MTi-LDH(M=Zn,Ni)的制备及其对乙硫醇的吸附性能研究

TiO_(2)是环境催化领域最常用、应用最广泛的催化剂之一,但其表面羟基常显酸性,限制了其在乙硫醇等酸性气体中的吸附性能。用Zn和Ni元素对其进行修饰,构建ZnTi-LDH、NiTi-LDH等钛基层状双金属氢氧化物,在对其结构特征进行表征的基础上,选择甲烷气中的乙硫醇为研究对象,研究二元的钛基层状双金属氢氧化物对甲烷气中乙硫醇的吸附作用,及层状化合物的层板和表面酸碱性等对乙硫醇吸附性能的影响。研究结果表明,采用固定床反应器动态吸附乙硫醇,发现ZnTi-LDH的穿透硫容为8.04 mg·g^(-1),而NiTi-LDH的吸附性能要优于ZnTi-LDH,其穿透硫容为13.79 mg·g^(-1)。该催化剂优异的吸附脱硫活性使其在工业应用上具有一定的前景。

Ag_(2)O-NiTi-LDH复合材料的构建及其光催化氧化乙硫醇性能研究

本文将氧化银(Ag_(2)O)负载到镍-钛层状双金属氢氧化物(NiTi-LDH)上以构建Ag_(2)O-NiTi-LDH复合材料。通过XRD、SEM、TEM、XPS、UV-vis、电化学工作站和FT-IR等技术对样品进行表征。采用静态吸附-光催化的方法对乙硫醇进行吸附氧化降解。结果表明:复合材料中Ag_(2)O和NiTi-LDH之间存在相互作用,使得Ag_(2)O-NiTi-LDH复合材料比单一基体材料的带隙能小,光生电子-空穴的分离和迁移效率高;在光催化实验中,单一的基体材料NiTi-LDH对乙硫醇的光催化效果不明显,Ag_(2)O和Ag_(2)O-NiTi-LDH虽然都能将乙硫醇光催化氧化成硫酸盐,但Ag_(2)O-NiTi-LDH复合材料光催化氧化降解效率高于Ag_(2)O。

硫醇加成/氧化构建具稳定阻转异构体的萘醌化合物

轴手性是自然界的本征特性之一,在有机化学和药物化学研究中具有重要意义。醌类化合物广泛存在于天然产物、药物和其他功能性分子中,对构建含稳定阻转异构体的醌类化合物有重要研究价值。(1,2′-联萘)-1′,4′-二酮为一类含有C—C手性轴的化合物,但与常见的2,2′-双取代的1,1′-联萘不同,其手性轴的旋转能垒较小,室温下构型不稳定,故通过简单高效反应构建具稳定阻转异构体的1,2′-联萘醌是一项有吸引力的课题。本文以不同位阻取代的(1,2′-联萘)-1′,4′-二酮为底物,Cu(OAc)_(2)为助氧剂,EtOH为溶剂,在Et_(3)N的作用下,通过硫醇的加成/氧化反应直接构建了一系列具有稳定阻转异构体的联萘醌衍生物,共经^(1)H NMR,^(13)C NMR和HR-MS表征。

Ni-Ti-LDHs的合成、表征及其对乙硫醇的吸附性能

天然气中乙硫醇的脱除是一项研究重点课题。采用共沉淀法合成Ni-Ti-LDHs,对样品进行XRD、SEM、FT-IR、TG-DTA测试与表征,通过动态吸附法评价Ni-Ti-LDHs对乙硫醇的吸附性能。研究结果表明,通过共沉淀法合成的Ni-Ti-LDHs具有层状结构,其层间为NO3-,层状Ni-Ti-LDHs对乙硫醇的穿透吸附量为19.74 mg/g。碱性层状Ni-Ti-LDHs对乙硫醇有较好的吸附性能。

延迟焦化装置液化石油气降低总硫技术改造总结

中国石油化工股份有限公司镇海炼化分公司1号产品精制装置焦化液化石油气脱硫脱硫醇系统,通过使用脱羰基硫溶剂UDS、纤维膜换代、投用碱液再生系统,解决了精制焦化液化石油气羰基硫高、脱硫醇效果差、碱渣外排量高等问题,使得焦化液化石油气羰基硫脱除率达到90%以上,精制焦化液化石油气产品羰基硫的质量浓度由99 mg/m^(3)降至10 mg/m^(3)以内,远低于去气分装置回收丙烯的质量要求(质量浓度不大于60 mg/m^(3))。自投用运行以来,回收焦化液化石油气中丙烯,每年可增加经济效益约4063万元。为同类装置焦化液化石油气降低总硫工艺优化提供了参考借鉴。

汽油中大分子硫醇催化转化反应过程强化

选择性脱除加氢后催化裂化汽油中的大分子硫醇硫,是低成本高效生产国六清洁汽油的有效方法。采用孔饱和浸渍法制备孔径不同的CoMo/Al2O3加氢催化剂,破碎至不同粒径后,对其进行硫化处理;在固定床反应器中分别使用模拟催化裂化汽油和加氢后催化裂化真实汽油进行评价,并考察工艺条件对催化剂脱除大分子硫醇的反应效果,采用原位吸附反应过程强化方法,强化大分子硫醇的选择性脱除。结果表明:加氢后催化裂化汽油中的硫醇是汽油中烯烃与硫化氢化合生成的大分子硫醇,种类多,每一种硫醇的含量低;再生成硫醇的脱除反应在低温下受传质限制,硫化氢与烯烃再生成硫醇的化学反应达到热力学平衡,依靠目前MoS2类催化剂无法高效脱除,通过减小催化剂粒径和增大催化剂孔径的手段可有效减弱硫醇脱除反应的扩散限制,提高催化剂硫醇脱除效果,同时通过原位吸附反应过程强化方法将硫醇脱除反应过程中生成的硫化氢移出反应区,避免硫化氢与烯烃再结合反应发生,可以在反应温度160℃、体积空速4h−1、反应压力0.3MPa、氢油体积比10的缓和条件下高效脱除大分子硫醇,低成本生产清洁汽油。

叔十二碳硫醇合成研究进展

叔十二碳硫醇(TDM)是一种在橡胶、树脂等生产中用于控制聚合物分子量的链调节剂,国内需求几乎全部依赖进口,迫切需要开发经济环保的TDM合成技术。目前,TDM的合成主要取决于原料碳源和催化剂类型的选择。介绍了TDM合成技术的发展现状,总结了适用于高碳硫醇合成的催化剂类型,对比了各类催化剂的优缺点,并指出了适用于TDM合成的不同体系催化剂的未来发展趋势。

没食子提取物对体外口腔异味影响的研究

目的:探究没食子提取物对于口腔主要致臭菌变形链球菌和牙龈卟啉单胞菌的作用,以及对硫化物的抑制作用。方法:培养变形链球菌和牙龈卟啉单胞菌菌群,抑菌环法评估没食子对菌群的抑制作用,观察没食子提取物对变形链球菌产生的不溶性葡聚糖的影响,最后检测没食子对致臭物质甲硫醇的作用。结果:没食子组与氯己定组可显著降低变形链球菌和牙龈卟啉单胞菌抑菌环直径(均P<0.05),抑制不溶性葡聚糖的产生(P<0.05),而两者之间比较无统计学差异(P>0.05);没食子提取物可以显著降低甲硫醇的产生,与空白对照组和氯己定组比较有统计学差异(均P<0.05)。结论:没食子提取物可以去除口腔异味,又可以提供持续的口腔健康控制,是一种优良的口腔维护中药。

仿生混合润湿图案表面的制备及其水收集性能

目的全球淡水资源短缺,高效和环保地获取淡水是一项重大挑战。方法受沙漠甲虫和叶脉的启发,采用氨腐蚀法在铜网表面生长一层氢氧化铜纳米带,随后在氢氧化铜表面覆盖掩膜,使局部附着正十二烷基硫醇分子,制备出仿生混合润湿图案表面,采用接触角测量仪、扫描电子显微镜(SEM)、X射线衍射仪(XRD)及傅里叶变换红外光谱仪(FT-IR)分别对样品的润湿性、表面形貌及化学成分进行分析,以仿生混合润湿图案表面为基础搭建雾水收集装置,模拟潮湿环境来表征样品的水收集速率及样品在不同恶劣环境下的稳定性。结果在亲水表面构建疏水图案为后续实验提供了基础,所制备的仿生混合润湿图案表面与原始表面、亲水表面、超疏水表面的集水速率相比分别提高了146%、111%、61%,有效提高了集水速率,水收集速率与图案尺寸、图案间隔成反比关系,与图案形状无关。仿生混合润湿图案表面经过紫外线照射和100℃加热处理后,仍保持稳定的集水性能。结论样品具有制备简单、成本低廉、高效耐用等优点,在大气集水中具有潜在的应用前景,有望为解决水资源短缺问题提供新思路。

Investigation of factors on a fungal biofilter to treat waste gas with ethyl mercaptan

The biofilter is cost-effective for the waste gases treatment. The bacterial is the main microorganism in the conventional biofilters. However, it faces some problems on the elimination of hydrophobic compounds. In order to overcome these problems, the biofilters with fungi were developed. The objective of this study is to investigate the factors affecting ethyl mercaptan(EM)-degradation using a fungal biofilter. A laboratory experiment was set up. The effects of loading rate, empty bed residence times(EBRT) and pH on EM degradation were investigated. Over 95% removals of EM could be achieved, under the condition of the influent loadings below 50 g/(m·h). Removal efficiencies improved to 98% with EM loading decreased to 45 g/(m·h). For long EBRT of 58 s corresponding to a flow rate of 0.3 m3/h, the EM removal efficiencies of over 98% were observed. However, when EBRT was decreased to 14 s, the removal efficiencies fell under 80%. The pH range of 3—5 was feasible to fungi.

Efficient one-pot synthesis of n-butyl levulinate from carbohydrates catalyzed by Fe_2(SO_4)_3

Butyl levulinate（BL） is a promising new candidate as diesel fuel and fuel additive. In this study, an efficient process for a one-pot synthesis of BL from biomass-derived carbohydrates in butanol medium with the catalysis of metal sulfates was developed. The catalytic activity of a series of metal sulfates for the synthesis of BL from fructose was investigated. Among various metal sulfates, ferric sulfate Fe（SO）was found to be the most efficient catalyst, which gave a remarkably high BL yield of 62.8 mol% under the conditions of 463 K, 3 h, a catalyst dosage of 5.0 g/L, and fructose concentration of 25 g/L. Different carbohydrates including glucose, cellulose, inulin and sucrose were also used for one-pot synthesis of BL with the catalysis of Fe（SO）, showing the yields of 39.6, 30.5, 56.6 and 50.1 mol%, respectively. In addition,the recycling and reuse of Fe（SO）was studied by characterizing them using powder X-ray diffraction（XRD）, scanning electron microscope（SEM）, X-ray photoelectron spectroscopy（XPS）. A plausible reaction pathway for the one-pot synthesis of BL from fructose was proposed. This study provides a facile and feasible way for the synthesis of BL from biomass.

Prevalence of gastric varices and results of sclerotherapy with N-butyl 2 cyanoacrylate for controlling acute gastric variceal bleeding

AIM： To study the prevalence, predictors and control of bleeding following N-butyl 2 cyanoacrylate （NBC） sclerotherapy of gastric varix （GV）. METHODS： We analyzed case records of 1436 patients with portal hypertension, who underwent endoscopy during the past five years for variceal screening or upper gastrointestinal （GI） bleeding. Fifty patients with bleeding GV underwent sclerotherapy with a mean of 2 mL NBC for control of bleeding. Outcome parameters were primary hemostasis （bleeding control within the first 48 h）, recurrent bleeding （after 48 h of esophagogastro-duodenoscopy） and in-hospital mortality were analyzed. RESULTS： The prevalence of GV in patients with portal hypertension was 15% （220/1436） and the incidence of bleeding was 22.7% （50/220）. Out of the 50 bleeding GV patients, isolated gastric varices （IGV-Ⅰ） were seen in 22 （44%）, gastro-oesophageal varices （GOV） on lesser curvature （GOV-Ⅰ） in 16 （32%）, and GOV on greater curvature （GOV-Ⅱ） in 15 （30%）. IGV-Ⅰ was seen in 44% （22/50） patients who had bleeding as compared to 23% （39/170） who did not have bleeding （P 〈 0.003）. Primary hernostasis was achieved with NBC in all patients. Re-bleeding occurred in 7 （14%） patients after 48 h of initial sclerotherapy. Secondary hemostasis was achieved with repeat NBC sclerotherapy in 4/7 （57%）. Three patients died after repeat sclerotherapy, one during transjugular intrahepatic portosystemic stem shunt （TIPSS）, one during surgery and one due to uncontrolled bleeding. Treatment failure-related mortality rate was 6% （3/50）. CONCLUSION： GV can be seen in 15% of patients with portal hypertension and the incidence of bleeding is 22.7%. NBC is highly effective in controlling GV bleeding. In hospital mortality of patients with bleeding GV is 6%.

Preparation,Characterization of Dawson-type Heteropoly Acid Cerium（Ⅲ） Salt and Its Catalytic Performance on the Synthesis of n-Butyl Acetate

A novel cerium(Ⅲ) salt of Dawson type tungstophosphoric acid(Ce2P2W18O62·16H2O) was prepared by doping cerous nitrate in H6P2W18O62·13H2O powder and characterized by thermogravimetry and differential thermal analyses(TG/DTA),Fourier transform infrared spectroscopy(FT-IR),X-ray powder diffraction(XRD),pyridine infrared spectroscopy(Py-IR) and scanning electron microscopy(SEM).Its catalytic activity was evaluated by the probe reaction of synthesis of n-butyl acetate with acetic acid and n-butanol.The effects of various parameters such as molar ratio of n-butanol to acetic acid,reaction temperature,reaction time,and catalyst amount have been studied by single factor experiment.The results show that Ce2P2W18O62·16H2O behaved as an excellent heterogeneous catalyst in the synthesis of n-butyl acetate.The optimum synthetic conditions were determined as follows︰molar ratio of n-butanol to acetic acid at 2.0︰1.0,mass of the catalyst being 1.44% of the total reaction mixture,reaction temperature of 120 ℃ and reaction time of 150 min.Under above conditions,the conversion of acetic acid was above 97.8%.The selectivity of n-butyl acetate based on acetic acid was,in all cases,nearly 100%.The catalysts could be recycled and still exhibited high catalytic activity with 90.4% conversion after five cycles of reaction.It was found by means of TG-DTA and Py-IR that the catalyst deactivation was due to the adsorption of a complex of by-product on the active sites on catalysts surface or the catalyst loss in its separation from the products.Compared with using sulfuric acid as catalyst,the present procedure with Ce2P2W18O62·16H2O is a green productive technology due to simple process,higher yield,catalyst recycling and no corrosion for the production facilities.

Esterification of levulinic acid to n-butyl levulinate over heteropolyacid supported on acid-treated clay

Levulinic acid has been identified as a promising green, biomass-derived platform chemical. n-Butyl levulinate is used as an important intermediate having diverse applications. The present work focuses on the synthesis of n-butyl levulinate by esterification of levulinic acid with n-butanol using heteropolyacid （HPA） supported on acid-treated clay montmorillonite （K10）. 20% （w/w） dodecatungestophosphoric acid （DTPA） supported on K10 was found to be the most efficient catalyst with 97% levulinic acid conversion and 100% selectivity towards n-butyl levulinate. Effects of various process parameters were studied to examine the efficacy of 20% （w/w） DTPA/K10 for optimization of the activity.

n-Butyl Pyridinium Nitrate as a Reusable Ionic Liquid Medium for Knoevenagel Condensation

The Knoevenagel condensation of carbonyl substrates with active methylene compounds proceeds smoothly with ammonium acetate as catalyst in n-butyl pyridinium nitrate to afford the desired products of good purity in moderate yields.

Reactive Distillation for Producing n-Butyl Acetate:Experiment and Simulation

In this paper, a reactive distillation (RD) column was applied for synthesis n-butyl acetate from n-butanol and acetic acid. The Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetic model and an equilibrium stage model for separation were employed to study the RD process. The results obtained from the equilibrium stage model agreed well with the experiments. The effects of operating variables on the n-butanol conversion and n-butyl acetate purity were further investigated. The optimal column configuration for the production of n-butyl acetate was designed with 5 rectifying stages, 8 reaction stages and 13 stripping stages by the simulation study. According to the simulation results, n-butanol conversion and n-butyl acetate purity all reached greater than 96%.

Tailoring the mercaptan ligands for high performance inverted perovskite solar cells with efficiency exceeding 21%

Interface passivation engineering has been recognized as an effective way to simultaneously contribute to the optoelectronic characteristic and stability of perovskite solar cells(PSCs). Herein, a p-conjugated dual-ligand 1,4-phenylmercaptan(PHMT) is explored to rationally tailor the surface of perovskite film.The experimental and theoretical results show that the PHMT presents planar structure and obvious electron delocalization characteristics, which allow it to anchor on the surface of perovskite with a certain orientation, thereby promoting the transport of interface charge. Moreover, the two sulfhydryl groups in PHMT reduce the trap density of the perovskite film by passivating under-coordinated lead ions.Consequently, the PHMT-modified inverted device based on MAPbI_(3)(MA: methylammonium) achieves enhanced efficiency from 18.11%(control) to 21.11%, along with the ambient stability up to 3500 h.After being placed at 85 °C for 500 h or illuminated for 600 h, the modified device remains over 89%or 86% of initial efficiency. This discovery opens a new window for the choice of passivators to improve the performance of PSCs.

Di-(n-butyl)-phthalate-induced Oxidative Stress and Depression-like Behavior in Mice with or without Ovalbumin Immunization

Objective To investigate the relationship between atopic allergy and depression and the role of DBP in the development of depression. Methods BALB/c mice were randomly divided into eight groups：saline;ovalbumin （OVA）-immunized;saline＋DBP （0.45 mg/kg·183;d）; saline＋DBP （45 mg/kg·d）; DBP （0.45 mg/kg·d） OVA-immunized; DBP （45 mg/kg·d） OVA-immunized; saline＋hydrocortisone （30 mg/kg·d）; and hydrocortisone （30 mg/kg·d）-exposed OVA-immunized. Behavior （e.g. open-field, tail suspension, and forced swimming tests）, viscera coefficients （brain and spleen）, oxidative damage [e.g. reactive oxygen species （ROS）, malondialdehyde （MDA）, and glutathione （GSH）], as well as levels of IgE and IL-4, were then analyzed. Results In the saline and OVA groups, the degree of depression symptoms in mice increased with increasing DBP concentration. Additionally, the OVA-immunity groups were associated with more serious depressive behavior compared with the same exposure concentration in the saline group. Oxidative damage was associated with a dose-dependent increase in DBP in the different groups. IL-4 and IgE levels were associated with low-dose DBP stimulation, which changed to high-dose inhibition with increasing DBP exposure, possibly due to spleen injury seen at high DBP concentrations.Conclusion Development of an atopic allergy has the potential to increase the risk of depression in mice, and it seems that DBP helps OVA to exert its effect in our present model. Moreover, the results of our study implicate a certain connection between brain oxidative stress and depression, which deserves a further exploration.

Reactive dividing-wall column for the co-production of ethyl acetate and n-butyl acetate

Reactive dividing-wall column(RDWC) technology plays a critical role in the energy saving and high efficiency of chemical process.In this article, the process of co-producing ethyl acetate(EA) and n-butyl acetate(BA) with RDWC was studied.BA was not only the product, but also acted as entrainer to remove the water generated by the two esterification reactions.Experiments and simulations of the co-production process were carried out.It was found that the experimental results were in good agreement with the simulation results.Two kinds of RDWC structures(RDWC-FC and RDWC-RS) were proposed, and the co-production process operating parameters of the two types of RDWC were optimized by Aspen Plus respectively.The optimal operating parameters of the RDWC-FC were determined as follows: 0.6 of the reflux ratio of aqueous phase(RR), 0.66 of the vapor split(R_V) and 0.51 of the liquid split(R_L).And the optimal operating parameters of the RDWC-RS were shown as follows: RR was 0.295 and R_V was 0.61.Furthermore, the energy saving analysis of the co-production process was based on the annual output of 10000 tons of EA, compared with the traditional reaction distillation(RD) to prepare EA and BA, the reboiler duty of the RDWC-FC column could save 20.4%, TAC saving 23.6%; RDWC-RS reboiler energy consumption could save 17.0%, TAC 22.2%.

Vapor-Liquid Equilibria for Dimethyl Carbonate-n-Butyl Acetate Binary System at 101.325kPa

The vapor-liquid equilibrium (VLE) data for the dimethyl carbonate-n-butyl acetate binary system were measured by an Ellis equilibrated distillator. The experimental data were checked for their thermodynamic consistency through statistical methods. The VLE data was correlated with Wilson and NRTL activity coefficient models and also with the calculation of the vapor phase fugacity coefficient by the modified Peng-Robinson equation of state.