高稳定性CaO-ZrO2固体碱催化剂的表征和催化性能

用共沉淀法经高温焙烧制备了CaO摩尔分数从10%至50%的CaO-ZrO₂系列催化剂, 将其应用于碳酸丙烯酯和甲醇酯交换合成碳酸二甲酯过程, 并通过XRD, FT-IR, BET, ICP, CO₂-TPD, XPS等表征手段研究了催化剂的物性及其催化性能随组成变化的的规律. 结果表明, 当CaO摩尔分数高于30%时, 表面出现游离的CaO, 虽然具有强碱性和高活性, 但是稳定性差; 而当CaO摩尔分数低于30%时, Ca^2＋进入ZrO₂晶格, CaO与ZrO₂形成连续固溶体, 并且随着CaO含量的增加, 晶格氧的电荷密度增加, 催化剂的碱性增强, 使得CaO-ZrO₂催化剂在碳酸丙烯酯和甲醇酯交换合成碳酸二甲酯过程中获得了高活性和高稳定性.     

高稳定性CaO-ZrO2固体碱催化剂的表征和催化性能

用共沉淀法经高温焙烧制备了CaO摩尔分数从10%至50%的CaO-ZrO₂系列催化剂, 将其应用于碳酸丙烯酯和甲醇酯交换合成碳酸二甲酯过程, 并通过XRD, FT-IR, BET, ICP, CO₂-TPD, XPS等表征手段研究了催化剂的物性及其催化性能随组成变化的的规律. 结果表明, 当CaO摩尔分数高于30%时, 表面出现游离的CaO, 虽然具有强碱性和高活性, 但是稳定性差; 而当CaO摩尔分数低于30%时, Ca^2＋进入ZrO₂晶格, CaO与ZrO₂形成连续固溶体, 并且随着CaO含量的增加, 晶格氧的电荷密度增加, 催化剂的碱性增强, 使得CaO-ZrO₂催化剂在碳酸丙烯酯和甲醇酯交换合成碳酸二甲酯过程中获得了高活性和高稳定性.     

金属基介孔固体碱催化剂的制备与应用

应可持续发展与绿色化学的需要,非均相催化剂替代传统的均相催化剂引起研究者的广泛重视。其中,金属基介孔固体碱具有比表面积大、腐蚀性小、传质速率快、易分离等优点,是一种理想的绿色催化剂。本文综述了近年来制备不同的金属基介孔固体碱(包括MgO、类水滑石(HTs)及改性的Al₂O₃、ZrO₂、CeO₂)的研究进展,重点讨论了软模板法、硬模板法、溶剂挥发自组装法、无模板剂法等制备各种金属基介孔固体碱的方法和机理。此外,还介绍了金属基介孔氧化物在催化、储能与环境领域中的实际应用。最后,简要分析了金属基介孔固体碱制备过程中存在的问题,并展望其在未来的发展趋势,为新型金属基介孔固体碱的构筑提供了新的思路。     

翅碱蓬炭基固体酸的制备及其对双氯芬酸钠吸附性能研究

通过限氧恒温炭化法将翅碱蓬草进行炭化制备生物炭C-800,又将生物炭经浓硫酸磺化得到翅碱蓬炭基固体酸S-800。利用SEM-EDS,XRD,FT-IR,NH3-TPD和比表面积及孔径分布等表征方法对材料结构、性质进行了分析。对影响材料吸附的单因素进行了探究,在此基础上进行了四因素三水平正交实验,得出在反应时间360 min,吸附剂用量0.010 g,双氯芬酸钠的初始浓度为150 mg/L,pH为3时,S-800对双氯芬酸钠的最大吸附量为310 mg/g。经过反应动力学研究和吸附等温线拟合,结果表明S-800材料更好的遵循拟二级动力学,说明该吸附过程主要是化学吸附,更符合Langmuir模型,说明主要是单分子层吸附。对潜在的吸附机理进行推断,主要通过静电作用和氢键作用实现对双氯芬酸钠的吸附。     

一步法制备钛负载介孔材料及其对CO2的吸附

以增溶了二氯二茂钛的P123胶束为模板,采用一步法得到了钛掺杂介孔材料Ti-SBA-15．FTIR、XRD、BET等测试结果显示Ti-SBA-15仍保持规整的孔道结构特征,样品经焙烧后茂环分解留下钛负载于介孔表面．对样品吸附CO2的测定结果表明,钛的负载有利于CO2的吸附,在N2气氛下焙烧的样品对C02的吸附性能显著提高,其中Ti-SBA-15（550-0．5-N2）对C02的最大吸附量为1．44mmolg^（-1）,钛在介孔材料中的存在形态对CO2吸附性能起决定性作用．     

介孔材料氨基表面修饰及其对CO2的吸附性能

采用接枝方法在介孔材料MCM-41和SBA-15的孔道内表面进行氨基化修饰, XRD、29Si-NMR、FT-IR、TGA、BET等测试结果表明, 氨丙基三乙氧基硅烷(APTS)和氨乙基氨丙基甲基二甲氧基硅烷(AEAPMDS)都分别接枝在介孔材料的孔道内, 表面氨基修饰量约为1.5-2.9 mmol·g-1. 表面修饰后介孔材料的孔道仍高度有序, 但比表面积减小. 表面修饰前后介孔材料对CO2的吸附性能发生显著变化, 由于物理吸附转化为以氨基为活性中心的化学吸附, 吸附量从修饰前的0.67 mmol·g-1提高到2.20 mmol·g-1.     

介孔硅复合氧化石墨烯多孔材料的制备及其CO2吸附性能研究

以P123为模板剂,以TEOS为硅源,以氧化石墨烯为复合组分,采用溶胶-凝胶法和自组装法制备了具有较大比表面积的介孔硅复合氧化石墨烯三维多孔材料（MSM/GOs）,进一步通过物理浸渍聚乙烯亚胺（PEI）制备了固态胺吸附材料。利用扫描电子显微镜（SEM）、氮气吸附-脱附曲线、元素分析等方法表征复合材料的结构和形貌,研究了氧化石墨烯添加量对材料的比表面积和胺化效果的影响以及吸附温度对其吸附CO₂性能的影响。研究结果表明,氧化石墨烯的引入能显著提高介孔硅复合氧化石墨烯多孔材料的比表面积,当GO添加量为4.5wt%时,其比表面积可高达841m²/g。高的比表面积有利于提高材料的氨基含量。在30wt%PEI的物理浸渍胺化后,MSM/GO-4.5@30%PEI拥有最大含氮量（9.59wt%）和CO₂吸附量（1.70mmol/g）。得益于良好的多孔基体和有机胺的均匀分布,MSM/GO-4.5@30%PEI在不同温度下的吸附量较稳定,循环再生吸附后仍能保持初始吸附量的80%。动力学研究表明,准一级模型和Avrami模型均能较好地拟合其吸...     

催化裂化汽油固体碱预碱洗的研究──负载固体碱对硫化氢的吸附过程分析

以活性炭为载体,碱金属化合物为活性组分,制备出负载固体碱,对其吸附硫化氢性能进行了研究。结果表明,此类固体碱吸附硫化氢能力较强,在固体碱孔外主要进行化学吸附,在固体碱孔内以物理吸附为主,化学吸附和物理吸附能力分别与固体碱、固体碱孔内所负载活性组分的量有关     

新型多级微/介孔固态胺吸附剂的制备及其CO2吸附性能研究

将HZSM-5与MCM-41按不同质量比混合得到复合分子筛载体,以四乙烯五胺(TEPA)为改性剂,采用浸渍法将其负载到复合分子筛上,制备了一系列新型的具有多级微/介孔结构的固态胺吸附剂。采用N₂吸脱附、傅里叶变换红外光谱(FT-IR)、热重分析(TGA)等手段对吸附剂进行表征。在固定床反应器中考察了HZSM-5和MCM-41的质量比、TEPA负载量、吸附温度、进气流量和CO₂分压等因素对CO₂吸附性能的影响。结果表明,当HZSM-5与MCM-41的质量比为1:1、TEPA负载量为30%、吸附温度为55℃、进气流量为30 mL/min时,平衡吸附量高达3.57 mmol/g,且经10次吸脱附循环后,吸附量仅下降8.1%。HZSM-5/MCM-41-30%TEPA对CO₂的吸附过程包括快速的穿透吸附和相对缓慢的逐渐平衡阶段,且穿透吸附量接近于平衡吸附量的80%。HZSM-5/MCM-41-30%TEPA对CO₂的吸附过程符合Avrami动力学模型,表明CO₂吸附是物理吸附和化学吸附的结果。     

四乙烯五胺修饰介孔硅胶吸附CO2性能的研究

采用浸渍法将四乙烯五胺(TEPA)负载到介孔硅胶(SG)上,制备了一系列胺功能化的CO₂吸附材料(TEPA-SG).利用傅里叶变换红外光谱(FT-IR)、热重分析(TGA)和N₂吸脱附等分析方法对样品进行了表征,并在固定床反应器中考察了TEPA负载量、吸附温度对CO₂吸附性能的影响,同时通过添加不同质量分数的聚乙二醇(PEG)考察了羟基对吸附性能及再生性能的促进作用.结果表明,当TEPA负载量为40%(质量分数)、吸附温度为70 ℃时,TEPA-SG的吸附量高达2.21 mmol/g;PEG的加入改变了氨基与CO₂的相互作用机理,当TEPA与PEG的质量比为3:1,总负载量为40%时,CO₂的吸附量为2.70 mmol/g,且经过10次吸脱附循环实验后,CO₂吸附量仍保持在2.66 mmol/g,表现出较好的循环稳定性.Clausius-Clapeyron方程计算得该过程的等量吸附热为30~40 kJ/mol,且随吸附量的增大等量吸附热逐渐减小,表明TEPA30/PEG10-SG吸附剂表面存在能量不均匀性.     

CaO高温吸附捕集CO2-制备CaO的钙基前驱体材料筛选

价格低廉的CaO材料在高温下能高效吸附捕集CO2气体,被认为是碳减排的有效方法之一．然而,CaO长时间循环碳酸化／煅烧解吸后,其CO2的化学吸附容量下降,稳定性较差,限制了该材料的工业应用．本文采用天然钙源（牡蛎壳和方解石等）和化学试剂（醋酸钙）为钙基前驱材料制备CaO．采用扫描电子显微镜（SEM）,X射线衍射仪（XRD）和氮气吸附仪等手段对制备的CaO材料进行形貌和物理结构的分析表征;在高温和模拟的烟道气氛条件下（10％C02和90％N2）,采用热重分析仪测量CaO吸附CO2的能力和长时间循环碳酸化／煅烧解吸后的稳定性．我们经过与目前所报道的其他钙基吸附材料进行比较,并结合钙基前驱材料的市场价格,发现CaO（醋酸钙）的CO2吸附能力和稳定性较为理想,醋酸钙在高温烟气捕碳方面具有非常好的应用前景．     

Preparation of biomass-derived phosphorus-doped microporous carbon material and its application in dye adsorption and CO2 capture

Microporous P-doped carbon materials are synthesized by a pyrolysis method using MCM-22 as a template, sucrose as a precursor, and phosphoric acid as phosphorus sources. The results show that the pore structure of the carbon materials can be adjusted by changing the amount of phosphoric acid and template. When the P/C molar ratio is 0.075, the obtained P-doped microporous carbon material shows excellent specific surface area up to 621 m²/g and shows a high adsorption capacity of 199.40 mg/g for crystal violet dye, with a removal rate of 98.9%. When testing the CO₂ adsorption capacity, it was found that the maximum adsorption capacity reached 63 mg/g and remained stable after 10 adsorption and desorption cycles, with excellent cycle stability. The adsorption obeys pseudo-second-order kinetic model, and the adsorption isotherm follows the Langmuir model.     

Innovative nano-layered solid sorbents for CO2 capture

Nano-layered sorbents for CO(2) capture, for the first time, were developed using layer-by-layer nanoassembly. A CO(2)-adsorbing polymer and a strong polyelectrolyte were alternately immobilized within porous particles. The developed sorbents had fast CO(2) adsorption and desorption properties and their CO(2) capture capacity increased with increasing nano-layers of the CO(2)-adsorbing polymer.     

H2 storage and CO2 capture on a nanoscale metal organic framework with high thermal stability

A nanoscale aluminium-based metal organic framework (NMOF) with high thermal stability has been synthesized, which shows high H(2) and CO(2) uptake capacities and an excellent selectivity for CO(2) over N(2) and O(2).     

Preparation of composite poly（ether block amide） membrane for CO2 capture

In this study, a poly（ether block amide） （Pebax 1657） composite membrane applied for COa capture was prepared by coating Pebax 1657 solution on polyacrylonitrile （PAN） ultrafiltration membrane. Ethanol/water mixture was used as the solvent of Pebax and the effects of ethanol/water mass ratios and Pebax concentration on the permeation properties of composite membrane were studied. To enhance the com- posite membrane permeance, the gutter layer, made from reactive amino silicone crosslinking with potydimethylsiloxane （PDMS）, was de- signed. The influence of crosslinldng degree of the gutter layer on membrane performance was investigated. As a result, a Pebardamino- PDMS/PAN multilayer membrane with hexane resistance was developed, showing CO2 permeance of 350 GPU and CO2/N2 selectivity over 50. The blend of polyethylene glycol dimethyl ether （PEG-DME） with Pebax as coating material was studied to further improve the membrane performance. After being combined with PEG-DME additive, CO2 permeance of the final Pebax-PEG-DME/amino-PDMS/PAN composite membrane reached 400 GPU above with CO2/Na selectivity over 65.     

化学链技术及其在化石能源转化与二氧化碳捕集领域的应用

化学链是指将某一特定的化学反应通过化学介质的作用分多步反应完成的过程．这一概念早在20世纪初就曾被用于以水蒸气与铁反应制备氢气,并于20世纪中期被提出用于二氧化碳的商业化生产．然而,时至今日,尚无商业化的化学链工艺用于化石燃料的转化．在近年来全球气候变暖及能源危机的急迫形势下,化学链循环过程由于其具有可以将碳基燃料直接转化为可供封存的二氧化碳的独特能力而格外受到关注,人们因而加大了对化学链工艺的研究开发力度．现代化学链工艺逐步克服了早期工艺的缺点,并不断尝试开发以煤或者其他固体燃料作为直接进料的新工艺．现有的各种小试及中试装置操作结果及系统模拟分析表明,化学链循环工艺可以有效地降低二氧化碳分离能耗并提高化石能源转化效率,极具商业化潜力．本文主要介绍目前世界范围内现行的使用化石燃料作为原料的化学链循环工艺,重点总结对比了化学链燃烧和化学链气化两个过程的发展现状,并对化学链循环工艺工业化进程中的机遇和挑战进行了简要的讨论．     

Preparation of zinc chabazite (ZnCHA) for CO2 capture

Research on Chemical Intermediates - ZnCHA was successfully synthesized, and their potentials for CO2 capture under different conditions were also evaluated for the first time. Furthermore, SrCHA,...     

Lithium silicate nanosheets with excellent capture capacity and kinetics with unprecedented stability for high-temperature CO2 capture

An excessive amount of CO₂ is the leading cause of climate change, and hence, its reduction in the Earth''s atmosphere is critical to stop further degradation of the environment. Although a large body of work has been carried out for post-combustion low-temperature CO₂ capture, there are very few high temperature pre-combustion CO₂ capture processes. Lithium silicate (Li₄SiO₄), one of the best known high-temperature CO₂ capture sorbents, has two main challenges, moderate capture kinetics and poor sorbent stability. In this work, we have designed and synthesized lithium silicate nanosheets (LSNs), which showed high CO₂ capture capacity (35.3 wt% CO₂ capture using 60% CO₂ feed gas, close to the theoretical value) with ultra-fast kinetics and enhanced stability at 650 °C. Due to the nanosheet morphology of the LSNs, they provided a good external surface for CO₂ adsorption at every Li-site, yielding excellent CO₂ capture capacity. The nanosheet morphology of the LSNs allowed efficient CO₂ diffusion to ensure reaction with the entire sheet as well as providing extremely fast CO₂ capture kinetics (0.22 g g⁻¹ min⁻¹). Conventional lithium silicates are known to rapidly lose their capture capacity and kinetics within the first few cycles due to thick carbonate shell formation and also due to the sintering of sorbent particles; however, the LSNs were stable for at least 200 cycles without any loss in their capture capacity or kinetics. The LSNs neither formed a carbonate shell nor underwent sintering, allowing efficient adsorption–desorption cycling. We also proposed a new mechanism, a mixed-phase model, to explain the unique CO₂ capture behavior of the LSNs, using detailed (i) kinetics experiments for both adsorption and desorption steps, (ii) in situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy measurements, (iii) depth-profiling X-ray photoelectron spectroscopy (XPS) of the sorbent after CO₂ capture and (iv) theoretical investigation through systematic electronic structure calculations within the framework of density functional theory (DFT) formalism.

Capturing CO₂ before its release. Lithium silicate nanosheets showed high CO₂ capture capacity (35.3 wt%) with ultra-fast kinetics (0.22 g g⁻¹ min⁻¹) and enhanced stability at 650 °C for at least 200 cycles, due to mixed-phase-model of CO₂ capture.     

Preparation and characterization of spherical mesoporous ZrO_2-Al_2O_3 composites with high thermal stability

Spherical mesoporous ZrO2-Al2O3 composites containing different zirconia content have been synthesized by an oil-column sol-gel method.A mixed alumina-zirconia hydrosol and hexamethylenetetramine solution were mixed together and added dropwise into a hot oil column.Due to the surface tension,spherical gel particles were formed in the oil column.The spherical gel particles were then aged and washed by deionized water and dried at 120 ℃ for 12 h and then calcined at 600 ℃ for 8 h,960 ℃ for 8 h or 1200 ℃ for 1...