甘油合成环氧氯丙烷的工艺研究.pdf

南京理工大学
硕士学位论文
甘油合成环氧氯丙烷的工艺研究
姓名:顾苗
申请学位级别:硕士
专业:应用化学
指导教师:吕春绪
20090525
顽士论文
甘油合成环氧氯丙烷的工艺研究
摘要
环氧氯丙烷是一种重要的有机化工原料和精细化工产品,用途十分广泛。本论文研
究以甘油和HCI气体为原料一步法合成二氯丙醇,再经过环化反应合成环氧氯丙烷,详
细研究了其工艺条件,并用GCMS、R和'H-NMR鉴定结构,得出如下结论:
(1)研究甘油为原料,分别考察了以羧酸及其衍生物,三种锆、钛原子比的固体超
强酸以及具有 Keggin型杂多酸为催化剂合成二氯丙醇的工艺条件,研究结果表明:以
H3PW12Oo为催化剂,HPW12O40的焙烧温度为300℃,用量为2.3g,n(HCI)n(甘
油)-2.5:1,反应温度110℃,帯水剂用量为15mL,收率可达97.8%,与羧酸及其行生
物作催化剂相比,收率提高了9.2%,与固体超强酸相比,收率提高了4.3%,主要原因
是因为H3PW12O40具有较强的酸性,加速碳正离子的生成。
(2)以Ca(OH2、NaOH、KOH和固体超强碱为催化剂,考察二氯丙醇环化反应合
成环氧氯丙烷的工艺条件,发现在固体超强碱存在下,环氧氯丙烷的收率可达96.8%,
比使用液体碱作催化剂的汽提法提高了5.5%,一方面是因为固体超强碱的碱性更强,
加快氧负离子的生成,另一方面是因为汽提方法的反应环境是液相,液相反应会加速环
氧氯丙烷的水解。
关键词:甘油;二氯丙醇;环氧氯两烷;环化
Abstract
论文
Abstract
Epichlorohydrin played an important role in organic raw materials and fine chemicals,
which was used in chemical industry widely. In this paper, direct preparation of
dichloropropanol from glycerol and hydrochloric acid gas was carried out in a single step
then dichloropropanol can be converted to epichlorohydrin by cyclization. Through analyzing
the factors of the reaction, found the optimum conditions. The structure of these compounds
were identified by means of GC/MS, IR and H-NMR, the results were introduced as follows
)The chlorination of glycerol catalyzed by carboxylic acid catalysts and its derivatives,
heteropolyacid catalysts and solid acid catalysts was studied. The optimum conditions of the
reaction were described as follows, when H; W 12O40 was used as catalyst was 2.3 g,
calcinations temperature of catalyst was 300 C, n(HC) n(glycerol)=2.5: 1, the reaction
temperature was 110 C, the yield of dichloropropanol was up to 97.8%. The yield of
dichloropropanol was increased by 9.2% compared with carboxylic acid catalysts and its
derivatives and the yield was increased by 4.3% compared with solid acid catalysts. The main
factors were their different catalytic mechanisms and their acid strengths
(2 )The cyclization of dichloropropanol catalyzed by Ca(OH), NAOH, KOH and solid
superbase catalysts was studied. It was found that, the yield of epichlorohydrin was increased
by 5.5 compared with Ca(OH) catalyst, the results were influenced by their basicity and
conditions
Key words: glycerol; dichloropropanol; epichlorohydrin; cyclization