生物柴油副产物粗甘油催化氧化脱水制备丙烯酸

用生物柴油副产物粗甘油催化氧化脱水制丙烯酸,该过程耦合了甘油脱水制丙烯醛和丙烯醛选择性氧化制备丙烯酸两步反应。结果表明,在甘油脱水反应中,使用Cs3PW12O40, P-ZSM-5和Co0.5H2PO4/SiO2等固体酸催化剂,可得到较高的丙烯醛收率(最高86.9%)。利用上述催化剂和MoVW基氧化催化剂,在脱水/氧化双催化剂床层构型反应器中,以甘油为原料合成丙烯酸的收率达50%~80%,直接加入粗甘油可获得相似的丙烯酸收率。     

The synthesis of acrolein and acrylic acid by direct propane oxidation with Ni–Mo–Te–P–O catalysts

Ni–Mo–Te–P–O systems were tested for the synthesis of acrolein and acrylic acid by direct oxidation of propane. The effects of the reaction variables and of the water vapour on the catalytic performances were examined. The addition of dopants, such as Te and P, improved the yields and selectivities of acrolein and acrylic acid.     

The influence of additives and their concentration on the selectivity of catalysts based on heteropoly compounds in the reaction of propane oxidation

The catalytic properties and X-ray phase structure of molybdophosphoric heteropoly acid modified with Sb, W, and Nb ions have been studied in the reaction of propane oxidation. The additive of Nb ions increases the total activity of catalyst and its selectivity to acrolein and acrylic acid and decreases the selectivity to propylene. The concentration of Nb ions in samples is varied from 0.025 to 1 mol %. The concentration of Nb ions at a level of 0.025–0.1 mol % has the most profound effect on the reaction selectivity and the yield of mild oxidation products. The reaction selectivity depends on both the concentration of added niobium and the reaction conditions. The growth in the reaction temperature increases the conversion and selectivity to acrolein and reduces the selectivity to acrylic acid and propylene. The use of reaction mixture with higher propane concentrations decreases sharply the selectivity to acrolein. The obtained data can be explained by the possibility of the rearrangement of Nb ions between the cationic and anionic sublattices of heteropoly acids and by the change in the ratio between the acrolein and acrylic acid formation rates. The development and application of heteropoly compounds modified with niobium permits to increase the yield of target products in the partial propane oxidation.     

工业丙烯酸催化剂研究进展Ⅰ.丙烯醛催化剂

催化剂是丙烯两步气相催化氧化法生产丙烯醛和丙烯酸的核心。跟踪了国内外主要丙烯醛催化剂专利商的研究动向,对工业生产关注的丙烯醛催化剂的研究进展进行综述,并展望丙烯醛催化剂的发展前景。     

丙烯氧化制丙烯酸催化剂研究进展

介绍丙烯氧化制丙烯酸催化剂,综述丙烯一步氧化法和两步氧化法制丙烯酸催化剂的研究进展。丙烯两步氧化法通过Mo-Bi系丙烯醛催化剂和Mo-V系丙烯酸催化剂完成丙烯酸生产,目前通过催化剂制备工艺的研究,催化剂达到了较高性能水平。今后还应对添加各种助剂、制备工艺优化和改变催化剂成型方式等进行研究,进一步提高丙烯酸收率与稳定性。提出开发高丙烯空速催化剂,提高装置负荷是下一步的研究重点。     

Soft sensor modelling of acrolein conversion based on hidden Markov model of principle component analysis and fireworks algorithm

Based on the existing propylene oxidation process, it is important to measure acrolein conversion for the production of acrylic acid. The gas chromatographic analyzer is generally used to analyze the acrolein conversion as an off‐line method. In this paper, a soft sensor modelling method of acrolein conversion based on the hidden Markov model with principle component analysis (PCA) and the fireworks algorithm (FWA) is proposed. Firstly, PCA is used to decrease the input variables of hidden Markov model. Then, FWA is applied to optimize the initial parameters of the hidden Markov model. Finally, the hidden Markov model based on PCA and the FWA is employed to predict the acrolein conversion. The proposed method is compared with the support vector machine (SVM), the artificial neural network (ANN), and the hidden Markov method (HMM) to show its superior performance.     

Heterogeneous Catalytic Oxidation of Acrolein to Acrylic Acid: Mechanism and Catalysts

Partial oxidation of acrolein is a commercially important reaction, its product—acrylic acid—being widely used industrially for producing resins, dyes, glues, nonwoven fabrics, etc.

Partial oxidation of acrolein is also a convenient model reaction because: (1) the number of reaction products is moderate (CO, CO₂, acrylic acid) and (2) their difference in acid-base properties from the starting material makes it possible to select desirable catalysts by applying directly and efficiently Boreskov's concept of intermediate chemical interaction of a catalyst with reaction mixture components. According to this concept [1], the transformation of surface intermediates (SI) formed in the interaction of reactants with a catalyst's surface is determined by the structure and bond energy of these SI.

The study of the reaction mechanism includes determination of structures and energy characteristics of the surface intermediates and the elucidation of their connection with catalyst chemical composition and reaction routes to particular products. This reliable information helps us to understand the nature of catalyst action and to elaborate the theory of catalyst selection. We have used this method to approach the problem of the systematic selection of catalysts for the oxidation of acrolein to acrylic acid. The review summarizes the research done in the lnstitute of Catalysis of the Siberian Branch of the Russian Academy of Sciences during recent years.     

THE MECHANISM OF THE SELECTIVE OXIDATION OF ETHYLENE TO ETHYLENE OXIDE

The modern petrochemical industry relies on several hydrocarbon raw materials: methane, ethylene, propylene, butene, higher olefins, and the aromatics. Some of the most important processes that such raw materials are initially subjected to are oxidation reactions[1]; for example, methane is converted to acetylene, ethylene to ethylene oxide, and propylene to acrolein, acrylic acid, or acrylonitrile. The complete oxidation of any of the hydrocarbons being favored thermodynamically, all partial oxidation reactions are kinetically limited, the nature of the products being determined mechanistically. In heterogeneous catalytic oxidations the mechanism essentially involves interaction between a hydrocarbon and surface oxygen species. In the case of the oxidation of ethylene to ethylene oxide, carbon dioxide, and water, silver is unique in giving a high selectivity to ethylene oxide. We believe it is the type of adsorbed oxygen species involved in the interaction that determines the course of the reaction and hence the selectivity.     

合成丙烯酸催化剂研究进展

对用于合成丙烯酸催化剂进行分类总结,综述丙烯氧化制丙烯酸催化剂和丙烷氧化制丙烯酸催化剂研究进展。丙烯两步氧化法制丙烯酸催化剂应用广泛,催化剂主要为Mo-Bi系和Mo-V系复合氧化物。提出扩大丙烯酸下游产品领域对调节产能扩张的重要性,提高国产丙烯酸催化剂性能、增强工业应用能力、降低生产成本、减少污染物排放和开发新型丙烯酸催化剂及其生产技术是下一步的研究重点。     

Role of steam in partial oxidation of propylene over a Pd/SDB catalyst

Step-response studies of propylene partial oxidation with oxygen over a hydrophobic Pd/SDB catalyst were conducted at 1000 kPa and 185°C in a fixed-bed reactor. CO₂ was found to be the only oxidation product when the feed contained only propylene and oxygen. CO₂ formation was significantly suppressed by addition of steam to the feed, and this addition leads to the formation of partial oxidation products: acrolein and acrylic acid. A competitive reaction mechanism involving water molecules is proposed to explain the significant influence of steam concentration on the rate of propylene oxidation and product selectivity.     

Influence of gel composition in the synthesis of MoVTeNb catalysts over their catalytic performance in partial propane and propylene oxidation

MoVTeNb mixed oxides catalysts have been prepared by a slurry method with different molar compositions (Mo/Te ratio from 2 to 6 and Nb/(V + Nb) ratio from 0 to 0.7) in the synthesis gel leading to different crystalline phases distribution and catalytic behaviour in the partial oxidation of both propane and propylene to acrylic acid. Chemical analysis indicates that the composition of samples before and after the heat-treatment changes, especially the Te-content, since a significant amount of Te is lost during the heat-treatment step when the amount of oxalate (from niobium oxalate) increases in the synthesis gel. Thus, the nature of the crystalline phases and the catalytic performance of heat-treated materials will be related to the final chemical composition. On the other hand, only the catalysts presenting Te₂M₂₀O₅₇ (M = Mo, V, Nb) crystalline structure, the so-called M1 phase, were active and selective in the partial oxidation of propane to acrylic acid. Moreover, all catalysts were active and relatively selective to the formation of O-containing products, i.e. acrolein and/or acrylic acid, during the partial propylene oxidation although the more active ones were those presenting M1 phase.     

Simple chemical processes based on low molecular-mass alkanes as chemical feedstocks

The present state of new developments in direct catalytic conversion of low-molecular-mass alkanes (C₁–C₃) to petrochemical feedstocks and petrochemicals is reviewed. Special attention is given to the following reactions: methane to methanol and formaldehyde by partial oxidation as well as to C₂ hydrocarbons by oxidative coupling, ethane and propane to their olefins by oxidative dehydrogenation and to their oxygenates, i.e., acetic acid, acrylic acid and acrolein by partial oxidation. Specific research results are presented on the oxidative dehydrogenation of ethane and propane.     

Direct gas-phase epoxidation of propylene over nanostructured molybdenum oxide film catalysts

Mixed molybdenum oxides are widely used catalysts for propylene oxidation to acrolein or acrylic acid or for methanol oxidation in the gas phase. In the present study, however molybdenum oxides exhibited an epoxidation activity in the gas phase. To achieve this activity, the oxidation state, particle sizes and accessibility of molybdenum oxides are needed to be controlled. Such active molybdenum species can be prepared by PVD deposition of molybdenum nanorods and their subsequent oxidation in a controlled atmosphere. Accordingly, monoclinic MoO₂ particles with a diameter of < 10 nm can be prepared, which exhibit 42% selectivity to propylene oxide (the byproducts of the oxidation being mainly acrolein and acetone). In comparison, molybdenum-containing catalysts prepared by traditional impregnation methods exhibited practically zero epoxidation activity in gas-phase epoxidation of propylene.     

关于对丙烯氧化催化剂的研究和分析

对丙烯酸催化剂进行的性能试验,获得了最佳的工艺条件：第一反应器盐浴温度：320±10℃;丙烯空速95 hr-1,丙烯转化率在98%以上,第二反应器盐浴温度260±10℃,丙烯醛空速96.5 hr-1,丙烯醛转化率在99.58%以上。     

Economic trade-offs in acrylic acid reactor design

The acrylic acid process using air oxidation of propylene presents many interesting design trade-offs, particularly in the design of the reactor. The desired and undesired reactions are highly exothermic and very temperature dependent (large activation energies), so a large flowrate of inert water is also fed to the reactor to act as a thermal sink. Propylene conversion increases with temperature and reactor size, but acrylic acid yield decreases with increasing temperature. The heat of reaction is removed by generaing steam, and the steam pressure is an important design optimization variable since it sets low limits on reactor temperature. Using low-pressure steam gives high acrylic acid yield and lower carbon dioxide generation but requires large reactors. Larger air flowrates increase reactor oxygen concentrations, which reduce reactor volume but increase air compression costs.This paper explores the effects of the many design trade-offs on capital investment, energy cost and product selectivity.     

Modèles cinétiques et mécanisme de l'oxydation catalytique. Du propene en présence de molybdate de fer

The kinetic study of propylene oxidation to acrolein over a ferric molybdate catalyst has been performed on a differential reactor. Among models derived on the assumptions of Langmuir Hinshelwood kinetic rate or on Mars and Van Krevelen oxido-reduction mechanism, a discrimination method has been realized. The discrimination leads on one hand to the conclusion that acrolein is obtained either from oxygen of the oxide lattice or from absorbed dissociated oxygen. On the other hand carbon dioxide is formed both by acrolein degradation and by a mechanism excluding dissociation of oxygen.     

丙烯酸化工废水处理研究进展

丙烯酸及其酯作为丙烯的重要工业衍生物发展迅速,但是在丙烯酸及其酯生产过程中会产生大量的高浓度有机废水,常含丙烯酸、乙酸、甲苯、甲基丙烯酸等有毒有害的生化难降解有机污染物,难以处理。现有的工业处理方法主要有焚烧法、生化法、催化湿式氧化法等,虽然工艺成熟,但存在处理成本高等问题。本文综述了丙烯酸废水的主要处理技术及回收利用现状的研究进展。     

干燥方式对丙烯醛部分氧化制丙烯酸催化剂的影响

钼钒钨复合金属氧化物是典型的丙烯醛部分氧化制丙烯酸催化剂,铜、锑是良好的助剂.干燥方式对催化剂性能有较大影响.评价结果表明,喷雾干燥得到无定型的催化剂粉末,较结晶干燥方式具有更好的催化活性和选择性,适应的温度范围较宽.采用XRD、SEM和EDX方法对催化剂进行了表征,表明喷雾干燥所得样品元素分布更均匀.     

Crystalline Mo-V–W-mixed Oxide with Orthorhombic and Trigonal Structures as Highly Efficient Oxidation Catalysts of Acrolein to Acrylic Acid

We succeeded in introducing W in Mo₃VO_x with keeping the orthorhombic, trigonal, and amorphous structures. Synthesized crystalline Mo(W)₃VO_x with orthorhombic and trigonal structures, both of which possess heptagonal channels, showed catalytic activity for gas-phase selective acrolein oxidation to acrylic acid superior to amorphous Mo(W)₃VO_x and to tetragonal Mo₃VO_x. The results strongly suggest that the crystalline Mo(W)₃VO_x with orthorhombic and trigonal structures are real active phase of industrial acrolein oxidation catalysts based on Mo, W, and V oxides. Furthermore, we found that the resulting W-containing catalyst showed less-dependency of water partial pressure in the reactant feed on the acrolein conversion.     

On the Role of the Vanadium Distribution in MoVTeNbO x Mixed Oxides for the Selective Catalytic Oxidation of Propane

The selective oxidation of propane to acrylic acid is studied over a series of nearly pure M1-phase MoVTeNbO _x catalysts. Quantitative analysis of the reaction network shows that the ratio of the rate constants for propane oxidative dehydrogenation to propene and for the further oxidation of propene is constant. The rates towards acrolein and acetone, however, vary subtly with the concentration of vanadium and the location of its substitution. The reaction of acrolein to acetic acid and carbon oxides, associated with accessible metal cations, contributes two-thirds towards the non-selective pathway. The other third is associated with acetone formation. Vanadium is first substituted selectively at sites that are inactive for propane activation. Depending on the selectivity of this substitution two groups of materials have been identified, which show a distinctly different dependence on the concentration of vanadium. Statistic distribution of vanadium in the M1 phase appears to be the most promising strategy to improve the performance of MoVTeNbO _x catalysts for a given vanadium concentration.