甲醛直接空气氧化生产甲酸技术

以BIC开发的V Ti O为催化剂 ,甲醛直接空气氧化生产甲酸的转化率可达到 96 %～ 98% ,一氧化碳的生成比例低于 4 %。中试生产的反应温度为 110～ 112℃ ,甲醛转化率为 92 %～ 99% ,甲酸收率大于 80 % ,同时给出了甲酸生产能力为 2 0 0 0t/a的主要设备和主要化学品和公用工程消耗。     

Effective Catalysts for Wet Oxidation Of Formic Acid by Oxygen and Ozone

The catalytic wet-air oxidation and catalytic ozonation of a formic acid solution have been studied at room temperature using more than 20 kinds of catalysts including Pt/C, Pt/Al₂O₃, Pd/Al₂O₃, etc. The most effective catalyst was Pt/Al₂O₃. The apparent activation energies for the catalytic wet-air oxidation and ozonation on Pt/Al₂O₃ were both about 5 kcal/mol. This fact suggests that these reactions on the catalyst were diffusion controlled, and thus, the potential of the catalyst is likely much higher.     

硅胶催化双氧水甲酸氧化噻吩类化合物的研究

1 INTRODUCTION Due to growing environmental concern to impact of sulfur oxides contained in engine exhaust emissions, sulfur content specifications in light oils are becoming more and more stringent worldwide[1,2]. The necessity of producing low sulfur fuels to meet new regulation mandates requires new desulfurization techniques. As for the current hydrodesulfurization (HDS) technology, higher temperature, higher pressure, larger reactor volume, and more active catalysts are unavoidable,…     

Acetic Acid from the Carbonylation of Chloride Methane Over Rhodium Based Catalysts

A new route for the indirect conversion of methane that makes use of the latest advance in methyl chloride production is reported. Acetic acid was produced from the carbonylation of methyl chloride by carbon monoxide over a variety of catalysts. The presence of promoters was crucial for the carbonylation reaction. The yield of acetic acid reached 84.7% with RhCl₃ as catalyst and PPh₃/KI as promoters. The effects of reaction temperature, carbon monoxide pressure, and reaction time were investigated. The possible reaction mechanism was discussed.     

化学氧化法制备草酸工艺述评

综述了化学氧化法制备草酸工艺过程的四个方面。从氧化剂种类、原料来源、加料顺序和废气治理四个方面分别进行了分析,对该工艺过程中出现的问题以及解决的方法进行了探讨,指出了今后的研究发展趋势。     

草酸的生产工艺评述

草酸的合成方法有很多种,工业生产方法主要有碳水化合物氧化法、一氧化碳偶联法、甲酸钠法、乙二醇氧化法、丙烯氧化法等,介绍了上述几种草酸合成工艺,评述了各工艺的优缺点,并对我国草酸工业的发展提出建议。     

高浓度甲酸的生产

综述了国内外高浓度甲酸的生产方法，研制出一种ＷＹＥ型复合添加剂。该复合添加剂价低，易购。工业化投资少，无污染，产品收率在７５％－８０％。     

葡萄糖氧化制草酸

针对目前国内草酸生产成本高、工艺复杂等缺点,开展了葡萄糖氧化制草酸的工艺研究。以蔗糖、葡萄糖等碳水化合物为原料,在硫酸、硝酸和水的混合物为氧化介质的反应体系中氧化为草酸。在优化工艺条件下:硫酸的浓度为50%,反应温度60～65℃,m(葡萄糖)∶m(硝酸)=1∶3.2,催化剂的加入量为0.05%(以葡萄糖计,m/m),加料时间6h,母液循环使用。每吨葡萄糖可产草酸1.65～1.75t,收率达90%以上。     

Effect of Water on Methane and Ethane Oxidation in the Conditions of Oxidative Coupling of Methane Over Model Catalysts

The effect of water onto the rate and selectivity of methane and ethane oxidation in the conditions of oxidative coupling of methane (OCM) is studied. The effect of water strongly depends on the OCM catalyst composition: whereas PbO_X/Al₂O₃ undergoes an irreversible deactivation, no effect of water is observed on both reaction rate and OCM selectivity over La/MgO. Over NaWMn/SiO₂ catalyst both rate of reaction and selectivity are enhanced by water addition to the feed at low conversions during methane oxidation. In the case of ethane oxidation, the rate of reaction is strongly affected by water addition, whereas selectivity to ethylene does not change at equal conversions. At increasing concentration of water in the feed gas its relative effect onto the methane oxidation substantially decreases, so the increasing concentration of water above ~8 vol% does not further enhance the rate of methane oxidation. The observed effects are explained by the participation of water in the active site turnover, namely in its re-oxidation by shifting the prevailing re-oxidation route from filling surface oxygen vacancies to oxidative dehydrogenation of surface hydroxy-groups.     

Pure H2 Production by Decomposition of Methane Over Ni Supported on Hydroxyapatite Catalysts

The catalytic decomposition of CH₄ for the production of pure H₂ is carried out over Ni supported on hydroxyapatite [Ca₅(PO₄)₃(OH)] catalysts at 650 °C and atmospheric pressure. CH₄ decomposition activity is decreased with time on stream and finally deactivated completely. The physicochemical properties of the fresh catalysts are characterized by XRD, DTA/TG, TPR and SEM techniques along with CHNS analyses of the used samples. It is found that the 30 wt% Ni/HAp displayed higher H₂ production rates over the other Ni loadings, which is correlated with Ni metal surface area measured by O₂ pulse chemisorption. IICT communication number: 051211.     

从一氧化碳生产草酸

介绍、对比了传统的草酸生产方法－甲酸钠法和技术先进的羰基合成法。     

Influence of Acid Modification on Selective Phenol Hydrogenation Over Pd/Activated Carbon Catalysts

The influence of the acid treatment on cyclohexanone selectivity of phenol hydrogenation over Pd on active carbon was studied in liquid phase reaction and by temperature-programmed desorption. Acid treatment of activated carbon led to an increased cyclohexanone/cyclohexanol ratio. Acid modification of the carbon support enriched the electron density of Pd, and enhanced the desorption of the phenoxy species, which resulted in improved cyclohexanone selectivity in phenol hydrogenation.     

甲酸的生产及应用

简要介绍了甲酸甲酯法制备甲酸的生产工艺以及甲酸的应用。     

Production of COX Free Hydrogen by Catalytic Decomposition of Methane Over Ni/HY Catalysts

In this present paper, we report catalytic decomposition of methane over Ni/HY catalysts, with varying Ni loading at 550 °C and atmospheric pressure. The relationships between catalyst performance and characterization of the fresh and used form of catalysts are discussed from the data obtained by scanning electron microscopy, X-ray diffraction analysis, temperature programmed reduction, O₂ pulse chemisorption and carbon elemental analyses. It is observed that, the catalytic activity of Ni/HY catalysts is high at initial stages and gradually decreased with time and finally deactivated completely. The yield of hydrogen and carbon nanofibers is strongly dependent on Ni loading. It is found that 20 wt% Ni/HY catalyst showed higher hydrogen yield over the other loadings.     

Aromatization of Methane Over Mo-Fe/ZSM-5 Catalysts

Two groups of samples were studied for the aromatization of methane over Mo-Fe/ZSM-5 catalysts. The first group contains fixed loading (5 wt%) and variable Mo/Fe ratio. The second group was prepared with fixed Mo/Fe ratio and variable loading. The samples were characterized by TGA, S _BET, XRD, NH₃-TPD and TPO analysis. NH₃-TPD results indicate that the strength of strong acid sites increases when Mo/Fe ratio decreases for samples with fixed loading. The amount of strong sites decreases and new intermediate acid sites appear on samples containing both Mo and Fe. XRD results show the presence of iron molybdate for samples impregnated with both Mo and Fe. The catalytic properties of these samples were related not only to the amount and strength of acid sites but also to the iron molybdate phase.     

Partial Oxidation and Dry Reforming of Methane Over Ca/Ni/K(Na) Catalysts

Partial oxidation and dry reforming of methane to synthesis gas over Ca/Ni/K(Na) catalysts have been studied. Effects of temperature, pressure, and oxygen/methane ratios on catalytic activity, selectivity, and carbon formation have been determined. Also reforming of ¹³CH₄ in the presence of CO₂ and Temperature-Programmed Oxidation (TPO) of deposited carbon after the reaction indicated that both methane and CO₂ contribute to carbon formation. The TPO of deposited carbon on Ca/Ni/K catalyst showed that the catalyst consumed a significant amount of oxygen, only a fraction of which was consumed by carbon species on the surface, indicating that the surface oxygen plays a significant role in oxidizing and removing carbon species from the catalyst surfaces     

一氧化碳生产草酸

简述CO生产草酸的甲酸钠法和CO氧化偶连法,着重介绍CO氧化偶联制草酸酯的发展历史和工艺研究的进展情况,并对草酸工业的发展提出建议.     

一氧化碳生产草酸

简述CO生产草酸的甲酸钠法和CO氧化偶连法,着重介绍CO氧化偶联制草酸酯的发展历史和工艺研究的进展情况,并对草酸工业的发展提出建议。     

草酸市场及生产技术现状

从草酸用途及深加工产品链方向,介绍草酸国内外市场状况及生产技术现状,分析我国目前一产中存在的问题,提出在近期应用富含一氧化碳的工业炉尾气作为草酸生产原料,发展方向应以工业废气二氧化碳作为原料,以期达到草酸生产方法更新换代和资源充分利用的目的。