高温钙基CO_2吸收剂的锆改性研究
摘要
氢是一种理想的能源载体,在清洁燃料领域具有重要的意义。甲烷水蒸汽重整制氢工艺是制氢的重要途径,二氧化碳吸收是强化该制氢过程的重要手段,而二氧化碳吸收剂性能将直接影响制氢工艺的优劣。本文对氧化钙基二氧化碳吸收剂进行氧化锆负载改性,并考察其吸收性能。
本文通过负载氧化锆,对氧化钙基高温CO2吸收剂进行改性,制得CaO-ZrO2粉体的前驱体,然后再经高温煅烧,即得到经锆改性后的吸收剂。实验采用XRD、SEM及热重分析仪对吸收剂进行测试表征,考察了不同制备方法和制备条件(前驱体、颗粒粒径、Zr/Ca比例等)对吸收剂的锆改性效果,研究得到如下结论：采用化学沉淀法制备的锆改性吸收剂,吸收剂颗粒粒径减小,降低了二氧化碳气体向吸收剂内部扩散的阻力；颗粒粒径为120～160目的吸收剂可降低吸收反应过程中的孔堵塞；当Zr/Ca=1/40时,吸收剂中掺杂ZrO2形成了良好的介孔结构,可缓解氧化钙在高温下的烧结和破碎程度,提高吸收剂的循环热稳定性。
实验采用直径为φ34mm固定床反应器对经锆改性的吸收剂进行高温CO2吸收及煅烧再生性能的测试和评价,考察碳酸化操作条件(碳酸化反应及再生时间、碳酸化温度、再生温度、CO2分压等)对二氧化碳吸收转化率的影响。测试结果表明,化学沉淀法制备的锆改性吸收剂,当Zr/Ca=1/40,颗粒粒径为120～160目时,CO2分压为30%,碳酸化温度为650℃,反应时间30 min,再生温度为800℃,再生时间30 min反应条件下,最大吸收转化率达到82.6%,且在10次循环吸收反应后仍保持较高的碳酸化转化率73.6%。
经锆改性的吸收剂,具有良好的内部孔隙结构,在高温下达到较高的C02吸收率,再生温度降低维持了吸收剂的循环热稳定性,对C02的吸收具有较大的潜力,为强化甲烷水蒸气重整制氢工艺的可行性研究提供了基础。
Hydrogen is an ideal clean energy carrier. Carbon dioxide sorption-enhanced steam methane reforming process can effectively increase the capacity of hydrogen production.Performance of absorbent for carbon dioxide will directly affect the characteristics and merits of hydrogen technology. The purpose of this paper is load-modified calcium oxide absorbent based zirconium oxide, and studied its absorption for carbon dioxide.
In this paper, calcium oxide based absorbent of CO2 in high-temperature, which are modified by zirconium, was prepared to be precursor powders of CaO-ZrO2 and then calcined at high temperature. XRD and SEM were used to analysis the modification effect of absorbent in experiments.The influence of different preparation methods, preparation conditions (precursor, particle size and Zr/Ca) conclusions as following:Zirconium modified absorbent prepared by chemical precipitation has smaller particle size. The decreasing of particle size reduced the resistance of carbon dioxide diffuse to the absorbent; Sintering and crushing in the high temperature can be alleviated after doping with ZrO2.The doping of Zr in the sorbent was benefit in maintaining the mesoporous structure of CaO, leading to a high conversion rate of carbonation and enhancing the thermal stability of the sorbent.
The CO2 absorption of zirconium-modified absorbent and evaluation of regeneration in high temperature were conducted in fixed bed reactor with a diameter ofφ34mm. The influence of carbonation operating conditions (carbonate temperature, regeneration reaction time and temperature, CO2 partial pressure, etc.)on the absorption rate of carbon dioxide was investigated. The results showed that absorbent with particle size of 120～160 mesh and Zr/Ca=1/40, under the experimental conditions of 30% CO2 partial pressure, carbonation temperature of 650℃, reaction time 30 min, and regeneration at 800℃for 30 min, the maximum conversion rate of sorption reached 82.6%, and remained 73.6% after 10 cycles without severe sintering.
本文通过负载氧化锆,对氧化钙基高温CO2吸收剂进行改性,制得CaO-ZrO2粉体的前驱体,然后再经高温煅烧,即得到经锆改性后的吸收剂。实验采用XRD、SEM及热重分析仪对吸收剂进行测试表征,考察了不同制备方法和制备条件(前驱体、颗粒粒径、Zr/Ca比例等)对吸收剂的锆改性效果,研究得到如下结论：采用化学沉淀法制备的锆改性吸收剂,吸收剂颗粒粒径减小,降低了二氧化碳气体向吸收剂内部扩散的阻力；颗粒粒径为120～160目的吸收剂可降低吸收反应过程中的孔堵塞；当Zr/Ca=1/40时,吸收剂中掺杂ZrO2形成了良好的介孔结构,可缓解氧化钙在高温下的烧结和破碎程度,提高吸收剂的循环热稳定性。
实验采用直径为φ34mm固定床反应器对经锆改性的吸收剂进行高温CO2吸收及煅烧再生性能的测试和评价,考察碳酸化操作条件(碳酸化反应及再生时间、碳酸化温度、再生温度、CO2分压等)对二氧化碳吸收转化率的影响。测试结果表明,化学沉淀法制备的锆改性吸收剂,当Zr/Ca=1/40,颗粒粒径为120～160目时,CO2分压为30%,碳酸化温度为650℃,反应时间30 min,再生温度为800℃,再生时间30 min反应条件下,最大吸收转化率达到82.6%,且在10次循环吸收反应后仍保持较高的碳酸化转化率73.6%。
经锆改性的吸收剂,具有良好的内部孔隙结构,在高温下达到较高的C02吸收率,再生温度降低维持了吸收剂的循环热稳定性,对C02的吸收具有较大的潜力,为强化甲烷水蒸气重整制氢工艺的可行性研究提供了基础。
Hydrogen is an ideal clean energy carrier. Carbon dioxide sorption-enhanced steam methane reforming process can effectively increase the capacity of hydrogen production.Performance of absorbent for carbon dioxide will directly affect the characteristics and merits of hydrogen technology. The purpose of this paper is load-modified calcium oxide absorbent based zirconium oxide, and studied its absorption for carbon dioxide.
In this paper, calcium oxide based absorbent of CO2 in high-temperature, which are modified by zirconium, was prepared to be precursor powders of CaO-ZrO2 and then calcined at high temperature. XRD and SEM were used to analysis the modification effect of absorbent in experiments.The influence of different preparation methods, preparation conditions (precursor, particle size and Zr/Ca) conclusions as following:Zirconium modified absorbent prepared by chemical precipitation has smaller particle size. The decreasing of particle size reduced the resistance of carbon dioxide diffuse to the absorbent; Sintering and crushing in the high temperature can be alleviated after doping with ZrO2.The doping of Zr in the sorbent was benefit in maintaining the mesoporous structure of CaO, leading to a high conversion rate of carbonation and enhancing the thermal stability of the sorbent.
The CO2 absorption of zirconium-modified absorbent and evaluation of regeneration in high temperature were conducted in fixed bed reactor with a diameter ofφ34mm. The influence of carbonation operating conditions (carbonate temperature, regeneration reaction time and temperature, CO2 partial pressure, etc.)on the absorption rate of carbon dioxide was investigated. The results showed that absorbent with particle size of 120～160 mesh and Zr/Ca=1/40, under the experimental conditions of 30% CO2 partial pressure, carbonation temperature of 650℃, reaction time 30 min, and regeneration at 800℃for 30 min, the maximum conversion rate of sorption reached 82.6%, and remained 73.6% after 10 cycles without severe sintering.
引文
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