混合甲胺的市场情况和工艺技术简析

本文介绍了甲胺的市场供需情况及以甲胺、液氨为原料生产甲胺的工艺过程,并对建设3600吨/年甲胺装置进行了技术经济分析。建议有条件的中氮厂可考虑建立甲胺装置,作为综合利用、提高经济效益的一种手段。     

无水甲胺的气相色谱分析法

无水甲胺的气相色谱分析法叶福祥（南化公司氮肥厂）甲胺是化学工业基本的有机原料，广泛应用于农药、化纤和国防工业等方面。有关甲胺水溶液的分析方法，国内已有标准可循。而对于无水甲胺，由于样品的一沸点较低，在常温下易汽化，使之不能用标样来校正。对于这种既无标...     

创新节能技术在甲胺工艺中的应用

介绍了3套甲胺装置改造前的生产运行状况;论述了技术改造方案:合成部分增设低温换热器,合成塔提馏段采用3级热量回收技术,增设蒸汽冷凝液闪蒸回收系统;对比了改造前后生产运行数据。结果表明,改造后甲胺生产能力从4万t/a扩大到6万t/a,产能提高了50%;吨甲胺蒸汽消耗从10 t降低到7.09 t;改造投资为746万元,年经济效益6 841万元,投资回收期约1.3月。     

3万t/a甲胺装置扩产小结

采用甲醇和液氨连续气相催化胺化法生产甲胺,对甲胺装置3万t/a改扩情况进行总结,针对原工艺萃取塔、脱水塔、分离塔存在的问题进行了相应的技术改造.改造后,甲醇吨耗由1.68 t降至1.66 t,蒸汽吨耗由7.2 t降至6.8 t.二甲胺、三甲胺产量增加,年增效益356.4万元.     

甲胺水溶液配制系统改造

分析甲胺水溶液配制系统存在的配制时间长、配制浓度不精准等问题.通过采取更换配制泵、改造配制槽内部结构、改变物料换热器投运模式等措施,缩短了甲胺水溶液配制时间、解决了配制浓度不精准的问题.     

甲胺装置电加热器泄漏的原因及处理

简要论述了甲胺生产原理、生产工艺,着重论述了电加热炉的作用、产生泄漏的原因分析,提出更换电加热管、PLC调控方案改造,增加氮气流量改造等措施,实施后,取得较好效果。     

我厂甲胺系统节能降耗途径

我厂甲胺系统节能降耗途径汪瑜（淮南化工总厂安徽省淮南市２３１２０３８）我厂甲胺装置自１９９３年３月化工试车成功后，经过这一年多的试生产，产量达到了设计能力，产品质量稳定，但消耗高，特别是蒸汽耗量和电耗超出设计消耗定额较多。这除了一甲胺、三甲胺因销售原...     

甲胺废水中氨氮污染物的处理方法

甲胺废水中主要的污染物为氨氮和甲醇,大量含氨氮的甲胺废水如果不经过处理就排入到水体中,会导致水体的富营养化和生态坏境的污染,甚至会对人体及生物产生毒害作用。因此,如何处理甲胺废水中的氨氮污染物具有非常重要的实际意义,本文对几种常见的去除甲胺废水中氨氮的方法进行了概述。     

活性炭负载纳米镍催化葡萄糖还原胺化反应

在活性炭存在下硼氢化钠还原氯化镍制备了炭负载纳米镍（Ni/AC）,用扫描电镜、透射电镜、X射线衍射分析表征了催化剂的结构,以一步法葡萄糖的还原胺化合成葡甲胺的反应为模型,考察了催化剂的制备、催化反应条件等因素对葡甲胺产率的影响。产物结构经核磁共振波谱表征。葡萄糖与甲胺先形成环状甲胺基葡萄糖,进而在催化剂作用下被还原成葡甲胺。研究发现,催化剂制备过程中的NaCl对催化反应具有抑制作用。三乙胺的加入能够提高催化剂的催化性能。在n_葡萄糖∶n_Ni=9∶1,n_葡萄糖∶n_甲胺=1∶1.8,n_Ni∶n_三乙胺=1∶2.5,80 ℃及氢气5.0 MPa下反应1 h,葡甲胺的产率达到了98%。     

甲胺及下游产品二甲基甲酰胺概述和发展前景探讨

本文从技术的角度介绍甲胺产品基本状况，特别对上海石油化工研究院甲胺工艺技术给予关注，并且在发展方面提出需要注意事项。     

Methylamine hydrogenolysis on a rhodium catalyst: kinetics at high hydrogen partial pressures

The kinetics of hydrogenolysis of methylamine to methane and ammonia on a rhodium catalyst were investigated at hydrogen partial pressures in the range of 2–10 atm at temperatures of 368, 383, and 408 K. At a fixed methylamine partial pressure, the rate decreased with increasing hydrogen partial pressure. When the hydrogen pressure was held constant, the rate increased with increasing methylamine pressure. Results of a previous investigation by our group at lower hydrogen partial pressures (0.01–1 atm) indicated that the hydrogenolysis rate passed through a maximum with increasing hydrogen pressure. Moreover, at the lower hydrogen pressures, there was an inverse rather than positive dependence of the rate on methylamine partial pressure. With the aid of the present results, there is a much clearer definition of the maximum in the experimental data relating the reaction rate to hydrogen partial pressure. The inversion of the effect of methylamine pressure on the rate as the hydrogen pressure is varied over a sufficiently wide range is also firmly established. With regard to the interpretation of the many interesting features of the kinetics, we retain the suggestion from our earlier work that the rate limiting step at the highest hydrogen pressures is the scission of the carbon-nitrogen bond in a partially dehydrogenated methylamine intermediate chemisorbed on the rhodium, with no direct participation of hydrogen as a reactant in this step. At the lowest hydrogen pressures, however, there is a different rate limiting step in which hydrogen does participate directly as a reactant.     

Kinetics of hydrogenolysis of methylamine on a rhodium catalyst

The kinetics of hydrogenolysis of methylamine to methane and ammonia were investigated over a catalyst consisting of small clusters of rhodium dispersed on silica. Data obtained in the temperature range 353–408 K exhibit a characteristic pattern in which the rate passes through a maximum as the hydrogen partial pressure is increased by two orders of magnitude from 0.01 to 1.0 atm. At a given temperature, the position of the maximum shifts slightly in the direction of higher hydrogen partial pressure when the methylamine partial pressure increases by one to two orders of magnitude. Of particular interest is the finding that the rate increases with decreasing methylamine partial pressure over a broad range of hydrogen partial pressures covered in the investigation. As the hydrogen pressure increases, the inverse dependence of the rate on methylamine pressure becomes less pronounced and eventually disappears at a sufficiently high hydrogen pressure. At hydrogen partial pressures somewhat higher than those at which the rate maxima are observed, there is some indication that the inverse dependence changes to a positive dependence, especially at the lowest temperatures investigated. It seems likely that the rate limiting step of the reaction changes when the hydrogen pressure varies over a wide range. At the highest hydrogen pressures studied, it is suggested that the limiting step is one in which the scission of the carbon-nitrogen bond occurs in a hydrogen deficient surface intermediate formed in the chemisorption of methylamine, with no direct participation of hydrogen as a reactant in the step. On the other hand, at the lowest hydrogen pressures investigated, it is proposed that the rate is limited by a step in which chemisorbed hydrogen does participate directly as a reactant.     

Waterborne methylamine adduct as corrosion inhibitor for surface coatings

Soybean oil was epoxidized using peracetic acid prepared in situ from acetic acid and hydrogen peroxide with Dowex 50 W‐8X as a catalyst. The epoxidized soybean oil was allowed to react with methylamine. The resulting adduct was identified and emulsified. The emulsified methylamine adduct was added at different concentrations to an emulsion (styrene/acrylic)‐based paint (blank). The effect of the methylamine adduct concentration on the physical, chemical, and mechanical properties of the paint was studied. Various tests such as metal substrate weight loss, corrosion, blister, and scratch resistance were performed to evaluate the efficiency of the prepared adduct. It was found that there is an optimum concentration at which the methylamine adduct is very effective as a corrosion inhibitor. This concentration is about 0.5% by weight. In comparison with chromate anticorrosive pigment, it was found that the methylamine adduct is superior with more economical and environmental advantages. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 286–296, 2001     

甲胺作还原剂的选择性非催化还原脱硝特性的实验研究

为改善工业窑炉以及锅炉低负荷运行工况下的脱硝特性,本文对甲胺作还原剂的选择性非催化还原（SNCR）脱硝特性进行了实验研究,探讨了各控制因素对脱硝特性的影响以及分析了反应机理。实验结果表明：脱硝效率随反应温度呈双峰特性,拐点温度为750℃,最佳温度窗口为450～600℃;脱硝效率随氨氮比（NSR）增大而升高,反应产生的副产物NO₂和N₂O浓度随之增大;氧含量对SNCR脱硝特性具有双重特性,高浓度和低浓度氧气均对脱硝反应不利;物料浓度随NO初始浓度增加而增大,脱硝效率和副产物也提高; SO₂浓度越高,脱硝效率下降越多;水汽含量增大,脱硝效率也随之增大。本文的实验结论有助于SNCR脱硝工艺应用于工业窑炉以及优化锅炉低负荷运行时的脱硝特性。     

A-6型甲胺催化剂的工业应用

A-6型甲醇胺化制甲胺催化剂,液空速11.7h^-1条件下考察,500h,甲醇转化率97.52mol%, 活性稳定, 产物分布几乎不随时间变化。该催化剂已工业运转150天, 转化率98~99mol%,N/C=1.95条件产物粗胺中一、二、三甲胺分别为(wt%)29.24、40.76和30.00.     

甲胺催化剂再生试验技术初探

甲胺催化剂通常使用1次后即废弃，我公司根据催化剂再生普遍原理进行甲胺催化剂再生试验并取得成功。阐述了再生试验的方法、原理、步骤及结果，针对再生过程中的技术特点和关键问题进行了分析。     

沸石催化剂在甲胺合成中的应用

介绍了有关沸石分子筛的择形改性研究及其在甲胺合成工业中的应用和进展。     

氯铬酸甲胺／硅胶氧化１—萘甲醇制备１—萘甲醛

采用一般新型氧化剂氯铬酸甲胺／硅胶（ＭＣＣ／硅胶）氧化１－萘甲醇制备１－萘甲醛,考察了温度、溶剂、氧化剂用量和１－萘甲醇浓度对反应的影响,结果发现ＭＣＣ／硅胶可在室温、高选择性地将１－萘甲醇氧化为１－萘甲醛,选择性达９０．２％。     

合成N-甲基-4-哌啶酮的新工艺

以甲胺溶液和丙烯酸乙酯为原料,经过加成、环合、成盐脱羧合成N-甲基-4-哌啶酮。对合成工艺进行了优化和改进,确定了较佳加成反应温度为50％,加成溶剂为三乙胺,缩合反应双酯与钠的较佳摩尔配比为1：1．4。产品总收率由文献值的53％提高到59．7％（以丙烯酸乙酯计算）。目标化合物经核磁共振分析确认。