Synthesis of Hydrotalcite-like Compound Pillared by Hetero-polyacid Anions in a Hydrothermal System

Hetero-polyacid anions (PW12O403-)-pillared hydrotalcite-like compound is directly and hydrothermally synthesized by the hot solution method. FTIR and XRD show that PW12O403- has been incorporated into the interstitial space with the dimension of 0.917 nm. The state of PW12O403- anion between the hydrotalcite sheets was also discussed. The title product can be expressed by formula [Zn0.68Al0.32(OH)2]×[PW12O40] 0.11×3H2O after a serious study of TGA and chemical analysis.     

超顺磁负载型催化剂 H3PW12O40/γ-Fe2O3催化噻吩和烯烃的烷基化反应简

The alkylation of sulfur compounds with olefine is considered to be an attractive way to attain high level of sulfur removal by raising the boiling point of sulfur-containing compounds to ease their separation from lighl fractions by distillation. A series of superparamagnetic supported catalysts, used for alkylation of thiophene with 1-octene, were prepared by loading H3PW12040 （HPW） onto commercially available nanoparticles γ-Fe2O3 through incipient wet impregnation method. The catalysts were characterized by X-ray diffraction （XRD）, Fourier transform infra-red （FT-IR）, thermo gravimetric analysis （TG）, N2-adsorption and vibrating sample magnetometer （VSM）. The physicochemical characterization reveals that 7-Fe203 could be accommodated to immobilize and disperse HPW. Moreover, possessing high magnetization of 26.1 A.mZ.kg-1 and with mesoporous structure with specific surface area of 35.9 m2·g^-1, the 40% （by mass） HPW loading catalyst is considered the proper catalyst for olefinic alkylation of thiophenic sulfur （OATS） and can be separated in an external magnetic field. The catalytic activity was investigated in the alkylation reaction of thiophene with 1-octene, and the conversion of thiophene is up to 46% at 160 ℃ in 3 h. The 40% （by mass） H3PW12O40/γ-Fe2O3 catalyst can be reused 6 times without too much loss of activit and keeps its property of superparamagnetism.     

Span 80-Tween 80/液体石蜡/AM-H2O反相微乳液体系

The reverse microemulsion system of Span 80-Tween 80/liquid paraffin/acrylamide-H2O was prepared, and the effects of n-butanol, NaC1, NaAc were studied with the conductivity method. The stability of reverse microemulsion was reflected, and the information of its dynamic process was obtained by measuring its state changes continuously through testing its electronic conductivity by using electrochemistry. The results showed that the Span 80-Tween 80/liquid paraffin/acrylamide-H2O system was most stable when the HLB value approached 7.5, and its stability was enhanced when 5.0% (mass) NaCl or 10% (mass) NaAc was added into this systerm.     

Preparation and Anti-coking Property of SiO2/S Coating on HP40 Tube

SiO2/S coating was prepared on the inner surface of an HP40 tube using dimethyldisulfide and tetraethylorthosilicate by atmospheric pressure chemical vapor deposition (APCVD) to alleviate catalytic coking on the inner surface of radiant tube for ethylene production in petrochemical plants. The comparative coking experiments with the coated and uncoated HP40 tubes were carried out under the same cracking conditions. SiO2/S coating was compact and had excellent anti-coking property. The coke on the coated HP40 tube was about 22% of that on the uncoated HP40 tube, and only small granular coke was deposited on the coated HP40 tube. However, the filamentous coke formed on the uncoated HP40 tube. The thermal stability of SiO2/S coating was satisfactory at cracking temperature, and the anti-coking property of SiO2/S coating was still over 60% after 3 coking and decoking cycles.     

WP/γ-Al2O3催化剂的制备、表征及加氢脱硫和加氢脱氮活性

Two series of WP/Al2O3 catalyst precursors with WP mass loading in the range 18.5%-37.1% were prepared using the impregnation method and mixing method, respectively, and the catalysts were then obtained by temperature-programmed reduction of supported tungsten phosphate (precursor of WP/Al2O3 catatlysts) in H2 at 650℃ for 4h. The catalysts were characterized by XRD, BET, TG/DTA, XPS and 31p MAS-NMR. The activities of these catalysts were tested in the hydrodenitrogenation (HDN) of pyridine and hydrodesulfurization (HDS) of thiophene at 340℃ and 3.0MPa. The results showed that owing to the stronger interaction of the support with the active species, the precursor of WP/Al2O3 catalyst was more difficultly phosphided and a greater amount of W species was in a high valence state W6 on the surface of the catalyst prepared by the impregnation method than that by the mixing method. 31p MAS-NMR results indicated that 31p shift from 85% H3PO4 of 2.55 × 10-4 for WP and 2.57 × 10-4 for WP/γ-Al2O3 catalysts prepared by mixing method. Such WP/Al2O3 catalysts showed higher HDN activities and lower HDS activities than those prepared by the impregnation method under the same loading of WP.WP/γ-Al2O3 catalysts with weak interaction between support and active species were favorable for HDN reaction while the WP/γ-Al2O3 catalysts with strong interaction were favorable for HDS reaction.     

CaCl2-LiBr-LiNO3-KNO3/H2O工质对的热物性和腐蚀性

The new working pair of CaCl2?LiBr?LiNO3?KNO3 (mass ratio 16.2:2:2:1)/H2O was systematically evaluated in terms of the crystallization temperature and the saturated vapor pressure. The corrosion rates of the carbon steel, 316L stainless steel and copper in CaCl2?LiBr?LiNO3?KNO3/H2O were measured with a weight loss method. The results showed that under the same refrigeration conditions, the temperature required for collecting solar energy or the generation temperature of CaCl2?LiBr?LiNO3? KNO3/H2O for a single-stage absorption refrigeration cycle decreases by 6.2℃ comparing with LiBr/H2O. The corrosion rates of 316L and copper are low enough for practical applications.     

钨取代磷钼杂多酸的制备、表征以及催化1,4-丁二醇环化脱水制备四氢呋喃

A series of tungsten-substituted molybdophosphoric acids (H3PMo12-nWnO40•xH2O) were synthesized and characterized by inductive coupled plasma atomic emission spectroscopy (ICPAES), thermal gravimetry and differential scanning calorimetry (TG-DSC), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and FTIR pyridine adsorption. The as-prepared heteropoly acids have a Keggin type structure. The synthe-sis of tetrahydrofuran by reactive distillation and cyclodehydration of 1,4-butanediol was studied using the tungsten- substituted molybdophosphoric acids as catalysts. The results of catalytic test indicated that the catalytic activity in-creased with the increase in the substitution number (n) of tungsten atom in H3PMo12-nWnO40•xH2O and was con-stant as the substitution number (n) was more than 8. The catalytic activity increased with the increase in the cata-lyst loading and the selectivity of tetrahydrofuran was nearly 100%.     

硅胶负载磷钨酸铯盐(Cs2.5H0.5PW12O40)催化合成2-乙酰噻吩的研究

采用二步浸渍法制备硅胶负载磷钨酸铯(Cs2.5H0.5PW12O40)催化剂催化合成药物中间体2-乙酰噻吩.运用IR和XRD测试技术进了Cs2.5H0.5PW12O40/SiO2催化剂的表征,考察了Cs2.5H0.5PW12O40负载量、催化剂用量、物料配比、反应温度、反应时间等对2-乙酰噻吩合成收率和选择性的影响.实验结果表明,Cs2.5H0.5PW12O40和Cs2.5H0.5PW12O40/SiO2催化剂保持H3PW12O40的Keggin结构不变,且Cs2.5H0.5PW12O40/SiO2催化剂中Cs2.5H0.5PW12O40主要聚集在SiO2载体表面.优化合成2-乙酰噻吩的工艺条件为:30%Cs2.5H0.5PW12O40/SiO2催化剂用量为3%(以总物料量计);噻吩与乙酐的摩尔比为4:1;反应温度为75～80℃;反应时间为90 min.在此所选择的条件下,2-乙酰噻吩的收率达94.6%～96.8%,选择性达99.8%～99.9%.     

Extraction of potassium from K-feldspar via the CaCl2 calcination route☆

The extraction of potassium from K-feldspar via a calcium chloride calcination route was studied with a focus on the effects of the calcination atmosphere, calcination temperature and time, mass ratio of CaCl2 to K-feldspar ore and particle size of the K-feldspar ore. The results demonstrated that a competing high-temperature hydrolysis reaction of calcium chloride with moisture in a damp atmosphere occurred concurrently with the conversion reaction of K-feldspar with CaCl2, thus reducing the amount of potassium extracted. The conversion reaction started at approximately 600 °C and accelerated with increasing temperature. When the temperature rose above 900 °C, the extraction of potassium gradually decreased due to the volatilization of the product, KCl. As much as approximately 41%of the potassium was volatilized in 40 min at 1100 °C. The mass ratio of CaCl2/K-feldspar ore significantly affected the extraction. At a mass ratio of 1.15 and 900 °C, the potassium extraction reached 91%in 40 min, while the extraction was reduced to only 22%at the theoretical mass ratio of 0.2. Optimal process conditions are as follows:ore particle size of 50–75μm, tablet forming pressure of 3 MPa, dry nitrogen atmosphere, mass ratio of CaCl2/ore 1.15:1, calcination temperature of 900 °C, and calcination time of 40 min. The XRD analysis revealed that a complex phase transition of the product SiO2 was also accompanied by the con-version reaction of K-feldspar/CaCl2. The SiO2 product formed at the initial stage was in the quartz phase at 900 °C and was gradually transformed into cristobalite after 30 min.     

Effects of Precursors for Preparing Intermediate Layer on the Performance of Ti/SnO2+Sb2O3/PbO2 Anode

The Ti/SnO2+Sb2O3/PbO2 anode with SnO2+Sb2O3 intermediate layer obtained by the polymeric precursor method (PPM) and with the conventional route was studied. The morphology and microstructure of SnO2+Sb2O3 intermediate layer derived from different precursors and the top PbO2 active layer were examined by means of ESEM and XRD. The lifetime and electrocatalytic activity of the anode were also assessed by the cyclic voltammetry and accelerated lifetime test in 1.0 mol/L H2SO4 solution. It was found that precursor solvents affected lifetime, microstructure and morphology of the anode, and had little influence on electrocatalysis activity of the electrodes. The accelerated lifetime of Ti/SnO2+Sb2O3/PbO2 anode with intermediate layer prepared by PPM was 29.5 h in 1.0 mol/L H2SO4 solution, which was respectively about four times and twice that of the anode prepared with ethylene glycol and ethanol. After the anode was subjected to thermal corrosion, the lifetime still reached 27 h in contrast to the others.     

负载型Cs2.5H0.5PW12O40醚化催化剂的制备与催化性能

制备了负载型磷钨酸铯(Cs_2.5H_0.5PW₁₂O₄₀)催化剂，考察了载体种类、载体性质、制备方法和制备条件对催化剂性能的影响,对制备的催化剂进行了表征，并考察了负载型Cs_2.5H _0.5PW₁₂O₄₀作为醚化催化剂的催化活性.结果表明,大孔硅胶是Cs_2.5H_0.5PW₁₂O₄₀的适宜载体，硅胶的钠含量越低制备的Cs_2.5H_0.5PW₁₂O₄₀/SiO₂催化剂的活性越高.采用一步法和二步法制备的Cs_2.5H_0.5PW₁₂O₄₀/SiO₂催化剂均具有较强的酸性、催化活性以及良好的稳定性,可以替代液体酸和阳离子交换树脂,成为一种环境友好的固体酸催化剂.     

Effects of Brønsted and Lewis Acidities on Catalytic Activity of Heteropolyacids in Transesterification and Esterification Reactions

Some salts of H₃PW₁₂O₄₀‐M_x/nH_3–xPW₁₂O₄₀ (abbreviated as M_x/nH_3–xPW) were prepared and used as acid catalysts for transesterification and esterification reactions. These catalysts have double acidity properties, i.e., Lewis acidity and Brønsted acidity, that are suitable for the conversion of waste cooking oil into biodiesel. The highest efficiency was 59.2 % and 94.7 % corresponding to transesterification and esterification reactions by Ti_0.6H_0.6PW with moderate Lewis acidity. The relationship between the acidic properties and the catalytic activity is discussed in detail.     

288 K下Li+,K+//CO2-3,B4O2-7-H2O四元体系的相平衡

Solubilities and properties (density, conductivity and pH value) of solutions in the quaternary system Li⁺,K⁺//CO^2-₃,B₄O^2-₇-H₂O at 288 K were experimentally studied with the isothermal equilibrium method. The phase diagram of the system consisted of two invariant points E and F, five univariant curves, and four crystallization fields that belonged to K₂CO₃·3/2H₂O,Li₂B₄O₇·3H₂O,K₂B₄O₇·4H₂O and Li₂CO₃. The composition of the solution corresponding to E was w（CO^2-₃）=2.27 %,w（B₄O^2-₇）=6.05 %,w（K⁺ ）=4.30%,w(Li⁺)=0.30 % and the equilibrium solids were Li₂B₄O₇· 3H₂O+K ₂B₄O₇·4H₂O+Li₂CO₃;The composition of the solution for F was w(CO^2-₃)=22.45%,w(B₄O^2-₇)=1.88%,w(K⁺ )=29.96%,w(Li⁺ )=0.03% and the equilibrium solids were K₂CO₃·3/2H₂O+K ₂B₄O₇·4H₂O+Li₂CO₃. K₂CO₃ possesses strong salting-out effect on K₂B₄O₇,Li₂CO₃ and Li₂B₄O₇.     

动态UV-vis/H2O2/草酸铁络合物法光解苯胺

UV -vis/H₂ O₂ /草酸铁络合物法是一种高级氧化工艺 ,这个工艺产生的羟自由基·OH是一种很强的氧化剂 ,能很快和水中有机物发生反应 .以苯胺为处理对象对该法的氧化能力和效果进行了研究 ,并确定了降解苯胺的最佳工艺条件 :pH =3 .5 ,Fe^{2 +} ∶H₂ O₂ ∶C₂ O^{2 -}₄ ≈ 1∶4∶6 (mole) .UV -vis/H₂ O₂ /草酸铁络合物法处理高浓度苯胺水样非常有效 ,12min内苯胺去除率均在 99%以上 .流动法处理苯胺模拟废水的效果明显好于静态法     

溶胶-凝胶法制备PEW/SiO2杂化材料及表征

通过熔融接枝反应将乙烯基三甲氧基硅烷（VTMS）接枝到聚乙烯蜡（PEW）分子链上,接枝物红外光谱（FTIR）的1090、1030、960 cm^-1等处出现了—Si—O—CH3的特征吸收峰。以正硅酸乙酯（TEOS）为前驱体,混入接枝PEW中,通过溶胶-凝胶法（sol-gel）制备了PEW/SiO₂杂化材料。使用透射电镜（TEM）和热重分析（TG）研究了杂化材料的形态及性能,结果表明,通过sol-gel可以制备SiO₂含量为0. 98%～4. 12%的杂化材料,SiO₂颗粒与PEW接枝物分子间具有良好的相容性,纳米SiO2的存在提高了PEW的耐热性能,当SiO₂含量为3. 75%时,PEW的分解温度提高了21. 34℃。     

包硅改性纳米碳酸钙应用于高温CO2吸附的性能

引言 二氧化碳吸附强化制氢(SERP)的原理是将甲烷水蒸气重整反应过程产生的CO2用吸附剂脱除,从而打破化学反应平衡,降低反应平衡常数,使反应温度由800～1000℃降低至500℃左右,使制氢反应条件更温和、能耗更低.该技术的工业可行性研究的关键是甲烷水蒸气重整反应过程中采用的高温CO2的吸附剂的性能研究[1].     

高性能钯膜及其在氨分解制氢中的应用

引 言 液氨催化分解制氢工艺具有价格低廉、安全性好、附加值低、产物不含COx杂质等优点[1].此外,氨分解制氢体系的理论质量储氢量是17.6%,明显高于电解水(11.1%)、甲醇-水蒸气重整(12%)、汽油-水蒸气重整(12.4%)、氢化物水解(5.2%～8.6%)等制氢体系.但是,以纯氨为原料分解后只能得到含氢75%的混合气,而燃料电池只有在使用纯氢为原料气时才具有最高的工作效率,因此应当对氨分解产物中的氢进行提纯.     

A heteropolyacid-based ionic liquid as a thermoregulated and environmentally friendly catalyst in esterification reaction under microwave assistance

A new kind of heteropolyacid (HPA) ionic liquid [(CH₃)₃NCH₂CH₂OH]H₂PW₁₂O₄₀ (ChH₂PW) has been synthesized using choline chloride and H₃PW₁₂O₄₀ (HPW) as precursors. The catalyst exhibited a novel switchable property based on temperature. The separation of the catalyst would be explored by simply decreasing reaction temperature without appreciable loss. Excellent conversions (97%) for esterification have been obtained under microwave-accelerated conditions.     

铜铁尾矿制酸烧渣制备纳米Fe/SiO2核壳复合粒子的微波吸收性能

以铜铁尾矿制酸烧渣为原料,经熟化、酸浸、还原和净化等步骤制备亚铁离子;在乙醇-水液相体系中,以NaBH₄作为还原剂,反应生成纳米Fe粒子;最后通过正硅酸四已酯（TEOS）水解包覆制得纳米Fe/SiO₂核壳复合粒子。产物分别采用XRD、TEM、IR等手段进行表征。进一步地,使用矢量网络分析仪在2.0 ~ 18.0 GHz波段内来研究样品的吸波性能。结果表明,IR光谱上在1389 cm^-1和878 cm^-1分别出现对应于四配位Si—O键和Si—O—Fe键的特征吸收峰,说明在Fe粒子表面包覆有SiO₂。通过测试计算得知,当吸波样品厚度为4.5 mm时,其微波吸收性能在17.2 GHz处达到最小值-39.0 dB。由此可见,以铜铁尾矿制酸烧渣为原料,可制得吸波性能优良的纳米Fe/SiO₂核壳复合粒子微波吸收材料。     

Biodiesel production from soybean oil catalyzed by multifunctionalized Ta2O5/SiO2-[H3PW12O40/R] (R = Me or Ph) hybrid catalyst

Mesoporous Ta₂O₅ materials functionalized with both alkyl group and a Keggin-type heteropoly acid, Ta₂O₅/SiO₂-[H₃PW₁₂O₄₀/R] (R = Me or Ph), was prepared by a single step sol–gel co-condensation method followed by a hydrothermal treatment in the presence of a triblock copolymer surfactant. The catalytic performance of the resulting multifunctionalized organic–inorganic hybrid materials was evaluated by a direct use of soybean oil for biodiesel production in the presence of 20 wt% myristic acid under atmosphere refluxing, and the influences of the catalyst preparation approaches, functional component loadings, and molar ratios of oil to methanol on the catalytic activity of the Ta₂O₅/SiO₂-[H₃PW₁₂O₄₀/R] were studied. In addition, the recyclability of the hybrid materials was evaluated via four catalytic runs. Finally, the network structures of the hybrid materials and the functions of the incorporated alkyl groups on the catalytic activity of the materials were put forward.