新型CO耐硫变换催化剂QDB-04的开发及应用

介绍了新型CO耐硫变换催化剂QDB-04的性能特点及工业应用情况，对Shell粉煤气化煤气第一变换炉反应深度的问题及控制第一变换炉“床层飞温”的办法进行了讨论，提出了ODB-04催化剂应用于低水气比Shell粉煤气化制氨变换工艺的设计方案。     

QDB-04型CO耐硫变换催化剂在Shell粉煤气化工艺中的应用

介绍了QDB-04型CO耐硫变换催化剂在Shell粉煤气化低水气比耐硫变换工艺中的应用情况。运行结果表明,选用QDB-04型催化剂,并采用控制反应水气比和床层入口温度等手段来控制反应深度和床层热点温度的办法是可行的。每段水气比的最高值不超过0.40,各段床层温升平稳,一段反应器温度一般为360~370℃,各段出口CO指标分配合理,最终出口CO体积分数小于0.4%,无甲烷化副反应的发生。     

Shell粉煤气化低水气比耐硫变换工艺运行总结

分析Shell粉煤气化高水气比耐硫变换工艺在生产中遇到的频繁超温、蒸汽消耗高、工艺冷凝液量大等问题,总结工业生产中针对高水气比工艺进行的技改措施。介绍了低水气比耐硫变换工艺在Shell粉煤气化高CO煤气变换中的应用,总结分析低水气比工艺在工业实际生产运行中的优点。     

低水气比耐硫变换新工艺在Shell粉煤气化装置上的工业应用

介绍了低水气比耐硫变换新工艺,并简单总结了该工艺在Shell粉煤气化制氨和制甲醇装置上的应用情况。选用QDB-04型催化剂,通过控制反应的水气比和床层入口温度等手段来控制反应深度和床层热点温度的办法是可行的。第1段反应的水气比最高值不超过0．30,床层的最高温度不超过400℃。各段出口CO指标分配合理,无甲烷化副反应发生。     

QDB-04型催化剂在“航天气化”耐硫变换装置上的工业应用

介绍了QDB-04型催化剂在濮阳龙宇化工股份有限公司"航天气化"低水/气比耐硫变换工艺制甲醇装置中的应用情况。运行结果表明:对于粉煤气化高CO原料气和高水/气比原料气,选用QDB-04型催化剂,采用控制反应水/气比和床层入口温度等措施来控制床层热点温度的办法是可行的;在装置运行期间,第一变换炉入口水/气比为0.30～0.38,入口温度200℃～245℃,床层热点温度不超过450℃,装置运行平稳,无甲烷化副反应发生,满足合成甲醇生产的要求。     

SHELL粉煤气化高水气比耐硫变换工艺改造及运行总结

分析造成Shell粉煤气化高水气比耐硫变换装置在试车和运行中出现蒸汽耗量大、催化剂床层超温等问题的原因,提出耐硫变换高水气比改为低水气比的具体改造方案。实施后装置运行稳定,节能效果显著。     

粉煤气化“双高”原料气耐硫变换新工艺的工业应用

针对"双高"原料气制甲醇等变换深度较浅的反应,青岛联信催化材料有限公司开发了废锅+两段低水气比耐硫变换工艺,通过废锅,降低原料气水气比,减少变换反应推动力,进而灵活控制床层反应深度及热点温度;针对"双高"原料气制合成氨等深度变换反应,开发了分层进气的专利反应器技术,通过精确计算催化剂的装填量和分层进气的办法,将反应温度控制在要求的范围内。开发的新工艺已实现了工业化应用,结果表明,新工艺不仅解决了"双高"原料气第一变换炉超温的难题,而且稳定了变换操作,节能效果显著。     

不同水气比耐硫变换工艺节能分析与比较

按照高水气比和低水气比耐硫变换工艺的设计理念,对与Shell粉煤气化工艺配套的高、低水气比耐硫变换工艺流程进行了动力学计算和工艺设计,分析并比较了2种工艺的流程特点、蒸汽消耗、外排冷凝液量、设备规格和能量消耗。结果表明,低水气比耐硫变换工艺与Shell粉煤气化工艺流程匹配性更加合理。     

Shell粉煤气化变换工艺的优化改造

分析与Shell粉煤气化配套的高水气比耐硫变换工艺在运行中出现的问题,并对其进行优化改造。对改造后的低串中水气比变换工艺与原工艺进行比较。     

高浓度CO变换气制甲醇问题的探讨及催化剂选型

通过动力学模拟计算和实验研究,对高浓度CO变换气制甲醇工艺中,第一反应器反应深度控制、甲烷化副反应和催化剂选型等问题进行了讨论,结果表明:通过控制反应的水/气和催化剂装量均可达到控制反应深度的目的;降低床层的热点温度,增加水/气和空速均可抑止甲烷化副反应发生;选用强稳定性、抗水合性能和低温活性高的CO耐硫变换催化剂,可以满足高CO浓度变换气对催化剂性能的要求。     

Steam reforming of ethanol over skeletal Ni‐based catalysts: A temperature programmed desorption and kinetic study

An investigation on reaction scheme and kinetics for ethanol steam reforming on skeletal nickel catalysts is described. Catalytic activity of skeletal nickel catalyst for low‐temperature steam reforming has been studied in detail, and the reasons for its high reactivity for H₂ production are attained by probe reactions. Higher activity of water gas shift reaction and methanation contributes to the low CO selectivity. Cu and Pt addition can promote WGSR and suppress methanation, and, thus, improve H₂ production. A reaction scheme on skeletal nickel catalyst has been proposed through temperature programmed reaction spectroscopy experiments. An Eley‐Rideal model is put forward for kinetic studies, which contains three surface reactions: ethanol decomposition, water gas shift reaction, and methane steam reforming reaction. The kinetics was studied at 300–400°C using a randomized algorithms method and a least‐squares method to solve the differential equations and fit the experimental data; the goodness of fit obtained with this model is above 0.95. The activation energies for the ethanol decomposition, methane steam reforming, and water gas shift reaction are 187.7 kJ/mol, 138.5 kJ/mol and 52.8 kJ/mol, respectively. Thus, ethanol decomposition was determined to be the rate determining reaction of ethanol steam reforming on skeletal nickel catalysts. © 2013 American Institute of Chemical Engineers AIChE J 60: 635–644, 2014     

碱金属助剂对铜系低变催化剂低汽气比条件下稳定性和选择性的影响

采用原粒度催化反应装置,结合物理分析化学手段,研究了添加碱金属助剂对铜系低变催化剂在低汽气比条件下稳定性和选择性的影响。发现添加一定量的某种碱金属氧化物助剂,可以减少低汽气比条件下铜系低变催化剂的甲醇生成量。在一定的添加量范围内,其变换反应性能稳定,并且甲醇副产物的生成量也较稳定,但碱金属助剂的添加对催化剂的比表面积和强度的影响较大。     

新型铜系低变催化剂在低汽气比条件下的性能研究

采用原粒度催化反应装置,结合物理分析和化学手段,研究添加碱金属助剂对铜系低变催化剂在低汽气比条件下稳定性的影响。发现添加适量的碱金属氧化物助剂可以减少低汽气比条件下铜系低变催化剂的甲醇生成量,一定的添加量范围内,变换反应性能和甲醇副产物的生成量较稳定,但碱金属助剂的添加对催化剂的比表面积和强度的影响较大。     

Biomass-derived hydrogen from an air-blown gasifier

The goal of this research is to produce high concentrations of hydrogen from gasification of biomass. Air-blown gasification of biomass in fluidized bed reactors produces relatively low concentrations of hydrogen (about 8 vol.%). Steam reforming of tars and light hydrocarbons and reacting steam with carbon monoxide via the water–gas shift reaction can increase hydrogen content in the producer gas to almost 30 vol.%. In these experiments, the temperature, space velocity, and steam/gas ratio were varied to determine the effect of these variables on hydrogen production. Characterization of the catalysts by X-ray photoelectron spectroscopy (XPS) and BET analysis was also performed. These analyses showed that coke and small quantities of sulfur and chlorine deposited on the catalysts, although catalytic deactivation was not evident during the tests.     

Pt and/or Pd Supported/Incorporated Catalyst on Perovskite-Type Oxide for Water Gas Shift Reaction

Catalytic properties of Pd and/or Pt supported/incorporated on/in perovskite-type oxides for water gas shift (WGS) reaction have been investigated. We found that the dominant reaction mechanism over these catalysts was redox mechanism by CO and steam, and their redox properties were controllable by the bulk structure of perovskite.     

PEM – Fuel Cell System for Residential Applications

Viessmann is developing a PEM fuel cell system for residential applications. The uncharged PEM fuel cell system has a 2 kW electrical and 3 kW thermal power output. The Viessmann Fuel Processor is characterized by a steam‐reformer/burner combination in which the burner supplies the required heat to the steam reformer unit and the burner exhaust gas is used to heat water. Natural gas is used as fuel, which is fed into the reforming reactor after passing an integrated desulphurisation unit. The low temperature (600 °C) fuel processor is designed on the basis of steam reforming technology. For carbon monoxide removal, a single shift reactor and selective methanisation is used with noble metal catalysts on monoliths. In the shift reactor, carbon monoxide is converted into hydrogen by the water gas shift reaction. The low level of carbon monoxide at the outlet of the shift reactor is further reduced, to approximately 20 ppm, downstream in the methanisation reactor, to meet PEM fuel cell requirements. Since both catalysts work at the same temperature (240 °C), there is no requirement for an additional heat exchanger in the fuel processor. Start up time is less than 30 min. In addition, Viessmann has developed a 2 kW class PEFC stack, without humidification. Reformate and dry air are fed straight to the stack. Due to the dry operation, water produced by the cell reaction rapidly diffuses through the electrolyte membrane. This was achieved by optimising the MEA, the gas flow pattern and the operating conditions. The cathode is operated by an air blower.     

壳牌粉煤气化高摩尔分数CO变换技术进展

介绍了目前与壳牌粉煤气化相配套的具有代表性的3种高摩尔分数CO变换技术,即高水气比(摩尔比)变换技术、低水气比变换技术和低串中水气比变换技术.对3种变换技术的蒸汽消耗、最高变换温度、甲烷化副反应等主要工艺参数进行了对比分析.详细总结了3种变换技术在化工企业的实际生产运行状况,并结合目前运行现状对3种变换技术各自的优缺点...     

Shell煤气变换高水气比改低水气比工艺总结

Shell炉制得的粗煤气CO含量高,变换采用高水气比工艺虽然无甲烷化副反应,但蒸汽消耗高。河南开祥化工有限公司的应用实践证明:选用低水气比耐硫变换工艺可以获得很好的效果。     

在工业催化剂上水煤气变换反应宏观动力学

用内循环式无梯度反应器,在不同的反应条件下,测定了B106及B109两种型号的原粒度工业变换催化剂的宏观反应速率.根据实验数据关联出两种催化剂都适用的宏观动力学方程,求定了相应的模型参数.该式可用以模拟工业变换反应器.此外,并由实验数据计算了各种情况下的有效因子.整个实验及计算结果表明,这两种催化剂对气体的内扩散阻力都是相当大的.