甲酸甲酯的合成及应用

介绍了甲酸酯化法，甲醇催化脱氢法，合成气直接合成法，甲醇羰基化法等甲酸甲酯的７种合成方法及制甲酰胺，二甲基甲酰胺，甲酸，醋酸等方法的７种用途。     

低温甲醇合成研究进展

日本学者Tsubaki等开创了一种全新的低温甲醇合成反应路径。该路径以含有二氧化碳的合成气为反应原料,使用单一低碳醇(包括甲醇)同时作为催化剂和溶剂,实现了反应原料一氧化碳在低温(443 K)条件下,一步转化率达到70%～100%。原位红外和多种表征手段证明,该反应能够在低温条件下进行,是由于催化剂上吸附的甲酸盐物种可以和多种低碳醇溶剂在低温条件发生酯化反应,生成相对应的甲酸酯。而生成的甲酸酯很容易在低温条件下,铜基催化剂表面,发生加氢反应,生成甲醇和相应的溶剂醇。该种全新的甲醇合成路径克服了常规甲醇合成过程中,甲酸盐必须在高温条件下才能发生加氢反应的关键步骤。同时,还介绍了适用于低温甲醇合成反应的金属Cu/ZnO催化剂制备方法的研究进展。全新的溶胶-凝胶-燃烧法、固相研磨-燃烧法以及甲酸辅助燃烧法直接制备高活性、纳米尺度、高分散的金属Cu/ZnO催化剂,而不需要额外的还原流程。     

甲酸新进展

<正> 全世界甲酸能力为400百万磅/年,美国占四分之一。美国主要用于织物印染及整理,鞣革及染色;西欧主要用作动物青饲料防腐剂。另外,甲酸可取代盐酸和硫酸用于钢铁酸洗,其除垢防锈效率与无机酸相同,并且不产生废水等环保问题。在造纸业中可用于取代苛性碱和亚硫酸盐。甲酸的工业生产方法,有甲酸盐法,甲酰胺法,烃类液相氧化法,甲醇法。一氧化碳直接合成法等。发展最快的是甲醇羰基化法。SD公司和Leonard公司都拥有自己的     

对于乙醛均相氧化生产醋酸工艺的一些探讨

<正>目前醋酸的工业生产方法,除烃类氧化法、乙炔水合法以及一氧化碳与甲醇在压力下进行羰基合成外,乙醛与氧或空气催化氧化法是目前生产常用的方法。乙醛与氧液相催化氧化合成醋酸所用的催化剂为醋酸锰。该法的合成过程除产生二氧化碳、一氧化碳、甲烷等气态杂质外,同时生成水、甲酸甲酯、醋酸甲酯、甲酸等副产物,其中严重的是0.2～0.3%的副产甲酸,它要腐蚀设备,影响产品质量。为了满足有机合成工业对优级醋酸的要求,除了分离其它杂质以外,还必须将粗醋酸中的甲酸尽可能地除净。     

甲酰胺的生产方法

<正> 甲酰胺的生产方法有:①一步法——CO和NH_3直接进行合成反应(需高压)。②羰基合成MF进而氨解法—CO和甲醇进行羰基合成,生成的MF再与氨反应生成甲酰胺。③甲醇脱氢制MF进而氨解法。④传统法—用焦炭发生煤气,将煤气净化,用NaOH溶液吸收煤气中的CO制得甲酸钠,甲酸钠酸化制得甲酸,甲酸与甲醇反应生成MF,MF氨解得甲酰胺。传统     

国内外甲酸生产、消费与市场

甲酸是一种基本有机化工原料，广泛应用于农药、医药、纺织印染、皮革加工、青贮饲料等方面。甲酸衍生物的用途也十分广泛。１９８０年以前，世界工业化生产甲酸均用甲酸钠法，该法消耗较高，已逐步被淘汰。８０年代初，美国、德国等公司对甲醇羰基化制甲酸甲酯的工艺进行...     

一种甲酸和醋酸联产的生产方法

正本发明涉及一种甲酸和醋酸联产的生产方法。该方法是在甲醇羰化法合成醋酸的基础上,引入原料甲酸甲酯,在含有液体组合物的羰基化反应釜中通过酯交换和羰基化反应实现甲酸和醋酸的联产。所述的液体反应组合物包括:铑或铱羰基化主催化剂或两者的混和物、碘甲烷助催化剂、醋酸、甲酸、甲酸甲酯、醋酸甲酯、水、以及金属盐促进剂。本发明     

甲醇脱氢制甲酸甲酯专利分析

<正>一、背景简介甲酸甲酯广泛用于制药、溶剂工业、农药和制取甲酸的原料.近年来,甲酸甲酯作为一种重要的有机合成中间体,在C1化学的地位越来越受到重视。因此日、美、俄等国和我国西南化工研究院以及中科院山西煤化所等进行了甲醇脱氢制甲酸甲酯催化剂的研究。目前,已经工业化的甲酸甲酯生产方法有甲酸酯化法、甲醇羰基化法和甲醇气相脱氢法。上世纪九十年代国内投产的甲酸甲酯小装置基本都停产,目     

CO_2高效利用翻开新篇章 有望成为甲醇、丙烯酸、丁二醇、合成树脂原料

<正>CO2被认为是导致全球变暖的元凶之一,但它也并非全无用处。今年以来,国内外科研人员相继在CO2高效利用上取得进展,CO2有望成为甲醇、丙烯酸、丁二醇、甲酸、新型树脂新的原料来源。加氢合成甲醇法国原子能委员会下属的萨克莱辐射材料研究所的研究人员首先将CO2加氢合成甲酸,然后使用稀有金属钌作为催化剂,将甲酸转化为甲醇,生成率高达50%。美国华盛顿大学在2013年曾以稀有金属铱为基础开发出可将甲酸转化成甲醇的催化剂,但铱的     

二氧化碳高效制取甲醇的新技术

正据报道,法国研究人员最新研发出一种利用二氧化碳高效制取甲醇的技术。法国原子能委员会下属的萨克莱辐射材料研究所的研究人员首先将二氧化碳加氢合成甲酸,然后使用稀有金属钌作为催化剂,将甲酸转化为甲醇,生成率高达50%。美国华盛顿大学的专家组在2013年便开发出以稀有金属铱为基础的可将甲酸转化成甲醇的催化剂。然而,一方面,铱的价格极高;另一方面,使用这一催化剂制造甲醇的生成     

Aspects of carbon dioxide utilization

Carbon dioxide reacts with hydrogen, alcohols, acetals, epoxides, amines, carbon–carbon unsaturated compounds, etc. in supercritical carbon dioxide or in other solvents in the presence of metal compounds as catalysts. The products of these reactions are formic acid, formic acid esters, formamides, methanol, dimethyl carbonate, alkylene carbonates, carbamic acid esters, lactones, carboxylic acids, polycarbonate (bisphenol-based engineering polymer), aliphatic polycarbonates, etc. Especially, the productions of formic acid, formic acid methyl ester and dimethylformamide with a ruthenium catalyst; dimethyl carbonate and urethanes with a dialkyltin catalyst; 2-pyrone with a nickel-phosphine catalyst; diphenyl carbonate with a lead phenoxide catalyst; the alternating copolymerization of carbon dioxide and epoxides with a zinc catalyst has attracted attentions as the industrial utilizations of carbon dioxide. The further development of these production processes is expected.     

Trimethoxymethane as an alternative fuel for a direct oxidation PBI polymer electrolyte fuel cell

The oxidation of trimethoxymethane (TMM) (trimethyl orthoformate) in a direct oxidation PBI fuel cell was examined by on-line mass spectroscopy and on-line FTIR spectroscopy. The results show that TMM was almost completely hydrolyzed in a direct oxidation fuel cell which employs an acid doped polymer electrolyte to form a mixture of methylformate, methanol and formic acid. It also found that TMM was hydrolyzed in the presence of water at 120°C even without acidic catalyst. The anode performance improves in the sequence of methanol, TMM, formic acid/methanol, and methylformate solutions. Since formic acid is electrochemically more active than methanol, these results suggest that formic acid is probably a key factor for the improvement of the anode performance by using TMM instead of methanol under these conditions.     

Activity of a novel titanium-supported bimetallic PtSn/Ti electrode for electrocatalytic oxidation of formic acid and methanol

Bimetallic platinum–tin nanoparticles were co-deposited on a titanium surface using a simple one step hydrothermal method process. The electrochemical catalytic activity of this titanium-supported nanoPtSn/Ti electrode towards the oxidation of formic acid and methanol in 0.5 M H₂SO₄ was evaluated by voltammetric techniques, chronoamperometric responses and electrochemical impedance spectra (EIS). According to the cyclic voltammograms of the oxidation of both formic acid and methanol, the nanoPtSn/Ti presents high anodic current densities and low onset potentials. Potential-time transient measurements show that the nanoPtSn/Ti exhibits high steady-state current densities for the oxidation of both formic acid and methanol. The EIS data indicate that the nanoPtSn/Ti presents very low electrochemical impedance values, showing that for the oxidation of both formic acid and methanol, low charge transfer resistances are present on the nanoPtSn/Ti catalyst. This confirms the high electrocatalytic activity of the nanoPtSn/Ti for the formic acid and methanol oxidation.     

Electrooxidation of methanol and formic acid on PtCu nanoparticles

Improving the catalytic activity of the anode catalyst is an important task in direct methanol and formic acid fuel cell development. In the present work, catalytic activity of shape-controlled PtCu nanoparticles toward methanol and formic acid oxidation was investigated. The results show that the addition of Cu to Pt increases the catalytic activity of both reactions. In addition, the shape of PtCu nanoparticles plays an important role on improving the reactivity of both reactions. Cubic PtCu nanoparticles are more active for methanol oxidation while spheres are better for formic acid oxidation. The present study demonstrates controlling shape of Pt alloy catalysts is an effective way of improving catalytic activity. Likely mechanisms of the activity enhancement are briefly discussed.     

反应精馏回收糠醛生产中产生的甲酸和醋酸

二步法甲酸/醋酸催化玉米芯生产糠醛工艺的水解过程会产生少量的醋酸和甲酸,因此水解液中醋酸和甲酸的质量分数不断增加。为了使糠醛生产中甲酸和醋酸质量分数适合工艺条件,文中采用反应精馏法回收该工艺中过量的醋酸和甲酸。分别考察了回流比、酸水进料流量、甲醇与醋酸进料摩尔比、醋酸质量分数和甲酸质量分数等因素对反应精馏回收甲酸和醋酸效果的影响。通过实验得出了适宜的工艺条件:对甲酸质量分数在0.5%以上、醋酸质量分数20%以下的水解液,酸水进料流量在9.0 mL/min、甲醇醋酸进料摩尔比为3∶1和回流比为5等条件下的处理效果最佳。最佳反应条件下对于醋酸质量分数为20%的水解液,醋酸转化率为50.4%,同时甲酸质量分数降低到0.5%。实验证明此方法在满足二步法生产糠醛工艺对水解液甲酸和醋酸质量分数的要求的同时,可回收过量的甲酸和醋酸。     

黄磷尾气的回收利用

黄磷尾气含有高浓度的一氧化碳,是一种重要的资源,经净化处理后可作为化工产品的原料气,生产高附加值产品,如草酸、甲酸、甲醇等.总结了中国黄磷尾气净化处理技术和综合利用经验,提出了降低黄磷尾气中磷、硫等杂质含量的技术措施.针对当前存在的问题,遵循科学发展观,以循环经济理念,提出了几点建议.     

Methanol and formic acid oxidation in zinc electrowinning under process conditions

The possibility of using methanol or formic acid oxidation as the anode process in zinc electrowinning was examined. The activity for methanol and formic acid oxidation on Pt coated high surface area electrodes was investigated over 36 h, at a current density used in industry. The activity could be maintained at a constant potential level in a synthetic electrowinning electrolyte if the current was reversed for short periods. During the tests, the anode potential was, more than 1.2 V below the potential for the oxygen evolving lead anodes used in modern zinc electrowinning. The lowered anode potential would lead to a significant energy reduction. However, tests in industrial electrolyte resulted in a very low activity for both methanol and formic acid oxidation. The low activity was shown to be caused mainly by chloride impurities. A reduction of the chloride content below 10⁻⁵ M is needed in order to obtain sufficient activity for methanol oxidation on Pt for use in zinc electrowinning. Pt and PtRu electrodes were compared regarding their activity for methanol oxidation and the latter was shown to be more affected by chloride impurities. However, at a potential of 0.7 V vs NHE, with a chloride content of 10⁻⁴ M, formic acid oxidation on PtRu gives the highest current density.     

Electrochemical effect of gold nanoparticles on Pt/α-Fe2O3/C for use in methanol oxidation in alkaline solution

A catalyst containing gold nanoparticles with Pt/α-Fe₂O₃/C was prepared by a co-precipitation method and its catalytic activity for the oxidation of methanol, formaldehyde, and formic acid in alkaline solutions was evaluated by an electrochemical method and high-performance liquid chromatography (HPLC). The addition of gold nanoparticles improved catalytic activity only for the oxidation of methanol and formaldehyde, and not for the oxidation of formic acid. HPLC analysis was performed for methanol oxidation to detect the oxidative products. In HPLC analysis, only formate anion could be detected in the electrolyte solution and the ratio of formate anion obtained to the total passed charge in Pt/nano-Au/α-Fe₂O₃/C was less than that in Pt/C, indicating that formic acid is not the final product of methanol oxidation. These results show that gold nanoparticles promoted methanol oxidation up to CO₂.     

Low-temperature conversion of methane to oxygenates by supported metal catalysts:From nanoparticles to single atoms

Direct cost-effective conversion of abundant methane to high value-added oxygenates (methanol,formic acid,acetic acid,etc.) under mild conditions is prospective for optimizing the structure of energy resources.However,the C-H bond of products is more reactive than that of high thermodynamic stable methane.Exploring an appropriate approach to eliminate the "seesaw effect" between methane conver-sion and oxygenate selectivity is significant.In this review,we briefly summarize the research progress in the past decade on low-temperature direct conversion of methane to oxygenates in gas-solid-liquid phase over various transition metal (Fe,Cu,Rh,Pd,AuPd,etc.) based nanoparticle or single-atom catalyst.Furthermore,the prospects of catalyst design and catalysis process are also discussed.     

Time course of the levels of oxidative intermediates during methanol utilisation by Candida boidinii 11 Bh

Growth kinetics of the methanol-utilising yeast Candida boidinii 11 Bh in shake flasks and in a fermenter have been studied in connection with the accumulation of the oxidative intermediates, formaldehyde and formic acid. The effect of the addition of substrate, formaldehyde and formic acid during batch growth showed that formic acid may accumulate to amounts inhibitory to growth. The amount of formic acid accumulated was proportional to the initial methanol concentration. On the other hand, formaldehyde, the first oxidative product, had no effect on growth under the same conditions.