N－甲基氧化吗啉的合成研究

以吗啉为原料分二步合成Ｎ－甲基氧化吗啉，讨论了温度、催化剂、时间等因素对反应结果的影响，并提出处理未反应的双氧水的有效方法。     

Physical agglomeration behavior in preparation of cellulose‐N‐methyl morpholine N‐oxide hydrate solutions by simple mixing

The different melting temperatures of N‐methyl morpholine N‐oxide (NMMO) hydrates in the cellulose–NMMO hydrate solution may be explained by the rather different crystal structures of NMMO hydrates, which are determined by the amount of the hydrates. The preparative process of cellulose–NMMO hydrate solution may result in cellulose structural change from cellulose I to cellulose II, depending on the amount of the hydrate. Mixtures of cellulose and NMMO hydrate in a blender was changed from the granules to slurry with increasing mixing time at 60–70°C, which is below the melting point of the NMMO hydrate. In the case of 15 wt % cellulose–NMMO hydrate granules, which were made by mixing for 20 min, the melting points of various NMMO hydrates were obtained as 77.8°C (n = 0.83), 70.2°C (n = 0.97), and 69.7°C (n = 1.23), respectively, depending on the hydrate number. However, the melting points of cellulose–NMMO hydrate slurry and solution were shifted lower than those of cellulose granules, while the mixing time of slurry and solution are 25 and 35 min, respectively. These melting behaviors indicate instantaneous liquefaction of the NMMO hydrate and the diffusion of the NMMO hydrate into cellulose during mixing in a blender. When cellulose was completely dissolved in NMMO hydrate, the crystal structure of cellulose showed only cellulose II structure. In the cellulose–NMMO products of granules or slurry obtained by high‐speed mixing, which is a new preparation method, they still retained the original cellulose I structure. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1687–1697, 2004     

N-丙烯酰吗啉的合成

以丙烯酸、三氯化磷为原料合成丙烯酰氯,再与吗啉酰基化生成N-丙烯酰吗啉。产品纯度99.5%以上。     

盐酸吗啉脒胍的合成研究

以吗啉和盐酸为原料合成盐酸吗啉,使其与双氰胺反应制备盐酸吗啉脒胍。重点讨论了原料配比、加料顺序、反应时间及溶剂等因素对合成工艺的影响。研究表明：吗啉：浓盐酸=1．06∶1(摩尔比),合成盐酸吗啉的收率可达98．27％,且加料顺序对反应无明显影响；以二甲苯为溶剂,盐酸吗啉：双氰胺=0．8∶1(质量比),反应时间为3．5h,盐酸吗啉脒胍的收率为97．01％。两步反应总收率可达96．97％。     

新型吗啉合成催化剂在3000t/a合成反应器的工业应用评价

采用自行研制开发的Ni-Cu-Mg/Al2O3催化剂,在3 000 t/a合成反应器上进行了工业应用,并得出了吗啉生产的最佳工艺操作参数:初期操作温度206℃,床层的温升13～18℃,二甘醇操作空速0.10 h-1,循环气空速1 670～1 780 h-1,合成操作压力1.55 MPa.二甘醇基本实现全转化,合成收率≥88%,过程总收率超过84%.     

吗啉副产物的开发利用

以吗啉工业生产中的副产物为原料,采用加压水解法,经分离后,可得到吗啉及混合醇。在210℃,2．0MPa下,水与副产物的质量比为1：1,采用氢氧化钠为催化剂,用量为副产物的1．5％,反应时间为4小时,吗啉的收率可达35％,混合醇的收率可达42％。混合醇可替代乙二醇作为防冻液的主要原料,60％的混合醇水溶液凝固点能达到-40℃以下。     

乙酰吗啉的合成

以吗啉和乙酰氯为原料合成农药中间体乙酰吗啉 ,反应条件温和 ,收率在 94 %以上 ,产品纯度 >95 %     

A bronsted basic ionic liquid as an efficient and environmentally benign catalyst for biodiesel synthesis from soybean oil and methanol

Morpholine basic ionic liquid was synthesized with N-methyl morpholine, N-butyl bromide, and KOH by two-step method and was used to catalyze the transesterification of soybean oil with methanol to biodiesel. The structure of the catalyst were examined by ¹H nuclear magnetic resonance. The effects of the molar ratio of methanol to oil, reaction temperature, and amount of catalyst on the biodiesel yield were investigated. Optimized biodiesel yield of 94.5% was achieved with catalyst amount of 3.0 wt%, and methanol to soybean oil molar ratio of 14:1 at reaction temperature of 60 °C for 6 h. The catalyst has maintained sustained activity after being employed to six cycles. The prepared biodiesel component was analyzed by gas chromatography-mass spectrometry (GC-MS) and the results showed that the biodiesel comprised of hexadecanoic acid methyl ester, 10, 13-octadecadienoic acid methyl ester, 9-octadecenoic acid methyl ester, and octadecanoic acid methyl ester, illustrating that fatty acids of soybean oil were converted completely.     

N-氨丙基吗啉合成研究

以吗啉和丙烯腈为原料,经加成、催化加氢和精制过程生产N-氨丙基吗啉,考察了催化剂种类及用量、原料配比、反应温度、压力、时间等因素对反应的影响,确定了最佳工艺条件为n(丙烯腈)∶n(吗啉)=1.0∶1.05,反应温度40℃,反应时间5~5.5h,加成收率99%以上,精制后中间产物质量分数99%;采用粉末金属钴为催化剂,w(催化剂)=2%,质量分数25%氨水为助催化剂,w(助催化剂)=50%,反应温度150℃,反应压力4.0 MPa,反应5h,加氢收率88%以上,精制后产品质量分数99.7%。