CO2吸附强化CH4/H2O重整制氢催化剂研究进展

CO_2吸附强化CH_4/H_2O重整制氢是提供低成本高纯氢气和实现CO_2减排的方法之一。其中,催化剂和吸附剂是该工艺的重要组成部分,其活性与选择性制约了反应速率和产率,寿命长短关系到生产成本。综述了CO_2吸附强化CH_4/H_2O重整制氢催化剂和吸附剂的研究现状及存在的问题,机械混合的催化剂与吸附剂在反应过程中存在吸附产物包覆催化活性位点的问题,导致催化剂活性迅速下降。针对该问题,进一步探讨了不同结构双功能复合催化剂的结构特性、研究现状及其在循环-再生过程中存在的问题,核壳型双功能催化剂具有吸附组分与催化剂组分相对独立、催化组分分散分布和比表面积大等优点,在吸附强化制氢中有进一步研究的潜力。利用双功能催化剂的结构特点,实现反复循环再生过程中催化与脱碳反应的匹配,是推动CO_2吸附强化CH_4/H_2O重整制氢技术工业化发展的关键。     

吸附强化的甲烷水蒸汽重整制氢反应特性

在实验室固定床反应器上研究了采用复合催化剂的吸附强化甲烷水蒸汽重整制氢反应,对吸附强化制氢反应条件进行了考查,得到了实验室条件下的最佳反应条件为温度600～640 ℃,压力0.2 MPa,水碳比4～5.在600 ℃,0.2 MPa,水碳比5的条件下,吸附强化段H2含量高达95.39%,吸附强化段CH4转化率达到81.37%,相对于理论平衡值的吸附强化因子达到26.76%.     

吸附强化甲醇水重整制氢工艺条件研究

研究了吸附增强技术对甲醇水重整制氢过程的作用效果。对商业水滑石、Ca基吸附剂、负载型MgO吸附剂3种吸附剂进行了CO2-TPD考察。考察了反应温度、液空速、水醇摩尔比对甲醇水重整制氢的影响。在此基础上,选择Ca基吸附剂,利用响应面法,进行了吸附强化甲醇水重整制氢条件考察。研究结果表明,适宜的工艺条件为反应温度245~247℃,液空速0.30~0.31 h-1,水醇摩尔比3.15~3.19。在此条件下,与无强化的甲醇水重整制氢相比,氢产率为2.528 mol/mol,提高了32.77%,氢含量为92.1451%,提高了26.49%,氢产率相同则反应温度可降低57℃,是一条高效节能减排的制氢路线。     

Mg/Y改性Ca基吸附剂强化吸附CO2试验

在碳中和背景下,CO₂捕集与封存技术的开发与应用刻不容缓。Ca基吸附剂对CO₂捕集能力强、吸附量高,是良好的碳捕集吸附剂,但其循环性能有待提升。为提升Ca基吸附剂的循环性能,采用溶胶凝胶自蔓延燃烧法制备镁/钇(Mg/Y)改性Ca基吸附剂,利用XRD/SEM等手段对其进行表征,通过热重仪和固定床在700℃高温下进行循环吸附试验,考察了改性Ca基吸附剂的吸附性能与循环稳定性。结果表明,Mg掺杂Ca基吸附剂中,Ca与Mg质量比为8∶2时吸附剂性能最佳,第1次循环中CO₂吸附量高达0.60 g/g(以吸附剂计),15次循环后衰减至0.49 g/g,优于未掺杂Ca基吸附剂。对Mg和Y掺杂Ca基吸附剂的研究表明,Ca/Mg吸附剂的初始吸附量高于Ca/Y吸附剂,但Ca/Y吸附剂的循环性能明显提升。保持吸附剂中CaO质量分数为80%,比较双掺杂(Ca/Mg/Y)和单一掺杂(Ca/Mg、Ca/Y)改性Ca基吸附剂的吸附性能和循环性能。结果表明,初始吸附量最高的为Ca/Mg吸附剂,达0.60 g/g, 5次循环后衰减至0.54 g/g左右,...     

炼化厂制氢装置中CO2的回收

随着炼化厂制氢装置的发展,制氢装置中CO2的回收利用,成为炼化厂节能减排的重要途径。介绍了制氢装置工艺,探讨了装置中CO2的来源,分析了PSA尾气和燃烧炉尾气中CO2回收的必要性,讨论了几种回收工艺的特点,综述了近年国内炼化厂制氢装置中CO2回收的进展情况。     

钙基材料捕集CO2强化煤水蒸气气化制氢研究进展

煤炭大规模燃烧产生的CO₂加剧了全球气候变暖和温室效应,钙基材料强化煤气化制氢技术能在捕集CO₂的同时获得较高浓度的H₂,工业应用前景良好。基于国内外钙基材料强化煤气化制氢技术的研究进展,论述了钙基材料强化煤气化制氢技术的系统流程,综述了钙基材料在系统中的CO₂捕集和强化制氢反应特性和活性降低机理,总结了改善钙基材料循环稳定性、CO₂捕集性能和催化制氢性能的方法,介绍了钙基材料强化煤气化过程中碱金属等微量元素的迁移路径,论述了微量元素对钙基材料在煤气化过程中脱碳/强化制氢活性的影响特性,分析了流态化和超临界气化条件下钙基材料对煤气化制氢特性的影响,介绍了基于热力学模拟的系统能量和经济性计算,归纳了钙基材料强化煤气化制氢系统和其他可再生能源系统的耦合性能及其对制氢特性的影响。基于当前钙基材料强化煤气化制氢技术的研究进展和潜在挑战,对未来可能的研究方向进行展望,认为筛选添加剂能多方位提高钙基材料的反应性能,采用解耦气化和煤/生物质共气化技术能实现更高的制氢性能和气化转化率,研究煤中...     

烃类水蒸汽重整制氢研究进展

烃类水蒸汽重整是工业上大规模制氢的主要方法.综述了近十年来国内外烃类水蒸汽重整制氢技术的研究进展,重点从催化剂以及反应工艺方面进行介绍及评述,并指出烃类水蒸汽重整制氢的重点发展方向.     

采用CO2吸附剂吸附强化的甲烷水蒸汽反应制药厂氢过程特点

The objective of the present study is to characterize the production of hydrogen with a sorptionenhanced steam-methane reaction process using Ca(OH)2 as the CO2 adsorbent. Theoretical equilibrium compositions at different operation conditions were calculated using an iterative method. It was found that with Ca(OH)2 as the CO2 sorbent, the concentration of CO2 adsorption was reduced in the product stream, that gave rise to higher methane conversion and higher H2 concentration. An experimental setup was built to test the theoretical calculation. The effects of sorbents and the particle size of Ca(OH)2 on the concentration of CO2 and H2 were investigated in detail. Results showed that the reactor packed with catalyst and Ca(OH)2 particles produced H2 concentration of 94%. It was nearly 96% of the theoretical equilibrium limit, much higher than H2 equilibrium concentration of 67.5% without CO2 sorption under the same conditions of 500℃, 0.2 MPa pressure and a steam-to-methane ratio 6. In addition, the residual mole fraction of CO2 was less than 0.001.     

CO2捕集及工业应用研究进展

碳捕集纯化技术中吸收剂和吸收工艺的开发以及二氧化碳(CO₂)的高效利用是该领域的研究热点。本文从CO₂捕集吸收剂、吸收工艺、工业应用及生产市场方面进行了详细综述和分析,总结了我国当前CO₂产业的发展情况和研究进展,探讨了CO₂吸收剂研制、工艺开发以及CO₂利用技术开发的发展方向,并对我国CO₂市场进行了展望。     

吸附强化蒸汽重整制氢中CO2固体吸附剂的研究进展

吸附强化蒸汽重整（SESR）制氢技术是集重整反应（H₂生产）和选择性分离（CO₂吸附）于一体的新型技术。该技术的特点为采用固体吸附剂在高温下对CO₂进行原位脱除,以改变反应的正常平衡极限,提高烃类转化率,提高H₂产量,减少CO₂排放。在整个SESR制氢技术中,吸附剂的选择与反应条件至关重要。本文探讨了CaO、水滑石、Li₂ZrO₃、Li₂SiO₃以及双功能吸附剂在SESR制氢过程中的性能,总结了提高这些吸附剂吸附性能的不同方法。确定了固体吸附剂的反应条件,如温度、压力、水蒸气量等因素的影响及相关的反应机理。分析表明,CaO基吸附剂由于其低廉的价格及较高的吸附能力,被认为是最具潜力的吸附剂,然而在SESR制氢过程中,CaO基吸附剂面临着多次循环再生后吸附能力衰减的挑战。集吸附与催化双重功能的吸附催化材料由于可以克服SESR制氢中不同固体催化剂和吸附剂的匹配问题、降低所用固体材料的成本,从而使其在吸附强化蒸汽重整制氢方面具有巨大优势,并成为该领域未来研究的一个重要方向。     

Sorption‐Enhanced Steam Reforming of Ethanol: Thermodynamic Comparison of CO2 Sorbents

A thermodynamic analysis is performed with a Gibbs free energy minimization method to compare the conventional steam reforming of ethanol (SRE) process and sorption‐enhanced SRE (SE‐SRE) with three different sorbents, namely, CaO, Li₂ZrO₃, and hydrotalcite‐like compounds (HTlc). As a result, the use of a CO₂ adsorbent can enhance the hydrogen yield and provide a lower CO content in the product gas at the same time. The best performance of SE‐SRE is found to be at 500 °C with an HTlc sorbent. Nearly 6 moles hydrogen per mole ethanol can be produced, when the CO content in the vent stream is less than 10 ppm, so that the hydrogen produced via SE‐SRE with HTlc sorbents can be directly used for fuel cells. Higher pressures do not favor the overall SE‐SRE process due to lower yielding of hydrogen, although CO₂ adsorption is enhanced.     

Hydrogen Production Via CH4 and CO Assisted Steam Electrolysis

Porous composite anodes consisting of a yttria-stabilized zirconia (YSZ) backbone that was impregnated with CeO₂ and various amounts of metallic components including Cu, Co and Pd were fabricated. The performance of these anodes was then tested in a solid oxide water electrolysis cell under conditions where the anode was exposed to the reducing gasses H₂, CH₄ and CO. The reducing gasses were used to decrease the electrochemical potential of the cell and increase overall efficiency. The results of this study show that Cu–CeO₂–YSZ anodes have low catalytic activity for the oxidation of CO and CH₄ and are not very effective in lowering the cell potential while operating in the reducing gas assisted mode. The addition of Co to the Cu–CeO₂–YSZ anode resulted in a modest increase in the catalytic activity and enhanced the thermal stability of the anode. A Pd–C–CeO₂–YSZ anode was found to have the highest catalytic activity of those tested and gave the largest reductions in the operating potential of the solid oxide electrolysis cell.     

以捕集CO_2、风电制氢和CO_2加氢反应构建绿色煤化工之探讨

分析了煤化工和风电产业发展面临的问题,指出应转换角度来看待产业发展中的瓶颈制约,提出了把捕集CO2、风电制氢和CO2加氢反应研究相结合的绿色煤化工的发展思路,供业界参考、探讨。     

Hydrogen Production for Fuel Cells from the Catalytic Ethanol Steam Reforming

Alumina-supported rhodium catalysts were shown to be active, selective and stable catalysts in the catalytic ethanol steam reforming when the reaction is carried out under pressure (1.1 MPa). Both the nature of the metal precursor salt, the metal loading and the reaction conditions were shown to influence the activity, the selectivity and the stability of the catalysts. Some trends observed when the reaction is carried out under moderate pressure were shown to be different from the conclusions drawn from earlier results obtained at atmospheric pressure. In fact, rhodium catalysts derived from a chlorinated metal precursor were shown to be the most active, selective and stable.     

甲醇水蒸汽重整制氢Au/TiO2催化剂

采用沉积-沉淀法制备了一系列Au/TiO2催化剂,考察了Au负载量、焙烧温度以及助剂等因素对甲醇水蒸汽重整制氢反应催化性能的影响;并利用XRD, TEM对催化剂进行了表征. 结果表明,制备条件对催化性能有明显影响;Au负载量为5%(w)时所得催化剂活性较好;助剂NiO可使催化剂催化甲醇水重整的催化活性明显提高;100℃烘干未焙烧制得的催化剂活性最好;TEM结果显示,NiO的加入使载体TiO2颗粒分散度提高,Au粒粒度变小.     

炼厂制氢装置副产二氧化碳的资源化利用

二氧化碳减排,对于实现我国社会经济可持续发展和营造良好的国际环境具有重要意义。文章分析了广州石化炼厂制氢装置副产二氧化碳的情况,比选食品级液体二氧化碳生产工艺技术路线,提出了二氧化碳资源有效回收利用途径。通过技术经济评价,二氧化碳的资源化利用不仅可以大幅减低温室气体排放,保护环境,更能带来可观的经济效益。     

甲烷蒸汽转化法制氢工艺评述

介绍甲烷蒸汽转化法制氢技术主要技术提供方及其大型单系列装置建厂业绩,并对制氢装置的工艺设计以及烟气废热和高温转化气热量的利用进行了综述评述。     

Development of a Scalable Method for Manufacturing High‐Temperature CO2 Capture Sorbents

An engineered process for scalable manufacture of a calcium aluminum carbonate CO₂ sorbent with production amounts of about 1000 g per hour has been developed. The process includes mixing and heating, solid‐liquid separation, drying and extrusion, crushing and conveying, and calcined molding steps. The sorbent preparation involves the coprecipitation of Ca²⁺, Al³⁺, and CO₃^2– under alkaline conditions. By adjusting the Ca:Al molar ratio, a series of Ca‐rich materials could be synthesized for use as CO₂ sorbents at 750 °C. A calcium acetate‐derived sorbent exhibited better cyclic stability than sorbents originating from CaCl₂ and Ca(NO₃)₂. The initial sorption capacity increased with CaO concentration. High stability of more than 90 % was maintained by the Ca:Al sorbents after 40 looping tests.