凹凸棒石改性钙基吸收剂循环碳酸化特性的试验分析

钙基吸收剂在较高的温度下可有效的循环捕集烟气中的较低浓度的CO2,通过升温释放出高浓度的CO2.但其弊端在于随着CO2释放/吸附的不断进行,吸收剂的烧结现象严重,CO2的吸收效率也显著的下降,若仅采用钙基材料作为CO2捕集剂,需不断的投入新鲜的吸收剂,消耗量较大.本论文以水泥工业为背景,研究其烟气中CO2的捕集,并采用一维结构的凹凸棒对吸收剂进行表面修饰处理,来缓解吸收剂的烧结现象,以提升CO2的吸收效率.试验结果表明:凹凸棒石物理吸附CO2的量对钙基吸收剂碳酸化率的提高有一定的贡献,但此贡献要小于吸收剂抗烧结性能的提高所带来的贡献;凹凸棒石对颗粒粒径较大的吸收剂的改性效果较好;不改变钙基吸收剂的粒径,当将提纯凹凸棒石的粒径减小时,其改性效果进一步提高.     

利用蛭石增强石灰石对CO2的循环捕集效率

天然石灰石经高温煅烧分解后所得CaO可以作为捕集CO2的吸收剂,用来捕集水泥、煤电等工业烟气中的CO2.但是由于烧结现象导致钙基吸收剂的循环碳酸化率在多次循环之后会发生迅速衰减,基于此,我们提出利用具有天然纳米片层结构的蛭石对石灰石颗粒表面进行修饰改性,以便提高石灰石颗粒的抗烧结能力及其循环捕集CO2的能力.利用TGA以及SEM对蛭石改性的石灰石进行了表征.试验结果表明:蛭石对石灰石改性有效果,当其添加量为1 wt％时,可以使石灰石的第一次循环碳酸化率提高8.21％.     

二氧化碳矿化磷石膏制硫酸铵和碳酸钙技术

针对目前CO2减排和工业固废磷石膏处理的问题,中石化与四川大学合作开展了利用磷石膏直接矿化尾气中低浓度CO2联产硫基复肥与碳酸钙的CCU技术路线研究,并逐步推进该技术产业化。该项目以废制废,把捕集与利用两个环节合二为一,节省捕集成本,具有显著的环境效益和社会效益。     

石膏类工业固废固碳技术研究进展

石膏类工业固废主要包括磷石膏、脱硫石膏、氟石膏及钛石膏等,由于其杂质成分复杂等,极大地制约了其综合利用.近年来,随着我国"碳达峰"和"碳中和"目标的提出,国内对于二氧化碳捕集、利用与封存技术的研究日益增多.介绍磷石膏氨法直接固碳技术和石膏分解渣二步法固碳技术的研究进展,利用石膏捕集二氧化碳具有良好的技术及经济效益,将其...     

钙基吸收剂脱除HCl的研究进展

对钙基吸收剂脱除HCl技术的国内外研究进展进行了综述,介绍了不同类型钙基吸收剂的脱氯特性和提高钙基吸收剂脱除HCl性能的各种方法,讨论了Ca/Cl摩尔比、反应温度、粒径、反应气氛等因素对吸收剂脱氯性能的影响规律。提出重点应加强钙基吸收剂脱氯反应机理研究,解决脱氯效率较低等关键问题。并论述了生物质气化重整制氢与钙基吸收剂捕集CO2耦合技术中HCl脱除的必要性,提出HCl对钙基吸收剂循环捕集CO2性能可能存在影响。指出需研究HCl和CO2与钙基吸收剂的竞争反应规律和相互作用机理并提出协同调控方法,这对于生物质气化重整制氢技术协同捕集CO2和HCl意义重大。     

废弃蛋壳源高性能钙基吸收剂的制备及其碳捕集性能

基于食品工业废弃蛋壳,本文利用不同有机酸反应制取乙酸钙、柠檬酸钙及葡萄糖酸钙共三种蛋壳源有机钙。在高温固定床反应器及热重分析仪上研究了不同前体所制成钙基吸收剂的碳循环捕集性能及碳酸化特性。进一步通过XRD分析了不同钙基吸收剂的物相组成,通过N₂吸附仪及SEM分析了循环前后钙基吸收剂结构特性及微观形貌的变化。结果表明,在三种蛋壳源有机钙中,葡萄糖酸钙所制成的钙基吸收剂具有较高的反应活性和相对最佳的碳捕集性能,首次碳酸化转化率高达85.33%,其钙基吸收剂相比其他吸收剂晶粒更小,20~100nm孔径范围内的孔隙较为发达,具有相对较强的抗烧结能力。经过20次循环实验发现,随着循环次数的增加,几种钙基吸收剂小颗粒均团聚烧结成大颗粒,造成孔隙结构缺失,孔隙率降低,影响其后续碳捕集性能。     

利用凹凸棒改性石灰石增强CO2循环捕集效率

石灰石作为天然的CO2吸收剂,可有效的捕集烟气中的CO2,但随着循环反应次数的增加,石灰石颗粒表面会发生严重的烧结,使其酸化率迅速发生衰减.本文中利用自然界储量丰富的凹凸棒石对石灰石颗粒进行改性来减缓这一现象的发生,从而提高其CO2的循环捕集效率.凹凸棒石具有的天然纳米纤维状结构可有效的减少石灰石颗粒之间的相互接触,延缓石灰石的烧结团聚现象,从而提高其碳酸化率.实验结果表明:凹凸棒石原矿和提纯后的凹凸棒石均可作为添加剂提高石灰石对CO2的捕集效率,其中经过提纯处理后的凹凸棒石的改性效果最好;通过比较凹凸棒石改性前后的钙基吸收剂经过多次CO2捕集循环后的颗粒微观形貌的变化,可以发现经过凹凸棒石改性后的石灰石颗粒表面仍留有较多的孔道,使其抗烧结能力得到大幅的提高.     

高温钙基碳捕集间接加热过程模拟及分析

根据某电厂烟气的成分及流量,采用Aspen Plus软件建立高温钙基碳捕集间接加热法工艺流程,考察了碳化器温度、排渣率、煅烧炉温度及补充流流量对碳化器内CO_2捕集率、系统CO_2捕集率、系统SO_2捕集率及系统余热量的影响,结果表明：碳化器温度和煅烧炉温度均通过影响吸收剂的活性来影响系统的性能。补充流流量、排渣率和气固分离效率则是通过改变系统内固体循环量和CaO吸收剂的循环量来影响系统性能。当碳化器温度为625℃,煅烧炉温度为1 000℃,补充流流量为1 400 kmol/h,排渣率为0.05时,系统捕集率达到最优。     

基于钙基吸收剂循环煅烧/碳酸化反应捕集CO2的试验

利用钙基吸收剂循环煅烧/碳酸化反应(CCCR)吸收CO2是一种新型、廉价、有效的CO2捕集方法.采用热重分析仪研究了吸收剂的矿物组成、颗粒粒径、煅烧温度和碳酸化温度对CCCR快速反应阶段吸收剂循环碳酸化率(XN)的影响.结果表明:吸收剂的碳酸化反应由快速化学反应控制阶段、过渡阶段和缓慢产物层扩散控制阶段组成;白云石具有良好的抗烧结能力,白云石的XN高于石灰石;随着颗粒粒径的增大,吸收剂的XN逐渐降低;当煅烧温度超过950℃时,随着循环反应次数的增加,吸收剂的XN严重降低;吸收剂在725℃碳酸化温度时的XN最高.     

不同钙源制备钙基CO_2吸收剂研究进展

综述了钙基吸收剂的循环捕集过程及CO_2吸收性能衰减原因,从天然矿物原料、杂质含量少的化学试剂以及钙含量高的工业固废3个方面,总结分析了不同钙原料制备钙基CO_2吸收剂的主要方式及改性效果。最后指出采用固废原料制备钙基吸收剂同样具有良好的CO_2吸收效率和循环稳定性,并能大幅降低吸收剂的制备成本。     

不同钙基吸附剂捕集CO2后的硫酸化反应特性研究

钙基吸附剂进行多次CO₂捕集后,碳酸化效率会大幅衰减,此时的吸附剂能否高效脱硫利用是值得重点关注的问题。鉴于此,筛选了高性能合成钙基吸附剂和天然石灰石吸附剂,通过热重分析仪分析对比其在多循环CO₂捕集后的碳酸化和硫酸化反应性能,采用微粒模型研究其硫酸化反应动力学特征。结果发现,高性能合成钙基吸附剂的碳酸化反应速率和CO₂吸附能力明显高于石灰石吸附剂。在长达500循环的CO₂捕集试验后,高性能合成钙基吸附剂的CO₂吸附能力比石灰石高10倍以上,其SO₂吸附能力相较于石灰石提升约40%。经历多次CO₂捕集反应循环后,2种吸附剂的硫酸化能力均有提升:其中,石灰石吸附剂的提升幅度更大,硫酸化转化率从26%提升到35%,而高性能合成钙基吸附剂的硫酸化转化率则从38%提升到43%。通过微粒模型计算发现,2种吸附剂的硫酸化反应均是与SO₂浓度相关的一级反应,多循环捕集CO₂反应后,石灰石吸附剂的硫酸化反应活化能下降接近30%,而高性能合成钙基吸附剂的硫酸化反应活化能只下降了5%。研究结果说明2种不同钙基吸附剂在进行循环CO₂捕集后,脱硫能力得到了不同程度的提高,且均可以较好地应用于SO₂的脱除。     

CO2 capture by double metal modified CaO-based sorbents from pyrolysis gases

High-temperature pyrolysis technology can effectively solve the problem of municipal solid waste pollution. However, the pyrolysis gas contains a large amount of CO₂, which would adversely affect the subsequent utilization. To address this problem, a novel method of co-precipitation modification with Ca, Mg and Zr metals was proposed to improve the CO₂ capture performance. X-ray diffraction (XRD) patterns and energy dispersive X-ray spectroscopy analysis showed that the two inert supports MgO and CaZrO₃ were uniformly distributed in the modified calcium-based sorbents. In addition, the XRD results indicated that CaZrO₃ was produced by the reaction of ZrO₂ and CaO at high temperatures. The effects of doping ratios, adsorption temperature, calcination temperature, CO₂ concentration and calcination atmosphere on the adsorption capacity and cycle stability of the modified calcium-based sorbent were studied. The modified calcium-based sorbent achieved the best CO₂ capture performance when the doping ratio was 10:1:1 with carbonation at 700 ℃ under 20% CO₂/80% N₂ atmosphere and calcination at 900 ℃ under 100% N₂ atmosphere. After ten cycles, the average carbonation conversion rate of Ca-10 sorbent was 72%. Finally, the modified calcium-based sorbents successfully reduced the CO₂ concentration of the pyrolysis gas from 37% to 5%.     

钙基碳载体造粒的捕集CO特性及力学性能

采用挤出滚圆法对钙基碳载体Ca（OH）₂进行造粒。在双固定床反应器上研究了黏结剂、支撑体和造孔剂对造粒后钙基碳载体循环捕集CO₂性能的影响,并提出采用多孔Al₂O₃球粉作为新型支撑体。结果表明,选择聚乙烯吡咯烷酮为颗粒黏结剂时最佳添加量为2%。高铝水泥和多孔Al₂O₃球粉均可作为支撑体造粒。多孔Al₂O₃球粉作为支撑体造粒后碳载体的循环捕集CO₂性能更高,其10次循环后CO₂吸收量为0.23g/g,是添加高铝水泥造粒碳载体的1.35倍。微晶纤维素作为造孔剂显著提高了造粒碳载体的循环捕集CO₂性能。多孔Al₂O₃球粉作为支撑体造粒后碳载体的抗压强度略高于高铝水泥作为支撑体。多孔Al₂O₃球粉造粒钙基碳载体拥有大量30~100nm孔隙,其比孔容高于高铝水泥造粒碳载体,这有利于CO₂捕集。     

新型钡基高温燃烧固硫剂的研究与应用

引　言燃烧脱硫技术是在高温燃烧过程中将煤中的硫转化为硫酸盐或硫化物 ,因而其固硫率与硫酸盐或硫化物的热力学形成过程密切相关 .据文献报道 ,ＣａＳＯ3和ＣａＳＯ4 分别在 10 0 4℃[1] 和 1195～ 12 14℃[2 ] 就已开始分解 .纯ＣａＳＯ4 在 12 5 0℃高温下的分解率为 85 % .纯ＢａＳＯ4 的分解温度为 15 80℃[3] ,大大高于ＣａＳＯ4 ,显示较高的热稳定性 .根据元素周期表递变规律 ,位于第 6周期的Ｂａ较位Ｆｉｇ .1　Ｓｃｈｅｍａｔｉｃｏｆｉｎｔｅｌｌｉｇｅｎｔｓｕｌｆｕｒｄｅｔｅｒｍｉｎａｔｉｏｎ1—ｍａｉｎｆｒａｍｅｏｆｉｎ…     

蒸汽活化钙基吸收剂联合脱碳脱硫特性

利用管式炉（TF）、蒸汽发生器和热重分析仪（TGA）研究了钙基吸收剂联合脱碳脱硫以及水合特性,并通过N2吸附实验对不同烧结程度以及水合前后样品的孔隙结构进行了测量。结果表明,无水合时,40次碳化循环后的样品碳化活性降至18%,但仍具有44%的硫化活性,比新鲜剂仅低4%,说明脱碳失效剂仍是良好的脱硫剂。碳循环失效剂经蒸汽活化后其碳化活性可提高至68%左右,且具有与新鲜剂类似的活性下降规律。每两次碳化循环后进行一次蒸汽活化,可使样品保持65%的平均转化率。蒸汽活化后吸收剂硫化率可提高至80%,远高于新鲜剂,由电镜扫描实验发现这是由于水合时颗粒产生了大的裂缝和破碎,提供了大量产物可自由生长的外表面积。不考虑颗粒磨损,利用钙基吸收剂先循环脱碳再蒸汽活化最后脱硫是一项联合脱除烟气中CO₂和SO₂的新方法。     

Simulation of a calcium looping CO2 capture process for pressurized fluidized bed combustion

The Canadian regulations on carbon dioxide emissions from power plants aim to lower the emissions from coal-fired units down to those of natural gas combined cycle (NGCC) units. Since coal is significantly more carbon intensive than natural gas, coal-fired plants must operate at higher net efficiencies and implement carbon capture to meet the new regulations. Calcium looping (CaL) is a promising post-combustion carbon capture (PCC) technology that, unlike other capture processes, generates additional power. By capturing carbon dioxide at elevated temperatures, the energy penalty that carbon capture technologies inherently impose on power plant efficiencies is significantly reduced. In this work, the CO₂ capture performance of a calcium-based sorbent is determined via thermogravimetric analysis under relatively high carbonation and low calcination temperatures. The results are used in an aspenONE™ simulation of a CaL process applied to a pressurized fluidized bed combustion (PFBC) system at thermodynamic equilibrium. The combustion of both natural gas and coal are considered for sorbent calcination in the CaL process. A sensitivity analysis on several process parameters, including sorbent feed rate and carbonator operating pressure, is undertaken. The energy penalty associated with the capture process ranges from 6.8–11.8 percentage points depending on fuel selection and operating conditions. The use of natural gas results in lower energy penalties and solids circulation rates, while operating the carbonator at 202 kPa(a) results in the lowest penalties and drops the solids circulations rates to below 1000 kg/s.     

负载型K2CO3/Al2O3二氧化碳吸收剂的碳酸化反应特性

引言 全球变暖已经成为一个备受关注的环境问题.据预测,如不采取积极的温室气体减排措施,从现在起到2100年,全球近地面平均气温将继续升高1.4～5.8℃[1].CO2是主要的温室气体,而我国燃煤电厂是CO2排放量最大、最集中的化石燃料燃烧场所.因此研究和开发适用于燃煤电厂的CO2减排技术至关重要.     

Cl含量对钙基吸收剂微观结构以及动力学性能的影响

通过浸渍法向分析纯CaCO₃中添加Cl,在双固定床反应器系统和热重分析仪上研究了其对钙基吸收剂循环捕集CO₂性能的影响,利用离子反应模型对添加Cl后吸收剂化学反应控制阶段进行动力学分析。结果显示：Cl对钙基吸收剂循环捕集CO₂性能具有不利影响。当Cl/Ca摩尔比大于0.25%后,随Cl/Ca摩尔比增加,化学反应控制阶段反应速率和持续时间均减小,导致在该阶段最终碳酸化转化率降低。对添加Cl前后吸收剂孔隙分布特性进行分析发现,添加Cl导致煅烧后吸收剂烧结加剧,比表面积降低,10~120nm范围内孔分布减少,导致CO₂在吸收剂内部扩散阻力增加,同时能与CO₂反应的CaO量减少,这是导致吸收剂化学反应控制阶段碳酸化反应速度较慢、最终碳酸化转化率较低的主要原因。鉴于Cl的不利影响,在选择钙基材料作为CO₂吸收剂或合成高活性复合吸收剂时,应避免吸收剂中Cl含量过高。     

Reactivity stabilization and capacity study of fabricated alumina and zirconia-supported CaO-based sorbents for high-temperature CO2 capture in a fixed-bed reactor

Calcium looping process is a promising approach for CO₂ capture from the flue gas of fossil fuel power plants and the cement industry. Even though the advantages of calcium-based sorbents are low cost and high uptake capacity, they suffer from low durability during cycles. Modified sorbents were fabricated by adding alumina and zirconia and the mixture of alumina and zirconia to calcium oxide via the co-precipitation method. The performance of synthesized sorbents in terms of stability and CO₂ capture capacity were evaluated using a fixed bed reactor in various CO₂ sorption/desorption cycles. The sorbents were fabricated by a co-precipitation methodology using 10% binders (alumina and/or silica). X-ray diffraction (XRD), BET/BJH, and scanning electron microscopy (SEM) were conducted for characterization of synthesized sorbents. CaO-10% ZrO₂ showed the best performance among the fabricated sorbents in terms of stability during 5 cycles and CO₂ capacity (14 mmol CO₂/g sorbent). The formation of CaZrO₃ with a perovskite structure and high-temperature resistance could be attributed to well performance of zirconia-supported sorbent. On the other hand, no sign of aluminum zirconate formation was approved in XRD analysis for the fabricated sorbent using mixed binders of zirconia and alumina to enhance its stability during cycles.     

Characterization of calcium oxide derived from waste eggshell and its application as CO2 sorbent

The carbonation-calcination looping cycle of calcium-based sorbents is considered as an attractive method for CO₂ capture from combustion gases because it can reduce the cost during the capture steps compared to conventional technologies, e.g., solvent scrubbing. In this study, waste eggshell was used as raw material for calcium oxide-based sorbent production. The commercially available calcium carbonate was employed for comparison purpose. Calcination behavior, crystal type and crystallinity, surface chemistry, qualitative and quantitative elemental information, specific surface area and pore size, morphology of the waste eggshell and the calcined waste eggshell were characterized by thermal gravimetric analysis (TGA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray fluorescence (XRF), N₂ sorption analysis and scanning electron microscopy (SEM), respectively. The carbonation-calcination cycles were carried out using a TGA unit with high purity CO₂ (99.999%). It was found that the carbonation conversion of the calcined eggshell was higher than that of the calcined commercially available calcium carbonate after several cycles at the same reaction conditions. This could be due to the fact that the calcined eggshell exhibited smaller particle size and appeared more macropore volume than the calcined commercially available calcium carbonate. As results, the calcined eggshell provided a higher exposed surface for the surface reaction of CO₂.