《工程(英文)》 >> 2017年 第3卷 第3期 doi: 10.1016/J.ENG.2017.03.003
尼龙-6 单体己内酰胺绿色生产技术
Research Institute of Petroleum Processing, China Petrochemical Corporation , Beijing 100083, China
收稿日期 :2016-11-17 修回日期 :2017-01-18 录用日期 : 2017-01-19 发布日期 :2017-05-10下一篇 上一篇
摘要
中国石化石油化工科学研究院(RIPP) 历经20 年的努力,成功开发出尼龙-6 单体己内酰胺绿色生产技术。该项技术主要包括:钛硅分子筛与浆态床反应器集成用于环己酮氨肟化合成环己酮肟,纯硅分子筛与移动床反应器集成用于环己酮肟气相贝克曼重排,非晶态Ni 催化剂与磁稳定床反应器集成用于己内酰胺精制。己内酰胺绿色生产技术在国际上率先实现工业化应用,建成了200 kt·a−1的工业装置。与已有技术相比,工业装置投资明显减少,氮原子利用率大幅提升,“三废”排放显著下降,没有副产硫酸铵。因此,已内酰胺与苯之间的价格差逐步减小。2015 年,己内酰胺绿色生产技术的产能达到3 × 106 kt·a−1,使我国成为世界第一己内酰胺生产大国,全球市场份额超过50 %。
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参考文献
[1] IHS chemical Week, nylon engineering resins. [cited 2016 Jan]. Available from: http://chemweek.com.
[2] Lin M, Shu X, Wang X, Zhu B, inventors; China Petrochemical Corporation, Research Institute of Petroleum Processing, Sinopec, assignees. Titanium-silicalite molecular sieve and the method for its preparation. United States patent US 6475465. 2002 Nov 5.
[3] Sun B, Wu W, Wang E, Li Y, Zhang S, Hu L inventors; China Petroleum & Chemical Corporation, Research Institute of Petroleum Processing, Sinopec, assignees. Process for regenerating titanium-containing catalysts. United States patent US 7384882. 2008 Jun 10.
[4] Wu W, Sun B, Li Y, Cheng S, Wang E, Zhang S, inventors; China Petroleum & Chemical Corporation, Research Institute of Petroleum Processing, Sinopec, assignees. Process for ammoximation of carbonyl compounds. United States patent US 7408080. 2008 Aug 5.
[5] Cheng S, Min E, Wu W, Sun B, Zhang S, Wang E, inventors; China Patent Agent (Hong Kong) Co., Ltd., assignee. A method of cyclohexanone oxime’s gas phase rearrangement to caprolactam. China patent CN 100497316. 2003 Nov 28. Chinese.
[6] Cheng S, Min E, Wu W, Sun B, Zhang S, Wang E, inventors; China Petroleum & Chemical Corporation, Research Institute of Petroleum Processing, Sinopec, assignees. A preparation method of zeolite catalyst with an MFI structure. China patent CN 1600428. 2003 Sep 28. Chinese.
[7] Mu X, Zong B, Min E, Wang X, Wang Y, Zhang X, et al.., inventors; China Petroleum Corporation, Research Institute of Petroleum Processing, Sinopec, assignees. Hydrogenation catalyst and its preparation. United States patent US 6368996. 2002 Apr 9.
[8] Meng X, Mu X, Zong B, Min E, Zhu Z, Fu S, et al.. Purification of caprolactam in magnetically stabilized bed reactor. Catal Today 2003;79–80:21–7. doi: 链接1
[9] Xu K, Sun B, Lin J, Wen W, Pei Y, Yan S, et al.. e-Iron carbide as a low-temperature Fischer-Tropsch synthesis catalyst. Nat Commun 2014;5:5783. PMID:25503569 doi: 链接1
[10] Zong B. Amorphous Ni alloy hydrogenation catalyst and magnetically stabilized bed reaction technology. Catal Surv Asia 2007;11(1):87–94 链接1
[11] Pei Y, Zhou G, Luan N, Zong B, Qiao M, Tao F. Synthesis and catalysis of chemically reduced metal-metalloid amorphous alloys. Chem Soc Rev 2012;41(24):8140–62. PMID:22907172 doi: 链接1
[12] Zong B, Mu X, Zhang X, Meng X, Qiao M. Research, development, and application of amorphous nickel alloy catalysts prepared by melt-quenching. Chinese J Catal 2013;34(5):828–37. doi: 链接1
[13] Zhou G, Pei Y, Jiang Z, Fan K, Qiao M, Sun B, et al.. Doping effects of B in ZrO2 on structural and catalytic properties of Ru/B-ZrO2 catalysts for benzene partial hydrogenation. J Catal 2014;311:393–403. doi: 链接1
[14] Zong B, Zhang X, Qiao M. Integration of methanation into the hydrogenation process of benzoic acid. AIChE J 2009;55(1):192–7. doi: 链接1
[15] Zhu L, Guo P, Chu X, Yan S, Qiao M, Fan K, et al.. An environmentally benign and catalytically efficient non-pyrophoric Ni catalyst for aqueous-phase reforming of ethylene glycol. Green Chem 2008;10(12):1323–30. doi: 链接1
[16] Hu J, Fan Y, Pei Y, Qiao M, Fan K, Zhang X, et al.. Shape effect of ZnO crystals as cocatalyst in combined reforming-hydrogenolysis of glycerol. ACS Catal 2013;3(10):2280–7. doi: 链接1
[17] Zong B, Meng X, Mu X, Zhang X. Magnetically stabilized bed reactors. Chinese J Catal 2013;34(1):61–8 链接1
[18] Fan J, Zong B, Zhang X, Meng X, Mu X, Yu G, et al.. Rapidly quenched skeletal Fe-based catalysts for Fischer-Tropsch synthesis. Ind Eng Chem Res 2008;47(16):5918–23 链接1
[19] Yu G, Sun B, Pei Y, Xie S, Yan S, Qiao M, et al.. FexOy@C spheres as an excellent catalyst for Fischer-Tropsch synthesis. J Am Chem Soc 2010;132(3):935–7. PMID:20028126 链接1
[20] Sun B, Yu G, Lin J, Xu K, Pei Y, Yan S, et al.. A highly selective Raney Fe@HZSM-5 Fischer-Tropsch synthesis catalyst for gasoline production: One-pot synthesis and unexpected effect of zeolites. Catal Sci Technol 2012;2:1625–9 链接1
[21] Sun B, Jiang Z, Fang D, Xu K, Pei Y, Yan S, et al.. One-pot approach to a highly robust iron oxide/reduced graphene oxide nanocatalyst for Fischer-Tropsch synthesis. ChemCatChem 2013;5(3):714–9. doi: 链接1
[22] Sun B, Lin J, Xu K, Pei Y, Yan S, Qiao M, et al.. Fischer-Tropsch synthesis over skeletal Fe-Ce catalysts leached from rapidly quenched ternary Fe-Ce-Al alloys. ChemCatChem 2013;5(12):3857–65. doi: 链接1
[23] Cheng Y, Lin J, Xu K, Wang H, Yao X, Pei Y, et al.. Fischer-Tropsch synthesis to lower olefins over potassium-promoted reduced graphene oxide supported iron catalysts. ASC Catal 2016;6(1):389–99 链接1
[24] Xu K, Cheng Y, Lin J, Wang H, Xie S, Pei Y, et al.. Nanocrystalline iron-boron catalysts for low-temperature CO hydrogenation: Selective liquid fuel production and structure-activity correlation. J Catal 2016;339:102–10. doi: 链接1
[25] Pan Z, Dong M, Meng X, Zhang X, Mu X, Zong B. Integration of magnetically stabilized bed and amorphous Nickel alloy catalyst for CO methanation. Chem Eng Sci 2007;62(10):2712–7. doi: 链接1
[26] Dong M, Pan Z, Peng Y, Meng X, Mu X, Zong B, et al.. Selective acetylene hydrogenation over core-shell magnetic Pd-supported catalysts in a magnetically stabilized bed. AIChE J 2008;54(5):1358–64 链接1
[27] Peng Y, Dong M, Meng X, Zong B, Zhang J. Light FCC gasoline olefin oligomerization over a magnetic NiSO4/γ-Al2O3 catalyst in a magnetically stabilized bed. AIChE J 2009;55(3):717–25 链接1
[28] Cheng M, Xie W, Zong B, Sun B, Qiao M. When magnetic catalyst meets magnetic reactor: Etherification of FCC light gasoline as an example. Sci Rep 2013;3:1973. PMID:23756855 链接1