LC210型联醇催化剂性能特点及工业应用

世界甲醇产量仅次于合成氨、乙烯居第三位。随着汽油添加剂甲基叔丁基醚（Mn记）需求量的增加，作为其原料的甲醇的需求量猛增，1999年世界甲醇消费量达2650万吨，2005年需求预测2980万吨。我国甲醇产量在“八五”期间年均增长率为18．1％，“九五”为8．2％。1996年甲醇生产能力243．6万吨，产量141．2万吨，2002年甲醇产量达到210：95万吨，表观消费量为390．0万吨，自给率为54％。2003年甲醇产量更是大幅增长，1～11月累计达到269．6万吨，同比增长28．9％，全年产量达到290万吨，比上年增长37％以上。随着M15（即在汽油和柴油中掺混15％甲醇）技术的日趋成熟，甲醇显示出良好的发展前景，2004年甲醇市场总年产能力将超过500万吨。     

2006年我国甲醇产量前10位的甲醇企业

2006年我国甲醇产量762万t，约为产能的68．2％，其中前10位的甲醇企业总产量达到259万t，约占全国总产量的34．0％。     

6-氨基-7-氟-2件1，4-苯并嗯嗪-3（4H）-酮的高效液相色谱法测定

叙述了采用反向高效液相色谱法，以甲醇为溶剂，甲醇与水（体积比65：35）为流动相，ODS为填料和紫外检测器分离测定6-氨基-7-氟-2H-1，4-苯并曝嗪-3（4H）-酮。该方法的标准偏差为0．29，变异系数为0．32％，回收率为99．85％，线性关系系数为0．9997。     

市场动态

世界甲醇需求趋缓预计今后5年，世界甲醇的需求量将年均增长2．7％，比过去5年的年均增长率6．7％有所趋缓。1991～1995年间，甲醇需求量年均增长率为18．5％，预计1996～2001年间，年均需求增长率将减缓为3．1％。与此同时，用于燃料的甲醇需求量年均增长仅为0．7％。预计从1996～2001年间，世界甲醇的生产能力年均增长率为2．9％，而过去5年的平均增长率为6．l％。1一案乙四甲自播求预测l一条乙酸甲酯目前国内仅有小试样品，根据我国工农业生产发展情况，该产品市场前景广阔：一是我国马铃薯年产量约1000万吨，用l一带乙酸甲酯抑制其发芽…     

国内外醋酸工业发展概况

0概述 醋酸是甲醇重要下游产品之一。据统计，2005年全球甲醇消费量约为3210万t，其中11％用于醋酸生产。作为重要有机化工原料，醋酸主要用作醋酸酯类的生产，在日本2005年统计数据中，全球消费量为787．4万t，其中醋酸酯类为334．0万t，占42．4％：醋酐101．6万t，占12．9％：溶剂130．3万t，占16．6％；精对苯二甲酸（PTA）141．1万t，占17．9％：其它用途80．3万t，占10．2％。     

铜氨液中甲醇含量的准确、快速测定

1问题的提出 我国现有众多的合成氨联产甲醇装置。联醇生产是：利用合成氨原料气中的一氧化碳和氢合成甲醇，这样既可以生产合成氨，又生产工业甲醇。众所周知，联醇生产作为合成氨系统中的一个环节，在一定程度上影响合成氨及整个系统的生产。如甲醇合成塔后气液分离状况会影响铜氨液的组成，经甲醇分离器分离甲醇后气相中仍含有一定量的甲醇，正常情况下约为0．3％左右；如果甲醇水冷器温度高或分离效果差，则气相中的甲醇含量将更高，如我公司曾有：分离器出口甲醇含量高达0．7％～1％的工况。     

柱前衍生反相高效液相色谱法快速测定3,5-二氯苯甲酰氯

以无水甲醇作柱前衍生试剂，建立了反相高效液相色谱法间接测定3，5-二氯苯甲酰氯的新方法。实验结果表明，在流动相：甲醇-水（85：15），流速：1．0mL／min，检测波长：288nm的条件下，定量校正曲线具有良好的线性关系，相关系数（r）为0．9999。方法用于样品中标题物质的测定，RSD=0．19％（n=6），加标回收率为99．9％-105％。     

啶虫脒乳油的高效液相色谱分析

采用Spheri-5 RP-18不锈钢柱，以甲醇＋水（64＋36）为流动相和紫外检测器（254nm)，对啶虫脒进行反相色谱分离和测定。其变异系数为0．03％，标准偏差为0．097％，平均回收率为99．99％。     

防霉剂富马酸单甲酯制备工艺的改进

以顺丁烯二酸酐和甲醇为原料，硫酸氢钠和氯化铝为催化剂，甲苯作溶剂合成了防霉剂富马酸单甲酯，考察了影响收率的因素，其最优条件为：顺丁烯二酸酐：甲醇：硫酸氢钠：氯化铝为0．2mol：0．2mol：1．5g：2g；酯化反应温度60℃，反应时间0．5h；异构化温度80℃，反应时间2h。收率可达90．0％以上。     

氢化钠催化法合成芴甲醇

研究了以NaH为催化剂，由芴与甲酸乙酯合成芴甲醇的工艺，当甲酸乙酯兼作溶剂时，芴甲醇总收率为87．0％。     

HPLC法测定吡·咪悬浮种衣剂中的有效成分

介绍了用一根C18柱,在同一色谱条件下,以甲醇和水为流动相,对吡虫啉和咪鲜胺混配制剂进行定量分析。该方法的标准偏差分别为0 012和0 014,变异系数分别为1 07%和2 64%,线性相关系数分别为0 9996和0 9997,回收率分别为98 93%～102 79%和98 7%～100 49%。     

Methanol recycling in the production of biodiesel in a membrane reactor

Membrane reactor technology was used to overcome challenges in biodiesel production. The membrane reactor produces a permeate stream which readily phase separates at room temperature into a fatty acid methyl ester (FAME)-rich non-polar phase and a methanol- and glycerol-rich polar phase. To decrease the overall methanol:oil molar ratio in the reaction system, the polar phase was recycled. Three recycle ratios were tested: 100%, 75% and 50%, at the same residence time and operating conditions. The permeate consistently separated to yield a FAME-rich non-polar phase containing a minimum of 85 wt.% FAME (the remainder being methanol) as well as a methanol/glycerol polar phase. At the highest recycle ratio, the FAME concentration ranged from 85.7 to 92.4 wt.% in the FAME-rich non-polar phase. In addition, the overall molar ratio of methanol:oil in the reaction system was significantly decreased to 10:1 while maintaining a FAME production rate of 0.04 kg/min. As a result, a high purity FAME product was produced.     

固相萃取-高效液相色谱法检测饮用水中痕量微囊藻毒素

介绍了建立固相萃取-高效液相色谱法检测水中痕量微囊藻毒素的方法。水样经固相萃取柱富集,净化,甲醇洗脱,氮吹浓缩,甲醇与磷酸盐缓冲溶液按45∶55混合作为流动相,色谱柱分离,检测用波长为238 nm。结果表明各组分在0~1μg/L内线性良好,平均回收率分别为100.9%和92%。该方法灵敏度高、操作简单、定量准确,适用于饮用水中痕量微囊藻毒素的检测。     

Biodiesel production from non-degummed vegetable oils: Phosphorus balance throughout the process

In this work, the biodiesel production process using high-phosphorous content raw materials is studied. The objective is to determine the phosphorous mass balances, in order to determine the amount of this element in each stream of an integrated process including esterification, transesterification, and glycerin purification. It was found that up to 97% of the initial phosphorous content in the oil is accumulated in the glycerin phase. The small amount of phosphorous left in the biodiesel phase after decantation is eliminated during the acid extraction carried out to purify the biodiesel. The evaporation of methanol after the reaction plays a major role in the quantity of phosphorous and soaps left in the biodiesel phase. For example, with a crude soybean oil containing 226 ppm of phosphorous, the methanol content at the end of the reaction in the biodiesel phase is 4.6 wt.%, being the phosphorous content 7.1 ppm, and the soap concentration 3.89 g/kg. The methanol was evaporated in such a way that its concentration dropped to 0.35 wt.%, and the phosphorous and soaps concentrations decreased to 4 ppm and 0.7 g/kg respectively. This has a direct impact in the quality of the final biodiesel. During the esterification, also an important amount of phosphorous is eliminated from the biodiesel phase.     

反相高效液相色谱法直接测定离子液体中咪唑杂质含量

研究了高效液相色谱法测定离子液体中的杂质(4-甲基咪唑)含量的测定方法。在不同色谱条件下,分离效果不同。在AllsphereODSC18色谱柱上,以水-甲醇为流动相,两者流速比为水∶甲醇=1∶9,流速为1.0mL/min,在215nm处进行紫外检测,离子液体能与4-甲基咪唑很好的分离。另外,在HypersilBDSC18色谱柱上用类似的条件分离效果也较好。采用该法的线性范围,检出限分析考察,结果表明,其灵敏度高、定量准确、重现性好,适合于离子液体中4-甲基咪唑这种杂质含量的测定。     

Liquid phase methanol and dimethyl ether synthesis from syngas

The Liquid Phase Methanol Synthesis (LPMeOH^TM) process has been investigated in our laboratories since 1982The reaction chemistry of liquid phase methanol synthesis over commercial Cu/ZnO/Al₂O₃ catalysts, established for diverse feed gas conditions including H₂-rich, CO-rich, CO₂-rich, and CO-free environments, is predominantly based on the CO₂ hydrogenation reaction and the forward water-gas shift reactionImportant aspects of the liquid phase methanol synthesis investigated in this in-depth study include global kinetic rate expressions, external mass transfer mechanisms and rates, correlation for the overall gas-to-liquid mass transfer rate coefficient, computation of the multicomponent phase equilibrium and prediction of the ultimate and isolated chemical equilibrium compositions, thermal stability analysis of the liquid phase methanol synthesis reactor, investigation of pore diffusion in the methanol catalyst, and elucidation of catalyst deactivation/regenerationThese studies were conducted in a mechanically agitated slurry reactor as well as in a liquid entrained reactorA novel liquid phase process for co-production of dimethyl ether (DME) and methanol has also been developedThe process is based on dual-catalytic synthesis in a single reactor stage, where the methanol synthesis and water gas shift reactions takes place over Cu/ZnO/Al₂O₃ catalysts and the in-situ methanol dehydration reaction takes place over -Al₂O₃ catalystCo-production of DME and methanol can increase the single-stage reactor productivity by as much as 80%. By varying the mass ratios of methanol synthesis catalyst to methanol dehydration catalyst, it is possible to co-produce DME and methanol in any fixed proportion, from 5% DME to 95% DMEAlso, dual catalysts exhibit higher activity, and more importantly these activities are sustained for a longer catalyst on-stream life by alleviating catalyst deactivation.     

The effect of phase transition of methanol on the reaction rate in the alkylation of hydroquinone

An O-alkylation reaction of hydroquinone with excess methanol was carried out by using alkaline metal ion-exchanged zeolite catalysts at various phases of methanol in a slurry type reactor. The amount of methanol, used as a methylating agent and also a solvent, significantly affected the reaction rate. When the amount of methanol was decreased from 2 mol to 0.6 mol, the reaction rate was increased more than nine times. These changes in the reaction rate could be explained by the pressure change and the phase transition of the reactant, methanol, depending on the temperature and the elimination of a diffusion limitation of reactants through the zeolite pores in a gas phase condition. Thus, higher than 89% selectivity to 4-methoxyphenol was obtained at 80% conversion of hydroquinone at a gas phase reaction condition using 1 mol of methanol for 2 hours.     

Effect of PVA in dispersion polymerization of MMA

Monodisperse poly(methylmethacrylate) microspheres having a diameter of 2.6 μm and a molecular weight of 102,277 g/mol with 5.3% of the C_v (the coefficient of variation) were synthesized by the dispersion polymerization using hydrophilic polyvinylalcohol (PVA) in methanol/water mixture media. Then, the structural verification of the synthesized materials is confirmed by using ¹H NMR and FT-IR spectroscopy. The effects of PVA and the polymerization parameters such as the initiator, monomer and stabilizer concentrations, and the reaction time on the characteristics of the final particles were studied. Thus, the role of PVA in the dispersion polymerization of MMA is not only a steric stabilizer by physically adsorbed in methanol phase, but also a colloid protective to give relatively monodisperse polymer particles in water phase, simultaneously.     

汉逊酵母高密度发酵表达乙型肝炎表面抗原的甲醇流加控制策略

目的考察不同甲醇流加策略对汉逊酵母(Hansenula polymorpha)高密度发酵表达重组乙型肝炎表面抗原的影响。方法在细胞生长阶段采用DO/pH在线测量的控制方法,使酵母细胞密度达到一个较高水平,诱导期比较DO-Stat/pH-Stat法和离线检测甲醇两种控制流加甲醇的方法,同时也比较用甘油和甲醇双碳源间断流加法与单纯流加甲醇法对目的蛋白表达的影响。结果诱导期用DO-Stat和pH-Stat法不能有效地提高乙肝表面抗原表达量,而离线检测甲醇的控制方法,在诱导阶段可将甲醇浓度控制在0~5g/L的范围,乙肝表面抗原表达量比DO-Stat/pH-Stat法提高了20%。甲醇氧化酶(MOX)酶活性的变化与乙肝表面抗原表达量变化存在对应关系,交替加入甘油和甲醇双碳源刺激,可以使乙肝表面抗原表达量达到395mg/L。结论已筛选出优化工艺配置,并建立了切实可行的规模化生产工艺。     

甲醇合成反应器与分离器工艺设计

概述甲醇合成反应器的设计和选材原则，介绍了均温列管式甲醇合成反应器和全收率甲醇分离器的技术特点。甲醇产能200—250kt／a和300-400kt／a装置的甲醇合成反应器直径分别为Ф3400～3600mm和Ф3800—4000mm，吨甲醇可副产中压蒸汽1．0t，具有操作适应性强、产品质量好等特点；甲醇分离器采用全收率甲醇分离技术，回收率近100％，分离后气相中含甲醇体积分数〈0．1％。通过实际生产检验，表明这2台设备具有设计先进性与可行性。