硫酸铝铵-氯化氢反应制备六水氯化铝过程中晶体形貌的研究

以十二水合硫酸铝铵为原料,采用氯化氢通气结晶法制备了六水氯化铝晶体,考察了通气速率、通气时间、反应温度、铝离子初始浓度对六水氯化铝晶体形貌的影响。结果表明,50 mL硫酸铝铵酸溶液中,当通气速率为60 mL/min、通气时间为2 h、反应温度为30 ℃、铝离子初始质量浓度为20 g/L时,可以得到形貌比较规整的棱柱形六水氯化铝晶体。该研究为提取、制备高品质六水氯化铝晶体提供了技术参考。     

三元体系AlCl3+CaCl2+H2O，AlCl3+FeCl3+H2O和CaCl2+FeCl3+H2O在35℃时的相平衡

缺少含AlCl₃、CaCl₂和FeCl₃的溶液相平衡,使通过蒸发结晶从粉煤灰盐酸浸取液中制备纯净的AlCl₃·6H₂O变得比较困难。采用等温溶解法研究了三元体系AlCl₃+CaCl₂+H₂O,AlCl₃+FeCl₃+H₂O和CaCl₂+FeCl₃+H₂O在35℃时的相平衡关系,测定了相应的溶解度及密度,并绘制了相应相图及密度-组成图。实验结果表明：三元体系AlCl₃+CaCl₂+H₂O和AlCl₃+FeCl₃+H₂O分别有两条溶解度曲线,两个单盐结晶区,无复盐和共溶体产生,同离子效应导致增加溶液中CaCl₂和FeCl₃浓度会有效降低AlCl₃的溶解度;CaCl₂+FeCl₃+H₂O体系会形成复盐CaCl₂·2FeCl₃·7H₂O;所得35℃相图与25℃相图相比,三元体系AlCl₃+CaCl₂+H₂O和AlCl₃+FeCl₃+H₂O中AlCl₃·6H₂O结晶区增大,CaCl₂·6H₂O结晶区转变成CaCl₂·4H₂O结晶区,CaCl₂+FeCl₃+H₂O体系中CaCl₂·2FeCl₃·8H₂O结晶区转变为CaCl₂·2FeCl₃·7H₂O结晶区。     

蔗糖在DMF-[BMIm]Cl溶剂中催化制备5-HMF

研究了在N,N-二甲基甲酰胺(DMF)-离子液体[BMIm]Cl混合溶剂中将蔗糖高效转化为5-羟甲基糠醛(5-HMF)的反应。运用紫外-可见分光光度计对水解液中5-HMF进行定量分析并计算其收率。考察了CrCl₃·6H₂O、AlCl₃·6H₂O、SnCl₄·5H₂O、FeCl₃、CoCl₂·6H₂O、ZnCl₂、CuCl₂·2H₂O、CaCl₂ 8种催化剂对反应的催化效果,结果表明AlCl₃·6H₂O催化效果最为明显。以AlCl₃·6H₂O为催化剂研究了不同反应条件如时间、温度、溶剂中DMF-[BMIm]Cl质量比、催化剂AlCl₃·6H₂O的用量对5-HMF收率的影响,得到的最佳条件为以0.5mmol蔗糖为反应物,0.4mmol AlCl₃·6H₂O为催化剂,反应时间2h,反应温度120℃,5g质量比为85:15的DMF-[BMIm]Cl混合溶剂,此条件下5-HMF收率最高可达63.4%。研究表明,DMF-[BMIm]Cl混合溶剂体系对蔗糖转化为5-HMF有一定的促进效果,在此溶剂体系中以AlCl₃·6H₂O为催化剂时可以得到较高的5-HMF产率。     

AlCl3·6H2O在盐酸体系中的结晶行为

研究了AlCl₃·6H₂O在盐酸体系中的结晶行为,考察了铁、钙、镁、钾、钠等杂质对AlCl₃·6H₂O结晶行为的影响,并利用聚焦光束反射测量技术（FBRM）和颗粒录影显微镜（PVM）探讨了不同盐酸滴加速度下AlCl₃·6H₂O的结晶粒度分布及形貌。结果表明,AlCl₃·6H₂O的结晶量随着盐酸加入量的增加而增加,当浓盐酸加入量为AlCl₃饱和溶液体积的2.25倍时,25℃时的结晶效率可达到80%。溶液中Fe的存在可促进AlCl₃·6H₂O的结晶,在1.5 mol·kg^-1的AlCl₃溶液中,当铝铁摩尔比低于3：1时,得到的AlCl₃·6H₂O晶体中铁的含量小于0.1%。钾、钙、镁、钠等杂质对AlCl₃·6H₂O的结晶影响不大。盐酸添加速度影响AlCl₃·6H₂O的形貌,快的盐酸添加速度易使晶体发生团聚,颗粒粒径小,盐酸添加速度较慢时,可得到颗粒较大、形貌好的单晶。     

AlCl3·6H2O在FeCl3、CaCl2、KCl及KCl–FeCl3溶液中溶解度的实验及预测

如何将AlCl₃·6H₂O从众多组分中选择性地结晶分离是从煤矸石中提Al的关键,而AlCl₃·6H₂O在煤矸石酸浸体系中的热力学平衡数据对于结晶过程的控制至关重要。在25～85℃的温度范围内,测定了不同温度和溶液浓度下AlCl₃·6H₂O在FeCl₃、CaCl₂、KCl及KCl-FeCl₃溶液中的溶解度。实验发现温度对AlCl₃·6H₂O在所有溶液体系中溶解度的影响均不明显,溶解度只随温度的升高略有增加;溶液浓度是影响溶解度的主要因素,AlCl₃·6H₂O在所有溶液体系中的溶解度均随溶液浓度的升高而明显下降,分析其原因是由于溶液浓度的增大使得Cl^–同离子效应增强。为了提高OLI软件预测结果的准确性,对其嵌入Bromley-Zemaitis模型中“Al³⁺–Cl<...     

[BMIM]Cl/AlCl3离子液体低温电沉积铝过程

采用玻碳/铂为惰性阳极,以1-丁基-3-甲基咪唑氯盐([BMIM]Cl/AlCl₃)离子液体体系为电解液,研究了离子液体电解铝工艺,优化了电解工艺条件,探讨了电解影响因素。结果表明,当电解液[BMIM]Cl∶AlCl₃摩尔比为1∶2.00时,随着温度的升高,铝的沉积槽电压逐渐减小,电流密度增加,但电解液的稳定性减弱,当温度达到90℃时,电解液分解明显。当电解温度一定时,随着[BMIM]Cl∶AlCl₃摩尔比的增加[(1∶1.25)~(1∶2.00)],电流密度增加。通过赫尔槽实验,SEM、XRD分析了电解铝的沉积形貌和晶相结构。随电流密度的逐渐减小,沉积层变薄,晶相结构变化不大;相同电流密度区随温度的升高,沉积层逐渐变得粗糙。计算了不同槽间距下的槽压与电流密度的关系。     

六水合氯化铝在不同氯化物 体系中的溶解度现象研究

以煤矸石酸浸滤液中六水合氯化铝的结晶为背景,以OLI软件为平台,用软件中嵌入的Bromley-Zemaitis 活度系数模型预测了温度范围为10~70 ℃、溶液浓度为0~17 mol/kg的条件下,六水合氯化铝分别在水、氯化钠、氯化钾、盐酸体系中的溶解度,并将预测结果同文献数据作了比较。结果表明,在水、氯化钠和氯化钾溶液中,温度和溶液浓度对六水合氯化铝溶解度的影响均可忽略;在盐酸溶液中,温度对六水合氯化铝溶解度的影响可忽略,但随着盐酸浓度的增大,六水合氯化铝的溶解度急剧降低。比较可知预测值与文献值吻合较好,说明Bromley-Zemaitis 活度系数模型可以作为研究手段用于预测六水合氯化铝在上述4个体系中的溶解度,为六水合氯化铝的工业结晶过程提供相平衡的预测。     

3,3-二甲基-1-丁烯的合成工艺研究

以叔丁醇为原料,优化了其与浓盐酸氯代合成叔丁基氯的反应,采用CaCl₂ 氯化盐助催化体系使反应收率提高到95%,产品质量分数为99%;3,3-二甲基-1-丁烯合成的关键步骤是叔丁基氯与乙烯反应制备3,3-二甲基-1-氯丁烷,探讨了催化剂用量、反应温度对反应收率的影响.反应以无水三氯化铝为催化剂,用量为n(AlCl₃):n[(CH₃)₃CCl]=0.018:1,反应温度为-17~-20 ℃时,产物3,3-二甲基-1-氯丁烷的收率可达80%;最后由3,3-二甲基-1-氯丁烷脱氯化氢制备3,3-二甲基-1-丁烯.考察了不同溶剂对反应收率的影响,以聚乙二醇-400为溶剂,无需加入相转移催化剂,收率可达88.5%,3,3-二甲基-1-丁烯的质量分数为可达95%以上.     

AlCl3-季戊四醇络合催化剂催化１-辛烯齐聚工艺

聚α-烯烃是高品质的润滑油基础油。使用AlCl₃-季戊四醇络合催化剂,对1-辛烯齐聚反应进行研究,考察催化剂物质的量分数、季戊四醇与A1Cl₃物质的量比、反应温度和反应时间对聚烯烃收率及不同聚合物选择性的影响。结果表明,1-辛烯齐聚合成聚α-烯烃最佳工艺条件：AlCl3物质的量分数为2％,季戊四醇与AlCl₃物质的量比为0.5,反应温度为50 ℃,反应时间为4 h,聚烯烃收率约为93.4％,合成的聚α-烯烃产品中润滑油的理想组分三聚体和四聚体选择性较好。     

精细化工与催化 阳离子交换树脂改性及其在乙醇酸甲酯水解制备乙醇酸反应中的应用

采用AlCl₃和SnCl₄对苯乙烯系强酸性阳离子交换树脂进行改性,考察树脂改性条件对乙醇酸甲酯水解制备乙醇酸反应的影响,并优化水解工艺条件。结果表明,最佳树脂改性条件为:采用AlCl₃-SnCl₄等物质的量混合物联合改性,其添加量为树脂质量的8%~10%,改性水浴温度(70~75) ℃,改性时间(8~10) h;优化的乙醇酸甲酯水解制备乙醇酸的工艺条件为:空速(3~6) h^-1,水解温度(75~85) ℃,去离子水与乙醇酸甲酯物质的量比(10~20)∶1。经过300 h的稳定性实验表明,树脂改性后稳定性良好。     

氯化铝-助催化剂体系催化葡萄糖转化制备5-羟甲基糠醛

以Al Cl3作催化剂,研究助催化剂类型和用量对葡萄糖转化生成5-羟甲基糠醛收率的影响。对溶剂类型、反应温度和反应时间进行优化,得出最佳反应条件为:葡萄糖用量为1 g,Al Cl3用量为反应物物质的量的10%,助催化剂NH4Br用量为0.32 mol·L-1,二甲基乙酰胺作溶剂,用量为10 m L,反应温度100℃,反应时间60 min,此条件下,5-羟甲基糠醛收率为47%,比采用单一Al Cl3作催化剂提高14个百分点。     

氯化铝催化葡萄糖制备5-羟甲基糠醛——助催化剂的作用

研究双助催化剂对AlCl₃催化葡萄糖转化制备5-羟甲基糠醛的促进作用,考察助催化剂种类和用量对反应的影响,并优化反应条件。结果表明,NH₄Br-NaBr双助催化剂体系对该反应的促进作用最显著,助催化剂NH₄Br用量为0.08 mol·L^-1和NaBr用量为0.32 mol·L^-1时,100 ℃反应60 min,5-羟甲基糠醛收率为54%,比单一AlCl₃作催化剂时提高21个百分点。     

二次水热合成法制备ZSM-5分子筛膜及其渗透汽化性能

采用二次水热合成法在管状多孔莫来石支撑体上制备高耐酸性ZSM-5分子筛膜,系统地研究分子筛晶种和合成溶胶中H₂O/SiO₂摩尔比率对ZSM-5分子筛膜生长与渗透汽化性能的影响,采用X射线衍射、冷场扫描电子显微镜和电子能谱等表征技术分别对制备的ZSM-5分子筛及其ZSM-5分子筛膜的结构、形貌和Si/Al比进行表征。针对分离75℃、90% HAc/H₂O的水溶液,最优化条件下制备的ZSM-5分子筛膜表现出优良的渗透汽化性能,渗透通量和分离因子分别为0.98kg/(m²·h)和890。此外,本研究所采用制备耐酸性ZSM-5分子筛膜的方法表现出良好的重现性,重复制备的12根ZSM-5分子筛膜在75℃下分离90% HAc/H₂O的水溶液时,平均通量和分离系数分别为（0.85±0.15）kg/(m²·h)和650±290。再者,ZSM-5分子筛膜在45～75℃的温度范围内分离50%～95% HAc/H₂O水溶液时都表现出优良的渗透汽化性能。     

Isomerization of n-pentane catalyzed by amide-AlCl3-based ionic liquid analogs with various additives

The isomerization of n-pentane to generate high-quality blending components for clean gasoline was catalyzed by several amide-AlCl_3-based ionic liquid(IL) analogs with various amides as donor molecules. The catalytic performance of these IL analogs was evaluated in a magnetic agitated autoclave operated in batch mode.IL analog based n-methylacetamide(NMA)-AlCl_3 with the amide/AlCl_3 molar ratio of 0.65 showed excellent performance toward n-pentane isomerization because 0.65 NMA-1.0 AlCl_3 had a low viscosity and bidentate coordination structure. The influences of reaction time, reaction temperature, and stirring speed on the catalytic performance were also investigated. Optimal reaction conditions comprised the reaction time of 1 h, the reaction temperature of 40 °C, and the stirring speed of 1500 r·min~(-1). Under optimal condition, the n-C5 conversion,research octane number(RON) increment, total liquids yield, and isoparaffin yield in isomerized oil were56.80%, 13.51, 89.90 wt%, and 44.32 wt%, respectively. A new mathematical model was constructed to predict the relationships among RON increment, RON increment/n-C5 conversion ratio, and n-C5 conversion. The new model indicated that an appropriate conversion per pass of n-C5 did not exceed 50%–55%. Various cycloparaffin additives were used to improve the catalytic performance of 0.65 NMA-1.0 AlCl_3. The n-C5 conversion increased from 56.80% to 67.32%. The RON increment, total liquids yield, and isoparaffin yield reached 17.83, 97.36 wt%,and 63.74 wt%, respectively.     

Simultaneous utilization of electro-generated O2 and H2 for H2O2 production: An upgrade of the Pd-catalytic electro-Fenton process for pollutants degradation

The Electro-Fenton (EF) process is one of the promising advanced oxidation processes (AOPs) for environmental remediation. The H₂O₂ yield of EF process largely determines its performance on organic pollutants degradation. Conventional Pd-catalytic EF process generates H₂O₂ via the combination reaction of anodic O₂ and cathodic H₂. However, the relatively expensive catalyst limits its application. Herein, a hybrid Pd/activated carbon (Pd/AC)-stainless steel mesh (SS) cathode (PACSS) was proposed, which enables more efficient H₂O₂ generation. It utilizes AC, the support of Pd catalyst, as part of cathode for H₂O₂ generation via 2-electron anodic O₂ reduction, and SS serve as a current distributor. Moreover, H₂O₂ could be catalytically decomposed upon AC to generate highly reactive ·OH, which avoids the use of Fe²⁺. Compared with conventional Pd catalyst, H₂O₂ concentration obtained by PACSS cathode is 248.2% higher, the O₂ utilization efficiency was also increased from 3.2% to 10.8%. Within 50 min, 26.3%, 72.5%, and 94.0% H₂O₂ was decomposed by Pd, AC, and Pd/AC. Fluorescence detection results implied that Pd/AC is effective upon H₂O₂ activation for OH generation. Finally, iron-free EF process enabled by PACSS cathode was examined to be effective for reactive blue 19 (RB19) degradation. After continuous running for 10 cycles (500 min), the PACSS cathode was still stable for H₂O₂ generation, H₂O₂ activation, and RB19 degradation, showing its potential application for organic pollutants degradation without increase in the running cost.     

[Bmim]Cl中CrCl3-AlCl3催化纤维素降解制取5-羟甲基糠醛

5-羟甲基糠醛是一种具有很高利用价值的化学平台化合物。以离子液体1-丁基-3-甲基咪唑氯盐（[Bmim]Cl）为溶剂,以CrCl₃和AlCl₃为复合催化剂,在油浴加热条件下催化纤维素降解制取5-羟甲基糠醛,研究了催化剂种类、催化剂量、温度、纤维素浓度、气氛、纤维素聚合度、反应规模等不同因素对纤维素降解制取5-羟甲基糠醛的影响。结果表明,[Bmim]Cl用量为10 g,棉花添加量为0.5 g,x（CrCl₃）=25%（mol）,x（AlCl₃）=2.5%（mol）,反应温度为120℃,反应气氛为N₂（dry）气氛,反应时间为4 h时,HMF产率最高,达到59%。此外,反应过程中水的作用机理也被给予了相应解释。     

Influence of temperature and Ca(OH)2 on releasing tar and coal gas during lignite coal pyrolysis and char gasification

The yield of tar and syngas has been investigated by catalytic pyrolysis of Pingzhuang lignite (PZL) over Ca(OH)₂ catalyst in temperature range of 600℃-1000℃ in a tube furnace. The results show that the yield of volatile pyrolysis increases and char decreases with rising temperature for both raw and catalyzed Pingzhuang lignite. The hydrogen fraction (H₂) increased from 20% to 40% for the PZL sample; but, for the PZL-Ca(OH)₂ sample, H₂ fraction fluctuated randomly between 35% to 42%, with the maximum H₂ fraction found at 1000℃. The Gaschromatography mass-spectroscopic (GC-MS) analysis revealed that the maximum tar yield at 800℃ and 700℃ was obtained for PZL and PZL-Ca(OH)₂, respectively. The surface morphology of PZL and PZL-Ca(OH)₂ chars underwent different transformation in the presence of catalyst as illustrated by SEM/EDX, FTIR, and BET analysis. Furthermore, char sample was investigated for the carbon conversion and reactivity index using TGA analysis under N₂ and CO atmosphere.     

无机相变材料CaCl2·6H2O的过冷特性

CaCl₂·6H₂O作为一种常见的常温无机水合盐相变材料,由于成本低、易获取、蓄热强而受到广泛的关注。按无水CaCl₂与H₂O的质量比为1.027：1制备了CaCl₂·6H₂O,经X射线衍射（XRD）表征其晶体结构;通过添加成核剂SrCl2·6H₂O和Ba（OH）₂对CaCl₂·6H₂O改性,发现两者的联合作用可抑制过冷,10次熔化-冷却循环平均过冷度1.07℃。采用差示扫描量热仪（DSC）测定CaCl₂·6H₂O添加成核剂前后相变潜热,发现潜热由223.54 J·g^-1降至160.41 J·g^-1;为了扩大CaCl₂·6H₂O相变温度的范围,通过添加质量分数分别为5%、10%、15%、20%和25%的MgCl₂·6H₂O,发现相变温度随MgCl₂·6H₂O质量分数的升高呈线性降低,但不宜超过20%;选取CaCl₂·6H₂O-20% MgCl₂·6H₂O二元共晶盐相变储热体系为改性目标,通过添加1% SrCl2·6H₂O和0.5% CMC,过冷度降至0.57℃,相变潜热为141.09 J·g^-1,低于单独组成盐CaCl₂·6H₂O的潜热223.54 J·g^-1和MgCl₂·6H₂O的潜热163.35 J·g^-1。研究表明,CaCl₂·6H₂O作为无机相变材料具有显著的应用价值。     

ZrOCl2催化琼脂糖制备5-羟甲基糠醛和乙酰丙酸

以琼脂糖为原料,分别采用CuCl₂、NiCl₂、MnCl₂、MgCl₂、FeCl₃、AlCl₃、ZrOCl₂、SnCl₄为催化剂催化转化制备5-羟甲基糠醛（5-HMF）和乙酰丙酸（LA）,筛选适用于琼脂糖转化的优选催化剂,并对制备条件如溶剂含水量、催化剂用量、反应温度以及反应时间等影响因素进行了考察。研究结果表明：以50mg琼脂糖为原料,ZrOCl₂为催化剂,二甲基亚砜（DMSO）为反应溶剂,在1 mL DMSO/H₂O（体积比为8:2）混合溶剂中,ZrOCl₂用量为琼脂糖中单糖物质的量的10%,140℃下反应60 min,5-羟甲基糠醛（5-HMF）的得率为26.9%,乙酰丙酸（LA）的得率为24.7%。对制备机理分析表明：反应过程中琼脂糖首先水解为醛型单糖,然后在催化剂作用下醛型单糖异构化再脱水转化为5-HMF,部分5-HMF在酸的作用下进一步转化为LA。     

Effects of additive NaI on electrodeposition of Al coatings in AlCl3-NaCl-KCl molten salts

Effects of NaI as an additive on electrodeposition of Al coatings in AlCl₃-NaCl-KCl(80-10-10 wt-%)molten salts electrolyte at 150°C were investigated by means of cyclic voltammetry,chronopotentiometry,scanning electron microscopy and X-ray diffraction(XRD).Results reveal that addition of NaI in the electrolyte intensifies cathodic polarization,inhibits growth of Al deposits and increases number density of charged particles.The electrodeposition of Al coatings in the AlCl₃-NaCl-KCl molten salts electrolyte proceeds via three-dimensional instantaneous nucleation which however exhibits irrelevance with NaI.Galvanostatic deposition results indicate that NaI could facilitate the formation of uniform Al deposits.A compact coating consisting of Al deposits with an average particle size of 3μm was obtained at a current density of 50 mA?cm^?2 in AlCl₃-NaCl-KCl molten salts electrolyte with 10 wt-%NaI.XRD analysis confirmed that NaI could contribute to the formation of Al coating with a preferred crystallographic orientation along(220)plane.