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催化氧化法合成环己酮技术研究进展 总被引:1,自引:0,他引:1
介绍了以环己烷为原料催化氧化合成环己酮的主要方法,分析了环己烷氧化采用的主要催化剂。环己烷硼酸催化氧化法和钴盐催化氧化法存在环己烷转化率低及结渣现象;分子筛催化氧化法、金属氧化物以及金属络合物仿生催化氧化法可提高环己烷转化率及醇酮选择性;金属络合物仿生催化氧化法具有良好的开发应用前景。 相似文献
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《化学工业与工程技术》2016,(6):17-27
针对环己烷氧化法制环己酮生产成本普遍偏高,技术路线缺乏竞争力的问题,比较分析了在当前苯价格4 500元/t情况下,苯酚法、环己烷氧化法以及环己烯法3种环己酮工艺路线的生产成本以及构成。介绍了环己烷氧化法制备环己酮技术发展的3个阶段,重点介绍了第3阶段的均相和非均相结合分解工艺技术,以及加氢和脱氢热联合改进技术。用技术改进后的工艺指标核算环己烷氧化法生产成本,提出采取综合技术改进措施后,在低苯价格时期,在目前技术水平下,环己烷氧化法生产成本可以在苯价低于5 372元/t时低于环己烯法;技术改进前景预测为当苯价低于7 410元/t时,环己烷氧化法生产成本将低于环己烯法。 相似文献
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金属卟啉催化氧化环己烷工业试验研究 总被引:1,自引:1,他引:0
在金属卟啉催化氧化环己烷模试研究的基础上,将金属卟啉催化氧化技术直接应用于70 kt/a环己酮无催化氧化工业生产装置,考察环己烷转化率和产物的选择性。结果表明:在现有的工业装置上,直接使用金属卟啉催化剂,环己烷的转化率达5%-6%,选择性为93.9%-95.3%(以摩尔计),均高于无催化氧化工艺,环己烷消耗比无催化氧化工艺降低76 kg/t。在相同转化率下,工业试验的氧化选择性也高于模试研究。 相似文献
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报道了通过金属卟啉选择性催化空气氧化甲基环己烷制备甲基环己醇和甲基环己酮的方法.在金属锰卟啉催化下,甲基环己烷被空气氧化为3种甲基环己酮的异构体、1-甲基环己醇和2-甲基环己醇.考察了不同反应条件和金属卟啉结构对甲基环己烷氧化反应转化率和选择性的影响.与四苯基锰卟啉相比较,烷氧基取代的金属锰卟啉为催化剂时,虽然反应转化率降低了,但明显提高了甲基环己醇和甲基环己酮的选择性.且金属上的取代基团体积越大,反应的转化率越高,同时选择性较高.以金属卟啉5,10,15,20-四(对庚烷氧基苯基)锰卟啉为催化剂,反应的转化率可以达到20%,甲基环己醇和甲基环己酮的总选择性为76%. 相似文献
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环己酮是重要的有机化工原料广泛应用于己内酰胺,聚酰胺6的生产,目前国内环己酮的生产工艺有环己烷氧化法和环己烯水合法,就两种方法的工艺路线、生产原理、原料化剂消耗、能源动力消耗、可变成本占地做了详细的分析对比。 相似文献
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金属卟啉催化烷烃氧化研究及工业应用进展 总被引:2,自引:3,他引:2
介绍了国内外金属卟啉及金属卟啉催化烷烃氧化的研究情况 ,对其催化氧化环己烷生产环己酮工业应用进行了连续性研究 ,实验表明 :环己烷在 14 3~ 14 7℃ ,0 .8~ 0 .9MPa和金属卟啉催化条件下 ,环己烷转化率达 7%左右时 ,环己醇、环己酮和环己基过氧化氢的选择性可达到 87%以上 ,其中环己醇和环己酮占75 %以上 相似文献
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RH-Cr and RH-Cr500 were synthesized from rice husk by solvent extraction and gel precipitation technique. The specific surface
area of RH-Cr and RH-Cr500 were found to be 0.542 and 1.20 m2 g−1 respectively. Energy dispersive X-ray (EDX) analysis showed that Cr(III) was homogenously incorporated in the matrix of both
samples to a maximum of ca. 16% in RH-Cr500. Elemental analysis showed that RH-Cr contained ca. 15% carbon, while RH-Cr500
contained negligible amounts. FTIR analysis showed the extracted solid contained silanol (Si–OH) and siloxane (Si–O–Si) groups.
Catalytic oxidation of cyclohexane with H2O2 using RH-Cr as the catalyst showed a 27.13% conversion to cyclohexanone and cyclohexanol with a selectivity of 57.37% and
42.63% respectively. However, RH-Cr500 showed only 14.01% conversion but with a selectivity of 64.83% of cyclohexanone and
35.17% of cyclohexanol. Epoxidation of cyclohexene using H2O2 with RH-Cr as the catalyst gave a conversion rate of 30.17% with a selectivity of 11.51% towards cyclohexene oxide, 63.21%
2-cyclohexen-1-one and 25.29% 2-cyclohexen-1-ol. The same reaction with RH-Cr500 as the catalyst showed 21.28% conversion
with 14.65% cyclohexene oxide, 68.71% 2-cyclohexen-1-one and 16.64% 2-cyclohexen-1-ol. In the catalytic oxidation of cyclohexanol
to cyclohexanone, RH-Cr showed a conversion of 12.25% while RH-Cr500 showed a conversion of 13.52%. No others products were
detected in the conversion. Comparison with published catalytic systems showed that RH-Cr and RH-Cr500 to be a better catalyst
even though the surface area of these catalysts were low. 相似文献
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金属卟啉类仿生催化剂的合成、构效关系及在催化氧化碳氢化合物中的应用 总被引:16,自引:3,他引:13
综述了金属卟啉类仿生催化剂的理论基础、合成、构效关系及其在仿生催化氧化烃类绿色合成有机中间体和产品方面的研究进展。重点报道了该课题组和郭灿城课题组近年来在金属卟啉类仿生催化剂的分子设计、合成方法、构效关系及其在催化空(氧)气选择氧化各种芳烃侧链、环烷烃绿色合成芳醛、芳酸、环己酮、己二酸等重要有机中间体及精细化学品方面的研究成果,特别是由湖南大学郭灿城教授与中石化联合开发的完全拥有我国知识产权的仿生催化空气氧化环己烷(80~140℃,0.5~0.8MPa下反应2h)制取环己醇及环己酮的新技术,已于2003年首次成功地实现了产业化,其中,环己烷的转化率可达8%~10%,环己醇及环己酮的选择性可达90%。最后,对仿生催化技术的发展方向及应用前景进行了展望。引用文献57篇。 相似文献
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Continuously Conducted Selective Hydrogenation of Benzene to Cyclohexene in a Four‐Phase System 下载免费PDF全文
Currently, the production of nylon 6 and nylon 6.6 is based on the complete hydrogenation of benzene to cyclohexane over nickel or platinum catalysts and its subsequent oxidation at very low conversions to a mixture of cyclohexanol/cyclohexanone. This mixture is further reacted to ?‐caprolactam or adipic acid. Alternatively, the reaction can be carried out by selective hydrogenation of benzene to cyclohexene and subsequent hydration with acidic catalysts to cyclohexanol. A laboratory method for the selective hydrogenation of benzene in a continuous stirred‐tank reactor (CSTR) using a gas/liquid/liquid/solid system is presented. 相似文献
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Amorphous silica was modified by doping with titania through a surface sol–gel process and applied as the support for depositing
gold. These doped silica-supported gold catalysts were tested in the selective cyclohexane oxidation to cyclohexanone and
cyclohexanol using oxygen. Under the oxidation conditions of 150 °C, 1.5 MPa and 3 h, a selectivity of 91.7% for cyclohexanone
and cyclohexanol could be reached over the gold catalyst, affording a cyclohexane conversion of 8.4% and a turnover frequency
up to 40,133 per hour. Moreover, the catalytic activity and selectivity could be well retained in 4 recycling oxidation reactions,
showing a high stability of the gold catalyst supported on titania-doped silica. 相似文献