Coal-to-SNG Scheme Avoids Gasification, CO2 Claims Cost Advantages

Dec.2020•32 •化肥设计Chemical Fertilizer Design第58卷第6期2020年12月子粉煤气化粉煤制备Aspen辅助设针介绍胡文佳，吴红亮，杜晓丹(中国天辰工程有限公司，天津300400)摘要针对目前干粉煤气化粉煤制备的特点，利用A s p e n软件建立模拟流程，并对粉煤制备过程进行流程模拟$通过工程运行数据及专利商数据与模拟数据的对比分析，结果表明，流程模拟具有很高的准确性$同时介绍了A s p e n辅助模拟粉煤制备过程在康乃尔项目及青海矿业项目中的应用，在模拟计算的帮助下，提高了设计准确度及工作效率$关键词干粉煤气化；粉煤制备；A s p e n模拟doi:10.3969'.issn.1004 — 8901.2020.06.010中图分类号T Q546 文献标识码B文章编号1004 —8901(2020)06 —0032 —04Introduction of Aspen-aided Design of Pulverized Coal Preparation for Dry Pulverized Coal Gasification PlantsHU Wen-jia,WU Hong-liang,DU Xiao-dan{China Tianchen Engineering Corporation /Tianjin300400 »China)Ab str a c t： Based on the characteristics pulverized coal preparation of dry pulverized coal gasification plants at present»the simulation process is es­tablished via Aspen software to simulate the preparation process of pulverized coal. Results from comparing and analyzing the engineering opera­tion data,the licensor's data and simulation data show that the process simulation results are highly accurate. The application of Aspen-aidedsimulated pulverized coal preparation in Cornell Project and Qinghai mining projects is introduced, which in tion calculation»the design accuracy and work efficiency are both elevated.K ey wo r d s： dry pulverized coal gasification； preparation of pulverized coal； Aspen simulationdoi:10. 3969/j. issn. 1004-8901. 2020. 06. 010近十几年来，我国煤气化技术取得了长足的发展，以水煤浆及粉煤气化为代表的气流床气化技术，具有单炉生产规模大、三废排放少等特点，被广 泛应用于大型煤化工项目中。

煤炭基础知识[我的钢铁] 2008-02-02 10:20:41（一）煤及其产品　序号术语名称英文名称定义符号允许使用的同义词停止使用的同义词2.1.1 煤 coal 植物遗体在覆盖地层下，压实、转化而成的固体有机可燃沉积岩煤炭2.1.2 煤的品种 Categories of coal 以不同方式加工成不同规格的煤炭产品 2.1.3 标准煤 Coal equivalent 凡能产生29.27MJ的热量（低位）的任何数量的燃料折合为1kg标准煤 2.1.4 毛煤 Run-of-mine coal 煤矿生产出来的，未经任何加工处理的煤 2.1.5 原煤 Raw coal 从毛煤中选出规定粒度的矸石（包括黄铁矿等杂物）以后的煤 2.1.6 商品煤 Commercial coal;salable coal 作为商品出售的煤　销煤2.1.7 精煤 clenedcoal 煤经精选（干选或湿选）后生产出来的、符合质量要求的产品　洗精煤2.1.8 中煤 Middings 煤经精选后的道德、灰分介于精煤和矸石之间的产品 2.1.9 洗选煤 Washed coal 经过洗选后的煤’ 2.1.10 筛选煤 Screened coal;sieved coal 经过筛选加工的煤 2.1.11 粒级煤 Sized coal 煤通过筛选或精选生产的,粒度下限大于6mm 并规定有限下率的产品 2.1.12 粒度 Size 颗粒的大小 2.1.13 限上率 Oversize fraction 筛下产品中大于规定粒度上限部分的质量百分数 2.1.14 限下率 Undersize fraction 筛上产品中小于规定中的粒度下限部分的质量百分数　含末率2.1.15 特大块 Uitra large coal(>100mm) 大于100mm的粒级煤 2.1.16 大块煤 Large coal(>50mm) 大于50mm的粒级煤 2.1.17 中块煤 Medium-sizldcoal(25～50mm) 5～50mm的粒级煤 2.1.18 小块煤 Small coal(13～25mm) 13～25mm的粒级煤 2.1.19 混中块 Mixed medium-sized coal (13～80mm) 13～80mm的粒级煤 2.1.20 混块 Mixedlumpcoal(13～300mm) 13～300mm之间的粒级煤 2.1.21 粒煤 Pea coal(6～13mm) 6～13mm的粒级煤 2.1.22 混煤 Mixed coal(>0～50mm) 0～50mm之间的煤 2.1.23 末煤 Slack;slack coal(>0～25mm) 0～25mm之间的煤 2.1.24 粉煤 Fine coal(>0～6mm) 0～6mm之间的煤 2.1.25 煤粉 Coal fines(>0～0.5mm) 小于0.5mm的煤 2.1.26 煤泥 slime 煤经洗选或水采后粒度在0.5mm以下的产品 2.1.27 矸石 Shale 采.掘过程中从顶、底板或煤层混入煤中的岩石　矸子2.1.28 夹矸 Dirt band 夹层在煤层中的矿物质层 2.1.29 洗矸 washeryrejects 从洗煤中排出的矸石 2.1.30 含矸率 Shale content 煤中大于50mm矸石的质量百分数 (二)煤的采样和制样序号术语名称英文名称定义符号允许使用的同义词停止使用的同义词2.2.1 煤样 Coals sample;sample 为确定某些特性而从煤中采取的、具有代表性的一部分煤 2.2.2 采样 Samping 采取煤样的过程 2.2.3 子样 Increment 采样器具操作一次或截取一次煤流分断面所采取的一份样 2.2.4 总样 Gros sample 从一个采样单元取出的全部子样合并成的煤样 2.2.5 随机采样 random sampling 在采取子样式，对采样的部位或时间均不施加任何人为的意志，能使任何部位的煤都有机会采出 2.2.6 系统采样 Systematic sampling 按相同的时间、空间或质量的间隔采取子样，但第一个子样在第一个间隔内随机采取，其余的子样按选定的间隔采取 2.2.7 批 Batch;lot 在相同的条件下，在一段时间内生产的一个量 2.2.8 采样单元 Sampling unit 从一批煤中采取一个总样的煤量。

科技创新导报 Science and Technology Innovation Herald 166技报告导读unit injection mode, Optimize the injection parameters vuggy reservoir water injection unit, Further improve the different types of karst fractured reservoir provides water technology policy. The subject completed the annual research program content and objectives.Key Words ：Tahe Oilfield；fractured-vuggy reserviors；Water flooding development；Water injection;Injection-production parameters阅读全文链接（需实名注册）：htt p://w w w.nstr s.c n/x ian g x iBG.as px?id=47982&f lag=1煤焦催化气化中非均相反应动力学的研究李伟伟1 张荣1 毕继诚1 郑岩2(1.中国科学院山西煤炭化学研究所；2.新奥集团煤基低碳能源国家重点实验室)摘　要：以神木煤焦为研究对象，在小型加压固定床上考察了不同气化剂（水蒸气、二氧化碳、氢气）、催化剂负载量、水蒸气分压、氢气分压和一氧化碳分压对碳转化率和气化反应速率的影响。

结果表明，对于非均相的催化气化反应来说，反应速率顺序为C-H 2O>C-CO 2>C-H 2。

H 2和CO不同程度地抑制煤焦水蒸气气化反应，CO的抑制作用明显大于H 2。

在700 ℃，当添加5%的CO，碳转化率降低约50%。

基于Langmuir-Hinshelwood （L-H）方程，结合随机孔模型，同时考虑催化剂负载量及气化产物分压的影响，建立了煤焦催化水蒸气气化动力学模型，模型预测反应速率常数与实验值误差在10%以内，说明建立的动力学模型可以较好地模拟煤焦的催化水蒸气气化反应过程。

化工进展Chemical Industry and Engineering Progress2023 年第 42 卷第 8 期煤气化渣资源化利用张丽宏，金要茹，程芳琴（山西大学资源与环境工程研究所，国家环境保护煤炭废弃物资源化高效利用技术重点实验室，山西 太原 030006）摘要：煤气化技术作为清洁利用技术得到迅速发展，但同时产生大量的煤气化渣。

本文从煤气化渣的来源及危害、煤气化渣的基本性质、煤气化渣制备材料（介孔材料、活性炭、复合材料）和煤气化渣的应用（废气废水处理、建工建材、农业）4个方面进行概述总结，对存在的问题、应用前景分别进行了分析和展望。

文中指出：煤气化渣含碳量高、铝硅资源丰富、比表面积较大、孔隙结构比较发达，可用于制备高值化产品，但制备过程中所产生的废液需要进行处理与处置，剩余的含铝、硅和碳残渣也需要进行回收利用。

煤气化渣的研究虽然取得了良好的效果，但大都处于实验室研究阶段或试验推广阶段，无法实现规模化利用。

建议开发工艺简单、可行性强且具有经济效益的煤气化渣资源化利用技术，在分级利用的基础上实现铝、硅、碳资源的协同利用；在全利用的基础上实现其规模化利用。

关键词：煤气化渣；资源化利用；介孔材料；活性炭；建工建材中图分类号：TQ536；X7 文献标志码：A 文章编号：1000-6613（2023）08-4447-11Resource utilization of coal gasification slagZHANG Lihong ，JIN Yaoru ，CHENG Fangqin(State Environmental Protection Key Laboratory of Efficient Utilization Technology of Coal Waste Resources, Institute ofResources and Environmental Engineering, Shanxi University, Taiyuan 030006, Shanxi, China)Abstract: Coal gasification technology has developed rapidly as a clean utilization technology, but a large amount of coal gasification slag has been produced at the same time. With the sources and hazards, the basic properties, the prepared materials (mesoporous materials, activated carbon, composite materials) and the application of coal gasification slag (in the field of waste gas and wastewater treatment, construction and building materials, agriculture) involved, this article reviews the research status, analyzes the existing problems and forecasts application prospects. Coal gasification slag is rich in carbon, aluminum and silicon, with large specific surface area and relatively developed pore structure. Then it can be used to prepare high-value products. However, the waste liquid generated during the preparation process needs to be urgently treated and disposed of. The remaining aluminum, silicon and carbon-containing residues also need to be recycled. Although the research on coal gasification slag has achieved good results, most are still in the stage of laboratory research or experimental promotion, and cannot achieve large-scale utilization. In this paper, it is suggested that developing resource utilization technology of coal gasification slag with simple process, strong feasibility and economic benefits, the synergistic utilization of aluminum, silicon and carbon resources should be realized on the basis of hierarchical utilization, and large-scale综述与专论DOI ：10.16085/j.issn.1000-6613.2022-1845收稿日期：2022-10-08；修改稿日期：2022-11-23。

aerosol propellant气溶胶喷射剂aftertreatment 后处理ammonia 氨Annual capacity factor年均利用率Annual capital charge rate 年均资本回收率aromatic 芳族化合物As-received收到基(煤)atmospheric pollution 大气污染Auto-ignition temperature自燃温度，自燃点biodiesel 生物柴油Biomass 生物质Blend 混和Boiling point沸点Capacity 容量capital intensity 资本强度Carbon balance 碳平衡Carbon emission 二氧化碳排放Carbon sequestration 埋存碳(二氧化碳)Carbon(CO2) capture and storage 回收并储存碳(二氧化碳) Catalyst 催化剂CBM 煤层气C-C bond 碳-碳化学键Cetane (number) 十六烷值Chemical feedstock 化工原料Chemicals 化工产品CNG 压缩天然气CO2 二氧化碳Coal (syngas) polygeneration 煤气化多联产Coal derived 煤基Coal mining 采煤Coal slurry 水煤浆coal steam-electric plant 火电厂Coalsteam plant with FGD 火力发电厂烟气脱硫Co-capture / Co-storage （或CC+CS）联合回收/联合存储cold start 冷态启动Commercial scale 大规模、工业规模Compression-ignition engine or CIE 压燃式发动机Cool Water demonstration 冷水示范电厂Cooling water 冷却水coproduct 副产物Co-production 联产Cost estimate 成本估计Cracking catalyst 裂化催化剂Crude oil 原油DCL / Direct coal liquefaction 煤直接液化Dehydration of methanol 甲醇脱水反应Density 密度Desulfurization 脱硫diesel engine 柴油发动机Dimethyl ether or DME CH3OCH3 二甲醚Direct liquefaction technology 直接液化技术Disengagement zone 分离区electricity or power generation 发电Energy balance 能量平衡Energy Mix 能源构成Equilibrium limit 化学平衡限制Equivalent 等价物ER for emission rate 排放率Externality 外部因素Financial cost 经济成本，财务成本Fischer-Tropsch synthesis or F-T 费脱合成Flammability limits 可燃极限FTL for F-T liquids 费脱合成液体燃料Fuel cycle 燃料循环Gasification 气化Gasoline 汽油Gas-phase reactor 气相反应器GHG emissions mitigation 减排温室气体Global warming 全球变暖Greenhouse gas or GHG 温室气体Grid 电网Grind 碾碎GTL for Gas To Liquids 气变油H2/CO ratio or H/C ratio 合成气中氢气/一氧化碳含量比，氢碳比H2S 硫化氢HC for hydrocarbon 烃，碳氢化合物HC fuel 烃类燃料Health cost 健康损害Heating 采暖heavy-duty 重型的Hybrid-electric 混合电能hydrogenation 加氢作用ICL for Indirect Coal Liquefaction 煤间接液化IGCC plant 整体煤气化联合循环电厂Installed capital cost 建设投资成本intellectual property 知识产权JV for joint venture 合资企业Life cycle 全生命周期Liquefaction 液化Liquid-phase 液相Liquid-phase reactor 液相反应器Location factor 区域因子LowEff Low efficiencyLower heat value 低位热值LPG 液化石油气Lube oil 润滑油methane 甲烷Methanol or MeOH CH3OH 甲醇middle distillate 中间馏份Mitigation 减少，减排Mtce 一种能量单位百万吨标煤NOx 氮氧化物noxious material 有害物质Off the shelf 现货供应One-through design 一次通过方式Operating &maintenance / O&M 运行维护Overnight 隔夜oxygenated fuel 氧化燃料Oxygen-blown gasification 氧吹气化Ozone 臭氧paraffin 石蜡Pilot plant scale 试验厂规模PM for particulate matter 颗粒物Poly-generation 多联产Poly-generation technology 多联产技术Power island 动力岛power sector 电力行业ppb level 十亿分率水平pressurized canister 加压罐Process configuration 工艺配置Process heat 工艺用热Production cost 生产成本Propane 丙烷public good 公共福利Purge gas 净化气体Quench 激冷Reaction conditions: P for pressure Tfor temperature 反应条件: P代表压力，T代表温度Recycle design 循环方式reduce 还原；减少refinery 炼油renewable energy 可再生能源residual 渣油Saturator 饱和器semi-refined 半精制的Single(or One)-pass conversion 一次通过的转化率Slurry 浆SO2 二氧化硫social cost 社会成本Soot 烟灰Spark-ignition engine 火花引燃式发动机Stand-alone 单独的Streamline 简化使有效率Sulfur 硫Syncrude 合成原油Syngas or synthesis gas 合成气Syngas park 合成气园Synthesis 合成Synthesis conversion 合成转化率synthesis reactor 合成反应器Synthetic fuel 合成燃料TFESTTI for Technical Infrastructure 技术基础设施toxic metal 有毒金属物Unreacted 未反应的USDOE 美国能源部Vapor pressure 蒸汽压Vent 排放Water gas shift / WGS 水煤气变换aerosol propellant 气溶胶喷射剂aftertreatment 后处理ammonia 氨Annual capacity factor 年均利用率Annual capital charge rate 年均资本回收率aromatic 芳族化合物As-received 收到基(煤)atmospheric pollution 大气污染Auto-ignition temperature 自燃温度，自燃点biodiesel 生物柴油Biomass 生物质Blend 混和Boiling point 沸点Capacity 容量capital intensity 资本强度Carbon balance 碳平衡Carbon emission 二氧化碳排放Carbon sequestration 埋存碳(二氧化碳)Carbon(CO2) capture and storage 回收并储存碳(二氧化碳) Catalyst 催化剂CBM 煤层气C-C bond 碳-碳化学键Cetane (number) 十六烷值Chemical feedstock 化工原料Chemicals 化工产品CNG 压缩天然气CO2 二氧化碳Coal (syngas) polygeneration 煤气化多联产Coal derived 煤基Coal mining 采煤Coal slurry 水煤浆coal steam-electric plant 火电厂Coalsteam plant with FGD 火力发电厂烟气脱硫Co-capture / Co-storage （或CC+CS）联合回收/联合存储cold start 冷态启动Commercial scale 大规模、工业规模Compression-ignition engine or CIE 压燃式发动机Cool Water demonstration 冷水示范电厂Cooling water 冷却水coproduct 副产物Co-production 联产Cost estimate 成本估计Cracking catalyst 裂化催化剂Crude oil 原油DCL / Direct coal liquefaction 煤直接液化Dehydration of methanol 甲醇脱水反应Density 密度Desulfurization 脱硫diesel engine 柴油发动机Dimethyl ether or DME CH3OCH3 二甲醚Direct liquefaction technology 直接液化技术Disengagement zone 分离区electricity or power generation 发电Energy balance 能量平衡Energy Mix 能源构成Equilibrium limit 化学平衡限制Equivalent 等价物ER for emission rate 排放率Externality 外部因素Financial cost 经济成本，财务成本Fischer-Tropsch synthesis or F-T 费脱合成Flammability limits 可燃极限FTL for F-T liquids 费脱合成液体燃料Fuel cycle 燃料循环Gasification 气化Gasoline 汽油Gas-phase reactor 气相反应器GHG emissions mitigation 减排温室气体Global warming 全球变暖Greenhouse gas or GHG 温室气体Grid 电网Grind 碾碎GTL for Gas To Liquids 气变油H2/CO ratio or H/C ratio 合成气中氢气/一氧化碳含量比，氢碳比H2S 硫化氢HC for hydrocarbon 烃，碳氢化合物HC fuel 烃类燃料Health cost 健康损害Heating 采暖heavy-duty 重型的Hybrid-electric 混合电能hydrogenation 加氢作用ICL for Indirect Coal Liquefaction 煤间接液化IGCC plant 整体煤气化联合循环电厂Installed capital cost 建设投资成本intellectual property 知识产权JV for joint venture 合资企业Life cycle 全生命周期Liquefaction 液化Liquid-phase 液相Liquid-phase reactor 液相反应器Location factor 区域因子LowEff Low efficiencyLower heat value 低位热值LPG 液化石油气Lube oil 润滑油methane 甲烷Methanol or MeOH CH3OH 甲醇middle distillate 中间馏份Mitigation 减少，减排Mtce 一种能量单位百万吨标煤NOx 氮氧化物noxious material 有害物质Off the shelf 现货供应One-through design 一次通过方式Operating &maintenance / O&M 运行维护Overnight 隔夜oxygenated fuel 氧化燃料Oxygen-blown gasification 氧吹气化Ozone 臭氧paraffin 石蜡Pilot plant scale 试验厂规模PM for particulate matter 颗粒物Poly-generation 多联产Poly-generation technology 多联产技术Power island 动力岛power sector 电力行业ppb level 十亿分率水平pressurized canister 加压罐Process configuration 工艺配置Process heat 工艺用热Production cost 生产成本Propane 丙烷public good 公共福利Purge gas 净化气体Quench 冷Reaction conditions: P for pressure T for temperature 反应条件: P代表压力，T代表温度Recycle design 循环方式reduce 还原；减少refinery 炼油renewable energy 可再生能源residual 渣油Saturator 饱和器semi-refined 半精制的Single(or One)-pass conversion 一次通过的转化率Slurry 浆SO2 二氧化硫social cost 社会成本Soot 烟灰Spark-ignition engine 火花引燃式发动机Stand-alone 单独的Streamline 简化使有效率Sulfur 硫Syncrude 合成原油Syngas or synthesis gas 合成气Syngas park 合成气园Synthesis 合成Synthesis conversion 合成转化率synthesis reactor 合成反应器Synthetic fuel 合成燃料TFESTTI for Technical Infrastructure 技术基础设施toxic metal 有毒金属物Unreacted 未反应的USDOE 美国能源部Vapor pressure 蒸汽压Vent 排放Water gas shift / WGS 水煤气变换。

燃煤分析培训Coal Analysis Training1.1 煤质分析的一般规定General rules for coal analysis.1.1.1 样品要求及保存Sample required and storage.1.1.1.1 各种样品按规定进行采样和缩制。

除另外说明应将其制成粒度小于0.2mm的分析样。

All kinds of sample shall be sampling and sample reduction by regulation. Except asspecial illustration, they shall be made as analysis sample which particle size less than0.2mm1.1.1.2 分析试样应装入带有严密玻璃塞的广口瓶中。

煤粉样品保存期为1周。

The analysis sample shall be put into the wild-mouth bottle with tight glass stopper. Theretention period for coal dust sample is 1 week.1.1.1.3 测全水分的煤样应密封保存，从采样到分析不得超过1天。

The coal sample for testing total moisture shall be keeping sealed and can not exceed 1day from sampling to analysis.1.1.2 测定Determination1.1.2.1 称取试样时，应先用药勺或其它适当用具把试样充分搅匀，然后在不同部位取足所需的试样。

除另有规定外，称取10～20g试样时，一般称准至0.01g；称取1～2g时，一般称准至0.0002g。

When weighting sample, use medicine spoon or other proper appliance to full mix the testsample, then sampling necessary amount from different position of sample. Except asspecial illustration, when weighting 10～20g test sample, general accurate to 0.01g; forweighting 1～2g test sample, general accurate to 0.0002g。

一.专业名词解释(选取几个)动力煤：fuel coal；steam coal水煤浆：coal water mixture煤阶：rank实验室煤样：laboratory sample of coal工业分析：proximate analysis元素分析：ultimate analysis挥发分：volatile matter固定碳：fixed carbon煤炭焦化：coal carbonization孔隙率porosity 发热量：calorific value灰成分分析：ash analysis粘结指数：caking index干燥无灰基：dry ash-free basis 灰融融性：ash fusibility洁净煤技术：clean coal technology炼焦配煤：coal blending for coking煤炭气化：coal gasification煤基活性炭：coal-based activated carbon二.短语解释Coal formation 成煤作用Coal forming process 成煤作用Peatification 泥炭化作用metamorphism 变质作用三.文章中词语翻译1.The coalification process is, in essence （本质）, the progressive （渐进的，累进的）change in the plant debris as it becomes transformed from peat to lignite （褐煤）and then through the higher ranks （高阶）of coal （such as subbituminous（次烟煤）and bituminous （烟煤）coals）to anthracite （无烟煤）. The degreeof coalification generally determines the rank of the coal, but the process is not aseries of straightforward （简单的，直截了当的）chemical changes. For example,the metamorphism （变质作用）of the plant debris not only relies on （＝dependon）geological time （地质年代）but also on temperature and pressure.A. Clay Minerals (Aluminosilicates)粘土矿物（铝硅酸盐）B. Quartz (Silica)石英（硅石）C. Carbonate Minerals碳酸盐矿物质D. Sulfur (Sulfide and Sulfate) Minerals硫（硫化物和硫酸盐）矿物质4. Indeed, a high ash content also introduces additional problems such as a loss inthe combustion efficiency (燃烧效率) as well as problems related to handling (处理)and disposing (处理) of larger amounts of mineral ash. Obviously, mineral matter incoal will (and often does) cause problems during utilization, and measures (措施) to counteract (抵消) any adverse effects (反作用，不利作用) that will arise from (起于)the presence (到场，存在) of the mineral matter are necessary. On the other hand,the potential benefits that could arise from the presence of this same mineral mattershould not be ignored (忽视); catalytic effects (催化效果) in processes designed forthe liquefaction (液化)and the gasification (气化) of coal may be cited (引用) asexamples(P74)四：英译汉煤的定义—煤是由古代植物遗体在一定的气候，生物，环境和地质条件下经历复杂的生物和物理化学变化形成的一种沉积有机岩。

Energy ProcediaEnergy Procedia 00 (2008) 000–000/locate/XXXGHGT-9“High Temperature Gas Separation Membranes in Coal Gasification ”a*J. C. Diniz da C osta, b G.P. Reed and c K. Thambimu thuaThe University of Queensland, FIMLab – Films and Inorganic Membrane Laboratory, Division of Chemical Engineering, Brisbane Qld 4072,Australia.bCentre for Low Emission Technology, Pullenvale Qld 4069, AustraliaE lsev ier use only: Received date here; revised date here; accepted date hereAbstractIn this work we investigate the proof of concept of metal (Cobalt) doped silica membranes for H 2/CO 2 separation in single and multi tube membrane modules, in addition to a membrane reactor (MR) configuration for the high temperature water gas shift (WGS) reaction. The membranes were prepared by a sol-gel process using tetraethylorthosilicate (TEOS) in ethanol and H 2O 2 with cobalt nitrate hexahydrate (Co(NO 3)26H 2O). The membranes delivered high H 2/CO 2 single gas selectivity up to 131. A multi tube membrane module was tested up to 300o C and 4 atmospheres for 55 days (1344 hours) for binary feed gas mixtures containing H 2 and CO 2 at 40:60 concentration ratio. The best membrane performance delivered H 2 purity in excess of 98%. For the high temperature water gas shift reaction and a ternary mixture of 40% (H 2), 40% (CO 2) and 20% (CO), which is equivalent to 67.5% CO conversion, the membrane delivered a permeate stream containing 92.5% H 2. The membranes complied with a flux temperature dependency mechanism, as H 2 permeation had a positive energy of activation whilst CO 2 was negative. As a result, H 2 permeation and separation to other gases increased with temperature. In turn, this effect was combined with high CO conversion for the water gas shift reaction, thus allowing for high throughput of H 2 production and separation in a single processing step. The process integration provided by this work is potentially beneficial for the next generation of high temperature processing unit operations in low emissions coal gasification.© 2008 Elsevier Ltd. All rights reserved Keywords: IGCC; metal doped silica membranes; membrane reactors, hydrogen separation1. IntroductionIn this new paradigm of decarbonised energy economies, security of fuel supply still plays a major role in sustainable development. These issues are socially, economically and politically sensitive around the globe, and in particular for those economies driven by energy derived from fossil fuels. Governments are currently assessing a basket of options to enhance the robustness of the energy mix for their respective countries. However, as demand for energy is unlikely to reduce, many industrialised nations will continue to rely on coal as a primary energy supply, which is likely to outlast gas and oil for centuries, based on current reserves and consumption rat es [1, 2]. To* C orresponding au thor. Tel.: +61 7 3365 6960; fax: +61 7 3365 4199. E-mail address : j.dacosta@.auc2009Elsevier Ltd.All rights reserved.Energy Procedia 1(2009)295–/locate/procediadoi:10.1016/j.egypro.2009.01.041296J.C.Diniz da Costa et al./Energy Procedia1(2009)295–3022Author name / Energy Procedia 00 (2008) 000–000address the need to reduce CO2 and associated greenhouse gas emissions, research has intensified in the last decade on post combustion, pre combustion and oxy-fuel as modes of operating coal power plants with carbon capture.The pre-combustion option via coal gasification is getting the attention of governments, industry and the research community as an attractive alternative process to deliver electricity. Coal gasification is a flexible process which can be integrated with a combined cycle of gas and steam turbines to deliver power, called an Integrated Gasification Combined Cycle (IGCC). This process has a potential advantage over conventional power generation, as it also has the capability for delivering synthetic fuels for industrial feedstock and hydrogen for the energy and transportation sectors. An IGCC scheme for the production of hydrogen with CO2 capture for bituminous coals using the current best available technology is shown in Figure 1. The process can be divided into four steps as follows: (1) airseparation & gasification, (2) gas cleaning, (3) gas conditioning, and (4) gas separation.Using conventional technology, it is possible to build the IGCC plant shown in Figure 1. There are several mature technologies that can be employed as gas separation processes such as cryogenics, solvent extraction, adsorbents in pressure or temperature swing adsorption, and low temperature polymeric membranes. Due to compliance with sorption mechanisms, these technologies operate best at low temperatures (<50o C). Examples of gas separation include physical solvents such as Selexol or Rectisol, zeolite beds in pressure swing adsorption or polycarbonate, polydimethylsiloxane PDMS membranes. The problem here is that gas separation follows downstream from gas conditioning. The gasification of coal predominantly produces syngas (CO and H2) with some remaining hydrocarbons, CO2 and water. The syngas requires further processing through the WGS reaction (Equation 1), in order to maximise H2 production [4, 5].1)CO + H2O ÅÆ CO2 + H2ΔH =-41.2 kJ.mol-1(EquationThe WGS reaction is exothermic and the conversion is limited by thermodynamic equilibrium as the conversion to H2 and CO2 decreases with increasing temperature. The reaction is therefore carried out in two stages, in high (350-400o C) and low temperature (250-300o C) shift reactors with interstage cooling. In addition, further cooling to <50o C is required to reduce the temperature to the temperature acceptable by conventional gas separation technologies. Cooling large stream of hot gases is capital intensive, and incurs a loss of power production; furthermore, these processes are likely to deliver CO2 at reduced pressures, which will have to be re-compressed to > 100 atm for transportation and storage. Hence, conventional processes will attract large energy penalties.In order to reduce efficiency losses, an alternative is to separate gases at higher temperatures. In this case, inorganic membranes derived from ceramics [6], silica [7-9], metal [10], and by further doping or alloying [11] showed preferential H2 selectivity over CO2 at high temperatures (>200o C). These technologies can also operate in membrane reactor arrangements for the water gas shift reaction [12-14], which allow for shifting the reactions to higher conversions due to the extraction of hydrogen from the reaction chamber [15]. The advantage here is twofold;1.CO2 is kept at high pressure thus reducing requirements for CO2 compression downstream.J.C.Diniz da Costa et al./Energy Procedia1(2009)295–302297Author name / Energy Procedia 00 (2008) 000–000 32.As H2 is selectivity taken, the syngas stream is reduced by up 30-35% depending on the recovery rate.Although CO2 will have to be cooled down prior to compression, the volumes are reduced thus requiring a lower cooling duty.Therefore, inorganic membranes and their incorporation in MRs are foreseen to be the technology of choice foradvanced IGCC plants as depicted in Figure 2.Figure 2 An Advanced scheme for IGCC with carbon capture [3]The scheme shown above in Figure 2 for gas separation and conditioning is being developed in Australia by The University of Queensland as the research provider under the R&D program directed by the Centre for Low Emission Technology (). The use of a higher temperature membrane allows further simplification of the gas cooling, conditioning and separation step, but this scheme requires a high temperature membrane tolerant to the syngas. The R&D program is currently focusing on metal doped silica membranes. In this work, we report on proof of concept and long term testing of membranes for H2 separation in a single membrane and multi tube membrane module similar to the schematic shown in Figure 3, in addition to a membrane operating in a membrane reactor (MR) arrangement for the high temperature W GS reaction. The membranes are tested for several temperature and pressure regimes, for single gas and binary mixtures, and for gas separation during WGS reactions, to determine their performance in terms of permeation and gas separation properties.Figure 3 – Schematic of a multi tube membrane module for H2 and CO2 separation4Author name / Energy Procedia 00 (2008) 000–0002. ExperimentalCommercial D -alumina tubes (OD-11mm Length-120mm) coated with a top γ-alumina layer were purchased fromNoritaki (Japan). Cobalt silica sol was prepared through the hydrolysis and condensation of tetraethyl orthosilicate (TEOS) in ethanol and H 2O 2 with cobalt nitrate hexahydrate (Co(NO 3)26H 2O) as described elsewhere [16]. A solution of 42.2g TEOS in 600g ethanol was added to a second solution of 51.8g cobalt nitrate in 30%w/w aqueous H 2O 2 and vigorously stirred for 3 hours in an ice-cooled bath. The tubular alumina substrates were dip-coated at the outer shell of the tube at a removal speed of 2cm.min -1 and an immersion time of 1 minute prior to removal. The final tube membrane had a total of six layers which were sequentially calcined in air to 600°C at a ramp rate of 0.7°C.min -1, and held at 600°C for 4 hours. Finally the membranes were sintered in H 2 at 500°C for 15 hours to reduce the cobalt oxide within the selective silica layer. Both ends of the tube were glazed to provide a good surface for sealing. The membrane had a length of 60mm and an effective permeation area of 20cm 2.The cobalt silica membranes were are also tested in a membrane reactor (MR) arrangement. The catalyst was activated prior to experimentation following manufacturer’s protocols at 250°C with 20% H 2 and 20% H 2O in N 2 at 20 ml.min -1 total flow. After activation, H 2 was switched off and the H 2O/CO reactant flow was fed to the reactor, with all gas flows controlled using high precision Cole Palmer rotameters. Water liquid flow was controlled by a Bronkhurst liquid mass flow controller, prior to injection into an evaporator. The water to CO feed ratio 1:1 was used in the experimental work.In these experiments, the membrane and MR temperature was maintained within a muffle furnace using a Eurotherm PID temperature controller. A back pressure valve maintained the feed pressure at the desired pressures which was measured with a pressure transducer. Reactants, feed, retentate and permeate gases were tested in a Shimadzu GC-2014 gas chromatograph using a Porapak Q column with a thermal conductor detector (TCD) and flame ionising detector (FID) to determine gas concentrations.3. Results and DiscussionFigure 4 shows the single gas permeation results for the cobalt silica membrane. The permeation of molecules with the smaller kinetic diameter such as He (d k = 2.6Ǻ) and H 2 (d k = 2.9Ǻ) increased as a function of the temperature whilst the opposite trend was observed for the larger molecules like CO 2 (d k = 3.3Ǻ) and N 2 (d k = 3.64Ǻ). These permeation trends as observed elsewhere [18-20] are indicative of activated transport or molecular sieving mechanis m following a temperature dependency flux equation derived from the model of transport through microporous crystalline membrane proposed by Barrer [17]:dxdp RT E K D J act O O x ¸¹·¨©§ exp (Equation 2)where J is the flux (mol.m -2.s -1) through the membrane, E act (kJ.mol -1) is an activation energy, R the gas constant and T the absolute temperature (K), D o and K o are temperature independent proportionalities. The activation energies in kJ.mol -1 calculated from an Arrhenius relationship for single gas permeation were 8.0 (He), 16.4 (H 2), -6.3 (N 2) and -6.3 (CO 2).A membrane module containing 4 cobalt doped silica membrane tubes was subsequently assembled similarly to the concept shown in Figure 3. Each tube membrane was individually tested with He and N 2 (see Figure 5) prior to any H 2 and CO 2 permeation testing to verify their performance and whether leaks were occurring. Tests were carried out up to 4 bar feed pressure and 400o C. Membrane 2 (M2) showed the best performance in terms of flux and selectivity. The He flux reached 14.2 cc.cm -2.min -1 and single gas He/N 2 selectivity of 76 at the tested conditions. It was found that increasing the pressure caused a small reduction of selectivity, in particular for M4,298J.C.Diniz da Costa et al./Energy Procedia 1(2009)295–302Author name / Energy Procedia 00 (2008) 000–0005which was attributed to a small leak rate. In other words, the other membranes (M1, M3 and M4) could possiblyhave higher selectivities if they were leak free. The module was dis mantled and re-assembled three times, and leak rates reduced or increased each time. At this stage, the importance of certain aspects of the mechanical design of a multi tube membrane module became very apparent. The tubes require precise alignment to allow for Kalrez ‘o’rings to deliver good sealing capabilities. In our initial multi tube design, alignment tolerance did not meet this mechanical design requirement.Temperature ( o C )P e r m e a n c e ( m o l . m -2 . s -1 . P a -1 )4060801001201401601E-102E-103E-105E-107E-101E-92E-93E-95E-97E-91E-82E-83E-85E-87E-81E-7Figure 4 – Single gas permeance of gases as a function of temperature.After one week of testing, M2 and M4 started having a high gas leak rate. The seals were changed, but the high leak rate remained. Hence, it was decided to continue the tests with M1 and M3 only. The membranes were tested for 56 days (1344 hours) of operation between 100-300o C and feed pressures 2.8-4.0 bar. The feed gas concentration was generally 35-40 vol.% H 2 and 60-65 vol.% CO 2. The performance of the membrane M1 (Figure 6) shows the permeate H 2 purity increased with temperature, and preferably in excess of 200o C. The 100o C isotherm was shown as an example of the effect of a very small leak on the H 2 purity of gases in the permeate stream as the feed pressure increased. Again, these results highlight the molecular sieving mechanis m which was regulated by the temperature flux dependency as discussed above. The membrane M1 delivered almost 98% H 2 purity at a single pass.J.C.Diniz da Costa et al./Energy Procedia 1(2009)295–3022996Author name / Energy Procedia 00 (2008) 000–000Feed Pressure (kPa absolute)H 2 P e r m e a t e C o n c e n t r a t i o n (%)280300320340360380400Figure 6 – Isotherms of H 2 purity as a function of total gas mixture pressure for 40:60 (H 2:CO 2) mixture.A single membrane tube was also tested in a MR arrangement at operating temperatures from 300 to 375o C as shown in Figure 7a. CO conversion increased with temperature and started levelling off at 67.5% at 375o C due to equilibrium limitations. Membrane seals failed after this temperature. The H 2/CO molar ratio in the permeate stream increased from 1.9 to 40.5 as a function of temperature, whilst the same ratio in the MR reaction chamber increased from 0.32 to 2.05. There are two important aspects associated with these changes. As temperature increased, so did CO conversion. This means that for every mole of CO reacted it generated one mole of H 2 (and CO 2) resulting in a higher H 2 partial pressure in the MR reaction chamber. The permeation of H 2 is directly proportional to the driving force, which in this case i s the H 2 partial pressure difference between the MR reaction chamber and the permeate stream. As the permeate stream was kept at 1 atm, then it was essential that the H 2 partial pressure in the reaction chamber to be above 1 atm. The second aspect relates to the membrane’s activation energy as described in Equation 2. This can be clearly observed in Figure 7b. The purity of H 2 in the permeate stream increased from 60 to 92.5% as the temperature increased from 300 to 375o C, respectively. In a single separation step, the MR was able to enrich H 2 in the permeate stream by 39% at 300o C and 48.5% at 375o C as compared to the MR reaction chamber. Notwithstanding that the H 2 and CO 2 concentration in the MR reaction chamber were equivalent, H 2 selectively permeate through the membrane. Hence, higher temperature allowed for the combined effect of higher CO conversion and H 2 permeation to act synergistically.Temperature ( o C )300305310315320325330335340345350355360365370375Temperature ( o C )C o n c e n t r a t i o n ( v o l /v o l % )300305310315320325330335340345350355360365370375Figure 7a (left) MR CO conversion and H 2/CO ratios and 7b (right) H 2 concentration in the permeate stream and MR reaction chamber, both figures as a function of temperature.300J.C.Diniz da Costa et al./Energy Procedia 1(2009)295–302J.C.Diniz da Costa et al./Energy Procedia1(2009)295–302301Author name / Energy Procedia 00 (2008) 000–000 7The flux temperature dependency trend of H2 and CO2 permeation makes cobalt silica membranes attractive for application in coal gasification processes. The H2/CO2 single gas selectivity increased from 17 to 131, as the temperature increased from 50 to 150o C, respectively. The positive energy of activation for H2 permeation coupled with the negative energy of activation for CO2 permeation of metal doped silica membranes provide a favourable fundamental property for engineering design of gas separation at higher temperatures (up to 500o C) such as those required in a coal gasification process. This point can be further supported by the multi tube membrane module, which delivered H2 purity in excess of 98% at 300o C and feed pressures ranging from 2.8 to 4 atmospheres. The temperature testing was limited to 300o C as Kalrez ‘o’rings start melting at about 315o C. The membranes were also showed to be encouragingly robust, as they performed consistently for 55 days.For the WGS reaction, the MR delivered lower gas purity for a gas mixture containing ~40% H2. For instance, a CO conversion of 67.5 moles at 375o C lead to the production of 67.5 moles of H2 and CO2, whist 32.5 moles of CO were not consumed. This gives approximately a ternary mixture of 40% (H2), 40% (CO2) and 20%(CO). In this case the membrane was able to deliver a permeate stream containing 92.5% H2, about 5.5% lower than the result obtained for a binary mixture. These results strongly suggest that the separation of a ternary gas mixture is more complex than a binary mixture, thus slightly reducing H2 purity in the permeate stream.4.ConclusionsMetal (cobalt) doped silica membranes delivered high H2/CO2 single gas selectivity up to 131. The flux temperature dependency allowed for a positive energy of activation for H2 permeation whilst the energy of activation for CO2 was negative. A multi tube membrane module was tested up to 300o C and 4 atmospheres for 55 days(1344 hours) for binary feed gas mixtures containing H2 and CO2 at 40:60 concentration ratio. The best membrane performance for H2 purity was in excess of 98%. For the high temperature WGS reaction, H2 selectively permeated through the membrane; this effect also increased with temperature. Higher temperature also aided in CO conversion which translated into more H2 (and CO2) being produced in the MR reaction chamber. Hence, higher temperature allowed for the combined effect of higher CO conversion and higher H2 permeation. Nevertheless, the MR delivered lower gas purity for a ternary gas mixture containing ~40% H2 as compared to binary gas mixture separation. For a ternary mixture of 40% (H2), 40% (CO2) and 20% (CO), which is equivalent to 67.5% CO conversion, the membrane delivered a permeate stream containing 92.5% H2, about 5.5% lower than the results obtained for a binary mixture. These results strongly suggest that the separation of a ternary gas mixture is more complex than a binary mixture. The purity of H2 in the permeate stream increased from 60 to 92.5% as the temperature increased from 300 to 375o C, respectively.AcknowledgementsThe authors acknowledge financial support for project GS001 by the Centre for Low Emission Technology (). Special thanks to Dr Shaomin Liu, Dr Suraj Gopalakrishnan, Mr Tsutomu Tasaki and Mr Scott Battersby for their experimental work.References1.BP, BP statistical review of world energy, 2002.2.R. H. Williams, Toward zero emissions for transportation using fossil fuel, in VIII Biennal conference ontransportantion, energy and environmental policy, 2001, Monterey, CA, USA.3.J. C. Diniz da Costa, D. Sholl, G. Reed and K. Thambimuthu, Gas separation in Coal Gasification, AIChESpring Meeting, Orlando Fl, USA, 24-28 April 2006, vol 1(2006) 142f.4.S. Giessler, L. Jordan, J.C. Diniz da Costa, and G.Q.M. Lu, Performance of hydrophobic and hydrophilic silicamembrane reactors for the water gas shift reaction, Separation and Purification Technology, 32 (2003) 255.5. C. Wheeler, A. Jhalani, E.J. Klein, S. Tummala, and L.D. Schmidt, The water-gas-shift reaction at shortcontact times, Journal of Catalysis, 223 (2004) 191.6.Y. S. Lin, Microporous and dense inorganic membranes: current status and prospective, Sep. PurificationTech., 25 (2001) 39.302J.C.Diniz da Costa et al./Energy Procedia1(2009)295–3028Author name / Energy Procedia 00 (2008) 000–0007. D. Lee, L. Zhang, S. T. Oyama, S. Niu, R. F. Saraf, Synthesi s, characterization, and gas permeation propertiesof a hydrogen permeable silica membrane supported on porous alumina, J. Membrane Sci., 231 (2004) 117. 8.S. Morooka, K. Kusakabe, Inorganic membranes for gas separation at elevated temperatures, IndustrialCeramics, 20 (2000) 15.9.J. C. Diniz da Costa, G. Q. Lu, V. Rudolph, Y. S. Lin, Novel molecular sieve silica (MSS) membranes:characterisation and permeation of single-step and two-step sol–gel membranes, J. Membrane Sci., 198 (2002)9.10. D. S. Sholl, Y. S. Ma, Dense Metal Membranes for Production of High Purity Hydrogen, MRS Bulletin, 31(2006) 770.11.P. Kamakoti, B. D. Morreale, M. V. Ciocco, B. H. Howard, R. P. Killmeyer, A. Cugini, D. S. Sholl, Predictionof hydrogen flux through sulfur tolerant binary alloy membranes, Science, 307 (2005) 569.12.G. Barbieri, A. Brunetti, T. Granato, P. Bernardo, and E. Drioli, Engineering evaluations of a catalyticmembrane reactor for the water gas shift reaction, Industrial and Engineering Chemistry Research, 44 (2005) 7676.13.J. N. Armor, Applications of catalytic inorganic membrane reactors to refinery products, Journal of Memb raneScience, 147 (1998) 217.14.S. Battersby, D. Miller, M. Zed, J. Patch, V. Rudolph, M.C. Duke, and J.C.d. Costa, Silica membrane reactorsfor hydrogen processing, Advances in Applied Ceramics, 106 (2007) 29.15. A. Julbe, D. Farrusseng, and C. Guizard, Porous ceramic membranes for catalytic reactors - overview and newideas, Journal of Membrane Science, 181 (2001) 3.16.S. Battersby, M. C. Duke, S. Liu, V. Rudolph, J. C. Diniz da Costa, Metal Doped Silica Membrane Reactor:Operational effects of reaction and permeation for the water gas shift reaction, Journal of Me mbrane Science, 316 (2008) 46.17.R. M. Barrer, Porous crystal membranes, J. Chem. Soc. Faraday Transaction., 86 (1990) 1123.18.M.C. Duke, J.C. Diniz da Costa, G.Q. (Max) Lu, M. Petch, and P. Gray, Carbonised template molecular sievesilica membranes in fuel processing systems: permeation, hydrostability and regeneration, J. Memb. Sci, 241 (2004) 325.19.R.M. de Vos and H. Verweij, High-selectivity, high-flow rate silica membranes for gas separation, Science,279 (1998) 1710.20.M. Kanezashi and M. Asaeda, Hydrogen permeation characteristics and stability of Ni-doped silica membranesin steam at high temperature, J. Membrane Sci, 271 (2006) 86.。

煤矿瓦斯预防治理中英文对照外文翻译文献(文档含英文原文和中文翻译)翻译:西班牙Riosa–Olloniego煤矿瓦斯预防和治理摘要矿井中一直控制存在不同的气体在采矿环境。

这些气体中，甲烷是最重要的，他伴随着煤的产生而存在。

尽管在技术在近几十年来的发展，瓦斯灾害尚未完全避免。

瓦斯气体随着开采深度的增加而增多，甲烷排放量高的地方，也适用于其他采矿有关的情况，如生产的增长率及其后果：难以控制的甲烷浓度增加，机械化程度提高，使用炸药和不重视气控制系统。

本文的主要目的是建立实地测量，使用一些不标准的采矿控制风险评估方法的一部分，并分析了深部煤层瓦斯矿井直立的行为，以及防止发生瓦斯事故的关键参数。

最终目标是在开采条件的改善，提高矿井的安全性。

为此，设置了两个不同的地雷仪表进行矿井控制和监测。

这两个煤矿属于Riosa-Olloniego煤田，在西班牙阿斯图里亚斯中央盆地。

仪器是通过subhorizontal能级开采的，一个约1000米的山Lusorio根据实际深度覆盖的地区。

在本研究中，一个是有利于瓦斯突出的易发煤（第八层），测定其气体压力及其变化，这将有助于提供以前的特征以完成数据，并评估第一次测量的网站潜在的爆发多发地区提供一些指导。

本文运用一个气体测量管设计了一套用于测量一段时间由于附近的运作的结果，计算低渗气压力以及其变化。

本文建立了作品的重叠效应，但它也表明了两个预防措施和适用功效，即高压注水和一个保护煤层（第七层）的开采，必须优先开采保护层以防止瓦斯气体的涌出。

这两项措施构成的开采顺序，提高矿井安全性。

因此，应该完成系统的测量控制风险：在8煤层瓦斯压力影响的其他地区，要建立最合适的时刻进行开采作业。

进一步的研究可以把重点放在确定的渗透，不仅在瓦斯爆炸危险区，而且在那些还没有受到采矿的工作和更精细的调整过载时间的影响范围和矿井第7煤层和第8煤层之间的瓦斯气体。

关键词：煤矿，煤层气，气体压力渗透率瓦斯突出1 简介近年来，煤层气体和煤矿瓦斯研究蓬勃发展。