不同粒度纳米碳酸钙的可控制备

不同粒度的纳米碳酸钙具有不同的特性和应用范围,目前不同粒度纳米碳酸钙的可控制备方法还未见报道。以氯化钙、碳酸铵为原料,以乙醇、柠檬酸和焦磷酸钠为分散剂,采用复分解法研究了不同制备条件对纳米碳酸钙粒径的影响规律,在此基础上制备出平均粒径为17~71 nm的碳酸钙,并对其进行了表征。实验结果表明,所制备的纳米碳酸钙均为球霰石型,纯度很高,而且形貌近似球形。制备条件对纳米碳酸钙的粒径有显著的影响：随着反应温度升高,纳米碳酸钙的粒径减小;随着氯化钙滴加时间的增加,纳米碳酸钙的粒径增大;随着反应物浓度的提高,纳米碳酸钙的粒径先减小后增大;当分散剂为柠檬酸和焦磷酸钠的混合溶液时所得纳米碳酸钙的粒径最小,当分散剂为乙醇和焦磷酸钠的混合溶液时所得纳米碳酸钙的粒径最大。利用这些影响规律通过控制制备条件可以实现所需粒径纳米碳酸钙的可控制备。     

孔雀绿褪色光度法研究麦壳对SDBS的吸附性能

采用麦壳为生物吸附剂,研究其对十二烷基苯磺酸钠（SDBS）的吸附作用。结果表明：麦壳能迅速有效地吸附SDBS,40min基本达到平衡;增大SDBS的初始浓度,吸附量随之增大;增加吸附剂的用量,吸附量随之减小;SDBS溶液pH值在5~8范围内,吸附效果较好;升高温度对吸附有利;麦壳对SDBS的吸附符合Langmuir等温模型。     

脱镁母液制备磷酸铵镁过程中的粒度分布

以脱镁母液和磷酸为原料,采用半间歇操作方式制备磷酸铵镁,研究了操作条件（包括搅拌转速、加料位置、加料速度、反应物浓度、晶种加入量）对磷酸铵镁晶体粒度分布的影响。结果表明：适当提高搅拌转速、降低加料速度和降低反应物浓度均可增大产品的平均粒径并减小其变异系数;在桨区加料所得产品平均粒径较大且粒度分布较好;加入适量晶种可以显著增大产品的平均粒径并使其粒度分布更加均匀。     

纳米钛酸锶粉体制备及其表面改性工艺研究

钛酸锶（SrTiO3）是制备陶瓷电容器和热敏电阻器等电子陶瓷的重要原料,在电子工业上的应用非常广泛。以四氯化钛和氯化锶、氢氧化钠为原料,采用直接沉淀法合成纳米钛酸锶粉体,重点研究了表面活性剂十二烷基苯磺酸钠（SDBS）在合成过程中对纳米钛酸锶粉体性能的影响,并应用XRD,TEM,SEM,BET等一系列手段对其微观结构进行表征。结果表明表面活性剂SDBS的添加浓度有一最佳值（0.15 mol/L）。通过SDBS改性后的纳米钛酸锶粉体,其晶型结构没有发生改变,颗粒的形状为球形,平均粒径约为25 nm,粒度分布较窄,团聚现象也大为改善。     

SDBS对多壁碳纳米管悬浮液分散性的影响

以十二烷基苯磺酸钠(SDBS)为分散剂,氯化胆碱-丙二酸类离子液体为溶剂,通过超声分散处理多壁碳纳米管,制备了分散性良好的多壁碳纳米管悬浮液。采用紫外-可见分光光度法和粒径测试考察了SDBS对多壁碳纳米管悬浮液分散性的影响。结果表明,在多壁碳纳米管悬浮液中,当SDBS的浓度为1.2 mmol?L~(-1)左右时,悬浮碳纳米管的浓度最大,约为初始浓度的89%。悬浮液中多壁碳纳米管的平均粒径随着SDBS的浓度的增大而逐渐降低,在SDBS的浓度大于1.0 mmol?L~(-1)时,下降趋势变缓慢。添加SDBS后的多壁碳纳米管悬浮液的稳定性显著提高,192 h后基本趋于稳定。     

糠醛渣木质素/聚乙烯亚胺微球的制备

木质素和聚乙烯亚胺（PEI）对重金属离子有良好的亲和力,且木质素来源广泛、具有良好的生物降解性能,在水处理方面有很好的前景。本文以糠醛渣木质素和聚乙烯亚胺为主要原料,十二烷基苯磺酸钠（SDBS）为分散剂,环氧氯丙烷（EPI）为交联剂,液体石蜡为油相,采用反相悬浮聚合法,制备了糠醛渣木质素/PEI微球（LMS）。通过FTIR、XRD、SEM和激光粒度仪对微球的结构和形貌进行表征,研究了木质素用量、PEI用量、EPI用量、SDBS用量、油水比和反应温度对木质素微球制备的影响。结果显示,在木质素用量为0.600g,PEI用量为2.25g,EPI用量为2.25mL,SDBS用量为0.075g,温度为56℃,油水体积比为4.5∶1的条件下,制得的糠醛渣木质素/PEI微球平均粒径为135μm,粒径分散度为0.290,比表面积为46.5m²/g,球型度良好,球体表面有少量微孔。     

超声预乳化环硅氧烷乳液共聚合

以十二烷基苯磺酸钠(SDBS)为乳化剂、硫酸为催化剂,将八甲基环四硅氧烷(D4)与四甲基四乙烯基环四硅氧烷(D4^Vi)进行正离子开环共聚,制备了聚硅氧烷乳液。比较了超声预乳化方式和机械搅拌预乳化方式对预乳液粒径分布、乳液粒径分布及聚合反应动力学的影响,考察了单体质量比、聚合温度、催化剂浓度和乳化剂浓度对聚合动力学及乳液粒径分布的影响。结果表明,超声预乳化聚合中同时存在单体小液滴成核和胶束成核2种机理,超声预乳液稳定性较好,平均粒径为180nm,最终转化率可达90％左右;当聚合温度为80℃、SDBS质量分数为l％、硫酸质量分数为3％时,可以制得稳定的聚硅氧烷乳液。     

管式气体分散式反应器制备纳米碳酸钙

以石灰石为原料，利用管式气体分散式反应器新工艺制备出了粒径30～70nm的碳酸钙粉体。采用X射线衍射（XRD）、扫描电镜（SEM）、粒度分布仪及红外光谱仪（Fr-IR）等测试手段，对产品的物相、形貌和粒度分布进行了表征。X射线衍射表明产物为六方晶系方解石型碳酸钙并且产品结晶性能良好；扫描电镜及粒度分析表明粒度大小均匀、分散性良好；红外光谱表明改性后硬脂酸钠已吸附在碳酸钙表面，碳酸钙颗粒基本呈单分散状态。管式气体分散式反应器制备纳米碳酸钙粉体的优点是工艺简单，操作容易，原料易得，生产的产品粒径小，粒度分布窄，易于工业化生产。     

苯乙烯-对氯甲基苯乙烯共聚物胶乳微球的制备及表征

以苯乙烯（St）和对氯甲基苯乙烯（VBC）为共聚单体,过硫酸钾（KPS）为引发剂,十二烷基苯磺酸钠（SDBS）为乳化剂,采用乳液聚合法制备了富含氯甲基的苯乙烯-对氯甲基苯乙烯共聚物功能微球。采用红外光谱（FT-IR）、扫描电镜（SEM）、激光粒度仪和X射线光电子能谱（XPS）对样品进行表征,研究了乳化剂用量、单体用量、引发剂用量、反应时间、反应温度等因素对微球粒径、乳液转化率的影响。结果表明,产物微球粒径均一,表面光滑、富含氯甲基功能基团,采用此方法可以制备粒径在100～250 nm的功能高分子微球。     

碳酸钙的形貌控制及表面改性探究

应用复分解法制备不同形貌的碳酸钙颗粒,选用聚乙二醇(PEG)、十二烷基苯磺酸钠(SDBS)、十六烷基三甲基溴化铵(CTAB)和四丁基溴化铵(TBAB)为表面活性剂。改变其加入比例、反应温度等条件,制备出不同条件下的碳酸钙产品。运用扫描电镜技术、XRD、红外光谱分析实验所合成的产品。优化出制备形貌均一、分散性好的碳酸钙的最佳条件。     

Hydrothermal synthesis of calcium sulfate whisker from flue gas desulfurization gypsum

Plenty of flue gas desulfurization (FGD) gypsum generated from coal-fired power plants for sulfur dioxide se-questration caused many environmental issues. Preparing calcium sulfate whisker (CSW) from FGD gypsum by hydrothermal synthesis is considered to be a promising approach to solve this troublesome problem and uti-lize calcium sulfate in a high-value-added way. The effects of particle size of FGD gypsum, slurry concentration, and additives on CSW were investigated in this work. The results indicated that fine particle size of FGD gypsum and moderately high slurry concentration were beneficial for crystal nucleation and growth. Three additives of magnesium chloride, citric acid, and sodium dodecyl benzene sulfonate (SDBS) were employed in this study. It was found that mean length and aspect ratio of CSW were both decreased by the usage of magnesium chloride, while a small quantity of citric acid or SDBS could improve the CSW morphology. When multi-additives of citric acid-SDBS were employed, the mean length and aspect ratio increased more than 20%. Moreover, surface morphology of CSW went better, and the particle size and crystal shape became more uniform.     

Synthesis of pure aragonite by sonochemical mineral carbonation

The objective of this work was to promote the formation of the aragonite polymorph of calcium carbonate, which has some valuable applications in industry, via the mineral carbonation route. The combination of ultrasound with magnesium ions promoted the formation of pure aragonite crystals at optimum conditions. It was possible to synthesize high purity aragonite precipitates at temperatures ranging from 24 °C to 70 °C, with the resulting powders possessing varying particle size distributions (from sub-micron up to 20 μm) and crystal morphologies (from acicular needles to novel hubbard squash-like particles). Several process parameters were found to influence the produced calcium carbonate polymorph ratios (aragonite over calcite). Higher values of magnesium-to-calcium ratio, intermediate ultrasound amplitude (60%), continuous ultrasound application (100% cycle), introduction of ultrasound pre-breakage, lowering of the CO₂ flow rate, and increase in the relative concentration (g/L Ca(OH)₂), all promoted aragonite formation. A potential route for industrial production of this material has been identified via a fed-batch process, which effectively reutilizes magnesium chloride while maintaining high aragonite yield. The results presented herein are significantly superior to aragonite formation using only single promoting techniques, typically found in literature, and go beyond by focusing on pure (>99%) aragonite formation.     

氨碱盐泥碳化反应宏观动力学研究

盐泥是氨碱法纯碱生产过程中盐水精制过程产生的固体废弃物,有效成分为氢氧化镁、硫酸钙、碳酸钙、氯化钠等,全球每年产生大约5 500万t盐泥,其资源化利用已成为纯碱生产企业亟待解决的问题。提出采用碳化法分离盐泥中的钙和镁,使其转化为碳酸钙和硫酸镁产品,探讨了固液比、反应温度、盐泥颗粒粒度等工艺条件对镁提取率的影响。研究结果表明：随着固液比、盐泥颗粒粒度的减小以及反应温度的升高,镁的提取率逐渐升高,当固液质量体积比（g/mL）为1/10、反应温度为50 ℃、盐泥颗粒粒度≤75 μm条件下,盐泥中镁的提取率达到96.04%;通过将实验数据带入缩芯模型中进行拟合,结果表明氨碱盐泥碳化过程符合颗粒粒径不变的缩芯模型,经计算该反应的活化能为24.22 kJ/mol,并且该过程为盐泥中氢氧化镁的溶解控制。此为碳化反应器的放大提供了理论基础。     

电石渣和烟道气为原料生产碳酸钙

根据电石渣组成和烟道气成分,提出了加压碳化的工艺路线。该工艺将电石渣利用和烟道气中二氧化 碳捕集封存技术结合起来,不仅解决了电石渣和烟道气的环境问题,同时又生产了高附加值的纳米碳酸钙。考察了 工艺路线中各项工艺参数的影响,得到最佳工艺条件：煅烧温度为900 ℃、消化灰水质量比为1∶7、碳化压力为0.4 MPa、碳化气速为0.093 m/s。在此条件下,添加晶型控制剂制备出了粒径为60 nm、粒径分布窄的球形纳米碳酸钙。     

软锰矿和菱锰矿脱除烧结烟气中SO2的实验研究

采用软锰矿加菱锰矿脱除烧结烟气中SO2的试验研究表明,本实验较适宜的工艺条件为反应温度45℃,软锰矿平均粒度为0．075mm,液固比在5：I,其平均脱硫率在较长一段时间内能保持在95％以上。     

Precipitation of calcium carbonate in the presence of citrate and EDTA

The influence of process conditions such as feed rate, calcium/carbonate ratio, pH, complexing agents [ethylenediaminetetraacetic acid (EDTA), citrate (CIT)] and their concentration on the average particle size and shape of precipitated calcium carbonate was studied. The precipitation was performed in a semi-batch operated agitated vessel at constant pH by adding sodium hydrogen carbonate to a solution containing calcium chloride. In the absence of a complexing agent, agglomerates of needle-shaped crystals, probably aragonite, are obtained. Increasing feed time and the calcium/carbonate ratio increases the average particle size, whereas the opposite effect is observed for increasing pH. The observations can be related to the level of supersaturation. In the presence of complexing agents and at a concentration ratio of calcium vs. a complexing agent of 6, differently shaped and smaller particles were obtained. Furthermore, the effect of the other parameters on particle size becomes much weaker in the presence of complexing agents. In the presence of EDTA mostly spherical particles were obtained, and in the presence of citrate mainly rhombic particles corresponding to calcite were obtained. The effect on particle shape and size is attributed to interactions of the complexing agents with the faces of the crystalline calcium carbonate.     

Synthesis of CaCO3 nanoparticles by controlled precipitation of saturated carbonate and calcium nitrate aqueous solutions

Calcium carbonate nanoparticles (CCNP) were synthesised by precipitation from saturated sodium carbonate and calcium nitrate aqueous solutions. The effect of agitation rate, mixing time, calcium/carbonate ions concentration and temperature on particle size and morphology were investigated. Particles were characterised using X‐ray diffraction (XRD), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). Increasing the mixing time from 30 to 180 min resulted in a decrease in particles size. Mixing rate variation between 300 and 14 000 rpm decreased the particle size. Temperature increase favoured a significant growth in particle size and in the formation of aragonite beginning from 80°C. Calcium and carbonate ion concentrations are key parameters controlling the CCNP particle size. Calcite is the main polymorph obtained as revealed by XRD analysis. © 2011 Canadian Society for Chemical Engineering     

NaOH–烟道气法卤水净化中成垢离子的沉降行为

卤水中的成垢离子(Ca2+, Mg2+和CO32–等)在真空蒸发浓缩过程中易形成低热力学活性和强吸附性的碳酸钙和硫酸钙垢层,降低换热管传热效率。NaOH–烟道气法卤水净化可利用电厂废气–烟道气以及氯碱厂低浓度的废碱,在节能环保方面具有绝对的优势和广阔的前景。为研究NaOH–烟道气法卤水净化过程中成垢离子的沉降行为规律,采用CO2替代烟道气开展卤水净化实验研究。采用Factsage热力学软件、XRD和SEM–EDS等分析手段探究了不同CO2通入时间和pH值对Ca2+, Mg2+和CO32–沉降行为的影响及所得沉淀物的矿物学特征。结果表明,当控制pH=11.5,CO2通入时间60 min时,可将卤水中的Ca2+浓度降低至6.0~8.0 mg/L,延长沉降时间至80 min,Mg2+浓度可降低至0.65 mg/L。此外,该pH值条件下沉淀反应的平衡常数最大,钙、镁的净化效果较其他pH条件下更佳。控制过程pH=9.5时,所得沉淀物为球霰石(Vaterite)型碳酸钙晶体;当pH升至10,碳酸钙的晶型由球霰石转化为霰石型(Aragonite)晶体,其形貌由规则的球形转变为椭圆形;当pH=11和11.5时,沉淀物为钙和镁的共晶体,碳酸钙的晶型由球霰石转换为热力学更加稳定的方解石型(Calcite)晶体。     

Equilibria in a Limestone Based FGD Process: A Pure System and with Chloride Addition

On the basis of physical and chemical equilibria conditions a model of gaseous sulfur dioxide solubility in the solutions applied in an FGD (flue‐gas desulfurization) process was developed. The dependencies of solution pH in the bulk liquid and in the limestone particle vicinity on the calcium carbonate and/or on the dissolved sulfur dioxide content are presented. The influence of the concentration of dissolved carbon dioxide on pH, sulfite to sulfate oxidation conditions, limestone and calcium sulfite solubility are also discussed. The mechanisms leading to a decrease in calcium carbonate solubility or limestone particle blinding are explained. The restrictions in calcium chloride concentration for the reliable operation of an FGD process are predicted.     

超细碳酸钙制备的研究

利用电导仪跟踪碳化反应历程,详细研究了反应温度、ＣＯ２浓度、Ｃａ（ＯＨ）２浓度、气体流量和活加剂用量等因素对反应时间及ＣａＣＯ３产品粒径的影响。