燃烧源颗粒及co2
English

化学链燃烧及部分氧化


燃煤二氧化碳捕集与封存(CCS)技术必须克服减排能耗高、成本高等问题,故急需CCS的理论创新和技术突破。基于固体氧载体颗粒循环的化学链燃烧技术被广泛认为是最具有前景的碳捕集技术之一,它所具有高能源转化效率、低CO2捕集成本和污染物协同控制等综合优点,代表了能源与环境领域的崭新发展方向,尚有诸多挑战性的基础理论问题有待解决。化学链燃烧利用氧载体在气氛隔离的燃料反应器和空气反应器间循环来传递活性氧,来实现把常规一步剧烈燃烧反应分解为多步氧化/还原反应,可见,化学链燃烧的成功实施离不开高性能氧载体颗粒和串行流化床反应器,这也是我们的研究热点。我们也关注利用化学链这种思想来实现燃料的部分氧化(气化、重整、提质等)、污染物控制(抑制二噁英等)、及其他新颖的功能应用。

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主要研究工作包括:

1. 氧载体晶格氧传递和利用原理

通过量子化学密度泛函理论(DFT)计算分析,发现CuO释氧包括三个步骤:邻近氧原子结合形成氧分子,氧分子脱离氧载体表面和内部氧负离子扩散迁移,释氧速率限制步骤为表界面氧分子形成和脱附。对于CuO/Cu2O/Cu体系的氧化,阳离子的外扩散过程是氧化过程中的主导扩散机制。对于活性组分与惰性组分之间的相互作用,DFT和分子动力学模拟结果均表明,惰性载体的存在对其释氧过程不利,但有利于抑制高温时CuO晶粒的迁移和团聚。对活性晶格氧传输原理、组分相互作用等原子/分子微观尺度层面理解,将有助于氧载体颗粒的裁剪设计和探究气固表界面反应动力学机理。

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CuO释氧过程晶格氧传递的微观理解



CuO活性组分与惰性组分相互作用的微观理解

参考文献:

1. Yongliang Zhang, Haibo Zhao*, Lei Guo, Chuguang Zheng. Decomposition mechanism of Cu-based oxygen carriers for chemical looping with oxygen uncoupling based on density functional theory calculation. Combustion and Flame, 2015, 162: 1265-1274

2. Haibo Zhao*, Yongliang Zhang, Yijie Wei, Jinfa Gui. Understanding CuO-support interaction in Cu-based oxygen carriers at a microcosmic level. Proceedings of the Combustion Institute, 2017, 36(3): 4069–4077


1. 氧载体设计、功能制备和改性提质

氧载体颗粒起着反应器间活性氧传递和能量流传递的桥梁作用,高性能氧载体的优化设计和批量制备是低成本和规模化的化学链碳捕集的关键。发展了NiO/NiAl2O4CuO/CuAl2O4CuFe2O4Cu等修饰铁矿石、铜矿石、水泥修饰的铜矿石、铜矿石铁矿石物理混合、水泥粘结铜矿石和铁矿石等作为煤化学链燃烧/化学链氧解耦燃烧的氧载体,并发展了溶胶凝胶燃烧合成法、自组装模板燃烧合成法、喷动流化床批量造粒方法和工艺等。

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自组装荷尘工艺流程示意图

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铜矿石和铁矿石混合的协同效应

参考文献:

1. Zuwei Xu, Haibo Zhao*, Yijie Wei, Chuguang Zheng. Self-assembly template combustion synthesis of a core-shell CuO@TiO2-Al2O3 hierarchical structure as an oxygen carrier for the chemical-looping processes. Combustion and Flame, 2015, 162(8): 3030-3045

2. Weijin Yang, Haibo Zhao*, Kun Wang, Chuguang Zheng. Synergistic effects of a mixture of iron ore and copper ore as oxygen carriers in chemical-looping combustion. Proceeding of the Combustion Institute, 2015, 35: 2811-2818

3. Xin Tian, Yijie Wei, Haibo Zhao*. Evaluation of a SATCS-derived CuO@TiO2-Al2O3 oxygen carrier for chemical looping with oxygen uncoupling (CLOU). Fuel, 2017, 209: 402-410

4. Weijin Yang, Haibo Zhao*, Jinchen Ma, Daofeng Mei, Chuguang Zheng. Copper-decorated hematite as oxygen carrier for in situ gasification chemical looping combustion of coal. Energy & Fuels, 2014, 28, 3970-3981

5. Daofeng Mei, Alberto Abad, Haibo Zhao*, Juan Adánez, Chuguang Zheng. On a Highly Reactive Fe2O3/Al2O3 Oxygen Carrier for in-situ Gasification Chemical Looping Combustion. Energy & Fuels, 2014, 28 (11): 7043–7052

6. Daofeng Mei, Haibo Zhao*, et al. Using sol-gel derived CuO/CuAl2O4 oxygen carrier in chemical looping with oxygen uncoupling for three typical coals. Energy & Fuels, 2013, 27 (5): 2723–2731

7. Haibo Zhao*, Liming Liu, Baowen Wang, Di Xu, Linlin Jiang, Chuguang Zheng. Sol-Gel-Derived NiO/NiAl2O4 Oxygen Carriers for Chemical-Looping Combustion by Coal Char. Energy & Fuels, 2008, 22(2): 898-905

8. Kun Wang, Haibo Zhao*, Yanfei Fang, Jinchen Ma, Chuguang Zheng. Chemical-looping with oxygen uncoupling of different coals using natural copper ore as oxygen carrier. Energy & Fuels, 2015, 29(10): 6625–6635

9. Jinchen Ma, Xin Tian, Haibo Zhao*, Sankar Bhattacharya*, Sharmen Rajendran, Chuguang Zheng. Investigation of Two Different Hematite as Oxygen Carrier and Two Low-rank Coals as Fuel in Chemical Looping Combustion (CLC). Energy & Fuels, 2017, 31(2): 1896–1903

10. Xin Tian, Haibo Zhao*, Jinchen Ma. Cement bonded fine hematite and copper ore particles as oxygen carrier in chemical looping combustion. Applied Energy, 2017, 204: 242-253

11. Haibo Zhao*, Kun Wang, et al. Characterization of natural copper ore as oxygen carrier in chemical looping with oxygen uncoupling of anthracite. International Journal of Greenhouse Gas Control, 2014, 22: 154-164

12. Xin Tian, Haibo Zhao*, Kun Wang, Jinchen Ma, Chuguang Zheng. Performance of Cement Decorated Copper Ore as Oxygen Carrier in Chemical-Looping with Oxygen Uncoupling. International Journal of Greenhouse Gas Control, 2015, 41: 210–218

13. Lei Guo, Haibo Zhao*, Jinchen Ma, Daofeng Mei, Chuguang Zheng. Comparison of Large-Scale Production Methods of Fe2O3/Al2O3 Oxygen Carriers for Chemical Looping Combustion. Chemical Engineering & Technology, 2014, 37(7): 1211-1219

2. 化学链过程气固反应动力学

研究了典型氧载体(包括NiO/NiAl2O4Fe2O3/Al2O3CuO/CuAl2O4CuFe2O4、天然铁矿石、天然铜矿石、及活化改性的天然矿石等)与典型煤热解气化产物、以及中国典型煤种的热化学反应特征和循环性能,对煤基化学链燃烧/化学链氧解耦燃烧特征进行了较为系统的研究,并对关键气固反应进行化学反应动力学机理研究。例如,对铁矿石与CO的还原反应动力学进行了表界面尺度研究,发现赤铁矿氧载体还原第一阶段受到颗粒表界面内扩散控制,而第二阶段主要受气固异相化学反应速率的控制;在CLOU气氛下研究煤焦低氧燃烧和高CO2气化的竞争过程,在煤焦转化率小于0.6时,煤焦与高浓度CO2气化反应速率要高于煤焦与低浓度O2燃烧反应速率,煤焦同时气化燃烧过程可以用其单独气化和单独燃烧的反应动力学模型来线性预测。

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CuO氧载体与H2反应过程中CLOU(释氧)效应和直接CLC效应的辨识

          

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考虑热力学驱动力和化学反应驱动力的CuO释氧反应动力学

参考文献:

1. Daofeng Mei, Alberto Abad, Haibo Zhao*, Juan Adánez. Characterization of a Sol-gel Derived CuO/CuAl2O4 Oxygen Carrier for Chemical Looping Combustion (CLC) of Gaseous Fuels: Relevance of Gas-Solid and Oxygen Uncoupling Reactions. Fuel Processing Technology, 2015, 133: 210-219

2. Mingze Su, Jinchen Ma, Xin Tian, Haibo Zhao*. Reduction Kinetics of Hematite as Oxygen Carrier in Chemical Looping Combustion. Fuel Processing Technology, 2017, 155: 160-167

3. Lei Guo, Haibo Zhao*, Kun Wang, Daofeng Mei, Zhaojun Ma, Chuguang Zheng. Reduction Kinetics of sol-gel Derived CuO/CuAl2O4 Oxygen Carrier for Chemical Looping with Oxygen Uncoupling. Journal of Thermal Analysis and Calorimetry, 2016, 123: 745-756

4. Haibo Zhao*, Daofeng Mei, Jinchen Ma, Chuguang Zheng. Comparison of preparation methods for iron-alumina oxygen carrier and its reduction kinetics with hydrogen in chemical looping combustion. Asia-Pacific Journal of Chemical Engineering, 2014, 9(4): 610–622

5. Mingze Su*, Haibo Zhao, Baozhou Du, Pengfei Zhang, Zhigang Liu*. Intrinsic Reduction Kinetics Investigation on a Hematite Oxygen Carrier in Chemical Looping Combustion. Energy & Fuels, 2017, 31 (3): 3010–3018


4. 污染物迁移和控制

对煤化学链燃烧过程中的硫、氮等污染物排放特征和迁移特性、煤灰与氧载体之间的相互作用、汞等重金属排放、可吸入颗粒物排放等,并针对排放较多的污染物进行重点脱除。例如,研究了铜矿石氧载体与含H2S合成气以及在煤化学链氧解耦燃烧过程中与杂质组分的相互作用,发现燃料反应器出口有双峰SO2及少量H2SH2S与氧载体会反应产生少量Cu2SFeS,加入CaO可达到98%的脱硫效率。

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不同温度下SCCLOU过程中典型SO2释放曲线

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SCCLOU过程中加入CaO与不加入时的SO2释放曲线


参考文献:

1. Xin Tian, Kun Wang, Haibo Zhao*, Mingze Su. Chemical Looping with Oxygen Uncoupling of high-sulfur coal using copper ore as oxygen carrier. Proceedings of the Combustion Institute, 2017, 36(3): 3381–3388

2. Kun Wang, Xin Tian, Haibo Zhao*. Sulfur behavior in chemical-looping with oxygen uncoupling using a copper ore oxygen carrier. Applied Energy, 2016, 166: 84–95


5. 串行流化床反应器研究

设计和运行了5kWth50kWth的双循环流化床实验台架,对其流体动力学规律进行实验测量和CFD数值模拟,并检验各种类型氧载体与燃料的连续化学链燃烧/化学链氧解藕燃烧的燃烧效率、CO2捕集效率等,得到合适的运行条件和匹配规律,为进一步放大和工程应用奠定基础。例如50kWth煤基化学链燃烧串行流化床,燃料反应器采用鼓泡床设计,提高氧载体与燃料的停留时间,提高转化率;空气反应器采用气固相混合相对均匀的湍动流化床,防止氧载体的烧结。在氧载体的循环方式中,取消限制固体循环流量的溢流口设计,采用提升管提供氧载体颗粒循环的动力。针对固体燃料(特别是低挥发分的烟煤或煤焦),采用流动密封阀与碳分离器相结合的设计方式提高燃料转化率。在120分钟连续运行中,以天然铁矿石作为氧载体,神华烟煤为固体燃料,CO2气产率最高达到约90%

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参考文献:

1. Jinchen Ma, Haibo Zhao*, Xin Tian, Yijie Wei, Yongliang Zhang, Chuguang Zheng. Continuous Operation of Interconnected Fluidized Bed Reactor for Chemical Looping Combustion of CH4 Using Hematite as Oxygen Carrier. Energy & Fuels, 2015, 29(5): 3257-3267

2. Jinchen Ma, Haibo Zhao*, Xin Tian, Yijie Wei, Sharmen Rajendran, Yongliang Zhang, Sankar Bhattacharya, Chuguang Zheng. Chemical looping combustion of coal in a 5 kWth interconnected fluidized bed reactor using hematite as oxygen carriers. Applied Energy, 2015, 157: 304-313

3. Mingze Su, Haibo Zhao*, Jinchen Ma. Computational Fluid Dynamics Simulation for Chemical Looping Combustion of Coal in a Dual Circulation Fluidized Bed. Energy Conversion and Management, 2015, 105: 1–12


6. 钙循环和钙铜循环

钙基吸收剂被广泛用于燃烧后CO2捕捉过程,然而,钙基吸收剂的发展主要受到两方面限制:一是 吸收剂性能随着循环次数增加而迅速衰减,二是煅烧过程中需要大量热。我们用自组装模板法制备具备核壳结构的CaO/TiO2-Al2O3CaO-CuO/MgO-Al2O3吸收剂,核结构微米Al2O3作为载体支架承担着颗粒机械强度、提高载体的抗烧结能力,壳结构纳米TiO2 MgO包裹在核结构周围,以隔绝惰性载体与活成分之间的化学反应,这种碳载体可有效解决钙循环和钙铜循环过程中的吸附剂性能衰减问题。另外一方面,为了解决钙循环煅烧过程中热量需求问题,利用联合钙铜循环,将CuO还原过程释放的热量来满足煅烧过程所需的热量。

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CaO@TiO2-Al2O3在钙循环中的性能演变

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自组装模板合成法制备的CaO@TiO2-Al2O3颗粒

参考文献:

1. Weiwei Peng, Zuwei Xu, Cong Luo, Haibo Zhao*. A Tailor-Made Core-Shell CaO/TiO2-Al2O3 Architecture as a High-Capacity and Long-Life CO2 Sorbent. Environmental Science & Technology, 2015, 49(13): 8237–8245

2. Weiwei Peng, Zuwei Xu, Haibo Zhao*. Batch fluidized bed test of SATS-derived CaO/TiO2-Al2O3 sorbent for calcium looping. Fuel, 2016, 170: 226-234


7. 化学链重整和气化

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参考文献:

1. Haibo Zhao*, Lei Guo, XixianZou. Chemical-looping auto-thermal reforming of biomass using Cu-based oxygen carrier. Applied Energy, 2015, 157: 408-415

2. Lei Guo, Haibo Zhao*, Chuguang Zheng. Synthesis Gas Generation by Chemical-looping Reforming of Biomass with Natural Copper Ore as Oxygen Carrier. Waste and Biomass Valorization, 2015, 6(1): 81-89


8. 化学链脱氯抑制二噁英生成

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参考文献:

1. Jinxing Wang, Haibo Zhao*. Chemical Looping Dechlorination through Decorated Fe2O3/Al2O3 Oxygen Carrier. Combustion and Flame, 2015, 162: 3503-3515

2. Jinxing Wang, Haibo Zhao*. Evaluation of CaO-decorated Fe2O3/Al2O3 as an oxygen carrier for in-situ Gasification Chemical Looping Combustion of Plastic Wastes. Fuel, 2016, 165: 235-243

3. Jinxing Wang, Haibo Zhao*. Application of CaO-decorated iron ore for inhibiting chlorobenzene during in-situ gasification chemical looping combustion of plastic waste. Energy & Fuels, 2016, 30(7): 5999-6008


9. 化学链其他应用

化学链作为一种具有反应气氛隔绝、便于产物分离、化学能梯级利用等独特特点的反应方式,在很多领域可能具有比常规技术更显著的优点。如化学链制氧,并与富氧燃烧耦合,大幅降低制氧能耗;煤热解与煤焦化学链氧解耦耦合,实现煤分级利用和碳捕集;等。例如,对于耦合化学链氧解耦燃烧的煤分级利用系统,通过Aspen Plus对该新型系统进行过程模拟和分析,结果表明:耦合CLOU的煤分级利用系统的系统效率为46.3%,高出常规煤分级利用系统2.12个百分点。对两个煤分级利用系统进行能量集成分析。发现系统无需外部热源。但需要冷公用工程与系统进行换热。对换热网络进行夹点分析,耦合CLOU的煤分级利用系统中可以用于生产高压蒸汽与发电的热量高于常规煤分级利用系统,表明其能量利用效率较常规系统的能量利用效率要高。对两系统进行火用分析,耦合CLOU的煤分级利用系统的火用效率高于常规煤分级利用系统的火用效率十个百分点左右,整个系统的火用损降低了22.04%

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常规煤分级利用系统和耦合CLOU的煤分级利用系统


参考文献:

1. Yongliang Zhang, Xixian Zou, Haibo Zhao*, Chuguang Zheng. A clean coal utilization technology based on coal pyrolysis and chemical looping with oxygen uncoupling: principle and experimental validation. Energy, 2016, 98: 181–189




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