浅谈预热器／回转窑煅烧白云石制取轻烧白云石技术

用预热器／回转窑煅烧白云石,以优质轻烧白云石作为金属镁生产原料。此种方法生产能力大,机械化程度高,维护操作简单,煅白活性高,灼减量低,镁的提取率较高。     

煅烧和消化工艺对白云石活性的影响

以白云石为原料,采用柠檬酸测定法,通过控制煅烧温度、保温时间、消化温度和消化时间等因素,研究了煅烧和消化工艺对白云石活性的影响及最佳的煅烧和消化条件。结果表明:煅烧温度为950℃,保温时间为1.5 h时,煅烧产物中的氧化镁活性最好;以最佳煅烧条件下得到的白云灰粉进行消化反应,消化温度为80℃、消化时间为30 m in时,得到的消化产物活性最高。工艺简单、操作方便,对进一步利用白云石制备氢氧化镁和氧化镁产品具有重要的参考价值。     

煅烧和消化工艺对白云石活性的影响

以白云石为原料,采用柠檬酸测定法,通过控制煅烧温度、保温时间、消化温度和消化时间等因素,研究了煅烧和消化工艺对白云石活性的影响及最佳的煅烧和消化条件.结果表明:煅烧温度为950℃,保温时间为1.5 h时,煅烧产物中的氧化镁活性最好;以最佳煅烧条件下得到的白云灰粉进行消化反应,消化温度为80 ℃、消化时间为30 min时,得到的消化产物活性最高.工艺简单、操作方便,对进一步利用白云石制备氢氧化镁和氧化镁产品具有重要的参考价值.     

石灰石和白云石高温循环脱除CO2过程分析

在N2气氛和高浓度CO2气氛两种典型锻烧气氛下,对石灰石和白云石在循环煅烧/碳酸化捕集CO2过程中的主要系统参数包括长周期循环碳酸化转化率、平均碳酸化转化率、CO2捕集效率和煅烧炉能量需求进行了实验研究和计算分析.结果表明,吸收剂补充流率和吸收剂循环流率对平均碳酸化转化率、CO2捕集效率和煅烧炉所需能量具有直接影响.在...     

制取白云石胶凝材料的流化床煅烧工艺

采用流化床分解炉直接由白云石煅烧生产活性氧化镁，用于进一步生产氯氧镁水泥制品及免烧地砖等建筑装饰材料。所得氧化镁产品品位为：活性氧化镁含量大于２５％（理论最佳值为２６．４％），游离氧化钙含量小于３．５％。装置可以使用烟煤、贫煤、无烟煤及其它劣质煤种，煅烧温度６８０－８５０℃。     

高浓度CO2气氛下白云石强化煅烧工艺研究

CO₂循环煅烧白云石是具有前景的低碳炼镁新工艺。为研究新工艺下高浓度(摩尔分数)CO₂氛围中白云石强化煅烧措施,文中根据煅烧理论,建立了基于双环缩核的白云石煅烧反应动力学模型;计算分析了白云石分解过程传热传质和化学反应动力学的耦合特征,剖析了CO₂分压、温度和炉内总压等因素对单个白云石矿料分解动力学特征的影响;进一步考虑竖窑煅烧过程矿料粒径分布和矿料温度均匀性,研究不同炉内总压、温度、颗粒粒径等因素对竖炉容积利用系数的影响规律。结果表明：温度一定时,总压提高可强化热气流与矿料间的传热,促进白云石煅烧。通过合理调控煅烧过程温度和压力可有效提高新工艺的容积利用系数,最高可达0.967 1 t/(m³·h)。     

岩峰白云石二步煅烧制备镁钙砂

以湖北岩峰地区的天然白云石为原料,在实验室内采用二步煅烧法制备了镁钙砂,研究了轻烧温度(分别为750、800、850、900、950、1000℃)和轻烧保温时间(分别为1、1.5、2、2.5、3、3.5h)对轻烧白云石的活性度,镁钙砂的体积密度、显气孔率和抗水化性的影响,以及煅烧温度(分别为1550、1600、1650、1700℃)对镁钙砂的体积密度、显气孔率和抗水化性的影响,确定了实验室制备镁钙砂的最佳工艺为:轻烧温度850℃,轻烧保温时间3h,烧结温度1650℃.     

CO2载体CaO循环煅烧/碳酸化反应的分形特征

捕捉煤燃烧释放出的CO₂时,作为CO₂载体的CaO微观结构特性对其循环碳酸化性能具有显著影响。采用分形维数作为表征CaO微观结构的特征参数,研究在循环煅烧/碳酸化反应过程中CaO的分形特征及其对CO₂捕捉性能的影响规律。结果表明,随着循环次数的增加CaO分形维数逐渐下降,CaO孔道也由粗糙和不规则变得越来越平滑和有规则性。煅烧温度升高则CaO分形维数下降。分形维数较大的CaO具有较高的碳酸化速率。在碳酸化过程的前10 min内CaO的分形维数迅速减小,此后随时间变化缓慢。在分形维数D≤2.61的实验范围内,CaO分形维数与其循环碳酸化转化率呈线性正相关;当D＞2.61时,可能存在临界分形维数D_cr,当D＞D_cr时随着分形维数的进一步增大CaO转化率反而减小。     

CO2载体CaO循环煅烧/碳酸化反应的分形特征

捕捉煤燃烧释放出的CO₂时,作为CO₂载体的CaO微观结构特性对其循环碳酸化性能具有显著影响。采用分形维数作为表征CaO微观结构的特征参数,研究在循环煅烧/碳酸化反应过程中CaO的分形特征及其对CO₂捕捉性能的影响规律。结果表明,随着循环次数的增加CaO分形维数逐渐下降,CaO孔道也由粗糙和不规则变得越来越平滑和有规则性。煅烧温度升高则CaO分形维数下降。分形维数较大的CaO具有较高的碳酸化速率。在碳酸化过程的前10 min内CaO的分形维数迅速减小,此后随时间变化缓慢。在分形维数D≤2.61的实验范围内,CaO分形维数与其循环碳酸化转化率呈线性正相关;当D＞2.61时,可能存在临界分形维数D_cr,当D＞D_cr时随着分形维数的进一步增大CaO转化率反而减小。     

煅烧白云石制造硫酸镁水泥及其机理研究

对利用白云石为原料制备硫氧镁水泥(MOS)进行研究。首先研究氯化钙煅烧助剂对煅烧白云石烧失量、活性氧化镁(α-MgO)、游离氧化钙(f-CaO)及比表面积(BET)的影响,优选白云石煅烧条件。然后对煅烧白云石中α-MgO、f-CaO的含量以及硫酸镁浓度对硫氧镁水泥性能的影响进行研究,并采用XRD、SEM和DTA/TG对各过程机理进行分析。试验结果表明,在700℃下对掺入5%氯化钙的白云石煅烧3h,所得煅烧白云石活性氧化镁含量可达到21%,且f-CaO可控制在2%以下。将所得煅烧白云石与硫酸镁溶液混合制成MOS水泥,在硫酸镁浓度为50%时其强度最优。在上述硫酸镁溶液中添加1%的柠檬酸制备MOS,MOS的强度较空白样提高91.6%。微观分析结果表明,硫酸镁溶液中柠檬酸的添加促进了MOS微观结构中针状交叉分布517相的形成,提高了MOS的强度。     

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.     

化学链反应器研究进展

化学链技术是目前能源技术研究的热点之一,其关键技术包括载体材料的制备和反应器的设计。综述了化学链技术的应用前景,总结了化学链反应器设计原理,回顾了目前世界上公开报道的设计完成、在建或已经运行的化学链反应器,归纳讨论了不同反应器设计细节的共同点及目的。开展以微小颗粒、纳米颗粒作为载体材料时,颗粒聚团在宏观反应器尺度下的流动传递规律、循环反应机理和系统运行控制特性的研究;开展反应器内颗粒流动-传递-反应耦合机制研究,建立多尺度统一模型;在全尺寸化学链反应器上进行系统自热实验研究;利用数值模拟方法研究和开发用于固体燃料转化过程的高效炭/灰分离器是未来化学链反应器发展需要关注的几个方面。     

Effect of the CaO sintering on the calcination rate of CaCO3 under atmospheres containing CO2

For the calcination of CaCO₃ under CO₂‐containing atmospheres, a mathematical model taking into account the CO₂‐catalyzed sintering of the CaO product layer is developed. In this model, a modified shrinking core model is coupled with a population balance‐based sintering model. By comparing model predictions with experimental data, it is found that CO₂ strongly affects the overall calcination rate both at high temperature and CO₂ partial pressure, since under these conditions CaO densification considerably reduces the effective diffusivity of CO₂ within product layer. It is observed that for large particles, the CO₂‐catalyzed sintering of CaO can produce the “die off” phenomenon, which takes place when the reaction stops due to the blockage of pores within product layer. Finally, it was determined that limestone impurities do not significantly affect the calcination reaction under atmospheres containing CO₂, because CO₂ causes a much greater increase of the CaO sintering rate than limestone impurities do. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3638–3648, 2018     

Co-Fe2O3纳米载氧体作用下CO化学链燃烧富集CO2

制备了不同量级Co掺杂Fe₂O₃载氧体Co-Fe₂O₃,利用BET和TEM对载氧体结构进行表征。通过在不同温度下Co-Fe₂O₃与气体燃料CO的还原反应,考察Co-Fe₂O₃对CO化学链燃烧特性。结果表明,同一温度条件下,掺杂量越高,还原反应转化率越高;掺杂量不变的情况下,温度升高促使还原程度加深,缩短了载氧体完全还原转化的时间。根据TGA曲线进行了化学动力学分析,发现Co_0.2Fe还原反应过程在344.7～391.0℃和414.7～472.5℃温度范围反应动力学对应扩散控制的Jander方程模型,607.6～681.5℃温度范围对应二维扩散反应模型,并分别计算出相应模型的表观活化能和频率因子。结果可为化学链燃烧技术应用提供理论指导。     

磷尾矿煅烧及酸浸过程动力学研究

以湿法磷酸生产的经浮选后的废弃磷尾矿为原料,从其中分离回收钙镁,制备新型土壤调节剂糖醇钙镁,对磷尾矿进行了煅烧活化和酸浸动力学的实验研究。基于热重分析及钙镁酸解浸出率分析的研究结果表明,磷尾矿中白云石热分解过程为吸热反应,白云石热分解遵循二维相界面反应模型;钙、镁浸出反应表观活化能分别为13.157、23.023 kJ/mol;煅烧活化后的尾矿酸浸出速率受内扩散控制,获得白云石热分解及钙、镁浸出反应的动力学方程。     

Cyclic calcination/carbonation looping of dolomite modified with acetic acid for CO2 capture

The dolomite modified with acetic acid solution was proposed as a CO₂ sorbent for calcination/carbonation cycles. The carbonation conversions for modified and original dolomites in a twin fixed-bed reactor system with increasing the numbers of cycles were investigated. The carbonation temperature in the range of 630 °C–700 °C is beneficial to the carbonation reaction of modified dolomite. The carbonation conversion for modified dolomite is significantly higher than that for original sorbent at the same reaction conditions with increasing numbers of reaction cycles. The modified dolomite exhibits a carbonation conversion of 0.6 after 20 cycles, while the unmodified sorbent shows a conversion of 0.26 at the same reaction conditions, which is calcined at 920 °C and carbonated at 650 °C. At the high calcination temperature over 920 °C modified dolomite can maintain much higher conversion than unmodified sorbent. The mean grain size of CaO derived from modified dolomite is smaller than that from original sorbent with increasing numbers of reaction cycles. The calcined modified dolomite possesses greater surface area and pore volume than calcined original sorbent during the multiple cycles. The pore volume and pore area distributions for calcined modified dolomite are also superior to those for calcined unmodified sorbent during the looping cycle. The modified dolomite is proved as a new and promising type of regenerable CO₂ sorbent for industrial applications.     

蛋白土与硫酸铵煅烧反应产物及过程动力学

蛋白土具有良好的应用前景,但是其自然白度较低制约了其开发应用。蛋白土硫酸铵煅烧法可去除其中的显色金属氧化物,提高蛋白土的白度,同时提取其中Al₂O₃。本文采用热重-差示扫描量热（TG-DSC）、同步热分析与红外质谱（TG-FTIR-MS）联用系统,结合X射线衍射对煅烧过程的固相及气相产物进行了表征分析,明析了其化学过程。结果表明,蛋白土中的Al₂O₃和Fe₂O₃在200~350℃时反应生成（NH₄）₃（Al,Fe）（SO₄）₃,同时逸出NH₃和H₂O;350~450℃时,进一步反应转化为NH₄（Al,Fe）（SO₄）₂,同时逸出NH₃、H₂O、SO₂和O₂;450~550℃时,NH₄（Al,Fe）（SO₄）₂分解生成（Al,Fe）₂（SO₄）₃,同时逸出NH₃、H₂O、SO₂和O₂;550~750℃时（Al,Fe）₂（SO₄）₃分解生成Al₂O₃和Fe₂O₃,同时逸出SO₂和O₂。采用Kissinger微分法与Ozawa积分法分别计算出4个阶段表观活化能后取二者平均值,分别为101.74kJ/mol、104.52kJ/mol、201.40kJ/mol、232.51kJ/mol,并获得对应4个热化学反应阶段的频率因子、反应级数和动力学方程。     

流化床锅炉内石灰石同时煅烧/硫化反应中煅烧动力学特性

采用恒温热重实验台研究了循环流化床内石灰石同时煅烧硫化反应中煅烧反应与硫化反应的相互作用。当煅烧环境中存在SO₂时,煅烧反应与硫化反应同时发生,并在颗粒中生成CaSO₄。与纯煅烧工况相比,在含有SO₂的气氛中煅烧石灰石时,颗粒的质量下降速率降低,而煅烧终质量升高。SO₂的存在能够降低石灰石的煅烧速率,而且在0～0.3%的范围内,SO₂浓度越高,煅烧越慢。对该现象提出以下机理：当煅烧过程中存在SO₂时,SO₂会与正在煅烧的石灰石颗粒的CaO层发生硫化反应生成CaSO₄,所生成的CaSO₄会堵塞颗粒的孔隙,增加CO₂的扩散阻力,进而减慢煅烧反应速率。对煅烧产物孔结构的测试和计算表明在同时煅烧硫化中部分孔隙被堵塞、封闭,孔内CO₂有效扩散系数下降,证明所提出的机理能够合理解释SO₂对石灰石煅烧的减缓作用。随着粒径由0.4～0.45 mm减小到0.2～0.25 mm,无论反应环境是否存在SO₂,石灰石的煅烧速率均加快。温度对煅烧速率有明显的影响,850℃下SO₂对石灰石煅烧速率的减缓程度大于880℃,这可能是由于880℃下CaSO₄对颗粒孔隙的堵塞作用下降导致的。     

The combined effect of H2O and SO2 on the simultaneous calcination/sulfation reaction in CFBs

The combined effect of H₂O and SO₂ on the reaction kinetics and pore structure of limestone during simultaneous calcination/sulfation reactions under circulating fluidized bed (CFB) conditions was first studied in a constant-temperature reactor. H₂O can accelerate the sulfation reaction rate in the slow-sulfation stage significantly but has a smaller effect in the fast-sulfation stage. H₂O can also accelerate the calcination of CaCO₃, and should be considered as a catalyst, as the activation energy for the calcination reaction was lower in the presence of H₂O. When the limestone particles are calcining, SO₂ in the flue gas can react with CaO on the outer particle layer and the resulting CaSO₄ blocks the CaO pores, increases the diffusion resistance of CO₂, and, in consequence, decreases the calcination rate of CaCO₃. Here, gases containing 15% H₂O and 0.3% SO₂ are shown to increase the calcination rate. This means that the accelerating effect of 15% H₂O on CaCO₃ decomposition is stronger than the impeding effect caused by 0.3% SO₂. The calcination rate of limestone particles was controlled by both the intrinsic reaction and the CO₂ diffusion rate in the pores, but the intrinsic reaction rate played a major role as indicated by the effectiveness factors determined in this work. This may explain the synergic effect of H₂O and SO₂ on CaCO₃ decomposition observed here. Finally, the effect of H₂O and SO₂ on sulfur capture in a 600 MWe CFB boiler burning petroleum coke is also analyzed. The sulfation performance of limestone evaluated by simultaneous calcination/sulfation is shown to be much higher than that by sulfation of CaO. Based on our calculations, a novel use of the wet flue gas recycle method was put forward to improve the sulfur capture performance for high-sulfur low-moisture fuels such as petroleum coke. © 2019 American Institute of Chemical Engineers AIChE J, 65: 1256–1268, 2019