Study on trifluoromethanesulfonic acid-promoted synthesis of daidzein: Process optimization and reaction mechanism

Daidzein has been widely used in pharmaceuticals,nutraceuticals,cosmetics,feed additives,etc.Its preparation process and related reaction mechanism need to be further investigated.A cost-effective process for synthesizing daidzein was developed in this work.In this article,a two-step synthesis of daidzein(Friedel–Crafts acylation and[5+1]cyclization)was developed via the employment of trifluoromethanesulfonic acid(TfOH)as an effective promoting reagent.The effect of reaction conditions such as solvent,the amount of TfOH,reaction temperature,and reactant ratio on the conversion rate and the yield of the reaction,respectively,was systematically investigated,and daidzein was obtained in 74.0%isolated yield under optimal conditions.Due to the facilitating effect of TfOH,the Friedel–Crafts acylation was completed within 10 min at 90℃ and the[5+1]cyclization was completed within 180 min at 25℃.In addition,a possible reaction mechanism for this process was proposed.The results of the study may provide useful guidance for industrial production of daidzein on a large scale.

Dimensionality Reduction with Input Training Neural Network and Its Application in Chemical Process Modelling

Many applications of principal component analysis (PCA) can be found in dimensionality reduction. But linear PCA method is not well suitable for nonlinear chemical processes. A new PCA method based on im-proved input training neural network (IT-NN) is proposed for the nonlinear system modelling in this paper. Mo-mentum factor and adaptive learning rate are introduced into learning algorithm to improve the training speed of IT-NN. Contrasting to the auto-associative neural network (ANN), IT-NN has less hidden layers and higher training speed. The effectiveness is illustrated through a comparison of IT-NN with linear PCA and ANN with experiments. Moreover, the IT-NN is combined with RBF neural network (RBF-NN) to model the yields of ethylene and propyl-ene in the naphtha pyrolysis system. From the illustrative example and practical application, IT-NN combined with RBF-NN is an effective method of nonlinear chemical process modelling.

Surface Analysis of Chemical Stripping Titanium Alloy Oxide Films

The chemical stripping method of titanium alloy oxide films was studied. An environment friendly solution hydrogen peroxide and sodium hydroxide without hydrofluoric acid or fluoride were used to strip the oxide films. The morphologies of the surface and cross-section of the oxide films before and after the films stripping were characterized by using scanning electron microscopy （SEM）. The microstructure and chemical compositions of the oxide films before and after the films stripping were investigated by using Raman spectroscopy （Raman） and X-ray photoelectron spectroscopy （XPS）. It was shown that the thickness of the oxide film was in the range of 5-6 μm. The oxide films were stripped for 2 to 8 min in the solution. Moreover, the effect of the stripping time on the efficiency of the film stripping was investigated, and the optimum stripping time was between 6-8 min. When the stripping solution completely dissolved the whole film, the α/β microstructure of the titanium alloy Ti-10V-2Fe-3Al was partly revealed. The stripping mechanism was discussed in terms of the dissolution of film delamination. The hydrogen peroxide had a significant effect on the dissolution of the titanium alloy anodic oxide film. The feasibility of the dissolution reaction also was evaluated.

Synthesis and Characterization of Pr(DPM)_3 Served as Precursor for MOCVD

Praseodymium β-diketone chelate, Pr （DPM）3 [ DPM = 2,2,6,6 -tetramethyl-3,5-heptanedionato ], was successfully synthesized from the inorganic salt praseodymium chloride and HDPM（2,2,6,6-tetramethyl-3,5-heptane-dione） in an ethanol/aqueous solution followed distillation at low pressure and recrystallization from toluene. The physical and thermal properties of the chelate, including volatility, stability, and thermal decomposition, were investigated by elemental analyses, 1^H NMR spectroscopy, XRD, TG/DTG/DTA analysis, infrared spectroscopy, and mass spectroscopy. The chelate with high purity prepared by the authors of this study also shows sufficient volatility and Stability in inert gases, which could be used as the precursor for metal-organic chemical vapor deposition（MOCVD）.

Probabilistic Approach to Risk Analysis of Chemical Spills at Sea

Risk analysis of chemical spills at sea and their consequences for sea environment are discussed. Mutual interactions between the process of the sea accident initiating events, the process of the sea environment threats, and the process of the sea environment degradation are investigated. To describe these three particular processes, the separate semi-Markov models are built. Furthermore, these models are jointed into one general model of these processes interactions. Moreover, some comments on the method for statistical identification of the considered models are proposed.

Synthesis, Crystal Structure and Characterization of a New Dihydrogenomonophosphate: (C₇H₉N₂O)H₂PO₄

Chemical preparation, X-ray single-crystal, thermal behavior, and IR spectroscopy investigations are given for a new organic cation dihydrogenomonophosphate (C7H9N2O)H2PO4 (denoted ABHP) in the solid state. This compound crystallizes in the monoclinic space group P21/n. The unit cell dimensions are: a = 11.011(5) &Aring, b = 5.861(1) &Aring, c = 15.944(4) &Aring and β = 100.81(5) with V = 1010.7(6) &Aring3 and Z = 4. The structure has been solved using direct method and refined to a reliability R factor of 0.048. The atomic arrangement can be described as inorganic clusters [H4P2O8]2- anions between which are located the organic dimmers (C14H18N4O2)2+ through multiple hydrogen bonds (Figure 1)

Facile Synthesis and Thermal Stability of Nanocrystalline Molybdenum Carbide

Nanocrystalline molybdenum carbide (Mo2C) was prepared via one simple route by the reaction of metallic magnesium powders with molybdenum trioxide and potassium acetate in an autoclave at the condition of 600℃ and 4 h. X-ray powder diffraction (XRD) pattern indicated that the product was hexagonal α-Mo2C, and the cell constant was a = 3.0091 ?, c = 4.7368 ?. Scanning electron microscopy (SEM) image showed that the sample consisted of particles with an average size of about 100 nm in diameter. The product was also studied by the thermogravimetric analysis (TGA). It had good thermal stability and oxidation resistance below 450℃ in air.

On the Regression-Tensor Analysis of the Hardening Process of Metal Coatings

This paper constructs and studies a nonlinear multivariate regression-tensor model for substantiation of necessary/sufficient conditions of optimization of technological calculation of multifactor physical and chemical process of hardening of complex composite media for metal coatings. An adaptive a posteriori procedure for parametric formation of the target quality functional of integrative physical and mechanical properties of the designed metal coating has been proposed. The results of the research may serve as elements of a mathematical language when creating automated design of precision nanotechnologies for surface hardening of complex composite metal coatings on the basis of complex tribological and anticorrosive tests.

基于UPLC-Q-TOF-MS分析江西特色炮制技术对中药升麻化学成分的影响

目的比较江西特色炮制技术对升麻化学成分的影响,筛选优质饮片品种。方法采用超高效液相色谱-四极杆-飞行时间串联质谱(ultra performance liquid chromatography-quadrupole-time of flight tandem mass spectrometry,UPLC-Q-TOF-MS)技术,在正、负离子模式下分析升麻不同炮制品的化学成分,通过对照品、相对分子质量、质谱裂解规律和文献信息进行鉴定。利用SIMCA-P13.0软件建立升麻各炮制品主成分分析(principal component analysis,PCA)和偏最小二乘法-判别分析(partial least squares discriminant analysis,PLS-DA)模型,获取PCA得分图、PLA-DA得分图和变量重要性投影(variable importance plot,VIP)值,筛选造成升麻炮制前后主要差异的物质基础。利用MetaboAnatyst网页绘图工具,制作得到热图,可更直观地观察升麻化学成分经炮制后的变化趋势。结果鉴定出71个化学成分,PCA显示经不同方法炮制后升麻组间差异性大,PLS-DA筛选出VIP值>1的33个化学成分作为炮制前后差异性的主要化学标记物。其中生品和蜜炙升麻中三萜类含量较高,蜜麸、蜜糠炒升麻中酚酸类物质含量较高,蜜麸升麻中阿魏酸含量较高。结论酚酸类和三萜皂苷类是区分升麻不同炮制品最重要的化合物类别,为江西特色升麻饮片的药效物质基础及优势品种研究提供了依据。

Multimode Process Fault Detection Using Local Neighborhood Similarity Analysis

Traditional data driven fault detection methods assume unimodal distribution of process data so that they often perform not well in chemical process with multiple operating modes. In order to monitor the multimode chemical process effectively, this paper presents a novel fault detection method based on local neighborhood similarity analysis(LNSA). In the proposed method, prior process knowledge is not required and only the multimode normal operation data are used to construct a reference dataset. For online monitoring of process state, LNSA applies moving window technique to obtain a current snapshot data window. Then neighborhood searching technique is used to acquire the corresponding local neighborhood data window from the reference dataset. Similarity analysis between snapshot and neighborhood data windows is performed, which includes the calculation of principal component analysis(PCA) similarity factor and distance similarity factor. The PCA similarity factor is to capture the change of data direction while the distance similarity factor is used for monitoring the shift of data center position. Based on these similarity factors, two monitoring statistics are built for multimode process fault detection. Finally a simulated continuous stirred tank system is used to demonstrate the effectiveness of the proposed method. The simulation results show that LNSA can detect multimode process changes effectively and performs better than traditional fault detection methods.

Improved process monitoring using the CUSUM and EWMA-based multiscale PCA fault detection framework

Process monitoring techniques are of paramount importance in the chemical industry to improve both the product quality and plant safety.Small or incipient irregularities may lead to severe degradation in complex chemical processes,and the conventional process monitoring techniques cannot detect these irregularities.In this study to improve the performance of monitoring,an online multiscale fault detection approach is proposed by integrating multiscale principal component analysis(MSPCA) with cumulative sum(CUSUM) and exponentially weighted moving average(EWMA) control charts.The new Hotelling's T~2 and square prediction error(SPE) based fault detection indices are proposed to detect the incipient irregularities in the process data.The performance of the proposed fault detection methods was tested for simulated data obtained from the CSTR system and compared to that of conventional PCA and MSPCA based methods.The results demonstrate that the proposed EWMA based MSPCA fault detection method was successful in detecting the faults.Moreover,a comparative study shows that the SPEEWMA monitoring index exhibits a better performance with lower values of missed detections ranging from 0% to 0.80% and false alarms ranging from 0% to 21.20%.

A blast furnace fault monitoring algorithm with low false alarm rate:Ensemble of greedy dynamic principal component analysis-Gaussian mixture model

The large blast furnace is essential equipment in the process of iron and steel manufacturing. Due to the complex operation process and frequent fluctuations of variables, conventional monitoring methods often bring false alarms. To address the above problem, an ensemble of greedy dynamic principal component analysis-Gaussian mixture model(EGDPCA-GMM) is proposed in this paper. First, PCA-GMM is introduced to deal with the collinearity and the non-Gaussian distribution of blast furnace data.Second, in order to explain the dynamics of data, the greedy algorithm is used to determine the extended variables and their corresponding time lags, so as to avoid introducing unnecessary noise. Then the bagging ensemble is adopted to cooperate with greedy extension to eliminate the randomness brought by the greedy algorithm and further reduce the false alarm rate(FAR) of monitoring results. Finally, the algorithm is applied to the blast furnace of a large iron and steel group in South China to verify performance.Compared with the basic algorithms, the proposed method achieves lowest FAR, while keeping missed alarm rate(MAR) remain stable.

基于UPLC-Q-TOF-MS和多元统计分析樟帮米泔水漂白术漂制过程中化学成分的动态变化研究

目的研究樟帮米泔水漂白术漂制过程中化学成分的动态变化,为白术漂制工艺的合理制定及炮制机制的阐释提供参考。方法以白术生品及其5个不同漂制阶段的漂制品(第1、2阶段漂制品分别为生品用9倍量米泔水各漂12、24 h;第3-5阶段漂制品分别为生品先用9倍量米泔水漂24 h,再用9倍量清水各漂12、24、48 h,漂洗温度均为26℃)为研究对象,采用超高效液相色谱串联四极杆飞行时间质谱法(UPLC-Q-TOF-MS)检测其化学成分,以0.1%甲酸水溶液(A)-乙腈(B)为流动相进行梯度洗脱(0-5 min,5%-30%B;5-14 min,30%-60%B;14-23 min,60%-70%B;23-31 min,70%-95%B;31-32 min,95%-5%B;32-35 min,5%B),柱温40℃,进样量2μL,流速0.3 mL·min^(-1);运用电喷雾离子源(ESI),在正离子模式下进行扫描并采集质谱数据,扫描范围m/z 50-1250;利用PeakView 1.2进行数据分析,结合对照品、chemicalbook数据库及相关文献对白术生品及其5个不同漂制阶段漂制品的化学成分进行鉴定;质谱数据通过MarkerView1.2软件归一化处理后应用多元统计分析方法找出差异化合物,分析差异化合物的相对含量随漂制时间不同的变化规律。结果从白术生品及其5个不同漂制阶段漂制品中共鉴别出55个化学成分,包含白术内酯Ⅰ、Ⅱ、Ⅲ等在内的40个共有成分。其中,从白术生品、第1-5阶段漂制品中分别鉴别出了53、47、49、49、44、46个成分。与白术生品比较,漂制过程中新增了vitexin和dihydrosyrindine 2个成分,未检测到聚-L-组氨酸、尿苷等9个成分,而9-hydroxy-7-oxo-7H-furo[3,2-g]chromen-4-ylβ-D-glucopyranoside、4-octylbenzoic acid等4个成分在漂制过程中呈消失-出现的变化趋势。多元统计分析筛选出18个差异化合物,其中白术内酯Ⅰ、Ⅱ、Ⅲ这3个差异化合物的相对含量随着漂制时间的延长均呈现先上升后下降的变化趋势,且都是生品中为最低,第3阶段漂制品中为最高。结论漂制辅料(清水和米泔水)和漂制时间是白术漂制过程中化学成分产生动态变化的主要原因。漂白术饮片若以白术内酯Ⅰ、Ⅱ、Ⅲ为指标性成分和药效成分,则白术合理的漂制工艺为:白术生品先用9倍量米泔水漂24 h,再用9倍量清水漂12 h。该实验可为樟帮特色米泔水漂白术炮制科学内涵的阐释提供科学依据。

Monodisperse Fe3O4 spheres: Large-scale controlled synthesis in the absence of surfactants and chemical kinetic process

Fe3 O4 has attracted tremendous interest in vast areas of biomedicine and catalysis as well as environment engineering.However,it is highly desired to fully understand the chemical kinetic process and propose a general,surfactantfree,large-scale synthesis approach for Fe3 O4 spheres.Herein,we developed a facile scalable solvothermal method in the absence of surfactants to produce Fe3 O4 spheres with the yield of 5.1 g,which present tunable sizes from 107 to 450 nm by modulated molar ratio of Fe3+/COO-in the solution.Particularly,it is observed that the reactants undergo a redox process,composed of a precipitation-dissolution equilibrium combined with a coordination reaction(termed as RPC),to the final product based on the LaMer model.It is worth noting that the generation of di-carboxyl group and its coordination with iron cations determine the formation of Fe3 O4 spheres.This work not only offers a strategy to precisely tailor the particle size in scalable synthesis process,but also gives the insight on the role of dihydric alcohol in the formation mechanism of Fe3 O4 spheres in the absence of surfactants.

Recent progress towards mild-condition ammonia synthesis

Ammonia is essential for food and energy.Industrial ammonia synthesis via Haber–Bosch process is energy-intensive and releases large amount of CO2.Increasing research efforts are devoted to "green"ammonia synthesis.The present article reviews the recent progress in the fields of thermocatalytic, electrocatalytic, photocatalytic and chemical looping processes for dinitrogen reduction towards ammonia formation and discusses the challenges borne for mild-condition synthesis.

Enhanced Thermal Stability of Promising Nano-Porous Silicon Powder

A direct synthesis method is introduced to prepare nano-porous silicon-nickel nanocomposite (nPS/Ni) powder for thermal isolation applications. In this paper, we study the thermal stability of nanocomposites consisting of nanoparticles metal incorporated into the pores of a porous silicon by a very simple method. The nickel element is chemically deposited whereas the nanoparticles are precipitated on the pore surfaces. The (nPS) and (nPS/Ni) nano-materials are thermally measured under nitrogen at temperatures of 40&#8451 - 1000&#8451, noticeable, demonstrating better thermal stability of (nPS/Ni) until 900&#8451 than in the case of (nPS) at 600&#8451. Then, the improving of the thermal stability of the nPS powder is facilitated using it in many applications of the thermal insulation process.

页岩气链式重整制甲醇集成SOFC过程设计及分析

建立了页岩气化学链重整制甲醇联合固体燃料电池发电过程模型,并通过原料消耗、产品产出、过程能耗和㶲效率等指标对新流程进行技术分析。通过化学链重整制合成气和氢气来优化甲醇合成和实现页岩气的高效利用,通过将剩余氢气用于固体燃料电池发电和弛放气化学链燃烧供热实现电能自给并有盈余。还探讨了不同甲烷转化率对新过程技术性能的影响,甲烷转化率为60.0%的过程㶲效率仅为57%,而甲烷转化率为80.0%~99.3%的过程㶲效率高达71%~74%。

CNTs tuning and vertical alignment in anodic aluminium oxide membrane

Anodic aluminium oxide （AAOM） membranes were used for template growth of carbon nanotubes （CNT） inside their pores by chemical vapour deposition （CVD） of different hydrocarbons, in the absence of transition metal catalyst. A composite material, containing one nanotube for each channel, having the same length as the membrane thickness and the external diameter close to the diameter of the membrane holes, was obtained. Yield, selectivity, and quality of CNTs in terms of diameter （up to very thin CNT）, carbon order, length, arrangement （i.e. number of tubes for each channel）, purity, that are critical requisites for several applications were optimised by investigating the effect of changing the hydrocarbon feedstock gas, also in the presence of hydrogen. The samples produced using methane as a feedstock have a well ordered structure. The role of the alumina channels surface during the CNT growth has been investigated and its catalytic activity has been proved for the first time.

Energy consumption hierarchical analysis based on interpretative structural model for ethylene production

Interpretative structural model(ISM) can transform a multivariate problem into several sub-variable problems to analyze a complex industrial structure in a more efficient way by building a multi-level hierarchical structure model. To build an ISM of a production system, the partial correlation coefficient method is proposed to obtain the adjacency matrix, which can be transformed to ISM. According to estimation of correlation coefficient, the result can give actual variable correlations and eliminate effects of intermediate variables. Furthermore, this paper proposes an effective approach using ISM to analyze the main factors and basic mechanisms that affect the energy consumption in an ethylene production system. The case study shows that the proposed energy consumption analysis method is valid and efficient in improvement of energy efficiency in ethylene production.

专业认证背景下的“化工过程分析与合成”课程教学

“化工过程分析与合成”课程是化学工程与工艺专业学生的一门专业核心课程,然而目前存在“化工过程分析与合成”课程教学内容与化工人才培养目标脱节的问题,为此,本文提出将案例式教学融入化工过程分析与合成的教学内容中,通过对实际工程案例的提出、浓缩,并融合进入课堂教学,实现教学模式的创新,提升教学的深度和广度,培养学生解决复杂工程问题的能力。