丙二醇合成工艺

介绍了以环氧丙烷为原料合成丙二醇的催化剂开发、物料配比、工艺条件、反应器结构等国内外发展现状。     

丙二醇醚技术发展概况

评述了丙二醇醚的原料路线、催化剂开发、技术路线等，比较了各种合成方法的优缺点．     

Direct Oxidation of Propylene to Propylene Oxide with Molecular Oxygen: A Review

The direct oxidation of propylene to propylene oxide (PO) using molecular oxygen has many advantages over existing chlorohydrin and hydroperoxide process, which produce side products and require complex purification schemes. Recent advances in liquid-phase and gas-phase catalytic oxidation of propylene in the presence of only molecular oxygen as oxidant and in absence of reducing agents are summarized. Liquid-phase PO processes involving soluble or insoluble Mo, W, or V catalysts have been reported which provide moderate conversions and selectivities, but these likely involve autoxidation by homogeneous chain reactions. Gas-phase PO catalysts have been mostly Ag-, Cu-, or TiO₂-based substances, although other compositions such as Au-, MoO₃-, Bi-based catalysts and photocatalysts have also been suggested as possibilities. The Ag catalysts differ from those used for ethylene oxide production in having high Ag contents and numerous additives. The additives are solid-phase alkali metals, alkaline earth metals, and halogens, with the most common substances being NaCl and CaCO₃. Nitrogen oxides in the form of gas-phase species or nitrates have also been found to be effective in enhancing PO production. Direct epoxidation by surface nitrates is a possibility. Titania catalysts supported on silicates have also been reported. These have higher PO selectivities at high conversion than silver catalysts.     

Propylene epoxidation in a microreactor with electric heating

Gas phase propylene epoxidation on gold catalysts has attracted wide attention from industry and academia due to its high selectivity. However, it suffers from low propylene conversion and rapid catalyst deactivation. Experiments showed that propylene conversion could be increased by raising H₂, O₂, or C₃H₆ concentration in the feed, but the feed compositions were within the explosion limit. It was also shown that the activity of the used catalyst could be fully recovered, but the regeneration temperature was 280 °C, much higher than that for reaction. Therefore a microchannel reactor was devised to suppress explosion and was constructed with Fecralloy, to raise the temperature rapidly for catalyst regeneration by electric heating. In two minutes the temperature of the reactor could be raised from 50 to 300 °C. Catalysts were coated on the alloy belt by dip coating, and the performance of the reactor was evaluated under different operating conditions. Results showed that in the microreactor the overall reaction rate was controlled mainly by the intrinsic reaction rate, and also influenced by film diffusion to a certain extent. The deactivated catalyst was regenerated in the microchannel reactor and the activity was fully recovered.     

尿素醇解合成碳酸丙烯酯研究进展

综述了尿素醇解合成碳酸丙烯酯的现状和研究进展,详细介绍了酸碱催化剂的催化机理以及影响催化剂活性的因素,分析总结了目前催化剂体系存在的问题,并提出了今后催化剂的研究方向.     

Chemical Fixation of Carbon Dioxide to Propylene Carbonate Using Smectite Catalysts with High Activity and Selectivity

The reaction of propylene oxide and carbon dioxide to propylene carbonate was carried out using Mg-, Ni- and Mg-Ni-containing smectite catalysts which contain different amounts of alkali atoms such as sodium, potassium and lithium. These catalysts are highly active and selective for this reaction. The catalytic activity strongly depends on the elemental composition of the catalyst used. Particularly the amount of alkali atoms incorporated in the catalyst is the most important factor governing the catalytic performance. The most active catalyst among those prepared in the present study shows a turnover number of 105 mmol/g for the propylene carbonate formation, which is the highest turnover number compared with those reported so far (10 mmol/g) for the title reaction.     

丙烯氧化制备丙烯酸催化剂研究

考察了在丙烯氧化制备丙烯酸催化剂制备过程中,共沉淀反应时沉淀液加入速度的快慢以及沉淀液加入之前钼酸铵、偏钒酸铵、仲钨酸铵三者的反应时间对催化剂性能的影响,并通过优选酸性调整助剂改善了催化剂的表面酸性,确定了丙烯酸催化剂放大生产中重点控制工艺参数,在此条件下生产的6批次150Kg级催化剂的分析评价表明,丙烯酸的收率均在87％以上,催化剂制备重复性好.     

环氧丙烷与二氧化碳合成碳酸丙烯酯

介绍了PC的性质、应用情况和生产工艺。通过对影响合成PC的主要因素和机理的讨论,指出催化剂和溶剂是影响PC收率的重要因素,较高的压力对提高产品的选择性有利。     

Experimental and Kinetic Studies on a Homogeneous System for Diethyl Carbonate Synthesis by Transesterification

A synthesis of diethyl carbonate through transesterification of propylene carbonate and ethanol, coproducing useful propylene glycol, was carried out in the presence of sodium ethoxide as catalyst. The effects of reaction parameters such as catalyst concentration, mole ratio of ethanol to propylene carbonate and reaction temperature on the transesterfication reaction were investigated. The results showed that the reaction is reversible with a propylene carbonate equilibrium conversion of about 64 % at an ethanol to propylene carbonate mole ratio of 8.0 and a reaction temperature of 303 K. A kinetic model was proposed based on the reaction mechanism. The model parameters were estimated by the Runge‐Kutta method. The statistical test showed that the model calculation results were in good agreement with the experimental data.     

氯丙醇减压皂化生产环氧丙烷

氯丙醇减压皂化生产环氧丙烷＊刘家祺孙广智刘禾（天津大学化工系，天津３０００７２）（天津化工设计院，天津３００１９３）氯丙醇减压皂化生产环氧丙烷＊刘家祺孙广智刘禾（天津大学化工系，天津３０００７２）（天津化工设计院，天津３００１９３）关键词氯丙醇环氧丙...     

尿素与丙二醇合成碳酸丙烯酯的中试研究

在小试基础上,对尿素与丙二醇合成碳酸丙烯酯进行了千吨级中试研究。中试试验结果表明,在反应温度120~180℃、反应压力30~60 kPa、反应时间2~4 h、尿素与丙二醇物质的量之比1.0∶1.5、催化剂使用量为1%(质量分数)的条件下,产品碳酸丙烯酯的收率为92%~95%。在反应过程中,催化剂采用过滤的方法回收后可循环使用;反应产物经减压精馏后,产品碳酸丙烯酯的纯度为99.5%(质量分数)以上,各项质量指标均达到了优级品的要求。     

Propylene aromatization on Ga-MFI Zeolites

Propylene aromatization reaction was performed on various MFI type zeolites containing Ga species. The Ga was introduced into the zeolites by substitution (Ga-MFI), ion exchange (GIZ) and physical mixing (GPZ). A com-mercialized zeolite (PQZSM-5) was also used for comparison. The catalysts prepared were characterized by using XRF, XPS, surface area measurement, NH₃-TPD, and H₂-TPR. Through the Ga substitution, the acidity of the modified catalysts was decreased, and dehydrogenation and aromatization reactions occurred more easily. The lattice Ga did not react well with hydrogen contrary to the Ga located at the outside of the lattice. It was also found that Ga-MFI catalysts facilitate alkylation reactions. This paper is dedicated to Professor Wha Young Lee on the occasion of his retirement from Seoul National University     

MgO催化尿素与1,2-丙二醇合成碳酸丙烯酯

采用8种金属氧化物为催化剂,考察了其在尿素与1,2-丙二醇合成碳酸丙烯酯反应中的催化性能。研究表明,以干燥法制备的MgO催化活性较好。通过工艺条件优化,在MgO用量为反应物总质量的3.2%,n(尿素)∶n(1,2-丙二醇)=1∶2,反应温度160℃,反应时间4 h的条件下,碳酸丙烯酯收率为87%。用XRD、BET对催化剂进行了表征。MgO比表面积是影响其催化活性的主要因素之一。     

Oxidative dehydrogenation of propane over monoliths at short contact times

A specially designed tubular microreactor with independent control of feed preheat as well as catalyst temperature and allowing to rapidly quench reaction products was used to test performance of supported Pt-based monolithic catalysts in the reaction of propane oxidative dehydrogenation at short contact times. To minimize the impact of undesired homogeneous reactions capable of decreasing propylene selectivity, proprietary straight-channel thin-wall high cell density corundum micromonoliths were chosen as supports. Catalytic properties of supported platinum were modified by using promoters known as dehydrogenation catalysts (tin, zinc aluminate spinel, transition metal pyrophosphates) as well as by tuning reaction mixture composition (propane/oxygen ratio, water and hydrogen content). In the operation temperature range up to 900°C with contact times 0.03–0.1 s, ethylene/propylene selectivities were found to strongly depend upon the chemical composition of the active component and type of feed. The results thus obtained demonstrate that for Pt-based catalysts, propylene yield can be substantially improved by suppressing secondary reactions of deep oxidation and cracking.     

铅、锌化合物催化尿素与1,2-丙二醇制备碳酸丙烯酯

以铅、锌的化合物为催化剂,进行尿素与1,2-丙二醇合成碳酸丙烯酯的反应,所用的铅、锌化合物催化剂均有活性,其中碳酸铅的催化活性最高。以碳酸铅为催化剂,在催化剂用量为反应物总质量的3%,n(1,2-丙二醇)/n(尿素)=3,反应温度160℃,反应时间6 h的条件下,碳酸丙烯酯的收率为98.2%。反应为多相催化体系,简单过滤即可实现催化剂与产物的分离。已完成5 L的扩试,碳酸丙烯酯收率为96%。     

丙烷脱氢制丙烯技术研究

介绍了催化脱氢、氧化脱氢、膜反应器脱氢等几种丙烷脱氢制丙烯技术,综述了丙烷催化脱氢制丙烯催化剂的研究现状,虽然丙烷催化脱氢生产丙烯已实现了工业化,但其催化剂的性能需进一步提高;对丙烷氧化脱氢制丙烯反应催化剂的研究现状及膜反应器在丙烷脱氢反应上所具有的优越性进行了描述,认为研发具有高稳定性和高透氢性能的氢分离膜,将有望能大幅度提高丙烯的收率。     

碳酸丙烯酯合成的工艺绿色化进展

以碳酸丙烯酯的合成为例,概要地介绍了这种化学品合成工艺的绿色化进展,其中包括各种合成方法采用的原始材料、催化剂选择和制备、副产物的生成、过程的原子经济性等。另外还介绍了以含叔胺基和季铵盐基团的大孔离子交换树脂和季铵化壳聚糖为多相催化剂由环氧丙烷和二氧化碳在超临界条件下合成碳酸丙烯酯过程中各自的一些工艺试验参数、影响因素、收率和选择性等。     

负载型碳酸钾催化剂上二氧化碳与1,2-丙二醇合成碳酸丙烯酯反应研究

在负载型碳酸钾催化剂上对二氧化碳与1,2-丙二醇(PG)合成碳酸丙烯酯(PC)反应进行了研究.结果表明,负载型碳酸钾催化剂的最佳制备条件为:活性炭为载体,碳酸钾负载量为15%(wt),焙烧温度423.15 K.在反应温度443.15 K、催化剂用量为2.0%(wt)、溶剂(乙腈)/PG/二氧化碳(摩尔比)为19.2:3:4、二氧化碳初始压力为2.0 MPa、反应时间12 h的条件下,PG的转化率为12.9%,PC的收率为9.6%,选择性为74.4%.对活性炭负载碳酸钾催化剂进行了XRD分析,发现存在K2CO3和K2O两种晶相.BET分析结果表明,载体的比表面积对负载型碳酸钾催化剂的催化活性有较大影响.与均相碳酸钾催化剂相比,负载型碳酸钾催化剂上PC的选择性提高了40.3%.     

Catalytic cracking of 1-butene to propylene by Ag modified HZSM-5

Silver modified HZSM-5 (AgHZ) zeolite catalysts were prepared by ion exchange method and their catalytic properties in the 1-butene cracking reaction were measured. The catalysts were characterized by infrared spec-troscopy with pyridine adsorption (Py-IR), N2 adsorption and X-ray diffraction (XRD). The effects of Ag loading and steaming treatment on catalytic performances were studied. It is found that the activity of HZSM-5 (HZ) cat-alyst significantly decreases with the steaming time, whereas AgHZ catalysts show stable activity in the steaming time of 24–48 h and their activities increase with the Ag loading. When the steaming time is 24–48 h, the yield of propylene over HZ catalyst significantly decreases, whereas it is stable over AgHZ catalysts. The AgHZ catalysts with Ag loadings of 0.28%–0.43%(by mass) show similar propylene yields (~30%), which are higher than that over the AgHZ catalyst with a Ag loading of 0.55%(by mass). These results indicate that the steam-treated AgHZ catalysts with optimum Ag loadings have higher yield of propylene and are more stable than the steam-treated HZ catalyst. The regeneration stability measurement in butene cracking also shows that the AgHZ catalyst steam-treated under a suitable condition has better stability than the HZ catalyst.     

Propylene metathesis over Re2O7/Al2O3-B2O3 catalysts

A series of alumina aluminum borate (AAB) with various Al/B molar ratios were prepared by the coprecipitation method. The supported rhenium oxide catalysts with various contents of Re₂O₇ were also prepared by the impregnation method with perrhenic acid. The catalytic activity and stability of Re₂O₇/AAB catalysts for the reaction of propylene metathesis were tested in a fixed-bed microreactor. It was found that Re₂O₇/AAB is more active, stable and regenerable than Re₂O₇/Al₂O₃ for propylene metathesis. The optimum Al/B molar ratio was found to be in the range of 4–10.