国内甲酸生产、技术、市场现状

简单介绍了甲酸的用途；介绍了国外甲酸生产技术进展，甲酸甲酯法生产甲酸四种主要工艺的优缺点，国内甲酸生产技术发展和肥城阿斯德化工有限公司在甲酸甲酯法生产甲酸项目中的技术创新情况：以及国内外甲酸产品的市场需求情况和未来几年甲酸发展前景。     

国内甲酸的生产、技术和市场现状

简单介绍了甲酸的用途；介绍了国外甲酸生产技术进展，甲酸甲酯法生产甲酸四种主要工艺的优缺点．国内甲酸生产技术发展和肥城阿斯德化工有限公司在甲酸甲酯法生产甲酸项目中的技术刨新情况；以及国内外甲酸产品的市场需求情况和未来几年甲酸发展前景。     

甲酸生产技术经济及市场分析

介绍了甲酸市场应用情况,国内外甲酸生产技术现状与发展趋势,对各种甲酸生产技术经济分析及近期市场分析预测。     

甲酸钾市场及生产工艺浅析

综述了国内外甲酸钾的应用领域,市场情况,预测了未来5年国内外甲酸钾供需关系。分析了近年来国内外甲酸钾的主要消费领域、市场容量,主要生产企业产能情况。介绍了2种甲酸钾的生产工艺。展望了今后行业的发展方向,对甲酸钾行业普遍存在的包括技术、生产、市场等问题进行了讨论。     

环氧化生产中废甲酸水的回收利用探讨

通过对环氧脂肪酸甲酯生产中产生的甲酸回收试验,提供了一种环氧脂肪酸甲酯生产中甲酸回收利用的方法。     

甲酸市场及技术方案探讨

分析甲酸的市场结构,用量及潜力,探讨甲酸生产常用工艺方案,指出了甲醇催化脱氢结合甲酸甲酯水解工艺是一条中,小氮联醇厂可选择的甲酸生产的工艺路线。     

色谱-质谱联用测定丙烯酸中的甲酸

本文给出了用色谱／质谱法定量分析丙烯酸中低含量甲酸的方法，并对丙烯酸生产系统中的甲酸进行了检测。     

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。     

甲酸生产工艺技术及应用

甲酸是甲醇深加工的重要下游产品之一。本文对甲酸钠法、丁烷液相氧化法、甲酰胺法、甲酸甲酯水解法制甲酸生产工艺进行了对比分析,同时简要介绍了甲酸生产与消费情况。     

印度GNFC公司甲酸装置介绍

甲酸是重要的基本有机化工原料。它是脂肪族羧酸中结构最简单、酸性最强的无色透明液体,在医药、化工、纺织、轻工等方面都有广泛的用途。我国甲酸生产有30多年的历史,现有生产厂家10余家,总生产能力约3万吨/年。目前国内的甲酸生产法均为传统的甲酸钠法,即用一氧化碳和氢氧化钠生成甲酸钠,再与硫酸作用生成甲酸。用该法生产1吨甲酸,约需消耗100％的硫酸和烧碱各1吨,因此能耗较高、三废量大,再加上烧碱和硫酸时常短缺,严重影响了甲酸生产的发展,使我国的甲酸市场供不应求。 80年代初,美国的SD-BETHLEHEM公司和LEONARD公司以及德国的BASF公司先后研制成甲酸甲醋水解制取甲酸的二步法     

Determination and Correlation of Solubility for D-Xylose in Volatile Fatty Acid Solvents

The solubility of D-xylose in formic acid and binary solvents of formic acid with formic acid and acetic acid, propionic acid, n-butyric acid or isobutyric acid was measured in the temperature range from 300.35 to 325.05 K using the synthetic method by a laser monitoring technique at atmospheric pressure. The solid-liquid equilibrium data will provide essential support for industrial design and further theoretical study. The experimental data show that the solubility of D-xylose in formic acid and in the mixtures of formic acid＋acetic acid （1︰1）, formic acid＋propionic acid （1︰1）, formic acid＋n-butyric acid （1︰1）, and formic acid＋isobutyric acid （1︰1） increases with temperature. The Apelblat equation, theλh model, and the ideal solution equation correlate the solubility data well.     

Vapour phase hydrogenation of olefins by formic acid over a Pd/C catalyst

It has been found that ethylene and propylene could be effectively hydrogenated by formic acid vapour over a Pd/carbon catalyst at low temperatures (<440 K). Surface hydrogen formation from formic acid is the rate-determining step for this hydrogenation reaction. Interaction of this hydrogen with the olefins is then fast. The conversion of formic acid in the presence of either of the olefins at any temperature is higher than in their absence. This has been explained by a much lower surface hydrogen concentration in the presence of the olefins. Direct experiments have confirmed that hydrogen inhibits the formic acid decomposition. Water vapour addition has a small positive effect on the decomposition of formic acid as well as on the hydrogenation of the olefins with formic acid. Catalysts consisting of gold supported on carbon or titania are both active in the production of hydrogen from formic acid. However, in contrast to the Pd/C catalyst, neither gives hydrogenation of the olefins with this acid.     

Low‐temperature and highly efficient conversion of saccharides into formic acid under hydrothermal conditions

Production of formic acid, which has been regarded as an important H₂ carrier, from biomass can be a highly potential way to provide human societies with renewable energy source. To attain economically viable production of formic acid from biomass on an industrial scale, the system operation at low reaction temperature is crucially important. In this work, a low‐temperature hydrothermal conversion of carbohydrates such as monosaccharides and disaccharides into formic acid is reported. A good formic acid yield of 80–85% was obtained at a lower temperature of 423 K for only 15–20 min in the presence of NaOH without any other catalyst. The alkali was found to act as two roles in enhancing the production of formic acid. One was inhibition of the formic acid decomposition; another was favorable for the oxidation selectively at C‐1 for aldoses, which leads to the formation of formic acid via the rupture of the C1–C2 bond. © 2016 American Institute of Chemical Engineers AIChE J, 62: 3657–3663, 2016     

Formation of formic acid from glycerine using a hydrothermal reaction

BACKGROUND: Glycerine, a main by‐product of the biodiesel manufacturing process, has potential to be an important biorefinery feedstock with the rapid increase in biodiesel production all over the world. Hydrothermal experiments with glycerine were carried out at 250 °C using H₂O₂ as an oxidant. RESULTS: Glycerine was converted into formic acid with a yield of 31.0% based on the starting mass of carbon in glycerine. A possible oxidation pathway for the formation of formic acid from glycerine is proposed. In the proposed pathway, glycerine may first be oxidised and then decomposed into formic acid and oxalic acid. Oxalic acid was indirectly attributed to the increase of formic acid production from glycerine, but it instead acts as a retardant to prevent further oxidation of formic acid. However, when an alkali was added to the experimental conditions, the yield of formic acid was not greatly improved, reaching only 34.7%. CONCLUSION: The present work should help to facilitate further studies to develop a new green process for the production of formic acid from renewable biomass. © 2012 Society of Chemical Industry     

从皂浆废液中提取核苷酸

研究了采用离子交换层析技术从皂浆废液中提取核苷酸的最佳条件,实验表明,用2 mol/L的NaOH溶液将样品调至pH=9,流速控制在1.0 mL/min,依次用0.02 mol/L甲酸溶液,0.15 mol/L甲酸溶液,0.01 mol/L甲酸—0.05 mol/L甲酸钠溶液,0.1 mol/L甲酸—0.1 mol/L甲酸钠溶液洗脱时,条件最佳,核苷酸的提取率是86.70%。     

磷酸法制备甲酸的工艺研究

研究了磷酸与甲酸钠制取甲酸和磷酸钠盐的工艺过程。同时考察物料配比、温度、反应时间、焦磷酸量对甲酸收率影响,确定最适宜的工艺条件。实验结果表明:甲酸钠与磷酸物料配比为1:1.03、温度55℃、反应时间为240min、焦磷酸量193.73g时,甲酸收率达到90%,甲酸最终浓度可达到96%。     

钯基催化剂应用于甲酸电氧化反应的研究进展

甲酸是一种很有前途的化学储氢材料,可作为低温液体燃料电池的直接燃料。钯基催化剂作为直接甲酸燃料电池（DFAFC）阳极材料,对甲酸氧化具有良好的催化活性,能克服一氧化碳的毒化,在甲酸电化学氧化反应中主要按直接途径进行。降低贵金属含量、提高催化活性、提升稳定性是当前钯基催化材料研究领域的主要方向。主要介绍了当前研究中钯催化剂对甲酸电氧化的催化机理,综述了近5 a的钯合金催化剂制备、特殊形貌控制、碳负载对甲酸氧化活性增强的研究,对钯基催化剂的持续开发具有实际应用意义。     

生物柴油副产甘油合成丙烯醇研究

以甲酸、生物柴油的副产物甘油为原料合成丙烯醇,考察了投料比、甘油含水量对甲酸转化率和丙烯醇产率的影响。结果表明,n（甘油）∶n（甲酸）=1∶0.6时,甲酸的转化率达到86.7%,丙烯醇收率（以甲酸计）75.0%;同样条件下,m（水）∶m（甘油）=1∶10,甲酸转化率83.3%,产品收率（以甲酸计）73.5%。     

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.