基于CO2循环的低碳高效白云石煅烧新工艺

白云石是一种广泛应用的冶金、建材和化工原料。针对白云石煅烧过程中CO₂排放严重等问题,构建了基于CO₂循环载热与资源化回收的白云石低碳煅烧竖窑新工艺。通过白云石（CaCO₃·MgCO₃）煅烧过程的Gibbs自由能变计算,发现提高煅烧温度（50~100 K）可有效克服CO₂对反应的抑制作用;通过纯CO₂环境中CaCO₃分解过程的热重实验分析,验证了CO₂循环煅烧白云石煅烧的可行性;通过化学反应动力学计算,解析了全CO₂组分环境下CO₂压力对CaCO₃·MgCO₃高温分解过程的影响,并发现提高CO₂压力可促进气固传热,从而提升分解速率和改善矿料分解均匀性;对CO₂循环煅烧工艺系统能-质平衡计算表明：该工艺理论能耗仅为140 kg/(t 煅白),且煅烧过程的CO₂排放降低70%以上,环境效益显著。     

纳米CaCO3孔径调控及其对碳酸化反应性能的影响

研究了纳米CaCO₃颗粒间孔径调控对CaO与CO₂碳酸化反应性能的影响。通过有机模板法制备得到一系列比表面积相近、孔径分布不同的纳米CaCO₃,并考察其再生和碳酸化反应性能差异。结果表明：增大平均孔径能促进纳米CaCO₃的热分解反应,并降低分解温度约15℃。将平均孔径由15 nm增大至113 nm可显著提高碳酸化反应速率和转化率。研究认为平均孔径和比表面积对碳酸化反应转化率的影响存在交互作用;比表面积小的纳米CaCO₃,表现出碳酸化反应转化率受扩散控制影响较大,而比表面积较大的表现为碳酸化反应转化率以表面反应影响控制为主的规律。     

转炉高温烟气中石灰石粉的分解特性研究

鉴于石灰窑煅烧石灰石工艺存在能耗大、成本高等问题，探讨利用转炉汽化冷却烟道内高温烟气余热分解石灰石粉的可行性。通过热重分析实验和管式炉实验研究了在转炉高温烟气环境下石灰石粉的分解特性及温度、时间、气氛和烟尘等影响因素对其特性的影响。结果表明：烟气中CO₂会抑制CaCO₃的分解，提高了起始分解温度，但随着温度的升高，反应速率加快，分解率增大，反应时间相应缩短；烟尘中的主要成分FeO和Fe₂O₃能够促进CaCO₃的分解；CaCO₃晶粒分解成CaO晶粒，CO₂气体被释放，晶粒表面孔隙明显增多，从而使活性增大。实验结果初步验证了利用转炉高温烟气余热分解石灰石粉具有一定的可行性。     

PP/TPE/表面改性CaCO3复合材料的制备及性能

采用硅烷偶联剂对纳米CaCO₃进行表面改性,将表面改性CaCO₃与热塑性弹性体(TPE)、聚丙烯(PP)熔融共混,制备了PP/TPE/表面改性CaCO₃复合材料,表征并研究了其结构与性能。结果表明:加入表面改性CaCO₃使复合材料的储能模量、损耗模量和复数黏度增加。表面改性CaCO₃含量为6%(w)时复合材料的拉伸强度、弯曲强度和冲击强度均最大,分别为29.85 MPa,25.67 MPa,43.79 kJ/m²;与纯PP相比,复合材料的拉伸强度、弯曲强度和冲击强度分别提高了6.5%,11.5%,3.0%。表面改性CaCO₃含量为10%(w)时,终止分解温度从466.9℃增加到473.7℃,分解速率最快时的温度从455.9℃增加到460.5℃,对体系的热解稳定性有一定的改善。     

磷石膏氨化制备硫酸铵溶液工艺研究

以磷石膏为原料制备(NH₄)₂SO₄溶液与CaCO₃，可将磷石膏中的钙、硫资源循环利用。考察氨化反应的温度、时间、物料比、液固质量比对CaSO₄转化率的影响，得到最佳工艺参数：反应温度40℃，反应时间1.5 h,m(磷石膏):m(碳酸氢铵):m(氨水)为1.00∶0.78∶1.33，液固质量比0.75，此时CaSO₄转化率超过99%。同时进行(NH₄)₂SO₄及CaCO₃分离实验，基本实现(NH₄)₂SO₄与CaCO₃完全分离，得到w((NH₄)₂SO₄)8.32%的溶液，为后续加工奠定基础。     

镁负载CaO基吸附剂捕集CO2性能及抗烧结机理

复合钙基吸附剂制备成本过高是限制其工业化应用的主要瓶颈问题。本文以不可溶的CaCO₃和Ca(OH)₂作为钙源,通过燃烧合成法制备钙镁复合吸附剂,在双固定床反应器上研究了其循环捕集CO₂性能。结果显示：制备得到的钙镁复合吸附剂具有更发达的孔隙结构,吸附剂表面Ca和Mg分散均匀,MgO均匀分布于CaO晶粒之间,有效提高了钙镁复合吸附剂的抗烧结特性,因此钙镁复合吸附剂循环反应过程中具有高捕集CO₂活性。以Ca(OH)₂作为钙源时,燃烧合成过程中Ca和Mg均匀同时析出,分散更加均匀,有效避免了CaCO₃作为钙源时Mg的团聚问题,因此得到的钙镁复合吸附剂循环捕集CO₂性能最优。最佳的Ca/Mg摩尔比为(8∶2)~(7.5∶2.5)。本研究以不可溶钙源制备得到高活性钙镁复合吸附剂,有效控制了吸附剂成本,具有更好的工程应用前景。     

CaCO3微粉对刚玉质弥散型透气砖性能的影响

弥散型透气砖因具有供气可靠性好、安全性高和精炼效果好等优点得到较多应用,然而其自身多孔结构导致的强度低和使用寿命短等缺陷限制了它的应用。为优化刚玉质弥散型透气砖的使用性能,本文以电熔白刚玉颗粒及细粉、α-Al₂O₃微粉、Cr₂O₃微粉等为主要原料,固定颗粒与细粉的质量比为85∶15,分别用质量分数为0%、1%、2%、3%的CaCO₃等量替代电熔白刚玉细粉,探索CaCO₃微粉的引入对弥散砖性能的影响。结果表明:随CaCO₃微粉加入量增加(0%~2%),弥散砖材料常温强度和高温强度增加,由于CaCO₃分解生成的CaO与基质中的Al₂O₃反应生成六铝酸钙,其相互穿插连接增加了基质间的结合程度,从而提高了材料的强度。     

三元复合钙基材料CaO-Ca3Al2O6-MgO的合成及其CO2吸附性能

采用Al₂O₃和MgO同时掺杂改性的方法制备了CaO-Ca₃Al₂O₆-MgO复合钙基高温吸附CO₂材料。复合钙基材料孔隙发达,活性物相为CaO,惰性骨架物相为Ca₃Al₂O₆和MgO。Ca₃Al₂O₆/MgO质量比偏小的材料,表面微粒粒径较小。在10%（体积分数,下同）CO₂和90% N₂的混合气气氛下,采用热重分析仪测量了复合钙基材料吸附CO₂容量、碳化反应速率以及循环碳化（670℃）/煅烧（900℃）过程的稳定性。结果发现,复合钙基材料CaO-Ca₃Al₂O₆-MgO具有较好的吸附CO₂性能,提高Ca₃Al₂O₆/MgO质量比,合成材料的循环稳定性较好;降低Ca₃Al₂O₆/MgO质量比,合成材料的碳化反应速率加快,CaO转化率提高。最后,通过对不同循环次数下复合钙材料的比表面积、孔径分布、微观形貌、表面元素分布,晶相、晶粒大小进行研究分析,对合成材料的失活以及掺杂物质对烧结的抑制机理进行了讨论。     

共聚PP及PP/CaCO3高填充体系的流变行为研究

以双螺杆挤出机制备了共聚PP/CaCO₃高填充复合材料,表征了CaCO₃粒子在基体中的分散行为,并对共聚PP及复合体系的流变行为进行了研究。结果表明:纯共聚PP的熔体呈现出明显的假塑性流体行为,提高熔体温度,熔体的弹性有所增强;高填充共聚PP/CaCO₃复合体系及高填充共聚PP/HDPE/CaCO₃复合体系的熔体的剪切行为与纯共聚PP的类似,高填充的CaCO₃粒子仅对共聚熔体的表观粘度产生轻微影响;共聚PP中大量存在的CaCO₃粒子,降低了熔体的假塑性行为;提高剪切速率是调节高填充共聚PP/HDPE/CaCO3_复合体系粘度的有效手段。     

CH3COONa-NH4OH-H2O体系下磷石膏矿化CO2-联产高纯CaCO3

基于我国面临CO₂减排与磷石膏资源化利用的巨大压力，本文提出助剂循环使用的CO₂矿化与磷石膏资源化利用过程耦合的学术思想，立题以磷石膏为原料，研究醋酸钠体系下氨水强化磷石膏浸出液矿化CO₂联产高纯CaCO₃的反应过程。实验过程中系统讨论了不同工艺条件对磷石膏中Ca²⁺的浸出及浸出液矿化CO₂反应效能的影响，并系统表征了反应条件对矿化产物晶粒尺寸、结构与形貌的影响。结果表明：低温常压条件下1t磷石膏可以矿化吸收208kg的CO₂，同时联产472kg纯度为99.63%的球形球霰石。通过调节矿化反应条件可有效调控矿化产物的晶粒尺寸；提高反应温度和延长反应时间有利于亚稳态的球霰石向热力学更稳定的文石和方解石转化。实验过程中实现了醋酸钠的循环利用与回收。本文为磷石膏的资源化利用与高纯CaCO₃的制备提供了新的思路。     

DBU-based CO_2 absorption–mineralization system: Reaction process,feasibility and process intensification

Amine-based carbon dioxide(CO_2) capture is still limited by high desorption energy consumption. Fixing CO_2 into carbonate is a safer and more permanent method. In this work, calcium oxide(CaO) is introduced to perform chemical desorption instead of thermal desorption on 1,8-diazabicyclo [5.4.0] undec-7-ene(DBU) aqueous solution after CO_2 absorption. The X-ray diffraction(XRD) patterns of solid products show the formation of calcite calcium carbonate(CaCO_3), which prove the feasibility of this method. The effects of reaction temperature, reaction time and Ca~(2+)/CO_3~(2-) molar ratios on the related reactions in CO_2 absorption–mineralization process and CaCO_3 precipitation are discussed, and purer CaCO_3 is obtained by ultrasonic treatment. The CaCO_3 content can be increased to 95.8% and the CO_2 desorption ratio can achieve 80% by 30 min ultrasonic dispersion treatment under the conditions(40℃, 180 min, Ca~(2+)/CO_3~(2-) molar ratio = 1.0). After five cycles, DBU aqueous solution shows stable CO_2 absorption and mineralization ability. Fourier transform infrared spectroscopy(FT-IR) spectra of the reaction process also indicate the regeneration of the solvent. Compared with thermal desorption, this process is exothermic, almost without no additional heat.     

CHARACTERISTICS OF THE REVERSIBLE REACTION BETWEEN CO2(g) AND CALCINED DOLOMITE

The noncatalytic gas-solid reaction between calcined dolomite and CO₂(g) has been studied in an electrobalance reactor as a function of temperature, pressure, and reactive gas composition. Multicycle tests consisting of as many as ten complete calcination-carbonation cycles were carried out to obtain information on sorbent durability. Surface area, pore volume, and pore size distribution measurements were made to supplement the reaction studies. This reaction is of interest both as a model for studying (he importance of structural property changes in gas-solid reactions, and as the basis for a possible process for the high temperature separation of CO₂ from gas streams.

Calcined dolomite is a superior sorbent to calcined CaCO₃ in that larger fractional conversions of CaO and improved multicycle durability are possible. With CaO obtained from CaCO₃, the first-cycle fractional recarbonation was limited to about 0.80, a value which decreased by 15 to 20% in each subsequent cycle. In contrast, the first-cycle fractional recarbonation of CaO in calcined dolomite was typically 0.90 to 0.95, and this value decreased by only 1 to 2% in each subsequent cycle. These advantages are atlributed to the “excess” pore volume created by the original decomposition of MgCO₃ in dolomite, and by a reduction in the rate of CaCO₃ sintering in the presence of MgO.     

两类复合无机相变储热材料高温热稳定性和安全性研究

以适合工业储热的复合无机相变储热材料硝酸盐（KNO₃、NaNO₃）和碳酸盐（Li₂CO₃、K₂CO₃、Na₂CO₃和CaCO₃）为相变组分,研究了4种不同配比硝酸盐相变组分和6种不同配比碳酸盐相变组分的热性能（熔点、潜热）差异,分别优选出一种熔融盐相变组分配比。利用多孔载体吸附原理,制备出两种最佳配比的复合熔融盐类储热材料,分析了储热材料在不同介质气氛中（Ar和air）分解难易程度,TG-DSC-MS联用测试的高温热分解产物表明,复合硝酸盐类储热材料在中温（300℃）储热时,物理化学性能稳定,安全性较好,但在高温（500℃以上）时易分解成NO和NO₂,且air气氛中更易生成有毒气体;而复合碳酸盐类储热材料在air中比在Ar中更易生成CO而影响储热过程中的安全性。     

温度对精炼渣碳酸化效果影响分析

为了有效改善精炼渣的安定性及致密性问题,采用正交试验探讨精炼渣碳酸化过程,以温度为单一影响因素,考察碳酸化粒度分布,结合XRD,SEM,FT-IR,TG-DTA等手段对精炼渣碳酸化效果进行探讨。结果表明,精炼渣碳酸化各因素主次关系为:粒径>CO₂通气量>反应温度>转速>液固比;碳酸化后精炼渣中f-CaO、Ca₂SiO₄、Ca₃SiO₅、12CaO·7Al₂O₃消失,CaCO₃晶型增加明显,且以方解石为主;不同温度(20 ℃、40 ℃、60 ℃、80 ℃)碳酸化后精炼渣总的热分解失重百分率分别为:35.26%、35.24%、34.36%和27.29%。     

Research on high temperature thermal stability and safety of two types of composite inorganic phase change thermal storage materials

In this paper, nitrate (KNO₃, NaNO₃) and carbonate (Li₂CO₃, K₂CO₃, Na₂CO₃ and CaCO₃), which are composite inorganic phase change thermal storage materials suitable for industrial thermal storage, non-toxic and less corrosive, are used as phase change components, respectively. The thermal properties (melting point, latent heat) of 4 different ratios of nitrate phase change components and 6 different ratios of carbonate phase change components were studied, and a distribution ratio of molten salt phase change components was selected respectively. Using the principle of porous carrier adsorption, two types of composite molten salt thermal storage materials with the best ratio were prepared. The ease of decomposition of the thermal storage materials in different media atmospheres (Ar and air) was analyzed. TG-DSC-MS tested high temperature thermal decomposition products show that the composite nitrate thermal storage materials have stable physical and chemical properties and good safety when storing thermal at medium temperature (300℃), but they are easy to decompose NO and high temperature (500℃) or higher. NO₂ and air atmosphere are more likely to generate toxic gases, and composite carbonate thermal storage materials are more likely to generate CO in air than Ar, which affects the safety of the thermal storage process.     

A STRUCTURAL PORE DEVELOPMENT MODEL FOR CALCINATION

A structural pore development model has been developed to describe microscopic pore evolution from the thermal decomposition reaction of a single calcium carbonate sphere, this model depicts a uniform distribution of equal sized pores growing from the surface of the sphere toward its center while CO₂ is evolved from the pore bottom. The chemical reaction at the interface, as well as heat transfer from the surroundings to the decomposing sphere and transport of CO₂ from the pore bottom to the bulk gas, are included in the model. The model shows good agreement with experimental data for CaCO₃, and limestone particles of size ranging from 10 μm to 1.1 cm in diameter at various background CO₂, pressures and temperatures

The simulation of the calcination reaction confirms the experimental observations indicating slower calcination rates at higher background CO₂ pressures, mainly due to internal unsteady-state buildup of CO₂ in the pore. The effect of the background₂ pressure is significantly more prominent in the smaller particles. The activation energy derived from the model is equal to 38.0 kcal/g-mol which is in the range of those reported by other investigators and is noticeably close to the heat of the calcination reaction.     

Formation of CaCO3 hollow microspheres in carbonated distiller waste from Solvay soda ash plants

For decades, distiller waste and CO₂ were not the first choice for production of high valued products. Here, CaCO₃ hollow microspheres, a high-value product was synthesized from such a reaction system. The synthetic methods, the formation mechanism and operational cost were discussed. When 2.5 L·min^–1·L^–1 CO₂ was flowed into distiller waste (pH = 11.4), spheres with 4–13 μm diameters and about 2 μm shell thickness were obtained. It is found that there is a transformation of CaCO₃ particles from solid-cubic nuclei to hollow spheres. Firstly, the Ca(OH)₂ in the distiller waste stimulated the nucleation of calcite with a non-template effect and further maintained the calcite form and prevented the formation of vaterite. Therefore, in absence of auxiliaries, the formation of hollow structures mainly depended on the growth and aging of CaCO₃. Studies on the crystal morphology and its changes during the growth process point to the inside–out Ostwald effect in the formation of hollow spheres. Change in chemical properties of the bulk solution caused changes in interfacial tension and interfacial energy, which promoted the morphological transformation of CaCO₃ particles from cubic calcite to spherical clusters. Finally, the flow process for absorption of CO₂ by distiller waste was designed and found profitable.     

间歇氯化对电石渣循环捕集CO2性能的影响

提出在碳酸化气氛中间歇加入HCl（间歇氯化）提高电石渣在循环煅烧/碳酸化反应中捕集CO₂性能的新思路。在双固定床反应器上,在不同循环次数加入HCl、碳酸化温度、CO₂/HCl体积比等条件下,研究HCl间歇加入对电石渣循环碳酸化特性的影响。结果表明,在循环煅烧/碳酸化反应中间歇加入HCl使电石渣间歇氯化能提高其循环捕集CO₂性能。在前N次循环碳酸化时加入0.1% HCl,当N=4时能使电石渣获得最优CO₂捕集性能,第10个循环时的CO₂吸收量比无HCl时提高了51%。HCl与CaCO₃发生氯化反应,破坏致密产物层对CO₂扩散的阻碍,提高了电石渣的碳酸化转化率。在碳酸化气氛加入HCl时,最佳碳酸化温度仍为700℃。随CO₂/HCl体积比增大,HCl对电石渣捕集CO₂性能的促进作用减弱。