邻苯二酚与甲醇合成愈创木酚的热力学分析

邻苯二酚与甲醇气相单醚化合成愈创木酚因经济、环保、原料廉价易得、可实现连续化生产等优点而备受关注。为了有效利用资源,对该反应过程进行了较为详细的热力学分析。根据邻苯二酚(catechol)、甲醇、愈创木酚(guaiacol)及水的标准摩尔生成焓Δ_fH^θ_m、标准熵变ΔS^θ_m和热熔C_p,m等热力学数据,讨论了温度对邻苯二酚与甲醇气相合成愈创木酚反应的焓变Δ_rH_m、自由能变Δ_rG_m及平衡常数K的影响。结果表明,在400～800 K温度范围内,该反应是一个放热自发反应,可在较低温度下顺利进行,有较大反应平衡常数。因此,该反应的研究关键主要是较低温度下高活性催化剂的研发和最适宜反应条件的选择。     

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。     

-15℃下Na+, K+, Mg2+// Cl-, SO4-2-H2O体系相平衡

采用等温溶解平衡法,研究了Na⁺, K⁺, Mg²⁺//Cl^-, SO₄^-2-H₂O, 五元水盐体系在-15℃下NaCl·2H₂O饱和时的相平衡关系,测定了溶解度和密度,并绘制出相应的相图。研究结果表明:该五元体系平衡相图中有3个四盐共饱点,7条单变量溶解度曲线及5个两盐结晶区,5个两盐结晶区分别对应于KCl+NaCl·2H₂O、Na₂SO₄·10H₂O+ NaCl·2H₂O、MgSO₄·7H₂O+NaCl·2H₂O、MgCl₂·8H₂O+NaCl·2H₂O、KCl·MgCl₂·6H₂O+ NaCl·2H₂O;所 得-15℃相图和25℃下相图相比,相图结构大为简化:K₂SO₄·MgSO₄·4H₂O、KCl·MgSO₄·3H₂O、Na₂SO₄·3K₂SO₄、Na₂SO₄·MgSO₄·4H₂O、MgSO₄·(4～6)H₂O、K₂SO₄·MgSO₄·6H₂O结晶区均消失,Na₂SO₄结晶区转变为Na₂SO₄·10H₂O且结晶区扩大,KCl、MgSO₄·7H₂O、KCl·MgCl₂·6H₂O结晶区缩小,MgCl₂·6H₂O结晶区转变为MgCl₂·8H₂O。在此基础上研究了不同组成的盐湖卤水在降温过程中的结晶规律,为低温盐田工艺的开发提供了理论依据。     

298 K四元体系LiCl-MgCl2-CaCl2-H2O相平衡实验及溶解度计算

采用等温溶解平衡法测定了四元体系LiCl-MgCl₂-CaCl₂-H₂O在298 K下的溶解度,由此绘制了相应的相图和水含量图。实验结果表明,该体系在298 K时有三种复盐生成,无固溶体生成。其相图中含有五个共饱点,十一条单变量曲线以及七个平衡固相结晶区,分别为四个单盐结晶区（CaCl₂·6H₂O、CaCl₂·4H₂O、MgCl₂·6H₂O和LiCl·H₂O）以及三个复盐结晶区（LiCl·MgCl₂·7H₂O、LiCl·CaCl₂·5H₂O和2MgCl₂·CaCl₂·12H₂O）。运用Pitzer模型,采用文献中报道的参数对该四元体系进行了298 K条件下的溶解度计算。对比发现,计算结果与实验数据基本吻合。     

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。     

四元体系LiCl-LiBO2-Li2SO4-H2O在298.15K时的相平衡

采用等温溶解平衡法开展了四元体系LiCl-LiBO₂-Li₂SO₄-H₂O在298.15 K时相平衡实验研究,测定体系溶解度和平衡溶液的折光率、密度、pH和电导率。根据实验数据,分别绘制该四元体系的干基图、水图以及相对应的物化性质-组成图。研究结果表明:在该四元体系298.15 K相图中,有2个无变度共饱点分别为相称共饱点(Li₂SO₄·H₂O + LiCl·H₂O + LiBO₂·2H₂O)和不相称共饱点(Li₂SO₄·H₂O + LiBO₂·2H₂O + LiBO₂·8H₂O)、5条溶解度曲线和4个单盐结晶相区(Li₂SO₄·H₂O、LiCl·H₂O、LiBO₂·8H₂O和LiBO₂·2H₂O),无复盐和固溶体产生,属于简单四元体系水合物Ⅱ型相图。实验研究中,发现2种偏硼酸锂水合矿物存在(LiBO₂·8H₂O和LiBO₂·2H₂O),LiCl对Li₂SO₄的盐析效应显著;四元体系平衡溶液物化性质随着溶液中氯化锂浓度的变化呈现规律性的变化。     

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。     

碳酸氢钠调控五水碳酸镁的合成

在NaHCO₃调控作用下, 通过MgCl₂和Na₂CO₃反应结晶合成了五水碳酸镁(MgCO₃·5H₂O)。利用SEM、XRD和TG等技术, 结合反应结晶过程中镁离子浓度变化, 研究了工艺参数对结晶过程和产物影响。实验结果表明, 合成五水碳酸镁过程中极易生成MgCO₃·3H₂O副产物。纯MgCO₃·5H₂O制备工艺条件为:NaHCO₃加入量≥3.00 g·L^-1, 碳酸钠加料速率2～50 ml·min^-1, 合成温度0～5.0℃。所合成的五水碳酸镁呈棱柱状形貌, 晶体表面光滑, 尺寸20～160 μm。分析表明, 添加碳酸氢钠促进了结晶动力学, 同时 基团对三水碳酸镁晶体的形成具有位阻效应, 但有利于五水碳酸镁晶体形成, 产生晶型调控的协同效果。工艺参数的改变将使得结晶过程发生热力学和动力学控制的转换, 影响结晶产物的晶型晶貌。     

粉煤灰浓硫酸焙烧过程及其非等温动力学

粉煤灰浓硫酸焙烧法提取Al₂O₃工艺中焙烧过程十分重要,研究发现适当提升硫酸浓度、酸灰质量比和温度可增大Al转化率,而延长焙烧时间影响并不显著;在硫酸浓度80%、酸灰质量比1.5:1、温度270℃和时间60 min条件下,Al转化率可达92 %～95%。TG/DSC与XRD分析表明,焙烧过程反应主要分为3个阶段:80～206℃时形成中间产物Al(HSO₄)₃及H₂O气化;206～241℃时生成Al(HSO₄)₃及Al₂(SO₄)₃·H₂O;241～304℃时由Al₂(SO₄)₃·H₂O和Al(HSO₄)₃二者分解转化成Al₂(SO₄)₃。由Kissinger微分法与Ozawa积分法分别计算出3个阶段表观活化能后取二者平均值,分别为52.61、74.11、96.08 kJ·mol^-1,并获得频率因子、反应级数和动力学方程,所获结果可为粉煤灰硫酸焙烧法提取Al₂O₃焙烧工艺设计和过程优化提供理论参考和基础数据。     

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。     

Hydrothermal mass production of MgBO2(OH) nanowhiskers and subsequent thermal conversion to Mg2B2O5 nanorods for biaxially oriented polypropylene resins reinforcement

Mass production of one-dimensional (1D) nanomaterials has emerged as one of the most significant challenges in powder technology. In this contribution, MgBO₂(OH) nanowhiskers were hydrothermally produced at a kilogram scale in a 150 L stainless steel autoclave at 200 °C for 12.0 h by using MgCl₂·6H₂O, H₃BO₃ and NaOH as the raw materials. The subsequent thermal conversion of the MgBO₂(OH) nanowhiskers at 700 °C for 6 h led to 3.75 kg of high crystallinity monoclinic Mg₂B₂O₅ nanorods, with a length of 0.47-1.3 µm, a diameter of 55-160 nm, and an aspect ratio of 3-15. After the nanorods have been surface modified with the silane coupling agent KH-550, the reinforcing and toughening effects of the Mg₂B₂O₅ nanorods on the biaxially oriented polypropylene resins (BOPP-D1) were evaluated. The filling of the Mg₂B₂O₅ nanorods into the resins resulted in the increase in the tensile strength, the impact strength, and the melt flow index of the BOPP-D1 composites. The appropriate ratio of coupling agent to fillers (Mg₂B₂O₅ nanorods) and the ratio of fillers to resins were determined within the range of 0.6-1.2 wt.% and 8-15 wt.%, respectively. The optimal ratio of fillers to resins was ca. 10 wt.%. The present mass production of MgBO₂(OH) nanowhiskers and Mg₂B₂O₅ nanorods is believed to be helpful for enlarging and propelling the applications of the 1D magnesium borate nanostructures in the near future.     

Hydrothermal Formation of the Head-to-Head Coalesced Szaibelyite MgBO2(OH) Nanowires

The significant effect of the feeding mode on the morphology and size distribution of the hydrothermal synthesized MgBO₂(OH) is investigated, which indicates that, slow dropping rate (0.5 drop s⁻¹) and small droplet size (0.02 mL d⁻¹) of the dropwise added NaOH solution are favorable for promoting the one-dimensional (1D) preferential growth and thus enlarging the aspect ratio of the 1D MgBO₂(OH) nanostructures. The joint effect of the low concentration of the reactants and feeding mode on the hydrothermal product results in the head-to-head coalesced MgBO₂(OH) nanowires with a length of 0.5–9.0 μm, a diameter of 20–70 nm, and an aspect ratio of 20–300 in absence of any capping reagents/surfactants or seeds.     

溶胶-凝胶法低温合成亚微米α-Al_2O_3的制备与表征

以硝酸铝、硝酸铜、钛酸丁酯为原料,采用溶胶-凝胶法低温合成亚微米氧化铝粉体,并对不同温度煅烧后粉体的物相与形貌进行表征。通过在硝酸铝的无水乙醇溶胶中引入少量CuO-TiO2氧化物助剂前驱体,在80℃水浴中长时间静置后获得浅蓝色凝胶,在不同温度下煅烧该凝胶,结果发现:煅烧温度低于950℃时,所获得的粉体主要为无定形态,仅含有少量的γ-Al2O3;将凝胶在1000℃煅烧2h后,全部变成粒径在80～100nm之间、粉体颗粒呈球形的α-Al2O3;当煅烧温度升高到1050℃时,α-Al2O3的颗粒直径长大到200～400nm。CuO-TiO2氧化物助剂前驱体的引入,不但降低了α-Al2O3的晶相合成温度,同时促进了α-Al2O3粉体颗粒的生长。     

Hydrotalcite synthesis via co-precipitation reactions using MgO and Al(OH)3 precursors

Hydrotalcite (Mg₆Al₂(OH)₁₆(CO₃)·4H₂O), also known as aluminum-magnesium layered double hydroxide (LDH) or anionic clay, is a synthetic compound that was broadly investigated in the past decade due to its many potential applications, such as clinic anti-acid, catalyst support, adsorptive flotation, flame retardant, acid scavengers in polymer composites and as a raw material for high temperature insulating porous ceramics. This compound is usually produced by controlled chemical equilibrium shifting processes (such as co-precipitation) that requires various other purification steps (centrifugation, for example) and careful drying (freeze drying or ultrafiltration). In this paper, a novel route to synthesize hydrotalcite is presented, based on the hydration, dissolution and co-precipitation reactions carried out almost simultaneously in aqueous suspension containing reactive magnesium oxide and aluminum hydroxide. Compared to other methods (the regular co-precipitation, particularly), it presents various technological advantages such as low time-energy consumption, no further purification step requirement, high output and competitive production costs.     

A new approach to the synthesis of nanosized powder CaO and its application as precursor for the synthesis of calcium borates

A procedure for the synthesis of calcium oxide has been developed, which consists in heat treatment of an aqueous solution of calcium acetate and d-glucose at 350 and then at 700 °C. The process parameters have been determined. It has been shown that when d-glucose is used and the reaction mixture is heat treated at 700 °C, highly dispersed calcium oxide with an average particle size of 77 nm is formed. CaO formed has been used as a precursor for the synthesis of priceite (Ca₂(B₅O₇)(OH)₅ · H₂O) during hydrothermal treatment of CaO in an aqueous solution of boric acid. It has been found that the optimal conditions for the synthesis of monophase priceite under hydrothermal conditions include the temperature range of 170–200 °C and the heating time of 12 h. When heating priceite at 800 °C in air for 1 h, highly dispersed powder calcium bis(borate) Ca(BO₂)₂ has been isolated as the final product. It is shown that the use of synthesized powder CaO leads to the formation of fine-crystalline powders of calcium borates. Samples obtained at each stage of the proposed synthesis of highly dispersed calcium oxide and calcium borates, using the example of priceite and calcium bis(borate), have been studied by powder X-ray diffraction, SEM, TEM, BET, IR spectroscopy, and DTA.     

Structure,stability and permeation properties of NaA zeolite membranes for H2O/H2 and CH3OH/H2 separations

NaA zeolite membranes were synthesised in the secondary growth hydrothermal method based on the seeding of the inner surface of a ceramic α-alumina tube. The impacts of crystallisation time and zeolite precursor concentration (in H₂O) were investigated. The structure and stability of the prepared NaA zeolite membranes were also investigated with operating temperatures, times and pressures. The results indicate that the optimal synthesis gel molar composition was 3Na₂O: 2SiO₂: Al₂O₃: 200H₂O. This led to cubic-shaped NaA zeolite which showed good stability. The optimal NaA zeolite membrane had H₂O and CH₃OH fluxes of 2.77 and 0.19 kg/m²h, with H₂O/H₂ and CH₃OH/H₂ separation factors of ∞ and 0.09 at a temperature of 30 °C. The NaA zeolite membrane had high thermal stability, but poor separation performance at high temperature (240 °C). The results suggested that the H₂ permeation flux is significantly influenced by preferential adsorption of vapour in the NaA zeolite membrane.     

Glycothermal process for barium magnesium tantalate nanopowders synthesis

Barium magnesium tantalate Ba(Mg_1/3Ta_2/3)O₃ (BMT) nanopowders were synthesized at a low temperature of 220 °C through glycothermal reaction by using Ba(OH)₂·8H₂O, Mg(NO₃)·6H₂O, and TaCl₅ as precursors and 1,4-butanediol as solvent. It is demonstrated that higher synthesis temperatures and co-precipitation of magnesium and tantalum improve the incorporation of magnesium into BMT nanopowders under glycothermal treatment and produce a homogeneous, stoichiometric powder. The glycothermally derived BMT nanopowders are very reactive and provide a high-density sintered body with 97.1% of theoretical density at a low temperature of 1350 °C. The average grain size of the sintered ceramics was 1.2 ± 0.2 μm and relatively uniform in comparison with the ceramics sintered with powders produced from the conventional method.     

New sulfur adsorbents derived from layered double hydroxides: II. DRIFTS study of COS and H2S adsorption

H₂S and COS adsorption were studied on two calcined layered double hydroxides (LDHs), Mg_0.75Al_0.25(OH)₂(CO₃)_0.125 and Mg_0.65Al_0.35(OH)₂(CO₃)_0.175, using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and a chemisorption apparatus. Both demonstrated the ability to irreversibly adsorb H₂S, corresponding to uptakes of 1.54 and 1.76 μmol/m², respectively, but Mg_0.75Al_0.25 had a significantly larger capacity for COS, 1.62 μmol/m² compared to 0.80 μmol/m² for Mg_0.65Al_0.35. Analysis of the DRIFT spectra suggests the adsorption of H₂S proceeds via the substitution of lattice oxygen with sulfur, resulting in the formation of H₂O on the surface. COS adsorption is more complicated, although it appears that a similar substitution of lattice oxygen with sulfur occurs. This results in the formation of CO₂ and subsequently bicarbonates and carbonates. The formation of hydrogen thiocarbonate is also involved, although this form is generally only observed in the later stages of adsorption and appears to form at the expense of bicarbonate. The Mg_0.75Al_0.25 LDH retained its ability to adsorb COS in the presence of propene.     

Controllable Synthesis of Magnesium Oxysulfate Nanowires with Different Morphologies

One-dimensional magnesium oxysulfate 5Mg(OH)₂ · MgSO₄ · 3H₂O (abbreviated as 513MOS) with high aspect ratio has attracted much attention because of its distinctive properties from those of the conventional bulk materials. 513MOS nanowires with different morphologies were formed by varying the mixing ways of MgSO₄ · 7H₂O and NH₄OH solutions at room temperature followed by hydrothermal treatment of the slurries at 150 °C for 12 h with or without EDTA. 513MOS nanowires with a length of 20–60 μm and a diameter of 60–300 nm were prepared in the case of double injection (adding MgSO₄ · 7H₂O and NH₄OH solutions simultaneously into water), compared with the 513MOS with a length of 20–30 μm and a diameter of 0.3–1.7 μm in the case of the single injection (adding MgSO₄ · 7H₂O solution into NH₄OH solution). The presence of minor amount of EDTA in the single injection method led to the formation of 513MOS nanowires with a length of 100–200 μm, a diameter of 80–200 nm, and an aspect ratio of up to 1000. The analysis of the experimental results indicated that the hydrothermal solutions with a lower supersaturation were favorable for the preferential growth of 513MOS nanowires along b axis.     

Efficient synthesis of orthorhombic lithium borate hydroxide micro-rods and their thermal conversion to lithium borate

Uniform orthorhombic Li₃B₅O₈(OH)₂ micro-rods were hydrothermally synthesized at 150-210 °C for 6.0-24.0 h, using LiOH·H₂O and H₃BO₃ as the reactants. The resulting Li₃B₅O₈(OH)₂ micro-rods had a length of 20-60 μm, an aspect ratio of 6-14, and a high crystallinity. The presence of hexadecyl trimethyl ammonium bromide was favorable for the oriented growth of the Li₃B₅O₈(OH)₂ micro-rods. The orthorhombic Li₃B₅O₈(OH)₂ was decomposed into Li₂B₄O₇ and α-LiBO₂. Pore-free high crystallinity Li₂B₄O₇ with quasi polyhedron morphology can be obtained by NaCl assisted calcination. This enlarged the controllable synthesis of the alkali borates, especially enriched the study on the lithium borates which can be potentially used as a perspective superionic conductor and electrode of lithium ion batteries.