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化学链燃烧工艺中载氧体的研究进展

刘海涛1，高海潮1，高志芳1,2

(1.安徽工业大学冶金工程学院，安徽马鞍山 243002;2.安徽工业大学冶金减排与资源综合利用教育部重点实验室，安徽马鞍山 243002)

摘要:化石燃料燃烧产生的CO2是主要的温室气体之一，化学链燃烧工艺不仅能够低能量消耗进行内分离捕集CO2，也是制备H2及其他工业合成气的重要手段，其中载氧体是整个化学链循环系统的关键。以化学链燃烧中的载氧体物化特性为核心，论述了载氧体的制备、组成以及掺杂优化等发展现状，分析了当前载氧体存在的问题及研究难点，并对载氧体研究方向进行展望。载氧体传统制备方法中机械混合法、浸渍法操作简单、成本低，但制备的载氧体样品均匀性差，活性和稳定性难以保证;化学共沉淀、冷冻成粒法和溶胶凝胶法能在一定程度上提高载氧体各成分的均匀性，但其载氧体的微观结构难以控制，操作复杂，制备成本较高，不适于大规模应用;载氧体制备方法应向低成本、高效以及精细化控制方向发展。目前常用的载氧体中铁基载氧体活性低，镍基和锰基载氧体对环境不利，而铜基载氧体易于烧结，惰性载体的加入和碱金属等元素的掺杂能在一定程度上改善其特性，但距离低成本、高活性、环境友好、工作寿命长还有一定差距，因而进一步研究载氧体组分和掺杂组分之间的协同机理是载氧体优化的关键。

关键词:温室效应;化学链燃烧;载氧体;掺杂改性

中图分类号:TK16

文献标志码:A

文章编号:1006-6772(2018)05-0012-08

收稿日期:2018-03-27;

责任编辑:白娅娜

DOI:10.13226/j.issn.1006-6772.18032701

基金项目:国家自然科学基金资助项目(U1660106)

作者简介:刘海涛(1992—)，男，安徽阜阳人，硕士研究生，从事固体废弃物综合利用及燃烧节能减排研究。E-mail:804571143@qq.com。通讯作者:高志芳(1978—)，女，河北沧州人，副教授，博士。E-mail:cancan20071007@163.com

引用格式:刘海涛，高海潮，高志芳.化学链燃烧工艺中载氧体的研究进展[J].洁净煤技术，2018，24(5):12-19.

LIU Haitao,GAO Haichao,GAO Zhifang.Progress on oxygen carrier in chemical-looping combustion[J].Clean Coal Technology，2018，24(5):12-19.

Progress on oxygen carrier in chemical-looping combustion

LIU Haitao1,GAO Haichao1,GAO Zhifang1,2

(1.School of Metallurgical Engineering,Anhui University of Technology,Maanshan 243002,China;2.Key Laboratory of Metallurgical Emission Reduction and Comprehensive Utilization of Resources,Anhui University of Technology,Maanshan 243002,China)

Abstract:CO2 produced by the combustion of fossil fuels is one of the major greenhouse gases.Chemical-looping combustion process can not only separate and capture CO2 with low energy consumption,but also is an important means for the preparation of hydrogen and other industrial synthesis gases.The oxygen carrier is the key to the entire chemical-looping combustion system.The development status of preparation,composition and doping modification of oxygen carrier were discuessed,and current problems,research difficulties and prospects of oxygen carrier were analyzed.In the traditional preparation method of oxygen carrier,the mechanical mixing and impregnation methods are simple in operation process and low in cost,but the prepared oxygen carrier sample has poor uniformity,and it is difficult to ensure the activity and stability.Chemical co-precipitation,freezing granulation method and sol-gel method can improve the uniformity of the components of the oxygen carrier to some extent,but it is not suitable for large-scale application because of unmanageable microstructure,complex operation and high preparation cost.The preparation method of the oxygen carrier should be low-cost,high-efficiency and refined control.At present,the iron-based oxygen carrier in the commonly used oxygen carrier has low activity,the nickel-based and manganese-based oxygen carrier is unfavorable to the environment,and the copper-based oxygen carrier is easy to be sintered.It can improve the characteristics to a certain extent by addition of the inert carrier and the alkali metal,but there is still a gap between low cost,high activity,environmental friendliness and long working life.Therefore,further research on the synergistic mechanism between oxygen carrier components and doping components is the key to oxygen carrier optimization.

Key words:greenhouse effect;chemical-looping combustion;oxygen carriers;doping modification

0 引言

近年来，温室效应的危害被人们所熟知，而CO2是主要的温室气体之一，因此CO2减排是控制温室效应的关键。化石燃料燃烧是CO2排放主要途径，通过CO2收集和储存(CCS)技术可有效减少CO2排放，但操作繁杂、费用高，且消耗大量能量[1-2]。化学链燃烧技术(chemical-looping combustion，CLC)是一种新型的能源利用形式，其概念由德国科学家Richter在1983年首次提出[3]。通过载氧体吸收空气中的氧气转化为载氧体内部的晶格氧，在高温条件下，燃料与载氧体内的晶格氧或载氧体高温分解的O2反应放出热量，燃烧过程中金属氧化物(Me/MeO)载氧体在燃料反应器中被燃料(合成气或天然气)还原成Me及在空气反应器中被空气氧化成MeO，还原和氧化交替进行，避免了燃烧过程中燃料和空气的直接接触，因无空气中N2参与，CO2分离储存，减少了燃料型NOx的生成[4]，且通过载氧体的梯级还原实现了燃料的梯级利用[5]，因此CLC具有CO2内分离、能量利用率高、能量消耗和NOx排放低等优点。固体燃料(如煤)的CLC中固体燃料和氧载体之间的固固反应非常缓慢，固体燃料气化后才能与载氧体充分反应，因而在CLC中固体燃料的气化是速率限制环节，导致化学链燃烧中固体燃料的燃烧效率和燃烧后CO2捕集效率较低[6]。Mattisson等[7]提出了氧解耦化学链燃烧(chemical-looping oxygen uncoupled，CLOU)技术的概念，燃料反应器中使用的特定载氧体在高温和缺氧环境条件下能够分解释放气态O2，与反应器中的固体燃料在无需气化的情况下发生气固反应，极大提高了化学链燃烧效率。然而CLOU中使用的载氧体种类有限，主要有CuO/Cu2O、Co3O4/CoO和Mn2O3/Mn3O4，其中CuO/Cu2O载氧体在高温下容易烧结，Co3O4/CoO载氧体成本较高，Mn2O3/Mn3O4载氧体活性较差不能完全满足当前化学链燃烧的要求。CLC和CLOU使用的固态载氧体的优点是能够精细化控制载氧体材料的特性，但容易磨损、结块和烧结，特别是高温条件下容易缩短载氧体颗粒的工作寿命[8]。同时操作温度和压力也受到限制，导致与燃烧和气化过程有关的能效降低。液体化学链气化(LCLG)和液体化学链燃烧(LCLC)分别是2种近期提出的从烃燃料燃烧中生产合成气和收集CO2的技术[9-11]，通过使用液体载氧体进行化学链燃烧或气化解决了固体载氧体磨损和烧结的问题，极大提高反应物接触效率，提高燃料转化率。Zhang等[12]研究了气态载氧体MoO3在化学链燃烧和气化系统的可行性，研究发现气态载氧体可用于化学链燃烧和气化系统，提出MoO3气态载氧体具有实现高反应速率、100%载氧体还原率和无限载氧体寿命的潜力。化学链燃烧技术经过了普通载氧体的晶格氧与燃料的燃烧、载氧体高温分解的分子氧与燃料的燃烧以及液态、固态载氧体，化学链燃烧技术因载氧体物化特性的改善而得到优化，因此载氧体特性对于化学链燃烧系统的运行至关重要。载氧体研发与选择是化学链燃烧系统发展和高效稳定运行的关键，本文以化学链燃烧中的载氧体物化特性为核心，从载氧体的制备、组成以及掺杂优化等方面进行论述，以求在客观认识载氧体发展现状的情况下，寻求未来化学链燃烧技术的发展方向以及解决载氧体存在问题的具体方法。

1 载氧体特性

近几年超过900种载氧体被检测，从来源看主要包括人工合成载氧体、廉价天然矿石[13-17]和废渣类[18-19]3种载氧体;从类型来看主要包括金属载氧体和非金属载氧体。对载氧体组分和结构的改造主要是通过调节制备方法，惰性载体和活性成分的种类、含量以及改性元素的掺杂来实现对载氧体活性和稳定性的控制。

1.1 制备方法

载氧体常用的制备方法有机械混合法、浸渍法、冷冻成粒法、化学共沉淀法以及溶胶凝胶法等，不同方法制备出的载氧体特性有所差异，具体见表1。

由表1可知，载氧体制备方法中浸渍法和化学共沉淀法应用较广泛，其制备成本低，样品均匀性好、操作易于控制;机械混合法制备过程简单，成本低，但样品组分间均匀性差;溶胶凝胶法和冷冻成粒法制备过程复杂，成本较高，可得到高均匀性、高比表面积的载氧体，但由于其成本较高目前只适合实验室操作，不利于大规模生产。除传统制备方法外，覃吴等[20]基于理论分析制备了高弥勒指数晶面的Fe2O3(104)/Al2O3载氧体，其具有发达的表面多孔结构和较大的比表面积，CO化学链燃烧的载氧体特性比传统浸渍法制备的载氧体Fe2O3/Al2O3具有更高的反应活性。赵铁鹏等[26]通过聚苯乙烯(PS)胶晶模板法合成了三维有序大孔(3DOM)α-Fe2O3载氧体，3DOM Fe2O3呈现排列规整的三维有序多孔形貌，层与层间通过三维孔道相连，并交替排列[27]，其发达的孔隙提高了载氧体比表面积和载氧体在化学链燃烧中的反应性[28]。

表1 载氧体制备方法及特点
Table 1 Preparation methods and characteristics of oxygen carriers

1.2 惰性载体

载氧体通常由活性成分和惰性成分组成，单独的金属氧化物的反应性及稳定性较差，容易烧结和破碎，如NiO被还原后其氧化反应只在颗粒表面进行，氧化率很低[29];CuO和Cu的熔点较低，在高温条件下易于烧结使得载氧体的孔隙率骤减，与反应气体的接触面积降低，导致载氧体反应性下降。为提高载氧体特性，可在载氧体活性组分中掺杂一些稳定性较高的惰性载体，惰性载体使活性组分具有良好的分散性，提高载氧体颗粒载热能力的同时，增加了载氧体的孔隙率和机械强度，有利于提高载氧体活性和循环稳定性[30]。宋涛等[31]研究了以赤铁矿作为载氧体、以H2作为燃料的化学链燃烧反应，研究表明载氧体中惰性载体SiO2、Al2O3的存在可以阻止铁矿石载氧体颗粒表面活性相Fe2O3晶粒在高温下的液相接触，从而有效抑制载氧体的烧结，从微观角度揭示了添加惰性载体后铁基载氧体稳定性提高的内部机理。秦翠娟等[32]以CaSO4为载氧体研究了煤的化学链燃烧反应，结果表明以纯CaSO4单独成分作为载氧体时，其在化学链燃烧过程中活性和机械强度都相对较差。周树理[33]向纯CaSO4载氧体中添加惰性载体探究其对载氧体的影响，研究表明惰性载体的存在不仅能提高CaSO4载氧体在化学链燃烧中的反应速率和机械强度，还能够降低反应温度。同一种活性成分，惰性成分不同得到的载氧体特性不同，Andy等[34]研究发现，NiO/ZrO2、NiO/Al2O3和NiO/NiAl2O4在低温650 ℃条件下仍具有较高的反应性，而NiO/SiO2和NiO/TiO2表现出低起始反应活性，且不到2 h就快速失活。Adánez等[35]制备了不同载体ZrO2和MgAl2O4的铜基载氧体，研究其在CLOU中的反应特性，研究表明为达到较好的反应性和稳定性，相对于CuO/MgAl2O，CuO/ZrO2中需掺入更多的惰性载体ZrO2。

近几年有序介孔材料也被用作惰性材料制备载氧体。有序介孔材料发达的孔隙结构和比表面积能提供大量活性位，具有负载金属颗粒的能力，在载氧体中广泛使用[36-38]，如介孔二氧化硅家族中的MCM-41和SBA-15、SBA-16等。

1.3 活性组分

载氧体主要包括金属氧化物和非金属氧化物，化学链燃烧系统中的载氧体要具有良好的反应性和稳定性，且材料易得，制备成本低，对环境友好。目前常用的载氧体有由Fe、Cu、Ni、Mn等过渡金属氧化物制备的金属载氧体和碱土金属(如Ca、Ba、Sr硫酸盐)制备的非金属载氧体[39-40]。载氧体活性成分不同，载氧体性质有所差异，具体见表2。

表2 传统载氧体的种类和特性
Table 2 Types and characteristics of traditional oxygen carriers

由表2可知，铜基载氧体易于烧结;镍基载氧体对环境有害;铁基载氧体活性一般，载氧能力差;锰基载氧体热稳定性差，污染环境;非金属载氧体不稳定、活性低、易烧结。近期研究主要是基于传统载氧体，通过掺杂改性传统载氧体，进而改善载氧体化学链燃烧特性。

1.4 掺杂改性

一些金属元素的掺杂不仅可提高载氧体的反应性，降低反应温度[50]，还可抑制载氧体积碳[51]，提高反应产物的选择性[52]，从而改善载氧体的活性和循环特性。程煜等[53]制备了掺杂K2CO3的Fe2O3/Al2O3载氧体，探究K元素掺杂对煤焦化学链气化中铁基载氧体特性的影响，研究发现载氧体引入K2CO3能够提高载氧体活性和循环特性。也有部分学者以低活性的铁矿石作为铁基载氧体，并掺杂K2CO3、Na2CO3、Li2CO3等。K2CO3含量达到6%时载氧体活性最高，高于或低于此值活性均降低;向纯铁矿掺入6%的Na2CO3，960 ℃时煤化学链的催化燃烧效果最显著，碳转化率高达92.7%，高于纯铁矿石约15.5%;掺杂元素不同提升效果有所差异，K元素掺杂优于Na和Li元素[54-56]。Ryua等[57]制备了掺杂CeO2的铁基载氧体，研究Ce掺杂对化学链燃烧中载氧体特性的影响，研究发现Fe2O3中加入少量CeO2可降低Fe2O3与H2反应的活化能，从而提高载氧体的反应性。对于非金属载氧体CaSO4的掺杂改性也有较多研究，在CaSO4载氧体掺入活性添加剂NiO、CuO、Fe2O3等可有效改善载氧体的反应性，掺入惰性添加剂Al2O3和SiO2等可提高CaSO4载氧体的稳定性，掺入固硫剂CaO可有效抑制化学链燃烧副反应的发生[58-60]。赤铁矿的加入可有效提高钙基载氧体的碳转化率和CO2收集效率，赤铁矿添加量达到7%时，2种效率趋于稳定，分别达到90%和91%，高于无赤铁矿添加的79%和88%，含硫气体的释放也得到了抑制。在CaSO4载氧体中掺杂CaO，物质的量比为1.99，900 ℃时含硫气体SO2和H2S的释放相对于无CaO掺入有较大幅度降低，分别为70.06%和50.09%，但气体硫化物的释放仍较显著;在钙基载氧体中添加CuO能提高载氧体的反应活性，CO2体积分数以及煤的燃烧效率均提高，CaSO4和CuO质量比为10∶1.5时复合载氧体的活性最高，在850 ℃时碳转化率达到91.2%，且10次循环反应中具有较好的反应性能。文圆圆等[61]通过浸渍法制备的CuO/Al2O3载氧体颗粒在化学链燃烧中，铜基载氧体烧结严重，添加CoO、NiO、MgO和SrO2四种氧化物制成复合载氧体后，由于高熔点的新成分有效分散在CuO晶粒之间形成晶粒和原子迁移阻力抑制了烧结，从而有效改善铜基载氧体的循环稳定性，但Cu-Sr复合载氧体中的Sr会与CO2化合生成碳酸锶，并在吸氧阶段释放出CO2，故Cu-Sr复合载氧体具有碳酸化的缺陷，会降低CO2捕集效率。

由上所知，载氧体中适宜掺杂可有效提高载氧体的化学链燃烧特性，但以化学纯试剂作为添加剂，成本较高，不利于大规模的工业化应用，因此有学者尝试选用廉价的富含碱金属和碱土金属的物质来修饰载氧体。沈来宏等[62]、张帅等[63]研究发现草木灰的掺入能有效提高Fe基载氧体的反应活性和循环特性，草木灰修饰反应后铁基载氧体的孔隙结构较为明显，高K/Si比能防止铁基载氧体的严重烧结，载氧体中负载的K在循环中流失，载氧体稳定性降低。高正平等[64]将草木灰掺入铁矿石载氧体，发现草木灰生物质修饰的铁矿石K的负载情况较为稳定，流失现象得到抑制。Saha[65]用秸秆混以煤作为化学链燃烧的燃料，分析以CaSO4为载氧体在化学链燃烧过程中特性，研究表明掺入较高比例的秸秆有利于提高化学链燃烧效率和载氧体还原后的氧化再生速率。杨明明等[27]将凹凸棒石黏土(ATP)加入铁基载氧体中以改善其特性，研究表明ATP黏土的掺入能明显改善铁基载氧体的结构特征，显著增加其比表面积和抗磨损性能。李媛等[66]向CuO/TiO2中加入分散剂分析其对载氧体性能的影响，研究表明添加分散剂能有效抑制高温条件下燃料不完全燃烧产生的芳香烃环化去氢积碳效应，有利于抑制载氧体的碳沉积。

2 结语

传统的载氧体制备方法中机械混合法、浸渍法操作简单、成本低，但制备的载氧体样品均匀性差，活性和稳定性难以保证;化学共沉淀、冷冻成粒法和溶胶凝胶法能在一定程度上提高载氧体各成分的均匀性，但其载氧体的微观结构难以控制，操作复杂，制备成本较高，不适于大规模应用，因此载氧体制备方法在低成本、高效以及精细化控制方面的优化研究仍是载氧体进一步发展的关键。目前常用的载氧体中铁基载氧体活性低，镍基和锰基载氧体对环境不利，而铜基载氧体易于烧结，惰性载体的加入和碱金属等元素的掺杂能在一定程度上改善其特性，但距离低成本、高活性、环境友好、工作寿命长还有一定差距。载氧体的掺杂能改善载氧体的化学链燃烧特性，而载氧体组分和掺杂组分之间的协同机理是载氧体掺杂优化的关键，是下一步的研究重点。

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