Integrating purifiers in refinery hydrogen networks: a retrofit case study

Hydrogen is an important utility in the production of clean fuels such as low-sulfur gasoline and diesel. The shortage of hydrogen resource motivates the integrated management of hydrogen networks with purifiers. In this paper, we propose a systematic approach for the retrofit design of these hydrogen networks. By establishing a state-space superstructure, all possible placements of existing compressors and purifiers are incorporated in the proposed MINLP model. Total annual cost (TAC) is employed as the optimizing object to understand the trade-offs between operating cost and capital cost. A real refinery system near Shanghai of China city is used to illustrate the applicability of the approach.     

Biological removal of air loaded with a hydrogen sulfide and ammonia mixture

The nuisance impact of air pollutant emissions from wastewater pumping stations is a major issue of concern to China. Hydrogen sulfide and ammonia are commonly the primary odor and are important targets for removal. An alternative control technology, biofiltration, was studied. The aim of this study is to investigate the potential of unit systems packed with compost in terms of ammonia and hydrogen sulfide emissions treatment, and to establish optimal operating conditions for a full-scale conceptual design. The laboratory scale biofilter packed with compost was continuously supplied with hydrogen sulfide and ammonia gas mixtures. A volumetric load of less than 150 gH2S/(m^3.d) and 230 gNH3/(m^3.d) was applied for about fifteen weeks. Hydrogen sulfide and ammonia elimination occurred in the biofilter simultaneously. The removal efficiency, removal capacity and removal kinetics in the biofilter were studied. The hydrogen sulfide removal efficiency reached was very high above 99%, and ammonia removal efficiency was about 80%. Hydrogen sulfide was oxidized into sulphate. The ammonia oxidation products were nitrite and nitrate. Ammonia in the biofilter was mainly removed by adsorption onto the carrier material and by absorption into the water fraction of the carrier material. High percentages of hydrogen sulfide or ammonia were oxidized in the first section of the column. Through kinetics analysis, the presence of ammonia did not hinder the hydrogen sulfide removal. According to the relationship between pressure drop and gas velocity for the biofilter and Reynolds number, non-Darcy flow can be assumed to represent the flow in the medium.     

Hydrogen distribution network optimization: a refinery case study

One of the most critical issues in the production of low-sulphur fuels is managing the impact of the new environmental requirements on the hydrogen balance of the refinery. The combination of low-sulphur fuel specifications and reduced production of hydrogen in catalytic reformers make hydrogen management a critical issue. More efficient use of hydrogen thus becomes unavoidable. This paper addresses the problem of the actual hydrogen distribution at the Porto Refinery of the GALP ENERGIA network, and uses a new tool based on the concept of hydrogen surplus. By means of different methodologies and resorting to linear programming, an efficient network design has been achieved that reduces the hydrogen utilities usage by 30% (achieving 30% more gas to the fuel system), while also dealing with the complexity and need for flexibility so characteristic of a refinery as well as the reduction of operating costs related to the pneumatic system. In terms of hydrogen manufacturing reduction in the platformings, it is possible to reduce by 6%.     

Hydrogen storage and distribution systems

Hydrogen storage and transportation or distribution is closely linked together. Hydrogen can be distributed continuously in pipelines or batch wise by ships, trucks, railway or airplanes. All batch transportation requires a storage system but also pipelines can be used as pressure storage system. Hydrogen exhibits the highest heating value per weight of all chemical fuels. Furthermore, hydrogen is regenerative and environment friendly. There are two reasons why hydrogen is not the major fuel of toady’s energy consumption: First of all, hydrogen is just an energy carrier. And, although it is the most abundant element in the universe, it has to be produced, since on earth it only occurs in the form of water. This implies that we have to pay for this energy, which results in a difficult economic task, because since the industrialization we are used to consuming energy for free. The second difficulty with hydrogen as an energy carrier is the low critical temperature of 33 K, i.e. hydrogen is a gas at room temperature. For mobile and in many cases also for stationary applications the volumetric and gravimetric density of hydrogen in a storage system is crucial. Hydrogen can be stored by six different methods and phenomena: high pressure gas cylinders (up to 800 bar), liquid hydrogen in cryogenic tanks (at 21 K), adsorbed hydrogen on materials with a large specific surface area (at T < 100 K), absorbed on interstitial sites in a host metal (at ambient pressure and temperature), chemically bond in covalent and ionic compounds (at ambient pressure), oxidation of reactive metals e.g. Li, Na, Mg, Al, Zn with water. These metals easily react with water to the corresponding hydroxide and liberate the hydrogen from the water. Finally, the metal hydroxides can be thermally reduced to the metals in a solar furnace.     

省级环境管理部门基础信息网络建设实践与思考

阐述省级环境管理部门基础信息网络建设的重要性及建设应遵循的基本要求,结合实践,讨论设计和实际施工中出现的问题及解决办法,为环境管理部门基础信息网络建设提供有益参考。     

个人乘用车用可替代燃料与我国未来的选择

个人乘用车排放量占道路交通运输二氧化碳(CO2)排放量的三分之一。因此,逐步实现其燃料由传统石化燃料汽柴油向新能源转变是交通运输行业低碳减排和绿色发展的重要抓手之一。本文对当前可供个人乘用车使用的4大类新能源即生物燃油、燃料乙醇、氢和电的属性,特别是其CO2减排效果和使用成本进行了分析和对比,并对新能源加注(充电)设施在欧盟和美国的布局战略和实施成果进行了介绍。结合欧美的实践和中国的实际,本文提出了未来个人乘用车用可替代燃油布局的建设,建议我国直接从传统石化汽油跨越至氢和/或电,并将其作为未来个人乘用车的燃料。     

循环流化床脱除氯化氢研究

在直径200mm、高2560mm自制循环流化床上进行了脱除氯化氢的研究。实验结果表明本实验采用的循环流化床尾气净化装置，在士湿两种状况下的净化效率都比周类型装置有较大提高。当喷水活化增湿以后，净化效率可达90％以上，并考察了停留时间、Ca/Cl 当量比、粒径和入口氯 化氢浓度等因素对氯化氢脱除效率的影响。证实延长停留时间、增大Ca/Cl当量比、减 小粒径和增加入口氯化浓度有利于提高氯化氢脱除效率。     

A material and energy flow model for co-production of heat and power

Co-production of electricity, district heat and industrial heat/process steam (heat and power, CHP) has been applied to a large, national scale, in only a few countries in the world, Denmark, The Netherlands and Finland. In this production method, the waste energy from electricity production is used in two quality levels. First, industrial process steam requirements can be met with this residual energy. Second, the waste energy is used in local district heating networks for households and other buildings in a city. In this integrated production method, a total fuel efficiency of 85% can be achieved. Through the technique of fluidized bed combustion, modern CHP plants can use coal and oil, and in addition, heterogeneous fuels such as biomass, industrial wastes and recycled fuels from households. In this paper, the CHP method is considered in terms of four categories of material and energy flows. For the purpose of considering the potential environmental gains and the difficulties of this production method when applied to integrated waste management and energy production, the four suggested categories are: matter (biomass) (1), nutrients (2), energy (3) and carbon (4). Corporate environmental management inventory tools, decision-making tools, management, organisational and administrative tools as well as information management tools that could be used in CHP-related material and energy flow management are shortly discussed. It is argued that for CHP energy and environmental management, it can be important to adopt an approach to networks of firms, rather than to an individual firm. The presented material and energy flow model may contribute to assessing, planning and implementing of CHP-based waste management and cleaner energy production.     

Hydrogen storage methods

Hydrogen exhibits the highest heating value per mass of all chemical fuels. Furthermore, hydrogen is regenerative and environmentally friendly. There are two reasons why hydrogen is not the major fuel of todays energy consumption. First of all, hydrogen is just an energy carrier. And, although it is the most abundant element in the universe, it has to be produced, since on earth it only occurs in the form of water and hydrocarbons. This implies that we have to pay for the energy, which results in a difficult economic dilemma because ever since the industrial revolution we have become used to consuming energy for free. The second difficulty with hydrogen as an energy carrier is its low critical temperature of 33 K (i.e. hydrogen is a gas at ambient temperature). For mobile and in many cases also for stationary applications the volumetric and gravimetric density of hydrogen in a storage material is crucial. Hydrogen can be stored using six different methods and phenomena: (1) high-pressure gas cylinders (up to 800 bar), (2) liquid hydrogen in cryogenic tanks (at 21 K), (3) adsorbed hydrogen on materials with a large specific surface area (at T<100 K), (4) absorbed on interstitial sites in a host metal (at ambient pressure and temperature), (5) chemically bonded in covalent and ionic compounds (at ambient pressure), or (6) through oxidation of reactive metals, e.g. Li, Na, Mg, Al, Zn with water. The most common storage systems are high-pressure gas cylinders with a maximum pressure of 20 MPa (200 bar). New lightweight composite cylinders have been developed which are able to withstand pressures up to 80 MPa (800 bar) and therefore the hydrogen gas can reach a volumetric density of 36 kg·m^–3, approximately half as much as in its liquid state. Liquid hydrogen is stored in cryogenic tanks at 21.2 K and ambient pressure. Due to the low critical temperature of hydrogen (33 K), liquid hydrogen can only be stored in open systems. The volumetric density of liquid hydrogen is 70.8 kg·m^–3, and large volumes, where the thermal losses are small, can cause hydrogen to reach a system mass ratio close to one. The highest volumetric densities of hydrogen are found in metal hydrides. Many metals and alloys are capable of reversibly absorbing large amounts of hydrogen. Charging can be done using molecular hydrogen gas or hydrogen atoms from an electrolyte. The group one, two and three light metals (e.g. Li, Mg, B, Al) can combine with hydrogen to form a large variety of metal–hydrogen complexes. These are especially interesting because of their light weight and because of the number of hydrogen atoms per metal atom, which is two in many cases. Hydrogen can also be stored indirectly in reactive metals such as Li, Na, Al or Zn. These metals easily react with water to the corresponding hydroxide and liberate the hydrogen from the water. Since water is the product of the combustion of hydrogen with either oxygen or air, it can be recycled in a closed loop and react with the metal. Finally, the metal hydroxides can be thermally reduced to metals in a solar furnace. This paper reviews the various storage methods for hydrogen and highlights their potential for improvement and their physical limitations.     

Effects of thermally pretreated temperature on bio-hydrogen production from sewage sludge

Hydrogen can be obtained by anaerobic fermentation of sewage sludge. Therefore, in this paper the effects of thermally pretreated temperatures on hydrogen production from sewage sludge were investigated under different pre-treatment conditions. In the thermal pretreatment, some microbial matters of sludge were converted into soluble matters from insoluble ones. As a result, the suspended solid（SS） and volatile suspended solid（VSS） of sludge decreased and the concentration of soluble COD（SCOD） increased, including soluble carbohydrates and proteins. The experimental results showed that all of those pretreated sludge could produce hydrogen by anaerobic fermentation and the hydrogen yields under the temperatures of 121℃ and 50℃ were 12.23 ml/g VS（most） and 1.17 ml/g VS （least）, respectively. It illuminated that the hydrogen yield of sludge was affected by the thermally pretreated temperatures. Additionally, the endurance of high hydrogen yield depended on the translation of microbial matters and inhibition of methanogens in the sludge. The temperatures of 100℃ and 121℃ （treated time, 30 min） could kill or inhibit completely the methanogens while the others could not. To produce hydrogen and save energy, 100℃ was chosen as the optimal temperature for thermal pretrcatment. The composition changes in liquid phase in the fermentation process were also discussed. The SCOD of sludge increased, which was affected by the pretreatment temperature. The production of volatile fatty acids in the anaerobic fermentation increased with the pretreatment temperature.     

Fueling Asian modernization

During upcoming industrialization, the human population of Asia will exert a strong influence on both the Pacific Rim environment and the total earth system. We review energy-use trajectories both likely and possible on the continent, taking the historical market penetration series as a framework. Today, the People's Republic of China is coal rich, but as its economy grows in the short term, fuel substitution from solid fossils will occur. Major automakers will exploit new niches in the Orient, adding petroleum to the mix of fuels and producing photochemical smog on the regional scale. Demand is rising in coastal cities for cleaner fuels such as natural gas, but they must be imported. Nuclear industries in India and China are small and expanding only slowly. The Tibetan plateau confers exceptional hydroelectric potential but peripheral concerns plague the big dams. Solar and hydrogen are decades from implementation even in Europe. Fossil resources are largely remote from the Asian consumer class. The disconnect feeds back into the design of new transportation networks. Since for the moment development lags, the option exists to view Asia as a crucible for the techniques of cogeneration, sequestration and pollutant recapture.     

厌氧生物滴滤法脱除冷煤气中硫化氢的研究

水煤气中硫化氢在燃烧时会转变成二氧化硫,对环境产生污染。文章采用厌氧生物滴滤塔法对冷煤气进行脱硫处理。因煤气对氧的严格限制,通过设计生物滴滤塔,经挂膜驯化后在厌氧条件下对浓度在1~5 g/m3左右的硫化氢进行脱除处理,考察滴滤塔运行条件对脱除效果的影响。结果表明,生物挂膜25 d后,生物滴滤塔达到稳定,喷淋液pH值为2.23,ORP值为283 mV,溶解氧为0.4 mg/L,对溶液中硫离子氧化效率达到94%。滴滤塔在液气比0.15,空塔气速0.088 m/s,pH值5.0~7.0,填料高度为82 cm,塔温为25~30℃左右时,达到较优的运行条件,此时该滴滤塔对以CO、CO2、H2和1 940 mg/m3H2S组成的模拟水煤气的脱硫效率达91.2%。     

Gas separation using porous cement membrane

Gas separation is a key issue in various industrial fields. Hydrogen has the potential for application in clean fuel technologies. Therefore, the separation and purification of hydrogen is an important research subject. CO2 capture and storage have important roles in ＂green chemistry＂. As an effective clean technology, gas separation using inorganic membranes has attracted much attention in the last several decades. Membrane processes have many applications in the field of gas separation. Cement is one type of inorganic material, with the advantages of a lower cost and a longer lifespan. An experimental setup has been created and improved to measure twenty different cement membranes. The purpose of this work was to investigate the influence of gas molecule properties on the material transport and to explore the influence of operating conditions and membrane composition on separation efficiency. The influences of the above parameters are determined, the best conditions and membrane type are found, it is shown that cementitious material has the ability to separate gas mixtures, and the gas transport mechanism is studied.     

混合培养对沼泽红假单孢菌产氢及代谢的影响

混合培养逐渐引起人们的关注,将沼泽红假单孢菌Rhodopseudomonas palustris和厌氧细菌Enterobacter aerogenes PCM 532的混合培养,并进行生长代谢、产氢及正交实验、Biolog碳源代谢实验。结果表明,混合菌在厌氧光照条件下生长迅速,在好氧黑暗条件下也有一定生长;混合培养的产氢量高于纯培养;正交实验得到,对混合培养产氢影响最大的是底物和混合比例;Biolog微孔板代谢中混合菌可以利用纯菌种培养不能利用的碳源。混合培养表现为协同作用,促进细菌生长和提高产氢能力。     

双氧水对废水化学需氧量测定的影响

废水中双氧水的存在影响化学需氧量的测定，其浓度增大，影响愈明显。加氢氧化钠碱化，对废水中低浓度双氧水分解作用不大，不能使用溶液碱化的方法去除废水中低浓度的双氧水。     

大型气候环境实验室上部运输系统的方案设计

目的设计出满足气候环境实验室的上部运输系统。方法根据国内外实验室上部运输系统的设计经验,结合实际使用情况,设计出满足实验室使用条件的上部运输系统方案。结果设计出的上部运输系统直接参与各环境试验的运输、吊装工作,满足气候实验室的环境条件,且具有安全可靠、便于操作维护等特点。结论设计出的上部运输系统满足气候环境实验室的使用要求。     

民用水上飞机机载设备腐蚀环境技术要求研究

目的针对民用水上飞机的机载设备构建一套更为严格的环境技术要求,以满足民用水上飞机在其特殊使用环境和使用模式下的安全性和可靠性。方法通过分析水上飞机的总体使用环境,提取影响机载设备腐蚀的主要环境因素,整理和归纳环境量值对相关环境要求进行修正。结果给出了RTCA DO-160G标准中湿热、霉菌和盐雾试验条件的改进建议。结论试验条件改进依据充分合理,能够适用于民用水上飞机机载设备的腐蚀环境适应性评估与验证。     

Hydrogen for a sustainable global economy

The topic of this special issue of the Journal of Cleaner Production is “Sustainable Hydrogen from Biomass.” It is of interest to practitioners in the energy sector, governmental policy makers, researchers, educators, as well as to the general public. The purpose of this special issue is to increase public awareness and to stimulate exchange of information among actors expected to play important roles in making hydrogen available for the sustainable energy system of the future.Hydrogen as a biofuel, that is, hydrogen produced from biomass in a sustainable way is recognised as an important component of the fuel market for the future low or non-carbon based energy systems. In this special issue, the main focus is on hydrogen produced from vegetable biomass by fermentation. The development of a two-stage bioprocess for the cost-effective and environmentally friendly production of pure hydrogen from multiple biomass feedstocks is elucidated by a collection of papers presenting preliminary results of Integrated Research Project HYVOLUTION supported by the 6th Framework Programme of the European Union. The attention is turned to:- the over-all concept and characteristics of the two-stage hydrogen fermentation process,- key technological issues of fermentative hydrogen production,- the availability of vegetable feedstocks including agricultural byproducts that suitable for fermentative processing,- prospects of societal integration and sustainability of the fermentative hydrogen production technology.Other papers included in this special issue are devoted to:- simultaneous production of hydrogen and methane by fermentation of lactose-containing feedstocks derived from byproducts of milk processing,- hydrogen gas generation from organic material by electrohydrogenesis, that is, a bioelectrochemical process performed in reactors known as a microbial electrolysis cells,- the ideas for Europe-wide effort on education of hydrogen users and training of skilled staff needed for facilitating the transition to the future hydrogen economy.     

硝酸贮存系统安全技术措施探讨

对硝酸贮存系统存在的危险性进行了分析 ,从设计、安装和操作管理提出了相应的处理措施 ,确保硝酸的贮存安全管理     

Exploring innovation in the automotive industry: new technologies for cleaner cars

The concept of innovation has been used in a wide range of contexts and the theoretical development has proven to be extremely valuable to provide important insights into intra-market competition, strategy and regulatory policy. The automotive industry offers a fertile terrain for progress of the uncompleted theory building process of innovation, especially with the introduction of alternative fuels and alternative powertrain technologies.This paper investigates the concept of innovation in the context of the modern automotive industry, by focusing on the notion of regulatory innovation of alternative fuels and alternative powertrain technologies. For the purpose of analysing this issue, special attention is given to the concepts of radical and incremental innovation, which are applied to existing alternative fuels and alternative powertrain technologies, including hybrids, biofuels and hydrogen power. The article explores these three categories looking at representative case studies: the Brazilian ethanol experience with biofuels, the development of the Toyota hybrid vehicle and the technological development of hydrogen fuel cells. These categories have been selected because they represent the most important advances in cleaner production for the automotive industry.