resources including oil shale and coal to produce unconventional liquid fuels to supplement conventional oil supplies. However, the production processes for these unconventional fossil fuels create large quantities of carbon dioxide (CO₂) and this remains one of the key arguments against such development. Carbon dioxide capture and storage (CCS) technologies could reduce these emissions and preliminary analysis of regional CO₂ storage capacity in locations where such facilities might be sited within the U.S. indicates that there appears to be sufficient storage capacity, primarily in deep saline formations, to accommodate the CO₂ from these industries. Nevertheless, even assuming wide-scale availability of cost-effective CO₂ capture and geologic storage resources, the emergence of a domestic U.S. oil shale or coal-to-liquids (CTL) industry would be responsible for significant increases in CO₂ emissions to the atmosphere. The authors present modeling results of two future hypothetical climate policy scenarios that indicate that the oil shale production facilities required to produce 3 MMB/d from the Eocene Green River Formation of the western U.S. using an in situ retorting process would result in net emissions to the atmosphere of between 3000 and 7000 MtCO₂, in addition to storing potentially 900–5000 MtCO₂ in regional deep geologic formations via CCS in the period up to 2050. A similarly sized, but geographically more dispersed domestic CTL industry could result in 4000–5000 MtCO₂ emitted to the atmosphere in addition to potentially 21,000–22,000 MtCO₂ stored in regional deep geologic formations over the same period. While this analysis shows that there is likely adequate CO₂ storage capacity in the regions where these technologies are likely to deploy, the reliance by these industries on large-scale CCS could result in an accelerated rate of utilization of the nation's CO₂ storage resource, leaving less high-quality storage capacity for other carbon-producing industries including electric power generation.     

改性活性炭脱除硫化氢工艺参数研究

针对改性活性炭脱除硫化氢过程,研究了空速、温度、原料气浓度、颗粒分布孔径4个主要工艺参数对脱硫效率的影响。结果表明:空速在1 500～4 200h-1时穿透硫容随着空速的降低而增加,当空速继续降低为1 200h-1时穿透硫容基本不变;当0～40℃时,随着温度的升高,穿透时间增加,脱硫效率提高,当温度超过40℃时,随着温度继续升高脱硫效率降低;相同空速下原料气硫化氢浓度变化只改变穿透时间;改性活性炭脱硫剂发挥脱硫作用的微孔结构范围是1～5nm。